Copper-Cobalt Bimetallic nanoparticles supported on Magnetic MOF Derived N-doped carbon as highly efficient Catalysts for the C–N coupling and one-pot multicomponent reaction

Copper-Cobalt Bimetallic nanoparticles supported on Magnetic MOF Derived N-doped carbon as highly efficient Catalysts for the C–N coupling and one-pot multicomponent reaction | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Copper-Cobalt Bimetallic nanoparticles supported on Magnetic MOF Derived N-doped carbon as highly efficient Catalysts for the C–N coupling and one-pot multicomponent reaction Arezoo Ahmadi, Heshmatollah Alinezhad, Yaghoub Sarrafi This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5726553/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Magnetic metal-organic frameworks (MOFs) are promising precursors for generating diverse carbon-based nanostructures due to their facile recovery and separation, as well as their robust mechanical and thermal properties. In this study, a novel Cu-Co bimetallic nanoparticle supported on magnetic MOF derived N-doped carbon was successfully synthesized. The copper ions preloaded within the pores of the Co MOF provide abundant exposed Cu active sites. The pyrolysis treatment results in a hierarchical porous structure with a high surface area, contributing to mass transfer and enhancing reactant diffusion to the active sites. The developed catalyst was characterized extensively using FT-IR, XRD, BET, BJH, EDX, TGA, VSM, FE-SEM, ICP, and XPS techniques. The catalyst exhibited exceptional catalytic activity for C-N coupling and one-pot multicomponent reactions. This superior performance can be attributed to the synergistic effect between copper nanoparticles incorporated in the composite, as well as the highly porous N-doped carbon structure. The catalyst demonstrated remarkable stability, maintaining its activity without significant degradation after five consecutive reaction cycles. This innovative approach, capitalizing on the reinforcing interplay of structural and compositional advantages, opens up opportunities for the rational design and synthesis of highly efficient bimetallic nanoparticle catalysts supported on magnetic MOF-derived N-doped carbon. Physical sciences/Chemistry/Catalysis Physical sciences/Chemistry/Green chemistry Physical sciences/Chemistry/Organic chemistry Physical sciences/Chemistry/Synthesis Bimetallic catalyst Metal organic Framework Ullmann coupling reaction Biginellie reaction Multi component reactions Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction Transition metals, with their inherent ability to form diverse coordination complexes through chelation with ligands, have emerged as indispensable catalysts for a multitude of chemical transformations 1 . Their capacity to adopt multiple oxidation states, a unique characteristic of transition metals, gives them exceptional versatility in homogeneous catalysis 2 . However, the intrinsic limitations associated with homogeneous catalysts, such as product separation, catalyst recovery, and the risk of catalyst leaching, have spurred significant research efforts toward the development of heterogeneous alternatives 3 . Through the immobilization of these catalytically active metal complexes onto solid supports, heterogeneous catalysts provide an opportunity to mitigate these challenges while preserving the fundamental catalytic efficacy of transition metals 4 . A diverse array of materials, encompassing porous carbon-based materials, namely activated carbon, carbon nanotubes, graphene, and metal-organic frameworks, have been explored for this purpose, each offering distinct properties that make them well-suited for metal complex loading 5 . Furthermore, N-doped carbon materials have garnered significant attention owing to their outstanding surface area and potential for generating highly active sites 6 . Metal-organic frameworks (MOFs), composed of metal ions or clusters coordinated to organic linkers, have proven to be highly promising precursors for synthesizing N-doped carbon materials 7 . N-doped carbon-derived MOFs reveal superior stability under harsh conditions, and their structural architecture powerfully improves catalytic performance 8 . This approach leverages the distinctive properties of MOFs, including their abundant sources of metals and organic components, diverse morphologies, inherent crystallinity, high surface area, and structural robustness 9 . This is primarily due to the fact that the pyrolysis of MOFs often yields materials that retain the original morphology of the MOFs while also providing a nano porous structure with a uniform pore size 10 . Furthermore, MOFs have been widely applied in various fields, ranging from gas storage and separation 11 , sensing 12 , and, notably catalysis 13 . Extensive research consistently demonstrates that integrating MOFs with functional materials significantly enhances their capabilities, as well as optimizing MOF performance requires precise control over their structural and surface characteristics 14 . When MOFs are coupled with magnetic nanoparticles (MNPs) exhibiting high saturation magnetization, they can be accurately manipulated and rapidly isolated using a magnetic field. Magnetite (Fe 3 O 4 ) is the most prevalent magnetic material for this purpose 15 . This magnetic separation technique surpasses traditional methods, particularly centrifugation and filtration, boosting sustainability while advancing catalyst reuse and recycling 16 .The silica coating on Fe 3 O 4 nanoparticles serves as a crucial interfacial layer between the magnetic core and the MOF shell, inhibiting the agglomeration of MNPs and promoting the growth of the MOF layer. Additionally, the silica coated magnetic nanoparticles facilitate the formation of a robust and well-defined core-shell structure, ultimately enabling the synthesis of N-doped magnetic carbon material 17 . Zeolitic imidazolate frameworks (ZIFs), a subclass of MOFs, are composed of transition metal cations coordinated with imidazole-based ligands. Specifically, ZIF-67 incorporates cobalt ions and 2-methylimidazolate ligands, forming a tetrahedral structure 18 . The combination of low density, high surface area, exceptional stability, and porosity renders ZIF-67 a highly attractive candidate for numerous applications, such as gas storage, catalysis, adsorption, and sensing 19 . Intriguingly, ZIF-67, which contains cobalt metal in its structure, can serve as a multifunctional sacrificial template to produce diverse micro/nanostructures with complex configurations. Bimetallic systems, by amplifying the synergistic interactions between the introduced metal nanoparticles and the inherent metal nodes within the MOF structure, have attracted significant interest from materials scientists 20 . A recent approach to producing these systems involves integrating transition metals into MOFs by exposing them to metal sources. The incorporation of copper-cobalt into nano porous carbon-derived MOFs can further elevate catalytic efficiency through synergistic effects that alter the material's geometric and electronic properties 21 , while the metals complement each other 22 N-arylation reactions have become a strategic approach for the construction of pharmaceutical, biological, and chemical materials 23 . The critical role of nitrogen containing compounds in biological molecules has sparked a lot of interest in developing efficient methods for their preparation 24 . Although palladium complexes have traditionally dominated the field of N-arylation catalysis, their drawbacks in terms of cost, toxicity, and availability have driven the exploration of alternative metal-based catalysts 25 . Consequently, researchers are now turning to environmentally friendly metals like iron, cobalt, nickel, and copper. Copper has evolved as a promising replacement on account of its abundance, affordability, low toxicity, and reduced environmental impact. Furthermore, copper offers a potential route for catalyzing C-N bond formation, particularly via the Ullmann coupling reaction 26 . However, challenges related to reaction rates, efficiency, and substrate scope remain. Despite these obstacles, the development of efficient copper catalysts for C-N bond formation continues to be an area of ongoing research 27 . Multicomponent reactions (MCRs) represent a powerful strategy for the construction of carbon-carbon and carbon-heteroatom bonds, playing a pivotal role in the efficient synthesis of chemotherapeutic agents and organic compounds. By merging several reactants in one step, MCRs provide distinct advantages over conventional multi-step approaches, including reduced waste, lower energy consumption, and simplified purification processes. These benefits make MCRs not only more cost-effective but also environmentally sustainable 28 . The Biginelli reaction, discovered in 1983, involves the condensation of benzaldehydes, β -keto esters, urea, and ethyl acetoacetate under acidic conditions to yield 3, 4dihydropyrimidin-2(1H)ones (DHPMs), a class of heterocyclic compounds. These DHPM derivatives have proven to be essential scaffolds in medicinal chemistry, showcasing a broad spectrum of biological activities, including anti-inflammatory, antibacterial, anticarcinogenic, antioxidant, antiviral, and antihypertensive agents, as well as calcium channel-blocking properties and tumor inhibition. However, traditional methods for these valuable transformations are hindered by drawbacks such as harsh conditions, prolonged reaction times, and poor product yields. In this regard, researchers have actively pursued alternative strategies to address these challenges 29 . This paper presents a novel approach for synthesizing bimetallic magnetic N-doped carbon materials through a simple ion exchange process followed by MOF derivatization. A generalizable method for the fabrication of Cu-Co bimetallic magnetic MOF composites (Cu-Co@N-C) is developed, which serves as a dual template for the efficient synthesis of hybridized magnetic nanostructures (Fig. 1 ). The catalytic performance of the resulting Cu-Co@N-C was evaluated in an N-arylation coupling reaction between anilines and aryl halides. Additionally, its applicability was extended to the transformation of a range of aldehydes, urea, and ethyl acetoacetate into the corresponding DHPM derivatives through the Biginelli reaction. The introduction of copper into the cobalt-based porous structure significantly enhances catalytic performance due to the synergistic electronic and structural effects. These findings highlight the critical role of bimetallic catalyst design in elaborating the properties of MOF-derived porous materials for catalytic applications. 2. Experimental section 2.1. Materials and techniques The following reagents used in this experiment were supplied by Merck, Aldrich, and Fluka with high purity: Co (NO 3 ) 2 ·6H 2 O, FeCl 2 .4H 2 O, FeCl 3 .6H 2 O, tetraethyl orthosilicate (TEOS), (Cu (NO 3 ) 2 .3H 2 O), and 2-Methylimidazole (2-MIM). The structure of the synthesized catalysts was investigated through Fourier transform infrared spectroscopy (FT-IR) at the wavelength of 400–4000 cm -1 (Avatar, USA). The crystal structure of the samples was characterized by powder X-ray diffraction (XRD) patterns with Bruker D8 Advance diffractometer using CuKα (λ = 1.5418 A ◦ ) radiation. The micrographs and elemental distribution of the prepared materials were taken using a scanning electron microscope (SEM, Hitachi S-3400 N), equipped with a Bruker AXS XFlash 4010 EDS system to enable multi elemental analysis. Thermogravimetric analysis (TGA) was carried out in an air atmosphere using a TA Instrument SDT 2960. Nitrogen adsorption isotherms were measured at 77 K using a TriStar II (Micromeritics) gas adsorption analyzer. Data were analyzed using the Brunauer-Emmett-Teller (BET) at UIB (University of De Les Illes Balears Island) in Spain. Moreover, magnetic properties were measured using a vibrating sample magnetometer (VSM; LBKFB, Meghnatis Kavir Kashan). X-ray photoelectron spectroscopy (XPS) analyses were implemented using a Thermo Scientific K-Alpha XPS system. Inductively coupled plasma (ICP) was performed by (AGILENT 7500, Santa Clara, CA). The structure of the prepared products was assigned using 1 H and 13 C NMR spectra on a Bruker-400 Avance III spectrometer (Bruker, Germany) and comparing their melting points using an Electrothermal IA9100 (Essex, UK). 2.2. Preparation of Cu-Co bimetallic magnetic nano porous carbon material s (Cu-Co@N-C) 2.2.1. Synthesis of Fe 3 O 4 NPs The Fe 3 O 4 nanoparticles were synthesized via chemical co-precipitation using chlorine salts of Fe 3+ and Fe 2+ ions with a molar ratio of 2:1 in the presence of an ammonia solution, followed by the hydrothermal treatment. Typically, a mixture of FeCl 3 ·6H 2 O (2.70 g) and FeCl 2 .4H 2 O (1 g) was dissolved in the deionized water (100 mL), and the solution was vigorously stirred for 1 h under a nitrogen atmosphere. Afterward, NH 4 OH 25% (6 mL) was dropwise added to the reaction mixture. The mixture was heated for 1 h at 80 ° C, and the cooled black magnetite solid was collected with an external magnet, washed with distilled water, and dried under vacuum at 60 ° C for 24 h. 2.2.2. Preparation of MSiO 2 core–shell microspheres Magnetite nanoparticles were coated with a silica layer through sol–gel reaction 30 . Fe 3 O 4 NPs (1 g) were dispersed in 200 mL ethanol and 10 mL distilled water under ultrasonication for 30 min. Then 15.0 mL of ammonia aqueous solution (25 wt%) was added, and 2 ml of TEOS was slowly dropped into the mixture over 10 min. After sonicating, the obtained MSiO 2 nanoparticles were separated by an external magnet, washed several times with ethanol, and dried under vacuum. 2.2.3. Preparation of Co MOF@ MSiO 2 0.1 g of MSiO 2 was added to 1 g of Co (NO 3 ) 2. 6H 2 O in 60 mL methanol and the mixture was heated at 70 ◦ C for 20 min. Thereafter, a solution of 2-MIM (2.26 g in 60 mL methanol) was added dropwise to the mixture and was allowed to stir for 2 h. The solid was separated by a magnet and washed twice with methanol and dried under vacuum at 40 ◦ C to obtain ZIF-67@ MSiO 2 31 . 2.2.5. Synthesis of Cu-Co MOF@MSiO 2 0.2 g of Co MOF@MSiO 2 was added to the mixture solution of deionized water (15 mL) and ethanol (60 mL) containing 0.1 g of Cu (NO 3 ) 2 .3H 2 O and then sonicated at 60 ◦ C for 30 min. The product was collected by centrifugation, washed three times with deionized water and ethanol, then dried under vacuum at 60 ◦ C for 6 h to obtain Cu- Co MOF@MSiO 2 32 . 2.2.6. Synthesis of Cu-Co bimetallic magnetic nano porous carbon material s (Cu-Co@N-C) The as-Cu- Co MOF@MSiO 2 was heated in a nitrogen-filled furnace. The increase in temperature triggered the decomposition of organic linkers in ZIF-67, forming N-doped carbon (N-C). Simultaneously, cobalt precursors were reduced, incorporating cobalt into the N-C matrix. The nitrogen flow during this process prevented oxidation and ensured uniform heating, resulting in Cu–Co@N-C composites with desirable catalytic and adsorption capabilities 33 . 2.3 General procedure for N ‑ arylation reactions A mixture of Aryl halide (1mmol), aniline (1.2 mmol), potassium carbonate K 2 CO 3 (2 mmol), and 50 mg of catalyst (including 2 mol % Cu) in DMF (3 mL) was heated at 110 ° C for 12 hours. Upon completion of the reaction (monitored by TLC), the mixture was cooled to room temperature and diluted with EtOAc (5 mL). The catalyst was separated using an external magnet and washed with EtOAc (2×10 mL). The product was obtained after evaporation of the solvent and purified by recrystallization with ethanol. The structures of products were confirmed by 1 H and 13 C NMR spectra and measuring their melting points. 2.4 General procedure for Biginelli reaction A mixture of aryl aldehyde (1 mmol), β -dicarbonyl compound (1 mmol), and urea (1.5 mmol) in ethanol (5 ml) was stirred at room temperature for the appropriate time. Upon completion of the reaction, as indicated by TLC, the catalyst was simply separated by an external magnet and washed with ethanol (5 ml), then the solid product was obtained after evaporation of the solvent. To achieve the pure product, the crude product was washed with water and ether and recrystallized with ethanol. The structures of all products were established based on their 1 H and 13 C NMR spectra and melting point analysis. 3.2 Catalyst characterization The FT-IR spectra of the Fe 3 O 4 , M@SiO 2 , Co MOF@MSiO 2 , and Cu-Co MOF@MSiO 2 are depicted in Fig. 2A. In all spectra, the absorption bands at 3650-3250 cm -1 correspond to the O–H stretching mode. The peak at 580 cm -1 in the FT-IR spectra of the Fe 3 O 4 is related to the Fe-O-Fe stretching vibrations. The presence of peaks at 1070-1080 cm -1 attributed to the Si–O–Si stretching vibration confirms successful coating of SiO 2 layers on the surface of Fe 3 O 4 NPs. The additional peaks at 2925 and 3133 cm -1 (C-H stretching vibrations), 1579 cm -1 (C=N stretching vibration), 1454 (N-H stretching vibration), 1141 (C-N stretching vibration), and 424 (Co-N stretching vibrations) demonstrate the successful fabrication of Co MOF@MSiO 2 catalyst 31 . Furthermore, slight shifts in the absorption bands of Cu-Co MOF@MSiO 2 indicate the successful immobilization of the copper ions onto the surface of Co MOF@MSiO 2 . The XRD analysis of the synthesized materials, including Fe 3 O 4 , Co MOF@MSiO 2 , Cu-Co MOF@MSiO 2 and Cu-Co@N-C, revealed the formation of well-defined crystalline structures (Fig. 2B). The XRD pattern of Fe 3 O 4 exhibited sharp peaks at 30.29 ◦ , 35.52 ◦ , 43.29 ◦ , 53.67 ◦ , 57.39 ◦ , and 62.81 ◦ , corresponding to the (220), (311), (400), (422), (511), and (440) planes of Fe 3 O 4 , respectively (JCPDS No. 19–0629), indicating the formation of a pure magnetite phase. The characteristic peaks of Co MOF were observed at 7.33 ◦ (011), 10.61 ◦ (002), 12.81 ◦ (112), 14.81 ◦ (0 22), 16.76 ◦ (013), 18.29 ◦ (222), 24.72 ◦ (233) and 26.47 ◦ (134) in the XRD patterns of Co MOF@MSiO 2 and Cu-Co MOF@MSiO 2 displayed both Fe 3 O 4 and Co MOF peaks, suggesting the successful encapsulation of Fe 3 O 4 nanoparticles by the Co MOF coating. The characteristic peaks at 2θ = 43.69 ◦ , 50.59 ° , and 74.29 ◦ were assigned to the Cu (111), Cu (200), and Cu (220) reflections, which confirmed the introduction of Cu into the Co MOF did not significantly alter the crystal structure but might have slightly reduced the crystallinity. Thermal treatment of Cu-Co MOF@MSiO 2 led to the disappearance of imidazolate rings in the Co MOF scaffolds and complete transformation to Co 3 O 4 , as evidenced by the emergence of new peaks at 31.1 ◦ , 36.31 ◦ , 45.01 ◦ , 59.35 ◦ , and 65.81 ◦ , corresponding to the face-centered cubic Co 3 O 4 phases of (220), (311), (400), (511), and (440), respectively (JCPDS No. 43-1003) 34 . Furthermore, a broad peak around 26 ◦ indicative of a disordered graphitic structure, along with peaks corresponding to metallic Co at 44.19 ◦ (111), 51.27 ◦ (200), and 76.56 ◦ (220) (JCPDS no. 15-0806) 35 , was observed. Additionally, weaker peaks at 35.51 ◦ and 38.78 ◦ attributed to the (111) and (220) planes of CuO (JCPDS NO 48–1548) suggest the coexistence of these components within the carbon matrix 36 . Considering the critical role of catalyst pore structure in facilitating reactant access to active sites, N 2 adsorption-desorption isotherms of the M@SiO 2, Co MOF@MSiO 2 , Cu-Co MOF@MSiO 2 and Cu-Co@N-C, were recorded (Fig. 2C). The isotherm for M@SiO 2 exhibited type II behavior based on the IUPAC classification, while the isotherms for Co MOF@MSiO 2 and Cu-Co MOF@MSiO 2 are classified as type I, confirming a typical microporous structure for these materials. In the case of Cu-Co @N-C, the sharp uptake at low relative pressure is significantly reduced, indicating that a majority of micropores collapse during thermal treatment. The hysteresis loop, with type IV behavior, and the gradual uptake observed at P/P 0 =0.4, approved the formation of a mesoporous structure after the calcination of Cu-Co MOF@MSiO 2 precursors 37 . The corresponding specific surface areas, total pore volumes, and mean pore diameters are summarized in Table 1. The introduction of Co MOF into M@SiO 2 led to a higher surface area due to the high porosity of formed Co MOF@MSiO 2 . However, the pore volume and BET surface area of Co MOF@MSiO 2 are markedly reduced in comparison to the Cu-Co MOF@MSiO 2 , indicating that the pores of the host Co MOF framework are occupied by the supported Cu NPs 38 . The pore size distribution of Cu-Co@N-C is mainly centered at 0-2 nm and 2-20 nm, as depicted in Fig. 2D, verifying the formation of hierarchical pores, which is attributed to the pyrolysis treatment 39 . The thermal stability of the composites was evaluated via TGA, as shown in Fig. 2E. The mass loss of Fe 3 O 4 and M@SiO 2 is 6.23% and 11.73%, respectively, attributed to the removal of water and solvent. Both materials demonstrated excellent thermal stability, with negligible mass loss observed up to 800 °C. Co MOF@MSiO 2 undergoes a significant mass loss in the range of 25-800 ° C, which can be divided into two stages. The initial weight loss (12%) occurred between room temperature and 389 ◦ C, primarily due to the volatilization of absorbed water molecules from the pores of the zeolitic imidazole framework and some residual molecular solvents. Subsequently, a severe weight loss (49.03%) was observed between 390-510 ° C, corresponding to the collapse of the ZIF-67 skeleton 40 . However, the thermal stability of Cu-Co MOF@MSiO 2 was enhanced due to the successful immobilization of Cu species onto the Co MOF@MSiO 2 41 . Additionally, the Cu-Co@N-C composite indicated higher thermal stability than Cu-Co MOF@MSiO 2, which can be related to the proper pyrolysis process. The magnetic properties of Co MOF@MSiO 2 , Cu-Co MOF@MSiO 2 , and Cu-Co@N-C composites were evaluated at ambient temperature via VSM as shown in Fig.2F. The magnetic phase present in Co MOF@MSiO 2 was identified as Fe 3 O 4 , which exhibits a higher magnetic moment compared to the Fe particles in Cu-Co MOF@MSiO 2 42 .The saturation magnetization values of Co MOF@MSiO 2 and Cu-Co MOF@MSiO 2 were determined to be 28.54 and 20.92 emu g -1 , respectively, which are lower than the reported saturation magnetization value for Fe 3 O 4 . This reduction in saturation magnetization is attributed to the incorporation of non-magnetic components. The hysteresis curve of Cu-Co@N-C demonstrates strong magnetic properties with a saturation magnetization of approximately 27.56 emu g -1 , which is higher than that of Cu-Co MOF@MSiO 2. This improvement is mainly ascribed to the significant magnetic contribution from the N-doped carbon framework. Table 1 Surface area analysis parameter of as-synthesized material Catalyst BET total specific surface area (S BET m 2 g -1 ) Total pore volume(cm 3 g -1 ) Mean pore diameter (nm) M @SiO 2 70.54 0.19 3.1 Co MOF@MSiO 2 467.54 0.24 4.3 Cu-Co MOF@MSiO 2 358.62 0.17 4.8 Cu-Co@N-C 126.43 0.11 6.3 To gain further insights into the chemical composition of Cu-Co@N-C, XPS measurements (Fig. 3), and EDS analysis (Fig. 4), were conducted. In addition to the presence of C 1s, N 1s, O 1s, Si 2p, the survey spectrum also confirmed the presence of Cu, Co and Fe elements in the Cu-Co@N-C catalyst. The high-resolution C 1s spectra exhibited peaks at 284.5, 285.6, 286.5, and 288.1 eV corresponding to C=C, C=N, C–O, and C–N, respectively. The N 1s binding energy displayed peaks centered at 398.7, 399, 400.1, and 401.5 eV, representing graphitic and N heterocycle compounds 43 . The peak at 529.78 eV was assigned to the typical metal–oxygen bond binding energy 44 , while the peak at 530.74 eV can be attributed to the lattice oxygen (O 2 −) in Fe 3 O 4 45 . The peak at 533.12 eV can be ascribed to the C–O bond binding energy on the surface of carbon nitrides 46 . It is important to note that the peaks at 711.40 and 725.38 eV are associated with Fe 3+ 2p 3/2 and Fe 3+ 2p 1/2 . Moreover, the peaks at 710.51 and 723.10 eV are related to Fe 2+ 2p 3/, Fe 2+ p 1/2, while the peak at 719.91 eV corresponds to Fe 0 . These results point to the role of Fe in facilitating a more uniform dispersion and the formation of a greater number of pores within the ZIF-67 47 . In addition, the Si 2p spectra contained two peaks attributable to Si-O-Si (103.7 eV) and Si (-O) 2 (102.1 eV) 48 . The Co 2p spectra revealed four peaks corresponding to the oxidation states of Co 3+ , Co 2+ , Co 0 , and satellite peaks. The peaks located at 780.15 and 796.09 eV correlated with Co 3+ 2p 3/2 and 2p 1/2 , while those at 781.55 and 797.93 eV were attributed to Co 2+ 2p 3/2 and 2p 1/2 , respectively. Additionally, the peaks at 788.94 and 804.33 eV were assigned to metallic Co (Co 0 ) 49 . For the Cu 2p spectrum, as illustrated in Fig. 3, the peaks at about 932.25 and 951.58 eV can be attributed to the 2p 3/2 and 2p 1/2 of Cu 2+ . Furthermore, the peaks at approximately 931.72 and 951.76 eV correspond to the 2p 3/2 and 2p 1/2 of Cu 1+ . The existence of Cu + can be ascribed to the interaction between cobalt and copper during the annealing process in air. Meanwhile, the peaks at 936.17 and 954.74 eV were assigned to the characteristic satellite peaks of Cu 2+ 50 . The presence of C, N, O, Fe, Si, Co, and Cu in the Cu-Co@N-C structure was confirmed by EDS analysis, as shown in Fig. 4. The surface morphology of the prepared materials was investigated through SEM. Figs. 5 a-d display the morphology of Fe 3 O 4 , M@SiO 2, Cu-Co MOF@MSiO 2 and Cu-Co@N-C samples, respectively. It can be observed that the Fe 3 O 4 MNPs, which are uniform in shape and size as shown in Fig. 5a, are quite small and agglomerated. In Fig. 5b, it is seen that the particle agglomeration decreases upon coating Fe 3 O 4 MNPs with SiO 2 . The SiO 2 coating appears to be distributed relatively homogeneously, as indicated by the reduction in the gray color and the increase in white color 51 . The morphology of the Cu-Co MOF@MSiO 2 (Fig. 5c) revealed a uniform rhombic dodecahedral morphology, which confirmed the decoration of spherical M@SiO 2 nanoparticles on the surface of the Co MOF without being destroyed, as well as uniform dispersion of Cu nanoparticles. However, the Cu-Co@N-C (Fig. 5d) possessed the original contour of Cu-Co MOF@MSiO 2 with slight shrinkage and distortion due to the decomposition of the organic species and the reduction of cobalt ions during the pyrolysis process 52 .The Cu and Co contents of the bimetallic catalyst Cu-Co@N-C were calculated and quantified by ICP. The exact Co and Cu contents were estimated to be 0.84 and 0.44 mmol. g -1 respectively, suggesting the successful loading of Cu on the modified magnetic nano porous carbon. 3.2. Investigation of catalysis activity In order to investigate the catalytic effect of the prepared catalyst, it was used in the classical Ullmann coupling reaction using aryl halides and anilines. as well as in the Biginelli reactions between aldehydes, alkyl acetoacetate, and urea through a one pot three-component reaction that resulted in products with yields ranging from good to excellent. 3.2.1. C-N Ullmann coupling reaction The potential of Cu-Co@N-C as a bimetallic magnetic N-doped carbon catalyst was investigated in C−N cross-coupling reactions for the synthesis of different N-arylated products. The reaction of iodobenzene (1.0 mmol) and aniline (1.2 mmol) was chosen as the precursors for the model reaction, conducted at 110 ◦ C. An investigation into the optimization of the Ullmann cross-coupling reaction was conducted by systematically altering various experimental parameters (Table 2). The model reaction was examined in the presence of various catalysts (as well as catalyst free reaction conditions); the best result was obtained when the model reaction was performed in the presence of the Cu-Co@N-C catalyst (entries 1–7). This included exploring different solvents and bases, adjusting the quantity of catalyst used, and modifying the reaction temperature. The goal was to identify the optimal conditions that would enhance the efficiency and yield of the Ullmann coupling process. The outcomes are shown in Table 2. While screening the reaction in different solvents such as EtOH, DMSO, toluene, CH 3 CN, H 2 O, EtOAC and DMF (entries 8-13), we got the best result in DMF (entry 13). The optimization experiments carried out so far, exploring the effect of catalyst amount in the reaction, indicated that increasing the catalyst amount up to 50 mg raised the yield of the product, and further catalyst loading did not change the yield of reaction (entries 13–15). As can be seen, the reaction does not proceed in the absence of a catalyst (entry 16). Also, the effect of various bases such as K 2 CO 3 , KOH, Na 2 CO 3 , Et 3 N, K 3 PO 4 and NaOH, as well as the absence of a base, has been investigated on the reaction yield. In the lack of a base, a poor yield was obtained, which signifies their importance in the reaction, when K 2 CO 3 providing the best yield (entries 17-22). The influence of temperature on the product conversion was investigated, and the best yield was obtained at 110 ° C (entries 14 and 23-26). Table 2 Optimization of Ullmann Reaction conditions a Entry Catalyst catalyst loading (mg) Solvent Base Temp( ◦ C) time(h) Yield (%) 1 M@SiO 2 40 EtOH K 2 CO 3 reflux 24 Trace 2 Co MOF 40 EtOH K 2 CO 3 reflux 22 21 3 Co MOF@M 40 EtOH K 2 CO 3 reflux 18 51 4 Co MOF@SiO 2 40 EtOH K 2 CO 3 reflux 19 50 5 Co MOF@MSiO 2 40 EtOH K 2 CO 3 reflux 12 54 6 Cu-Co MOF@MSiO 2 40 EtOH K 2 CO 3 reflux 12 57 7 Cu-Co@N-C 40 EtOH K 2 CO 3 reflux 12 65 8 Cu-Co@N-C 40 DMSO K 2 CO 3 110 12 81 9 Cu-Co@N-C 40 Toluene K 2 CO 3 110 12 62 10 Cu-Co@N-C 40 CH 3 CN K 2 CO 3 reflux 12 67 11 Cu-Co@N-C 40 H 2 O K 2 CO 3 reflux 12 30 12 Cu-Co@N-C 40 EtOAC K 2 CO 3 reflux 12 51 13 Cu-Co@N-C 40 DMF K 2 CO 3 110 12 89 14 Cu-Co@N-C 50 DMF K 2 CO 3 110 12 94 `15 Cu-Co@N-C 60 DMF K 2 CO 3 110 12 94 16 _ - DMF K 2 CO 3 110 12 Trace 17 Cu-Co@N-C 50 DMF _ 110 12 Trace 18 Cu-Co@N-C 50 DMF KOH 110 12 78 19 Cu-Co@N-C 50 DMF Na 2 CO 3 110 12 81 20 Cu-Co@N-C 50 DMF Et 3 N 110 12 73 21 Cu-Co@N-C 50 DMF K 3 PO 4 110 12 60 22 Cu-Co@N-C 50 DMF NaOH 110 12 74 23 Cu-Co@N-C 50 DMF K 2 CO 3 130 12 94 24 Cu-Co@N-C 50 DMF K 2 CO 3 120 12 94 25 Cu-Co@N-C 50 DMF K 2 CO 3 100 12 90 26 Cu-Co@N-C 50 DMF K 2 CO 3 90 12 87 a Reaction conditions: aniline (1.2 mmol), iodo benzene (1.0 mmol), solvent (4.0 mL), base (2 mmol), Cu-CO@N-C To explore the scope and limitations of this catalyst, a wide range of biaryl amine derivatives were synthesized by coupling diverse anilines with different substituted phenyl halides under the optimal reaction conditions, and the results are summarized in Table 3. It is shown that all of the substrates reacted well, affording high yields. Moreover, the results indicate that the reactions of aryl iodides were slightly faster than their chloro and bromo analogs, due to the lower C–I bond strength compared to C–Br and C–Cl bonds (C–Cl > C–Br > C–I). For both electron-withdrawing and electron-donating groups on aryl halides, moderate to good yields of the desired amination products were obtained. However, electron-poor aryl halides gave better product yields, while lower yields were obtained for aryl halides substituted with electron-donating groups. Table 4 provides a comparison of the catalytic performance for Cu-Co@N-C with other reported heterogeneous systems with either completely metallic or metal/ligand complexes in N-aryl bond formation reactions between aniline and aryl halides. We can conclude that the present catalyst exhibited higher yields compared to the other copper-based catalysts. The coexistence of two metals and porous carbon support in Cu-Co@N-C are likely responsible for its remarkable performance. Table 4 Comparison of the Catalytic Activity of Reported Heterogeneous Catalysts in the N-Aryl Bond Formation Reactions between Aniline with Aryl Halides Catalyst Conditions Time (h) Yie ld (%) Refs CuO NPs DMSO/t-BuOH, KOH, 110 ○ C 18 10-89 60 CuO/MWCNTs K 2 CO 3 /DMAc/120 ○ C 24 47-96 61 Fe 3 O 4 @SiO 2 /(Py)-copolymer- (chlorophyll b) Ni/Pd DMSO/120 ○ C 6-12 66-94 62 Fe 3 O 4 @PEG/Cu-Co H 2 O/80 ○ C/base-free 6-7 68-77 63 γ-Fe 2 O 3 @PEG@THMAM-Co H 2 O /100 ○ C/ NaOH 10 72-90 64 Cu-Co@N-C DMF /110 ° C/ K 2 CO 3 12 63-97 This work 3.2.3. Synthesis of 3,4-dihydropyrimidin-2(1H)-ones using Cu-CO@N–C catalyst The catalytic activity of the novel heterogenous bimetallic magnetic Cu-Co@N–C catalyst was investigated in the one-pot synthesis of DHPMs. The reaction was allowed to proceed using benzaldehyde (1 mmol), ethyl acetoacetate (1 mmol) and urea (1.5 mmol) as a model reaction. Various reaction conditions were optimized in terms of solvent, temperature, time, and catalyst amount (Table 5). The impact of the solvent on reaction yields was examined in a model reaction (entries 1-5). The best result was obtained when ethanol was used as a green solvent (entry 5). The optimization experiments performed with various catalyst amounts, demonstrated that 50 mg of nano catalyst led to the highest yield of the reaction (69%, entry 5). As can be seen, the reaction yield was increased up to 95% under refluxed EtOH (entry 10). Table 5 Optimization of the amount of the Catalyst, Solvent, and Temperature in the Biginelli Reaction a Entry Catalyst Catalyst loading Solvent Temp ( °C) Time Yield (%) b 1 Cu-Co@N-C 50 mg CH 3 CN r.t 6h 46 2 Cu-Co@N-C 50 mg Toluene r.t 6h trace 3 Cu-Co@N-C 50 mg H 2 O r.t 6h 38 4 Cu-Co@N-C 50 mg THF r.t 6h 42 5 Cu-Co@N-C 50 mg EtOH r.t 2h 72 6 Cu-Co@N-C 30 mg EtOH r.t 2h 57 7 Cu-Co@N-C 40 mg EtOH r.t 2h 64 8 Cu-Co@N-C 60 mg EtOH r.t 2h 72 9 Cu-Co@N-C 50 mg EtOH 50 2h 85 10 Cu-Co@N-C 50 mg EtOH reflux 30 min 95 a ethylacetoacetate (1mmol), benzaldehyde (1 mmol) and urea (1.5mmol), catalyst Cu-CO@N-C b Isolayted yield To explore scope and address potential limitations, the catalytic activity of Cu-CO@N-C was investigated in the synthesis of various DHPMs under optimized conditions. As tabulated in Table 6, the one pot condensation reaction of aromatic aldehydes, β-ketoesters, and urea in the presence of Cu-CO@N-C afforded the corresponding DHPMs in considerable yields. Moreover, reactions involving electron-withdrawing benzaldehydes (NO 2 , Cl, Br) were observed to proceed at a faster rate compared to those with electron-donating benzaldehydes (Me, OMe, and OH). A comparison of the catalytic performance of Cu-Co@N-C in the synthesis of DHPMs is provided in Table 7. As can be seen, the synthesis of DHMPs in the presence of the introduced catalytic system afforded the corresponding products 4a-u in higher yield, shorter reaction time and milder reaction conditions. Table 7 Comparison of the performance of this work with previously reported catalysts for the synthesis of DHPMs compound name conditions Time Yield (%) Refs Fe−Al/clay Solvent- free/100 ° C 3-5 h 86-98 68 Nb 2 O 5 /T Solvent-free / 130 ° C 38-80 min 60-94 69 Fe 3 O 4 @Cu–Mn Solvent-free/70 ° C 2-3 h 75-97 70 Fe 3 O 4 @C@OSO 3 H Solvent -free/80 ° C 20-105 80-97 71 Fe 3 O 4 @SiO 2 -GQDs/Cu (II) Solvent-free /110 ° C 50-120 min 75-95 72 Cu-Co@N-C EtOH / reflux 30-60 min 84-97 This work 3. Catalyst Stability and Recyclability From the perspective of green chemistry and catalytic sustainability, one of the advantages of heterogeneous catalyst systems is their potential for recyclability and reusability. We have investigated the recyclability and reusability of the Cu-Co@N-C nano catalyst in both Ullmann and Biginelli reactions by performing the model reactions under their optimized conditions. After completion of the first reaction cycle, the catalyst was separated via an external magnetic field, thoroughly washed with EtOAC and water, and then dried under vacuum. The recycled catalyst was subsequently reused in the next run under the same conditions as the first cycle. It is interesting to note that the bimetallic nano porous carbon preserved its catalytic activity over five consecutive runs, exhibiting no significant loss in conversion rate, as illustrated in Fig. 6A. Following the fifth reaction cycle, the recovered catalyst was characterized by XRD and nitrogen-sorption analysis. The XRD patterns of the reused Cu-Co@N-C were closely similar to those of the fresh nano catalyst, as depicted in Fig. 6B. The nitrogen-sorption experiment of the recovered catalyst after the fifth reaction cycle was also performed. The resulting isotherm displayed a similar pattern to that of the Cu-Co@N-C catalyst, with a BET surface area, pore volume, and mean pore diameter of 123.01 m 2 /g, 0.9 cm 3 /g, and 5.9 nm, respectively (Fig. 6C). The stability and heterogeneous structure of the catalyst under operative conditions were examined through a leaching test. In this context, the model reaction was stopped after 6 hours (half of the required time for reaction completion), and the catalyst was removed by an external magnet, and the reaction yield determined by gas chromatography was about 64%. The residual reaction mixture was then allowed to continue at the same reaction conditions for an additional 6 hours. The results indicated that the conversion remained unchanged during the reload of the reaction mixture after catalyst separation (Fig.6D). Additionally, we evaluated the possibility of cobalt and copper leaching into the reaction medium by conducting ICP analysis on the reused catalyst after the fifth cycle. Notably, the analysis revealed negligible leaching of Cu and Co, with no significant variation compared to the initial loaded amounts of Co (0.83 mmol. g -1 ) and Cu (0.4 mmol. g -1 ) This can be attributed to the strong interaction between the copper and cobalt nanoparticles and the nitrogen binding sites in the N-doped carbon structure, which effectively prevents metal leaching 43 . 3.4 . Mechanistic study Based on the control experiments, the bimetallic compounds provided higher selectivity and efficiency compared to the single-metal components. The presence of the second metal may act as a co-oxidant with a plausible electron exchange 73 . In this regard, the Cu and Co active sites provide a synergistic as well as cooperative performance in chemical reactions. Generally, our observations, along with the reported mechanisms, suggest a plausible mechanism for the Cu-Co@N-C catalyzed Ullmann cross-coupling reaction based on oxidative addition and reductive elimination steps 63,74 . A proposed mechanism is depicted in Fig. 7A. Initially, the coordination of the amine group on the formed active Cu (I) species generates intermediate ( A ) . The presence of K 2 CO 3 in the reaction mixture accelerates the deprotonation process, leading to the formation of intermediate ( B) . In the presence of K 2 CO 3 , oxidative addition of Cu-Co@N-C to aryl halides results in the formation of a MOF−aryl-halide intermediate ( C) , and the Cu(I) active sites are oxidized to Cu (III) 45 . The coordination of aryl halides to metal plays a crucial role in the efficiency of this system for coupling reactions. The nucleophilic substitution of intermediate ( C) with N-containing heterocycles, followed by reductive elimination, yields the desired product and regenerates Cu-Co@N-C 75 . According to the literature, for the preparation of DHMPs, the reaction initiates with the coordination of the metal active sites of the catalyst to the carbonyl group of aldehydes. This is followed by the nucleophilic addition of urea to the aldehyde, leading to the formation of intermediate ( I) , then one molecule of water is eliminated to produce intermediate ( Ⅱ). In the next step, the Michael-type addition of β-diketone to the iminium forms intermediate ( Ⅲ) . cyclization through the nucleophilic addition of an amine to the carbonyl group, yielding the desired product 4 after the removal of a water molecule (Fig. 7B). 4. Conclusion In this article, a novel copper-cobalt bimetallic magnetic MOF derived N-doped carbon has been successfully synthesized. The bimetallic magnetic MOF catalyst was obtained from the in situ reaction of Co MOF with magnetic silica coated NPs, followed by the immobilization of copper ions on the surface of magnetic Co MOF. Subsequently, the pyrolysis of as-synthesized bimetallic magnetic Co MOF led to the formation of copper-cobalt bimetallic magnetic MOF derived N-doped carbon (Cu-Co@N-C). The structure of the Cu-Co@N-C was identified using various analytical techniques including FT-IR, XRD, BET, BJH, TGA, VSM, XPS, FE-SEM, and ICP. To explore the synergistic effect of copper, cobalt, and nitrogen-doped carbon nanostructures, The catalytic activity of the Cu-Co@N-C catalyst was evaluated in the C-N coupling reactions and Biginelli three component reaction, which resulted in high reaction yields and easy separation of the catalyst using an external magnet. The prepared Cu-Co@N-C exhibited remarkable stability, reusability, and high catalytic performance after 5 cycles by taking advantage of the bimetallic synergistic effect and nano porous construction. The leaching experiment and the hot filtration test indicated that the introduced catalytic system was mainly of a heterogeneous nature, as there was no significant loss of Cu and Co species from the catalyst during the reaction. Declarations Competing interests The authors declare no competing interests. Ethical approval This work does not contain any studies with human participants or animals performed by any of the authors. Author Contribution Credit authorship contribution statementArezoo Ahmadi:A.AHeshmatollah Alinezhad:H.AYaghoub Sarrafi:Y.SWriting: A. A.; Conceptualization: A.A.; H.A. Data curation: A.A.; H.A. Formal analysis: A.A.; H.A. Project administration: A.A.; H.A.; Y.S. Methodology: A.A.; Validation: A.A.; H.A.; Y.S. Review and editing: A.A.; H.A.; Y.S. All authors reviewed the manuscript. Acknowledgements The authors acknowledge the Research Council of the University of Mazandaran Data Availability Data availability statementAll data generated or analysed during this study are included in this published article [and its supplementary information files]. References Osman, A. I. et al. Coordination-driven innovations in low-energy catalytic processes: advancing sustainability in chemical production. Coordination Chemistry Reviews 514 , 215900 (2024). Zhang, H. et al. Catalysis of a single transition metal site for water oxidation: from mononuclear molecules to single atoms. Advanced Materials 32 , 1904037 (2020). Hai, X. et al. Geminal-atom catalysis for cross-coupling. Nature 622 , 754-760 (2023). Gao, M. et al. Metal and metal oxide supported on ordered mesoporous carbon as heterogeneous catalysts. ACS Catalysis 13 , 4060-4090 (2023). Sabzehmeidani, M. M., Mahnaee, S., Ghaedi, M., Heidari, H. & Roy, V. A. Carbon based materials: a review of adsorbents for inorganic and organic compounds. Materials Advances 2 , 598-627 (2021). Pan, Y. et al. Constructing nitrogen‐doped carbon hierarchy structure derived from metal‐organic framework as high‐performance ORR cathode material for Zn‐air battery. Small 20 , 2304594 (2024). Liu, Q. et al. Multifunctional book-like CuCo-MOF for highly sensitive glucose detection and electrocatalytic oxygen evolution. New Journal of Chemistry 45 , 16714-16721 (2021). He, T., Kong, X.-J. & Li, J.-R. Chemically stable metal–organic frameworks: rational construction and application expansion. Accounts of Chemical Research 54 , 3083-3094 (2021). Qin, X., Kim, D. & Piao, Y. Metal‐organic frameworks‐derived novel nanostructured electrocatalysts for oxygen evolution reaction. Carbon Energy 3 , 66-100 (2021). Wang, L., Zhu, Y., Du, C., Ma, X. & Cao, C. Advances and challenges in metal–organic framework derived porous materials for batteries and electrocatalysis. Journal of Materials Chemistry A 8 , 24895-24919 (2020). Knebel, A. & Caro, J. Metal–organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation. Nature Nanotechnology 17 , 911-923 (2022). Koo, W.-T., Jang, J.-S. & Kim, I.-D. Metal-organic frameworks for chemiresistive sensors. Chem 5 , 1938-1963 (2019). Yarahmadi, H., Salamah, S. K. & Kheimi, M. Synthesis of an efficient MOF catalyst for the degradation of OPDs using TPA derived from PET waste bottles. Scientific Reports 13 , 19136 (2023). Han, T. et al. Synthesis of CNT@ MIL-68 (Al) composites with improved adsorption capacity for phenol in aqueous solution. Chemical Engineering Journal 275 , 134-141 (2015). Ramu, S. et al. Recent advances in metal organic frameworks–based magnetic nanomaterials for waste water treatment. Environmental Science and Pollution Research 31 , 167-190 (2024). Yeganeh, M. et al. Utilization of the copper recovered from waste printed circuit boards as a metal precursor for the synthesis of TiO2/magnetic-MOF (Cu) nanocomposite: Application in photocatalytic degradation of pesticides in aquatic solutions. Journal of Environmental Management 345 , 118755 (2023). Zisti, F. et al. Synthesis and characterization of Fe3O4@ SiO2-supported metal–organic framework PAEDTC@ MIL-101 (Fe) for degradation of chlorpyrifos and diazinon pesticides. Environmental Research 245 , 118019 (2024). Zheng, Z., Rong, Z., Nguyen, H. L. & Yaghi, O. M. Structural chemistry of zeolitic imidazolate frameworks. Inorganic Chemistry 62 , 20861-20873 (2023). Sani, M. A., Khezerlou, A. & McClements, D. J. Zeolitic imidazolate frameworks (ZIFs): Advanced nanostructured materials to enhance the functional performance of food packaging materials. Advances in Colloid and Interface Science , 103153 (2024). Zhou, Y. et al. Bimetallic metal–organic frameworks and MOF-derived composites: Recent progress on electro-and photoelectrocatalytic applications. Coordination Chemistry Reviews 451 , 214264 (2022). Kishore, D. R., Sreenivasulu, C., Dapkekar, A. B. & Satyanarayana, G. Recent applications on dual-catalysis for C–C and C–X cross-coupling reactions. SynOpen 6 , 179-194 (2022). Zhang, H. et al. Insights into the hydrogen generation and catalytic mechanism on Co-based nanocomposites derived from pyrolysis of organic metal precursor. Iscience 27 (2024). Nigam, V. et al. Revolutionizing Indole Synthesis: A Microwave‐Powered Approach. ChemistrySelect 9 , e202402171 (2024). Masand, V. H. et al. Leveraging nitrogen occurrence in approved drugs to identify structural patterns. Expert Opinion on Drug Discovery 19 , 111-124 (2024). Fui, C. J., Sarjadi, M. S., Sarkar, S. M. & Rahman, M. L. Recent advancement of ullmann condensation coupling reaction in the formation of aryl-oxygen (CO) bonding by copper-mediated catalyst. Catalysts 10 , 1103 (2020). Ma, X. & Davies, R. P. Tartramide Ligands for Copper‐Catalyzed N‐Arylation at Room Temperature. Advanced Synthesis & Catalysis 364 , 2023-2031 (2022). Averin, A. D. et al. Recent Achievements in the Copper-Catalyzed Arylation of Adamantane-Containing Amines, Di-and Polyamines. Catalysts 13 , 831 (2023). Kamanna, K. & Khatavi, S. Y. Microwave-accelerated carbon-carbon and carbon-heteroatom bond formation via multi-component reactions: a brief overview. Current Microwave Chemistry 7 , 23-39 (2020). Sánchez-Sancho, F. et al. Synthesis of 3, 4-dihydropyrimidin (thio) one containing scaffold: Biginelli-like reactions. Pharmaceuticals 15 , 948 (2022). Es’haghi, Z. & Esmaeili-Shahri, E. Sol–gel-derived magnetic SiO2/TiO2 nanocomposite reinforced hollow fiber-solid phase microextraction for enrichment of non-steroidal anti-inflammatory drugs from human hair prior to high performance liquid chromatography. Journal of Chromatography B 973 , 142-151 (2014). Weng, X., Chen, W., Cai, W., Owens, G. & Chen, Z. Synthesis of ferroferric oxide@ silicon dioxide/cobalt-based zeolitic imidazole frameworks for the removal of doxorubicin hydrochloride from wastewater. Journal of Colloid and Interface Science 624 , 108-120 (2022). Chen, T., Ren, H., Li, L., Tan, W. & He, H. Synergistic cobalt–copper metal–organic framework-derived oxide electrocatalyst for efficient oxygen evolution reaction. Materials Chemistry and Physics 313 , 128689 (2024). Ahmadi, A., Alinezhad, H., Sarrafi, Y. & Ghani, M. Nanoporous carbon derived ZIF-67@ MWCNTs-Fe3O4 reinforced hollow fiber to performe hollow fiber solid-phase micro extraction (HF-SPME) coupled with high-performance liquid chromatography to determine deltamethrin and cypermethrin. Journal of Food Composition and Analysis 136 , 106750 (2024). Gong, H. et al. In situ construction of ZIF-67-derived hybrid tricobalt tetraoxide@ carbon for supercapacitor. Nanomaterials 12 , 1571 (2022). Wu, Y. et al. Electrocatalytic oxygen reduction by a Co/Co 3 O 4@ N-doped carbon composite material derived from the pyrolysis of ZIF-67/poplar flowers. RSC advances 11 , 2693-2700 (2021). Weng, Y. et al. Defective porous carbon polyhedra decorated with copper nanoparticles for enhanced NIR‐driven photothermal cancer therapy. Small 16 , 1905184 (2020). Jiang, M. et al. ZIF-67 derived Ag-Co3O4@ N-doped carbon/carbon nanotubes composite and its application in Mg-air fuel cell. Electrochemistry Communications 77 , 5-9 (2017). Sharma, S., Sharma, C., Kaur, M. & Paul, S. The in situ fabrication of ZIF-67 on titania-coated magnetic nanoparticles: a new platform for the immobilization of Pd (ii) with enhanced catalytic activity for organic transformations. New Journal of Chemistry 45 , 20309-20322 (2021). Li, C., Meng, Y., Yang, S. & Li, H. ZIF‐67 Derived Co/NC Nanoparticles Enable Catalytic Leuckart‐type Reductive Amination of Bio‐based Carbonyls to N‐Formyl Compounds. ChemCatChem 13 , 5166-5177 (2021). Yin, L. et al. Multifunctional ZIF-67@ SiO2 membrane for high efficiency removal of particulate matter and toxic gases. Industrial & Engineering Chemistry Research 59 , 17876-17884 (2020). Khan, S. B. et al. CuO embedded chitosan spheres as antibacterial adsorbent for dyes. International journal of biological macromolecules 88 , 113-119 (2016). Wang, Y. et al. Metal organic frameworks-derived Fe-Co nanoporous carbon/graphene composite as a high-performance electromagnetic wave absorber. Journal of Alloys and Compounds 785 , 765-773 (2019). Salarinejad, N., Dabiri, M. & Movahed, S. K. CuPd bimetallic nanoparticles supported magnetic ionic liquid-derived N-doped carbon as a highly efficient heterogeneous catalyst for the one-pot oxidative multicomponent reactions. Journal of the Taiwan Institute of Chemical Engineers 159 , 105496 (2024). Liu, S., Hui, K. & Hui, K. Flower-like copper cobaltite nanosheets on graphite paper as high-performance supercapacitor electrodes and enzymeless glucose sensors. ACS applied materials & interfaces 8 , 3258-3267 (2016). Nasseri, F., Nasseri, M. A., Kassaee, M. Z. & Yavari, I. Synergistic performance of a new bimetallic complex supported on magnetic nanoparticles for Sonogashira and C–N coupling reactions. Scientific Reports 13 , 18153 (2023). Mattevi, C. et al. Evolution of electrical, chemical, and structural properties of transparent and conducting chemically derived graphene thin films. Advanced functional materials 19 , 2577-2583 (2009). Xiong, J. et al. Fe/Co/N–C/graphene derived from Fe/ZIF-67/graphene oxide three dimensional frameworks as a remarkably efficient and stable catalyst for the oxygen reduction reaction. RSC advances 12 , 2425-2435 (2022). Wei, Z. et al. High-efficiency adsorption of phenanthrene by Fe3O4-SiO2-dimethoxydiphenylsilane nanocomposite: Experimental and theoretical study. Journal of hazardous materials 422 , 126948 (2022). Gholinejad, M., Naghshbandi, Z. & Sansano, J. M. Zeolitic imidazolate frameworks-67 (ZIF-67) supported PdCu nanoparticles for enhanced catalytic activity in Sonogashira-Hagihara and nitro group reduction under mild conditions. Molecular Catalysis 518 , 112093 (2022). Mu, X. et al. Doping of Cr to regulate the valence state of Cu and Co contributes to efficient water splitting. ACS Applied Materials & Interfaces 15 , 16552-16561 (2023). Ece, M. Ş., Ekinci, A., Kutluay, S., Şahin, Ö. & Horoz, S. Facile synthesis and comprehensive characterization of Ni-decorated amine groups-immobilized Fe3O4@ SiO2 magnetic nanoparticles having enhanced solar cell efficiency. Journal of Materials Science: Materials in Electronics 32 , 18192-18204 (2021). Zhu, C., Wang, M., Li, T., Lu, T. & Pan, L. In situ synthesis of porous Co 3 O 4 polyhedra/carbon nanotubes heterostructures for highly efficient supercapacitors. Ionics 23 , 2175-2183 (2017). Mohammadinezhad, A. & Akhlaghinia, B. Co II immobilized on an aminated magnetic metal–organic framework catalyzed C–N and C–S bond forming reactions: a journey for the mild and efficient synthesis of arylamines and arylsulfides. New Journal of Chemistry 43 , 15525-15538 (2019). Park, S.-E. et al. Efficient Palladium-Catalyzed Amination of Aryl Chlorides Using Dicyclohexylamino [(2, 6-dimethyl) morpholino] phenylphosphine as a PN2 Ligand. Synthesis 2009 , 815-823 (2009). Bagheri, H. & Baharfar, R. Magnetic MCR-Functionalized Graphene Oxide Complexed with Copper Nano-Particles: An Efficient and Recyclable Nanocatalyst for Ullmann C–N Coupling Reaction. Polycyclic Aromatic Compounds 43 , 7580-7596 (2023). Huang, L., Yu, R., Zhu, X. & Wan, Y. A recyclable Cu-catalyzed C–N coupling reaction in water and its application to synthesis of imidazo [1, 2-a] quinoxaline. Tetrahedron 69 , 8974-8977 (2013). Ding, X. et al. Room-temperature CuI-catalyzed amination of aryl iodides and aryl bromides. The Journal of Organic Chemistry 82 , 5416-5423 (2017). Yi, Z., Huang, M., Wan, Y. & Zhu, X. An effective heterogeneous copper catalyst system for C–N coupling and its application in the preparation of 2-methyl-4-methoxydiphenylamine (MMDPA). Synthesis 50 , 3911-3920 (2018). Modha, S. G., Popescu, M. V. & Greaney, M. F. Synthesis of triarylamines via sequential C–N bond formation. The Journal of organic chemistry 82 , 11933-11938 (2017). Jammi, S. et al. CuO nanoparticles catalyzed C− N, C− O, and C− S cross-coupling reactions: Scope and mechanism. The Journal of organic chemistry 74 , 1971-1976 (2009). Gopiraman, M. et al. An efficient, reusable copper-oxide/carbon-nanotube catalyst for N-arylation of imidazole. Carbon 62 , 135-148 (2013). Kazemnejadi, M., Ahmed, R. O. & Mahmoudi, B. Ni/Pd-catalyzed Suzuki–Miyaura cross-coupling of alcohols and aldehydes and C–N cross-coupling of nitro and amines via domino redox reactions: base-free, hydride acceptor-free. RSC advances 10 , 43962-43974 (2020). Nasseri, M. A., Rezazadeh, Z., Kazemnejadi, M. & Allahresani, A. A Co–Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C–N cross-coupling reactions in water. Dalton Transactions 49 , 10645-10660 (2020). Sheikh, S. et al. Water-Dispersible, Magnetically Recyclable Heterogeneous Cobalt Catalyst for C–C and C–N Cross-Coupling Reactions in Aqueous Media. ACS omega 9 , 31393-31400 (2024). Rezayati, S. et al. Magnetic silica-coated picolylamine copper complex [fe3o4@ sio2@ gp/picolylamine-cu (ii)]-catalyzed biginelli annulation reaction. Inorganic chemistry 61 , 992-1010 (2021). Elhamifar, D., Hosseinpoor, F., Karimi, B. & Hajati, S. Ionic liquid-based ordered mesoporous organosilica-supported copper as a novel and efficient nanocatalyst for the one-pot synthesis of Biginelli products. Microporous and Mesoporous Materials 204 , 269-275 (2015). Najafi, M. et al. Decorated Cu nanoparticles on ZPD as a novel and highly proficient nanocatalyst for synthesis of chromene and Biginelli reactions. Research on Chemical Intermediates 50 , 1177-1209 (2024). Dar, B. A. et al. Fe–Al/clay as an efficient heterogeneous catalyst for solvent-free synthesis of 3, 4-dihydropyrimidones. Journal of Chemical Sciences 125 , 545-553 (2013). do Nascimento, L. G. et al. Niobium oxides as heterogeneous catalysts for Biginelli multicomponent reaction. The Journal of Organic Chemistry 85 , 11170-11180 (2020). Nasseri, M. A., Rezazadeh, Z., Kazemnejadi, M. & Allahresani, A. Cu-Mn bimetallic complex immobilized on magnetic NPs as an efficient catalyst for domino one-pot preparation of benzimidazole and Biginelli reactions from alcohols. Catalysis Letters 151 , 1049-1067 (2021). Taheri Hatkehlouei, S. F., Mirza, B. & Soleimani-Amiri*, S. Solvent-free one-pot synthesis of diverse dihydropyrimidinones/tetrahydropyrimidinones using biginelli reaction catalyzed by Fe3O4@ C@ OSO3H. Polycyclic Aromatic Compounds 42 , 1341-1357 (2022). Najjar, M., Nasseri, M. A., Darroudi, M. & Allahresani, A. Synthesis of dihydropyrimidinone and dihydropyridine derivatives by a GQDs-based magnetically nanocatalyst under solvent-free conditions. Journal of Environmental Chemical Engineering 10 , 108854 (2022). Alshammari, A., Kalevaru, V. N. & Martin, A. Bimetallic catalysts containing gold and palladium for environmentally important reactions. Catalysts 6 , 97 (2016). Sharma, N. et al. Modified graphene supported Ag–Cu NPs with enhanced bimetallic synergistic effect in oxidation and Chan–Lam coupling reactions. RSC advances 10 , 30048-30061 (2020). Esrafili, L., Morsali, A., Dehghani Firuzabadi, F. & Retailleau, P. Development of porous cobalt-/copper-doped carbon nanohybrids derived from functionalized MOFs as efficient catalysts for the Ullmann cross-coupling reaction: Insights into the active centers. ACS Applied Materials & Interfaces 12 , 43115-43124 (2020). Tables Table 3 and 6 are available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files Supplementarymaterial.docx Table3and6.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5726553","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":398851165,"identity":"c5e25cc3-0278-442f-a0d0-8d8c8d3d1bb3","order_by":0,"name":"Arezoo Ahmadi","email":"","orcid":"","institution":"Faculty of Chemistry, University of Mazandaran","correspondingAuthor":false,"prefix":"","firstName":"Arezoo","middleName":"","lastName":"Ahmadi","suffix":""},{"id":398851166,"identity":"30551e5b-543f-4e41-b498-729c12e837bd","order_by":1,"name":"Heshmatollah Alinezhad","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAuklEQVRIiWNgGAWjYBACgwMMbCBaDibAQ6wWA2PStSQ2EO+w4+3PHt2o+ZO+4drxBww/ahhkzAlptj9zxtw455hB7obbCQmMPccYeGQOELLlRg6bdA4bWMsBBt4GBh4Jgg67//yZdM4/g3SD24kNjH+J0nKDwUw6t80gweB2MgMzcbacyQFq6TM2nHk7jeGwzDEJIrQcPw502Dc5eb7b6Q8fvqmxsSeoBQUcYGAgTcMoGAWjYBSMAhwAAFzvPS7rgKbDAAAAAElFTkSuQmCC","orcid":"","institution":"Faculty of Chemistry, University of Mazandaran","correspondingAuthor":true,"prefix":"","firstName":"Heshmatollah","middleName":"","lastName":"Alinezhad","suffix":""},{"id":398851167,"identity":"eb2c88aa-2901-4e9d-9297-fd556ef192bc","order_by":2,"name":"Yaghoub Sarrafi","email":"","orcid":"","institution":"Faculty of Chemistry, University of Mazandaran","correspondingAuthor":false,"prefix":"","firstName":"Yaghoub","middleName":"","lastName":"Sarrafi","suffix":""}],"badges":[],"createdAt":"2024-12-28 14:08:13","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5726553/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5726553/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":73349463,"identity":"207a0f59-f06f-4d3e-bc6e-cacdfcbef94d","added_by":"auto","created_at":"2025-01-09 06:55:48","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":156690,"visible":true,"origin":"","legend":"\u003cp\u003eIllustration of the preparation of Cu-Co@N-C.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/b3205d81a539a556dde57fd8.png"},{"id":73348207,"identity":"fcdd5f10-4baf-47ee-ae7b-1d09883fd15f","added_by":"auto","created_at":"2025-01-09 06:47:47","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1270527,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(A). \u003c/strong\u003eThe FT-IR spectra of a) Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, b) M@SiO\u003csub\u003e2\u003c/sub\u003e, c) Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, d) Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, \u003cstrong\u003e(B)\u003c/strong\u003e. The XRD patterns of a) Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, b) Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, c) Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, and d) Cu-Co@N-C (\u003cstrong\u003eC\u003c/strong\u003e). N2 isothermal adsorption/desorption curves of a) M@SiO\u003csub\u003e2\u003c/sub\u003e, b) Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, c) Cu-Co MOF@MSiO\u003csub\u003e2, \u003c/sub\u003eand d) Cu-Co@N-C, (\u003cstrong\u003eD\u003c/strong\u003e) The pore size distribution of a) Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, b) Cu-Co MOF@MSiO\u003csub\u003e2, \u003c/sub\u003eand c) Cu-Co@N-C \u003cstrong\u003e(E\u003c/strong\u003e) The TGA analysis of a) Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, b) M@SiO\u003csub\u003e2\u003c/sub\u003e, c) Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, d) Cu-Co MOF@MSiO\u003csub\u003e2 \u003c/sub\u003eand e) Cu-Co@N-C (\u003cstrong\u003eF\u003c/strong\u003e). The Magnetization curves of a) Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, b) Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e and c) Cu-Co@N-C\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/aeebf786760db5a5e0bec084.png"},{"id":73348208,"identity":"0e369e3b-e2ae-4d84-83f3-2c09bc4275f3","added_by":"auto","created_at":"2025-01-09 06:47:47","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1923751,"visible":true,"origin":"","legend":"\u003cp\u003eXPS spectra of Cu-Co@N-C\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/2cc0519f32ea11fff8c0b43d.png"},{"id":73348205,"identity":"a316d086-a98f-4ed1-9b23-e92f87b41798","added_by":"auto","created_at":"2025-01-09 06:47:47","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":463952,"visible":true,"origin":"","legend":"\u003cp\u003eEDX spectra of Cu-Co@N-C\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/19ae4edc63b12f5c53b25114.png"},{"id":73349479,"identity":"b9eda73b-1ed6-45d5-abc6-868985fb6a68","added_by":"auto","created_at":"2025-01-09 06:55:50","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":690930,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of a) Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, b) M@SiO\u003csub\u003e2\u003c/sub\u003e, c) Cu-Co MOF@MSiO\u003csub\u003e2,\u003c/sub\u003e and d) Cu-Co@N-C \u0026nbsp;\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/7559b1892820698a7c38e3ff.png"},{"id":73348209,"identity":"7c998241-a92e-486b-8ba8-cc824cc51865","added_by":"auto","created_at":"2025-01-09 06:47:47","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":843939,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eA\u003c/strong\u003e) \u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eReusability of the catalyst in the Ullmann Coupling and Biginelli reaction \u003cstrong\u003eB\u003c/strong\u003e) XRD spectra and \u003cstrong\u003ec\u003c/strong\u003e) N\u003csub\u003e2\u003c/sub\u003e sorption isotherms of recycled Cu-Co@N-C after 5 runs. \u003cstrong\u003eD\u003c/strong\u003e) Hot filtration test for Cu-Co@N-C catalyst\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/66a0658306932c7739d83863.png"},{"id":73348265,"identity":"e4e15f2f-13f5-4bbd-ab9d-3843d0314806","added_by":"auto","created_at":"2025-01-09 06:47:50","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":90510,"visible":true,"origin":"","legend":"\u003cp\u003eplausible reaction mechanism for the Cu-Co@N-C- catalyzed \u003cstrong\u003e(A)\u003c/strong\u003e C–N cross-coupling reactions, and \u003cstrong\u003e(B)\u003c/strong\u003e preparation of DHMPs\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/ba53c37e3ef5a3607e9b43da.png"},{"id":74934005,"identity":"814c1d50-f1ff-4510-81c2-cf247dc11ac9","added_by":"auto","created_at":"2025-01-28 13:02:04","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5947790,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/b756b110-4b76-4fd4-84ca-100613931ba8.pdf"},{"id":73348212,"identity":"dd40cbb3-cf97-450f-80a4-498d872243fb","added_by":"auto","created_at":"2025-01-09 06:47:47","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4347675,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementarymaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/5fb7307171156d9843ce1329.docx"},{"id":73349466,"identity":"6d4d700b-7f6e-4a67-b9ea-2ee11c651bae","added_by":"auto","created_at":"2025-01-09 06:55:48","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":59744,"visible":true,"origin":"","legend":"","description":"","filename":"Table3and6.docx","url":"https://assets-eu.researchsquare.com/files/rs-5726553/v1/892b9bdaa65254d9c99083de.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Copper-Cobalt Bimetallic nanoparticles supported on Magnetic MOF Derived N-doped carbon as highly efficient Catalysts for the C–N coupling and one-pot multicomponent reaction","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eTransition metals, with their inherent ability to form diverse coordination complexes through chelation with ligands, have emerged as indispensable catalysts for a multitude of chemical transformations\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. Their capacity to adopt multiple oxidation states, a unique characteristic of transition metals, gives them exceptional versatility in homogeneous catalysis\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. However, the intrinsic limitations associated with homogeneous catalysts, such as product separation, catalyst recovery, and the risk of catalyst leaching, have spurred significant research efforts toward the development of heterogeneous alternatives\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. Through the immobilization of these catalytically active metal complexes onto solid supports, heterogeneous catalysts provide an opportunity to mitigate these challenges while preserving the fundamental catalytic efficacy of transition metals\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e. A diverse array of materials, encompassing porous carbon-based materials, namely activated carbon, carbon nanotubes, graphene, and metal-organic frameworks, have been explored for this purpose, each offering distinct properties that make them well-suited for metal complex loading \u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. Furthermore, N-doped carbon materials have garnered significant attention owing to their outstanding surface area and potential for generating highly active sites\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eMetal-organic frameworks (MOFs), composed of metal ions or clusters coordinated to organic linkers, have proven to be highly promising precursors for synthesizing N-doped carbon materials\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e. N-doped carbon-derived MOFs reveal superior stability under harsh conditions, and their structural architecture powerfully improves catalytic performance\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. This approach leverages the distinctive properties of MOFs, including their abundant sources of metals and organic components, diverse morphologies, inherent crystallinity, high surface area, and structural robustness \u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e. This is primarily due to the fact that the pyrolysis of MOFs often yields materials that retain the original morphology of the MOFs while also providing a nano porous structure with a uniform pore size\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e. Furthermore, MOFs have been widely applied in various fields, ranging from gas storage and separation\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e, sensing\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e, and, notably catalysis\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eExtensive research consistently demonstrates that integrating MOFs with functional materials significantly enhances their capabilities, as well as optimizing MOF performance requires precise control over their structural and surface characteristics\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. When MOFs are coupled with magnetic nanoparticles (MNPs) exhibiting high saturation magnetization, they can be accurately manipulated and rapidly isolated using a magnetic field. Magnetite (Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) is the most prevalent magnetic material for this purpose\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e. This magnetic separation technique surpasses traditional methods, particularly centrifugation and filtration, boosting sustainability while advancing catalyst reuse and recycling\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e.The silica coating on Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles serves as a crucial interfacial layer between the magnetic core and the MOF shell, inhibiting the agglomeration of MNPs and promoting the growth of the MOF layer. Additionally, the silica coated magnetic nanoparticles facilitate the formation of a robust and well-defined core-shell structure, ultimately enabling the synthesis of N-doped magnetic carbon material\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eZeolitic imidazolate frameworks (ZIFs), a subclass of MOFs, are composed of transition metal cations coordinated with imidazole-based ligands. Specifically, ZIF-67 incorporates cobalt ions and 2-methylimidazolate ligands, forming a tetrahedral structure\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. The combination of low density, high surface area, exceptional stability, and porosity renders ZIF-67 a highly attractive candidate for numerous applications, such as gas storage, catalysis, adsorption, and sensing\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e. Intriguingly, ZIF-67, which contains cobalt metal in its structure, can serve as a multifunctional sacrificial template to produce diverse micro/nanostructures with complex configurations. Bimetallic systems, by amplifying the synergistic interactions between the introduced metal nanoparticles and the inherent metal nodes within the MOF structure, have attracted significant interest from materials scientists\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e. A recent approach to producing these systems involves integrating transition metals into MOFs by exposing them to metal sources. The incorporation of copper-cobalt into nano porous carbon-derived MOFs can further elevate catalytic efficiency through synergistic effects that alter the material's geometric and electronic properties\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e, while the metals complement each other\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eN-arylation reactions have become a strategic approach for the construction of pharmaceutical, biological, and chemical materials\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. The critical role of nitrogen containing compounds in biological molecules has sparked a lot of interest in developing efficient methods for their preparation\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. Although palladium complexes have traditionally dominated the field of N-arylation catalysis, their drawbacks in terms of cost, toxicity, and availability have driven the exploration of alternative metal-based catalysts\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e. Consequently, researchers are now turning to environmentally friendly metals like iron, cobalt, nickel, and copper. Copper has evolved as a promising replacement on account of its abundance, affordability, low toxicity, and reduced environmental impact. Furthermore, copper offers a potential route for catalyzing C-N bond formation, particularly via the Ullmann coupling reaction\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. However, challenges related to reaction rates, efficiency, and substrate scope remain. Despite these obstacles, the development of efficient copper catalysts for C-N bond formation continues to be an area of ongoing research\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eMulticomponent reactions (MCRs) represent a powerful strategy for the construction of carbon-carbon and carbon-heteroatom bonds, playing a pivotal role in the efficient synthesis of chemotherapeutic agents and organic compounds. By merging several reactants in one step, MCRs provide distinct advantages over conventional multi-step approaches, including reduced waste, lower energy consumption, and simplified purification processes. These benefits make MCRs not only more cost-effective but also environmentally sustainable\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe Biginelli reaction, discovered in 1983, involves the condensation of benzaldehydes, \u003cem\u003eβ\u003c/em\u003e-keto esters, urea, and ethyl acetoacetate under acidic conditions to yield 3, 4dihydropyrimidin-2(1H)ones (DHPMs), a class of heterocyclic compounds. These DHPM derivatives have proven to be essential scaffolds in medicinal chemistry, showcasing a broad spectrum of biological activities, including anti-inflammatory, antibacterial, anticarcinogenic, antioxidant, antiviral, and antihypertensive agents, as well as calcium channel-blocking properties and tumor inhibition. However, traditional methods for these valuable transformations are hindered by drawbacks such as harsh conditions, prolonged reaction times, and poor product yields. In this regard, researchers have actively pursued alternative strategies to address these challenges\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThis paper presents a novel approach for synthesizing bimetallic magnetic N-doped carbon materials through a simple ion exchange process followed by MOF derivatization. A generalizable method for the fabrication of Cu-Co bimetallic magnetic MOF composites (Cu-Co@N-C) is developed, which serves as a dual template for the efficient synthesis of hybridized magnetic nanostructures (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The catalytic performance of the resulting Cu-Co@N-C was evaluated in an N-arylation coupling reaction between anilines and aryl halides. Additionally, its applicability was extended to the transformation of a range of aldehydes, urea, and ethyl acetoacetate into the corresponding DHPM derivatives through the Biginelli reaction. The introduction of copper into the cobalt-based porous structure significantly enhances catalytic performance due to the synergistic electronic and structural effects. These findings highlight the critical role of bimetallic catalyst design in elaborating the properties of MOF-derived porous materials for catalytic applications.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental section","content":"\u003cp\u003e\u003cstrong\u003e2.1. Materials and techniques\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe following reagents used in this experiment were supplied by Merck, Aldrich, and Fluka with high purity: Co (NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, FeCl\u003csub\u003e2\u003c/sub\u003e.4H\u003csub\u003e2\u003c/sub\u003eO, FeCl\u003csub\u003e3\u003c/sub\u003e.6H\u003csub\u003e2\u003c/sub\u003eO, tetraethyl orthosilicate (TEOS), (Cu (NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e.3H\u003csub\u003e2\u003c/sub\u003eO), and 2-Methylimidazole (2-MIM). The structure of the synthesized catalysts was investigated through\u0026nbsp;Fourier transform infrared spectroscopy (FT-IR) at the wavelength of 400\u0026ndash;4000 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003e(Avatar, USA).\u0026nbsp;The crystal structure of the samples was characterized by powder X-ray diffraction (XRD) patterns with Bruker D8 Advance diffractometer using CuK\u0026alpha; (\u0026lambda; = 1.5418 A\u003csup\u003e◦\u003c/sup\u003e) radiation. The micrographs and elemental distribution of the prepared materials were taken using a scanning electron microscope (SEM, Hitachi S-3400 N), equipped with a Bruker AXS XFlash 4010 EDS system to enable multi elemental analysis. Thermogravimetric analysis (TGA) was carried out in an air atmosphere using a TA Instrument SDT 2960. Nitrogen adsorption isotherms were measured at 77 K using a TriStar II (Micromeritics) gas adsorption analyzer. Data were analyzed using the Brunauer-Emmett-Teller (BET) at UIB (University of De Les Illes Balears Island) in Spain. Moreover, magnetic properties were measured using a vibrating sample magnetometer (VSM; LBKFB, Meghnatis Kavir Kashan). X-ray photoelectron spectroscopy (XPS) analyses were implemented using a Thermo Scientific K-Alpha XPS system. Inductively coupled plasma (ICP) was performed by (AGILENT 7500, Santa Clara, CA). The structure of the prepared products was assigned using \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra on a Bruker-400 Avance III spectrometer (Bruker, Germany) and comparing their melting points using an Electrothermal IA9100 (Essex, UK).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2. Preparation of Cu-Co bimetallic magnetic nano porous carbon material\u003c/strong\u003e\u003cstrong\u003es\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;(Cu-Co@N-C)\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2.1. Synthesis of\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026nbsp;\u003c/sub\u003eNPs\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles were synthesized via chemical co-precipitation using chlorine salts of Fe\u003csup\u003e3+\u003c/sup\u003e and Fe\u003csup\u003e2+\u003c/sup\u003e ions with a molar ratio of 2:1 in the presence of an ammonia solution, followed by the hydrothermal treatment. Typically, a mixture of FeCl\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO (2.70 g) and FeCl\u003csub\u003e2\u003c/sub\u003e.4H\u003csub\u003e2\u003c/sub\u003eO (1 g) was dissolved in the deionized water (100 mL), and the solution was vigorously stirred for 1 h under a nitrogen atmosphere. Afterward, NH\u003csub\u003e4\u003c/sub\u003eOH 25% (6 mL) was dropwise added to the reaction mixture. The mixture was heated for 1 h at 80 \u003csup\u003e\u0026deg;\u003c/sup\u003eC, and the cooled black magnetite solid was collected with an external magnet, washed with distilled water, and dried under vacuum at 60\u003csup\u003e\u0026deg;\u003c/sup\u003eC for 24 h.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2.2. Preparation\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eof MSiO\u003csub\u003e2\u003c/sub\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003ecore\u0026ndash;shell microspheres\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eMagnetite nanoparticles were coated with a silica layer through sol\u0026ndash;gel reaction\u003csup\u003e30\u003c/sup\u003e. Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e NPs (1 g) were dispersed in 200 mL ethanol and 10 mL distilled water under ultrasonication for 30 min. Then 15.0 mL of ammonia aqueous solution (25 wt%) was added, and 2 ml of TEOS was slowly dropped into the mixture over 10 min. After sonicating, the obtained MSiO\u003csub\u003e2\u003c/sub\u003e nanoparticles were separated by an external magnet, washed several times with ethanol, and dried under vacuum.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2.3. Preparation of Co MOF@\u003c/strong\u003e\u003cstrong\u003eMSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e0.1 g of MSiO\u003csub\u003e2\u003c/sub\u003e was added to 1 g of Co (NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2.\u003c/sub\u003e6H\u003csub\u003e2\u003c/sub\u003eO in 60 mL methanol and the mixture was heated at 70 \u003csup\u003e◦\u003c/sup\u003eC for 20 min. Thereafter, a solution of 2-MIM (2.26 g in 60 mL methanol) was added dropwise to the mixture and was allowed to stir for 2 h. The solid was separated by a magnet and washed twice with methanol and dried under vacuum at 40\u003csup\u003e◦\u003c/sup\u003eC to obtain ZIF-67@ MSiO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e31\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2.5.\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eSynthesis of Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e0.2 g of Co MOF@MSiO\u003csub\u003e2\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/sub\u003ewas added to the mixture solution of deionized water (15 mL) and ethanol (60 mL) containing 0.1 g of Cu (NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e.3H\u003csub\u003e2\u003c/sub\u003eO and then sonicated at 60\u003csup\u003e◦\u003c/sup\u003eC for 30 min. The product was collected by centrifugation, washed three times with deionized water and ethanol, then dried under vacuum at 60\u003csup\u003e◦\u003c/sup\u003eC for 6 h to obtain Cu-\u0026nbsp;Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e32\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.2.6. Synthesis of Cu-Co bimetallic magnetic nano porous carbon material\u003c/strong\u003e\u003cstrong\u003es\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;(Cu-Co@N-C)\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe as-Cu-\u0026nbsp;Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ewas heated in a nitrogen-filled furnace. The increase in temperature triggered the decomposition of organic linkers in ZIF-67, forming N-doped carbon (N-C). Simultaneously, cobalt precursors were reduced, incorporating cobalt into the N-C matrix. The nitrogen flow during this process prevented oxidation and ensured uniform heating, resulting in Cu\u0026ndash;Co@N-C composites with desirable catalytic and adsorption capabilities\u003csup\u003e33\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.3 General procedure for N\u003c/strong\u003e\u003cstrong\u003e‑\u003c/strong\u003e\u003cstrong\u003earylation reactions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA mixture of Aryl halide (1mmol), aniline (1.2 mmol), potassium carbonate K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e (2 mmol), and 50 mg of catalyst (including 2 mol % Cu) in DMF (3 mL) was heated at 110\u003csup\u003e\u0026deg;\u003c/sup\u003eC for 12 hours. Upon completion of the reaction (monitored by TLC), the mixture was cooled to room temperature and diluted with EtOAc (5 mL). The catalyst was separated using an external magnet and washed with EtOAc (2\u0026times;10 mL). The product was\u0026nbsp;obtained\u0026nbsp;after evaporation of the solvent and purified by recrystallization with\u0026nbsp;ethanol. The structures of products were confirmed by\u003csup\u003e\u0026nbsp;1\u003c/sup\u003eH and\u003csup\u003e\u0026nbsp;13\u003c/sup\u003eC NMR spectra and measuring their melting points.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2.4 General procedure for Biginelli reaction\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA mixture of aryl aldehyde (1 mmol), \u003cem\u003e\u0026beta;\u003c/em\u003e-dicarbonyl compound (1 mmol), and urea (1.5 mmol) in ethanol (5 ml) was stirred at room temperature for the appropriate time. Upon completion of the reaction, as indicated by TLC, the catalyst was simply separated by an external magnet and washed with ethanol (5 ml), then the solid product was obtained after evaporation of the solvent. To achieve the pure product, the crude product was washed with water and ether and recrystallized with ethanol. The structures of all products were established based on their \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra and melting point analysis.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003e3.2 Catalyst characterization \u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe FT-IR spectra of the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, M@SiO\u003csub\u003e2\u003c/sub\u003e, Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, and Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eare depicted in Fig. 2A. In all spectra, the absorption bands at 3650-3250 cm\u003csup\u003e-1\u003c/sup\u003e correspond to the O\u0026ndash;H stretching mode. The peak at 580 cm\u003csup\u003e-1\u003c/sup\u003e in the FT-IR spectra of the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026nbsp;\u003c/sub\u003eis related to the Fe-O-Fe stretching vibrations. The presence of peaks at 1070-1080 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003eattributed to the Si\u0026ndash;O\u0026ndash;Si stretching vibration confirms successful coating of SiO\u003csub\u003e2\u003c/sub\u003e layers on the surface of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026nbsp;\u003c/sub\u003eNPs. The additional peaks at 2925 and 3133 cm\u003csup\u003e-1\u003c/sup\u003e (C-H stretching vibrations), 1579 cm\u003csup\u003e-1\u003c/sup\u003e (C=N stretching vibration), 1454 (N-H stretching vibration), 1141 (C-N stretching vibration), and 424 (Co-N stretching vibrations) demonstrate the successful fabrication of Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e catalyst\u003csup\u003e31\u003c/sup\u003e. Furthermore, slight shifts in the absorption bands of Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eindicate\u0026nbsp;the successful immobilization of the copper ions onto the surface of Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eThe XRD analysis\u003c/strong\u003e of the synthesized materials, including Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand Cu-Co@N-C, revealed the formation of well-defined crystalline structures (Fig. 2B). The XRD pattern of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e exhibited sharp peaks at 30.29\u003csup\u003e◦\u003c/sup\u003e, 35.52\u003csup\u003e◦\u003c/sup\u003e, 43.29\u003csup\u003e◦\u003c/sup\u003e, 53.67\u003csup\u003e◦\u003c/sup\u003e, 57.39\u003csup\u003e◦\u003c/sup\u003e, and 62.81\u003csup\u003e◦\u003c/sup\u003e, corresponding to the (220), (311), (400), (422), (511), and (440) planes of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, respectively (JCPDS No. 19\u0026ndash;0629), indicating the formation of a pure magnetite phase. The characteristic peaks of Co MOF were observed at 7.33\u003csup\u003e◦\u003c/sup\u003e (011), 10.61\u003csup\u003e◦\u0026nbsp;\u003c/sup\u003e(002), 12.81\u003csup\u003e◦\u003c/sup\u003e (112), 14.81\u003csup\u003e◦\u003c/sup\u003e (0 22), 16.76\u003csup\u003e◦\u003c/sup\u003e (013), 18.29\u003csup\u003e◦\u003c/sup\u003e (222), 24.72\u003csup\u003e◦\u003c/sup\u003e (233) and 26.47\u003csup\u003e◦\u003c/sup\u003e (134) in the XRD patterns of Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e and Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003edisplayed both Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and Co MOF peaks, suggesting the successful encapsulation of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles by the Co MOF coating. The characteristic peaks at 2\u0026theta; = 43.69\u003csup\u003e◦\u003c/sup\u003e, 50.59\u003csup\u003e\u0026deg;\u003c/sup\u003e, and 74.29\u003csup\u003e◦\u003c/sup\u003e were assigned to the Cu (111), Cu (200), and Cu (220) reflections, which confirmed the introduction of Cu into the Co MOF did not significantly alter the crystal structure but might have slightly reduced the crystallinity. Thermal treatment of Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e led to the disappearance of imidazolate rings in the Co MOF scaffolds and complete transformation to Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, as evidenced by the emergence of new peaks at 31.1\u003csup\u003e◦\u003c/sup\u003e, 36.31\u003csup\u003e◦\u003c/sup\u003e, 45.01\u003csup\u003e◦\u003c/sup\u003e, 59.35\u003csup\u003e◦\u003c/sup\u003e, and 65.81\u003csup\u003e◦\u003c/sup\u003e, corresponding to the face-centered cubic Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026nbsp;\u003c/sub\u003ephases of (220), (311), (400), (511), and (440), respectively (JCPDS No. 43-1003)\u003csup\u003e34\u003c/sup\u003e. Furthermore, a broad peak around 26\u003csup\u003e◦\u003c/sup\u003e indicative of a disordered graphitic structure, along with peaks corresponding to metallic Co at 44.19\u003csup\u003e◦\u003c/sup\u003e (111), 51.27\u003csup\u003e◦\u003c/sup\u003e (200), and 76.56\u003csup\u003e◦\u003c/sup\u003e (220) (JCPDS no. 15-0806)\u003csup\u003e35\u003c/sup\u003e, was observed.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eAdditionally, weaker peaks at 35.51\u003csup\u003e◦\u003c/sup\u003e and 38.78\u003csup\u003e◦\u003c/sup\u003e attributed to the (111) and (220) planes of CuO (JCPDS NO 48\u0026ndash;1548) suggest the coexistence of these components within the carbon matrix\u003csup\u003e36\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eConsidering\u0026nbsp;the critical role of catalyst pore structure in facilitating reactant access to active sites, N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherms of the M@SiO\u003csub\u003e2,\u003c/sub\u003e Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand Cu-Co@N-C, were recorded (Fig. 2C). The isotherm for\u0026nbsp;M@SiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eexhibited type II\u0026nbsp;behavior based on the IUPAC classification,\u0026nbsp;while the isotherms for Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e and Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eare classified as type I, confirming a typical microporous structure for these materials. In the case of Cu-Co\u0026nbsp;@N-C, the sharp uptake at low relative pressure\u0026nbsp;is significantly reduced, indicating that a majority of micropores collapse during thermal treatment. The hysteresis loop, with type IV behavior, and the gradual uptake\u0026nbsp;observed\u0026nbsp;at P/P\u003csub\u003e0\u003c/sub\u003e=0.4, approved the formation of a mesoporous structure after the calcination of Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eprecursors\u003csup\u003e37\u003c/sup\u003e. The corresponding specific surface areas, total pore volumes, and mean pore diameters are summarized in Table 1. The introduction of Co MOF into M@SiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eled to a higher surface area due to the high porosity of formed Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e. However, the pore volume and BET surface area of \u0026nbsp;Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e are markedly reduced in comparison to the Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, indicating that the pores of the host Co MOF framework are occupied by the supported Cu NPs\u003csup\u003e38\u003c/sup\u003e. The pore size distribution of Cu-Co@N-C is mainly centered at 0-2 nm and 2-20 nm, as depicted in Fig. 2D, verifying the formation of hierarchical pores, which is attributed to the pyrolysis treatment \u003csup\u003e39\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eThe thermal stability of the composites was\u0026nbsp;evaluated\u0026nbsp;via TGA,\u0026nbsp;as shown in Fig. 2E. The mass loss of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and M@SiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eis 6.23% and 11.73%,\u0026nbsp;respectively, attributed\u0026nbsp;to the\u0026nbsp;removal of water and solvent.\u0026nbsp;Both materials demonstrated excellent thermal stability,\u0026nbsp;with negligible mass loss observed up to 800 \u0026deg;C. Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eundergoes a significant mass loss in the range of 25-800 \u003csup\u003e\u0026deg;\u003c/sup\u003eC, which can be divided into two\u0026nbsp;stages. The\u0026nbsp;initial weight loss (12%) occurred between room temperature and 389\u003csup\u003e◦\u003c/sup\u003eC,\u0026nbsp;primarily due to the volatilization of absorbed water molecules from the pores of the zeolitic imidazole framework and some residual molecular solvents.\u0026nbsp;Subsequently, a severe weight loss (49.03%)\u0026nbsp;was observed between 390-510\u003csup\u003e\u0026deg;\u003c/sup\u003eC,\u0026nbsp;corresponding to the collapse of the ZIF-67 skeleton\u003csup\u003e40\u003c/sup\u003e. However, the thermal stability of Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ewas enhanced due to the successful\u0026nbsp;immobilization of Cu species onto the Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e41\u003c/sup\u003e. Additionally, the Cu-Co@N-C composite indicated higher thermal stability than Cu-Co MOF@MSiO\u003csub\u003e2,\u003c/sub\u003e which can be related to the proper pyrolysis process.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe magnetic properties of Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e, Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003csub\u003e,\u003c/sub\u003e and Cu-Co@N-C composites were evaluated at ambient temperature via VSM as shown in Fig.2F. The magnetic phase present in Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ewas\u0026nbsp;identified as\u0026nbsp;Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, which\u0026nbsp;exhibits\u0026nbsp;a\u0026nbsp;higher magnetic moment\u0026nbsp;compared to the\u0026nbsp;Fe particles in Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e42\u003c/sup\u003e.The saturation magnetization values\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eof Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand Cu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ewere determined\u0026nbsp;to be 28.54 and 20.92 emu g\u003csup\u003e-1\u003c/sup\u003e, respectively, which are lower than the reported saturation magnetization value for Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e. This\u0026nbsp;reduction\u0026nbsp;in saturation magnetization is\u0026nbsp;attributed\u0026nbsp;to the incorporation of non-magnetic components.\u0026nbsp;The hysteresis curve of Cu-Co@N-C\u0026nbsp;demonstrates\u0026nbsp;strong magnetic properties\u0026nbsp;with a saturation magnetization of approximately\u0026nbsp;27.56 emu g\u003csup\u003e-1\u003c/sup\u003e,\u0026nbsp;which is higher\u003cspan dir=\"RTL\"\u003e\u0026nbsp;\u003c/span\u003ethan that of\u0026nbsp;Cu-Co MOF@MSiO\u003csub\u003e2.\u003c/sub\u003e This improvement is mainly ascribed to the significant magnetic contribution from the N-doped carbon framework.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 1\u0026nbsp;\u003c/strong\u003eSurface area analysis parameter of as-synthesized material\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" align=\"\" width=\"614\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eCatalyst\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 170px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eBET total specific surface area\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003e(S\u003csub\u003eBET\u003c/sub\u003e m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e)\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003e\u0026nbsp;\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 137px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eTotal pore volume(cm\u003csup\u003e3\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e)\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003e\u0026nbsp;\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eMean pore diameter (nm)\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003e\u0026nbsp;\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eM\u003c/span\u003e\u003c/strong\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003e@SiO\u003csub\u003e2\u003c/sub\u003e\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 170px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e70.54\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 137px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e0.19\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e3.1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eCo MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 170px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e467.54\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 137px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e0.24\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e4.3\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eCu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 170px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e358.62\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 137px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e0.17\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e4.8\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cstrong\u003e\u003cspan dir=\"LTR\"\u003eCu-Co@N-C\u003c/span\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 170px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e126.43\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 137px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e0.11\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 154px;\"\u003e\n \u003cp dir=\"RTL\"\u003e\u003cspan dir=\"LTR\"\u003e6.3\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eTo gain further insights into the chemical composition of Cu-Co@N-C, XPS measurements (Fig. 3), and EDS analysis (Fig. 4), were conducted. In addition to the presence of C 1s, N 1s, O 1s, Si 2p, the survey spectrum also confirmed the presence of Cu, Co and Fe elements in the Cu-Co@N-C catalyst. The high-resolution C 1s spectra exhibited peaks at 284.5, 285.6, 286.5, and 288.1 eV corresponding to C=C, C=N, C\u0026ndash;O, and C\u0026ndash;N, respectively. The N 1s binding energy displayed peaks centered at 398.7, 399, 400.1, and 401.5 eV, representing graphitic and N heterocycle compounds \u003csup\u003e43\u003c/sup\u003e. The peak at 529.78 eV was assigned to the typical metal\u0026ndash;oxygen bond binding energy\u003csup\u003e44\u003c/sup\u003e, while the peak at 530.74 eV can be attributed to the lattice oxygen (O\u003csub\u003e2\u003c/sub\u003e\u0026minus;) in Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e45\u003c/sup\u003e. The peak at 533.12 eV can be ascribed to the C\u0026ndash;O bond binding energy on the surface of carbon nitrides \u003csup\u003e46\u003c/sup\u003e. It is important to note that the peaks at 711.40 and 725.38 eV are associated with Fe\u003csup\u003e3+\u003c/sup\u003e 2p\u003csub\u003e3/2\u0026nbsp;\u003c/sub\u003eand Fe\u003csup\u003e3+\u003c/sup\u003e 2p\u003csub\u003e1/2\u003c/sub\u003e. Moreover, the peaks at 710.51 and 723.10 eV are related to Fe\u003csup\u003e2+\u003c/sup\u003e 2p\u003csub\u003e3/,\u003c/sub\u003e Fe\u003csup\u003e2+\u003c/sup\u003e p\u003csub\u003e1/2,\u0026nbsp;\u003c/sub\u003ewhile the peak at 719.91 eV corresponds to Fe\u003csup\u003e0\u003c/sup\u003e. These results point to the role of Fe in facilitating a more uniform dispersion and the formation of a greater number of pores within the ZIF-67\u003csup\u003e47\u003c/sup\u003e. In addition, the Si 2p spectra contained two peaks attributable to Si-O-Si (103.7 eV) and Si (-O)\u003csub\u003e2\u003c/sub\u003e (102.1 eV) \u003csup\u003e48\u003c/sup\u003e. The Co 2p spectra revealed four peaks corresponding to the oxidation states of Co\u003csup\u003e3+\u003c/sup\u003e, Co\u003csup\u003e2+\u003c/sup\u003e, Co\u003csup\u003e0\u003c/sup\u003e, and satellite peaks. The peaks located at 780.15 and 796.09 eV correlated with Co\u003csup\u003e3+\u003c/sup\u003e 2p\u003csub\u003e3/2\u0026nbsp;\u003c/sub\u003eand 2p\u003csub\u003e1/2\u003c/sub\u003e, while those at 781.55 and 797.93 eV were attributed to Co\u003csup\u003e2+\u0026nbsp;\u003c/sup\u003e2p\u003csub\u003e3/2\u0026nbsp;\u003c/sub\u003eand 2p\u003csub\u003e1/2\u003c/sub\u003e, respectively. Additionally, the peaks at 788.94 and 804.33 eV were assigned to metallic Co (Co\u003csup\u003e0\u003c/sup\u003e) \u003csup\u003e49\u003c/sup\u003e. For the Cu 2p spectrum, as illustrated in Fig. 3, the peaks at about 932.25 and 951.58 eV can be attributed to the 2p\u003csub\u003e3/2\u0026nbsp;\u003c/sub\u003eand 2p\u003csub\u003e1/2\u003c/sub\u003e of Cu\u003csup\u003e2+\u003c/sup\u003e. Furthermore, the peaks at approximately 931.72 and 951.76 eV correspond to the 2p\u003csub\u003e3/2\u003c/sub\u003e and 2p\u003csub\u003e1/2\u003c/sub\u003e of Cu\u003csup\u003e1+\u003c/sup\u003e. The existence of Cu\u003csup\u003e+\u003c/sup\u003e can be ascribed to the interaction between cobalt and copper during the annealing process in air. Meanwhile, the peaks at 936.17 and 954.74 eV were assigned to the characteristic satellite peaks of Cu\u003csup\u003e2+\u0026nbsp;\u003c/sup\u003e\u003csup\u003e50\u003c/sup\u003e. The presence of C, N, O, Fe, Si, Co, and Cu in the Cu-Co@N-C structure was confirmed by EDS analysis, as shown in Fig. 4.\u003c/p\u003e\n\u003cp\u003eThe surface morphology of the prepared materials was investigated through SEM. Figs. 5 a-d display the morphology of Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, M@SiO\u003csub\u003e2,\u0026nbsp;\u003c/sub\u003eCu-Co MOF@MSiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand Cu-Co@N-C samples, respectively. It can be observed that the Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026nbsp;\u003c/sub\u003eMNPs, which are uniform in shape and size as shown in Fig. 5a, are quite small and agglomerated. In Fig. 5b, it is seen that the particle agglomeration decreases upon coating Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e MNPs with SiO\u003csub\u003e2\u003c/sub\u003e. The SiO\u003csub\u003e2\u003c/sub\u003e coating appears to be distributed relatively homogeneously, as indicated by the reduction in the gray color and the increase in white color\u003csup\u003e51\u003c/sup\u003e. The morphology of the Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e (Fig. 5c) revealed a uniform rhombic dodecahedral morphology, which confirmed the decoration of spherical M@SiO\u003csub\u003e2\u003c/sub\u003e nanoparticles on the surface of the Co MOF without being destroyed, as well as uniform dispersion of Cu nanoparticles. However, the Cu-Co@N-C (Fig. 5d) possessed the original contour of Cu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e with slight shrinkage and distortion due to the decomposition of the organic species and the reduction of cobalt ions during the pyrolysis process\u003csup\u003e52\u003c/sup\u003e.The Cu and Co contents of the bimetallic catalyst Cu-Co@N-C were calculated and quantified by ICP. The exact Co and Cu contents were estimated to be 0.84 and 0.44 mmol. g\u003csup\u003e-1\u003c/sup\u003e respectively, suggesting the successful loading of Cu on the modified magnetic nano porous carbon.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.2. Investigation of catalysis activity\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eIn order to investigate the catalytic effect of the prepared catalyst, it was used in the classical Ullmann coupling reaction using aryl halides and anilines. as well as in the Biginelli reactions between aldehydes, alkyl acetoacetate, and urea through a one pot three-component reaction that resulted in products with yields ranging from good to excellent.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.2.1. C-N Ullmann coupling reaction\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe potential of Cu-Co@N-C as a bimetallic magnetic N-doped carbon catalyst was investigated in C\u0026minus;N cross-coupling reactions for the synthesis of different N-arylated products. The reaction of iodobenzene (1.0 mmol) and aniline (1.2 mmol) was chosen as the precursors for the model reaction, conducted at 110\u003csup\u003e◦\u003c/sup\u003eC. An investigation into the optimization of the Ullmann cross-coupling reaction was conducted by systematically altering various experimental parameters (Table 2). The model reaction\u0026nbsp;was examined in the presence of various catalysts (as well as catalyst free reaction conditions); the best result was obtained when the model reaction was performed in the presence of the\u0026nbsp;Cu-Co@N-C catalyst (entries 1\u0026ndash;7). This included exploring different solvents and bases, adjusting the quantity of catalyst used, and modifying the reaction temperature. The goal was to identify the optimal conditions that would enhance the efficiency and yield of the Ullmann coupling process. The outcomes are shown in Table 2. While screening the reaction in different solvents such as EtOH, DMSO, toluene, CH\u003csub\u003e3\u003c/sub\u003eCN, H\u003csub\u003e2\u003c/sub\u003eO, EtOAC and DMF (entries 8-13), we got the best result in DMF (entry 13). The optimization experiments carried out so far, exploring the effect of catalyst amount in the reaction, indicated\u0026nbsp;that\u0026nbsp;increasing the catalyst amount up to 50 mg raised the yield of the product, and further catalyst loading did not change the yield of reaction\u0026nbsp;(entries 13\u0026ndash;15). As can be seen,\u0026nbsp;the reaction does not proceed in the absence of a catalyst (entry 16). Also, the effect of various bases such as K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e, KOH, Na\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e, Et\u003csub\u003e3\u003c/sub\u003eN, K\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e and NaOH, as well as the absence of a base, has been investigated on the reaction yield. In the lack of a base, a poor yield was obtained, which signifies their importance in the reaction, when K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e providing the best yield (entries 17-22). The influence of temperature on the product conversion was investigated, and the best yield was obtained at 110\u003csup\u003e\u0026deg;\u003c/sup\u003eC (entries 14 and 23-26).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eTable 2\u0026nbsp;\u003c/strong\u003eOptimization of Ullmann Reaction conditions\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" align=\"\" width=\"609\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eEntry\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCatalyst\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003cstrong\u003ecatalyst loading (mg)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eSolvent\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eBase\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eTemp(\u003csup\u003e◦\u003c/sup\u003eC)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 72px;\"\u003e\n \u003cp\u003e\u003cstrong\u003etime(h)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 63px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eYield (%)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eM@SiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e24\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003eTrace\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCo MOF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e22\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e21\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCo MOF@M\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e18\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e51\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCo MOF@SiO\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e19\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCo MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e54\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co MOF@MSiO\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e57\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e65\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMSO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e81\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eToluene\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e62\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e67\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e30\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eEtOAC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e51\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e13\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e89\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e14\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCu-Co@N-C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e50\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eDMF\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e110\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e12\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e94\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e`15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e_\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003eTrace\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e17\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003e_\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003eTrace\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e18\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eKOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e78\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e19\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eNa\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e81\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eEt\u003csub\u003e3\u003c/sub\u003eN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e73\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e21\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e22\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eNaOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e74\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e23\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e130\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e24\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e120\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e100\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 54px;\"\u003e\n \u003cp\u003e26\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 77px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003eDMF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 61px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 78px;\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 59px;\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e87\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"9\" valign=\"top\" style=\"width: 609px;\"\u003e\n \u003cp\u003e\u003csup\u003ea\u003c/sup\u003eReaction conditions: aniline (1.2 mmol), iodo benzene (1.0 mmol), solvent (4.0 mL), base (2 mmol), Cu-CO@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eTo explore the scope and limitations of this catalyst, a wide range of biaryl amine derivatives were synthesized by coupling diverse anilines with different substituted phenyl halides under the optimal reaction conditions, and the results are summarized in Table 3. It is shown that all of the substrates reacted well, affording high yields. Moreover, the results indicate that the reactions of aryl iodides were slightly faster than their chloro and bromo analogs, due to the lower C\u0026ndash;I bond strength compared to C\u0026ndash;Br and C\u0026ndash;Cl bonds (C\u0026ndash;Cl \u0026gt; C\u0026ndash;Br \u0026gt; C\u0026ndash;I). For both electron-withdrawing and electron-donating groups on aryl halides, moderate to good yields of the desired amination products were obtained. However, electron-poor aryl halides gave better product yields, while lower yields were obtained for aryl halides substituted with electron-donating groups.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTable 4 provides a comparison of the catalytic performance for Cu-Co@N-C with other reported heterogeneous systems with either completely metallic or metal/ligand complexes in N-aryl bond formation reactions between aniline and aryl halides. We can conclude that the present catalyst exhibited higher yields compared to the other copper-based catalysts. The coexistence of two metals and porous carbon support in Cu-Co@N-C are likely responsible for its remarkable performance.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eTable 4\u0026nbsp;\u003c/strong\u003eComparison of the Catalytic Activity of Reported Heterogeneous Catalysts in the N-Aryl Bond Formation Reactions between Aniline with Aryl Halides\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" align=\"\" width=\"588\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 152px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCatalyst\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 220px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eConditions\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 66px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eTime (h)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eYie\u003c/strong\u003e\u003cstrong\u003eld (%)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eRefs\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"2\" style=\"width: 222px;\"\u003e\n \u003cp\u003eCuO NPs\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 156px;\"\u003e\n \u003cp\u003eDMSO/t-BuOH, KOH, 110\u003csup\u003e○\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 60px;\"\u003e\n \u003cp\u003e18\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e10-89\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003csup\u003e60\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"2\" style=\"width: 222px;\"\u003e\n \u003cp\u003eCuO/MWCNTs\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 156px;\"\u003e\n \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e/DMAc/120\u003csup\u003e○\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 60px;\"\u003e\n \u003cp\u003e24\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e47-96\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003csup\u003e61\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"2\" style=\"width: 222px;\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@SiO\u003csub\u003e2\u003c/sub\u003e/(Py)-copolymer- (chlorophyll b) Ni/Pd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 156px;\"\u003e\n \u003cp\u003eDMSO/120\u003csup\u003e○\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 60px;\"\u003e\n \u003cp\u003e6-12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e66-94\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003csup\u003e62\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"2\" style=\"width: 222px;\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@PEG/Cu-Co\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 156px;\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO/80\u003csup\u003e○\u003c/sup\u003eC/base-free\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 60px;\"\u003e\n \u003cp\u003e6-7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e68-77\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003csup\u003e63\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"2\" style=\"width: 222px;\"\u003e\n \u003cp\u003e\u0026gamma;-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e@PEG@THMAM-Co\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 156px;\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO /100\u003csup\u003e○\u003c/sup\u003eC/ NaOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 60px;\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e72-90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003csup\u003e64\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"2\" style=\"width: 222px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCu-Co@N-C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd colspan=\"2\" style=\"width: 156px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eDMF /110\u003csup\u003e\u0026deg;\u003c/sup\u003eC/ K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 60px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e12\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e63-97\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 78px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eThis work\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cstrong\u003e3.2.3. Synthesis of 3,4-dihydropyrimidin-2(1H)-ones using Cu-CO@N\u0026ndash;C catalyst\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe catalytic activity of the novel heterogenous bimetallic magnetic Cu-Co@N\u0026ndash;C catalyst was investigated in the one-pot synthesis of DHPMs. The reaction was allowed to proceed using benzaldehyde (1 mmol), ethyl acetoacetate (1 mmol) and urea (1.5 mmol) as a model reaction. Various reaction conditions were optimized in terms of solvent, temperature, time, and catalyst amount (Table 5). The impact of the solvent on reaction yields was examined in a model reaction (entries 1-5). The best result was obtained when ethanol was used as a green solvent (entry 5). The optimization experiments performed with various catalyst amounts, demonstrated that 50 mg of nano catalyst led to the highest yield of the reaction (69%, entry 5). As can be seen, the reaction yield was increased up to 95% under refluxed EtOH (entry 10).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eTable 5\u0026nbsp;\u003c/strong\u003eOptimization of the amount of the Catalyst, Solvent, and Temperature in the Biginelli Reaction\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" align=\"\" width=\"623\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eEntry\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCatalyst\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCatalyst loading\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eSolvent\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eTemp (\u003c/strong\u003e\u003cstrong\u003e\u0026deg;C)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eTime\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eYield (%)\u003csup\u003e\u0026nbsp;b\u003c/sup\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e46\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eToluene\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003etrace\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e38\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eTHF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e42\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e5\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e72\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e30 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e57\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e40 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e64\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e60 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003er.t\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e72\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003eCu-Co@N-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003eEtOH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e85\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 67px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e10\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 109px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCu-Co@N-C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 113px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e50 mg\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 69px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eEtOH\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e\u003cstrong\u003ereflux\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e30 min\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 88px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e95\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003csup\u003ea\u003c/sup\u003e ethylacetoacetate (1mmol), benzaldehyde (1 mmol) and \u0026nbsp; urea (1.5mmol), catalyst\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eCu-CO@N-C\u003c/p\u003e\n\u003cp\u003e\u003csup\u003eb\u0026nbsp;\u003c/sup\u003eIsolayted yield\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo explore scope and address potential limitations, the catalytic activity of Cu-CO@N-C was investigated in the synthesis of various DHPMs under optimized conditions. As tabulated in Table 6, the one pot condensation reaction of aromatic aldehydes, \u0026beta;-ketoesters, and urea in the presence of Cu-CO@N-C afforded the corresponding DHPMs in considerable yields. Moreover, reactions involving electron-withdrawing benzaldehydes (NO\u003csub\u003e2\u003c/sub\u003e, Cl, Br) were observed to proceed at a faster rate compared to those with electron-donating benzaldehydes (Me, OMe, and OH).\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA comparison of the catalytic performance of Cu-Co@N-C in the synthesis of DHPMs is provided in Table 7. As can be seen, the synthesis of DHMPs in the presence of the introduced catalytic system afforded the corresponding products \u003cstrong\u003e4a-u\u003c/strong\u003e in higher yield, shorter reaction time and milder reaction conditions. \u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 7\u0026nbsp;\u003c/strong\u003eComparison of the performance of this work with previously reported catalysts for the synthesis of DHPMs\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" align=\"\" width=\"581\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003e\u003cstrong\u003ecompound name\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003e\u003cstrong\u003econditions\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eTime\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eYield (%)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eRefs\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003eFe\u0026minus;Al/clay\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003eSolvent- free/100\u003csup\u003e\u0026deg;\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e3-5 h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e86-98\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003csup\u003e68\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003eNb\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e/T\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003eSolvent-free\u003csub\u003e/\u003c/sub\u003e130\u003csup\u003e\u0026deg;\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e38-80 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e60-94\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003csup\u003e69\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Cu\u0026ndash;Mn\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003eSolvent-free/70\u003csup\u003e\u0026deg;\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e2-3 h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e75-97\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003csup\u003e70\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@C@OSO\u003csub\u003e3\u003c/sub\u003eH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003eSolvent -free/80\u003csup\u003e\u0026deg;\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e20-105\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e80-97\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003csup\u003e71\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e @SiO\u003csub\u003e2\u003c/sub\u003e-GQDs/Cu (II)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003eSolvent-free /110\u003csup\u003e\u0026deg;\u003c/sup\u003eC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e50-120 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e75-95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003csup\u003e72\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 186px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCu-Co@N-C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 144px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eEtOH / reflux\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 102px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e30-60 min\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 72px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e84-97\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 77px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eThis work\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e"},{"header":"3. Catalyst Stability and Recyclability","content":"\u003cp\u003eFrom the perspective of green chemistry and catalytic sustainability, one of the advantages of heterogeneous catalyst systems is their potential for recyclability and reusability. We have investigated the recyclability and reusability of the Cu-Co@N-C nano catalyst in both Ullmann and Biginelli reactions by performing the model reactions under their optimized conditions. After completion of the first reaction cycle, the catalyst was separated via an external magnetic field, thoroughly washed with EtOAC and water, and then dried under vacuum. The recycled catalyst was subsequently reused in the next run under the same conditions as the first cycle. It is interesting to note that the bimetallic nano porous carbon preserved its catalytic activity over five consecutive runs, exhibiting no significant loss in conversion rate, as illustrated in Fig. 6A. Following the fifth reaction cycle, the recovered catalyst was characterized by XRD and nitrogen-sorption analysis. The XRD patterns of the reused Cu-Co@N-C were closely similar to those of the fresh nano catalyst, as depicted in Fig. 6B. The nitrogen-sorption experiment of the recovered catalyst after the fifth reaction cycle was also performed. The resulting isotherm displayed a similar pattern to that of the Cu-Co@N-C catalyst, with a BET surface area, pore \u0026nbsp;volume, and mean pore diameter of 123.01 m\u003csup\u003e2\u003c/sup\u003e/g, 0.9 cm\u003csup\u003e3\u003c/sup\u003e/g, and 5.9 nm, respectively (Fig. 6C).\u003c/p\u003e\n\u003cp\u003eThe stability and heterogeneous structure of the catalyst under operative conditions were examined through a leaching test. In this context, the model reaction was stopped after 6 hours (half of the required time for reaction completion), and the catalyst was removed by an external magnet, and the reaction yield determined by gas chromatography was about 64%. The residual reaction mixture was then allowed to continue at the same reaction conditions for an additional 6 hours. The results indicated that the conversion remained unchanged during the reload of the reaction mixture after catalyst separation (Fig.6D). Additionally, we evaluated the possibility of cobalt and copper leaching into the reaction medium by conducting ICP analysis on the reused catalyst after the fifth cycle. Notably, the analysis revealed negligible leaching of Cu and Co, with no significant variation compared to the initial loaded amounts of Co (0.83 mmol. g\u003csup\u003e-1\u003c/sup\u003e) and Cu (0.4 mmol. g\u003csup\u003e-1\u003c/sup\u003e) This can be attributed to the strong interaction between the copper and cobalt nanoparticles and the nitrogen binding sites in the N-doped carbon structure, which effectively prevents metal leaching \u003csup\u003e43\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.4\u003c/strong\u003e\u003cstrong\u003e. Mechanistic study\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eBased on the control experiments, the bimetallic compounds provided higher selectivity and efficiency compared to the single-metal components. The presence of the second metal may act as a co-oxidant with a plausible electron exchange \u003csup\u003e73\u003c/sup\u003e. In this regard, the Cu and Co active sites provide a synergistic as well as cooperative performance in chemical reactions. Generally, our observations, along with the reported mechanisms, suggest a plausible mechanism for the Cu-Co@N-C catalyzed Ullmann cross-coupling reaction based on oxidative addition and reductive elimination steps\u003csup\u003e63,74\u003c/sup\u003e. A proposed mechanism is depicted in Fig. 7A. Initially, the coordination of the amine group on the formed active Cu (I) species generates intermediate (\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003e)\u003c/strong\u003e.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eThe presence of K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e in the reaction mixture accelerates the deprotonation process, leading to the formation of intermediate (\u003cstrong\u003eB)\u003c/strong\u003e. In the presence of K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e, oxidative addition of Cu-Co@N-C to aryl halides results in the formation of a MOF\u0026minus;aryl-halide intermediate (\u003cstrong\u003eC)\u003c/strong\u003e, and the Cu(I) active sites are oxidized to Cu (III)\u003csup\u003e45\u003c/sup\u003e. The coordination of aryl halides to metal plays a crucial role in the efficiency of this system for coupling reactions. The nucleophilic substitution of intermediate (\u003cstrong\u003eC)\u003c/strong\u003e with N-containing heterocycles, followed by reductive elimination, yields the desired product and regenerates Cu-Co@N-C\u003csup\u003e75\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;According to the literature, for the preparation of DHMPs, the reaction initiates with the coordination of the metal active sites of the catalyst to the carbonyl group of aldehydes. This is followed by the nucleophilic addition of urea to the aldehyde, leading to the formation of intermediate (\u003cstrong\u003eI)\u003c/strong\u003e\u003cstrong\u003e,\u003c/strong\u003e then one molecule of water is eliminated to produce intermediate (\u003cstrong\u003eⅡ).\u0026nbsp;\u003c/strong\u003eIn the next step,\u0026nbsp;the Michael-type addition of\u0026nbsp;\u0026beta;-diketone to the iminium forms intermediate (\u003cstrong\u003eⅢ)\u003c/strong\u003e. cyclization through the nucleophilic addition of an amine to the carbonyl group, yielding the desired product\u003cstrong\u003e\u0026nbsp;4\u0026nbsp;\u003c/strong\u003eafter the removal of a water molecule (Fig. 7B).\u0026nbsp;\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn this article, a novel copper-cobalt bimetallic magnetic MOF derived N-doped carbon has been successfully synthesized. The bimetallic magnetic MOF catalyst was obtained from the in situ reaction of Co MOF with magnetic silica coated NPs, followed by the immobilization of copper ions on the surface of magnetic Co MOF. Subsequently, the pyrolysis of as-synthesized bimetallic magnetic Co MOF led to the formation of copper-cobalt bimetallic magnetic MOF derived N-doped carbon (Cu-Co@N-C). The structure of the Cu-Co@N-C was identified using various analytical techniques including FT-IR, XRD, BET, BJH, TGA, VSM, XPS, FE-SEM, and ICP. To explore the synergistic effect of copper, cobalt, and nitrogen-doped carbon nanostructures, The catalytic activity of the Cu-Co@N-C catalyst was evaluated in the C-N coupling reactions and Biginelli three component reaction, which resulted in high reaction yields and easy separation of the catalyst using an external magnet. The prepared Cu-Co@N-C exhibited remarkable stability, reusability, and high catalytic performance after 5 cycles by taking advantage of the bimetallic synergistic effect and nano porous construction. The leaching experiment and the hot filtration test indicated that the introduced catalytic system was mainly of a heterogeneous nature, as there was no significant loss of Cu and Co species from the catalyst during the reaction.\u0026nbsp;\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eCompeting interests\u003c/h2\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003ch2\u003eEthical approval\u003c/h2\u003e\n\u003cp\u003eThis work does not contain any studies with human participants or animals performed by any of the authors.\u003c/p\u003e\n\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\n\u003cp\u003eCredit authorship contribution statementArezoo Ahmadi:A.AHeshmatollah Alinezhad:H.AYaghoub Sarrafi:Y.SWriting: A. A.; Conceptualization: A.A.; H.A. Data curation: A.A.; H.A. Formal analysis: A.A.; H.A. Project administration: A.A.; H.A.; Y.S. Methodology: A.A.; Validation: A.A.; H.A.; Y.S. Review and editing: A.A.; H.A.; Y.S. All authors reviewed the manuscript.\u003c/p\u003e\n\u003ch2\u003eAcknowledgements\u003c/h2\u003e\n\u003cp\u003eThe authors acknowledge the Research Council of the University of Mazandaran\u003c/p\u003e\n\u003ch2\u003eData Availability\u003c/h2\u003e\n\u003cp\u003eData availability statementAll data generated or analysed during this study are included in this published article [and its supplementary information files].\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eOsman, A. I.\u003cem\u003e et al.\u003c/em\u003e Coordination-driven innovations in low-energy catalytic processes: advancing sustainability in chemical production. \u003cem\u003eCoordination Chemistry Reviews\u003c/em\u003e \u003cstrong\u003e514\u003c/strong\u003e, 215900 (2024).\u003c/li\u003e\n\u003cli\u003eZhang, H.\u003cem\u003e et al.\u003c/em\u003e Catalysis of a single transition metal site for water oxidation: from mononuclear molecules to single atoms. \u003cem\u003eAdvanced Materials\u003c/em\u003e \u003cstrong\u003e32\u003c/strong\u003e, 1904037 (2020).\u003c/li\u003e\n\u003cli\u003eHai, X.\u003cem\u003e et al.\u003c/em\u003e Geminal-atom catalysis for cross-coupling. \u003cem\u003eNature\u003c/em\u003e \u003cstrong\u003e622\u003c/strong\u003e, 754-760 (2023).\u003c/li\u003e\n\u003cli\u003eGao, M.\u003cem\u003e et al.\u003c/em\u003e Metal and metal oxide supported on ordered mesoporous carbon as heterogeneous catalysts. \u003cem\u003eACS Catalysis\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 4060-4090 (2023).\u003c/li\u003e\n\u003cli\u003eSabzehmeidani, M. M., Mahnaee, S., Ghaedi, M., Heidari, H. \u0026amp; Roy, V. A. Carbon based materials: a review of adsorbents for inorganic and organic compounds. \u003cem\u003eMaterials Advances\u003c/em\u003e \u003cstrong\u003e2\u003c/strong\u003e, 598-627 (2021).\u003c/li\u003e\n\u003cli\u003ePan, Y.\u003cem\u003e et al.\u003c/em\u003e Constructing nitrogen‐doped carbon hierarchy structure derived from metal‐organic framework as high‐performance ORR cathode material for Zn‐air battery. \u003cem\u003eSmall\u003c/em\u003e \u003cstrong\u003e20\u003c/strong\u003e, 2304594 (2024).\u003c/li\u003e\n\u003cli\u003eLiu, Q.\u003cem\u003e et al.\u003c/em\u003e Multifunctional book-like CuCo-MOF for highly sensitive glucose detection and electrocatalytic oxygen evolution. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e45\u003c/strong\u003e, 16714-16721 (2021).\u003c/li\u003e\n\u003cli\u003eHe, T., Kong, X.-J. \u0026amp; Li, J.-R. Chemically stable metal\u0026ndash;organic frameworks: rational construction and application expansion. \u003cem\u003eAccounts of Chemical Research\u003c/em\u003e \u003cstrong\u003e54\u003c/strong\u003e, 3083-3094 (2021).\u003c/li\u003e\n\u003cli\u003eQin, X., Kim, D. \u0026amp; Piao, Y. Metal‐organic frameworks‐derived novel nanostructured electrocatalysts for oxygen evolution reaction. \u003cem\u003eCarbon Energy\u003c/em\u003e \u003cstrong\u003e3\u003c/strong\u003e, 66-100 (2021).\u003c/li\u003e\n\u003cli\u003eWang, L., Zhu, Y., Du, C., Ma, X. \u0026amp; Cao, C. Advances and challenges in metal\u0026ndash;organic framework derived porous materials for batteries and electrocatalysis. \u003cem\u003eJournal of Materials Chemistry A\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 24895-24919 (2020).\u003c/li\u003e\n\u003cli\u003eKnebel, A. \u0026amp; Caro, J. Metal\u0026ndash;organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation. \u003cem\u003eNature Nanotechnology\u003c/em\u003e \u003cstrong\u003e17\u003c/strong\u003e, 911-923 (2022).\u003c/li\u003e\n\u003cli\u003eKoo, W.-T., Jang, J.-S. \u0026amp; Kim, I.-D. Metal-organic frameworks for chemiresistive sensors. \u003cem\u003eChem\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 1938-1963 (2019).\u003c/li\u003e\n\u003cli\u003eYarahmadi, H., Salamah, S. K. \u0026amp; Kheimi, M. Synthesis of an efficient MOF catalyst for the degradation of OPDs using TPA derived from PET waste bottles. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 19136 (2023).\u003c/li\u003e\n\u003cli\u003eHan, T.\u003cem\u003e et al.\u003c/em\u003e Synthesis of CNT@ MIL-68 (Al) composites with improved adsorption capacity for phenol in aqueous solution. \u003cem\u003eChemical Engineering Journal\u003c/em\u003e \u003cstrong\u003e275\u003c/strong\u003e, 134-141 (2015).\u003c/li\u003e\n\u003cli\u003eRamu, S.\u003cem\u003e et al.\u003c/em\u003e Recent advances in metal organic frameworks\u0026ndash;based magnetic nanomaterials for waste water treatment. \u003cem\u003eEnvironmental Science and Pollution Research\u003c/em\u003e \u003cstrong\u003e31\u003c/strong\u003e, 167-190 (2024).\u003c/li\u003e\n\u003cli\u003eYeganeh, M.\u003cem\u003e et al.\u003c/em\u003e Utilization of the copper recovered from waste printed circuit boards as a metal precursor for the synthesis of TiO2/magnetic-MOF (Cu) nanocomposite: Application in photocatalytic degradation of pesticides in aquatic solutions. \u003cem\u003eJournal of Environmental Management\u003c/em\u003e \u003cstrong\u003e345\u003c/strong\u003e, 118755 (2023).\u003c/li\u003e\n\u003cli\u003eZisti, F.\u003cem\u003e et al.\u003c/em\u003e Synthesis and characterization of Fe3O4@ SiO2-supported metal\u0026ndash;organic framework PAEDTC@ MIL-101 (Fe) for degradation of chlorpyrifos and diazinon pesticides. \u003cem\u003eEnvironmental Research\u003c/em\u003e \u003cstrong\u003e245\u003c/strong\u003e, 118019 (2024).\u003c/li\u003e\n\u003cli\u003eZheng, Z., Rong, Z., Nguyen, H. L. \u0026amp; Yaghi, O. M. Structural chemistry of zeolitic imidazolate frameworks. \u003cem\u003eInorganic Chemistry\u003c/em\u003e \u003cstrong\u003e62\u003c/strong\u003e, 20861-20873 (2023).\u003c/li\u003e\n\u003cli\u003eSani, M. A., Khezerlou, A. \u0026amp; McClements, D. J. Zeolitic imidazolate frameworks (ZIFs): Advanced nanostructured materials to enhance the functional performance of food packaging materials. \u003cem\u003eAdvances in Colloid and Interface Science\u003c/em\u003e, 103153 (2024).\u003c/li\u003e\n\u003cli\u003eZhou, Y.\u003cem\u003e et al.\u003c/em\u003e Bimetallic metal\u0026ndash;organic frameworks and MOF-derived composites: Recent progress on electro-and photoelectrocatalytic applications. \u003cem\u003eCoordination Chemistry Reviews\u003c/em\u003e \u003cstrong\u003e451\u003c/strong\u003e, 214264 (2022).\u003c/li\u003e\n\u003cli\u003eKishore, D. R., Sreenivasulu, C., Dapkekar, A. B. \u0026amp; Satyanarayana, G. Recent applications on dual-catalysis for C\u0026ndash;C and C\u0026ndash;X cross-coupling reactions. \u003cem\u003eSynOpen\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 179-194 (2022).\u003c/li\u003e\n\u003cli\u003eZhang, H.\u003cem\u003e et al.\u003c/em\u003e Insights into the hydrogen generation and catalytic mechanism on Co-based nanocomposites derived from pyrolysis of organic metal precursor. \u003cem\u003eIscience\u003c/em\u003e \u003cstrong\u003e27\u003c/strong\u003e (2024).\u003c/li\u003e\n\u003cli\u003eNigam, V.\u003cem\u003e et al.\u003c/em\u003e Revolutionizing Indole Synthesis: A Microwave‐Powered Approach. \u003cem\u003eChemistrySelect\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, e202402171 (2024).\u003c/li\u003e\n\u003cli\u003eMasand, V. H.\u003cem\u003e et al.\u003c/em\u003e Leveraging nitrogen occurrence in approved drugs to identify structural patterns. \u003cem\u003eExpert Opinion on Drug Discovery\u003c/em\u003e \u003cstrong\u003e19\u003c/strong\u003e, 111-124 (2024).\u003c/li\u003e\n\u003cli\u003eFui, C. J., Sarjadi, M. S., Sarkar, S. M. \u0026amp; Rahman, M. L. Recent advancement of ullmann condensation coupling reaction in the formation of aryl-oxygen (CO) bonding by copper-mediated catalyst. \u003cem\u003eCatalysts\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 1103 (2020).\u003c/li\u003e\n\u003cli\u003eMa, X. \u0026amp; Davies, R. P. Tartramide Ligands for Copper‐Catalyzed N‐Arylation at Room Temperature. \u003cem\u003eAdvanced Synthesis \u0026amp; Catalysis\u003c/em\u003e \u003cstrong\u003e364\u003c/strong\u003e, 2023-2031 (2022).\u003c/li\u003e\n\u003cli\u003eAverin, A. D.\u003cem\u003e et al.\u003c/em\u003e Recent Achievements in the Copper-Catalyzed Arylation of Adamantane-Containing Amines, Di-and Polyamines. \u003cem\u003eCatalysts\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 831 (2023).\u003c/li\u003e\n\u003cli\u003eKamanna, K. \u0026amp; Khatavi, S. Y. Microwave-accelerated carbon-carbon and carbon-heteroatom bond formation via multi-component reactions: a brief overview. \u003cem\u003eCurrent Microwave Chemistry\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 23-39 (2020).\u003c/li\u003e\n\u003cli\u003eS\u0026aacute;nchez-Sancho, F.\u003cem\u003e et al.\u003c/em\u003e Synthesis of 3, 4-dihydropyrimidin (thio) one containing scaffold: Biginelli-like reactions. \u003cem\u003ePharmaceuticals\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 948 (2022).\u003c/li\u003e\n\u003cli\u003eEs\u0026rsquo;haghi, Z. \u0026amp; Esmaeili-Shahri, E. Sol\u0026ndash;gel-derived magnetic SiO2/TiO2 nanocomposite reinforced hollow fiber-solid phase microextraction for enrichment of non-steroidal anti-inflammatory drugs from human hair prior to high performance liquid chromatography. \u003cem\u003eJournal of Chromatography B\u003c/em\u003e \u003cstrong\u003e973\u003c/strong\u003e, 142-151 (2014).\u003c/li\u003e\n\u003cli\u003eWeng, X., Chen, W., Cai, W., Owens, G. \u0026amp; Chen, Z. Synthesis of ferroferric oxide@ silicon dioxide/cobalt-based zeolitic imidazole frameworks for the removal of doxorubicin hydrochloride from wastewater. \u003cem\u003eJournal of Colloid and Interface Science\u003c/em\u003e \u003cstrong\u003e624\u003c/strong\u003e, 108-120 (2022).\u003c/li\u003e\n\u003cli\u003eChen, T., Ren, H., Li, L., Tan, W. \u0026amp; He, H. Synergistic cobalt\u0026ndash;copper metal\u0026ndash;organic framework-derived oxide electrocatalyst for efficient oxygen evolution reaction. \u003cem\u003eMaterials Chemistry and Physics\u003c/em\u003e \u003cstrong\u003e313\u003c/strong\u003e, 128689 (2024).\u003c/li\u003e\n\u003cli\u003eAhmadi, A., Alinezhad, H., Sarrafi, Y. \u0026amp; Ghani, M. Nanoporous carbon derived ZIF-67@ MWCNTs-Fe3O4 reinforced hollow fiber to performe hollow fiber solid-phase micro extraction (HF-SPME) coupled with high-performance liquid chromatography to determine deltamethrin and cypermethrin. \u003cem\u003eJournal of Food Composition and Analysis\u003c/em\u003e \u003cstrong\u003e136\u003c/strong\u003e, 106750 (2024).\u003c/li\u003e\n\u003cli\u003eGong, H.\u003cem\u003e et al.\u003c/em\u003e In situ construction of ZIF-67-derived hybrid tricobalt tetraoxide@ carbon for supercapacitor. \u003cem\u003eNanomaterials\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 1571 (2022).\u003c/li\u003e\n\u003cli\u003eWu, Y.\u003cem\u003e et al.\u003c/em\u003e Electrocatalytic oxygen reduction by a Co/Co 3 O 4@ N-doped carbon composite material derived from the pyrolysis of ZIF-67/poplar flowers. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e11\u003c/strong\u003e, 2693-2700 (2021).\u003c/li\u003e\n\u003cli\u003eWeng, Y.\u003cem\u003e et al.\u003c/em\u003e Defective porous carbon polyhedra decorated with copper nanoparticles for enhanced NIR‐driven photothermal cancer therapy. \u003cem\u003eSmall\u003c/em\u003e \u003cstrong\u003e16\u003c/strong\u003e, 1905184 (2020).\u003c/li\u003e\n\u003cli\u003eJiang, M.\u003cem\u003e et al.\u003c/em\u003e ZIF-67 derived Ag-Co3O4@ N-doped carbon/carbon nanotubes composite and its application in Mg-air fuel cell. \u003cem\u003eElectrochemistry Communications\u003c/em\u003e \u003cstrong\u003e77\u003c/strong\u003e, 5-9 (2017).\u003c/li\u003e\n\u003cli\u003eSharma, S., Sharma, C., Kaur, M. \u0026amp; Paul, S. The in situ fabrication of ZIF-67 on titania-coated magnetic nanoparticles: a new platform for the immobilization of Pd (ii) with enhanced catalytic activity for organic transformations. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e45\u003c/strong\u003e, 20309-20322 (2021).\u003c/li\u003e\n\u003cli\u003eLi, C., Meng, Y., Yang, S. \u0026amp; Li, H. ZIF‐67 Derived Co/NC Nanoparticles Enable Catalytic Leuckart‐type Reductive Amination of Bio‐based Carbonyls to N‐Formyl Compounds. \u003cem\u003eChemCatChem\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 5166-5177 (2021).\u003c/li\u003e\n\u003cli\u003eYin, L.\u003cem\u003e et al.\u003c/em\u003e Multifunctional ZIF-67@ SiO2 membrane for high efficiency removal of particulate matter and toxic gases. \u003cem\u003eIndustrial \u0026amp; Engineering Chemistry Research\u003c/em\u003e \u003cstrong\u003e59\u003c/strong\u003e, 17876-17884 (2020).\u003c/li\u003e\n\u003cli\u003eKhan, S. B.\u003cem\u003e et al.\u003c/em\u003e CuO embedded chitosan spheres as antibacterial adsorbent for dyes. \u003cem\u003eInternational journal of biological macromolecules\u003c/em\u003e \u003cstrong\u003e88\u003c/strong\u003e, 113-119 (2016).\u003c/li\u003e\n\u003cli\u003eWang, Y.\u003cem\u003e et al.\u003c/em\u003e Metal organic frameworks-derived Fe-Co nanoporous carbon/graphene composite as a high-performance electromagnetic wave absorber. \u003cem\u003eJournal of Alloys and Compounds\u003c/em\u003e \u003cstrong\u003e785\u003c/strong\u003e, 765-773 (2019).\u003c/li\u003e\n\u003cli\u003eSalarinejad, N., Dabiri, M. \u0026amp; Movahed, S. K. CuPd bimetallic nanoparticles supported magnetic ionic liquid-derived N-doped carbon as a highly efficient heterogeneous catalyst for the one-pot oxidative multicomponent reactions. \u003cem\u003eJournal of the Taiwan Institute of Chemical Engineers\u003c/em\u003e \u003cstrong\u003e159\u003c/strong\u003e, 105496 (2024).\u003c/li\u003e\n\u003cli\u003eLiu, S., Hui, K. \u0026amp; Hui, K. Flower-like copper cobaltite nanosheets on graphite paper as high-performance supercapacitor electrodes and enzymeless glucose sensors. \u003cem\u003eACS applied materials \u0026amp; interfaces\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 3258-3267 (2016).\u003c/li\u003e\n\u003cli\u003eNasseri, F., Nasseri, M. A., Kassaee, M. Z. \u0026amp; Yavari, I. Synergistic performance of a new bimetallic complex supported on magnetic nanoparticles for Sonogashira and C\u0026ndash;N coupling reactions. \u003cem\u003eScientific Reports\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 18153 (2023).\u003c/li\u003e\n\u003cli\u003eMattevi, C.\u003cem\u003e et al.\u003c/em\u003e Evolution of electrical, chemical, and structural properties of transparent and conducting chemically derived graphene thin films. \u003cem\u003eAdvanced functional materials\u003c/em\u003e \u003cstrong\u003e19\u003c/strong\u003e, 2577-2583 (2009).\u003c/li\u003e\n\u003cli\u003eXiong, J.\u003cem\u003e et al.\u003c/em\u003e Fe/Co/N\u0026ndash;C/graphene derived from Fe/ZIF-67/graphene oxide three dimensional frameworks as a remarkably efficient and stable catalyst for the oxygen reduction reaction. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 2425-2435 (2022).\u003c/li\u003e\n\u003cli\u003eWei, Z.\u003cem\u003e et al.\u003c/em\u003e High-efficiency adsorption of phenanthrene by Fe3O4-SiO2-dimethoxydiphenylsilane nanocomposite: Experimental and theoretical study. \u003cem\u003eJournal of hazardous materials\u003c/em\u003e \u003cstrong\u003e422\u003c/strong\u003e, 126948 (2022).\u003c/li\u003e\n\u003cli\u003eGholinejad, M., Naghshbandi, Z. \u0026amp; Sansano, J. M. Zeolitic imidazolate frameworks-67 (ZIF-67) supported PdCu nanoparticles for enhanced catalytic activity in Sonogashira-Hagihara and nitro group reduction under mild conditions. \u003cem\u003eMolecular Catalysis\u003c/em\u003e \u003cstrong\u003e518\u003c/strong\u003e, 112093 (2022).\u003c/li\u003e\n\u003cli\u003eMu, X.\u003cem\u003e et al.\u003c/em\u003e Doping of Cr to regulate the valence state of Cu and Co contributes to efficient water splitting. \u003cem\u003eACS Applied Materials \u0026amp; Interfaces\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 16552-16561 (2023).\u003c/li\u003e\n\u003cli\u003eEce, M. Ş., Ekinci, A., Kutluay, S., Şahin, \u0026Ouml;. \u0026amp; Horoz, S. Facile synthesis and comprehensive characterization of Ni-decorated amine groups-immobilized Fe3O4@ SiO2 magnetic nanoparticles having enhanced solar cell efficiency. \u003cem\u003eJournal of Materials Science: Materials in Electronics\u003c/em\u003e \u003cstrong\u003e32\u003c/strong\u003e, 18192-18204 (2021).\u003c/li\u003e\n\u003cli\u003eZhu, C., Wang, M., Li, T., Lu, T. \u0026amp; Pan, L. In situ synthesis of porous Co 3 O 4 polyhedra/carbon nanotubes heterostructures for highly efficient supercapacitors. \u003cem\u003eIonics\u003c/em\u003e \u003cstrong\u003e23\u003c/strong\u003e, 2175-2183 (2017).\u003c/li\u003e\n\u003cli\u003eMohammadinezhad, A. \u0026amp; Akhlaghinia, B. Co II immobilized on an aminated magnetic metal\u0026ndash;organic framework catalyzed C\u0026ndash;N and C\u0026ndash;S bond forming reactions: a journey for the mild and efficient synthesis of arylamines and arylsulfides. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 15525-15538 (2019).\u003c/li\u003e\n\u003cli\u003ePark, S.-E.\u003cem\u003e et al.\u003c/em\u003e Efficient Palladium-Catalyzed Amination of Aryl Chlorides Using Dicyclohexylamino [(2, 6-dimethyl) morpholino] phenylphosphine as a PN2 Ligand. \u003cem\u003eSynthesis\u003c/em\u003e \u003cstrong\u003e2009\u003c/strong\u003e, 815-823 (2009).\u003c/li\u003e\n\u003cli\u003eBagheri, H. \u0026amp; Baharfar, R. Magnetic MCR-Functionalized Graphene Oxide Complexed with Copper Nano-Particles: An Efficient and Recyclable Nanocatalyst for Ullmann C\u0026ndash;N Coupling Reaction. \u003cem\u003ePolycyclic Aromatic Compounds\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 7580-7596 (2023).\u003c/li\u003e\n\u003cli\u003eHuang, L., Yu, R., Zhu, X. \u0026amp; Wan, Y. A recyclable Cu-catalyzed C\u0026ndash;N coupling reaction in water and its application to synthesis of imidazo [1, 2-a] quinoxaline. \u003cem\u003eTetrahedron\u003c/em\u003e \u003cstrong\u003e69\u003c/strong\u003e, 8974-8977 (2013).\u003c/li\u003e\n\u003cli\u003eDing, X.\u003cem\u003e et al.\u003c/em\u003e Room-temperature CuI-catalyzed amination of aryl iodides and aryl bromides. \u003cem\u003eThe Journal of Organic Chemistry\u003c/em\u003e \u003cstrong\u003e82\u003c/strong\u003e, 5416-5423 (2017).\u003c/li\u003e\n\u003cli\u003eYi, Z., Huang, M., Wan, Y. \u0026amp; Zhu, X. An effective heterogeneous copper catalyst system for C\u0026ndash;N coupling and its application in the preparation of 2-methyl-4-methoxydiphenylamine (MMDPA). \u003cem\u003eSynthesis\u003c/em\u003e \u003cstrong\u003e50\u003c/strong\u003e, 3911-3920 (2018).\u003c/li\u003e\n\u003cli\u003eModha, S. G., Popescu, M. V. \u0026amp; Greaney, M. F. Synthesis of triarylamines via sequential C\u0026ndash;N bond formation. \u003cem\u003eThe Journal of organic chemistry\u003c/em\u003e \u003cstrong\u003e82\u003c/strong\u003e, 11933-11938 (2017).\u003c/li\u003e\n\u003cli\u003eJammi, S.\u003cem\u003e et al.\u003c/em\u003e CuO nanoparticles catalyzed C\u0026minus; N, C\u0026minus; O, and C\u0026minus; S cross-coupling reactions: Scope and mechanism. \u003cem\u003eThe Journal of organic chemistry\u003c/em\u003e \u003cstrong\u003e74\u003c/strong\u003e, 1971-1976 (2009).\u003c/li\u003e\n\u003cli\u003eGopiraman, M.\u003cem\u003e et al.\u003c/em\u003e An efficient, reusable copper-oxide/carbon-nanotube catalyst for N-arylation of imidazole. \u003cem\u003eCarbon\u003c/em\u003e \u003cstrong\u003e62\u003c/strong\u003e, 135-148 (2013).\u003c/li\u003e\n\u003cli\u003eKazemnejadi, M., Ahmed, R. O. \u0026amp; Mahmoudi, B. Ni/Pd-catalyzed Suzuki\u0026ndash;Miyaura cross-coupling of alcohols and aldehydes and C\u0026ndash;N cross-coupling of nitro and amines via domino redox reactions: base-free, hydride acceptor-free. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 43962-43974 (2020).\u003c/li\u003e\n\u003cli\u003eNasseri, M. A., Rezazadeh, Z., Kazemnejadi, M. \u0026amp; Allahresani, A. A Co\u0026ndash;Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C\u0026ndash;N cross-coupling reactions in water. \u003cem\u003eDalton Transactions\u003c/em\u003e \u003cstrong\u003e49\u003c/strong\u003e, 10645-10660 (2020).\u003c/li\u003e\n\u003cli\u003eSheikh, S.\u003cem\u003e et al.\u003c/em\u003e Water-Dispersible, Magnetically Recyclable Heterogeneous Cobalt Catalyst for C\u0026ndash;C and C\u0026ndash;N Cross-Coupling Reactions in Aqueous Media. \u003cem\u003eACS omega\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 31393-31400 (2024).\u003c/li\u003e\n\u003cli\u003eRezayati, S.\u003cem\u003e et al.\u003c/em\u003e Magnetic silica-coated picolylamine copper complex [fe3o4@ sio2@ gp/picolylamine-cu (ii)]-catalyzed biginelli annulation reaction. \u003cem\u003eInorganic chemistry\u003c/em\u003e \u003cstrong\u003e61\u003c/strong\u003e, 992-1010 (2021).\u003c/li\u003e\n\u003cli\u003eElhamifar, D., Hosseinpoor, F., Karimi, B. \u0026amp; Hajati, S. Ionic liquid-based ordered mesoporous organosilica-supported copper as a novel and efficient nanocatalyst for the one-pot synthesis of Biginelli products. \u003cem\u003eMicroporous and Mesoporous Materials\u003c/em\u003e \u003cstrong\u003e204\u003c/strong\u003e, 269-275 (2015).\u003c/li\u003e\n\u003cli\u003eNajafi, M.\u003cem\u003e et al.\u003c/em\u003e Decorated Cu nanoparticles on ZPD as a novel and highly proficient nanocatalyst for synthesis of chromene and Biginelli reactions. \u003cem\u003eResearch on Chemical Intermediates\u003c/em\u003e \u003cstrong\u003e50\u003c/strong\u003e, 1177-1209 (2024).\u003c/li\u003e\n\u003cli\u003eDar, B. A.\u003cem\u003e et al.\u003c/em\u003e Fe\u0026ndash;Al/clay as an efficient heterogeneous catalyst for solvent-free synthesis of 3, 4-dihydropyrimidones. \u003cem\u003eJournal of Chemical Sciences\u003c/em\u003e \u003cstrong\u003e125\u003c/strong\u003e, 545-553 (2013).\u003c/li\u003e\n\u003cli\u003edo Nascimento, L. G.\u003cem\u003e et al.\u003c/em\u003e Niobium oxides as heterogeneous catalysts for Biginelli multicomponent reaction. \u003cem\u003eThe Journal of Organic Chemistry\u003c/em\u003e \u003cstrong\u003e85\u003c/strong\u003e, 11170-11180 (2020).\u003c/li\u003e\n\u003cli\u003eNasseri, M. A., Rezazadeh, Z., Kazemnejadi, M. \u0026amp; Allahresani, A. Cu-Mn bimetallic complex immobilized on magnetic NPs as an efficient catalyst for domino one-pot preparation of benzimidazole and Biginelli reactions from alcohols. \u003cem\u003eCatalysis Letters\u003c/em\u003e \u003cstrong\u003e151\u003c/strong\u003e, 1049-1067 (2021).\u003c/li\u003e\n\u003cli\u003eTaheri Hatkehlouei, S. F., Mirza, B. \u0026amp; Soleimani-Amiri*, S. Solvent-free one-pot synthesis of diverse dihydropyrimidinones/tetrahydropyrimidinones using biginelli reaction catalyzed by Fe3O4@ C@ OSO3H. \u003cem\u003ePolycyclic Aromatic Compounds\u003c/em\u003e \u003cstrong\u003e42\u003c/strong\u003e, 1341-1357 (2022).\u003c/li\u003e\n\u003cli\u003eNajjar, M., Nasseri, M. A., Darroudi, M. \u0026amp; Allahresani, A. Synthesis of dihydropyrimidinone and dihydropyridine derivatives by a GQDs-based magnetically nanocatalyst under solvent-free conditions. \u003cem\u003eJournal of Environmental Chemical Engineering\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 108854 (2022).\u003c/li\u003e\n\u003cli\u003eAlshammari, A., Kalevaru, V. N. \u0026amp; Martin, A. Bimetallic catalysts containing gold and palladium for environmentally important reactions. \u003cem\u003eCatalysts\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 97 (2016).\u003c/li\u003e\n\u003cli\u003eSharma, N.\u003cem\u003e et al.\u003c/em\u003e Modified graphene supported Ag\u0026ndash;Cu NPs with enhanced bimetallic synergistic effect in oxidation and Chan\u0026ndash;Lam coupling reactions. \u003cem\u003eRSC advances\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 30048-30061 (2020).\u003c/li\u003e\n\u003cli\u003eEsrafili, L., Morsali, A., Dehghani Firuzabadi, F. \u0026amp; Retailleau, P. Development of porous cobalt-/copper-doped carbon nanohybrids derived from functionalized MOFs as efficient catalysts for the Ullmann cross-coupling reaction: Insights into the active centers. \u003cem\u003eACS Applied Materials \u0026amp; Interfaces\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 43115-43124 (2020).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTable 3 and 6 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Bimetallic catalyst, Metal organic Framework, Ullmann coupling reaction, Biginellie reaction, Multi component reactions","lastPublishedDoi":"10.21203/rs.3.rs-5726553/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5726553/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eMagnetic metal-organic frameworks (MOFs) are promising precursors for generating diverse carbon-based nanostructures due to their facile recovery and separation, as well as their robust mechanical and thermal properties. In this study, a novel Cu-Co bimetallic nanoparticle supported on magnetic MOF derived N-doped carbon was successfully synthesized. The copper ions preloaded within the pores of the Co MOF provide abundant exposed Cu active sites. The pyrolysis treatment results in a hierarchical porous structure with a high surface area, contributing to mass transfer and enhancing reactant diffusion to the active sites. The developed catalyst was characterized extensively using FT-IR, XRD, BET, BJH, EDX, TGA, VSM, FE-SEM, ICP, and XPS techniques. The catalyst exhibited exceptional catalytic activity for C-N coupling and one-pot multicomponent reactions. This superior performance can be attributed to the synergistic effect between copper nanoparticles incorporated in the composite, as well as the highly porous N-doped carbon structure. The catalyst demonstrated remarkable stability, maintaining its activity without significant degradation after five consecutive reaction cycles. This innovative approach, capitalizing on the reinforcing interplay of structural and compositional advantages, opens up opportunities for the rational design and synthesis of highly efficient bimetallic nanoparticle catalysts supported on magnetic MOF-derived N-doped carbon.\u003c/p\u003e","manuscriptTitle":"Copper-Cobalt Bimetallic nanoparticles supported on Magnetic MOF Derived N-doped carbon as highly efficient Catalysts for the C–N coupling and one-pot multicomponent reaction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-09 06:47:42","doi":"10.21203/rs.3.rs-5726553/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"f399191f-c760-4c5d-a5ac-e466fde3eeea","owner":[],"postedDate":"January 9th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":42493086,"name":"Physical sciences/Chemistry/Catalysis"},{"id":42493087,"name":"Physical sciences/Chemistry/Green chemistry"},{"id":42493088,"name":"Physical sciences/Chemistry/Organic chemistry"},{"id":42493089,"name":"Physical sciences/Chemistry/Synthesis"}],"tags":[],"updatedAt":"2025-01-28T12:53:56+00:00","versionOfRecord":[],"versionCreatedAt":"2025-01-09 06:47:42","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5726553","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5726553","identity":"rs-5726553","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}