Post-Synthetic Modification of Zr-Based Metal Organic Framework by Schiff Base Zinc Complex for Catalytic Applications in a Click Reaction

Post-Synthetic Modification of Zr-Based Metal Organic Framework by Schiff Base Zinc Complex for Catalytic Applications in a Click 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 Post-Synthetic Modification of Zr-Based Metal Organic Framework by Schiff Base Zinc Complex for Catalytic Applications in a Click Reaction Mohammad-Aqa Rezaie, Amir Khojastehnezhad, Ali Shiri This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4695524/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Oct, 2024 Read the published version in Scientific Reports → Version 1 posted 10 You are reading this latest preprint version Abstract A novel nanocatalyst, denoted as UiO-66/Sal-ZnCl 2 , has been synthesized and systematically characterized employing a range of analytical techniques, including Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area analysis, and inductively coupled plasma (ICP) analysis. The comprehensive analyses collectively affirm the effective coordination of zinc chloride onto the functionalized UiO-66. Subsequently, the catalytic efficacy of UiO-66/Sal-ZnCl 2 was assessed in a one-pot, three-component click reaction involving terminal alkynes, alkyl halides, and sodium azide, conducted in an aqueous medium. The catalyst demonstrated remarkable catalytic activity, showcasing the capability to facilitate the reaction with high yields and exceptional regioselectivity. Noteworthy attributes of this nanocatalyst and the method include its elevated efficiency, recyclability, convenient product workup, and, significantly, the utilization of a sustainable solvent medium. The synthesis, characterization, and catalytic performance of this catalyst collectively contribute to its potential as an innovative and reusable nanocatalyst for diverse synthetic transformations. Physical sciences/Chemistry/Catalysis Physical sciences/Chemistry/Organic chemistry nanocatalyst metal organic framework click reaction post-synthetic modification triazole Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 1. Introduction Metal-organic frameworks (MOFs) have attracted considerable attention within the scientific community due to their unique characteristics as porous crystalline coordination polymers. These attributes encompass a substantial surface area, remarkable porosity, facile structural adaptability, and the ability to be functionalized with diverse organic linkers, along with adjustable pore sizes. These features contribute to their remarkable performance as catalysts, particularly in catalytic organic transformations [ 1 – 3 ]. MOFs also have found applications as gas absorbers, storage devices and separators, water purifiers, sensors, magnets, photocatalysts, and in drug delivery systems [ 4 – 8 ]. Their porous structure with available and large holes allows the transfer of reactants to the inner parts of the framework, enabling proper interaction with the catalytic active sites and subsequently the release of materials from the pores to the reaction environment [ 3 , 9 ]. MOFs have been employed extensively in catalytic reactions, either by creating inherent acidic and basic sites on their surfaces or by serving as supports for other catalysts. They can be used directly, without any alterations to their structure, and the desired catalyst developed on the surface or in its pores [ 9 ]. Also, it is advisable to carry out a structural modification prior to the loading of efficient catalytic systems [ 10 ]. By means of post-synthesis modification of MOFs, it is possible to adjust their chemical and physical properties, as well as to introduce a diverse array of organic and inorganic functionalities [ 11 , 12 ]. Among various MOFs, Zirconium-based MOFs (Zr-MOFs) have garnered substantial attention in chemical research [ 13 ]. UiO-66, the first synthesized Zr-MOF, consists of a zirconium-oxo cluster and 1,4-benzenedicarboxylic acid. This MOF exhibits unparalleled hydrothermal stability [ 14 ] and has been applied in water treatment [ 15 ], remediation [ 16 ], catalysis [ 17 ], and various other fields [ 18 – 21 ]. Zr-MOFs have been employed in the synthesis of diverse organic compounds through multicomponent reactions [ 22 ]. Ionic liquid-supported Zr-MOF BAIL@UiO-66 was utilized in the preparation of pyrimidine and spirooxindole derivatives [ 23 , 24 ]. Pyrimidopyrimidines were prepared via TEDA-BAIL@UiO-66 catalyzed reaction [ 25 ]. Zr-MOF-FePC was reported for synthesis of α-acyloxy amides [ 26 ]. Additionally, UiO-66 modified with ethylene diamine (ED), UiO-66-SO3H, and Zr-MOF have been employed for the synthesis of 2-aminotiophenes [ 27 ], dihydro-2-oxopyrroles [ 28 ], imidazo[1,2-a]pyridines, 3,4-dihydroquinoxaline-2-amines, and trisubstituted pyridine derivatives [ 29 ], respectively. In the pursuit of novel catalytic systems for organic transformations [ 30 – 34 ], this study presents the synthesis of a UiO-66 metal-organic framework post-modified with salicylaldehyde via Schiff base reaction, followed by coordination of Zinc chloride (UiO-66/Sal-ZnCl 2 ). This method presents a robust catalyst for the efficient synthesis of 1,2,3-triazoles via a one-pot click coupling reaction involving terminal alkynes, aryl or alkyl halides, and sodium azide. Numerous methods have been developed for the synthesis of triazole derivatives, as recently reviewed [ 35 – 37 ]. Notable examples include the use of L-Proline‐MCM‐41‐CuCl [ 38 ], [(Cell-ThP-Cu(II))] [ 39 ], Cell/SiO 2 -Sal-Pd(II) [ 40 ], and CuIL 1 PPh 3 (L 1 = bis(pyrazolyl)methane) [ 41 ] as catalysts for triazole synthesis. Nevertheless, a majority of the aforementioned catalysts and methodologies encountered significant challenges, notably arising from costly catalyst preparation procedures, the employment of hazardous solvents and reagents, and complexities associated with catalyst recovery techniques. Consequently, the imperative to develop a novel and efficient catalyst becomes paramount within the domain of organic synthesis. This imperative is particularly emphasized in the synthesis of triazole derivatives, where the inadequacies of existing catalysts and methods underscore the urgency and desirability of advancing catalytic approaches for enhanced efficacy and sustainability in the synthesis of such compounds. 2. Experimental All substrates, reagents, and solvents were procured from reputable suppliers, namely Merck and Aldrich. TEM Images were acquired using a Leo 912AB microscope at 120 kV and SEM images were acquired using a Leo 1450VP microscope. Thermogravimetric analyses were recorded with Mettler Toledo LF -Switzerland and FT-IR spectra with Nicolet Fourier spectrophotometer using KBr pellets. The energy dispersive X-ray analysis (XRD) was utilized to examine the crystalline structure of the catalyst. The 1 H- and 13 C-NMR spectra of the products were acquired in CDCl 3 solvent utilizing the Bruker DRX-300 AVANCE spectrometer operating at frequencies of 300 and 75 MHz, respectively. 2.1. General procedure for the synthesis of UiO-66-NH 2 According to the literature [ 42 ], ZrCl 4 (11.652 g, 50 mmol) was dissolved in 250 ml DMF in a three-necked flask with vigorous stirring. Then 2-aminoterephthalic acid (9.058 g, 50 mmol) was added and stirred to give a yellow clear solution. Then concentrated HCl 37% (35 ml) was added to the flask with stirring. The solution was kept under reflux for 10 hours. The suspension was then cooled to 30°C and the light-yellow solid was filtered off. The precipitate was washed with DMF (2 × 10 ml) and deionized water (2 × 10 ml) and dried at 70°C for 6 hours to prepare UiO-66-NH 2 . 2.2. General procedure for the synthesis of UiO-66-Sal UiO-66-NH 2 (0.15 g) was dispersed in absolute ethanol (100 ml) by sonication and then stirred with salicylaldehyde (1250 µL, 12 mmol) at 75°C for 12 hours. After this time, the mixture was cooled to 30°C, then the solid was filtered, washed with water and ethanol (3 × 15 ml), and dried overnight at 75°C (UiO-66/Sal) [ 42 ]. 2.3. General procedure for the synthesis of UiO-66/Sal-ZnCl 2 The prepared UiO-66/Sal salt (0.15 g) and zinc chloride (0.82 g, 0.6 mmol) were dispersed in absolute ethanol (20 ml), and the suspension was then stirred for 24 hours at 50°C. The prepared solid catalyst was filtered off, washed with absolute ethanol (3 × 20 ml), and dried at 70°C for 12 hours (UiO-66/Sal-ZnCl 2 ). 2.4. General procedure for the synthesis of 1,2,3-Triazoles Phenylacetylene (1 mmol), sodium azide (1 mmol), halide (1 mmol), and UiO-66/Sal-ZnCl 2 (20 mg) were mixed in water (2 mL) and stirred at 50°C for the appropriate time. The progress of the reaction was monitored by thin-layer chromatography (TLC). After completion of the reaction, the reaction mixture was cooled to 30°C and the catalyst was filtered off. The reaction mixture underwent extraction using a combination of ethyl acetate and water, followed by the subsequent evaporation of the organic layer. Subsequently, the product was subjected to a drying process at a temperature of 50°C for 4 hours. 3. Results and discussion The synthesis of the heterogeneous UiO-66/Sal-ZnCl 2 nanocatalyst was successfully accomplished through a three-step process. Initially, UiO-66-NH 2 was synthesized by combining ZrCl 4 and 2-aminoterephthalic acid. Subsequently, the -NH 2 groups were chemically reacted with salicylaldehyde in a post-modification step, resulting in the formation of UiO-66/Sal. Finally, the coordination of ZnCl 2 salt with UiO-66/Sal led to the creation of UiO-66/Sal-ZnCl 2 , as illustrated in Fig. 1 . Comprehensive characterization of the UiO-66/Sal-ZnCl 2 structure was performed using various techniques, including ICP, FT-IR, TGA, BET, TEM, SEM, EDX, and XRD, as detailed in this section. The quantification of zinc ions on the UiO-66/Sal-ZnCl 2 nanocatalyst was conducted through ICP-OES analysis. The zinc concentration was determined to be 0.5 wt.% of the catalyst. The chemical structure and functional groups of UiO-66-NH 2 , UiO-66/Sal, and UiO-66/Sal-ZnCl 2 were examined via FT-IR analysis, as depicted in Fig. 2 . For UiO-66-NH 2 (Fig. 2 a), peaks at 3458 and 3348 cm -1 were assigned to asymmetric and symmetric vibrations, while the 1658 cm -1 peak indicated the bending vibration of NH 2 groups. The symmetric and asymmetric stretching vibrations of carboxyl groups associated with Zr 4+ were observed at 1580 and 1386 cm -1 , respectively. A peak at 1509 cm -1 corresponded to the stretching vibration of C = C units in benzene rings, while the shear vibration of N-H groups appeared at 1436 cm -1 . Additionally, a unique C-N stretching absorption of aromatic amines was evident at 1262 cm -1 . Peaks at 768 and 662 cm -1 were attributed to the stretching vibration of µ3-O in Zr-(OC) [ 43 , 44 ]. After salicylaldehyde modification of UiO-66-NH 2 , the characteristic amine group peaks disappeared (Fig. 2 b), and the peaks at 1580 and 1262 cm -1 sharpened due to the formation of C = N bonds of salicylidene imine [ 45 , 46 ], indicating successful post-modification. Notably, the FT-IR spectrum of UiO-66/Sal-ZnCl 2 (Fig. 2 c) did not exhibit characteristic peaks of ZnCl 2 , possibly due to the weak bands associated with immobilized zinc ions on the nanocatalyst's surface [ 47 ]. The crystalline structure of UiO-66-NH 2 and UiO-66/Sal-ZnCl 2 was investigated using XRD analysis within the 2θ range of 6–80° (Fig. 3 ). The XRD pattern of UiO-66-NH 2 (Fig. 3 a) displayed characteristic diffraction peaks at 2θ values of 7.5°, 8.7°, 14.6°, 17.5°, 22.3°, 25.6°, 30.5°, 31.2°, 35.9°, 37.8°, 40.2°, 43.5°, 50.6°, and 56.9°, corresponding to the crystal lattice with Fm3m symmetry of zirconium benzene carboxylate units [ 48 ]. These diffraction peaks were also observed in the XRD pattern of UiO-66/Sal-ZnCl 2 (Fig. 3 b), indicating that the catalyst's crystalline structure remained unchanged after modification and coordination of zinc units on the surface. The characteristic peaks of ZnCl 2 should be at 2θ of 16.2°, 17.2°, 26.0°, 29.9°, 35.5°, 38.9°, 49.3°, 49.8°, 51.9°, 52.9°, and 56.8° (JCPDS card no. 96-810-3830) [ 49 ] (Trivedi et al., 2017), however the intensity of these expected peaks was quite low, likely due to the results from the ICP analysis and the relatively low metal loading. As depicted in Fig. 4 , the elemental composition of UiO-66-NH 2 and UiO-66/Sal-ZnCl 2 was determined through EDX analysis. In the EDX spectrum of UiO-66-NH 2 (Fig. 4 a), signals corresponding to Zirconium (Zr), Oxygen (O), and Nitrogen (N) were observed, representing the primary elements of the intended MOF structure [ 50 ]. In the case of UiO-66/Sal-ZnCl 2 EDX analysis (Fig. 4 b), these expected elements (Zr, O, and N) were again observed, alongside the presence of elemental zinc and chlorine [ 50 ]. Following the elemental composition analysis, the distribution of these elements on the catalyst's surface was examined. Figure 5 presents the X-ray elemental mapping of UiO-66/Sal-ZnCl 2 , demonstrating the even dispersion of elements within the catalyst framework. Zirconium (Zr), being the fundamental building block with a considerably higher density compared to other elements, exhibited a uniform distribution. This observation further underscores the crucial role of uniform zinc (Zn) distribution within the catalyst matrix, which contributes significantly to its exceptional catalytic performance. These observations are in agreement with ICP and EDX analyses and confirm the successful coordination of Zn complexes onto the surface of modified MOF. In order to ascertain the loading capacity of the organic linker and examine the thermal stability of UiO-66-NH 2 and UiO-66/Sal-ZnCl 2 , thermal gravimetric analysis (TGA) was conducted across a temperature range spanning from 25 to 700°C (Fig. 6 ). Three weight losses were observed in the thermogravimetric analysis (TGA) curve of UiO-66-NH 2 , as depicted in Figure (Fig. 6 a). The initial weight reduction step, occurring up to 150°C, involved the removal of trapped water, solvent, and CO 2 molecules. During the second phase of weight loss, occurring at temperatures exceeding 180°C, the organic linker initiates decomposition. The third stage of weight loss, occurring between 350°C and 500°C, can be attributed to the complete disassembly of the framework. In the case of UiO-66/Sal-ZnCl 2 , a greater weight loss was observed during this stage compared to UiO-66-NH 2 , primarily due to the presence of a surface-bound organic linker (Fig. 6 b) [ 51 ]. From these results, the amount of organic linker was estimated to be about 6% by weight These results are in accordance with other analyses approve the successful synthesis and post-synthetic modification of UiO-66. The porous structures of UiO-66-NH 2 and UiO-66/Sal-ZnCl 2 were characterized using N 2 adsorption-desorption analysis (Fig. 7 ). According to Brunauer-Emmett-Teller (BET) calculations, the surface areas of UiO-66-NH 2 and UiO-66/Sal-ZnCl 2 were determined to be 909.59 and 550.11 m 2 g − 1 , respectively (Fig. 7 a, 7 b). This reduction in surface area for UiO-66/Sal-ZnCl 2 compared to UiO-66-NH 2 suggests that the post-modification and coordination steps involving ZnCl 2 primarily occurred on the support surface. The adsorption-desorption isotherm of UiO-66-NH 2 displayed a type I isotherm, indicative of a microporous structure (Fig. 7 a). The Barrett-Joyner-Halenda (BJH) diagram for UiO-66-NH 2 revealed the presence of a single type of micropores with a pore diameter of 1.21 nm (Fig. 7 c). Similarly, the BJH plot for UiO-66/Sal-ZnCl 2 also indicated reduced-intensity micropores, consistent with changes in surface area and pore filling resulting from the coordination of the zinc salt (Fig. 7 d) [ 51 ]. In the TEM image of UiO-66-NH 2 (Fig. 8 a), one can observe aggregated octahedral particles measuring less than 50 nm in size. Interestingly, the TEM image of UiO-66/Sal-ZnCl 2 (Fig. 8 b) displayed an identical morphology, suggesting that the post-modification of the (MOF with salicylaldehyde and the coordination of zinc units did not have any discernible impact on the MOF's morphology. Furthermore, SEM images (Figs. 8 d & 8 e) supported these findings, confirming the preservation of the MOF's morphology throughout the modification and coordination processes. Following the successful synthesis and characterization of UiO-66/Sal-ZnCl 2 , its catalytic activity was evaluated in a one-pot multicomponent reaction involving benzyl halides/alkyl halides, phenylacetylene/propargyl alcohol, and sodium azide for the synthesis of 1,2,3-triazole, as depicted in Fig. 9 . In this specific context, a thorough analysis was conducted to investigate the influence of various parameters, including reaction time, solvent, temperature, and catalyst quantity. Initially, the selection of phenylacetylene, benzyl bromide, and NaN 3 was made as model substrates to optimize the reaction conditions, as presented in Table 1 . It was observed that the model reaction failed to proceed without the presence of a catalyst after 3 h in water at 60°C, confirming the necessity of a catalyst (Table 1 , entry 1). In model reactions catalyzed by UiO-66-NH 2 and ZnCl 2 , the product yields were only 30% and 15%, respectively (Table 1 , entries 2 and 3). However, upon the addition of 5 mol% UiO-66/Sal-ZnCl 2 as a catalyst in the model reaction, the yield of the isolated product reached 98% (Table 1 , entry 4). Various polar and nonpolar solvents were examined while using UiO-66/Sal-ZnCl 2 as the catalyst (Table 1 , entries 5–9). Ultimately, considering the green nature of water and the achieved yield, water was chosen as the reaction solvent for further investigation. Model reactions were monitored at different time intervals, such as 2, 1, and 0.5 h. The results indicated that the reaction was completed after 2 h (Table 1 , entries 10–12). Different quantities of catalysts were also tested in the model reaction. It was observed that the product yield decreased from 5 to 3.1 mol% with decreasing catalyst loading (Table 1 , entries 13 and 14). Additionally, the reaction temperature was evaluated, revealing a decrease in yield with decreasing temperature. Consequently, the optimal reaction conditions were determined as follows: phenylacetylene (1.0 mmol), benzyl bromide (1.0 mmol), sodium azide (1.0 mmol), and a catalyst (5 mol%) in an aqueous medium at a temperature of 60°C for 2 h. Table 1 The optimized reaction conditions for the synthesis of triazole via the model reaction. a Entry Catalyst Catalyst amount Solvent Temp. (°C) Time (h) Yield (%) 1 - - Water 60 3 0 2 UiO-66-NH 2 0.1 g Water 60 3 30 3 ZnCl 2 0.1 g Water 60 3 15 4 UiO-66/Sal-ZnCl 2 5 mol% Water 60 3 98 5 UiO-66/Sal-ZnCl 2 5 mol% EtOH 60 3 95 6 UiO-66/Sal-ZnCl 2 5 mol% DMF 60 3 96 7 UiO-66/Sal-ZnCl 2 5 mol% Toluene 60 3 65 8 UiO-66/Sal-ZnCl 2 5 mol% Hexane 60 3 50 9 UiO-66/Sal-ZnCl 2 5 mol% CH 3 CN 60 3 85 10 UiO-66/Sal-ZnCl 2 5 mol% water 60 2 98 11 UiO-66/Sal-ZnCl 2 5 mol% water 60 1 70 12 UiO-66/Sal-ZnCl 2 5 mol% water 60 0.5 50 13 UiO-66/Sal-ZnCl 2 3 mol% water 60 2 80 14 UiO-66/Sal-ZnCl 2 1 mol% water 60 2 70 15 UiO-66/Sal-ZnCl 2 5 mol% water 50 2 85 16 UiO-66/Sal-ZnCl 2 5 mol% water 40 2 65 a Reaction conditions: phenylacetylene (1.0 mmol), benzyl bromide (1.0 mmol), sodium azide (1.0 mmol), catalyst (x mol%), and solvent (2 ml). The versatility of UiO-66/Sal-ZnCl 2 was further explored with different substrates under the optimized reaction conditions. Substituted phenylacetylene and propargyl alcohol were successfully converted to terminal alkynes and benzyl /alkyl halides (Table 2 ). Employing various terminal alkynes, corresponding triazoles were obtained with exceptional performance under these optimal conditions. Additionally, a range of aryl and alkyl halides exhibited favorable reactivity in the presence of UiO-66/Sal-ZnCl 2 , as demonstrated in Table 2 . The potential for reusing the UiO-66/Sal-ZnCl 2 catalyst was also explored. In this investigation, the model reaction was performed using a fresh catalyst under the optimized conditions. After confirming the completion of the reaction through thin-layer chromatography (TLC), the catalyst was subjected to filtration, followed by washing with both water and ethyl acetate multiple times. Subsequently, the recovered catalyst was dried in an oven at 70°C. Remarkably, this regenerated catalyst demonstrated activity for five consecutive cycles in model reactions with new substrates. The efficiency of the catalyst slightly decreased from 99% in the first cycle to 86% in the last one, as illustrated in Fig. 10. A plausible mechanism for a model click reaction catalyzed by UiO-66/Sal-ZnCl 2 is shown in Fig. 11 . In the first step, coordination between the catalyst and the terminal alkyne transforms the activated acetylene (I) into a more potent dienophile. In the next step, the intermediate alkyl azide formed by the reaction of alkyl halide and sodium azide interacts with complex (I) to form complex (II). Complex (II) gives complex (III) via a 1,3-dipolar cycloaddition reaction. The final step converts the complex (III) to the desired triazole (IV) and regenerates the catalyst. Hot filtration test The hot filtration test as a strong test was conducted to evaluate the heterogeneity nature of the catalytic species in the model reaction under the optimal conditions through the possibility of zinc leaching into the reaction mixture (Fig. 12 ). Precisely, at the midway of the reaction (60 minutes), the nanocatalyst was separated from the reaction mixture by filtration. In this step, only 53% conversion was achieved. Subsequently, the reaction mixture was allowed to continue without a catalyst for another 60 minutes under similar conditions. The reaction progress before and after the separation was checked by TLC. Assessment of the rate of the desired product preparation demonstrates that no remarkable increase in conversion was observed even after an expanded time. Also, to elucidate the stability of the catalyst, after five cycles in the model reaction, any structural changes of the catalyst were studied by FT-IR, TEM techniques. It is evident from the FT-IR spectrum of the 5th reused catalyst that no significant changes in the frequencies, intensities, and shapes of absorption bands were observed (Fig. 1 d). Moreover, the TEM image of the 5th reused catalyst confirmed the aggregated octahedral particles measuring less than 50 nm in size which was approximately similar to the TEM image of the fresh catalyst, and there were not any significant differences in size and morphology (Fig. 8 c). There is also negligible leaching of Zn species in the reaction medium, justifying its true heterogeneity. By knowing the effectiveness of the prepared nanocatalyst, a comparison investigated between its catalytic performance and that of zinc-based catalyst systems documented in the existing literature in the reaction of benzyl bromide, sodium azide, and phenylacetylene under various catalytic conditions (Table 3 , entries 1–5). Nearly all the catalysts mentioned below exhibit notable yields of the desired products. However, the limitations including the long reaction time (Table 3 , entries 1 & 2), the high reaction temperature (Table 3 , entries 1 & 5), and applying hazardous solvent and reaction conditions (Table 3 , entries 2 & 4) represent the drawbacks of some of these methods. As is evident, our studied system (Table 3 , entry 6) has advantages such as an excellent yield in a shorter reaction time, simple separation, easy preparation of the catalyst, and milder reaction conditions. Table 3 Comparison of UiO-66/Sal-ZnCl 2 catalyst with other catalysts that used for the synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole. Entry Catalyst Solvent Temp.(°C) Time (h) Yield (%) Ref. 1 Zn(OAc) 2 / ascorbic acid Water 75 6 87 52 2 Zn/C DMF 50 15 90 53 3 GO-Salen-Zn Water 100 2 92 54 4 SMI/ZnCl 2 DMF - 0.4 94 55 5 Zinc(II) L-prolinate Water 100 2 91 56 6 UiO-66/Sal-ZnCl 2 Water 60 2 98 This study 4. Conclusion In conclusion, the UiO-66/Sal-ZnCl 2 catalyst was successfully synthesized using a post-modification approach. A comprehensive characterization of the catalyst was carried out utilizing various techniques, including TEM, SEM, FTIR, ICP, TGA, Mapping, XRD, and BET. The results confirmed the effective incorporation of Zn units into the UiO-66-NH 2 post-modified salicylaldehyde nanoreactor. Importantly, the morphology of the catalyst remained unaltered throughout the modification and coordination processes. The UiO-66/Sal-ZnCl 2 catalyst exhibited remarkable catalytic activity in the click reaction involving benzyl halides/alkyl halides, phenylacetylene/propargyl alcohol, and sodium azide, leading to the synthesis of 1,2,3-triazole. Furthermore, this catalyst displayed reusability, retaining its activity for five consecutive cycles. These findings underscore the potential of UiO-66/Sal-ZnCl 2 as an efficient and recyclable nanocatalyst for click reactions and related applications. Declarations Author Contribution MR and AK designed and planned the catalyst, the experiments, and the final analyses. MR contributed with AK to perform the analyses of the results and wrote the initial manuscript with consulting with AS. AS supervised the finding results and provided critical feedback on the final main manuscript. All authors reviewed the manuscript. Acknowledgements: The authors gratefully acknowledge the Research Council of Ferdowsi University of Mashhad (3/57052). Data availability: The data sets used and analyzed during the current study are available in supporting information. References Farrusseng, D., Aguado, S., Pinel, C. Metal–organic frameworks: opportunities for catalysis. Angew. Chem. Int. Ed. 48, 7502–7513 (2009). Chughtai, A. H., Ahmad, N., Younus, H. A., Laypkov, A., Verpoort, F. 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Highly efficient and green approach for the synthesis of spirooxindole derivatives in the presence of novel Brønsted acidic ionic liquids incorporated in UiO‐66 nanocages. Appl. Organomet. Chem. 33, 5027–5040 (2019). Mirhosseini-Eshkevari, B., Ghasemzadeh, M.A. Esnaashari, M., Ganjali, S.T. Introduction a novel Brønsted acidic ionic liquid incorporated in UiO‐66 nanocages for the efficient synthesis of pyrimido[4,5‐d]pyrimidines. Chem. Select. 4, 12920–12927 (2019). Azarifar, D., Ghorbani-Vaghei, R., Daliran, S., Oveisi, A.R. A Multifunctional zirconium-based metal–organic framework for the one‐pot tandem photooxidative Passerini three‐component reaction of alcohols. ChemCatChem. 9, 1992–2000 (2017). Erfaninia, N., Tayebee, R., Dusek, M., Amini, M.M. Ethylene diamine grafted nanoporous UiO-66 as an efficient basic catalyst in the multi‐component synthesis of 2‐aminithiophenes. Appl. Organomet. Chem. 32, 4307–4317 (2018). Ghorbani-Vaghei, R., Azarifar, D., Daliran, S., Oveisi, A.R. The UiO-66-SO 3 H metal–organic framework as a green catalyst for the facile synthesis of dihydro-2-oxypyrrole derivatives. RSC Adv. 6, 29182–29189 (2016). Shaabani, A., Mohammadian, R., Hooshmand, S.E., Hashemzadeh, A., Amini, M.M., Zirconium metal-organic framework (UiO‐66) as a robust catalyst toward solvent‐free synthesis of remarkable heterocyclic rings. Chem. Select. 2, 11906–11911 (2017). Arefi, E., Khojastehnezhad, A., Shiri, A. A magnetic copper organic framework material as an efficient and recyclable catalyst for the synthesis of 1,2,3-triazole derivatives. Sci. Report. 11, 20514 (2021). Arefi, E., Khojastehnezhad, A., Shiri, A. A core–shell superparamagnetic metal–organic framework: a recyclable and green catalyst for the synthesis of propargylamines. New J. Chem. 45, 21342–21349 (2021). Taghavi, F. et al . Design and synthesis of a new magnetic metal organic framework as a versatile platform for immobilization of acidic catalysts and CO 2 fixation reaction. New J. Chem. 45, 15405–15414 (2021). Keyhaniyan, M., Shiri, A., Eshghi, H., Khojastehnezhad, A. Synthesis, characterization and first application of covalently immobilized nickel-porphyrin on graphene oxide for Suzuki cross-coupling reaction. New J. Chem. 42, 19433–19441 (2018). Ghadamyari, Z., Shiri, A., Khojastehnezhad, A., Seyedi, S.M. Zirconium (IV) porphyrin graphene oxide: a new and efficient catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones. Appl. Organomet. Chem. 33, 5091 (2019). Matin, M.M. et al . Triazoles and their derivatives: Chemistry, synthesis, and therapeutic applications. Front. Mol. Biosci. 9, 864286 (2022). Dai, J., Tian, S., Yang, X., Liu, Z. Synthesis methods of 1,2,3-/1,2,4-triazoles: A review. Frontiers in Chem. 10, 891484 (2022). Jaiswal, S. et al . Emerging approaches for synthesis of 1,2,3-triazole derivatives. a review. Org. Prep. Proc. Inter. , 54, 387–422 (2022). Yadav, S. et al . Harnessing the untapped catalytic potential of a CoFe 2 O 4 /Mn-BDC hybrid MOF composite for obtaining a multitude of 1,4-disubstituted 1,2,3-triazole scaffolds. Inorg. Chem. 59, 8334–8344 (2020). Jia, X., Xu, G., Du, Z., Fu, Y. Cu(BTC)-MOF catalyzed multicomponent reaction to construct 1,4-disubstituted-1,2,3-triazoles. Polyhedron. 151, 515–519 (2018). Wang, Z., Zhou, X., Gong, S., Xie, J. MOF-Derived Cu@ NC catalyst for 1,3-dipolar cycloaddition reaction. Nanomaterials, 12, 1070 (2022). Castillo, J-C. et al . Water-Compatible Synthesis of 1,2,3-Triazoles under Ultrasonic Conditions by a Cu(I) Complex-Mediated Click Reaction. ACS Omega. 5, 30148–30159 (2020). Du, Z., Li, B., Jiang, C., Sun, R., Chen, S. Sorption of U (VI) on Schiff-base functionalized metal-organic frameworks UiO-66-NH 2 . J. Radioanal. Nucl. Chem. 327, 811–819 (2021). Wang, K., Gu, J., Yin, N. Efficient removal of Pb(II) and Cd(II) using NH 2 -functionalized Zr-MOFs via rapid microwave-promoted synthesis. Ind. Eng. Chem. Res. 56, 1880–1887 (2017). Tian, F., Weng, R., Huang, X., Chen, G., Huang, Z. Fabrication of silver-doped UiO-66-NH 2 and characterization of antibacterial materials. Coatings. 12, 1939 (2022). Lili, L., Xin, Z., Jinsen, G., Chunming, X. Engineering metal-organic frameworks immobilize gold catalysts for highly efficient one-pot synthesis of propargylamines. Green Chem. 14, 1710–1720 (2012). Leus, K. et al . A Mo-grafted metal organic framework: synthesis, characterization and catalytic investigations. J. Catal. 316, 201–209 (2014). Song, Q., Jia, M.K., Ma, W.H., Fang, Y.F., Huang, Y.P. Heterogeneous degradation of toxic organic pollutants by hydrophobic copper Schiff-base complex under visible irradiation. Sci. China Chem. 56, 1775–1782 (2013). Kandiah, M. et al . Synthesis and stability of tagged UiO-66 Zr-MOFs. Chem. Mater. 22, 6632–6640 (2010). Trivedi, M. K., Sethi, K. K., Panda, P., Jana, S. A comprehensive physicochemical, thermal, and spectroscopic characterization of zinc (II) chloride using X-ray diffraction, particle size distribution, differential scanning calorimetry, thermogravimetric analysis/differential thermogravimetric analysis, ultraviolet-visible, and fourier transform-infrared spectroscopy. Int. J. Pharm. Investig. 7, 33–40 (2017). Veisi, H. et al . Pd immobilization biguanidine modified Zr-UiO-66 MOF as a reusable heterogeneous catalyst in Suzuki–Miyaura coupling. Sci. Rep. 11, 21883 (2021). Hou, J. et al . Synthesis of UiO-66-NH 2 derived heterogeneous copper (II) catalyst and study of its application in the selective aerobic oxidation of alcohols. J. Mol. Catal. A Chem. 407, 53–59 (2015). Morozova, M.A. et al . Regioselective Zn(OAc) 2 -catalyzed azide–alkyne cycloaddition in water: the green click-chemistry. Org. Chem. Front. 4, 978–985 (2017). Meng, X., Xu, X., Gao, T., Chen, B. Zn/C-Catalyzed Cycloaddition of Azides and Aryl Alkynes. Eur. J. Org. Chem. 5409–5414 (2010). Ghadamyari, Z., Khojastehnezhad, A., Seyedi, S.M., Taghavi, F., Shiri, A. Graphene oxide functionalized Zn(II) salen complex: an efficient and new route for the synthesis of 1,2,3-triazole derivatives. Chem. Select. 5, 10233–10242 (2020). Daraie, M., Heravi, M., Sarmasti, N. Synthesis of polymer-supported Zn(II) as a novel and green nanocatalyst for promoting click reactions and using design of experiment for optimization of reaction conditions. J. Macromol. Sci. Chem., A. 57, 488–498 (2020). Kidwai, M., Jain, A. Regioselective synthesis of 1,4-disubstituted triazoles using bis[(L)prolinato-N,O]Zn complex as an efficient catalyst in water as a sole solvent. Appl. Organometal. Chem. 25, 620–625 (2011). Table 2 Table 2 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files supportinginformation.pdf Table2.docx Cite Share Download PDF Status: Published Journal Publication published 20 Oct, 2024 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Revision requested 13 Aug, 2024 Reviews received at journal 22 Jul, 2024 Reviews received at journal 12 Jul, 2024 Reviewers agreed at journal 12 Jul, 2024 Reviewers agreed at journal 12 Jul, 2024 Reviewers invited by journal 11 Jul, 2024 Editor assigned by journal 11 Jul, 2024 Editor invited by journal 11 Jul, 2024 Submission checks completed at journal 08 Jul, 2024 First submitted to journal 06 Jul, 2024 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. 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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-4695524","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":330428615,"identity":"ccbe2ef9-0b7c-42fa-b72b-54baf0ffa3e8","order_by":0,"name":"Mohammad-Aqa Rezaie","email":"","orcid":"","institution":"Ferdowsi University of Mashhad","correspondingAuthor":false,"prefix":"","firstName":"Mohammad-Aqa","middleName":"","lastName":"Rezaie","suffix":""},{"id":330428616,"identity":"5e7cffd6-622a-4d6a-aa7b-5de3867e128d","order_by":1,"name":"Amir Khojastehnezhad","email":"","orcid":"","institution":"Ferdowsi University of Mashhad","correspondingAuthor":false,"prefix":"","firstName":"Amir","middleName":"","lastName":"Khojastehnezhad","suffix":""},{"id":330428617,"identity":"a1ca8d62-c673-4bd3-89b5-042ef480d9ce","order_by":2,"name":"Ali Shiri","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAvklEQVRIiWNgGAWjYDACdsYGZgYDBh5+KJ+HsBZmqBbJBuK1gBEDg8EBYt3F38zc/Lmg4J6M8Y3sBIYfNQwy5g0EtEgcZmyTnmFQzGN2I3cDY88xBh4ZgtYBtTDzGCSAtTDwNjDwSBDSIX+YsfkzSIvxDKAtf4nRYnCYsUEapMVAIncDM1G2GIL8AtIicebthsMyxyQIa5E73v74M8+fBHv+9tyND9/U2NgT1IICDgBDkCQNo2AUjIJRMApwAAAi8DMKAL/ZLwAAAABJRU5ErkJggg==","orcid":"","institution":"Ferdowsi University of Mashhad","correspondingAuthor":true,"prefix":"","firstName":"Ali","middleName":"","lastName":"Shiri","suffix":""}],"badges":[],"createdAt":"2024-07-06 07:23:02","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4695524/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4695524/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-024-76199-y","type":"published","date":"2024-10-20T15:57:18+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":62152405,"identity":"d3f2d7dc-786a-4bae-ab27-67c20c42913f","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":35112,"visible":true,"origin":"","legend":"\u003cp\u003eThe synthetic pathway for the production of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/e6ebf9d375e5f2a14927c6b9.png"},{"id":62154343,"identity":"552e8b7e-f044-4fbb-b83c-d3f7937c7586","added_by":"auto","created_at":"2024-08-09 20:58:38","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":120650,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectrum of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (a), UiO-66/Sal (b), UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e(c), 5\u003csup\u003eth\u003c/sup\u003e reused UiO-66/Sal-ZnCl\u003csub\u003e2 \u003c/sub\u003e(d), \u003csub\u003e\u0026nbsp;\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/431c11e7d0bb45a9aa96b5f4.png"},{"id":62152408,"identity":"85e46cef-2084-47f8-b6c4-b4f373ad3d0c","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":31838,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of UiO-66-NH\u003csub\u003e2 \u003c/sub\u003e(black PXRD pattern), and UiO-66/Sal-ZnCl\u003csub\u003e2 \u003c/sub\u003e(red thin-layer PXRD pattern).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/1fbb17f4a0051849cdd8bb83.png"},{"id":62152419,"identity":"2f7a710c-3115-4fbd-ab38-004ce843ce2f","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":59500,"visible":true,"origin":"","legend":"\u003cp\u003eEDX analysis of a) UiO-66-NH\u003csub\u003e2\u003c/sub\u003e, and b) UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/9d1e8c64f82e4cb48a114cd2.png"},{"id":62154345,"identity":"400c3c9b-4d89-4fa3-b2cd-095b3a7f1972","added_by":"auto","created_at":"2024-08-09 20:58:38","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":485379,"visible":true,"origin":"","legend":"\u003cp\u003eElemental mapping of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (the atomic distribution: Zr, O, C, N, Cl and Zn).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/81cca892d80f1db77ce78062.png"},{"id":62152411,"identity":"a71956c3-bf2f-4b83-a05e-5edb6b3fac50","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":44271,"visible":true,"origin":"","legend":"\u003cp\u003eTGA curve of UiO-66-NH\u003csub\u003e2 \u003c/sub\u003e(a), and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (b).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/b41ec281e4a6e667b2c4442c.png"},{"id":62157058,"identity":"44f11c83-fb36-4f08-a863-c24f4e327969","added_by":"auto","created_at":"2024-08-09 21:14:38","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":30537,"visible":true,"origin":"","legend":"\u003cp\u003eThe BET of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (a), and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (c), BJH of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (c), and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (d).\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/5f035261f7e61af4bf7b4912.png"},{"id":62152413,"identity":"3fceea45-3dae-4add-b315-a09fad95c27d","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":295205,"visible":true,"origin":"","legend":"\u003cp\u003eThe TEM images of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (a), and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (b), 5\u003csup\u003eth\u003c/sup\u003e reused UiO-66/Sal-ZnCl\u003csub\u003e2 \u003c/sub\u003e(c),\u003csub\u003e \u003c/sub\u003eSEM images of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (d), UiO-66/Sal-ZnCl\u003csub\u003e2 \u003c/sub\u003e(e).\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/a840d18d52726284b51ef556.png"},{"id":62152416,"identity":"a93cf761-eb36-4006-ab42-be4b38b13532","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":13596,"visible":true,"origin":"","legend":"\u003cp\u003eThe UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e catalyzed click reaction\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/5f814ac15f41b48bfb5b5cab.png"},{"id":62155759,"identity":"a18be905-a4f7-42c6-981f-63838672f61b","added_by":"auto","created_at":"2024-08-09 21:06:39","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":41544,"visible":true,"origin":"","legend":"\u003cp\u003eThe study of the catalyst recyclability.\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/8ac2b8ac2d7c1a97b31369c5.png"},{"id":62155757,"identity":"203326ed-2647-47de-85ed-e46f2107cc43","added_by":"auto","created_at":"2024-08-09 21:06:38","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":38017,"visible":true,"origin":"","legend":"\u003cp\u003ePlausible mechanistic route for the UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e mediated synthesis of triazoles.\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/ee5134596b3b7d515575fdb7.png"},{"id":62152418,"identity":"ef0b1fd1-ed02-401f-bca5-03e93c309422","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":15760,"visible":true,"origin":"","legend":"\u003cp\u003eTime-dependent correlation of the product yield in hot filtration test.\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/03f54801dd43a31791d0fd05.png"},{"id":67148937,"identity":"29a88c99-241b-485e-8ac2-922ec7fd37e0","added_by":"auto","created_at":"2024-10-21 16:10:05","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1755910,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/75df9577-a5ac-4416-a11a-504a253e2881.pdf"},{"id":62154348,"identity":"ea4ac1ce-203f-442e-84a9-6205dff619d7","added_by":"auto","created_at":"2024-08-09 20:58:38","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3348552,"visible":true,"origin":"","legend":"","description":"","filename":"supportinginformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/b2a5636ce1a67bf17ebac9b0.pdf"},{"id":62152406,"identity":"7ffcc3df-e3e2-40cd-ba46-d1b6785ac586","added_by":"auto","created_at":"2024-08-09 20:50:38","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":57980,"visible":true,"origin":"","legend":"","description":"","filename":"Table2.docx","url":"https://assets-eu.researchsquare.com/files/rs-4695524/v1/b07985010ebb1c994b8b9c78.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Post-Synthetic Modification of Zr-Based Metal Organic Framework by Schiff Base Zinc Complex for Catalytic Applications in a Click Reaction","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eMetal-organic frameworks (MOFs) have attracted considerable attention within the scientific community due to their unique characteristics as porous crystalline coordination polymers. These attributes encompass a substantial surface area, remarkable porosity, facile structural adaptability, and the ability to be functionalized with diverse organic linkers, along with adjustable pore sizes. These features contribute to their remarkable performance as catalysts, particularly in catalytic organic transformations [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. MOFs also have found applications as gas absorbers, storage devices and separators, water purifiers, sensors, magnets, photocatalysts, and in drug delivery systems [\u003cspan additionalcitationids=\"CR5 CR6 CR7\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. Their porous structure with available and large holes allows the transfer of reactants to the inner parts of the framework, enabling proper interaction with the catalytic active sites and subsequently the release of materials from the pores to the reaction environment [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. MOFs have been employed extensively in catalytic reactions, either by creating inherent acidic and basic sites on their surfaces or by serving as supports for other catalysts. They can be used directly, without any alterations to their structure, and the desired catalyst developed on the surface or in its pores [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Also, it is advisable to carry out a structural modification prior to the loading of efficient catalytic systems [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. By means of post-synthesis modification of MOFs, it is possible to adjust their chemical and physical properties, as well as to introduce a diverse array of organic and inorganic functionalities [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Among various MOFs, Zirconium-based MOFs (Zr-MOFs) have garnered substantial attention in chemical research [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. UiO-66, the first synthesized Zr-MOF, consists of a zirconium-oxo cluster and 1,4-benzenedicarboxylic acid. This MOF exhibits unparalleled hydrothermal stability [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e] and has been applied in water treatment [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e], remediation [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], catalysis [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e], and various other fields [\u003cspan additionalcitationids=\"CR19 CR20\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. Zr-MOFs have been employed in the synthesis of diverse organic compounds through multicomponent reactions [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. Ionic liquid-supported Zr-MOF BAIL@UiO-66 was utilized in the preparation of pyrimidine and spirooxindole derivatives [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Pyrimidopyrimidines were prepared via TEDA-BAIL@UiO-66 catalyzed reaction [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Zr-MOF-FePC was reported for synthesis of α-acyloxy amides [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Additionally, UiO-66 modified with ethylene diamine (ED), UiO-66-SO3H, and Zr-MOF have been employed for the synthesis of 2-aminotiophenes [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e], dihydro-2-oxopyrroles [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], imidazo[1,2-a]pyridines, 3,4-dihydroquinoxaline-2-amines, and trisubstituted pyridine derivatives [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e], respectively.\u003c/p\u003e \u003cp\u003eIn the pursuit of novel catalytic systems for organic transformations [\u003cspan additionalcitationids=\"CR31 CR32 CR33\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e], this study presents the synthesis of a UiO-66 metal-organic framework post-modified with salicylaldehyde via Schiff base reaction, followed by coordination of Zinc chloride (UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e). This method presents a robust catalyst for the efficient synthesis of 1,2,3-triazoles via a one-pot click coupling reaction involving terminal alkynes, aryl or alkyl halides, and sodium azide. Numerous methods have been developed for the synthesis of triazole derivatives, as recently reviewed [\u003cspan additionalcitationids=\"CR36\" citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. Notable examples include the use of L-Proline‐MCM‐41‐CuCl [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e], [(Cell-ThP-Cu(II))] [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e], Cell/SiO\u003csub\u003e2\u003c/sub\u003e-Sal-Pd(II) [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e], and CuIL\u003csub\u003e1\u003c/sub\u003ePPh\u003csub\u003e3\u003c/sub\u003e (L\u003csub\u003e1\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;bis(pyrazolyl)methane) [\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e] as catalysts for triazole synthesis. Nevertheless, a majority of the aforementioned catalysts and methodologies encountered significant challenges, notably arising from costly catalyst preparation procedures, the employment of hazardous solvents and reagents, and complexities associated with catalyst recovery techniques. Consequently, the imperative to develop a novel and efficient catalyst becomes paramount within the domain of organic synthesis. This imperative is particularly emphasized in the synthesis of triazole derivatives, where the inadequacies of existing catalysts and methods underscore the urgency and desirability of advancing catalytic approaches for enhanced efficacy and sustainability in the synthesis of such compounds.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cp\u003eAll substrates, reagents, and solvents were procured from reputable suppliers, namely Merck and Aldrich. TEM Images were acquired using a Leo 912AB microscope at 120 kV and SEM images were acquired using a Leo 1450VP microscope. Thermogravimetric analyses were recorded with Mettler Toledo LF -Switzerland and FT-IR spectra with Nicolet Fourier spectrophotometer using KBr pellets. The energy dispersive X-ray analysis (XRD) was utilized to examine the crystalline structure of the catalyst. The \u003csup\u003e1\u003c/sup\u003eH- and \u003csup\u003e13\u003c/sup\u003eC-NMR spectra of the products were acquired in CDCl\u003csub\u003e3\u003c/sub\u003e solvent utilizing the Bruker DRX-300 AVANCE spectrometer operating at frequencies of 300 and 75 MHz, respectively.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. General procedure for the synthesis of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eAccording to the literature [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e], ZrCl\u003csub\u003e4\u003c/sub\u003e (11.652 g, 50 mmol) was dissolved in 250 ml DMF in a three-necked flask with vigorous stirring. Then 2-aminoterephthalic acid (9.058 g, 50 mmol) was added and stirred to give a yellow clear solution. Then concentrated HCl 37% (35 ml) was added to the flask with stirring. The solution was kept under reflux for 10 hours. The suspension was then cooled to 30\u0026deg;C and the light-yellow solid was filtered off. The precipitate was washed with DMF (2 \u0026times; 10 ml) and deionized water (2 \u0026times; 10 ml) and dried at 70\u0026deg;C for 6 hours to prepare UiO-66-NH\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. General procedure for the synthesis of UiO-66-Sal\u003c/h2\u003e \u003cp\u003eUiO-66-NH\u003csub\u003e2\u003c/sub\u003e (0.15 g) was dispersed in absolute ethanol (100 ml) by sonication and then stirred with salicylaldehyde (1250 \u0026micro;L, 12 mmol) at 75\u0026deg;C for 12 hours. After this time, the mixture was cooled to 30\u0026deg;C, then the solid was filtered, washed with water and ethanol (3 \u0026times; 15 ml), and dried overnight at 75\u0026deg;C (UiO-66/Sal) [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. General procedure for the synthesis of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eThe prepared UiO-66/Sal salt (0.15 g) and zinc chloride (0.82 g, 0.6 mmol) were dispersed in absolute ethanol (20 ml), and the suspension was then stirred for 24 hours at 50\u0026deg;C. The prepared solid catalyst was filtered off, washed with absolute ethanol (3 \u0026times; 20 ml), and dried at 70\u0026deg;C for 12 hours (UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. General procedure for the synthesis of 1,2,3-Triazoles\u003c/h2\u003e \u003cp\u003ePhenylacetylene (1 mmol), sodium azide (1 mmol), halide (1 mmol), and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (20 mg) were mixed in water (2 mL) and stirred at 50\u0026deg;C for the appropriate time. The progress of the reaction was monitored by thin-layer chromatography (TLC). After completion of the reaction, the reaction mixture was cooled to 30\u0026deg;C and the catalyst was filtered off. The reaction mixture underwent extraction using a combination of ethyl acetate and water, followed by the subsequent evaporation of the organic layer. Subsequently, the product was subjected to a drying process at a temperature of 50\u0026deg;C for 4 hours.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eThe synthesis of the heterogeneous UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e nanocatalyst was successfully accomplished through a three-step process. Initially, UiO-66-NH\u003csub\u003e2\u003c/sub\u003e was synthesized by combining ZrCl\u003csub\u003e4\u003c/sub\u003e and 2-aminoterephthalic acid. Subsequently, the -NH\u003csub\u003e2\u003c/sub\u003e groups were chemically reacted with salicylaldehyde in a post-modification step, resulting in the formation of UiO-66/Sal. Finally, the coordination of ZnCl\u003csub\u003e2\u003c/sub\u003e salt with UiO-66/Sal led to the creation of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Comprehensive characterization of the UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e structure was performed using various techniques, including ICP, FT-IR, TGA, BET, TEM, SEM, EDX, and XRD, as detailed in this section.\u003c/p\u003e \u003cp\u003eThe quantification of zinc ions on the UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e nanocatalyst was conducted through ICP-OES analysis. The zinc concentration was determined to be 0.5 wt.% of the catalyst.\u003c/p\u003e \u003cp\u003eThe chemical structure and functional groups of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e, UiO-66/Sal, and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e were examined via FT-IR analysis, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. For UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea), peaks at 3458 and 3348 cm\u003csup\u003e-1\u003c/sup\u003e were assigned to asymmetric and symmetric vibrations, while the 1658 cm\u003csup\u003e-1\u003c/sup\u003e peak indicated the bending vibration of NH\u003csub\u003e2\u003c/sub\u003e groups. The symmetric and asymmetric stretching vibrations of carboxyl groups associated with Zr\u003csup\u003e4+\u003c/sup\u003e were observed at 1580 and 1386 cm\u003csup\u003e-1\u003c/sup\u003e, respectively. A peak at 1509 cm\u003csup\u003e-1\u003c/sup\u003e corresponded to the stretching vibration of C\u0026thinsp;=\u0026thinsp;C units in benzene rings, while the shear vibration of N-H groups appeared at 1436 cm\u003csup\u003e-1\u003c/sup\u003e. Additionally, a unique C-N stretching absorption of aromatic amines was evident at 1262 cm\u003csup\u003e-1\u003c/sup\u003e. Peaks at 768 and 662 cm\u003csup\u003e-1\u003c/sup\u003e were attributed to the stretching vibration of \u0026micro;3-O in Zr-(OC) [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e, \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. After salicylaldehyde modification of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e, the characteristic amine group peaks disappeared (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb), and the peaks at 1580 and 1262 cm\u003csup\u003e-1\u003c/sup\u003e sharpened due to the formation of C\u0026thinsp;=\u0026thinsp;N bonds of salicylidene imine [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e, \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e], indicating successful post-modification. Notably, the FT-IR spectrum of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec) did not exhibit characteristic peaks of ZnCl\u003csub\u003e2\u003c/sub\u003e, possibly due to the weak bands associated with immobilized zinc ions on the nanocatalyst's surface [\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe crystalline structure of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e was investigated using XRD analysis within the 2θ range of 6\u0026ndash;80\u0026deg; (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The XRD pattern of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea) displayed characteristic diffraction peaks at 2θ values of 7.5\u0026deg;, 8.7\u0026deg;, 14.6\u0026deg;, 17.5\u0026deg;, 22.3\u0026deg;, 25.6\u0026deg;, 30.5\u0026deg;, 31.2\u0026deg;, 35.9\u0026deg;, 37.8\u0026deg;, 40.2\u0026deg;, 43.5\u0026deg;, 50.6\u0026deg;, and 56.9\u0026deg;, corresponding to the crystal lattice with Fm3m symmetry of zirconium benzene carboxylate units [\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. These diffraction peaks were also observed in the XRD pattern of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb), indicating that the catalyst's crystalline structure remained unchanged after modification and coordination of zinc units on the surface. The characteristic peaks of ZnCl\u003csub\u003e2\u003c/sub\u003e should be at 2θ of 16.2\u0026deg;, 17.2\u0026deg;, 26.0\u0026deg;, 29.9\u0026deg;, 35.5\u0026deg;, 38.9\u0026deg;, 49.3\u0026deg;, 49.8\u0026deg;, 51.9\u0026deg;, 52.9\u0026deg;, and 56.8\u0026deg; (JCPDS card no. 96-810-3830) [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e] (Trivedi et al., 2017), however the intensity of these expected peaks was quite low, likely due to the results from the ICP analysis and the relatively low metal loading.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, the elemental composition of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e was determined through EDX analysis. In the EDX spectrum of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea), signals corresponding to Zirconium (Zr), Oxygen (O), and Nitrogen (N) were observed, representing the primary elements of the intended MOF structure [\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e]. In the case of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e EDX analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb), these expected elements (Zr, O, and N) were again observed, alongside the presence of elemental zinc and chlorine [\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFollowing the elemental composition analysis, the distribution of these elements on the catalyst's surface was examined. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e presents the X-ray elemental mapping of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, demonstrating the even dispersion of elements within the catalyst framework. Zirconium (Zr), being the fundamental building block with a considerably higher density compared to other elements, exhibited a uniform distribution. This observation further underscores the crucial role of uniform zinc (Zn) distribution within the catalyst matrix, which contributes significantly to its exceptional catalytic performance. These observations are in agreement with ICP and EDX analyses and confirm the successful coordination of Zn complexes onto the surface of modified MOF.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn order to ascertain the loading capacity of the organic linker and examine the thermal stability of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, thermal gravimetric analysis (TGA) was conducted across a temperature range spanning from 25 to 700\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e). Three weight losses were observed in the thermogravimetric analysis (TGA) curve of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e, as depicted in Figure (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). The initial weight reduction step, occurring up to 150\u0026deg;C, involved the removal of trapped water, solvent, and CO\u003csub\u003e2\u003c/sub\u003e molecules. During the second phase of weight loss, occurring at temperatures exceeding 180\u0026deg;C, the organic linker initiates decomposition. The third stage of weight loss, occurring between 350\u0026deg;C and 500\u0026deg;C, can be attributed to the complete disassembly of the framework. In the case of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, a greater weight loss was observed during this stage compared to UiO-66-NH\u003csub\u003e2\u003c/sub\u003e, primarily due to the presence of a surface-bound organic linker (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb) [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e]. From these results, the amount of organic linker was estimated to be about 6% by weight These results are in accordance with other analyses approve the successful synthesis and post-synthetic modification of UiO-66.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe porous structures of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e were characterized using N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e). According to Brunauer-Emmett-Teller (BET) calculations, the surface areas of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e and UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e were determined to be 909.59 and 550.11 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb). This reduction in surface area for UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e compared to UiO-66-NH\u003csub\u003e2\u003c/sub\u003e suggests that the post-modification and coordination steps involving ZnCl\u003csub\u003e2\u003c/sub\u003e primarily occurred on the support surface. The adsorption-desorption isotherm of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e displayed a type I isotherm, indicative of a microporous structure (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea). The Barrett-Joyner-Halenda (BJH) diagram for UiO-66-NH\u003csub\u003e2\u003c/sub\u003e revealed the presence of a single type of micropores with a pore diameter of 1.21 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec). Similarly, the BJH plot for UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e also indicated reduced-intensity micropores, consistent with changes in surface area and pore filling resulting from the coordination of the zinc salt (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ed) [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn the TEM image of UiO-66-NH\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ea), one can observe aggregated octahedral particles measuring less than 50 nm in size. Interestingly, the TEM image of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003eb) displayed an identical morphology, suggesting that the post-modification of the (MOF with salicylaldehyde and the coordination of zinc units did not have any discernible impact on the MOF's morphology. Furthermore, SEM images (Figs.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ed \u0026amp; \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ee) supported these findings, confirming the preservation of the MOF's morphology throughout the modification and coordination processes.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFollowing the successful synthesis and characterization of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, its catalytic activity was evaluated in a one-pot multicomponent reaction involving benzyl halides/alkyl halides, phenylacetylene/propargyl alcohol, and sodium azide for the synthesis of 1,2,3-triazole, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn this specific context, a thorough analysis was conducted to investigate the influence of various parameters, including reaction time, solvent, temperature, and catalyst quantity. Initially, the selection of phenylacetylene, benzyl bromide, and NaN\u003csub\u003e3\u003c/sub\u003e was made as model substrates to optimize the reaction conditions, as presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. It was observed that the model reaction failed to proceed without the presence of a catalyst after 3 h in water at 60\u0026deg;C, confirming the necessity of a catalyst (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 1). In model reactions catalyzed by UiO-66-NH\u003csub\u003e2\u003c/sub\u003e and ZnCl\u003csub\u003e2\u003c/sub\u003e, the product yields were only 30% and 15%, respectively (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 2 and 3). However, upon the addition of 5 mol% UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e as a catalyst in the model reaction, the yield of the isolated product reached 98% (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 4). Various polar and nonpolar solvents were examined while using UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e as the catalyst (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 5\u0026ndash;9). Ultimately, considering the green nature of water and the achieved yield, water was chosen as the reaction solvent for further investigation. Model reactions were monitored at different time intervals, such as 2, 1, and 0.5 h. The results indicated that the reaction was completed after 2 h (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 10\u0026ndash;12). Different quantities of catalysts were also tested in the model reaction. It was observed that the product yield decreased from 5 to 3.1 mol% with decreasing catalyst loading (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 13 and 14). Additionally, the reaction temperature was evaluated, revealing a decrease in yield with decreasing temperature. Consequently, the optimal reaction conditions were determined as follows: phenylacetylene (1.0 mmol), benzyl bromide (1.0 mmol), sodium azide (1.0 mmol), and a catalyst (5 mol%) in an aqueous medium at a temperature of 60\u0026deg;C for 2 h.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThe optimized reaction conditions for the synthesis of triazole \u003cem\u003evia\u003c/em\u003e the model reaction.\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eEntry\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCatalyst\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCatalyst amount\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSolvent\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTemp. (\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eTime (h)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eYield (%)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66-NH\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.1 g\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.1 g\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e98\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eEtOH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eDMF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e96\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eToluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e65\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eHexane\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e98\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5 mol%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e65\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"7\" nameend=\"c7\" namest=\"c1\"\u003e \u003cp\u003e\u003csup\u003ea\u003c/sup\u003e Reaction conditions: phenylacetylene (1.0 mmol), benzyl bromide (1.0 mmol), sodium azide (1.0 mmol), catalyst (x mol%), and solvent (2 ml).\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe versatility of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e was further explored with different substrates under the optimized reaction conditions. Substituted phenylacetylene and propargyl alcohol were successfully converted to terminal alkynes and benzyl /alkyl halides (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). Employing various terminal alkynes, corresponding triazoles were obtained with exceptional performance under these optimal conditions. Additionally, a range of aryl and alkyl halides exhibited favorable reactivity in the presence of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, as demonstrated in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe potential for reusing the UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e catalyst was also explored. In this investigation, the model reaction was performed using a fresh catalyst under the optimized conditions. After confirming the completion of the reaction through thin-layer chromatography (TLC), the catalyst was subjected to filtration, followed by washing with both water and ethyl acetate multiple times. Subsequently, the recovered catalyst was dried in an oven at 70\u0026deg;C. Remarkably, this regenerated catalyst demonstrated activity for five consecutive cycles in model reactions with new substrates. The efficiency of the catalyst slightly decreased from 99% in the first cycle to 86% in the last one, as illustrated in Fig.\u0026nbsp;10.\u003c/p\u003e\u003cp\u003eA plausible mechanism for a model click reaction catalyzed by UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e11\u003c/span\u003e. In the first step, coordination between the catalyst and the terminal alkyne transforms the activated acetylene (I) into a more potent dienophile. In the next step, the intermediate alkyl azide formed by the reaction of alkyl halide and sodium azide interacts with complex (I) to form complex (II). Complex (II) gives complex (III) \u003cem\u003evia\u003c/em\u003e a 1,3-dipolar cycloaddition reaction. The final step converts the complex (III) to the desired triazole (IV) and regenerates the catalyst.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eHot filtration test\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThe hot filtration test as a strong test was conducted to evaluate the heterogeneity nature of the catalytic species in the model reaction under the optimal conditions through the possibility of zinc leaching into the reaction mixture (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e12\u003c/span\u003e).\u003c/p\u003e \u003cp\u003ePrecisely, at the midway of the reaction (60 minutes), the nanocatalyst was separated from the reaction mixture by filtration. In this step, only 53% conversion was achieved. Subsequently, the reaction mixture was allowed to continue without a catalyst for another 60 minutes under similar conditions. The reaction progress before and after the separation was checked by TLC.\u003c/p\u003e \u003cp\u003eAssessment of the rate of the desired product preparation demonstrates that no remarkable increase in conversion was observed even after an expanded time.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAlso, to elucidate the stability of the catalyst, after five cycles in the model reaction, any structural changes of the catalyst were studied by FT-IR, TEM techniques. It is evident from the FT-IR spectrum of the 5th reused catalyst that no significant changes in the frequencies, intensities, and shapes of absorption bands were observed (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed). Moreover, the TEM image of the 5th reused catalyst confirmed the aggregated octahedral particles measuring less than 50 nm in size which was approximately similar to the TEM image of the fresh catalyst, and there were not any significant differences in size and morphology (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ec). There is also negligible leaching of Zn species in the reaction medium, justifying its true heterogeneity.\u003c/p\u003e \u003cp\u003eBy knowing the effectiveness of the prepared nanocatalyst, a comparison investigated between its catalytic performance and that of zinc-based catalyst systems documented in the existing literature in the reaction of benzyl bromide, sodium azide, and phenylacetylene under various catalytic conditions (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 1\u0026ndash;5).\u003c/p\u003e \u003cp\u003eNearly all the catalysts mentioned below exhibit notable yields of the desired products. However, the limitations including the long reaction time (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 1 \u0026amp; 2), the high reaction temperature (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 1 \u0026amp; 5), and applying hazardous solvent and reaction conditions (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 2 \u0026amp; 4) represent the drawbacks of some of these methods. As is evident, our studied system (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, entry 6) has advantages such as an excellent yield in a shorter reaction time, simple separation, easy preparation of the catalyst, and milder reaction conditions.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComparison of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e catalyst with other catalysts that used for the synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eEntry\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCatalyst\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSolvent\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eTemp.(\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTime (h)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eYield (%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eRef.\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZn(OAc)\u003csub\u003e2\u003c/sub\u003e/ ascorbic acid\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e52\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZn/C\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDMF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e53\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eGO-Salen-Zn\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e92\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e54\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSMI/ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDMF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e94\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e55\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZinc(II) L-prolinate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e91\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e56\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eWater\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eThis study\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn conclusion, the UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e catalyst was successfully synthesized using a post-modification approach. A comprehensive characterization of the catalyst was carried out utilizing various techniques, including TEM, SEM, FTIR, ICP, TGA, Mapping, XRD, and BET. The results confirmed the effective incorporation of Zn units into the UiO-66-NH\u003csub\u003e2\u003c/sub\u003e post-modified salicylaldehyde nanoreactor. Importantly, the morphology of the catalyst remained unaltered throughout the modification and coordination processes. The UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e catalyst exhibited remarkable catalytic activity in the click reaction involving benzyl halides/alkyl halides, phenylacetylene/propargyl alcohol, and sodium azide, leading to the synthesis of 1,2,3-triazole. Furthermore, this catalyst displayed reusability, retaining its activity for five consecutive cycles. These findings underscore the potential of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e as an efficient and recyclable nanocatalyst for click reactions and related applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eMR and AK designed and planned the catalyst, the experiments, and the final analyses. MR contributed with AK to perform the analyses of the results and wrote the initial manuscript with consulting with AS. AS supervised the finding results and provided critical feedback on the final main manuscript. All authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements:\u003c/h2\u003e \u003cp\u003eThe authors gratefully acknowledge the Research Council of Ferdowsi University of Mashhad (3/57052).\u003c/p\u003e\u003ch2\u003eData availability:\u003c/h2\u003e \u003cp\u003eThe data sets used and analyzed during the current study are available in supporting information.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eFarrusseng, D., Aguado, S., Pinel, C. Metal\u0026ndash;organic frameworks: opportunities for catalysis. Angew. Chem. Int. Ed. 48, 7502\u0026ndash;7513 (2009).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChughtai, A. H., Ahmad, N., Younus, H. A., Laypkov, A., Verpoort, F. Metal\u0026ndash;organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chem. Soc. 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Chem. 25, 620\u0026ndash;625 (2011).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Table 2","content":"\u003cp\u003eTable 2 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"nanocatalyst, metal organic framework, click reaction, post-synthetic modification, triazole","lastPublishedDoi":"10.21203/rs.3.rs-4695524/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4695524/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA novel nanocatalyst, denoted as UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e, has been synthesized and systematically characterized employing a range of analytical techniques, including Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area analysis, and inductively coupled plasma (ICP) analysis. The comprehensive analyses collectively affirm the effective coordination of zinc chloride onto the functionalized UiO-66. Subsequently, the catalytic efficacy of UiO-66/Sal-ZnCl\u003csub\u003e2\u003c/sub\u003e was assessed in a one-pot, three-component click reaction involving terminal alkynes, alkyl halides, and sodium azide, conducted in an aqueous medium. The catalyst demonstrated remarkable catalytic activity, showcasing the capability to facilitate the reaction with high yields and exceptional regioselectivity. Noteworthy attributes of this nanocatalyst and the method include its elevated efficiency, recyclability, convenient product workup, and, significantly, the utilization of a sustainable solvent medium. The synthesis, characterization, and catalytic performance of this catalyst collectively contribute to its potential as an innovative and reusable nanocatalyst for diverse synthetic transformations.\u003c/p\u003e","manuscriptTitle":"Post-Synthetic Modification of Zr-Based Metal Organic Framework by Schiff Base Zinc Complex for Catalytic Applications in a Click Reaction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-08-09 20:50:33","doi":"10.21203/rs.3.rs-4695524/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-08-13T11:13:17+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-07-22T13:20:50+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-07-12T06:23:35+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"42943515217914316259549921705314602952","date":"2024-07-12T04:29:45+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"219326933422271810564359127169062094700","date":"2024-07-12T04:14:26+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-07-12T00:29:54+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-07-12T00:24:08+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2024-07-11T14:04:35+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-07-08T08:40:01+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2024-07-06T07:21:41+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"254220c8-78a4-4fd7-9e83-51810cfd4cc5","owner":[],"postedDate":"August 9th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":34978309,"name":"Physical sciences/Chemistry/Catalysis"},{"id":34978310,"name":"Physical sciences/Chemistry/Organic chemistry"}],"tags":[],"updatedAt":"2024-10-21T16:01:12+00:00","versionOfRecord":{"articleIdentity":"rs-4695524","link":"https://doi.org/10.1038/s41598-024-76199-y","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2024-10-20 15:57:18","publishedOnDateReadable":"October 20th, 2024"},"versionCreatedAt":"2024-08-09 20:50:33","video":"","vorDoi":"10.1038/s41598-024-76199-y","vorDoiUrl":"https://doi.org/10.1038/s41598-024-76199-y","workflowStages":[]},"version":"v1","identity":"rs-4695524","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4695524","identity":"rs-4695524","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}