Facile Preparation of Pd-BN Nanocatalyst for Suzuki Reaction: Synergistic Boron Nitride Effect in a Green Solvent System

Facile Preparation of Pd-BN Nanocatalyst for Suzuki Reaction: Synergistic Boron Nitride Effect in a Green Solvent System | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 8 April 2025 V1 Latest version Share on Facile Preparation of Pd-BN Nanocatalyst for Suzuki Reaction: Synergistic Boron Nitride Effect in a Green Solvent System Authors : Fuqing Lu , Cui Wang , Yuanyuan Zhang , Daixin Zhao , Yongnan Xu , Yajun Liu , and Yan Xiao [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.174408492.20309692/v1 Published Sustainable Chemistry and Pharmacy Version of record Peer review timeline 162 views 121 downloads Contents Abstract Supplementary Material Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract A scalable in situ pyrolysis strategy was developed for the synthesis of Pd/BN nanocatalysts using melamine, boric acid, and palladium acetate as precursors. Strong electronic interactions between Pd nanoparticles and the BN support significantly enhanced catalytic performance, enabling highly efficient Suzuki coupling reactions. The Pd/BN catalyst achieved up to 99% yield across a broad substrate scope under ambient conditions in a 50% aqueous ethanol system. Additionally, it exhibited excellent stability and recyclability, maintaining high catalytic activity over at least ten cycles with minimal deactivation. Experimental studies and density functional theory (DFT) calculations confirmed that charge transfer at the Pd/BN interface lowered the energy barrier of the rate-determining step, accelerating reaction kinetics. The combination of mild conditions, high efficiency, and operational simplicity highlights the sustainability and scalability of this catalytic system, making it a strong candidate for industrial applications. Cite this paper: Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.202500XXX Facile Preparation of Pd-BN Nanocatalyst for Suzuki Reaction: Synergistic Boron Nitride Effect in a Green Solvent System Fuqing Lu, † Cui Wang, † Yuanyuan Zhang, Daixin Zhao, Yongnan Xu,* Yajun Liu,* Yan Xiao* School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Wenhua Road 103, Shenyang110016, China. † These authors contributed equally to this work. * Corresponding authors. Boron nitride support | Pd/BN nanocatalyst | Electron transfer interactions | Suzuki reaction | Catalytic reusability Comprehensive Summary A scalable in situ pyrolysis strategy was developed for the synthesis of Pd/BN nanocatalysts using melamine, boric acid, and palladium acetate as precursors. Strong electronic interactions between Pd nanoparticles and the BN support significantly enhanced catalytic performance, enabling highly efficient Suzuki coupling reactions. The Pd/BN catalyst achieved up to 99% yield across a broad substrate scope under ambient conditions in a 50% aqueous ethanol system. Additionally, it exhibited excellent stability and recyclability, maintaining high catalytic activity over at least ten cycles with minimal deactivation. Experimental studies and density functional theory (DFT) calculations confirmed that charge transfer at the Pd/BN interface lowered the energy barrier of the rate-determining step, accelerating reaction kinetics. The combination of mild conditions, high efficiency, and operational simplicity highlights the sustainability and scalability of this catalytic system, making it a strong candidate for industrial applications. Background and Originality Content The Suzuki coupling reaction is a fundamental transformation in synthetic organic chemistry, widely applied in the pharmaceutical industry, agrochemicals, and material sciences. [1-7] Its broad functional group tolerance, mild reaction conditions, and high efficiency make it an indispensable tool for carbon-carbon bond formation. Notably, Suzuki coupling ranks as the second most frequently used reaction in drug discovery and development, highlighting its critical role in both industrial and academic research. [8] Despite its widespread adoption, the reaction primarily relies on palladium-based catalysts, which pose significant challenges. Homogeneous palladium catalysts, while highly efficient, [9-11] suffer from drawbacks such as air and moisture sensitivity, high cost, and difficulties in catalyst recovery, limiting their practicality in large-scale applications. [12-16] Heterogeneous palladium catalysts have been developed as viable alternatives due to their superior recyclability and ease of separation. [17-22] However, many existing heterogeneous systems are hampered by complex synthesis procedures, suboptimal catalytic efficiency, and poor stability under operational conditions. This necessitates the development of robust, efficient, and sustainable catalytic systems that can address these limitations. Boron nitride (BN) has emerged as an attractive support material for heterogeneous catalysis due to its high thermal stability, chemical inertness, and distinctive electronic properties. [23-31] The strong electronic interactions between BN and metal nanoparticles enable the stabilization of active catalytic sites, leading to enhanced catalytic performance. [32-39] Specifically, the synergy between BN and palladium can modulate electronic density at the active sites, lowering reaction energy barriers and promoting reaction efficiency. [40] However, conventional Pd/BN catalyst synthesis methods often involve multiple tedious steps, making them time-consuming and resource-intensive, thereby restricting their practical applications. [41,42] To address these challenges, we report a facile and scalable in situ pyrolysis strategy for synthesizing Pd/BN nanocatalysts. This approach significantly simplifies the preparation process while ensuring superior catalytic performance. The as-prepared Pd/BN catalyst exhibits remarkable activity, stability, and recyclability in Suzuki coupling reactions conducted under mild ambient conditions, using K₂CO₃ as the base and 50% aqueous ethanol as the solvent. To the best of our knowledge, this is the first report of a non-pot in situ pyrolysis method for Pd/BN synthesis and its application in Suzuki coupling. Our study not only presents a highly sustainable and efficient catalytic system but also provides new insights into rational catalyst design, particularly in tuning metal-support interactions to enhance catalytic efficiency. Results and Discussion Synthesis and characterization of Pd/BN A heterogeneous Pd/BN nanocatalyst was successfully synthesized via a simple method using low-cost precursors. Specifically, Pd(OAc)₂, melamine, and boric acid were mixed to form a gel-like precursor, followed by calcination at 1100 °C to yield Pd/BN. The pristine BN was synthesized through the same procedure, excluding Pd(OAc)₂ (Figure 1a). The morphology and structure of the synthesized materials were analyzed using scanning electron microscopy (SEM). As shown in Figures 1b & c, both BN and Pd/BN exhibited a rod-like morphology with polygonal cross-sections and rough surfaces, with diameters ranging from 400–600 nm. Energy-dispersive spectroscopy (EDS) mapping (Figure 1d & S1) revealed that Pd nanoparticles were uniformly dispersed on the BN support. Transmission electron microscopy (TEM) further confirmed the well-embedded Pd nanoparticles on the BN rods (Figures 1e & g), with an average particle size of 7.25 nm (Figure S2). High-resolution TEM images (Figures 1f & g) displayed an interplanar distance of 0.242 nm, corresponding to the (111) crystal plane of metallic Pd, further confirming the formation of Pd nanoparticles. X-ray photoelectron spectroscopy (XPS) was performed to investigate the elemental composition and chemical states of Pd/BN (Figure 2a). The presence of B, C, N, O, and Pd was confirmed, and the B/N atomic ratio was determined to be 1.1, suggesting B vacancies and an N-rich basic nature of the BN support. [43] Deconvolution of the N 1s spectrum (Figure 2b) revealed a peak at 398.08 eV, assigned to N-B bonds. Similarly, the B 1s spectrum (Figure 2c) exhibited two peaks at 190.83 eV (B-N bonds) and 192.16 eV (B-O bonds), [44] with the B-N peak being 10.7 times more intense than the B-O peak, further confirming the strong basicity of Pd/BN. The Pd 3d XPS spectrum (Figure 2d) displayed characteristic peaks at 341.17 eV and 335.69 eV, corresponding to the Pd(0) oxidation state, indicating the presence of metallic Pd species. X-ray diffraction (XRD) analysis was conducted to investigate the crystallographic structures of BN and Pd/BN (Figure 2e). Both materials exhibited diffraction peaks at 2θ = 26.7°, 42.6°, and 45.6°, corresponding to the (002), (101), and (012) lattice planes of BN (PDF#45-1171), confirming that the BN structure remained intact after Pd deposition. [45] Additionally, characteristic diffraction peaks at 40.1°, 46.6°, and 68.1° were assigned to the (111), (200), and (220) lattice planes of metallic Pd, consistent with standard Pd data (PDF#46-1043). [46] Figure 1 (a) Schematic diagram of the Pd/BN preparation process, (b) SEM image of BN, (c) SEM image of Pd/BN, (d) EDS mapping for the Pd/BN, (e-g) TEM images of Pd/BN and the size distribution of Pd. Figure 2 (a) Survey scans XPS spectrum and corresponding high-resolution deconvoluted (b) N 1s, (c) B 1s, and (d) Pd 3d XPS spectrum of Pd/BN; (e) XRD analysis of the BN and Pd/BN; (f) FT-IR spectra of the BN and Pd/BN. Fourier-transform infrared (FT-IR) spectroscopy was used to further investigate the chemical structure evolution (Figure 2f). The pristine BN exhibited two broad peaks at 1379.52 cm⁻¹ and 802.09 cm⁻¹, corresponding to B-N stretching and B-N-B bending vibrations, respectively. [47] Upon Pd immobilization, these peaks slightly shifted to 1378.29 cm⁻¹ and 786.51 cm⁻¹, indicating a localized fixation effect. [43,48] The thermal stability of BN and Pd/BN was assessed using thermogravimetric analysis (TGA) (Figure S3). Both materials exhibited two weight-loss stages at approximately 150 °C and 350 °C. The first weight loss was attributed to the removal of adsorbed solvents, while the second was associated with NH₃ decomposition from BN. Notably, BN exhibited a total weight loss of 6.15%, whereas Pd/BN showed a slightly higher weight loss of 11.55%, suggesting an interaction between Pd and BN. Inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis revealed a Pd loading of 2.68 wt% in Pd/BN. Catalytic performance in the Suzuki reaction The catalytic performance of Pd/BN in the Suzuki coupling reaction was systematically assessed using bromobenzene (1a) and 4-methylphenylboronic acid (2a) as model substrates (Table S1). Reactions were conducted at 25 °C with 0.38 mol% Pd/BN to optimize reaction conditions. Solvent screening with K₂CO₃ as the base revealed that EtOH, i -PrOH, and CH₃CN afforded cross-coupled product 3a in 90%, 10%, and 9% yields after 8 h, respectively (Table S1, entries 1-3), while pure water yielded only 22% (Table S1, entry 4). Notably, a 1:1 (v/v) EtOH/H₂O mixture, a green solvent system, enhanced the yield to 99% within 2 h (Table S1, entry 5), attributed to the “on-water” effect, which optimizes the organic-water interface for catalysis. [49,50] Water also improves K₂CO₃ solubility, facilitating aryl boronic acid deprotonation and promoting the transmetallation step. Base screening (Table S1, entries 6-10) identified Na₂CO₃ as comparable to K₂CO₃ (97% yield), while Cs₂CO₃, NaOH, NaHCO₃, and Et₃N gave lower yields (73%, 31%, 34%, and 11%, respectively). The reaction did not proceed without a base (Table S1, entry 11). Catalyst loading studies showed that 0.25 mol% Pd/BN maintained high efficiency (Table S1, entry 12), whereas further reductions (0.20 mol% and 0.13 mol%) resulted in lower yields and incomplete reactions (Table S1, entries 13 & 14). No reaction occurred without Pd/BN (Table S1, entry 15), confirming its essential role. The optimized reaction conditions were established as follows: aryl bromide (1.0 mmol), aryl boronic acid (1.02 mmol), Pd/BN (0.25 mol%), K₂CO₃ (2.0 mmol), EtOH/H₂O (v:v = 1:1, 6 mL), 25 °C, 1.5 h. The substrate scope was investigated using various aryl halides and boronic acids (Schemes 1a-c). The reaction was tolerant to diverse functional groups (OH, OCH₃, CN, CHO, NO₂, NH₂, halogens) and heterocycles (indolyl, pyrimidinyl, quinolyl, pyridyl), yielding excellent product conversion. Recyclability and scale-up studies The recyclability of Pd/BN was assessed over ten catalytic cycles (Figure S4). The catalyst was easily separated by filtration, washed, and reused without significant loss of activity. ICP-OES analysis of the recycled Pd/BN showed a Pd content of 2.57 wt%, indicating minimal leaching. XPS analysis of the recovered catalyst (Figure S5) revealed an increase in Pd oxidation, suggesting partial Pd oxidation after multiple uses. To evaluate industrial feasibility, a gram-scale Suzuki reaction was conducted using 2-bromobenzonitrile (20 mmol) and 4-methylphenylboronic acid (20.4 mmol) in EtOH/H₂O (60 mL) at room temperature for 3 hours. The reaction yielded 98% (3.79 g) of the product, demonstrating the scalability and practicality of Pd/BN. Compared to conventional Pd catalysts, Pd/BN exhibited superior catalytic activity, recyclability, and environmental friendliness (Table 1). Reaction kinetics and mechanistic studies Kinetic studies conducted at 298-323 K revealed that an increase in temperature significantly accelerated the reaction (Figure 3a). The reaction followed first-order kinetics (Figure 3b), and Arrhenius plots yielded an activation energy of 0.86 eV (Figure 3c). Scheme 1 Suzuki coupling reaction of aryl bromides and aryl boronic acids a a Reaction conditions: aryl bromides (1 mmol), 4-methylphenylboronic acid (1.02 mmol), K 2 CO 3 (2.0 mmol), Pd/BN (0.25 mol%), EtOH/H 2 O (1:1) (6 mL), room temperature (25 °C). b Determination of yield by silica gel column chromatography. c EtOH/H 2 O (1:1) (8 mL). First-principles calculations were conducted to explore the structural and mechanistic aspects of the Pd/BN nanocatalyst. Based on experimental characterization and catalytic performance in Suzuki coupling reactions, two catalyst models were developed (Figure S6) to represent distinct active sites: an icosahedral Pd-centered Pd₁₃ cluster embedded in boron nitride (Pd₁₃/BN) and Pd(111), simulating BN-supported Pd nanoparticles and commercial Pd/C, respectively. Density functional theory (DFT) calculations confirmed the unique geometric features and relative energy variations during the Suzuki coupling of bromobenzene (Figure 3d & e). Reaction pathway analysis revealed that bromobenzene adsorption energy was lower on Pd₁₃/BN compared to Pd(111), indicating enhanced activity of Pd/BN in the initial reaction stage. As the reaction proceeded, the decomposition of adsorbed bromobenzene was thermodynamically favored on Pd₁₃/BN, with an energy barrier of 0.57 eV. Additionally, the decomposition of 4-methylphenylboronic acid was facilitated at the adsorption site, with a lower energy barrier (0.83 eV) on Pd₁₃/BN than on Pd(111) (0.95 eV). This enhancement was attributed to electron transfer from nitrogen in BN to Pd, generating electron-rich Pd active sites that promoted the oxidative addition step in Suzuki coupling. [13] For the overall reaction, the rate-determining step on Pd₁₃/BN exhibited an energy barrier of 0.83 eV, whereas on Pd(111), phenyl activation was effective, but the formation of tolyl from 4-methylphenylboronic acid was hindered, with a higher barrier of 0.95 eV, making it the rate-limiting step. As a result, Pd₁₃/BN demonstrated superior catalytic activity for Suzuki coupling compared to Pd(111), confirming its higher efficiency over commercial Pd/C (Figure 4). DFT calculations conclusively showed that the Pd/BN nanocatalyst significantly lowers the energy barriers for transmetalation and reductive elimination, thereby enhancing the overall Suzuki reaction kinetics. These findings confirm Pd/BN as an efficient, reusable, and scalable nanocatalyst for green Suzuki coupling reactions. Conclusions In this study, we developed a heterogeneous Pd/BN nanocatalyst via a scalable in situ pyrolysis strategy and systematically investigated its structural and catalytic properties. The strong Pd–BN interactions facilitated efficient Suzuki coupling under mild conditions, achieving high yields across diverse substrates. Pd/BN exhibited excellent stability and recyclability, maintaining catalytic activity over ten cycles. Compared with conventional homogeneous Pd catalysts, Pd/BN offered easy separation, superior reusability, and scalability, making it a promising candidate for sustainable catalysis. Gram-scale synthesis further validated its industrial feasibility. DFT calculations confirmed that charge transfer at the Pd/BN interface lowered the reaction barrier, enhancing kinetics and overall efficiency. These findings provide valuable insights into metal-support interactions and establish Pd/BN as a robust catalyst for practical Suzuki coupling applications. Table 1. Comparison of Pd/BN with recently reported catalysts for Suzuki coupling reaction. Entry R 1 X R 2 Catalyst Reaction conditions Solvent/base/temperature/time Yields Ref. 1 H I H PdZn 30 –NC EtOH:H 2 O (1:1)/K 2 CO 3 /70 ℃/40 min 97.7% [51] 2 CF 3 Br F Pd-P(t-Bu) 3 -G3 THF/TMSOK/23 ℃/5 min/3 h 75%-98% [52] 3 H I H Pd@MOF–808 MeOH/K 2 CO 3 /40 ℃/1.5 h 99% [53] 4 H I H GO–N 2 S 2 /Pd EtOH/K 2 CO 3 /75 ℃/3 h 94% [54] 5 H I H Pd@COF–QA H 2 O/Triethylamine/50 ℃/6 h 99% [17] 6 H I H Pd(II-0)@m-SiO 2 EtOH:H 2 O(1:1)/K 2 CO 3 /80 ℃/20 min 100% [55] 7 H I H 3D-SiO 2 -Pd(0) t-BuOH&H 2 O/K 2 CO 3 /90 ℃/3 h 95% [56] 8 H Br H PdO x /NiFe 2 O 4 NFs EtOH:H 2 O (1:1)/K 2 CO 3 /35 ℃/ 40 min 79.62% [57] 9 CH 3 Br H Pd@PUF@PDA EtOH:H 2 O (1:1)/K 2 CO 3 /65 ℃/ 4 h 92% [58] 10 H I CH 3 Pd-SAs/3DOM-CeO 2 EtOH:H 2 O (1:1)/K 2 CO 3 /25 ℃/ 4 h 91.37% [21] 11 H I H Pd@C-800 EtOH:H 2 O (4:1)/K 2 CO 3 /70 ℃/ 3 h 96% [59] 12 H Br H Pd/N-CNS800 EtOH:H 2 O (3:1)/K 2 CO 3 /100 ℃/50 min 99.6% [60] 13 H I H Pd@NH 2 -MIL-53(Al)@CCF EtOH:H 2 O (1:1)/Cs 2 CO 3 /80 ℃/12 h 96% [61] 14 H Br CH 3 Pd/BN EtOH:H 2 O (1:1)/K 2 CO 3 /25 ℃/ 2.5 h 99% This work Figure 3 (a) Time-dependent conversion of bromobenzene, (b) The corresponding ln(C 0 /C t )-time curves for Suzuki coupling reactions over Pd/BN catalysts at varied temperatures (298 K, 303 K, 313 K and 323 K), (c) Arrhenius plots of the reaction over Pd/BN catalysts, DFT calculated reaction pathway and the corresponding energy profiles of Suzuki reaction between bromobenzene and 4-Methylphenylboronic acid on (d) Pd (111) and (e) Pd 13 /BN catalyst model. C, H, Br, B, O, N and Pd was shown in gray, white, mauve, pink, red, blue and baby blue, respectively. Figure 4 Reaction pathways of the Suzuki coupling of bromobenzene and 4-methylphenylboronic acid over Pd/BN nanocatalyst. Experimental Preparation of Pd/BN and BN In a typical synthesis, 1.58 g of melamine powder and 1.55 g of boric acid (molar ratio of 1:2) were dissolved in 100 mL of deionized water under continuous stirring. Subsequently, an appropriate amount of calcium hydroxide and ammonia were added to adjust the pH to approximately 8. A solution of palladium acetate (0.112 g of Pd(OAc)₂ in 10 mL of acetone) was then added dropwise into the melamine–boric acid solution under stirring. The resulting mixture was heated at 40 °C for 24 h, forming a faint yellow gel. The gel was then freeze-dried to obtain the Pd/BN precursor. The dried precursor was transferred to a quartz tube in a tube furnace. The tube was initially evacuated using a mechanical pump and purged three times with nitrogen (N₂). The precursor was then calcined at 1100 °C for 2 h under a continuous N₂ flow (100 mL·min⁻¹). After cooling to room temperature, the resulting gray-black solid was washed three times with deionized water and ethanol to remove impurities. Finally, the product was dried to obtain the Pd/BN nanocatalyst. For comparison, pristine BN was synthesized using the same procedure, except that the Pd(OAc)₂ solution was omitted. Suzuki coupling reaction The Suzuki coupling reaction was conducted as follows: Aryl bromide (1.0 mmol), aryl boronic acid (1.02 mmol), base (2.0 mmol), solvent (EtOH:H₂O = 1:1, 6 mL or 8 mL), and the Pd/BN catalyst (0.25 mol%) were added to a flask equipped with a magnetic stirrer. The reaction mixture was stirred at room temperature for several hours, and the reaction progress was monitored by thin-layer chromatography (TLC). Upon completion, the catalyst was recovered by centrifugation, thoroughly washed with deionized water and ethanol to remove residual materials, and dried for reuse. The organic phase was washed with water, dried over anhydrous Na₂SO₄, and the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel column chromatography and identified using ¹H NMR, ESI-MS, or GC-MS. DFT calculations Density functional theory (DFT) calculations were performed using the DMol³ module in the Materials Studio package. The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) functional was used to describe electron exchange and correlation effects, and the double numerical plus polarization (DNP) basis set was employed. The convergence tolerance parameters for energy change, maximum force, and maximum displacement were set at 2.0×10 -5 Ha, 0.004 Ha Å -1 , and 0.005 Å, respectively. The self-consistent field was set as a convergence criterion of 1×10 -5 Ha. Transition state (TS) structures were identified using the linear synchronous transit/quadratic synchronous transit (LST/QST) method and confirmed by vibrational frequency analysis, ensuring that each transition state exhibited only one imaginary vibrational frequency. Due to the complexity of the structural models, Brillouin zone integration was performed using a 2 × 2 × 1 Monkhorst-Pack k-point sampling scheme. The reaction energy (\(\mathrm{\Delta}E\)) and activation energy (Ea) were calculated using the following equations: \begin{equation} \mathrm{\Delta}E=E\left(\text{FS}\right)-E\left(\text{IS}\right)\nonumber \\ \end{equation}\begin{equation} Ea=E\left(\text{TS}\right)-E(IS)\nonumber \\ \end{equation} Where \(E(TS)\), \(E(IS)\), and \(E(FS)\) represent the calculated energies of the transition state, initial state, and final state, respectively. Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202500xxx. Acknowledgement This work is supported by Research Project of Education Department of Liaoning Province, China (LJKZ0955) and Career Development Support Plan for Young and Middle-aged Teachers in Shenyang Pharmaceutical University (grant no. ZQN2021007). References 1. Agarwal S, Bairagi S, Khatun M M, Deori K. Hierarchical NiZn Solid Solution as a Highly Efficient Palladium Free Heterogeneous Catalyst for Suzuki-Miyaura Cross-Coupling Reaction. ACS Appl. Mater. Interfaces 2023 , 15 , 41073-41080. 2. Geng B, Chu X, Liu L, Zhang L, Zhang S, Wang X, Song S, Zhang H. High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chin. Chem. Lett. 2024 , 35 , 108924. 3. Srivastava A, Kaur H, Pahuja H, Rangarajan T M, Varma R S, Pasricha S. Optimal exploitation of supported heterogenized Pd nanoparticles for C-C cross-coupling reactions. Coord Chem Rev. 2024 , 507 . 4. Mao C, Yin K, Yang C, Dong G, Tian G, Zhang Y, Zhou Y. Fe-based MOFs@ Pd@ COFs with spatial confinement effect and electron transfer synergy of highly dispersed Pd nanoparticles for Suzuki-Miyaura coupling reaction. J. Colloid Interface Sci. 2022 , 608 , 809-819. 5. Nasseri M A, Rezazadeh Z, Kazemnejadi M, Allahresani A. A Co-Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C-N cross-coupling reactions in water. Dalton Transactions 2020 , 49 , 10645-10660. 6. Niakan M, Masteri-Farahani M. Pd-Ni bimetallic catalyst supported on dendrimer-functionalized magnetic graphene oxide for efficient catalytic Suzuki-Miyaura coupling reaction. Tetrahedron 2022 , 108 , 132655. 7. Tian P, Tong R. In-water oxidative Suzuki coupling of arenes and arylboronic acids using H 2 O 2 as a terminal oxidant. Green Chem. 2023 , 25 , 1345-1350. 8. Wang Y, Liao J, Xie Z, Zhang K, Wu Y, Zuo P, Zhang W, Li J, Gao Z. Zeolite-enhanced sustainable Pd-catalyzed C-C cross-coupling reaction: Controlled release and capture of palladium. ACS Appl. Mater. Interfaces 2020 , 12 , 11419-11427. 9. Boström J, Brown D G, Young R J, Keserü G M. Expanding the medicinal chemistry synthetic toolbox. Nat. Rev. Drug Discovery 2018 , 17 , 709-727. 10. Monnereau L, Sémeril D, Matt D, Toupet L. Cavity-Shaped Ligands: Calix [4] arene-Based Monophosphanes for Fast Suzuki-Miyaura Cross-Coupling. Chem. - Eur. J. 2010 , 16 , 9237-9247. 11. Johansson Seechurn C C, Parisel S b L, Colacot T J. Air-stable Pd (R-allyl) LCl (L= Q-Phos, P (t-Bu) 3, etc.) systems for C-C/N couplings: insight into the structure-activity relationship and catalyst activation pathway. J. Org. Chem. 2011 , 76 , 7918-7932. 12. Zaborova E, Deschamp J, Guieu S, Blériot Y, Poli G, Ménand M, Madec D, Prestat G, Sollogoub M. Cavitand supported tetraphosphine: cyclodextrin offers a useful platform for Suzuki-Miyaura cross-coupling. Chem. Commun. 2011 , 47 , 9206-9208. 13. Pei X, Li Y, Lu L, Jiao H, Gong W, Zhang L. Highly dispersed Pd clusters anchored on nanoporous cellulose microspheres as a highly efficient catalyst for the Suzuki coupling reaction. ACS Appl. Mater. Interfaces 2021 , 13 , 44418-44426. 14. Wei H, Li X, Deng B, Lang J, Huang Y, Hua X, Qiao Y, Ge B, Ge J, Wu H. Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions. Chin. J. Catal. 2022 , 43 , 1058-1065. 15. Srivastava A, Kaur H, Pahuja H, Rangarajan T, Varma R S, Pasricha S. Optimal exploitation of supported heterogenized Pd nanoparticles for CC cross-coupling reactions. Coord. Chem. Rev. 2024 , 507 , 215763. 16. Sun X, Li S, Cao J, Wang Y, Yang W, Zhang L, Liu Y, Qiu J, Tao S. A hierarchical-structured impeller with engineered Pd nanoparticles catalyzing Suzuki coupling reactions for high-purity biphenyl. ACS Appl. Mater. Interfaces 2021 , 13 , 17429-17438. 17. Wang J-C, Liu C-X, Kan X, Wu X-W, Kan J-L, Dong Y-B. Pd@ COF-QA: a phase transfer composite catalyst for aqueous Suzuki-Miyaura coupling reaction. Green Chem. 2020 , 22 , 1150-1155. 18. Shen H, He J, He F, Xue Y, Li Y, Li Y. Nitrogen-doped graphdiyne for effective metal deposition and heterogeneous Suzuki-Miyaura coupling catalysis. Appl. Catal. A Gen. 2021 , 623 , 118244. 19. Wang F, Mielby J, Richter F H, Wang G, Prieto G, Kasama T, Weidenthaler C, Bongard H J, Kegnæs S, Fürstner A. A polyphenylene support for Pd catalysts with exceptional catalytic activity. Angew. Chem. 2014 , 126 , 8789-8792. 20. Bhattacharjee P, Dewan A, Boruah P K, Das M R, Mahanta S P, Thakur A J, Bora U. Bimetallic Pd-Ag nanoclusters decorated micro-cellulose bio-template towards efficient catalytic Suzuki-Miyaura coupling reaction of nitrogen-rich heterocycles. Green Chem. 2022 , 24 , 7208-7219. 21. Tao X, Long R, Wu D, Hu Y, Qiu G, Qi Z, Li B, Jiang R, Xiong Y. Anchoring positively charged Pd single atoms in ordered porous ceria to boost catalytic activity and stability in Suzuki coupling reactions. Small 2020 , 16 , 2001782. 22. Zheng X, Li Y, Li W, Pei X, Ye D. Chitosan derived efficient and stable Pd nano-catalyst for high efficiency hydrogenation. Int. J. Biol. Macromol 2023 , 241 , 124615. 23. Zhou C, Lai C, Zhang C, Zeng G, Huang D, Cheng M, Hu L, Xiong W, Chen M, Wang J. Semiconductor/boron nitride composites: synthesis, properties, and photocatalysis applications. Appl. Catal., B 2018 , 238 , 6-18. 24. Li W, Wang Q, Huang L, Li Y, Xu Y, Song Y, Zhang Q, Xu H, Li H. Synthesis and characterization of BN/Bi 2 WO 6 composite photocatalysts with enhanced visible-light photocatalytic activity. RSC Adv. 2015 , 5 , 88832-88840. 25. Baik S, Lee J W. Effect of boron-nitrogen bonding on oxygen reduction reaction activity of BN Co-doped activated porous carbons. RSC Adv. 2015 , 5 , 24661-24669. 26. Xu Y, Yao J, Lin H, Lv Q, Liu B, Wu L, Tan L, Dai Y, Zong X, Tang Y. Functional CeO x Stabilized Metallic Ni Catalyst Supported on Boron Nitride for Durable Partial Oxidation of Methane to Syngas at High Temperature. ACS Catal. 2024 , 14 , 11845-11856. 27. Kim Y, Choi H, Kim T Y, Kang S, Choi C, Kim J, Song C K, Sung J, Han J W, Park J. Lattice-Disordered Boron Nitride Colloidal Catalyst for Low-Temperature Selective Methane Oxidation. ACS Catal . 2024 , 14 , 15622-15632. 28. Chan C W A, Mahadi A H, Li M M-J, Corbos E C, Tang C, Jones G, Kuo W C H, Cookson J, Brown C M, Bishop P T. Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation. Nat. Commun. 2014 , 5 , 5787. 29. Liu B, Yao H, Song W, Jin L, Mosa I M, Rusling J F, Suib S L, He J. Ligand-free noble metal nanocluster catalysts on carbon supports via “soft” nitriding. J. Am. Chem. Soc. 2016 , 138 , 4718-4721. 30. Wang L, Chen M-X, Yan Q-Q, Xu S-L, Chu S-Q, Chen P, Lin Y, Liang H-W. A sulfur-tethering synthesis strategy toward high-loading atomically dispersed noble metal catalysts. Sci. Adv. 2019 , 5 , eaax6322. 31. [31] Wang L, Yin P, Zhang L-L, Shen S-C, Xu S-L, Chen P, Liang H-W. Nitrogen-fixing of ultrasmall Pd-based bimetallic nanoclusters on carbon supports. J. Catal . 2020 , 389 , 297-304. 32. Zhen J, Sun J, Xu X, Wu Z, Song W, Ying Y, Liang S, Miao L, Cao J, Lv W. M− N3 Configuration on Boron Nitride Boosts Singlet Oxygen Generation via Peroxymonosulfate Activation for Selective Oxidation. Angew. Chem. Int. Ed. 2024 : e202402669. 33. Zhao Y, Liu Z, Cao C, Wang C, Fang Y, Huang Y, Yu C, Zhang J, Li L, Hu L. Self-sacrificed template synthesis of ribbon-like hexagonal boron nitride nano-architectures and their improvement on mechanical and thermal properties of PHA polymer. Scientific reports 2017 , 7 , 9006. 34. Fan M, Jimenez J D, Shirodkar S N, Wu J, Chen S, Song L, Royko M M, Zhang J, Guo H, Cui J. Atomic Ru immobilized on porous h-BN through simple vacuum filtration for highly active and selective CO 2 methanation. ACS Catal . 2019 , 9 , 10077-10086. 35. Liang J, Song Q, Wu J, Lei Q, Li J, Zhang W, Huang Z, Kang T, Xu H, Wang P. Anchoring copper single atoms on porous boron nitride nanofiber to boost selective reduction of nitroaromatics. ACS nano 2022 , 16 , 4152-4161. 36. Wang J, Sun C, Xia W, Cao Z, Sheng G, Xie X. Pd/BN catalysts for highly efficient hydrogenation of maleic anhydride to succinic anhydride. Appl. Catal., A 2022 , 630 , 118471. 37. Yabe Y, Yamada T, Nagata S, Sawama Y, Monguchi Y, Sajiki H. Development of a palladium on boron nitride catalyst and its application to the semihydrogenation of alkynes. Adv. Synth. Catal. 2012 , 354 , 1264-1268. 38. Zhang L, Fang Y, Du Z, Bi D, Guo Z, Liu Z, Huang Y, Lin J, Tang C. Highly Selective Hydrogenation of Phenol Catalyzed by Porous BN Supported Ni-Pd Catalysts. ChemistrySelect 2021 , 6 , 5975-5982. 39. Xiang J, Zhao H, Chen K, Li X, Li X, Chu K. Atomically dispersed Pd on defective BN nanosheets for nitrite electroreduction to ammonia. J. Colloid Interface Sci. 2024 , 653 , 390-395. 40. Li Q, Li L, Yu X, Wu X, Xie Z, Wang X, Lu Z, Zhang X, Huang Y, Yang X. Ultrafine platinum particles anchored on porous boron nitride enabling excellent stability and activity for oxygen reduction reaction. Chem. Eng. J. 2020 , 399 , 125827. 41. Yang Y, Shen Z, Yang H, Zou X, Meng Y, Jiang L, Liu Y, Xia Q, Cao Y, Li X. Construction adsorption and photocatalytic interfaces between C, O co-doped BN and Pd-Cu alloy nanocrystals for effective conversion of CO 2 to CO. J. Colloid Interface Sci. 2023 , 640 , 949-960. 42. Rabani I, Tahir M S, Lee W-I, Truong H B, Dastgeer G, Seo Y-S. Palladium nanoparticle formation on boron nitride nanotubes and their photocatalytic performance with visible light. J. Cleaner Prod. 2023 , 420 , 138324. 43. Zhang Z, Su J, Matias A S, Gordon M, Liu Y-S, Guo J, Song C, Dun C, Prendergast D, Somorjai G A. Enhanced and stabilized hydrogen production from methanol by ultrasmall Ni nanoclusters immobilized on defect-rich h-BN nanosheets. Proc. Natl. Acad. Sci. 2020 , 117 , 29442-29452. 44. Wu J, Wang L, Yang X, Lv B, Chen J. Support effect of the Fe/BN catalyst on Fischer-Tropsch performances: Role of the surface B-O defect. Ind. Eng. Chem. Res. 2018 , 57 , 2805-2810. 45. Liang J, Song Q, Lin J, Li G, Fang Y, Guo Z, Huang Y, Lee C-S, Tang C. In situ Cu-loaded porous boron nitride nanofiber as an efficient adsorbent for CO 2 capture. ACS Sustainable Chem. Eng. 2020 , 8 , 7454-7462. 46. Du F, Zhang L, Ma J, Peng X. Hemicelluloses supported palladium/xylan nanocomposites containing N and O ligands: highly-performance heterogeneous catalysts for Suzuki reaction. Carbohydr. Polym. 2019 , 217 , 224-231. 47. Chen H, Yang Z, Zhang Z, Chen Z, Chi M, Wang S, Fu J, Dai S. Construction of a nanoporous highly crystalline hexagonal boron nitride from an amorphous precursor for catalytic dehydrogenation. Angew. Chem. 2019 , 131, 10736-10740. 48. Wu C, Wang B, Wu N, Han C, Zhang X, Shen S, Tian Q, Qin C, Li P, Wang Y. Molecular-scale understanding on the structure evolution from melamine diborate supramolecule to boron nitride fibers. Ceram. Int . 2020 , 46 , 1083-1090. 49. Wang M, Xue H, Ju F, Yang H. Acceleration of batch-type heterogeneous ligand-free Suzuki-Miyaura reactions with polymer composite supported Pd catalyst. Sci. Rep. 2017 , 7 , 7006. 50. Li X, Zhang Y, Liu J, Cao J, Ma N, Tao M, Zhang W. Synthesis of spiroindoline derivatives and biphenyl compounds in green solvent via a “capture-release” mechanism using modified polyacrylonitrile fiber as a catalyst. Chem. Eng. J. 2024 , 496 , 153906. 51. He H, Ma Z, Zhang S, Cai A, Ye H, Fan X, Peng W, Li Y. Boosting Suzuki coupling reaction via pore expanding and palladium-zinc alloying. J. Colloid Interface Sci. 2025 , 679 , 152-160. 52. Delaney C P, Kassel V M, Denmark S E. Potassium Trimethylsilanolate Enables Rapid, Homogeneous Suzuki-Miyaura Cross-Coupling of Boronic Esters. ACS Catal. 2019 , 10 , 73-80. 53. Wang J, Li T, Zhao Z, Zhang X, Pang W. Pd nanoparticles embedded into MOF-808: Synthesis, structural characteristics, and catalyst properties for the Suzuki-Miyaura coupling reaction. Catal. Lett. 2022 : 1-10. 54. Zarnegaryan A, Elhamifar D. An efficient and heterogeneous Pd-containing modified graphene oxide catalyst for preparation of biaryl compounds. Heliyon 2020 , 6 . 55. Zhao Y, Huang Z, Wang L, Chen X, Zhang Y, Yang X, Pang D, Kang J, Guo L. Highly efficient and recyclable amorphous Pd (II)/crystal Pd (0) catalyst for boosting Suzuki reaction in aqueous solution. Nano Res. 2022 , 15 , 1193-1198. 56. Díaz‐Marta A S, Yañez S, Lasorsa E, Pacheco P, Tubío C R, Rivas J, Piñeiro Y, Gómez M A G, Amorín M, Guitián F. Integrating Reactors and Catalysts through Three-Dimensional Printing: Efficiency and Reusability of an Impregnated Palladium on Silica Monolith in Sonogashira and Suzuki Reactions. ChemCatChem 2020 , 12 , 1762-1771. 57. Lu X, Yu Q, Tao X, Wang T, Zhang K, Li B. Magnetic PdOx/NiFe 2 O 4 hybrid nanofibers with high catalysis and reusability for Suzuki coupling reactions. Colloids Surf., A 2021 , 610 , 125914. 58. Peng H, Zhang X, Papaefthimiou V, Pham-Huu C, Ritleng V. Pd-functionalized polydopamine-coated polyurethane foam: a readily prepared and highly reusable structured catalyst for selective alkyne semi-hydrogenation and Suzuki coupling under air. Green Chem. 2023 , 25 , 264-279. 59. Huang X, Chen H, Shi Z, Xing G, Shao L, Qi C. Palladium nanoparticles embedded polyimide derived carbon nanofibers for Suzuki reactions. J. Phys. Chem. Solids 2024 , 188 , 111927. 60. Cui S, Xu D, Wang Z, Wang L, Zhao Y, Deng W, Zhao Q, Wu M. Pd Nanoparticles Immobilized on Pyridinic N-Rich Carbon Nanosheets for Promoting Suzuki Cross-Coupling Reactions. Nanomaterials 2024 , 14, 1690. 61. Pan S, Li W, Liu D, Mamba B B, Gui J. Towards effective Pd nanoparticles immobilization on NH 2 -MIL-53 (Al) coated cellulose fiber: A stable and efficient catalyst for Suzuki reaction. Int. J. Biol. Macromol. 2025 : 141750. Manuscript received: XXXX, 2025 Manuscript revised: XXXX, 2025 Manuscript accepted: XXXX, 2025 Version of record online: XXXX, 2025 Left to Right: Fuqing Lu, Cui Wang, Yuanyuan Zhang, Daixin Zhao, Yongnan Xu, Yajun Liu, Yan Xiao Entry for the Table of Contents Facile Preparation of Pd/BN Nanocatalyst for Suzuki Reaction: Synergistic Boron Nitride Effect in a Green Solvent System Fuqing Lu,† Cui Wang,† Yuanyuan Zhang, Daixin Zhao, Yongnan Xu,* Yajun Liu,* Yan Xiao* Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.202500XXX Pd/BN nanocatalyst, synthesized by an in situ pyrolysis method, exploit the high temperature stability and electron transfer properties of BN to enhance catalytic performance, achieving up to 99% yield in Suzuki reactions at room temperature, with excellent stability and recyclability over 10 cycles, making it a promising, scalable catalyst for sustainable C-C coupling reactions. 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Keywords boron nitride support catalytic reusability electron transfer interactions pd/bn nanocatalyst suzuki reaction Authors Affiliations Fuqing Lu Shenyang Pharmaceutical University View all articles by this author Cui Wang Shenyang Pharmaceutical University View all articles by this author Yuanyuan Zhang Shenyang Pharmaceutical University View all articles by this author Daixin Zhao Shenyang Pharmaceutical University View all articles by this author Yongnan Xu Shenyang Pharmaceutical University View all articles by this author Yajun Liu Shenyang Pharmaceutical University View all articles by this author Yan Xiao [email protected] Shenyang Pharmaceutical University View all articles by this author Metrics & Citations Metrics Article Usage 162 views 121 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Fuqing Lu, Cui Wang, Yuanyuan Zhang, et al. 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