Configured droplet reactor by Pd/g-C3N4 for the Suzuki-Miyaura cross-coupling reaction under water condition

doi:10.1016/j.cjche.2025.02.004

Abstract

Abstract: The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds. Currently, the organic solvents employed during reaction may cause serious environmental problems. Moreover, the low solubility of inorganic bases in organic solvents leads to enormous mass transfer resistance. To address this issue, the Pickering droplets reactor stabilized by Pd/g-C₃N₄ at substrate-water two-phase interface is reported. Benefiting from the hydrophobic conjugated framework and hydrophilic terminal groups, Pd/g-C₃N₄ can configure stable Pickering emulsion without additional functionalization. The Pd loaded catalysts exhibits excellent performance (TOF = 21852 h^-1) for the Suzuki-Miyaura coupling reaction, which is deriving from unique electronic structure of g-C₃N₄ and high interfacial area of emulsion. Moreover, there is no clear decrease in reactivity after six cycles (conversion >86%). In this study, the organic solvent was replaced by reaction substrate, and the high activity can be achieved for various halogenated aromatic hydrocarbons and their derivatives.

Key words: Pickering emulsion, G-C₃N₄, Suzuki-Miyaura cross-coupling, Pd nanoparticles, Droplet reactor

摘要： The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds. Currently, the organic solvents employed during reaction may cause serious environmental problems. Moreover, the low solubility of inorganic bases in organic solvents leads to enormous mass transfer resistance. To address this issue, the Pickering droplets reactor stabilized by Pd/g-C₃N₄ at substrate-water two-phase interface is reported. Benefiting from the hydrophobic conjugated framework and hydrophilic terminal groups, Pd/g-C₃N₄ can configure stable Pickering emulsion without additional functionalization. The Pd loaded catalysts exhibits excellent performance (TOF = 21852 h^-1) for the Suzuki-Miyaura coupling reaction, which is deriving from unique electronic structure of g-C₃N₄ and high interfacial area of emulsion. Moreover, there is no clear decrease in reactivity after six cycles (conversion >86%). In this study, the organic solvent was replaced by reaction substrate, and the high activity can be achieved for various halogenated aromatic hydrocarbons and their derivatives.

关键词: Pickering emulsion, G-C₃N₄, Suzuki-Miyaura cross-coupling, Pd nanoparticles, Droplet reactor

Lulu Xing, Mingshuang Li, Yuanyuan Shan, Xingbao Wang. Configured droplet reactor by Pd/g-C₃N₄ for the Suzuki-Miyaura cross-coupling reaction under water condition[J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 232-240.

Lulu Xing, Mingshuang Li, Yuanyuan Shan, Xingbao Wang. Configured droplet reactor by Pd/g-C₃N₄ for the Suzuki-Miyaura cross-coupling reaction under water condition[J]. 中国化学工程学报, 2025, 81(5): 232-240.

References

[1] T. Niwa, Y. Uetake, M. Isoda, T. Takimoto, M. Nakaoka, D. Hashizume, H. Sakurai, T. Hosoya, Lewis acid-mediated suzuki-miyaura cross-coupling reaction, Nat. Catal. 4 (2021) 1080-1088.
[2] N.H. Angello, V. Rathore, W. Beker, A. Wolos, E.R. Jira, R. Roszak, T.C. Wu, C.M. Schroeder, A. Aspuru-Guzik, B.A. Grzybowski, M.D. Burke, Closed-loop optimization of general reaction conditions for heteroaryl Suzuki-Miyaura coupling, Science 378 (6618) (2022) 399-405.
[3] M.A. Almaradhi, H.M.A. Hassan, M.S. Alhumaimess, Fe₃O₄-carbon spheres core-shell supported palladium nanoparticles: a robust and recyclable catalyst for suzuki coupling reaction, Chin. J. Chem. Eng. 51 (2022) 75-85.
[4] J.Y. Chen, Y.X. Yang, C.H. Wu, L. Huo, X.G. Xie, H.L. Li, X.G. She, De novo diastereoselective synthesis of 1-hydroxyl allogibberic methyl ester en route to diverse bioactive molecules, Org. Lett. 24 (35) (2022) 6402-6406.
[5] C. Yang, L. Zhang, C.X. Lu, S.Y. Zhou, X.X. Li, Y.W. Li, Y. Yang, Y. Li, Z.R. Liu, J.L. Yang, K.N. Houk, F.Y. Mo, X.F. Guo, Unveiling the full reaction path of the Suzuki-Miyaura cross-coupling in a single-molecule junction, Nat. Nanotechnol. 16 (11) (2021) 1214-1223.
[6] Y. Watanabe, H. Morozumi, H. Mutoh, K. Hagiwara, M. Inoue, Total synthesis of (-)-batrachotoxin enabled by a Pd/Ag-promoted suzuki-miyaura coupling reaction, Angew. Chem. Int. Ed 62 (40) (2023) e202309688.
[7] D. Liu, Y.C. Yao, Z.Y. Sun, Z.H. Xia, Z. Chen, Highly effective photoativation Pd catalyst for Suzuki coupling reaction, Mol. Catal. 551 (2023) 113659.
[8] K.R. Chaudhari, A.P. Wadawale, A.K. Pathak, S. Dey, Linkage isomers of triangular Pd metallacycles and catalysis in aqueous suzuki coupling reaction, Inorg. Chem. 63 (2) (2024) 1427-1438.
[9] R. Pocklanova, I.R. Warkad, R. Prucek, A. Balzerova, A. Panacek, R.G. Kadam, L. Kvitek, M.B. Gawande, Nanodiamond supported ultra-small palladium nanoparticles as an efficient catalyst for suzuki cross-coupling reactions, Catalysts 14 (1) (2024) 53.
[10] B. Kim, H. Cho, Y. Jeon, S. Chun, B. Bayarkhuu, J. Byun, H. Lee, The role of immobilization supports for light-assisted Suzuki coupling reaction with low-loading Pd nanocatalyst, Catal. Commun. 187 (2024) 106856.
[11] J.L. Lu, Z.Z. Chen, Y. Shen, H. Yuan, X.H. Sun, J.H. Hou, F. Guo, C.S. Li, W.L. Shi, Boosting photothermal-assisted photocatalytic H₂ production over black g-C₃N₄ nanosheet photocatalyst via incorporation with carbon dots, J. Colloid Interface Sci. 670 (2024) 428-438.
[12] M.C. D’Alterio, E. Casals-Cruanas, N.V. Tzouras, G. Talarico, S.P. Nolan, A. Poater, Mechanistic aspects of the palladium-catalyzed suzuki-miyaura cross-coupling reaction, Chemistry 27 (54) (2021) 13481-13493.
[13] Y.F. Jiang, B.Q. Xie, J.S. Zhang, Highly reactive and reusable heterogeneous activated carbons-based palladium catalysts for Suzuki-Miyaura reaction, Chin. J. Chem. Eng. 60 (2023) 165-172.
[14] X.L. Guo, H. Dang, S.R. Wisniewski, E.M. Simmons, Nickel-catalyzed suzuki-miyaura cross-coupling facilitated by a weak amine base with water as a cosolvent, Organometallics 41 (11) (2022) 1269-1274.
[15] P. Chatelain, A. Sau, C.N. Rowley, J. Moran, Suzuki-miyaura coupling of (hetero)aryl sulfones: complementary reactivity enables iterative polyaryl synthesis, Angew. Chem. Int. Ed 58 (42) (2019) 14959-14963.
[16] Y. Shen, Y.H. Wang, P.N. Shan, R. Xu, X.H. Sun, J.H. Hou, F. Guo, C.S. Li, W.L. Shi, Boosted photo-self-Fenton degradation activity by Fe-doped carbon dots as dual-function active sites for in situ H₂O₂ generation and activation, Sep. Purif. Technol. 353 (2025) 128529.
[17] E.K. Reeves, E.D. Entz, S.R. Neufeldt, Chemodivergence between electrophiles in cross-coupling reactions, Chemistry 27 (20) (2021) 6161-6177.
[18] O.Y. Yuen, S.S. Ng, W.H. Pang, C.M. So, Palladium-catalyzed chemoselective Suzuki-Miyaura cross-coupling reaction of poly(pseudo)halogenated arenes, J. Organomet. Chem. 1005 (2024) 122983.
[19] B.S. Kadu, Suzuki-Miyaura cross coupling reaction: recent advancements in catalysis and organic synthesis, Catal. Sci. Technol. 11 (4) (2021) 1186-1221.
[20] P. Houbing Zou, P. Qibiao Li, R.Y. Zhang, Z.S. Xiong, B.H. Li, P. Junhao Wang, P. Runwei Wang, P. Qianrong Fang, P. Hengquan Yang, Amphiphilic covalent organic framework nanoparticles for Pickering emulsion catalysis with size selectivity, Angew. Chem. Int. Ed. 63 (13) (2024) e202314650.
[21] H.B. Zou, H. Shi, S.J. Hao, Y.J. Hao, J. Yang, X.X. Tian, H.Q. Yang, Boosting catalytic selectivity through a precise spatial control of catalysts at Pickering droplet interfaces, J. Am. Chem. Soc. 145 (4) (2023) 2511-2522.
[22] Y.Y. Shan, C. Yu, M.D. Zhang, Q.B. Wei, J.L. An, H.H. Lv, L. Ni, J.S. Qiu, Passivating the pH-responsive sites to configure a widely pH-stable emulsifier for high-efficiency benzyl alcohol oxidation, ChemSusChem 15 (7) (2022) e202102473.
[23] Y.B. Zhang, R. Ettelaie, B. Binks, H.Q. Yang, Highly selective catalysis at the liquid-liquid interface microregion, ACS Catal., (2023).
[24] A.M.B. Rodriguez, Catalysis in Pickering emulsions, Soft Matter 16 (45) (2020) 10221-10243.
[25] J.J. Xu, W. Xu, D.Y. Sun, H.H. Xiao, Z.Z. Yang, The stepwise organization of nanoparticles into a Pickering emulsion, Soft Matter 17 (7) (2021) 1796-1801.
[26] Y. Shen, X. Du, Y.X. Shi, L.J. Nguetsa Kuate, Z.Z. Chen, C. Zhu, L. Tan, F. Guo, S.J. Li, W.L. Shi, Bound-state electrons synergy over photochromic high-crystalline C₃N₅ nanosheets in enhancing charge separation for photocatalytic H₂ production, Adv. Powder Mater. 3 (4) (2024) 100202.
[27] Y.J. Hao, S.J. Hao, Q.B. Li, X. Liu, H.B. Zou, H.Q. Yang, Metal-nanoparticles-loaded ultrathin g-C₃N₄ nanosheets at liquid-liquid interfaces for enhanced biphasic catalysis, ACS Appl. Mater. Interfaces 13 (39) (2021) 47236-47243.
[28] S. Lu, D.J. Yang, M. Wang, M.Z. Yan, Y. Qian, D.F. Zheng, X.Q. Qiu, Pickering emulsions synergistic-stabilized by amphoteric lignin and SiO₂ nanoparticles: Stability and pH-responsive mechanism, Colloids Surf. A Physicochem. Eng. Aspects 585 (2020) 124158.
[29] B.Y. Su, X.Q. Ma, L.T. Ran, S.W. Wu, B.L. Hou, Improving the photodegradation efficiency of POPs in oily sewage: Design and synthesis of G-C₃N₄-based photocatalysts incorporating a Pickering emulsion catalytic strategy, J. Environ. Chem. Eng. 11 (6) (2023) 111297.
[30] Z.Z. Su, J.L. Zhang, Z.H. Tan, J.Y. Hu, F.T. Zhang, R. Duan, L. Yao, B.X. Han, Y.Z. Zhao, Y.S. Yang, Facilitated photocatalytic H₂ production on Cu-coordinated mesoporous g-C₃N₄nanotubes, Green Chem. 25 (7) (2023) 2577-2582.
[31] X.H. Sun, Z.Z. Chen, Y. Shen, H.Y. Qin, H. Yuan, J.L. Lu, F. Guo, C.S. Li, W.L. Shi, Efficient photothermal-assisted photocatalytic H₂ production using carbon dots-infused g-C₃N₄ nanoreactors synthesized via one-step template-free thermal polymerization, Chem. Eng. J. 488 (2024) 151041.
[32] Y. Huang, S.L. Yang, M.Y. Jiang, J. Li, L. Peng, C.Y. Cao, W.G. Song, Facile synthesis of Pd nanoparticles incorporated into ultrathin crystalline g-C₃N₄ with enhanced photocatalytic performance, Cryst. Growth Des. 20 (11) (2020) 7526-7532.
[33] X.Y. Jiang, X. Li, Y.M. Liu, H.F. Zhai, G.K. Wang, The oxidative thermal exfoliation-dependent microstructure and photocatalytic performance of g-C₃N₄ nanosheets, Diam. Relat. Mater. 143 (2024) 110918.
[34] S.Y. Hou, C. Yu, X.D. Song, Y.W. Ding, J.W. Chang, Y.B. Liu, L. Chen, Q.B. Wei, X.B. Zhang, J.S. Qiu, Modulating in-plane defective density of carbon nanotubes by graphitic carbon nitride quantum dots for enhanced triiodide reduction, Adv. Funct. Mater. 33 (23) (2023) 2212112.
[35] Y. Guo, J.T. Yang, J.Y. Zhuang, H.M. Sun, H.W. Zhang, Y.Y. Yue, H.B. Zhu, X.J. Bao, P. Yuan, Selectively catalytic hydrogenation of styrene-butadiene rubber over Pd/g-C₃N₄ catalyst, Appl. Catal. A Gen. 589 (2020) 117312.
[36] A.E. ElMetwally, M.S. Sayed, Y.Q. Zhou, J.B. Domena, J.J. Shim, R.M. Leblanc, M.R. Knecht, L.G. Bachas, Photocatalytic partial oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran using exfoliated g-C₃N₄/Pd nanoarchitectures, J. Phys. Chem. C 126 (37) (2022) 15671-15684.
[37] C. Rajalakshmi, A. Krishnan, S. Saranya, G. Anilkumar, V.I. Thomas, A detailed theoretical investigation to unravel the molecular mechanism of the ligand-free copper-catalyzed Suzuki cross-coupling reaction, Org. Biomol. Chem. 20 (22) (2022) 4539-4552.
[38] D.C.F.R.A.C. Lima, A.S.M.C. Rodrigues, D.V.L.M. Silva, P.A.M.S. Silva, P.L.M.N.B.F. Santos, Role of the base and control of selectivity in the suzuki-miyaura cross-coupling reaction, ChemCatChem 6 (5) (2014) 1291-1302.
[39] P. Bhuyan, A.J. Bhuyan, P.J. Gogoi, A. Mahanta, C. Tamuly, L. Saikia, Pd-NPs@MMT-K10 catalysis of suzuki-miyaura cross-coupling reaction: in situ generation and ex situ use, Catal. Lett. 152 (9) (2022) 2705-2715.
[40] M. Dabiri, H. Fazli, N. Salarinejad, S.K. Movahed, Pd nanoparticles supported on cubic shaped ZIF-based materials and their catalytic activates in organic reactions, Mater. Res. Bull. 133 (2021) 111015.
[41] E. Niknam, F. Panahi, A. Khalafi-Nezhad, Immobilized Pd on a NHC functionalized metal-organic framework MIL-101(Cr): an efficient heterogeneous catalyst in Suzuki-Miyaura coupling reaction in water, Appl. Organomet. Chem. 34 (4) (2020) e5470.
[42] C.T. Zhong, H.L. Tang, B.Q. Cui, Y.H. Shi, C.S. Cao, Pd-NHC catalyzed Suzuki cross-coupling of benzyl ammonium salts, Res. Chem. Intermed. 48 (10) (2022) 4017-4032.
[43] N. Bugday, S. Altin, S. Yasar, Palladium nanoparticle supported on nitrogen-doped porous carbon: Investigation of structural properties and catalytic activity on Suzuki-Miyaura reactions, Appl Organomet Chem 35 (11) (2021) e6403.
[44] M. Beiranvand, D. Habibi, The Pd(0) and Pd(II) SBA-TU-anchored catalysts in the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions: a comparative catalytic study, J. Mol. Struct. 1273 (2023) 134174.
[45] E.M. Zhou, J.Z. Jin, K. Zheng, L.T. Zhang, H. Xu, C. Shen, Novel recyclable Pd/H-MOR catalyst for suzuki-miyaura coupling and application in the synthesis of crizotinib, Catalysts 11 (10) (2021) 1213.
[46] X.X. Jia, J.W. Zhao, Y.J. Lv, X.L. Fu, Y.J. Jian, W.Q. Zhang, Y.Y. Wang, H.M. Sun, X.X. Wang, J.L. Long, P. Yang, Q. Gu, Z.W. Gao, Low-crystalline PdCu alloy on large-area ultrathin 2D carbon nitride nanosheets for efficient photocatalytic Suzuki coupling, Appl. Catal. B Environ. 300 (2022) 120756.
[47] B. Liu, Z. Yan, T. Xu, C.P. Li, R. Gao, H.G. Hao, J. Bai, Co-construction of oxygen vacancies and heterojunctions on CeO₂ via one-step Fe doping for enhanced photocatalytic activity in Suzuki reaction, Chem. Eng. J. 442 (2022) 136226.
[48] A. Aschenaki, F. Ren, J. Liu, W. Zheng, Q. Song, W. Jia, J.J. Bao, Y. Li, Preparation of a magnetic and recyclable superparamagnetic silica support with a boronic acid group for immobilizing Pd catalysts and its applications in Suzuki reactions, RSC Adv. 11 (53) (2021) 33692-33702.
[49] F.F. Ren, S.M. Li, W.Q. Zheng, Q.Y. Song, W.H. Jia, Y.Q. Nan, H.J. Jia, J. Liu, J.J. Bao, Y.X. Li, Preparation of a novel heterogeneous palladium nanocatalyst based on carboxyl modified magnetic nanoparticles and its applications in Suzuki-Miyaura coupling reactions, Colloids Surf. A Physicochem. Eng. Aspects 642 (2022) 128611.

Configured droplet reactor by Pd/g-C₃N₄ for the Suzuki-Miyaura cross-coupling reaction under water condition

Configured droplet reactor by Pd/g-C₃N₄ for the Suzuki-Miyaura cross-coupling reaction under water condition

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