Advances in Multiple Active Site Catalysts for Urea Synthesis via Electrocatalytic C–N Coupling

Yihang Yu; Jingwei Li; Zhongwei Yue; Meiting Guo; Zhishan Li; Mohamed Nawfal Ghazzal; Wei Li; San Ping Jiang; Yi-Bing Cheng; Jianyun Zheng

doi:10.1007/s12209-025-00444-2

Transactions of Tianjin University ›› 2025, Vol. 31 ›› Issue (5) :478 -497. DOI: 10.1007/s12209-025-00444-2

Review

review-article

Advances in Multiple Active Site Catalysts for Urea Synthesis via Electrocatalytic C–N Coupling

Author information +

¹State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070, Wuhan, China

²National Energy Key Laboratory for New Hydrogen-Ammonia Energy Technologies, Foshan Xianhu Laboratory, 528200, Foshan, China

³State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, China

⁴UMR 8000 CNRS, Institut de Chimie Physique, Université Paris-Saclay, 91405, Orsay, France

^a lijingwei@xhlab.cn

^b yibing.cheng@whut.edu.cn

^c jyzheng@hnu.edu.cn

Yihang Yu

Yihang Yu He pursued his master's degree at the School of Materials Science and Engineering, Wuhan University of Technology. Currently, he is a joint-training master's student between Wuhan University of Technology and Foshan Xianhu Laboratory, with his current research focus on electrocatalytic ammonia synthesis.

Dr. Jingwei Li

Jingwei Li is affiliated at the National Energy Key Laboratory for New Hydrogen Ammonia Energy Technologies Foshan Xianhu Laboratory. He earned his Ph.D. from Sun Yat sen University, complemented by joint Ph.D. training at the Université Paris Saclay France. He is also a joint Master's training program at Curtin University, Australia. Following his doctorate, he conducted postdoctoral research at Université Paris Saclay. From September 2022 to September 2024, he served as an Associate Professor at Guangzhou University. Dr. Li's research focuses on heterojunction materials for photo/electrocatalytic nitrogen fixation and hydrogen production.

Zhongwei Yue

Zhongwei Yue obtained his Ph.D. degree in Materials Science at Fuzhou University, China, in June 2023. He is now a postdoc at Foshan Xianhu Laboratory, China. His research interests include development of electrode materials for PCFCs/protonic ceramic electrolysis cells (PCECs) and evolution of electrode/electrolyte interface.

Dr. Meiting Guo

Meiting Guo the assistant research fellow of National Energy Key Laboratory for New Hydrogen-ammonia Energy Technologies, Foshan Xianhu Laboratory. Her research interest focuses on the full coupled multiphysics modeling and performance optimization of large-scale solid oxide fuel cell and solid oxide electrolysis cell, the first-principle calculation, and the materials design based one experiment.

Zhishan Li

Zhishan Li obtained her Ph.D. degree in Chemical Engineering at Nanjing University of Science and Technology, China, in June, 2020. She is now an assistant researcher in Foshan Xianhu Laboratory, China. Her research interests include development of electrode materials for solid oxide fuel cells (SOFCs)/solid oxide electrolysis cells (SOECs) and preparation of renewable synthetic fuels (green hydrogen/green ammonia).

Mohamed Nawfal Ghazzal

Mohamed Nawfal Ghazzal is an Associate Professor at the Université Paris-Saclay. He is now investigating strategies aiming at improving the light harvesting ability, the stability and designing photoactive material, such as core-shell, strong metal-support interactions, perovskites, graphdiyne for photocatalytic applications.

Wei Li

Wei Li is a full professor at Wuhan University of Technology (WHUT). He received his Bachelor’s and Master’s degrees from WHUT in 2006 and 2009, respectively. In 2013, he obtained his PhD degree from the University of New South Wales (UNSW). From 2013 to 2018, he worked as a research fellow at UNSW and Monash University. His current research interest focuses on high-efficiency perovskite solar cells and micro structure characterizations for photovoltaic materials.

Dr. San Ping Jiang

San Ping Jiang is John Curtin Distinguished Emeritus Professor at WASM: Minerals, Energy & Chemical Engineering, Curtin University, Australia and Distinguished Visiting Professor at the Foshan Xianhu laboratory, Foshan, China. He obtained his Bachelor’s degrees from the South China University of Technology and PhD from The City University, London. Before joining Curtin University in 2010, Dr. Jiang worked at Essex University in UK, CSIRO Materials Science and Manufacturing Division, Australia, and Nanyang Technological University in Singapore. Dr Jiang’s research interests encompass both solid oxide and proton exchange membrane fuel cells, water splitting, photocatalysis, nano-structured functional materials and high temperature solid state electrochemistry.

Yi-Bing Cheng

Yi-Bing Cheng Yi-Bing Cheng is a full professor at WHUT, China, and emeritus professor of the Department of Materials Science and Engineering, Monash University, Australia. He is an elected fellow of the Australian Academy of Technology and Engineering.

Jianyun Zheng

Jianyun Zheng received his Ph.D. degree in Physical Chemistry from Shanghai Institute of Ceramics, Chinese Academy of Sciences in 2015. From September, 2015 to September, 2019, he successively worked in Lanzhou Institute of Chemical Physics as an assistant research fellow and Hunan University and Curtin University as a united postdoctoral researcher. Currently, he is as professor of College of Chemistry and Chemical Engineering in Hunan University. His main interests focus on the preparation of semiconductor materials, design and assembly of photoelectrodes and photoelectrochemical devices, and their performance in photo(electro) catalysis including nitrogen reduction reaction, lithium extraction and water splitting.

Show less

History +

PDF

Abstract

Electrocatalytic C–N coupling technology offers a promising route for green and sustainable urea synthesis. However, this route faces challenges of low urea yield and Faradaic efficiency due to the high dissociation energy of atomic bonds in reactants, complex reaction intermediates, high reaction energy barriers, and competing side reactions. As C–N coupling involves the synergistic action of two or more active sites, it is crucial to develop efficient multi-active-site catalysts to address these challenges. This review analyzes the reaction mechanisms of electrocatalytic C–N coupling for urea synthesis and summarizes effective strategies to achieve multi-active-site catalysts, including heteroatom doping, defect engineering, heterojunctions, and diatomic catalysts. Furthermore, based on this analysis, we propose the universal design principles for high-efficiency multi-activesite catalysts.

Keywords

Electrocatalysis / Urea / Catalyst design / C–N coupling / Multi-active-site catalyst

Cite this article

Download citation ▾

Yihang Yu, Jingwei Li, Zhongwei Yue, Meiting Guo, Zhishan Li, Mohamed Nawfal Ghazzal, Wei Li, San Ping Jiang, Yi-Bing Cheng, Jianyun Zheng. Advances in Multiple Active Site Catalysts for Urea Synthesis via Electrocatalytic C–N Coupling. Transactions of Tianjin University, 2025, 31(5): 478-497 DOI:10.1007/s12209-025-00444-2

登录浏览全文

4963

注册一个新账户忘记密码

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Wang D, Botte GG. In situ x-ray diffraction study of urea electrolysis on nickel catalysts. ECS Electrochem Lett, 2014, 3(9): H29-H32.

[2]	Li JX, Wang SL, Sun SJ, et al. . A review of hetero-structured Ni-based active catalysts for urea electrolysis. J Mater Chem A, 2022, 10(17): 9308-9326.

[3]	Zhao XF, Li JQ, Zhang J, et al. . Urea electrooxidation: research progress and application of supported nickel-based catalysts. Ionics, 2023, 29(8): 2969-2987.

[4]	Liu SX, Wang TY, Elbaz L, et al. . Recent progress in C–N coupling for electrochemical CO₂ reduction with inorganic nitrogenous species in aqueous solution. Mater Rep Energy, 2023, 3(1): 100178

[5]	Zhu XR, Zhou XC, Jing Y, et al. . Electrochemical synthesis of urea on MBenes. Nat Commun, 2021, 12(1): 4080.

[6]	Chen C, He NH, Wang SY. Electrocatalytic C-N coupling for urea synthesis. Small Sci, 2021, 1(11): 2100070.

[7]	Wang YJ, Chen DW, Chen C, et al. . Electrocatalytic urea synthesis via C–N coupling from CO₂ and nitrogenous species. Acc Chem Res, 2024, 57(2): 247-256.

[8]	Zhao YL, Ding YX, Li WL, et al. . Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites. Nat Commun, 2023, 14(1): 4491.

[9]	Li JW, Li SK, Zhang YH, et al. . Principles of designing electrocatalysts to boost C–N coupling reactions for urea synthesis. EcoEnergy, 2024, 2(4): 679-694.

[10]	Tao ZX, Rooney CL, Liang YY, et al. . Accessing organonitrogen compounds via C–N coupling in electrocatalytic CO₂ reduction. J Am Chem Soc, 2021, 143(47): 19630-19642.

[11]	Wan YC, Zheng MY, Yan W, et al. . Fundamentals and rational design of heterogeneous C–N coupling electrocatalysts for urea synthesis at ambient conditions. Adv Energy Mater, 2024, 14(28): 2303588.

[12]	Liu SS, Wang MF, Cheng QY, et al. . Turning waste into wealth: sustainable production of high-value-added chemicals from catalytic coupling of carbon dioxide and nitrogenous small molecules. ACS Nano, 2022, 16(11): 17911-17930.

[13]	Ji YA, Du J, Chen AB. Review on heteroatom doping carbonaceous materials toward electrocatalytic carbon dioxide reduction. Trans Tianjin Univ, 2022, 28(4): 292-306.

[14]	Li RC, Zhang XY, Qu ZY, et al. . One-step controlled electrodeposition nickel sulfides heterointerfaces favoring the desorption of hydroxyl groups for efficient hydrogen generation. Rare Met, 2024, 43(9): 4377-4386.

[15]	Liu S, Zhao Q, Han X, et al. . Proximity effect of Fe–Zn bimetallic catalysts on CO₂ hydrogenation performance. Trans Tianjin Univ, 2023, 29(4): 293-303.

[16]	Meng NN, Ma XM, Wang CH, et al. . Oxide-derived core–shell Cu@Zn nanowires for urea electrosynthesis from carbon dioxide and nitrate in water. ACS Nano, 2022, 16(6): 9095-9104.

[17]	Lv LY, Tan H, Kong Y, et al. . Breaking the scaling relationship in C−N coupling via the doping effects for efficient urea electrosynthesis. Angew Chem Int Ed, 2024, 63(24): e202401943.

[18]	Wei XX, Chen C, Fu XZ, et al. . Oxygen vacancies-rich metal oxide for electrocatalytic nitrogen cycle. Adv Energy Mater, 2024, 14(1): 2303027.

[19]	Lv CD, Lee C, Zhong LX, et al. . A defect engineered electrocatalyst that promotes high-efficiency urea synthesis under ambient conditions. ACS Nano, 2022, 16(5): 8213-8222.

[20]	Cao N, Quan YL, Guan AX, et al. . Oxygen vacancies enhanced cooperative electrocatalytic reduction of carbon dioxide and nitrite ions to urea. J Colloid Interface Sci, 2020, 577: 109-114.

[21]	Sun MM, Wu GZ, Jiang JD, et al. . Carbon-anchored molybdenum oxide nanoclusters as efficient catalysts for the electrosynthesis of ammonia and urea. Angew Chem Int Ed, 2023, 62(19): e202301957.

[22]	Liu SL, Yin SL, Wang ZQ, et al. . AuCu nanofibers for electrosynthesis of urea from carbon dioxide and nitrite. Cell Rep Phys Sci, 2022, 3(5): 100869.

[23]	Kong LY, Jiao DX, Wang ZX, et al. . Single metal atom anchored on porous boron nitride nanosheet for efficient collaborative urea electrosynthesis: a computational study. Chem Eng J, 2023, 451(3): 138885.

[24]	Meng NN, Huang YM, Liu Y, et al. . Electrosynthesis of urea from nitrite and CO₂ over oxygen vacancy-rich ZnO porous nanosheets. Cell Rep Phys Sci, 2021, 2(12): 100697.

[25]	Mukherjee J, Paul S, Adalder A, et al. . Understanding the site-selective electrocatalytic Co-reduction mechanism for green urea synthesis using copper phthalocyanine nanotubes. Adv Funct Mater, 2022, 32(31): 2200882.

[26]	Chen C, Zhu XR, Wen XJ, et al. . Coupling N₂ and CO₂ in H₂O to synthesize urea under ambient. Nat Chem, 2020, 12(8): 717-724.

[27]	Zhang XR, Zhu XR, Bo SW, et al. . Electrocatalytic urea synthesis with 63.5% faradaic efficiency and 100% N-selectivity via one-step C–N coupling. Angew Chem Int Ed, 2023, 62(33): e202305447.

[28]	Yuan ML, Zhang HH, Xu Y, et al. . Artificial frustrated Lewis pairs facilitating the electrochemical N₂ and CO₂ conversion to urea. Chem Catal, 2022, 2(2): 309-320

[29]	Jiao DX, Dong YL, Cui XQ, et al. . Boosting the efficiency of urea synthesis via cooperative electroreduction of N₂ and CO₂ on MoP. J Mater Chem A, 2023, 11(1): 232-240.

[30]	Zhu CY, Wen CX, Wang M, et al. . Non-metal boron atoms on a CuB₁₂ monolayer as efficient catalytic sites for urea production. Chem Sci, 2022, 13(5): 1342-1354.

[31]	Jiang MH, Zhu MF, Wang MJ, et al. . Review on electrocatalytic coreduction of carbon dioxide and nitrogenous species for urea synthesis. ACS Nano, 2023, 17(4): 3209-3224.

[32]	Camargo JA, Alonso A. Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: a global assessment. Environ Int, 2006, 32(6): 831-849.

[33]	Shibata M, Yoshida K, Furuya N. Electrochemical synthesis of urea on reduction of carbon dioxide with nitrate and nitrite ions using Cu-loaded gas-diffusion electrode. J Electroanal Chem, 1995, 387: 143-145.

[34]	Feng YG, Yang H, Zhang Y, et al. . Te–doped Pd nanocrystal for electrochemical urea production by efficiently coupling carbon dioxide reduction with nitrite reduction. Nano Lett, 2020, 20(11): 8282-8289.

[35]	Lv CD, Zhong LX, Liu HJ, et al. . Selective electrocatalytic synthesis of urea with nitrate and carbon dioxide. Nat Sustain, 2021, 4(10): 868-876.

[36]	Wang C, Yu C, Qian BZ, et al. . FeOOH with low spin state iron as electron acceptors for high yield rate electrosynthesis of urea from nitrate and carbon dioxide. Small, 2024, 20(11): 2307349.

[37]	Qing G, Ghazfar R, Jackowski ST, et al. . Recent advances and challenges of electrocatalytic N₂ reduction to ammonia. Chem Rev, 2020, 120(12): 5437-5516.

[38]	Zhang A, Liang YX, Zhang H, et al. . Doping regulation in transition metal compounds for electrocatalysis. Chem Soc Rev, 2021, 50(17): 9817-9844.

[39]	Ge ZQ, Chu C, Wang C, et al. . Recent progress on layered double hydroxides for electrocatalytic small molecules oxidation to synthesize high-value chemicals and degrade pollutants. Sci Energy Environ, 2024, 1(1): 10.

[40]	Jiang JD, Wu GZ, Sun MM, et al. . Cu–Mo dual sites in Cu-doped MoSe₂ for enhanced electrosynthesis of urea. ACS Nano, 2024, 18(21): 13745-13754.

[41]	Mao YN, Jiang Y, Gou Q, et al. . Indium-activated bismuth-based catalysts for efficient electrocatalytic synthesis of urea. Appl Catal B Environ, 2024, 340: 123189.

[42]	Yu YD, Sun YY, Han JN, et al. . Achieving efficient urea electrosynthesis through improving the coverage of a crucial intermediate across a broad range of nitrate concentrations. Energy Environ Sci, 2024, 17(14): 5183-5190.

[43]	Gao WT, Wu QY, Fan XF, et al. . Promoting electrocatalytic reduction of CO₂ and nitrate to urea on N-doped porous hollow carbon spheres. ACS Appl Mater Interfaces, 2024, 16(38): 50726-50735.

[44]	Song XN, Jin XY, Chen TH, et al. . Boosting urea electrosynthesis via asymmetric oxygen vacancies in Zn-doped Fe₂O₃ catalysts. Angew Chem Int Ed, 2025, 64(28): e202501830.

[45]	Zhang YQ, Tao L, Xie C, et al. . Defect engineering on electrode materials for rechargeable batteries. Adv Mater, 2020, 32(7): 1905923.

[46]	Li W, Wang DD, Zhang YQ, et al. . Defect engineering for fuel-cell electrocatalysts. Adv Mater, 2020, 32(19): 1907879.

[47]	Guo WH, Zhang KX, Liang ZB, et al. . Electrochemical nitrogen fixation and utilization: theories, advanced catalyst materials and system design. Chem Soc Rev, 2019, 54(11): 5735-5735.

[48]	Xu S, Ruan XW, Ganesan M, et al. . Transition metal-based catalysts for urea oxidation reaction (UOR): catalyst design strategies, applications, and future perspectives. Adv Funct Mater, 2024, 34(18): 2313309.

[49]	Zhao TT, Wang SY, Ye DF, et al. . Oxygen-vacancy-engineered Cr₂CO₂ electrocatalysts for efficient urea synthesis from nitrite and carbon monoxide. Appl Catal B Environ Energy, 2025, 372: 125327.

[50]	Wei XX, Wen XJ, Liu YY, et al. . Oxygen vacancy-mediated selective C-N coupling toward electrocatalytic urea synthesis. J Am Chem Soc, 2022, 144(26): 11530-11535.

[51]	Mao YN, Ren F, Gou Q, et al. . Enhanced performance of oxygen vacancy-rich In-TiO₂ materials for electrocatalytic urea synthesis via a relay catalysis strategy. Chem Eng J, 2024, 485: 150052.

[52]	Li ZY, Zhou P, Zhou M, et al. . Synergistic electrocatalysis of crystal facet and O-vacancy for enhancive urea synthesis from nitrate and CO₂. Appl Catal B Environ, 2023, 338: 122962.

[53]	Lv Z, Zhou SL, Zhao L, et al. . Coactivation of multiphase reactants for the electrosynthesis of urea. Adv Energy Mater, 2023, 13(25): 2300946.

[54]	Wang YJ, Zhu XR, An QZ, et al. . Electron deficiency is more important than conductivity in C−N coupling for electrocatalytic urea synthesis. Angew Chem Int Ed, 2024, 63(49): e202410938.

[55]	Wang HL, Zhang LS, Chen ZG, et al. . Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances. Chem Soc Rev, 2014, 43(15): 5234.

[56]	Li HJ, Zhou Y, Tu WG, et al. . State-of-the-art progress in diverse heterostructured photocatalysts toward promoting photocatalytic performance. Adv Funct Mater, 2015, 25(7): 998-1013.

[57]	Li ZX, Hu ML, Wang P, et al. . Heterojunction catalyst in electrocatalytic water splitting. Coord Chem Rev, 2021, 439: 213953.

[58]	Yuan M, Chen J, Bai Y, et al. . Unveiling electrochemical urea Synthesis by Co-activation of CO₂ and N₂ with Mott-Schottky heterostructure catalysts. Angew Chem Int Ed, 2021, 60(19): 10910-10918.

[59]	Yuan ML, Chen JW, Bai YL, et al. . Electrochemical C-N coupling with perovskite hybrids toward efficient urea synthesis. Chem Sci, 2021, 12: 6048-6058.

[60]	Ma LJ, Yuan JL, Liu ZT, et al. . Mesoporous electrocatalysts with p–n heterojunctions for efficient electroreduction of CO₂ and N₂ to urea. ACS Appl Mater Interfaces, 2024, 16(20): 26015-26024.

[61]	Du XH, Li WP, Chang HT, et al. . Dual heterogeneous structures lead to ultrahigh strength and uniform ductility in a Co–Cr–Ni medium-entropy alloy. Nat Commun, 2020, 11(1): 2390.

[62]	Zhang TJ, Walsh AG, Yu JH, et al. . Single-atom alloy catalysts: structural analysis, electronic properties and catalytic activities. Chem Soc Rev, 2021, 50(1): 569-588.

[63]	Xin Y, Li SH, Qian YY, et al. . High-entropy alloys as a platform for catalysis: progress, challenges, and opportunities. ACS Catal, 2020, 10(19): 11280-11306.

[64]	Su B, Cao ZC, Shi ZJ. Exploration of earth-abundant transition metals (Fe Co, and Ni) as catalysts in unreactive chemical bond activations. Acc Chem Res, 2015, 48(3): 886-896.

[65]	Han L, Dong SJ, Wang EK. Transition-metal (Co, Ni, and Fe)-based electrocatalysts for the water oxidation reaction. Adv Mater, 2016, 28(42): 9266-9291.

[66]	Sun ZS, Xiang XY, Zhao QP, et al. . Efficient electrocatalytic urea synthesis from CO₂ and nitrate over the scale-up produced FeNi alloy-decorated nanoporous carbon. Chin J Catal, 2024, 65: 153-162.

[67]	Hou T, Ding JY, Zhang H, et al. . FeNi₃ nanoparticles for electrocatalytic synthesis of urea from carbon dioxide and nitrate. Mater Chem Front, 2023, 7(20): 4952-4960.

[68]	Gawande MB, Goswami A, Felpin FX, et al. . Cu and Cu-based nanoparticles: synthesis and applications in catalysis. Chem Rev, 2016, 116(6): 3722-3811.

[69]	Zhang SB, Geng J, Zhao Z, et al. . High-efficiency electrosynthesis of urea over bacterial cellulose regulated Pd–Cu bimetallic catalyst. EES Catal, 2023, 1: 45-53.

[70]	Yu WT, Porosoff MD, Chen JG. Review of Pt-based bimetallic catalysis: from model surfaces to supported catalysts. Chem Rev, 2012, 112(11): 5780-5817.

[71]	Fan JX, Du HX, Zhao Y, et al. . Recent progress on rational design of bimetallic Pd based catalysts and their advanced catalysis. ACS Catal, 2020, 10(22): 13560-13583.

[72]	Zhang XR, Zhu XR, Bo SW, et al. . Identifying and tailoring C-N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst. Nat Commun, 2022, 13(1): 5337.

[73]	Pan L, Wang JN, Lu F, et al. . Single-atom or dual-atom in TiO₂ nanosheet: Which is the better choice for electrocatalytic urea synthesis?. Angew Chem Int Ed, 2023, 62(8): e202216835.

[74]	Geng J, Ji SH, Jin M, et al. . Ambient electrosynthesis of urea with nitrate and carbon dioxide over iron-based dual-sites. Angew Chem Int Ed, 2023, 62(6): e202210958.