Advancing metal cluster-based electrocatalysis for C-N synthesis: Fundamental, design strategies, and applications

doi:10.1016/S1872-2067(26)65185-6

Chinese Journal of Catalysis ›› 2026, Vol. 90: 82-116.DOI: 10.1016/S1872-2067(26)65185-6

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Advancing metal cluster-based electrocatalysis for C-N synthesis: Fundamental, design strategies, and applications

Irshad Ahmad^a^,^b, Shasha Wang^a^,^*(), Mohammed Qasem Alfaifi^c, Yousef I. Alrashed^d, Fahad M. Albaqi^d, Gao Li^a^,^*()

^a College of Chemistry and Environmental Science, Inner Mongolia Normal University, Hohhot 010022, Inner Mongolia, China
^b Department of Physics, University of Agriculture, Faisalabad 38040, Pakistan
^c Hydrogen Technologies Institute, King Abdulaziz City for Science and Technology (KACST), Riyadh 11442, Saudi Arabia
^d Refining Technologies and Petrochemicals Institute (RTPI), King Abdulaziz City for Science and Technology (KACST), Riyadh 11442, Saudi Arabia

Received:2026-01-21 Accepted:2026-03-20 Online:2026-11-05 Published:2026-09-09
About author:Shasha Wang (Inner Mongolia Normal University) received his B.A. degree from Inner Mongolia University of Technology (China, 2011), Master from Dalian Maritime University (2013) and Ph.D. from Inner Mongolia University (China, 2018). And then she joined Inner Mongolia Normal University as a Associate Professor. Her current research interests include the controlled synthesis of nanomaterials (e.g. rare-earth upconversion luminescent materials) and their applications in energy catalysis. She has published > 10 peer-reviewed papers and granted 2 authorized patents.
Gao Li (Inner Mongolia Normal University) received his B.A. degree from Hunan Normal University (China) in 2004, and Ph.D. degree from Shanghai Jiaotong University (China) in 2011. He carried out postdoctoral research at Carnegie Mellon University (USA. 2011 to 2014). And then he worked for State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences from 2014 to 2025. After that he joined Inner Mongolia Normal University. His current research interests focused on the preparation and application of gold clusters. His research interests mainly focus on (i) Synthesis and application of metal nanoclusters: structure-composition-function correlations, and (ii) Functionalization of metal nanoclusters for emerging deployments: structure-activity correlation structure-performance relationship. He has published over 200 peer-reviewed papers.
First author contact:CRediT authorship contribution statement
Irshad Ahmad: Writing-original draft, review and editing manuscript. Shasha Wang: Writing - original draft, validation. Qasem Alfaifi: Review and editing manuscript. Yousef I. Arashed: Review and editing manuscript. Fahad M. Albaqi: Review and editing manuscript. Gao Li: Conceptualization, funding acquisition, Writing - review.
Supported by:
National Natural Science Foundation of China(22065029)

Abstract

Abstract:

The escalating demand for sustainable nitrogen-containing chemicals calls for transformative electrocatalytic strategies that can precisely orchestrate C-N bond formation. Atomically defined metal nanoclusters have emerged as a frontier in electrocatalysis, enabling the direct synthesis of chemicals via C-N coupling. Their discrete electronic structures and tunable ligand environments permit atomic-level control over adsorption, activation, and proton-electron transfer dynamics, overcoming the intrinsic kinetic and thermodynamic challenges of multi-electron C-N coupling reactions. Here, we present a comprehensive overview of cluster-based electrocatalysts, encompassing cluster properties, synthetic routes, mechanistic insights, performance descriptors critical for evaluating catalytic efficiency, and their applications in the synthesis of urea, ammonia, amines, amides, oximes, and amino acids. We focus on the correlations between cluster composition, size, and local coordination in dictating product distribution and catalytic durability. Finally, we identify current bottlenecks in stability, scalability, and industrial integration, and propose rational design principles for engineering next-generation clusters to achieve sustainable, high-value nitrogen chemical production. This review frames a roadmap for exploiting atomic precision in electrocatalysis, charting a path toward transformative C-N bond-forming technologies.

Key words: Electrocatalyst, Metal clusters, C-N coupling, Synthesis methods, Faradic efficiency

Irshad Ahmad, Shasha Wang, Mohammed Qasem Alfaifi, Yousef I. Alrashed, Fahad M. Albaqi, Gao Li. Advancing metal cluster-based electrocatalysis for C-N synthesis: Fundamental, design strategies, and applications[J]. Chinese Journal of Catalysis, 2026, 90: 82-116.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65185-6

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Figures/Tables 14

Fig. 1. Schematic illustration of this review.

Fig. 2. Timeline of cluster-based electrocatalysts for CO2RR, HER, NH3 synthesis, OER, amino acid, oxime, and amine synthesis reactions is outlined.

Fig. 3. Properties of nanoclusters for electrocatalytic C-N coupling reactions.

Fig. 4. Schematic illustration of significant evaluation indices for electrocatalytic performance.

Fig. 5. Schematic illustration of urea synthesis via electroreduction vs. electrocatalytic C-N coupling under ambient conditions.

Fig. 6. The advantages and disadvantages of different synthesis methods for cluster-based electrocatalysts.

Fig. 7. (a,b) FEs comparison of Pd4Cu1-Ni(OH)2 and Pd4Cu1-FeNi(OH)2 for electrosynthesis of urea. Reprinted with permission from Ref. [11]. Copyright 2024, John Wiley and Sons. (c) In-situ FTIR spectroscopy analysis under applied bias for Cu1-CeO2 during electrocatalytic CO2-NO3-electroreduction. Reprinted with permission from Ref. [13]. Copyright 2023, John Wiley and Sons. (d) Various intermediates’ free energy and reaction routes on POP in the electroreduction of nitrogen and carbon dioxide. Reprinted with permission from Ref. [12]. Copyright 2024, Elsevier B.V.

Fig. 8. STEM image (a), Fe 2p (b), and N 1s (c) XPS spectra, and potential dependent urea synthesis performance (d) of FeNC-Fe1N4. Reprinted with permission from Ref. [16]. Copyright 2024, John Wiley and Sons. TGA analysis (e) and UV-vis spectra (f) verifying the light resistance of Au13Ag12:BMIm. Reprinted with permission from Ref. [17]. Copyright 2025, John Wiley and Sons.

Fig. 9. (a) Synthesis scheme of Ni6@CuFe-LDH. (b) Mechanistic pathway of CuFe-LDH and Ni6@CuFe-LDH. Reprinted with permission from Ref. [18]. Copyright 2025, American Chemical Society. Synthesis (c) and electroreduction NO3- to NH3 (d) over clusters (Fe2M-MOF, M = Fe, Co, Ni, Zn). Reprinted with permission from Ref. [41]. Copyright 2022, John Wiley and Sons.

Fig. 10. (a) Synthesis scheme of Ru1Cu SAA. Reprinted with permission from Ref. [46]. Copyright 2023, Springer Nature. Catalytic performance (b) and durability (c) of Cu12Ag17, Cu12Ag16Au1 and Ag28Au1 for the formylation of CO2 with secondary amines. Reprinted with permission from Ref. [48]. Copyright 2023, American Chemical Society.

Fig. 11. (a) Synthesis scheme. (b) ATR-SEIRAS measurements of Ag16Cu18(C≡C-C6H11)24 nanocluster. Reprinted with permission from Ref. [119]. Copyright 2023, John Wiley and Sons. (c) DFT and (d) electroreduction route of NO3− to NH2OH over Ag4Pd2-S-Ti4. Reprinted with permission from Ref. [50]. Copyright 2025, John Wiley and Sons.

Fig. 12. Cu k-edge XANES (a) and k3-weighted FT-EXAFS (b) spectra of Cu-SAs-CBC and Cu-SAs/ACs-CBC. Reprinted with permission from Ref. [64]. Copyright 2023, John Wiley and Sons. Synthesis scheme (c) and FE (d) of cyclohexanone oxime. Reprinted with permission from Ref. [65]. Copyright 2024, John Wiley and Sons.

Fig. 13. Synthesis scheme (a) and EXFAS spectra (b) of AD-Fe/NC. Synthesis scheme (c) and trinuclear copper sites (d) for F-Cu3-OFobtained from XANES analysis. Reprinted with permission from Refs. [66] and [67]. Copyright 2024, American Chemical Society and Elsevier B.V.

Fig. 14. Schematic illustration of unaddressed current gaps, research targets, and future avenues for cluster-based electrocatalysts for C-N coupling reactions [165-168].

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Advancing metal cluster-based electrocatalysis for C-N synthesis: Fundamental, design strategies, and applications

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