Geometry-Controlled Synergy of Adjacent Cu(I) Sites Enhances C–C Coupling for Efficient CO2-to-C2+ Electroreduction

An Zhang; Yuhua Zhu; Yuhui Tian; Bernt Johannessen; Pria Ramkissoon; Kwun Nam Hui; Guohua Jia; Mingkai Liu; Zhirong Zhang; Jie Zeng

doi:10.1021/jacs.6c01543

Geometry-Controlled Synergy of Adjacent Cu(I) Sites Enhances C–C Coupling for Efficient CO₂-to-C₂₊ Electroreduction

An Zhang
, Yuhua Zhu
, Yuhui Tian^*
, Bernt Johannessen
, Pria Ramkissoon
, Kwun Nam Hui
, Guohua Jia
, Mingkai Liu
, Zhirong Zhang^*
, Jie Zeng^*

^*Corresponding author for this work

Department of Mechanical Engineering

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

Abstract

The electrochemical reduction of CO₂ to multicarbon (C₂₊) products offers a promising route to sustainable fuels and chemicals, while controlling the critical C–C coupling step remains a fundamental challenge. Here, we demonstrate that engineering the molecular geometry of Cu(I) sites in crystalline Cu-triazine frameworks directly tunes the selectivity of CO₂RR. Two structurally well-defined copper frameworks, the Cu₃I₃-triazine and Cu₂I₂-triazine with different Cu–I–Cu bridge geometries, are employed as catalysts for CO₂ electroreduction. The Cu₂I₂-triazine catalysts achieved a high Faradaic efficiency of 73.7% for C₂₊ products at a current density of −300 mA cm^–2, significantly outperforming the Cu₃I₃-triazine counterpart in CO₂ electroreduction. Through a combination of in situ spectroscopy and density functional theory calculations, we elucidate that the adjacent Cu(I) sites in Cu₂I₂-triazine catalyst facilitate interfacial water dissociation for the stabilization of critical *CHO intermediates, and steer the C–C coupling pathway for efficient C₂₊ formation. This work establishes a direct link between molecular-scale spatial symmetry of molecular catalysts and their catalytic synergy for C₂₊ products in CO₂RR. © 2026 American Chemical Society

Original language	English
Pages (from-to)	20600-20610
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	148
Issue number	20
Online published	14 May 2026
DOIs	https://doi.org/10.1021/jacs.6c01543
Publication status	Published - 27 May 2026

Funding

This work was supported by National Key Research and Development Program of China (2021YFA1500500), CAS Project for Young Scientists in Basic Research (YSBR-051), NSFC (22209164, 22525021, 22221003, 22250007, 22361162655), the Science and Technology Development Fund (FDCT) of Macao S.A.R (0070/2023/AFJ), Fundamental Research Funds for the Central Universities, Special Science and Technology Innovation Program for Carbon Peak and Carbon Neutralization of Jiangsu Province (Grant No. BE2025014), the State Key Laboratory of Catalysis (2024SKL-A-011), University of Science and Technology of China-Xinjiang Normal University Counterpart Cooperation and Development Joint Fund, and International Partnership Program of Chinese Academy of Sciences (123GJHZ2022101GC). J.Z. acknowledges support from the New Cornerstone Science Foundation through the XPLORER PRIZE. This work was partially carried out at the Instruments Center for Physical Science, University of Science and Technology of China. The authors are grateful to the Australian Synchrotron, part of Australia’s Nuclear Science and Technology Organisation (ANSTO) in Melbourne, for providing XAS measurements.

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title = "Geometry-Controlled Synergy of Adjacent Cu(I) Sites Enhances C–C Coupling for Efficient CO2-to-C2+ Electroreduction",

abstract = "The electrochemical reduction of CO2 to multicarbon (C2+) products offers a promising route to sustainable fuels and chemicals, while controlling the critical C–C coupling step remains a fundamental challenge. Here, we demonstrate that engineering the molecular geometry of Cu(I) sites in crystalline Cu-triazine frameworks directly tunes the selectivity of CO2RR. Two structurally well-defined copper frameworks, the Cu3I3-triazine and Cu2I2-triazine with different Cu–I–Cu bridge geometries, are employed as catalysts for CO2 electroreduction. The Cu2I2-triazine catalysts achieved a high Faradaic efficiency of 73.7\% for C2+ products at a current density of −300 mA cm–2, significantly outperforming the Cu3I3-triazine counterpart in CO2 electroreduction. Through a combination of in situ spectroscopy and density functional theory calculations, we elucidate that the adjacent Cu(I) sites in Cu2I2-triazine catalyst facilitate interfacial water dissociation for the stabilization of critical *CHO intermediates, and steer the C–C coupling pathway for efficient C2+ formation. This work establishes a direct link between molecular-scale spatial symmetry of molecular catalysts and their catalytic synergy for C2+ products in CO2RR. {\textcopyright} 2026 American Chemical Society",

author = "An Zhang and Yuhua Zhu and Yuhui Tian and Bernt Johannessen and Pria Ramkissoon and Hui, \{Kwun Nam\} and Guohua Jia and Mingkai Liu and Zhirong Zhang and Jie Zeng",

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T1 - Geometry-Controlled Synergy of Adjacent Cu(I) Sites Enhances C–C Coupling for Efficient CO2-to-C2+ Electroreduction

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AU - Zhu, Yuhua

AU - Tian, Yuhui

AU - Johannessen, Bernt

AU - Ramkissoon, Pria

AU - Hui, Kwun Nam

AU - Jia, Guohua

AU - Liu, Mingkai

AU - Zhang, Zhirong

AU - Zeng, Jie

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Y1 - 2026/5/27

N2 - The electrochemical reduction of CO2 to multicarbon (C2+) products offers a promising route to sustainable fuels and chemicals, while controlling the critical C–C coupling step remains a fundamental challenge. Here, we demonstrate that engineering the molecular geometry of Cu(I) sites in crystalline Cu-triazine frameworks directly tunes the selectivity of CO2RR. Two structurally well-defined copper frameworks, the Cu3I3-triazine and Cu2I2-triazine with different Cu–I–Cu bridge geometries, are employed as catalysts for CO2 electroreduction. The Cu2I2-triazine catalysts achieved a high Faradaic efficiency of 73.7% for C2+ products at a current density of −300 mA cm–2, significantly outperforming the Cu3I3-triazine counterpart in CO2 electroreduction. Through a combination of in situ spectroscopy and density functional theory calculations, we elucidate that the adjacent Cu(I) sites in Cu2I2-triazine catalyst facilitate interfacial water dissociation for the stabilization of critical *CHO intermediates, and steer the C–C coupling pathway for efficient C2+ formation. This work establishes a direct link between molecular-scale spatial symmetry of molecular catalysts and their catalytic synergy for C2+ products in CO2RR. © 2026 American Chemical Society

AB - The electrochemical reduction of CO2 to multicarbon (C2+) products offers a promising route to sustainable fuels and chemicals, while controlling the critical C–C coupling step remains a fundamental challenge. Here, we demonstrate that engineering the molecular geometry of Cu(I) sites in crystalline Cu-triazine frameworks directly tunes the selectivity of CO2RR. Two structurally well-defined copper frameworks, the Cu3I3-triazine and Cu2I2-triazine with different Cu–I–Cu bridge geometries, are employed as catalysts for CO2 electroreduction. The Cu2I2-triazine catalysts achieved a high Faradaic efficiency of 73.7% for C2+ products at a current density of −300 mA cm–2, significantly outperforming the Cu3I3-triazine counterpart in CO2 electroreduction. Through a combination of in situ spectroscopy and density functional theory calculations, we elucidate that the adjacent Cu(I) sites in Cu2I2-triazine catalyst facilitate interfacial water dissociation for the stabilization of critical *CHO intermediates, and steer the C–C coupling pathway for efficient C2+ formation. This work establishes a direct link between molecular-scale spatial symmetry of molecular catalysts and their catalytic synergy for C2+ products in CO2RR. © 2026 American Chemical Society

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