Steering the Reaction Pathway of CO2 Electroreduction by Tuning the Coordination Number of Copper Catalysts

Jiapeng Jiao; Xinchen Kang; Jiahao Yang; Shuaiqiang Jia; Yaguang Peng; Shiqiang Liu; Chunjun Chen; Xueqing Xing; Mingyuan He; Haihong Wu; Buxing Han

doi:10.1021/jacs.4c02607

Steering the Reaction Pathway of CO₂ Electroreduction by Tuning the Coordination Number of Copper Catalysts

J Am Chem Soc. 2024 Jun 12;146(23):15917-15925. doi: 10.1021/jacs.4c02607. Epub 2024 May 28.

Authors

Jiapeng Jiao^{1

2}, Xinchen Kang^{3

4}, Jiahao Yang^{3

4}, Shuaiqiang Jia^{1

2}, Yaguang Peng³, Shiqiang Liu³, Chunjun Chen^{1

2}, Xueqing Xing⁵, Mingyuan He^{1

2}, Haihong Wu^{1

2}, Buxing Han^{1

2

3

4}

Affiliations

¹ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
² Institute of Eco-Chongming, Chongming District, Shanghai 202162, China.
³ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
⁴ School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
⁵ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.

PMID: 38805725
DOI: 10.1021/jacs.4c02607

Abstract

Cu-based catalysts are optimal for the electroreduction of CO₂ to generate hydrocarbon products. However, controlling product distribution remains a challenging topic. The theoretical investigations have revealed that the coordination number (CN) of Cu considerably influences the adsorption energy of *CO intermediates, thereby affecting the reaction pathway. Cu catalysts with different CNs were fabricated by reducing CuO precursors via cyclic voltammetry (Cyc-Cu), potentiostatic electrolysis (Pot-Cu), and pulsed electrolysis (Pul-Cu), respectively. High-CN Cu catalysts predominantly generate C₂₊ products, while low-CN Cu favors CH₄ production. For instance, over the high-CN Pot-Cu, C₂₊ is the main product, with the Faradaic efficiency (FE) reaching 82.5% and a partial current density (j) of 514.3 mA cm^-2. Conversely, the low-CN Pul(3)-Cu favors the production of CH₄, achieving the highest FE_CH4 value of 56.7% with a j_CH4 value of 234.4 mA cm^-2. In situ X-ray absorption spectroscopy and Raman spectroscopy studies further confirm the different *CO adsorptions over Cu catalysts with different CN, thereby directing the reaction pathway of the CO₂RR.