Citation: Lihui Ou, Zhancheng Liu, Dai-Huo Liu, Zhi Zhang. Cl-adsorbed Cu(111)/H₂O interface selectively realizes electrochemical CO₂ reduction towards C₂H₄ product: Mechanistic understanding[J]. Chinese Chemical Letters, ;2026, 37(2): 111920. doi: 10.1016/j.cclet.2025.111920 shu

Cl-adsorbed Cu(111)/H₂O interface selectively realizes electrochemical CO₂ reduction towards C₂H₄ product: Mechanistic understanding

Lihui Ou ^{a, *,} ,
Zhancheng Liu ^a ,
Dai-Huo Liu ^{b, *,} ,
Zhi Zhang ^a

a.
Hunan Provincial Key Laboratory of Water Treatment Functional Materials, Hunan Province Engineering Research Center of Electroplating Wastewater Reuse Technology, School of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde 415000, China
b.
Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China

lihuiou@huas.edu.cn

liudaihuo@htu.edu.cn

Received Date: 20 June 2025
Revised Date: 28 September 2025
Accepted Date: 28 September 2025
Available Online: 29 September 2025

Figures(4)

Cu electrocatalysts have been demonstrated to have unique ability to reduce CO₂ to various high value-added C₂ products like ethylene and alcohols. However, realizing high selectivity of C₂ products are still a main challenge due to complex CO₂ electroreduction pathways and small opportunity of C–C coupling reactions. Here, we found the origin of enhanced CO₂ electroreduction reaction activity and product selectivity towards C₂ products and C–C coupling mechanism at halogen atoms-adsorbed Cu/H₂O interfaces, the corresponding CO₂ electroreduction evolution mechanisms at the halogen atoms-modified Cu/H₂O interfaces are systematically studied via theoretical modeling and calculations. The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer, especially Cl⁻-adsorbed Cu(111)/H₂O interface has the optimum activity and selectivity towards OCCO dimer, subsequent Cl-adsorbed Cu(111)/H₂O interface can selectively reduce CO₂ into C₂H₄ product. The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl⁻ can enhance selectivity of C₂H₄ product. The determinations of onset potentials indicate that electroreduction pathways of CO₂ towards C₂H₄ product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C₂H₄ product selectivity. This work on selective realization of CO₂ electroreduction towards C₂H₄ product via Cl⁻-modified Cu(111)/H₂O interface provide a theoretical guideline for how to selectively realize other high value-added C₂ products.
- CO₂,
- Cl-adsorbed Cu(111) surface,
- C₂H₄ product,
- C-C coupling,
- Selective electroreduction
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Cl-adsorbed Cu(111)/H₂O interface selectively realizes electrochemical CO₂ reduction towards C₂H₄ product: Mechanistic understanding