Temperature-dependent pathways in carbon dioxide electroreduction

Shiqiang Liu; Yaoyu Yin; Jiahao Yang; Wenling Zhao; Meng Zhou; Huisheng Qin; Jiapeng Jiao; Yiyong Wang; Hengan Wang; Xing Tong; Yi Xu; Xiaofu Sun; Qinggong Zhu; Maohong Fan; Xinchen Kang; Buxing Han

doi:10.1016/j.scib.2024.12.052

Temperature-dependent pathways in carbon dioxide electroreduction

Sci Bull (Beijing). 2025 Jan 2:S2095-9273(24)00989-7. doi: 10.1016/j.scib.2024.12.052. Online ahead of print.

Authors

Shiqiang Liu¹, Yaoyu Yin², Jiahao Yang², Wenling Zhao², Meng Zhou², Huisheng Qin², Jiapeng Jiao³, Yiyong Wang², Hengan Wang², Xing Tong², Yi Xu², Xiaofu Sun², Qinggong Zhu², Maohong Fan⁴, Xinchen Kang⁵, Buxing Han⁶

Affiliations

¹ 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.
² 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; School of Chemistry, University of Chinese Academy of Sciences, Beijing 100049, China.
³ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
⁴ Departments of Chemical and Petroleum Engineering, University of Wyoming, Laramie 82071, USA; School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta 30332, USA.
⁵ 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; School of Chemistry, University of Chinese Academy of Sciences, Beijing 100049, China. Electronic address: kangxinchen@iccas.ac.cn.
⁶ 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; School of Chemistry, University of Chinese Academy of Sciences, Beijing 100049, China; Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China. Electronic address: hanbx@iccas.ac.cn.

PMID: 39800629
DOI: 10.1016/j.scib.2024.12.052

Abstract

Temperature affects both the thermodynamics of intermediate adsorption and the kinetics of elementary reactions. Despite its extensive study in thermocatalysis, temperature effect is typically overlooked in electrocatalysis. This study investigates how electrolyte temperature influences CO₂ electroreduction over Cu catalysts. Theoretical calculations reveal the significant impact of temperature on *CO and *H intermediate adsorption thermodynamics, water microenvironment at the electrode surface, and the electron density and covalent property of the C-O bond in the *CH-COH intermediate, crucial for the reaction pathways. The theoretical calculations are strongly verified by experimental results over different Cu catalysts. Faradaic efficiency (FE) toward multicarbon (C₂₊) products is favored at low temperatures. Cu nanorod electrode could achieve a [Formula: see text] value of 90.1 % with a current density of ∼400 mA cm^-2 at -3 °C. [Formula: see text] and [Formula: see text] show opposite trends with decreasing temperature. The [Formula: see text] ratio can decrease from 1.86 at 40 °C to 0.98 at -3 °C.

Keywords: Adsorption thermodynamics; CO(2) reduction reaction; Electrocatalysis; Electrolyte temperature; Reaction kinetic.