Synergistic Effect of Mixed Cations in the Electrochemical Double Layer Enables Highly Efficient Electrochemical CO <sub>2</sub> Methanation

M Meng Zhou Y Yiyong Wang (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) S Shiqiang Liu (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) Y Yaoyu Yin (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) Y Yaguang Peng (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) J Jiapeng Jiao (Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering) J Jiahao Yang (Xiamen University , , ,) W Wengling Zhao (Beijing National Laboratory for Molecular Sciences CAS Laboratory of Colloid and Interface and Thermodynamics CAS Research/Education Center for Excellence in Molecular Sciences Center for Carbon Neutral Chemistry Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China) H Hengan Wang (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) R Ran Duan Q Qinggong Zhu (Institute of Chemistry, Chinese Academy of Sciences , , ,) X Xiaofu Sun (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry) Y Yi Xu J Jianling Zhang (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry) X Xinchen Kang (Institute of Chemistry, Chinese Academy of Sciences , , ,) B Buxing Han (Institute of Chemistry, Chinese Academy of Sciences , , ,)

Abstract

Abstract Electrochemical CO 2 methanation is crucial for sustainable carbon recycling, transforming a greenhouse gas into a valuable fuel. However, achieving high selectivity toward CH 4 , particularly at high current densities, remains a significant challenge. In this study, a remarkable Faradaic efficiency for CH 4 (FE CH4 ) of 88.7% with a current density of 461.0 mA cm −2 was achieved at −1.3 V vs. RHE over CuCeSiO x electrode in a ternary electrolyte of 1 M tetrapropylammonium hydroxide (TPAOH) + 5 mM KCl, setting a new record for CO 2 electroreduction to CH 4 . By employing other Cu‐based catalysts, high CH 4 selectivity can also be obtained in this ternary electrolyte. Mechanistic studies reveal the synergistic effect of mixed K + and TPA + in the electrochemical double layer plays a critical role in controlling the reaction pathway. Specifically, K + modulates *CO adsorption and promotes water dissociation, generating abundant H • radicals, while TPA + aggregates stabilize these radicals, accelerating the reaction kinetics, and facilitating the deep hydrogenation from *CO to CH 4 .

Article Details

Volume / Issue Vol. 65, Issue 2
Published January 09, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (16)

M

Meng Zhou

Y

Yiyong Wang

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

S

Shiqiang Liu

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

Y

Yaoyu Yin

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

Y

Yaguang Peng

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

J

Jiapeng Jiao

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering

J

Jiahao Yang

Xiamen University , , ,

W

Wengling Zhao

Beijing National Laboratory for Molecular Sciences CAS Laboratory of Colloid and Interface and Thermodynamics CAS Research/Education Center for Excellence in Molecular Sciences Center for Carbon Neutral Chemistry Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China

H

Hengan Wang

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

R

Ran Duan

Q

Qinggong Zhu

Institute of Chemistry, Chinese Academy of Sciences , , ,

X

Xiaofu Sun

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry

Y

Yi Xu

J

Jianling Zhang

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry

X

Xinchen Kang

Institute of Chemistry, Chinese Academy of Sciences , , ,

B

Buxing Han

Institute of Chemistry, Chinese Academy of Sciences , , ,