Switching CO <sub>2</sub> Electroreduction Pathways via Polyvinylpyrrolidone‐Mediated Water Configuration Control

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) Z Zhongnan Ling (Beijing Synchrotron Radiation Facility) K Keke Chai H Huisheng Qin (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) S Shipeng Zhang (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 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) J Jiahao Yang (Xiamen University , , ,) R Rongjuan Feng (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) Q Qingli Qian (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 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) Q Qinnggong Zhu (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 China 100049) Y Yi Xu Y Yongquan Zhou X Xinchen Kang (Institute of Chemistry, Chinese Academy of Sciences , , ,) B Buxing Han (Institute of Chemistry, Chinese Academy of Sciences , , ,)

Abstract

Abstract The water configuration plays a critical role in steering the CO 2 electroreduction pathway, yet achieving precise control over water arrangement remains a significant challenge. In this study, we demonstrate that introducing trace amounts of polyvinylpyrrolidone (PVP) into 3 M KCl enables targeted control over the CO 2 electroreduction product distribution by simply adjusting the PVP concentration. Using a Cu 19 CeO x (molar ratio of Cu:Ce = 19:1) electrode, in the absence of PVP, multicarbon (C 2+ ) products dominate, but substantial CO and H 2 are also generated, with negligible CH 4 formation. Remarkably, the addition of just 25 ppm PVP shifts the primary product to CH 4 , achieving a Faradaic efficiency (FE) of 60.4% at 500 mA cm −2 . Further increasing the PVP concentration to 125 ppm switches the dominant product back to C 2+ , with an impressive FE of 90.8% at 800 mA cm −2 . This trend is consistent across various Cu‐based catalysts, highlighting the universality of this approach. Mechanistic studies reveal that PVP reconstructs the water configuration at the cathode surface, modulating not only the adsorption strength and coverage of *CO intermediates but also the kinetics of water dissociation, thereby dictating the reaction pathway.

Article Details

Volume / Issue Vol. 65, Issue 4
Published January 22, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (16)

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

Z

Zhongnan Ling

Beijing Synchrotron Radiation Facility

K

Keke Chai

H

Huisheng Qin

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

S

Shipeng Zhang

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

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

J

Jiahao Yang

Xiamen University , , ,

R

Rongjuan Feng

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

Q

Qingli Qian

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

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

Q

Qinnggong Zhu

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 China 100049

Y

Yi Xu

Y

Yongquan Zhou

X

Xinchen Kang

Institute of Chemistry, Chinese Academy of Sciences , , ,

B

Buxing Han

Institute of Chemistry, Chinese Academy of Sciences , , ,