Gas–Proton Microenvironment Modulation for Enhanced CO <sub>2</sub> ‐to‐Formate Electroreduction

J Jifeng Wu Y Yu Li M Miao Hu (Center for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division) T Tingsong Li M Moyu Yi (Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia) X Xiangyun Xiao (Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia) H Honglin Li (Innovation Center for AI and Drug Discovery, School of Pharmacy, East China Normal University) Y Yongfeng Guo (Aiiso Yufeng Li Family Department of Chemical and Nano Engineering Program in Materials Science and Engineering University of California San Diego La Jolla California USA) Y Yoji Kobayashi (KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology (KAUST) Thuwal 23955‐6900 Saudi Arabia) M Magnus Rueping (Division of Physical Sciences and Engineering) W Wan‐Lu Li (Aiiso Yufeng Li Family Department of Chemical and Nano Engineering University of California La Jolla California USA) H Huabin Zhang (Center of Excellence for Renewable Energy and Storage Technologies (CREST), Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, Kingdom of Saudi Arabia.) K Kuo‐Wei Huang (Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia)

Abstract

Abstract Precise control of interfacial water structure is essential for suppressing side reactions and enabling selective CO 2 electroreduction at industrial current densities. Here, we synthesize a series of bismuth‐based catalysts with spatially encoded superhydrophilic–superhydrophobic nanodomains by partially embedding polyvinylidene fluoride (PVDF) into Bi nanoparticles. This strategy creates interfacial polarity patterns that stabilize *OCHO intermediates while suppressing hydrogen and CO evolution. Compared to the PVDF‐free control, the optimized Bi–PVDF catalyst exhibits significantly enhanced formate partial current density, Faradaic efficiency (FE), and long‐term stability. It achieves &gt; 90% FE at −200 mA cm −2 for 50 h and maintains high selectivity up to −700 mA cm −2 . Operando spectroscopy and multiscale simulations reveal that the dual‐wettability interface modulates local hydration and charge distribution, promoting selective intermediate formation while kinetically suppressing side pathways. By addressing the longstanding challenge of coupled gas–proton transport, this work offers a mechanism‐driven and scalable strategy to construct interfacial microenvironments for high‐rate, selective CO 2 electroreduction.

Article Details

Volume / Issue Vol. 65, Issue 1
Published January 02, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (13)

J

Jifeng Wu

Y

Yu Li

M

Miao Hu

Center for Renewable Energy and Storage Technologies (CREST), Physical Science and Engineering Division

T

Tingsong Li

M

Moyu Yi

Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia

X

Xiangyun Xiao

Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia

H

Honglin Li

Innovation Center for AI and Drug Discovery, School of Pharmacy, East China Normal University

Y

Yongfeng Guo

Aiiso Yufeng Li Family Department of Chemical and Nano Engineering Program in Materials Science and Engineering University of California San Diego La Jolla California USA

Y

Yoji Kobayashi

KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology (KAUST) Thuwal 23955‐6900 Saudi Arabia

M

Magnus Rueping

Division of Physical Sciences and Engineering

W

Wan‐Lu Li

Aiiso Yufeng Li Family Department of Chemical and Nano Engineering University of California La Jolla California USA

H

Huabin Zhang

Center of Excellence for Renewable Energy and Storage Technologies (CREST), Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, Kingdom of Saudi Arabia.

K

Kuo‐Wei Huang

Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia