Acidic CO <sub>2</sub> Electrolysis With Near‐Ideal Selectivity and Carbon Efficiency Enabled by Overcoming Its Inherent Trade‐Off

L Li‐Ping Chi (Division of Nanomaterials &amp; Chemistry, Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China) Y Yu‐Cai Zhang (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China) Z Zhuang‐Zhuang Niu (Division of Nanomaterials &amp; Chemistry, Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China) X Xiao‐Long Zhang (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China) Y Ye‐Cheng Li (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China) T Tian‐Yun Zhang (Division of Nanomaterials &amp; Chemistry, Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China) S Shu‐Ping Sun (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China) P Pu‐Gan Lu (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China) K Kai‐Bin Tang (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China) M Min‐Rui Gao (Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China)

Abstract

Abstract Carbon dioxide electroreduction (CO 2 R) in acid tends to be a promising route to avoid CO 2 loss in alkaline and neutral electrolytes; however, high alkali cation concentrations (typically ≥3 M) are required to activate CO 2 and suppress water electroreduction, causing carbonate formation and thus unsatisfied single‐pass carbon efficiency (SPCE). Based on theoretical and experimental analyses, we show that an inherent trade‐off exists: increasing cation concentrations improves Faradaic efficiency (FE) toward CO 2 R products but comes at the expense of reduced SPCE. We demonstrate a polyimide‐modification strategy to overcome this trade‐off by taking advantage of the amino groups that can effectively capture protons, creating a local alkaline microenvironment surrounding the electrode surface. In a proof‐of‐concept experiment, SnO 2 nanoparticles were modified with polyimide and acted as a CO 2 R catalyst, which achieved, simultaneously, near‐ideal SPCE of 95.7% and FE of 96% (toward HCOOH) at pH 1.36 with dilute potassium ions down to even 0.1 M. We expect that these findings will accelerate the development of carbon‐ and electron‐efficient acidic CO 2 electrolysis.

Article Details

Volume / Issue Vol. 64, Issue 25
Published June 17, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (10)

L

Li‐Ping Chi

Division of Nanomaterials &amp; Chemistry, Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China

Y

Yu‐Cai Zhang

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China

Z

Zhuang‐Zhuang Niu

Division of Nanomaterials &amp; Chemistry, Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China

X

Xiao‐Long Zhang

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China

Y

Ye‐Cheng Li

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China

T

Tian‐Yun Zhang

Division of Nanomaterials &amp; Chemistry, Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 China

S

Shu‐Ping Sun

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China

P

Pu‐Gan Lu

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China

K

Kai‐Bin Tang

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China

M

Min‐Rui Gao

Division of Nanomaterials &amp; Chemistry Hefei National Research Center for Physical Sciences at the Microscale University of Science and Technology of China Hefei 230026 P.R. China