Decoupling Site‐Selective CO Poisoning From Hydrogen Oxidation Activity on Pt/C in PEMFCs

J Jia‐Feng Du (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China) J Jin‐Yu Ye (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China) X Xiao‐Tian Wang (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China) Y Yu‐Cheng Wang (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China) N Na Tian Z Zhi‐You Zhou (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China) S Shi‐Gang Sun (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen P. R. China)

Abstract

ABSTRACT Trace CO impurities in reformed hydrogen severely impair the performance of proton exchange membrane fuel cells (PEMFCs), yet the site‐specific mechanism of CO poisoning on hydrogen oxidation reaction (HOR) activity at Pt anodes under realistic operating conditions remains poorly understood. Herein, we reveal the site‐selective relationship between CO poisoning and HOR activity on Pt/C under practical fuel cell conditions by combining operando infrared spectroscopy with molecular probe experiments that quantitatively distinguish Pt surface sites during operation. Spectroscopic descriptors derived from the evolution of CO vibrational frequency and full width at half maximum (FWHM) reveal concentration‐dependent spatial distribution of adsorbed CO: at comparable coverages, low CO concentrations favor dispersed adsorption, whereas higher concentrations promote locally compact CO adlayers. Operando infrared measurements show that CO initially adsorbs on low‐coordinated Pt sites and progressively extends to high‐coordinated sites as coverage increases, while molecular probe experiments demonstrate that the initially poisoned low‐coordinated sites contribute negligibly to HOR activity, with high‐coordinated Pt sites dominating the HOR current. This work provides a molecular‐level understanding of site‐selective HOR activity on Pt/C and a mechanistically guided approach to improve anodic CO tolerance in PEMFCs.

Article Details

Volume / Issue Vol. 65, Issue 22
Published May 25, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (7)

J

Jia‐Feng Du

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China

J

Jin‐Yu Ye

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China

X

Xiao‐Tian Wang

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China

Y

Yu‐Cheng Wang

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China

N

Na Tian

Z

Zhi‐You Zhou

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen China

S

Shi‐Gang Sun

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen P. R. China