Insight into the Carbon Monoxide Reduction Reaction on Cu(111) from Operando Electrochemical X-ray Photoelectron Spectroscopy
Journal article, 2025
In this work, we introduce a modified dip-and-pull electrochemical X-ray photoelectron spectroscopy (ECXPS) approach that offers new mechanistic insight into the alkaline carbon monoxide reduction reaction (CORR) over a Cu(111) single crystal surface. We tackle two major unresolved questions in the CORR mechanism that persist in the literature. Firstly, we address the mechanism for methane formation on Cu(111) and show that the mechanism likely proceeds via atomic carbon, which subsequently couples, leading to the accumulation of amorphous carbon on the surface. Secondly, we provide insight into whether the mechanism for acetate formation occurs entirely on the surface or partially within the solution phase, showing that acetate is present on the surface, indicating a surface-based reaction. These insights into surface-based mechanisms provide a handle for designing future catalysts that can efficiently target the binding of specific intermediates. Furthermore, we expect that our modified approach to dip-and-pull ECXPS - in which we have changed the electrode geometry, the method of introducing the reactant gas and used hard x-rays - will significantly expand the technique's applicability, enabling studies of the CO(2)RR and beyond.
Heterogeneous catalysis
CO2 reduction
Photoelectron spectroscopy
CO reduction
Electrochemistry
Author
Bernadette Davies
Stockholm University
Fernando Garcia-Martinez
Deutsches Elektronen-Synchrotron (DESY)
Christopher M. Goodwin
ALBA Synchrotron Light Facility
Stockholm University
David Degerman
Stockholm University
Markus Soldemo
Stockholm University
Patrick Loemker
Stockholm University
Vladimir Grigorev
Stockholm University
Sara Boscolo Bibi
Stockholm University
Harri Ali-Loytty
University of Tampere
Liquid Sun
Robin Y. Engel
Stockholm University
Joakim Halldin Stenlid
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Gabriel L. S. Rodrigues
University of Southern Denmark
Tony Hansson
Stockholm University
Christoph Schlueter
Deutsches Elektronen-Synchrotron (DESY)
Xiaodong Zou
Stockholm University
Anders Nilsson
Stockholm University
Sergey Koroidov
Stockholm University
Angewandte Chemie - International Edition
1433-7851 (ISSN) 1521-3773 (eISSN)
Vol. 64 33 e202506402WASP-WISE STRATIFIER
Wallenberg Initiative Materials Science for Sustainability, 2024-01-01 -- 2025-01-01.
Wallenberg AI, Autonomous Systems and Software Program, 2024-01-01 -- 2025-01-01.
Subject Categories (SSIF 2025)
Physical Chemistry
DOI
10.1002/anie.202506402
PubMed
40460091