Formate-Induced Dissolution and Reprecipitation of a Copper Electrocatalyst during Electrochemical CO2 Reduction Reaction

Lee, Seung-Hoon; Devi, Nishu; Li, Yuanyuan; Wu, Yiqing; Evans, Barbara R.; Boebinger, Matthew G.; Liu, Chang; Stack, Andrew G.; Wu, Zili; Weber, Juliane

doi:10.1021/acs.jpcc.5c03462

Title: Formate-Induced Dissolution and Reprecipitation of a Copper Electrocatalyst during Electrochemical CO₂ Reduction Reaction

Journal Article · Thu Sep 25 00:00:00 UTC 2025 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.5c03462 · OSTI ID:3002428

Lee, Seung-Hoon ^[1];

^[1];

^[1]; Wu, Yiqing ^[1];

^[1];

^[2]; Liu, Chang ^[1];

^[1];

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Catalyst size, morphology, and crystal structure play crucial roles in determining the activity and selectivity of electrochemical CO₂ reduction reactions, which are known to change during the reaction process. A comprehensive understanding of how, when, and why these parameters evolve under operational conditions is essential for developing stable, efficient, and selective catalysts. In this study, we reveal that formate, one of the reaction products, contributes to the degradation of copper catalysts through a ligand-assisted dissolution mechanism. Utilizing in situ electrochemical atomic force microscopy and ex-situ scanning and transmission electron microscopies, we observed a significant reduction in the size of copper nanoparticles, which decreased from over 30 nm to less than 10 nm in diameter within 60 min of CO₂RR. The temporal production of formate correlated with the particle size changes. Furthermore, analysis of the electrolyte using inductively coupled plasma optical emission spectroscopy confirmed the dissolution of copper nanoparticles. Control experiments involving various reaction products (H₂, CO, and HCOO^–) demonstrated that formate significantly promotes copper dissolution, thereby highlighting its role in the ligand-assisted dissolution mechanism of copper electrocatalysts. In conclusion, our findings provide critical insights into copper catalyst behavior during electrochemical CO₂ reduction, facilitating the design of more resilient and effective electrocatalysts.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0012577; SC0012704

OSTI ID:: 3002428

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 40 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Catalysts
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Dissolution
Nanoparticles
Oxides
Particle size
Redox reactions

Title: Formate-Induced Dissolution and Reprecipitation of a Copper Electrocatalyst during Electrochemical CO2 Reduction Reaction

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Title: Formate-Induced Dissolution and Reprecipitation of a Copper Electrocatalyst during Electrochemical CO₂ Reduction Reaction