Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction

Journal Article · Sun Jun 01 00:00:00 UTC 2025 · Nature Catalysis

DOI: https://doi.org/10.1038/s41929-025-01359-w · OSTI ID:3008732

Yang, Yao; Feijóo, Julian; Figueras-Valls, Marc; Chen, Chubai; Shi, Chuqiao; Fonseca Guzman, Maria V; Murhabazi Maombi, Yves; Liu, Shikai; Jain, Pulkit; Briega-Martos, Valentín; Peng, Zhengxing; Shan, Yu; Lee, Geonhui; Rebarchik, Michael; Xu, Lang; Pollock, Christopher J; Jin, Jianbo; Soland, Nathan E; Wang, Cheng; Salmeron, Miquel B ; Chen, Zhu; Han, Yimo; Mavrikakis, Manos; Yang, Peidong

Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.

• Research Organization: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 )
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 3008732
• Journal Information: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 6 Vol. 8
• Country of Publication: United States
• Language: English