Operando High-Energy-Resolution X-ray Spectroscopy of Evolving Cu Nanoparticle Electrocatalysts for CO2 Reduction

Feijóo, Julian; Yang, Yao; Fonseca Guzman, Maria V.; Vargas, Alfred; Chen, Chubai; Pollock, Christopher J.; Yang, Peidong

doi:10.1021/jacs.3c08182

Operando High-Energy-Resolution X-ray Spectroscopy of Evolving Cu Nanoparticle Electrocatalysts for CO₂ Reduction

Journal Article · Thu Sep 07 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c08182· OSTI ID:2294046

Feijóo, Julian ^[1]; ^[1]; Fonseca Guzman, Maria V. ^[1]; Vargas, Alfred ^[2]; ^[1]; ^[3]; ^[4]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
Cornell Univ., Ithaca, NY (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

Advances in electrocatalysis research rely heavily on building a thorough mechanistic understanding of catalyst active sites under realistic operating conditions. Only recently have techniques emerged that enable sensitive spectroscopic data collection to distinguish catalytically relevant surface sites from the underlying bulk material under applied potential in the presence of an electrolyte layer. Here, we demonstrate that operando high-energy-resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) is a powerful spectroscopic method which offers critical surface chemistry insights in CO₂ electroreduction with sub-electronvolt energy resolution using hard X-rays. Combined with the high surface area-to-volume ratio of 5 nm copper nanoparticles, operando HERFD-XAS allows us to observe with clear evidence the breaking of chemical bonds between the ligands and the Cu surface as part of the ligand desorption process occurring under electrochemical potentials relevant for the CO₂ reduction reaction (CO₂RR). In addition, the dynamic evolution of oxidation state and coordination number throughout the operation of the nanocatalyst was continuously tracked. With these results in hand, undercoordinated metallic copper nanograins are proposed to be the real active sites in the CO₂RR. In conclusion, this work emphasizes the importance of HERFD-XAS compared to routine XAS in catalyst characterization and mechanism exploration, especially in the complicated electrochemical CO₂RR.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2294046

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 37 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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