Manipulating adsorbed hydrogen on lanthanum-modified CuOₓ: Industrial-current-density CO₂ electroreduction to C₂₊ products or CH₄

Guo, Zeyu; Zhu, Huiwen; Yan, Zijun; Lei, Lei; Wang, Degao; Xi, Ziyun; Lian, Yirui; Yu, Jiahui; Fow, Kam Loon; Do, Hainam; Hirst, Jonathan D.; Wu, Tao; Xu, Mengxia

Abstract

The selective electrochemical CO2 reduction reaction (CO2RR) yields valuable C2+ and C1 products, yet the influence of adsorbed hydrogen (*H) on product distribution remains inadequately understood. This study explores this effect by developing bimetallic copper-based electrocatalysts with varied lanthanum (La) doping ratios. The oxide-derived (OD)-La0.10-CuOx catalyst exhibits a Faradaic efficiency (FE) over 80% for C2+ products at 300 mA cm−2, whereas OD-La0.40-CuOx achieves a 61.4% FECH4 at 400 mA cm−2. Kinetic isotope experiments reveal distinct dependencies of the rate-determining steps on *H transfer for CO2RR in OD-La0.10-CuOx and OD-La0.40-CuOx. In situ ATR-SEIRAS and DFT calculations demonstrate that the moderate H2O dissociation capability of OD-La0.10-CuOx lowers the energy barrier for *CHO → *OCCHO conversion, thus increasing the FEC2+. Conversely, OD-La0.40-CuOx, with its strong H2O dissociation capability, favors *CHO → *CH2O, thereby promoting CO2RR-to-CH4. These findings advance the understanding of the role of *H in CO2 electroreduction at industrial current densities and present avenues for tailored CO2RR products via doping engineering.

Citation

Guo, Z., Zhu, H., Yan, Z., Lei, L., Wang, D., Xi, Z., Lian, Y., Yu, J., Fow, K. L., Do, H., Hirst, J. D., Wu, T., & Xu, M. (2025). Manipulating adsorbed hydrogen on lanthanum-modified CuOₓ: Industrial-current-density CO₂ electroreduction to C₂₊ products or CH₄. Applied Catalysis B: Environmental, 364, Article 124839. https://doi.org/10.1016/j.apcatb.2024.124839

• Journal Article Type: Article
• Acceptance Date: Nov 17, 2024
• Online Publication Date: Nov 19, 2024
• Publication Date: May 5, 2025
• Deposit Date: Dec 14, 2024
• Publicly Available Date: Dec 18, 2024
• Journal: Applied Catalysis B: Environment and Energy
• Print ISSN: 0926-3373
• Electronic ISSN: 1873-3883
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 364
• Article Number: 124839
• DOI: https://doi.org/10.1016/j.apcatb.2024.124839
• Keywords: Electrochemical CO2 reduction; H2O dissociation; Kinetic isotopic effect; in situ spectroscopy; Density functional theory
• Public URL: https://nottingham-repository.worktribe.com/output/42839901
• Publisher URL: https://www.sciencedirect.com/science/article/pii/S0926337324011536?via%3Dihub
• Additional Information: This article is maintained by: Elsevier; Article Title: Manipulating adsorbed hydrogen on lanthanum-modified CuOx: Industrial-current-density CO2 electroreduction to C2+ products or CH4; Journal Title: Applied Catalysis B: Environment and Energy; CrossRef DOI link to publisher maintained version: https://doi.org/10.1016/j.apcatb.2024.124839; Content Type: article; Copyright: © 2024 The Author(s). Published by Elsevier B.V.