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

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

doi:10.1016/j.apcatb.2024.124839

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

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

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

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)-La_0.10-CuO_x catalyst exhibits a Faradaic efficiency (FE) over 80% for C₂₊ products at 300 mA cm⁻², whereas OD-La_0.40-CuO_x achieves a 61.4% FE_CH4 at 400 mA cm⁻². Kinetic isotope experiments reveal distinct dependencies of the rate-determining steps on *H transfer for CO₂RR in OD-La_0.10-CuO_x and OD-La_0.40-CuO_x. In situ ATR-SEIRAS and DFT calculations demonstrate that the moderate H₂O dissociation capability of OD-La_0.10-CuO_x lowers the energy barrier for *CHO → *OCCHO conversion, thus increasing the FE_C2+. Conversely, OD-La_0.40-CuO_x, 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.

Original language	English
Article number	124839
Journal	Applied Catalysis B: Environmental
Volume	364
DOIs	https://doi.org/10.1016/j.apcatb.2024.124839
Publication status	Published - 5 May 2025

Keywords

Density functional theory
Electrochemical CO reduction
HO dissociation
in situ spectroscopy
Kinetic isotopic effect

ASJC Scopus subject areas

Catalysis
General Environmental Science
Process Chemistry and Technology

Access to Document

10.1016/j.apcatb.2024.124839

Cite this

@article{2741c951ce514e09aa10a75cbde8bcb0,

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

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.",

keywords = "Density functional theory, Electrochemical CO reduction, HO dissociation, in situ spectroscopy, Kinetic isotopic effect",

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

note = "Publisher Copyright: {\textcopyright} 2024 The Authors",

year = "2025",

month = may,

day = "5",

doi = "10.1016/j.apcatb.2024.124839",

language = "English",

volume = "364",

journal = "Applied Catalysis B: Environmental",

issn = "0926-3373",

publisher = "Elsevier B.V.",

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TY - JOUR

T1 - Manipulating adsorbed hydrogen on lanthanum-modified CuOx

T2 - Industrial-current-density CO2 electroreduction to C2+ products or CH4

AU - Guo, Zeyu

AU - Zhu, Huiwen

AU - Yan, Zijun

AU - Lei, Lei

AU - Wang, Degao

AU - Xi, Ziyun

AU - Lian, Yirui

AU - Yu, Jiahui

AU - Fow, Kam Loon

AU - Do, Hainam

AU - Hirst, Jonathan D.

AU - Wu, Tao

AU - Xu, Mengxia

PY - 2025/5/5

Y1 - 2025/5/5

N2 - 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.

AB - 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.

KW - Density functional theory

KW - Electrochemical CO reduction

KW - HO dissociation

KW - in situ spectroscopy

KW - Kinetic isotopic effect

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DO - 10.1016/j.apcatb.2024.124839

M3 - Article

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JO - Applied Catalysis B: Environmental

JF - Applied Catalysis B: Environmental

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