Modulation of *CHxO Adsorption to Facilitate Electrocatalytic Reduction of CO2 to CH4 over Cu-Based Catalysts

Jing Zhao; Peng Zhang; Tenghui Yuan; Dongfang Cheng; Shiyu Zhen; Hui Gao; Tuo Wang; Zhi-Jian Zhao; Jinlong Gong

doi:10.1021/jacs.2c12006

Modulation of *CH_xO Adsorption to Facilitate Electrocatalytic Reduction of CO₂ to CH₄ over Cu-Based Catalysts

J Am Chem Soc. 2023 Mar 29;145(12):6622-6627. doi: 10.1021/jacs.2c12006. Epub 2023 Mar 20.

Authors

Jing Zhao^{1

2}, Peng Zhang^{1

2

3}, Tenghui Yuan^{1

2}, Dongfang Cheng^{1

2}, Shiyu Zhen^{1

2}, Hui Gao^{1

2}, Tuo Wang^{1

2

3

4}, Zhi-Jian Zhao^{1

2

3}, Jinlong Gong^{1

2

5

3}

Affiliations

¹ School of Chemical Engineering and Technology, Key Laboratory for Green Chemical Technology of Ministry of Education, Tianjin University, Tianjin 300072, China.
² Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China.
³ National Industry-Education Platform of Energy Storage, Tianjin University, 135 Yaguan Road, Tianjin 300350, China.
⁴ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, Fujian, China.
⁵ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China.

PMID: 36939299
DOI: 10.1021/jacs.2c12006

Abstract

Copper (Cu) can efficiently catalyze the electrochemical CO₂ reduction reaction (CO₂RR) to produce value-added fuels and chemicals, among which methane (CH₄) has drawn attention due to its high mass energy density. However, the linear scaling relationship between the adsorption energies of *CO and *CH_xO on Cu restricts the selectivity toward CH₄. Alloying a secondary metal in Cu provides a new freedom to break the linear scaling relationship, thus regulating the product distribution. This paper describes a controllable electrodeposition approach to alloying Cu with oxophilic metal (M) to steer the reaction pathway toward CH₄. The optimized La₅Cu₉₅ electrocatalyst exhibits a CH₄ Faradaic efficiency of 64.5%, with the partial current density of 193.5 mA cm^-2. The introduction of oxophilic La could lower the energy barrier for *CO hydrogenation to *CH_xO by strengthening the M-O bond, which would also promote the breakage of the C-O bond in *CH₃O for the formation of CH₄. This work provides a new avenue for the design of Cu-based electrocatalysts to achieve high selectivity in CO₂RR through the modulation of the adsorption behaviors of key intermediates.