Asymmetrical C–C Coupling for Electroreduction of CO on Bimetallic Cu–Pd Catalysts

Shen, Hao; Wang, Yunzhe; Chakraborty, Tanmoy; Zhou, Guangye; Wang, Canhui; Fu, Xianbiao; Wang, Yuxuan; Zhang, Jinyi; Li, Chenyang; Xu, Fei; Cao, Liang; Mueller, Tim; Wang, Chao

doi:10.1021/acscatal.2c00646

Asymmetrical C–C Coupling for Electroreduction of CO on Bimetallic Cu–Pd Catalysts

Journal Article · Mon Apr 18 00:00:00 EDT 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c00646· OSTI ID:2428946

Shen, Hao ^[1]; ^[2]; ^[2]; Zhou, Guangye ^[2]; Wang, Canhui ^[2]; ^[2]; Wang, Yuxuan ^[2]; Zhang, Jinyi ^[2]; ^[2]; Xu, Fei ^[2]; Cao, Liang ^[2]; ^[2]; ^[2]

Johns Hopkins University, Baltimore, MD (United States); Johns Hopkins University
Johns Hopkins University, Baltimore, MD (United States)

Electroreduction of carbon monoxide (CO) possesses great potential for achieving the renewable synthesis of hydrocarbon chemicals from CO₂. We report here selective reduction of CO to acetate using Cu–Pd bimetallic electrocatalysts. High activity and selectivity are demonstrated for CO-to-acetate conversion with >200 mA/cm² in geometric current density and >65% in Faradaic efficiency (FE). An asymmetrical C–C coupling mechanism is proposed to explain the composition-dependent catalytic performance and high selectivity toward acetate. This mechanism is supported by the computationally predicted shift of the *CO adsorption from the top-site configuration on Cu (or Cu-rich) surfaces to the bridge sites of Cu–Pd bimetallic surfaces, which is also associated with the reduction of the CO hydrogenation barrier. Further kinetic analysis of the reaction order with respect to CO and Tafel slope supports a reaction pathway with *CO–*CHO recombination following a CO hydrogenation step, which could account for the electroreduction of CO to acetate on the Cu–Pd bimetallic catalysts. Furthermore, our work highlights how heteroatomic alloy surfaces can be tailored to enable distinct reaction pathways and achieve advanced catalytic performance beyond monometallic catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins University, Baltimore, MD (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: EE0008501; SC0012704

OSTI ID:: 2428946

Alternate ID(s):: OSTI ID: 1978313

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 9 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Asymmetrical C–C Coupling for Electroreduction of CO on Bimetallic Cu–Pd Catalysts

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