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Title: Activity and Selectivity Control in CO 2 Electroreduction to Multicarbon Products over CuO x Catalysts via Electrolyte Design

Abstract

The CO2 electroreduction reaction (CO2RR) to chemicals and fuels is of both fundamental and practical significance, since it would lead to a more efficient storage of renewable energy while closing the carbon cycle. Here we report enhanced activity and selectivity for the CO2RR to multicarbon hydrocarbons and alcohols (~69% Faradaic efficiency and -45.5 mA cm–2 partial current density for C2+ at -1.0 V vs RHE) over O2-plasma-activated Cu catalysts via electrolyte design. Increasing the size of the alkali-metal cations in the electrolyte, in combination with the presence of subsurface oxygen species which favor their adsorption, significantly improved C–C coupling on CuOx electrodes. The coexistence of Cs+ and I induced drastic restructuring of the CuOx surface, the formation of shaped particles containing stable CuI species, and a more favorable stabilization of the reaction intermediates and concomitant high C2+ selectivity. This work, combining both experiment and density functional theory, provides insights into the active sites and reaction mechanism of oxide-derived Cu catalysts for the CO2RR.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [4];  [5];  [6];  [3]; ORCiD logo [4]
  1. Max Planck Society, Berlin (Germany). Fritz-Haber Inst., Dept. of Interface Science; Ruhr-Univ., Bochum (Germany). Dept. of Physics
  2. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemical Engineering
  3. ennsylvania State Univ., University Park, PA (United States). Dept. of Chemical Engineering
  4. Max Planck Society, Berlin (Germany). Fritz-Haber Inst., Dept. of Interface Science; Ruhr-Univ., Bochum (Germany). Dept. of Physics
  5. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  6. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1484885
Report Number(s):
BNL-209655-2018-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Gao, Dunfeng, McCrum, Ian T., Deo, Shyam, Choi, Yong-Wook, Scholten, Fabian, Wan, Weiming, Chen, Jingguang G., Janik, Michael J., and Roldan Cuenya, Beatriz. Activity and Selectivity Control in CO 2 Electroreduction to Multicarbon Products over CuO x Catalysts via Electrolyte Design. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b02587.
Gao, Dunfeng, McCrum, Ian T., Deo, Shyam, Choi, Yong-Wook, Scholten, Fabian, Wan, Weiming, Chen, Jingguang G., Janik, Michael J., & Roldan Cuenya, Beatriz. Activity and Selectivity Control in CO 2 Electroreduction to Multicarbon Products over CuO x Catalysts via Electrolyte Design. United States. doi:https://doi.org/10.1021/acscatal.8b02587
Gao, Dunfeng, McCrum, Ian T., Deo, Shyam, Choi, Yong-Wook, Scholten, Fabian, Wan, Weiming, Chen, Jingguang G., Janik, Michael J., and Roldan Cuenya, Beatriz. Tue . "Activity and Selectivity Control in CO 2 Electroreduction to Multicarbon Products over CuO x Catalysts via Electrolyte Design". United States. doi:https://doi.org/10.1021/acscatal.8b02587. https://www.osti.gov/servlets/purl/1484885.
@article{osti_1484885,
title = {Activity and Selectivity Control in CO 2 Electroreduction to Multicarbon Products over CuO x Catalysts via Electrolyte Design},
author = {Gao, Dunfeng and McCrum, Ian T. and Deo, Shyam and Choi, Yong-Wook and Scholten, Fabian and Wan, Weiming and Chen, Jingguang G. and Janik, Michael J. and Roldan Cuenya, Beatriz},
abstractNote = {The CO2 electroreduction reaction (CO2RR) to chemicals and fuels is of both fundamental and practical significance, since it would lead to a more efficient storage of renewable energy while closing the carbon cycle. Here we report enhanced activity and selectivity for the CO2RR to multicarbon hydrocarbons and alcohols (~69% Faradaic efficiency and -45.5 mA cm–2 partial current density for C2+ at -1.0 V vs RHE) over O2-plasma-activated Cu catalysts via electrolyte design. Increasing the size of the alkali-metal cations in the electrolyte, in combination with the presence of subsurface oxygen species which favor their adsorption, significantly improved C–C coupling on CuOx electrodes. The coexistence of Cs+ and I– induced drastic restructuring of the CuOx surface, the formation of shaped particles containing stable CuI species, and a more favorable stabilization of the reaction intermediates and concomitant high C2+ selectivity. This work, combining both experiment and density functional theory, provides insights into the active sites and reaction mechanism of oxide-derived Cu catalysts for the CO2RR.},
doi = {10.1021/acscatal.8b02587},
journal = {ACS Catalysis},
number = 11,
volume = 8,
place = {United States},
year = {2018},
month = {9}
}

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