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Title: Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen

Abstract

Producing liquid fuels such as ethanol from CO2, H2O, and renewable electricity offers a route to store sustainable energy. The search for efficient electrocatalysts for the CO2 reduction reaction relies on tuning the adsorption strength of carbonaceous intermediates. Here, we report a complementary approach in which we utilize hydroxide and oxide doping of a catalyst surface to tune the adsorbed hydrogen on Cu. Density functional theory studies indicate that this doping accelerates water dissociation and changes the hydrogen adsorption energy on Cu. We synthesize and investigate a suite of metal-hydroxide-interface-doped-Cu catalysts, and find that the most efficient, Ce(OH)x-doped-Cu, exhibits an ethanol Faradaic efficiency of 43% and a partial current density of 128 mA cm-2. Mechanistic studies, wherein we combine investigation of hydrogen evolution performance with the results of operando Raman spectroscopy, show that adsorbed hydrogen hydrogenates surface *HCCOH, a key intermediate whose fate determines branching to ethanol versus ethylene.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Toronto, ON (Canada)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC); Suncor Energy; Ontario Research Fund; Natural Sciences and Engineering Research Council of Canada (NSERC); Federal Economic Development Agency of Southern Ontario; Province of Ontario; IBM Canada Ltd.; Ontario Centres of Excellence; Mitacs; Canada Foundation for Innovation (CFI; Government of Ontario; Ontario Research Fund – Research Excellence; University of Toronto; Banting Postdoctoral Fellowships
OSTI Identifier:
1624231
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology - Other Topics; Electrocatalysis

Citation Formats

Luo, Mingchuan, Wang, Ziyun, Li, Yuguang C., Li, Jun, Li, Fengwang, Lum, Yanwei, Nam, Dae-Hyun, Chen, Bin, Wicks, Joshua, Xu, Aoni, Zhuang, Taotao, Leow, Wan Ru, Wang, Xue, Dinh, Cao-Thang, Wang, Ying, Wang, Yuhang, Sinton, David, and Sargent, Edward H. Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen. United States: N. p., 2019. Web. https://doi.org/10.1038/s41467-019-13833-8.
Luo, Mingchuan, Wang, Ziyun, Li, Yuguang C., Li, Jun, Li, Fengwang, Lum, Yanwei, Nam, Dae-Hyun, Chen, Bin, Wicks, Joshua, Xu, Aoni, Zhuang, Taotao, Leow, Wan Ru, Wang, Xue, Dinh, Cao-Thang, Wang, Ying, Wang, Yuhang, Sinton, David, & Sargent, Edward H. Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen. United States. https://doi.org/10.1038/s41467-019-13833-8
Luo, Mingchuan, Wang, Ziyun, Li, Yuguang C., Li, Jun, Li, Fengwang, Lum, Yanwei, Nam, Dae-Hyun, Chen, Bin, Wicks, Joshua, Xu, Aoni, Zhuang, Taotao, Leow, Wan Ru, Wang, Xue, Dinh, Cao-Thang, Wang, Ying, Wang, Yuhang, Sinton, David, and Sargent, Edward H. Fri . "Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen". United States. https://doi.org/10.1038/s41467-019-13833-8. https://www.osti.gov/servlets/purl/1624231.
@article{osti_1624231,
title = {Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen},
author = {Luo, Mingchuan and Wang, Ziyun and Li, Yuguang C. and Li, Jun and Li, Fengwang and Lum, Yanwei and Nam, Dae-Hyun and Chen, Bin and Wicks, Joshua and Xu, Aoni and Zhuang, Taotao and Leow, Wan Ru and Wang, Xue and Dinh, Cao-Thang and Wang, Ying and Wang, Yuhang and Sinton, David and Sargent, Edward H.},
abstractNote = {Producing liquid fuels such as ethanol from CO2, H2O, and renewable electricity offers a route to store sustainable energy. The search for efficient electrocatalysts for the CO2 reduction reaction relies on tuning the adsorption strength of carbonaceous intermediates. Here, we report a complementary approach in which we utilize hydroxide and oxide doping of a catalyst surface to tune the adsorbed hydrogen on Cu. Density functional theory studies indicate that this doping accelerates water dissociation and changes the hydrogen adsorption energy on Cu. We synthesize and investigate a suite of metal-hydroxide-interface-doped-Cu catalysts, and find that the most efficient, Ce(OH)x-doped-Cu, exhibits an ethanol Faradaic efficiency of 43% and a partial current density of 128 mA cm-2. Mechanistic studies, wherein we combine investigation of hydrogen evolution performance with the results of operando Raman spectroscopy, show that adsorbed hydrogen hydrogenates surface *HCCOH, a key intermediate whose fate determines branching to ethanol versus ethylene.},
doi = {10.1038/s41467-019-13833-8},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {12}
}

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Cited by: 13 works
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Figures / Tables:

Fig. 1 Fig. 1: Water activation on oxide-modified Cu surfaces. a Calculated water dissociation reaction energies and hydrogen adsorption energies on various surfaces. b Surface configurations of CeO2/Cu with and c without adsorbed hydrogen.

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