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:
-
- 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. doi: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}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel
journal, January 2016
- Gao, Shan; Lin, Yue; Jiao, Xingchen
- Nature, Vol. 529, Issue 7584
Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO
journal, June 2017
- Schreier, Marcel; Héroguel, Florent; Steier, Ludmilla
- Nature Energy, Vol. 2, Issue 7
Selective increase in CO 2 electroreduction activity at grain-boundary surface terminations
journal, November 2017
- Mariano, Ruperto G.; McKelvey, Kim; White, Henry S.
- Science, Vol. 358, Issue 6367
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013
- Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
- Chemical Reviews, Vol. 113, Issue 8
Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
journal, August 2016
- Liu, Min; Pang, Yuanjie; Zhang, Bo
- Nature, Vol. 537, Issue 7620
Nanostructured electrocatalysts with tunable activity and selectivity
journal, March 2016
- Mistry, Hemma; Varela, Ana Sofia; Kühl, Stefanie
- Nature Reviews Materials, Vol. 1, Issue 4
CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
journal, May 2018
- Dinh, Cao-Thang; Burdyny, Thomas; Kibria, Md Golam
- Science, Vol. 360, Issue 6390
A Step Closer to the Electrochemical Production of Liquid Fuels
journal, July 2014
- Schouten, Klaas Jan P.; Calle-Vallejo, Federico; Koper, Marc T. M.
- Angewandte Chemie International Edition, Vol. 53, Issue 41
A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2
journal, June 2016
- Verma, Sumit; Kim, Byoungsu; Jhong, Huei-Ru “Molly”
- ChemSusChem, Vol. 9, Issue 15
What Should We Make with CO2 and How Can We Make It?
journal, May 2018
- Bushuyev, Oleksandr S.; De Luna, Phil; Dinh, Cao Thang
- Joule, Vol. 2, Issue 5
A comparative technoeconomic analysis of pathways for commercial electrochemical CO 2 reduction to liquid products
journal, January 2018
- Spurgeon, Joshua M.; Kumar, Bijandra
- Energy & Environmental Science, Vol. 11, Issue 6
Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017
- Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.
- Science, Vol. 355, Issue 6321
Towards the computational design of solid catalysts
journal, April 2009
- Nørskov, J.; Bligaard, T.; Rossmeisl, J.
- Nature Chemistry, Vol. 1, Issue 1, p. 37-46
Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017
- Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
- Nature Communications, Vol. 8, Issue 1
Tuning the Selectivity of Carbon Dioxide Electroreduction toward Ethanol on Oxide-Derived Cu x Zn Catalysts
journal, November 2016
- Ren, Dan; Ang, Bridget Su-Hui; Yeo, Boon Siang
- ACS Catalysis, Vol. 6, Issue 12
Importance of Ag–Cu Biphasic Boundaries for Selective Electrochemical Reduction of CO 2 to Ethanol
journal, November 2017
- Lee, Seunghwa; Park, Gibeom; Lee, Jaeyoung
- ACS Catalysis, Vol. 7, Issue 12
Electrochemical CO 2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity
journal, October 2017
- Clark, Ezra L.; Hahn, Christopher; Jaramillo, Thomas F.
- Journal of the American Chemical Society, Vol. 139, Issue 44
Nanoporous Copper–Silver Alloys by Additive-Controlled Electrodeposition for the Selective Electroreduction of CO 2 to Ethylene and Ethanol
journal, April 2018
- Hoang, Thao T. H.; Verma, Sumit; Ma, Sichao
- Journal of the American Chemical Society, Vol. 140, Issue 17
Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst
journal, October 2018
- Morales-Guio, Carlos G.; Cave, Etosha R.; Nitopi, Stephanie A.
- Nature Catalysis, Vol. 1, Issue 10
Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols
journal, June 2018
- Zhuang, Tao-Tao; Liang, Zhi-Qin; Seifitokaldani, Ali
- Nature Catalysis, Vol. 1, Issue 6
Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons
journal, July 2018
- Zhou, Yansong; Che, Fanglin; Liu, Min
- Nature Chemistry, Vol. 10, Issue 9
Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2
journal, September 2018
- Liang, Zhi-Qin; Zhuang, Tao-Tao; Seifitokaldani, Ali
- Nature Communications, Vol. 9, Issue 1
Engineering Cu surfaces for the electrocatalytic conversion of CO 2 : Controlling selectivity toward oxygenates and hydrocarbons
journal, May 2017
- Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 23
Nanoporous Copper Films by Additive-Controlled Electrodeposition: CO 2 Reduction Catalysis
journal, April 2017
- Hoang, Thao T. H.; Ma, Sichao; Gold, Jake I.
- ACS Catalysis, Vol. 7, Issue 5
A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction
journal, October 2018
- Lv, Jing-Jing; Jouny, Matthew; Luc, Wesley
- Advanced Materials, Vol. 30, Issue 49
One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer
journal, January 2016
- Ma, Sichao; Sadakiyo, Masaaki; Luo, Raymond
- Journal of Power Sources, Vol. 301
Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO 2
journal, April 2016
- Li, Yawei; Sun, Qiang
- Advanced Energy Materials, Vol. 6, Issue 17
Atomistic Mechanisms Underlying Selectivities in C 1 and C 2 Products from Electrochemical Reduction of CO on Cu(111)
journal, December 2016
- Xiao, Hai; Cheng, Tao; Goddard, William A.
- Journal of the American Chemical Society, Vol. 139, Issue 1
Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products
journal, July 2018
- Lum, Yanwei; Cheng, Tao; Goddard, William A.
- Journal of the American Chemical Society, Vol. 140, Issue 30
pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019
- Liu, Xinyan; Schlexer, Philomena; Xiao, Jianping
- Nature Communications, Vol. 10, Issue 1
Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011
- Subbaraman, R.; Tripkovic, D.; Strmcnik, D.
- Science, Vol. 334, Issue 6060
Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules
journal, December 2018
- Dinh, Cao-Thang; Jain, Ankit; de Arquer, F. Pelayo García
- Nature Energy, Vol. 4, Issue 2
Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts
journal, May 2012
- Subbaraman, Ram; Tripkovic, Dusan; Chang, Kee-Chul
- Nature Materials, Vol. 11, Issue 6
Gold-supported cerium-doped NiOx catalysts for water oxidation
journal, April 2016
- Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal
- Nature Energy, Vol. 1, Issue 5
Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction
journal, January 2018
- De Luna, Phil; Quintero-Bermudez, Rafael; Dinh, Cao-Thang
- Nature Catalysis, Vol. 1, Issue 2
Copper adparticle enabled selective electrosynthesis of n-propanol
journal, November 2018
- Li, Jun; Che, Fanglin; Pang, Yuanjie
- Nature Communications, Vol. 9, Issue 1
Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K
journal, February 2017
- Cheng, Tao; Xiao, Hai; Goddard, William A.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 8
Synthesis of Cu/CeO 2-x Nanocrystalline Heterodimers with Interfacial Active Sites To Promote CO 2 Electroreduction
journal, April 2019
- Varandili, Seyedeh Behnaz; Huang, Jianfeng; Oveisi, Emad
- ACS Catalysis, Vol. 9, Issue 6
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Room-Temperature Activation of Methane and Dry Re-forming with CO 2 on Ni-CeO 2 (111) Surfaces: Effect of Ce 3+ Sites and Metal–Support Interactions on C–H Bond Cleavage
journal, November 2016
- Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan
- ACS Catalysis, Vol. 6, Issue 12
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
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