The role of atomic carbon in directing electrochemical CO(2) reduction to multicarbon products

Peng, Hongjie; Tang, Michael T.; Liu, Xinyan; Schlexer Lamoureux, Philomena; Bajdich, Michal; Abild-Pedersen, Frank

doi:10.1039/d0ee02826f

Title: The role of atomic carbon in directing electrochemical CO₍₂₎ reduction to multicarbon products

Journal Article · Mon Nov 23 00:00:00 EST 2020 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d0ee02826f· OSTI ID:1768257

^[1]; Tang, Michael T. ^[2]; Liu, Xinyan ^[1]; Schlexer Lamoureux, Philomena ^[1];

^[1];

^[1]

Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States)

Electrochemical reduction of carbon-dioxide/carbon-monoxide (CO₍₂₎R) to fuels and chemicals presents an attractive approach for sustainable chemical synthesis, but it also poses a serious challenge in catalysis. Understanding the key aspects that guide CO₍₂₎R towards value-added multicarbon (C₂₊) products is imperative in designing an efficient catalyst. Herein, we identify the critical steps toward C₂ products on copper through a combination of energetics from density functional theory and micro-kinetic modeling. We elucidate the importance of atomic carbon in directing C₂₊ selectivity and how it introduces surface structural sensitivity on copper catalysts. Overall, this insight enables us to propose two simple thermodynamic descriptors that effectively identify C₂₊ selectivity on metal catalysts beyond copper and hence it defines an intelligible protocol to screen for materials that selectively catalyze CO₍₂₎ to C₂₊ products.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0004993; SC0021266; AC02-05CH11231

OSTI ID:: 1768257

Alternate ID(s):: OSTI ID: 1742075

Journal Information:: Energy & Environmental Science, Vol. 14, Issue 1; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Theoretical Considerations on the Electroreduction of CO to C ₂ Species on Cu(100) Electrodes Calle-Vallejo, Federico; Koper, Marc T. M. Angewandte Chemie International Edition, Vol. 52, Issue 28 https://doi.org/10.1002/anie.201301470	journal	June 2013
Atomistic Mechanisms Underlying Selectivities in C ₁ and C ₂ Products from Electrochemical Reduction of CO on Cu(111) Xiao, Hai; Cheng, Tao; Goddard, William A. Journal of the American Chemical Society, Vol. 139, Issue 1 https://doi.org/10.1021/jacs.6b06846	journal	December 2016
First-principles microkinetics simulations of electrochemical reduction of CO2 over Cu catalysts Zijlstra, Bart; Zhang, Xue; Liu, Jin-Xun Electrochimica Acta, Vol. 335 https://doi.org/10.1016/j.electacta.2020.135665	journal	March 2020
Facet Dependence of CO ₂ Reduction Paths on Cu Electrodes Luo, Wenjia; Nie, Xiaowa; Janik, Michael J. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01967	journal	December 2015
Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO ₂ over Ag and Cu Singh, Meenesh R.; Kwon, Youngkook; Lum, Yanwei Journal of the American Chemical Society, Vol. 138, Issue 39 https://doi.org/10.1021/jacs.6b07612	journal	September 2016
Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products Wang, Lei; Nitopi, Stephanie A.; Bertheussen, Erlend ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b01200	journal	July 2018
What would it take for renewably powered electrosynthesis to displace petrochemical processes? De Luna, Phil; Hahn, Christopher; Higgins, Drew Science, Vol. 364, Issue 6438 https://doi.org/10.1126/science.aav3506	journal	April 2019
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Surface reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS Kim, Youn-Geun; Javier, Alnald; Baricuatro, Jack H. Journal of Electroanalytical Chemistry, Vol. 780 https://doi.org/10.1016/j.jelechem.2016.09.029	journal	November 2016
Hydroxide Is Not a Promoter of C ₂₊ Product Formation in the Electrochemical Reduction of CO on Copper Li, Jing; Wu, Donghuan; Malkani, Arnav S. Angewandte Chemie International Edition, Vol. 59, Issue 11 https://doi.org/10.1002/anie.201912412	journal	January 2020
Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K Cheng, Tao; Xiao, Hai; Goddard, William A. Proceedings of the National Academy of Sciences, Vol. 114, Issue 8 https://doi.org/10.1073/pnas.1612106114	journal	February 2017
Understanding cation effects in electrochemical CO ₂ reduction Ringe, Stefan; Clark, Ezra L.; Resasco, Joaquin Energy & Environmental Science, Vol. 12, Issue 10 https://doi.org/10.1039/C9EE01341E	journal	January 2019
Activity and Selectivity Control in CO ₂ Electroreduction to Multicarbon Products over CuO _x Catalysts via Electrolyte Design Gao, Dunfeng; McCrum, Ian T.; Deo, Shyam ACS Catalysis, Vol. 8, Issue 11 https://doi.org/10.1021/acscatal.8b02587	journal	September 2018
Nickel–Gallium-Catalyzed Electrochemical Reduction of CO ₂ to Highly Reduced Products at Low Overpotentials Torelli, Daniel A.; Francis, Sonja A.; Crompton, J. Chance ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02888	journal	February 2016
Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes Hori, Y.; Takahashi, I.; Koga, O. Journal of Molecular Catalysis A: Chemical, Vol. 199, Issue 1-2, p. 39-47 https://doi.org/10.1016/S1381-1169(03)00016-5	journal	May 2003
Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra Journal of the American Chemical Society, Vol. 139, Issue 32 https://doi.org/10.1021/jacs.7b06765	journal	August 2017
Direct Observation of the Local Reaction Environment during the Electrochemical Reduction of CO ₂ Clark, Ezra L.; Bell, Alexis T. Journal of the American Chemical Society, Vol. 140, Issue 22 https://doi.org/10.1021/jacs.8b04058	journal	April 2018
Copper nanoparticle ensembles for selective electroreduction of CO ₂ to C ₂ –C ₃ products Kim, Dohyung; Kley, Christopher S.; Li, Yifan Proceedings of the National Academy of Sciences, Vol. 114, Issue 40 https://doi.org/10.1073/pnas.1711493114	journal	September 2017
Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products Gao, Dunfeng; Arán-Ais, Rosa M.; Jeon, Hyo Sang Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0235-5	journal	March 2019
Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction Jiang, Kun; Sandberg, Robert B.; Akey, Austin J. Nature Catalysis, Vol. 1, Issue 2 https://doi.org/10.1038/s41929-017-0009-x	journal	January 2018
Self-Cleaning Catalyst Electrodes for Stabilized CO ₂ Reduction to Hydrocarbons Weng, Zhe; Zhang, Xing; Wu, Yueshen Angewandte Chemie International Edition, Vol. 56, Issue 42 https://doi.org/10.1002/anie.201707478	journal	September 2017
Theoretical Investigations of Transition Metal Surface Energies under Lattice Strain and CO Environment Tang, Michael T.; Ulissi, Zachary W.; Chan, Karen The Journal of Physical Chemistry C, Vol. 122, Issue 26 https://doi.org/10.1021/acs.jpcc.8b02094	journal	May 2018
Theoretical Insights into a CO Dimerization Mechanism in CO ₂ Electroreduction Montoya, Joseph H.; Shi, Chuan; Chan, Karen The Journal of Physical Chemistry Letters, Vol. 6, Issue 11 https://doi.org/10.1021/acs.jpclett.5b00722	journal	May 2015
Tuning the Selectivity of Carbon Dioxide Electroreduction toward Ethanol on Oxide-Derived Cu _x Zn Catalysts Ren, Dan; Ang, Bridget Su-Hui; Yeo, Boon Siang ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b02162	journal	November 2016
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders Angewandte Chemie International Edition, Vol. 54, Issue 17 https://doi.org/10.1002/anie.201412214	journal	February 2015
pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles Lamoureux, Philomena Schlexer; Singh, Aayush R.; Chan, Karen ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b00268	journal	May 2019
Progress and Perspectives of Electrochemical CO ₂ Reduction on Copper in Aqueous Electrolyte Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B. Chemical Reviews, Vol. 119, Issue 12 https://doi.org/10.1021/acs.chemrev.8b00705	journal	April 2019
Quantum-Dot-Derived Catalysts for CO2 Reduction Reaction Liu, Min; Liu, Mengxia; Wang, Xiaoming Joule, Vol. 3, Issue 7 https://doi.org/10.1016/j.joule.2019.05.010	journal	July 2019
Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst Morales-Guio, Carlos G.; Cave, Etosha R.; Nitopi, Stephanie A. Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0139-9	journal	October 2018
Designing materials for electrochemical carbon dioxide recycling Ross, Michael B.; De Luna, Phil; Li, Yifan Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0306-7	journal	July 2019
High-rate electroreduction of carbon monoxide to multi-carbon products Jouny, Matthew; Luc, Wesley; Jiao, Feng Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0133-2	journal	August 2018
Mechanism of CO ₂ Reduction at Copper Surfaces: Pathways to C ₂ Products Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03477	journal	January 2018
Electrochemical Reduction of CO at a Copper Electrode Hori, Yoshio; Takahashi, Ryutaro; Yoshinami, Yuzuru The Journal of Physical Chemistry B, Vol. 101, Issue 36 https://doi.org/10.1021/jp970284i	journal	September 1997
Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes Schouten, Klaas Jan P.; Qin, Zisheng; Pérez Gallent, Elena Journal of the American Chemical Society, Vol. 134, Issue 24 https://doi.org/10.1021/ja302668n	journal	June 2012
The Degree of Rate Control: A Powerful Tool for Catalysis Research Campbell, Charles T. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.7b00115	journal	March 2017
A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction Lv, Jing-Jing; Jouny, Matthew; Luc, Wesley Advanced Materials, Vol. 30, Issue 49 https://doi.org/10.1002/adma.201803111	journal	October 2018
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C. Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0450-y	journal	September 2019
CO ₂ electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface Dinh, Cao-Thang; Burdyny, Thomas; Kibria, Md Golam Science, Vol. 360, Issue 6390 https://doi.org/10.1126/science.aas9100	journal	May 2018
CO ₂ electrolysis to multicarbon products at activities greater than 1 A cm ⁻² García de Arquer, F. Pelayo; Dinh, Cao-Thang; Ozden, Adnan Science, Vol. 367, Issue 6478 https://doi.org/10.1126/science.aay4217	journal	February 2020
Electrochemical Barriers Made Simple Chan, Karen; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 6, Issue 14 https://doi.org/10.1021/acs.jpclett.5b01043	journal	June 2015
Universal transition state scaling relations for (de)hydrogenation over transition metals Wang, S.; Petzold, V.; Tripkovic, V. Physical Chemistry Chemical Physics, Vol. 13, Issue 46 https://doi.org/10.1039/c1cp20547a	journal	January 2011
Electrochemical CO ₂ Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity Clark, Ezra L.; Hahn, Christopher; Jaramillo, Thomas F. Journal of the American Chemical Society, Vol. 139, Issue 44 https://doi.org/10.1021/jacs.7b08607	journal	October 2017
In Situ Infrared Spectroscopy Reveals Persistent Alkalinity near Electrode Surfaces during CO ₂ Electroreduction Yang, Kailun; Kas, Recep; Smith, Wilson A. Journal of the American Chemical Society, Vol. 141, Issue 40 https://doi.org/10.1021/jacs.9b07000	journal	September 2019
Low Barrier Carbon Induced CO Dissociation on Stepped Cu Ng, M. L.; Abild-Pedersen, F.; Kaya, S. Physical Review Letters, Vol. 114, Issue 24 https://doi.org/10.1103/PhysRevLett.114.246101	journal	June 2015
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
From electricity to fuels: Descriptors for C1 selectivity in electrochemical CO2 reduction Tang, Michael T.; Peng, Hongjie; Lamoureux, Philomena Schlexer Applied Catalysis B: Environmental, Vol. 279 https://doi.org/10.1016/j.apcatb.2020.119384	journal	December 2020
Reduction of CO₂ and CO to methane on Cu foil electrodes Kim, J. J.; Summers, D. P.; Frese, K. W. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 245, Issue 1-2, p. 223-244 https://doi.org/10.1016/0022-0728(88)80071-8	journal	April 1988
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
Understanding heterogeneous electrocatalytic carbon dioxide reduction through operando techniques Handoko, Albertus D.; Wei, Fengxia Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0182-6	journal	December 2018
Understanding trends in electrochemical carbon dioxide reduction rates Liu, Xinyan; Xiao, Jianping; Peng, Hongjie Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15438	journal	May 2017
Accelerated discovery of CO2 electrocatalysts using active machine learning Zhong, Miao; Tran, Kevin; Min, Yimeng Nature, Vol. 581, Issue 7807 https://doi.org/10.1038/s41586-020-2242-8	journal	May 2020
pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper Liu, Xinyan; Schlexer, Philomena; Xiao, Jianping Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07970-9	journal	January 2019
Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2–CO co-feeds on Cu and Cu-tandem electrocatalysts Wang, Xingli; de Araújo, Jorge Ferreira; Ju, Wen Nature Nanotechnology, Vol. 14, Issue 11 https://doi.org/10.1038/s41565-019-0551-6	journal	October 2019
One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer Ma, Sichao; Sadakiyo, Masaaki; Luo, Raymond Journal of Power Sources, Vol. 301 https://doi.org/10.1016/j.jpowsour.2015.09.124	journal	January 2016

Similar Records

Trends in oxygenate/hydrocarbon selectivity for electrochemical CO₍₂₎ reduction to C₂ products

Journal Article · Thu Mar 17 00:00:00 EDT 2022 · Nature Communications · OSTI ID:1768257

Peng, Hong-Jie; Tang, Michael T.; Halldin Stenlid, Joakim; +2 more

Photoelectrochemical CO₂ Reduction toward Multicarbon Products with Silicon Nanowire Photocathodes Interfaced with Copper Nanoparticles

Journal Article · Wed Apr 27 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1768257

Roh, Inwhan; Yu, Sunmoon; Lin, Chung-Kuan; +3 more

Isolated copper single sites for high-performance electroreduction of carbon monoxide to multicarbon products

Journal Article · Mon Jan 11 00:00:00 EST 2021 · Nature Communications · OSTI ID:1768257

Bao, Haihong; Qiu, Yuan; Peng, Xianyun; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: The role of atomic carbon in directing electrochemical CO(2) reduction to multicarbon products

Citation Formats

References (54)

Similar Records

Related Subjects

Title: The role of atomic carbon in directing electrochemical CO₍₂₎ reduction to multicarbon products