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

Peng, Hong-Jie; Tang, Michael T.; Halldin Stenlid, Joakim; Liu, Xinyan; Abild-Pedersen, Frank

doi:10.1038/s41467-022-29140-8

Title: 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

DOI:https://doi.org/10.1038/s41467-022-29140-8· OSTI ID:1846004

^[1]; Tang, Michael T. ^[1];

^[1]; Liu, Xinyan ^[1];

^[1]

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

The electrochemical conversion of carbon di-/monoxide into commodity chemicals paves a way towards a sustainable society but it also presents one of the great challenges in catalysis. Herein, we present the trends in selectivity towards specific dicarbon oxygenate/hydrocarbon products from carbon monoxide reduction on transition metal catalysts, with special focus on copper. We unveil the distinctive role of electrolyte pH in tuning the dicarbon oxygenate/hydrocarbon selectivity. The understanding is based on density functional theory calculated energetics and microkinetic modeling. We identify the critical reaction steps determining selectivity and relate their transition state energies to two simple descriptors, the carbon and hydroxide binding strengths. The atomistic insight gained enables us to rationalize a number of experimental observations and provides avenues towards the design of selective electrocatalysts for liquid fuel production from carbon di-/monoxide.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Lab., 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:: 1846004

Journal Information:: Nature Communications, Vol. 13, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

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
Formation of carbon–nitrogen bonds in carbon monoxide electrolysis Jouny, Matthew; Lv, Jing-Jing; Cheng, Tao Nature Chemistry, Vol. 11, Issue 9 https://doi.org/10.1038/s41557-019-0312-z	journal	August 2019
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
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
Rate and mechanism of the ketene hydrolysis in aqueous solution Bothe, E.; Dessouki, A. M.; Schulte-Frohlinde, D. The Journal of Physical Chemistry, Vol. 84, Issue 24 https://doi.org/10.1021/j100461a027	journal	November 1980
The role of atomic carbon in directing electrochemical CO ₍₂₎ reduction to multicarbon products Peng, Hongjie; Tang, Michael T.; Liu, Xinyan Energy & Environmental Science, Vol. 14, Issue 1 https://doi.org/10.1039/D0EE02826F	journal	January 2021
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
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
Engineering Cu surfaces for the electrocatalytic conversion of CO ₂ : Controlling selectivity toward oxygenates and hydrocarbons Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun Proceedings of the National Academy of Sciences, Vol. 114, Issue 23 https://doi.org/10.1073/pnas.1618935114	journal	May 2017
mBEEF: An accurate semi-local Bayesian error estimation density functional Wellendorff, Jess; Lundgaard, Keld T.; Jacobsen, Karsten W. The Journal of Chemical Physics, Vol. 140, Issue 14 https://doi.org/10.1063/1.4870397	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
Structure-sensitive electroreduction of acetaldehyde to ethanol on copper and its mechanistic implications for CO and CO 2 reduction Ledezma-Yanez, Isis; Gallent, Elena Pérez; Koper, Marc T. M. Catalysis Today, Vol. 262 https://doi.org/10.1016/j.cattod.2015.09.029	journal	March 2016
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
Nanoporous Copper–Silver Alloys by Additive-Controlled Electrodeposition for the Selective Electroreduction of CO ₂ to Ethylene and Ethanol Hoang, Thao T. H.; Verma, Sumit; Ma, Sichao Journal of the American Chemical Society, Vol. 140, Issue 17 https://doi.org/10.1021/jacs.8b01868	journal	April 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
CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends Medford, Andrew J.; Shi, Chuan; Hoffmann, Max J. Catalysis Letters, Vol. 145, Issue 3 https://doi.org/10.1007/s10562-015-1495-6	journal	February 2015
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
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235149	journal	June 2012
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
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
Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide-Derived Copper Bertheussen, Erlend; Verdaguer-Casadevall, Arnau; Ravasio, Davide Angewandte Chemie International Edition, Vol. 55, Issue 4 https://doi.org/10.1002/anie.201508851	journal	December 2015
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
Catalysis-Hub.org, an open electronic structure database for surface reactions Winther, Kirsten T.; Hoffmann, Max J.; Boes, Jacob R. Scientific Data, Vol. 6, Issue 1 https://doi.org/10.1038/s41597-019-0081-y	journal	May 2019
Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH Varela, Ana Sofia; Kroschel, Matthias; Reier, Tobias Catalysis Today, Vol. 260 https://doi.org/10.1016/j.cattod.2015.06.009	journal	February 2016
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
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
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
Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts Granda‐Marulanda, Laura P.; Builes, Santiago; Koper, Marc T. M. ChemPhysChem, Vol. 20, Issue 22 https://doi.org/10.1002/cphc.201900512	journal	August 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
Carbon monoxide electroreduction as an emerging platform for carbon utilization Jouny, Matthew; Hutchings, Gregory S.; Jiao, Feng Nature Catalysis, Vol. 2, Issue 12 https://doi.org/10.1038/s41929-019-0388-2	journal	December 2019
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
Electrochemically converting carbon monoxide to liquid fuels by directing selectivity with electrode surface area Wang, Lei; Nitopi, Stephanie; Wong, Andrew B. Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0301-z	journal	June 2019
Importance of Solvation for the Accurate Prediction of Oxygen Reduction Activities of Pt-Based Electrocatalysts He, Zheng-Da; Hanselman, Selwyn; Chen, Yan-Xia The Journal of Physical Chemistry Letters, Vol. 8, Issue 10 https://doi.org/10.1021/acs.jpclett.7b01018	journal	May 2017
Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate Luc, Wesley; Fu, Xianbiao; Shi, Jianjian Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0269-8	journal	April 2019
Selective reduction of CO to acetaldehyde with CuAg electrocatalysts Wang, Lei; Higgins, Drew C.; Ji, Yongfei Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821683117	journal	January 2020
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
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
Binding Site Diversity Promotes CO ₂ Electroreduction to Ethanol Li, Yuguang C.; Wang, Ziyun; Yuan, Tiange Journal of the American Chemical Society, Vol. 141, Issue 21 https://doi.org/10.1021/jacs.9b02945	journal	May 2019
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
Electroreduction of CO on Polycrystalline Copper at Low Overpotentials Bertheussen, Erlend; Hogg, Thomas V.; Abghoui, Younes ACS Energy Letters, Vol. 3, Issue 3 https://doi.org/10.1021/acsenergylett.8b00092	journal	February 2018
Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold Ringe, Stefan; Morales-Guio, Carlos G.; Chen, Leanne D. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-13777-z	journal	January 2020
Low-Overpotential Electroreduction of Carbon Monoxide Using Copper Nanowires Raciti, David; Cao, Liang; Livi, Kenneth J. T. ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b01124	journal	June 2017
Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches Heenen, Hendrik H.; Gauthier, Joseph A.; Kristoffersen, Henrik H. The Journal of Chemical Physics, Vol. 152, Issue 14 https://doi.org/10.1063/1.5144912	journal	April 2020
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
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
The role of in situ generated morphological motifs and Cu(i) species in C2+ product selectivity during CO2 pulsed electroreduction Arán-Ais, Rosa M.; Scholten, Fabian; Kunze, Sebastian Nature Energy, Vol. 5, Issue 4 https://doi.org/10.1038/s41560-020-0594-9	journal	March 2020
Computational Comparison of Late Transition Metal (100) Surfaces for the Electrocatalytic Reduction of CO to C ₂ Species Hanselman, Selwyn; Koper, Marc T. M.; Calle-Vallejo, Federico ACS Energy Letters, Vol. 3, Issue 5 https://doi.org/10.1021/acsenergylett.8b00326	journal	April 2018
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
Electrochemical CO ₂ Reduction: Classifying Cu Facets Bagger, Alexander; Ju, Wen; Varela, Ana Sofia ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b01899	journal	July 2019
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
The effects of currents and potentials on the selectivities of copper toward carbon dioxide electroreduction Ren, Dan; Fong, Jinhuan; Yeo, Boon Siang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03286-w	journal	March 2018

Similar Records

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 · OSTI ID:1846004

Peng, Hongjie; Tang, Michael T.; Liu, Xinyan; +3 more

An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO ₂ Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates

Journal Article · Wed Dec 19 00:00:00 EST 2018 · Journal of Physical Chemistry. C · OSTI ID:1846004

Katayama, Yu; Nattino, Francesco; Giordano, Livia; +5 more

Mechanistic Insights into Aldehyde Production from Electrochemical CO₂ Reduction on CuAg Alloy via Operando X-ray Measurements

Journal Article · Thu Jun 29 00:00:00 EDT 2023 · ACS Catalysis · OSTI ID:1846004

Qiao, Yu; Kastlunger, Georg; Davis, Ryan C.; +13 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis
chemical engineering
electrochemistry
energy science and technology
materials for energy and catalysis

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

Citation Formats

References (58)

Similar Records

Related Subjects

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