Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals

Cave, Etosha R.; Shi, Chuan; Kuhl, Kendra P.; Hatsukade, Toru; Abram, David N.; Hahn, Christopher; Chan, Karen; Jaramillo, Thomas F.

doi:10.1021/acscatal.7b03807

Title: Trends in the Catalytic Activity of Hydrogen Evolution during CO₂ Electroreduction on Transition Metals

Journal Article · Fri Mar 09 00:00:00 EST 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b03807· OSTI ID:1469212

Cave, Etosha R. ^[1]; Shi, Chuan ^[1]; Kuhl, Kendra P. ^[1]; Hatsukade, Toru ^[1]; Abram, David N. ^[1];

^[1];

^[1]

Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

During CO₂ electroreduction (CO₂R), the hydrogen evolution reaction (HER) is a competing reaction. We present a combined experimental and theoretical investigation of the HER activity of transition metals under CO₂R conditions. Experimental HER polarization curves were measured for six polycrystalline metal surfaces (Au, Ag, Cu, Ni, Pt, and Fe) in the presence of CO₂ gas. We found that the HER activity of the transition metals is significantly shifted, relative to the CO₂-free case. Density functional theory (DFT) calculations suggest that this shift arises from adsorbate–adsorbate interactions between *CO and *H on intermediate and strong binding metals, which weakens the *H binding energy. Using a simple model for the effect of *CO on the *H binding energy, we construct an activity volcano for HER in the presence of CO₂ gas that is consistent with experimental trends. In conclusion, the significant changes in HER activity in the presence of CO₂ gas is an important consideration in catalyst design and could help develop catalysts that are more selective for CO₂R than the HER.

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:: SC0004993

OSTI ID:: 1469212

Journal Information:: ACS Catalysis, Vol. 8, Issue 4; Related Information: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.7b03807.; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 72 works

Citation information provided by
Web of Science

References (46)

Opportunities and challenges for a sustainable energy future Chu, Steven; Majumdar, Arun Nature, Vol. 488, Issue 7411, p. 294-303 https://doi.org/10.1038/nature11475	journal	August 2012
What to Do with CO ₂ Maginn, Edward J. The Journal of Physical Chemistry Letters, Vol. 1, Issue 24 https://doi.org/10.1021/jz101582c	journal	December 2010
Prospects of CO₂ Utilization via Direct Heterogeneous Electrochemical Reduction Whipple, Devin T.; Kenis, Paul J. A. The Journal of Physical Chemistry Letters, Vol. 1, Issue 24, p. 3451-3458 https://doi.org/10.1021/jz1012627	journal	December 2010
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels Qiao, Jinli; Liu, Yuyu; Hong, Feng Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60323G	journal	January 2014
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B. Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr300463y	journal	June 2013
Understanding the Influence of [EMIM]Cl on the Suppression of the Hydrogen Evolution Reaction on Transition Metal Electrodes Feaster, Jeremy T.; Jongerius, Anna L.; Liu, Xinyan Langmuir, Vol. 33, Issue 37 https://doi.org/10.1021/acs.langmuir.7b01170	journal	July 2017
Ionic Liquid-Mediated Selective Conversion of CO₂ to CO at Low Overpotentials Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R. Science, Vol. 334, Issue 6056, p. 643-644 https://doi.org/10.1126/science.1209786	journal	September 2011
Water Enhancement of CO₂ Conversion on Silver in 1-Ethyl-3-Methylimidazolium Tetrafluoroborate Rosen, B. A.; Zhu, W.; Kaul, G. Journal of the Electrochemical Society, Vol. 160, Issue 2, p. H138-H141 https://doi.org/10.1149/2.004303jes	journal	November 2012
Design of an Electrochemical Cell Making Syngas (CO + H₂) from CO₂ and H₂O Reduction at Room Temperature Delacourt, Charles; Ridgway, Paul L.; Kerr, John B. Journal of The Electrochemical Society, Vol. 155, Issue 1, p. B42-B49 https://doi.org/10.1149/1.2801871	journal	January 2008
Mathematical Modeling of CO[sub 2] Reduction to CO in Aqueous Electrolytes Delacourt, Charles; Ridgway, Paul L.; Newman, John Journal of The Electrochemical Society, Vol. 157, Issue 12 https://doi.org/10.1149/1.3502532	journal	January 2010
Controlling H ⁺ vs CO ₂ Reduction Selectivity on Pb Electrodes Lee, Chang Hoon; Kanan, Matthew W. ACS Catalysis, Vol. 5, Issue 1 https://doi.org/10.1021/cs5017672	journal	November 2014
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
Effect of Cations on the Electrochemical Conversion of CO₂ to CO Thorson, M. R.; Siil, K. I.; Kenis, P. J. A. Journal of the Electrochemical Society, Vol. 160, Issue 1, p. F69-F74 https://doi.org/10.1149/2.052301jes	journal	November 2012
Active and Selective Conversion of CO ₂ to CO on Ultrathin Au Nanowires Zhu, Wenlei; Zhang, Yin-Jia; Zhang, Hongyi Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja5095099	journal	November 2014
Nitrogen-Based Catalysts for the Electrochemical Reduction of CO ₂ to CO Tornow, Claire E.; Thorson, Michael R.; Ma, Sichao Journal of the American Chemical Society, Vol. 134, Issue 48 https://doi.org/10.1021/ja308217w	journal	November 2012
Electrocatalysis of the HER in acid and alkaline media Danilovic, Nemanja; Subbaraman, Ram; Strmcnik, Dusan Journal of the Serbian Chemical Society, Vol. 78, Issue 12 https://doi.org/10.2298/JSC131118136D	journal	January 2013
Work function, electronegativity, and electrochemical behaviour of metals Trasatti, Sergio Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 39, Issue 1 https://doi.org/10.1016/S0022-0728(72)80485-6	journal	September 1972
Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation Vesborg, Peter C. K.; Seger, Brian; Chorkendorff, Ib The Journal of Physical Chemistry Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acs.jpclett.5b00306	journal	March 2015
Computational high-throughput screening of electrocatalytic materials for hydrogen evolution Greeley, Jeff; Jaramillo, Thomas F.; Bonde, Jacob Nature Materials, Vol. 5, Issue 11, p. 909-913 https://doi.org/10.1038/nmat1752	journal	October 2006
Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media Ooka, Hideshi; Figueiredo, Marta C.; Koper, Marc T. M. Langmuir, Vol. 33, Issue 37 https://doi.org/10.1021/acs.langmuir.7b00696	journal	May 2017
Competition between CO ₂ Reduction and H ₂ Evolution on Transition-Metal Electrocatalysts Zhang, Yin-Jia; Sethuraman, Vijay; Michalsky, Ronald ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5012298	journal	September 2014
Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces Shi, Chuan; Hansen, Heine A.; Lausche, Adam C. Physical Chemistry Chemical Physics, Vol. 16, Issue 10 https://doi.org/10.1039/c3cp54822h	journal	January 2014
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
Infrared Spectroscopic Observation of Intermediate Species on Ni and Fe Electrodes in the Electrochemical Reduction of CO ₂ and CO to Hydrocarbons Koga, Osamu; Matsuo, Tadanori; Yamazaki, Hiroki Bulletin of the Chemical Society of Japan, Vol. 71, Issue 2 https://doi.org/10.1246/bcsj.71.315	journal	February 1998
Electroreduction of carbon dioxide on platinum single crystal electrodes: electrochemical and in situ FTIR studies Nikolic, B. Z.; Huang, H.; Gervasio, D. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 295, Issue 1-2, p. 415-423 https://doi.org/10.1016/0022-0728(90)85033-2	journal	November 1990
Carbon Monoxide Adsorption on Copper and Silver Electrodes during Carbon Dioxide Electroreduction Studied by Infrared Reflection Absorption Spectroscopy and Surface-Enhanced Raman Spectroscopy Oda, Ichiro; Ogasawara, Hirohito; Ito, Masatoki Langmuir, Vol. 12, Issue 4, p. 1094-1097 https://doi.org/10.1021/la950167j	journal	January 1996
Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes Pérez-Gallent, Elena; Figueiredo, Marta C.; Calle-Vallejo, Federico Angewandte Chemie International Edition, Vol. 56, Issue 13 https://doi.org/10.1002/anie.201700580	journal	February 2017
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R. Journal of the American Chemical Society, Vol. 136, Issue 40 https://doi.org/10.1021/ja505791r	journal	August 2014
Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals Grabow, Lars C.; Hvolbæk, Britt; Nørskov, Jens K. Topics in Catalysis, Vol. 53, Issue 5-6 https://doi.org/10.1007/s11244-010-9455-2	journal	February 2010
On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces Lausche, Adam C.; Medford, Andrew J.; Khan, Tuhin Suvra Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.08.002	journal	November 2013
Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 8 https://doi.org/10.1039/f19898502309	journal	January 1989
Trends in the Exchange Current for Hydrogen Evolution Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1856988	journal	January 2005
Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces Sheng, Wenchao; Myint, MyatNoeZin; Chen, Jingguang G. Energy & Environmental Science, Vol. 6, Issue 5 https://doi.org/10.1039/c3ee00045a	journal	January 2013
Design principles for hydrogen evolution reaction catalyst materials Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan Nano Energy, Vol. 29 https://doi.org/10.1016/j.nanoen.2016.04.017	journal	November 2016
Platinum and hybrid polyaniline–platinum surfaces for the electrocatalytic reduction of CO2 Abram, David N.; Kuhl, Kendra P.; Cave, Etosha R. MRS Communications, Vol. 5, Issue 2 https://doi.org/10.1557/mrc.2015.30	journal	June 2015
Insights into the electrocatalytic reduction of CO ₂ on metallic silver surfaces Hatsukade, Toru; Kuhl, Kendra P.; Cave, Etosha R. Phys. Chem. Chem. Phys., Vol. 16, Issue 27 https://doi.org/10.1039/C4CP00692E	journal	January 2014
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
Electrochemical CO ₂ reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P. Physical Chemistry Chemical Physics, Vol. 19, Issue 24 https://doi.org/10.1039/C7CP02855E	journal	January 2017
Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R. ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b00687	journal	June 2017
Activity Descriptors for CO ₂ Electroreduction to Methane on Transition-Metal Catalysts Peterson, Andrew A.; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201461p	journal	January 2012
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
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
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
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010
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

Cited By (12)

Theory-guided design of catalytic materials using scaling relationships and reactivity descriptors Zhao, Zhi-Jian; Liu, Sihang; Zha, Shenjun Nature Reviews Materials, Vol. 4, Issue 12 https://doi.org/10.1038/s41578-019-0152-x	journal	November 2019
Self-supported copper-based gas diffusion electrodes for CO ₂ electrochemical reduction Zhang, Jie; Luo, Wen; Züttel, Andreas Journal of Materials Chemistry A, Vol. 7, Issue 46 https://doi.org/10.1039/c9ta06736a	journal	January 2019
Switching of Kinetically Relevant Reactants for the Aqueous Cathodic Process Determined by Mass‐transport Coupled with Protolysis Shinagawa, Tatsuya; Obata, Keisuke; Takanabe, Kazuhiro ChemCatChem, Vol. 11, Issue 24 https://doi.org/10.1002/cctc.201901459	journal	October 2019
Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO ₂ Reduction Garg, Sahil; Li, Mengran; Rufford, Thomas E. ChemSusChem, Vol. 13, Issue 2 https://doi.org/10.1002/cssc.201902433	journal	November 2019
Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO ₂ RR) Kim, Cheonghee; Dionigi, Fabio; Beermann, Vera Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201805617	journal	December 2018
Lateral Adsorbate Interactions Inhibit HCOO ⁻ while Promoting CO Selectivity for CO ₂ Electrocatalysis on Silver Bohra, Divya; Ledezma-Yanez, Isis; Li, Guanna Angewandte Chemie, Vol. 131, Issue 5 https://doi.org/10.1002/ange.201811667	journal	December 2018
Robust and biocompatible catalysts for efficient hydrogen-driven microbial electrosynthesis Kracke, Frauke; Wong, Andrew Barnabas; Maegaard, Karen Communications Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/s42004-019-0145-0	journal	April 2019
Surface structure-dependent electrocatalytic reduction of CO ₂ to C1 products on SnO ₂ catalysts Fang, Minling; Zheng, Zhiping; Chen, Jiayu Sustainable Energy & Fuels, Vol. 4, Issue 2 https://doi.org/10.1039/c9se00678h	journal	January 2020
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
Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO ₂ Reduction and Hydrogen Evolution Wang, Tingting; Zhao, Qidong; Fu, Yuanyuan Small Methods, Vol. 3, Issue 10 https://doi.org/10.1002/smtd.201900210	journal	May 2019
Lateral Adsorbate Interactions Inhibit HCOO ⁻ while Promoting CO Selectivity for CO ₂ Electrocatalysis on Silver Bohra, Divya; Ledezma‐Yanez, Isis; Li, Guanna Angewandte Chemie International Edition, Vol. 58, Issue 5 https://doi.org/10.1002/anie.201811667	journal	January 2019
Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO ₂ Reduction Garg, Sahil; Li, Mengran; Rufford, Thomas E. ChemSusChem, Vol. 13, Issue 2 https://doi.org/10.1002/cssc.201903390	journal	December 2019

Figures / Tables (4)

Similar Records

Interface Engineering of Earth-Abundant Transition Metals Using Boron Nitride for Selective Electroreduction of CO₂

Journal Article · Thu Feb 01 00:00:00 EST 2018 · ACS Applied Materials and Interfaces · OSTI ID:1469212

Hu, Guoxiang; Wu, Zili; Dai, Sheng; +1 more

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Journal Article · Tue Dec 15 00:00:00 EST 2020 · Journal of Physical Chemistry. C · OSTI ID:1469212

Tang, Michael T.; Liu, Xinyan; Ji, Yongfei; +2 more

Understanding the Origin of Highly Selective CO ₂ Electroreduction to CO on Ni,N‐doped Carbon Catalysts

Journal Article · Tue Jan 28 00:00:00 EST 2020 · Angewandte Chemie · OSTI ID:1469212

Koshy, David M.; Chen, Shucheng; Lee, Dong Un; +10 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
adsorbate−adsorbate interactions
CO2 electroreduction
electrocatalysis
hydrogen evolution reaction
volcano plot

Title: Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals

Citation Formats