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

doi:10.1021/acscatal.7b03807

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

Abstract

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.

Authors:

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)

Publication Date:: 2018-03-09

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

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

OSTI Identifier:: 1469212

Grant/Contract Number:: SC0004993

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

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

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Cave, Etosha R., Shi, Chuan, Kuhl, Kendra P., Hatsukade, Toru, Abram, David N., Hahn, Christopher, Chan, Karen, and Jaramillo, Thomas F. Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals.  United States: N. p., 2018. 
        Web.  doi:10.1021/acscatal.7b03807.

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                    Cave, Etosha R., Shi, Chuan, Kuhl, Kendra P., Hatsukade, Toru, Abram, David N., Hahn, Christopher, Chan, Karen, & Jaramillo, Thomas F. Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals.  United States.  doi:10.1021/acscatal.7b03807.

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                    Cave, Etosha R., Shi, Chuan, Kuhl, Kendra P., Hatsukade, Toru, Abram, David N., Hahn, Christopher, Chan, Karen, and Jaramillo, Thomas F. Fri .  
        "Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals".  United States.  doi:10.1021/acscatal.7b03807.  https://www.osti.gov/servlets/purl/1469212.

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@article{osti_1469212,

  title        = {Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals},

  author       = {Cave, Etosha R. and Shi, Chuan and Kuhl, Kendra P. and Hatsukade, Toru and Abram, David N. and Hahn, Christopher and Chan, Karen and Jaramillo, Thomas F.},

  abstractNote = {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.},

  doi          = {10.1021/acscatal.7b03807},

  journal      = {ACS Catalysis},

  number       = 4,

  volume       = 8,

  place        = {United States},

  year         = {2018},

  month        = {3}

}

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Journal Article:

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DOI: 10.1021/acscatal.7b03807

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Cited by: 11 works

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Figures / Tables:

Figure 1: Hydrogen partial current densities under CO₂R conditions for six polycrystalline transition metals. The potential at 1 mA/cm² was used as an activity metric for the metals.

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Works referencing / citing this record:

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

Abstract

Citation Formats

Figures / Tables:

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

Designing materials for electrochemical carbon dioxide recycling
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Designing materials for electrochemical carbon dioxide recycling
journal, July 2019

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journal, December 2018

Lateral Adsorbate Interactions Inhibit HCOO ⁻ while Promoting CO Selectivity for CO ₂ Electrocatalysis on Silver
journal, December 2018

Switching of Kinetically Relevant Reactants for the Aqueous Cathodic Process Determined by Mass‐transport Coupled with Protolysis
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Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO ₂ Reduction
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CO ₂ reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions
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