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 CO ₂ Electroreduction on Transition Metals

Abstract

During CO ₂ electroreduction (CO ₂R), 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 CO ₂R conditions. Experimental HER polarization curves were measured for six polycrystalline metal surfaces (Au, Ag, Cu, Ni, Pt, and Fe) in the presence of CO ₂ gas. We found that the HER activity of the transition metals is significantly shifted, relative to the CO ₂-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 CO ₂ gas that is consistent with experimental trends. In conclusion, the significant changes in HER activity in the presence of CO ₂ gas is an important consideration in catalyst design and could help develop catalysts that are more selective for CO ₂R 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) (SC-22)

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.

Copy to clipboard


                    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.

Copy to clipboard


                    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.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acscatal.7b03807

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 11 works

Citation information provided by
Web of Science

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.

All figures and tables (4 total)

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Designing materials for electrochemical carbon dioxide recycling
journal, July 2019

Ross, Michael B.; De Luna, Phil; Li, Yifan
Nature Catalysis, Vol. 2, Issue 8
DOI: 10.1038/s41929-019-0306-7

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar records in OSTI.GOV collections:

Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

Technical Report Jaramillo, Thomas F.

In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo ₃S ₁₃] ^2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamentalmore »« less
DOI: 10.2172/1248342

Full Text Available
Interface Engineering of Earth-Abundant Transition Metals Using Boron Nitride for Selective Electroreduction of CO ₂

Journal Article Hu, Guoxiang ; Wu, Zili ; Dai, Sheng ; ... - ACS Applied Materials and Interfaces

Two-dimensional atomically thin hexagonal boron nitride (h-BN) monolayers have attracted considerable research interest. In this paper, given the tremendous progress in the synthesis of h-BN monolayers on transition metals and their potential as electrocatalysts, we investigate the electrocatalytic activities of h-BN/Ni, h-BN/Co, and h-BN/Cu interfaces for CO ₂ reduction by the first-principles density functional theory. We find that with the h-BN monolayer on the metal, electrons transfer from the metal to the interface and accumulate under the B atoms. By calculating the binding energies of three key intermediates (H, HCOO, and COOH) for hydrogen evolution and CO ₂ reduction, wemore »« less
Cited by 7
DOI: 10.1021/acsami.7b17600

Full Text Available
Mechanism of Hydrogen Evolution Reaction on 1T-MoS ₂ from First Principles

Journal Article Tang, Qing ; Jiang, De-en - ACS Catalysis

The 1T phase of transition-metal dichalcogenides (TMDs) has been shown in recent experiments to display excellent catalytic activity for hydrogen evolution reaction (HER), but the catalytic mechanism has not been elucidated so far. Herein, using 1T MoS ₂ as the prototypical TMD material, we studied the HER activity on its basal plane from periodic density functional theory (DFT) calculations. Compared to the nonreactive basal plane of 2H phase MoS ₂, the catalytic activity of the basal plane of 1T phase MoS ₂ mainly arises from its affinity for binding H at the surface S sites. Using the binding free energymore »« less
Cited by 102
DOI: 10.1021/acscatal.6b01211

Full Text Available
Rapid flame doping of Co to WS ₂ for efficient hydrogen evolution

Journal Article Shi, Xinjian ; Fields, Meredith ; Park, Joonsuk ; ... - Energy & Environmental Science

Transition metal sulfides have been widely studied as electrocatalysts for the hydrogen evolution reaction (HER). Though elemental doping is an effective way to enhance sulfide activity for the HER, most studies have only focused on the effect of doping sulfide edge sites. Few studies have investigated the effect of doping the basal plane or the effect of doping concentration on basal plane activity. Probing the dopant concentration dependence of HER activity is challenging due to experimental difficulties in controlling dopant incorporation. We overcome this challenge by first synthesizing doped transition metal oxides and then sulfurizing the oxides to sulfides, yieldingmore »« less
Cited by 9
DOI: 10.1039/c8ee01111g

Full Text Available
Quantum Mechanical Screening of Single-Atom Bimetallic Alloys for the Selective Reduction of CO ₂ to C ₁ Hydrocarbons

Journal Article Cheng, Mu-Jeng ; Clark, Ezra L. ; Pham, Hieu H. ; ... - ACS Catalysis

Electrocatalytic reduction of CO ₂ to energy-rich hydrocarbons such as alkanes, alkenes, and alcohols is a very challenging task. So far, only copper has proven to be capable of such a conversion. Here, we report density functional theory (DFT) calculations combined with the Poisson-Boltzmann implicit solvation model to show that single-atom alloys (SAAs) are promising electrocatalysts for CO ₂ reduction to C 1 hydrocarbons in aqueous solution. The majority component of the SAAs studied is either gold or silver, in combination with isolated single atoms, M (M = Cu, Ni, Pd, Pt, Co, Rh, and Ir), replacing surface atoms. Wemore »« less
Cited by 51
DOI: 10.1021/acscatal.6b01393

Full Text Available

Similar Records

Title: Trends in the Catalytic Activity of Hydrogen Evolution during CO 2 Electroreduction on Transition Metals

Abstract

Citation Formats

Figures / Tables:

Designing materials for electrochemical carbon dioxide recycling journal, July 2019

Title: Trends in the Catalytic Activity of Hydrogen Evolution during CO ₂ Electroreduction on Transition Metals

Designing materials for electrochemical carbon dioxide recycling
journal, July 2019