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Title: Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction

Abstract

Bimetallic catalysts are attractive alternatives to extend the parameter space that can be tuned for support interactions and catalytic performance. In this study, we have investigated the smallest bimetallic catalysts dimers supported on defective graphene for the electrochemical reduction of CO2 to CH4 based on a first-principles approach and the computational hydrogen electrode model. The monometallic and bimetallic dimers formed from Group 10 (Ni, Pd, Pt) and group 11 (Cu, Ag, Au) elements are characterized by a positively charged anchoring atom occupying the vacancy site of graphene and a neutral or slightly negatively charged antenna atom sticking out from the graphene surface. The strong selective binding of these dimers ensures their high stability. Possible rate-limiting steps are identified from the full reaction pathways to generate CH4. Overall, Pt-2, AgNi, Pd-2, and AgPt are the best candidates with the lowest overpotential values of 0.37, 0.69, 0.69, and 0.76 V, respectively. It is found that the alloy effect and the interaction with support help to optimize the property. These metallic dimers, however, retain nonmonotonous property relationships that give opportunity to go beyond scaling behavior and look for a few atom catalysts that have unique properties to reduce rate-limiting potentials and improve themore » catalytic performance.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Valparaiso Univ., IN (United States). Dept. of Physics and Astronomy
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1490428
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 50; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

He, Haiying, Morrissey, Christopher, Curtiss, Larry A., and Zapol, Peter. Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b07887.
He, Haiying, Morrissey, Christopher, Curtiss, Larry A., & Zapol, Peter. Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction. United States. https://doi.org/10.1021/acs.jpcc.8b07887
He, Haiying, Morrissey, Christopher, Curtiss, Larry A., and Zapol, Peter. Mon . "Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction". United States. https://doi.org/10.1021/acs.jpcc.8b07887. https://www.osti.gov/servlets/purl/1490428.
@article{osti_1490428,
title = {Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction},
author = {He, Haiying and Morrissey, Christopher and Curtiss, Larry A. and Zapol, Peter},
abstractNote = {Bimetallic catalysts are attractive alternatives to extend the parameter space that can be tuned for support interactions and catalytic performance. In this study, we have investigated the smallest bimetallic catalysts dimers supported on defective graphene for the electrochemical reduction of CO2 to CH4 based on a first-principles approach and the computational hydrogen electrode model. The monometallic and bimetallic dimers formed from Group 10 (Ni, Pd, Pt) and group 11 (Cu, Ag, Au) elements are characterized by a positively charged anchoring atom occupying the vacancy site of graphene and a neutral or slightly negatively charged antenna atom sticking out from the graphene surface. The strong selective binding of these dimers ensures their high stability. Possible rate-limiting steps are identified from the full reaction pathways to generate CH4. Overall, Pt-2, AgNi, Pd-2, and AgPt are the best candidates with the lowest overpotential values of 0.37, 0.69, 0.69, and 0.76 V, respectively. It is found that the alloy effect and the interaction with support help to optimize the property. These metallic dimers, however, retain nonmonotonous property relationships that give opportunity to go beyond scaling behavior and look for a few atom catalysts that have unique properties to reduce rate-limiting potentials and improve the catalytic performance.},
doi = {10.1021/acs.jpcc.8b07887},
journal = {Journal of Physical Chemistry. C},
number = 50,
volume = 122,
place = {United States},
year = {2018},
month = {11}
}

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Works referenced in this record:

Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes
journal, January 2013

  • Kondratenko, Evgenii V.; Mul, Guido; Baltrusaitis, Jonas
  • Energy & Environmental Science, Vol. 6, Issue 11
  • DOI: 10.1039/c3ee41272e

Electrocatalytic conversion of CO 2 to produce solar fuels in electrolyte or electrolyte-less configurations of PEC cells
journal, January 2015

  • Ampelli, C.; Genovese, C.; Marepally, B. C.
  • Faraday Discussions, Vol. 183
  • DOI: 10.1039/C5FD00069F

Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide
journal, September 2015

  • Kortlever, Ruud; Shen, Jing; Schouten, Klaas Jan P.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
  • DOI: 10.1021/acs.jpclett.5b01559

A review on the electrochemical reduction of CO2 in fuel cells, metal electrodes and molecular catalysts
journal, September 2014


Electrocatalytic conversion of CO2 to long carbon-chain hydrocarbons
journal, January 2007

  • Centi, Gabriele; Perathoner, Siglinda; Win?, Gauthier
  • Green Chemistry, Vol. 9, Issue 6
  • DOI: 10.1039/b615275a

Achieving Selective and Efficient Electrocatalytic Activity for CO 2 Reduction Using Immobilized Silver Nanoparticles
journal, October 2015

  • Kim, Cheonghee; Jeon, Hyo Sang; Eom, Taedaehyeong
  • Journal of the American Chemical Society, Vol. 137, Issue 43
  • DOI: 10.1021/jacs.5b06568

Fe and Pt carbon nanotubes for the electrocatalytic conversion of carbon dioxide to oxygenates
journal, May 2009


Carbon dioxide conversion into hydrocarbon fuels on defective graphene-supported Cu nanoparticles from first principles
journal, January 2014

  • Lim, Dong-Hee; Jo, Jun Ho; Shin, Dong Yun
  • Nanoscale, Vol. 6, Issue 10
  • DOI: 10.1039/C3NR06539A

Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane
journal, February 2009

  • Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P.
  • Nature Materials, Vol. 8, Issue 3
  • DOI: 10.1038/nmat2384

Catalysis by clusters with precise numbers of atoms
journal, July 2015


Computational studies of electrochemical CO 2 reduction on subnanometer transition metal clusters
journal, January 2014

  • Liu, Cong; He, Haiying; Zapol, Peter
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 48
  • DOI: 10.1039/C4CP02690J

Electrochemical reduction of CO 2 on graphene supported transition metals – towards single atom catalysts
journal, January 2017

  • He, Haiying; Jagvaral, Yesukhei
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 18
  • DOI: 10.1039/C7CP00915A

Single-atom catalysts for CO 2 electroreduction with significant activity and selectivity improvements
journal, January 2017

  • Back, Seoin; Lim, Juhyung; Kim, Na-Young
  • Chemical Science, Vol. 8, Issue 2
  • DOI: 10.1039/C6SC03911A

Why gold is the noblest of all the metals
journal, July 1995


Activity Descriptors for CO 2 Electroreduction to Methane on Transition-Metal Catalysts
journal, January 2012

  • Peterson, Andrew A.; Nørskov, Jens K.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 2
  • DOI: 10.1021/jz201461p

Synergy in the Catalytic Activity of Bimetallic Nanoparticles and New Synthetic Methods for the Preparation of Fine Chemicals
journal, August 2014

  • Notar Francesco, Irene; Fontaine-Vive, Fabien; Antoniotti, Sylvain
  • ChemCatChem, Vol. 6, Issue 10
  • DOI: 10.1002/cctc.201402252

Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns
journal, December 2016

  • Ma, Sichao; Sadakiyo, Masaaki; Heima, Minako
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b10740

CO 2 Electroreduction Performance of Transition Metal Dimers Supported on Graphene: A Theoretical Study
journal, October 2015


Graphene-supported small transition-metal clusters: A density functional theory investigation within van der Waals corrections
journal, June 2017


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Improved grid-based algorithm for Bader charge allocation
journal, January 2007

  • Sanville, Edward; Kenny, Steven D.; Smith, Roger
  • Journal of Computational Chemistry, Vol. 28, Issue 5
  • DOI: 10.1002/jcc.20575

Density Functional Theory Investigation on the Nucleation of Homo- and Heteronuclear Metal Clusters on Defective Graphene
journal, June 2016

  • Ferrante, Francesco; Prestianni, Antonio; Cortese, Remedios
  • The Journal of Physical Chemistry C, Vol. 120, Issue 22
  • DOI: 10.1021/acs.jpcc.6b02833

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010

  • Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00071j

Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water
journal, October 2016

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08534

Trends of Metal-Carbon Bond Strengths in Transition Metal Complexes
journal, August 1995

  • Siegbahn, Per E. M.
  • The Journal of Physical Chemistry, Vol. 99, Issue 34
  • DOI: 10.1021/j100034a007

The Nature of the Chemical Bond. iv. the Energy of Single Bonds and the Relative Electronegativity of Atoms
journal, September 1932

  • Pauling, Linus
  • Journal of the American Chemical Society, Vol. 54, Issue 9
  • DOI: 10.1021/ja01348a011

Density functional theory in surface chemistry and catalysis
journal, January 2011

  • Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
  • DOI: 10.1073/pnas.1006652108

Works referencing / citing this record:

In Situ Transmission Electron Microscopy on Energy‐Related Catalysis
journal, December 2019