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Title: Computational studies of electrochemical CO 2 reduction on subnanometer transition metal clusters

Here, computational studies of electrochemical reduction of CO 2 to CO, HCOOH and CH 4 were carried out using tetra-atomic transition metal clusters (Fe 4, Co 4, Ni 4, Cu 4 and Pt 4) at the B3LYP level of theory. Novel catalytic properties were discovered for these subnanometer clusters, suggesting that they may be good candidate materials for CO 2 reduction. The calculated overpotentials of producing CH 4 are in the order: Co 4 < Fe 4 < Ni 4 < Cu 4 < Pt 4 with both Co 4 and Fe 4 having overpotentials less than 1 V. Investigation of the effects of supports found that a Cu 4 cluster on a graphene defect site has a limiting potential for producing CH 4 comparable to that of a Cu (111) surface. However, due to the strong electronic interaction with the Cu 4 cluster, the defective graphene support has the advantage of significantly increasing the limiting potentials for the reactions competing with CH 4, such as the hydrogen evolution reaction (HER), and CO production.
Authors:
 [1] ;  [1] ;  [1] ;  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 16; Journal Issue: 48; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Materials Sciences and Engineering Division
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1356355

Liu, Cong, He, Haiying, Zapol, Peter, and Curtiss, Larry A. Computational studies of electrochemical CO2 reduction on subnanometer transition metal clusters. United States: N. p., Web. doi:10.1039/C4CP02690J.
Liu, Cong, He, Haiying, Zapol, Peter, & Curtiss, Larry A. Computational studies of electrochemical CO2 reduction on subnanometer transition metal clusters. United States. doi:10.1039/C4CP02690J.
Liu, Cong, He, Haiying, Zapol, Peter, and Curtiss, Larry A. 2014. "Computational studies of electrochemical CO2 reduction on subnanometer transition metal clusters". United States. doi:10.1039/C4CP02690J. https://www.osti.gov/servlets/purl/1356355.
@article{osti_1356355,
title = {Computational studies of electrochemical CO2 reduction on subnanometer transition metal clusters},
author = {Liu, Cong and He, Haiying and Zapol, Peter and Curtiss, Larry A.},
abstractNote = {Here, computational studies of electrochemical reduction of CO2 to CO, HCOOH and CH4 were carried out using tetra-atomic transition metal clusters (Fe4, Co4, Ni4, Cu4 and Pt4) at the B3LYP level of theory. Novel catalytic properties were discovered for these subnanometer clusters, suggesting that they may be good candidate materials for CO2 reduction. The calculated overpotentials of producing CH4 are in the order: Co4 < Fe4 < Ni4 < Cu4 < Pt4 with both Co4 and Fe4 having overpotentials less than 1 V. Investigation of the effects of supports found that a Cu4 cluster on a graphene defect site has a limiting potential for producing CH4 comparable to that of a Cu (111) surface. However, due to the strong electronic interaction with the Cu4 cluster, the defective graphene support has the advantage of significantly increasing the limiting potentials for the reactions competing with CH4, such as the hydrogen evolution reaction (HER), and CO production.},
doi = {10.1039/C4CP02690J},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 48,
volume = 16,
place = {United States},
year = {2014},
month = {8}
}