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Title: Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction

Abstract

Here, oxide-derived copper (OD-Cu) catalysts are promising candidates for the electrochemical CO2 reduction reaction (CO2RR) due to the enhanced selectivity toward ethylene over methane evolution, which has been linked to the presence of subsurface oxygen (Osb). In this work, Osb is investigated with theoretical methods. Although Osb is unstable in slab models, it becomes stabilized within a “manually” reduced OD-Cu nanocube model which was calculated by self-consistent charge density functional tight binding (SCC-DFTB). The results obtained with SCC-DFTB for the full nanocube were confirmed with subcluster models extracted from the nanocube, calculated with both density functional theory (DFT) and SCC-DFTB. The higher stability of Osb in the nanocube is attributed to the disordered structure and greater flexibility. The adsorption strength of CO on Cu(100) is enhanced by Osb withdrawing electron density from the Cu atom, resulting in reduction of the σ-repulsion. Hence, the coverage of CO may be increased, facilitating its dimerization.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1];  [2]; ORCiD logo [1];  [1]
  1. Stockholm Univ., Stockholm (Sweden)
  2. Univ. Federal de Minas Gerais (Brazil)
  3. Stockholm Univ., Stockholm (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1463400
Grant/Contract Number:  
AC02-76SF00515; 348-2013-6723; KAW-2013.0020
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 45; 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

Liu, Chang, Lourenço, Maicon P., Hedström, Svante, Cavalca, Filippo, Diaz-Morales, Oscar, Duarte, Hélio A., Nilsson, Anders, and Pettersson, Lars G. M. Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b08269.
Liu, Chang, Lourenço, Maicon P., Hedström, Svante, Cavalca, Filippo, Diaz-Morales, Oscar, Duarte, Hélio A., Nilsson, Anders, & Pettersson, Lars G. M. Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction. United States. https://doi.org/10.1021/acs.jpcc.7b08269
Liu, Chang, Lourenço, Maicon P., Hedström, Svante, Cavalca, Filippo, Diaz-Morales, Oscar, Duarte, Hélio A., Nilsson, Anders, and Pettersson, Lars G. M. Tue . "Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction". United States. https://doi.org/10.1021/acs.jpcc.7b08269. https://www.osti.gov/servlets/purl/1463400.
@article{osti_1463400,
title = {Stability and Effects of Subsurface Oxygen in Oxide-Derived Cu Catalyst for CO2 Reduction},
author = {Liu, Chang and Lourenço, Maicon P. and Hedström, Svante and Cavalca, Filippo and Diaz-Morales, Oscar and Duarte, Hélio A. and Nilsson, Anders and Pettersson, Lars G. M.},
abstractNote = {Here, oxide-derived copper (OD-Cu) catalysts are promising candidates for the electrochemical CO2 reduction reaction (CO2RR) due to the enhanced selectivity toward ethylene over methane evolution, which has been linked to the presence of subsurface oxygen (Osb). In this work, Osb is investigated with theoretical methods. Although Osb is unstable in slab models, it becomes stabilized within a “manually” reduced OD-Cu nanocube model which was calculated by self-consistent charge density functional tight binding (SCC-DFTB). The results obtained with SCC-DFTB for the full nanocube were confirmed with subcluster models extracted from the nanocube, calculated with both density functional theory (DFT) and SCC-DFTB. The higher stability of Osb in the nanocube is attributed to the disordered structure and greater flexibility. The adsorption strength of CO on Cu(100) is enhanced by Osb withdrawing electron density from the Cu atom, resulting in reduction of the σ-repulsion. Hence, the coverage of CO may be increased, facilitating its dimerization.},
doi = {10.1021/acs.jpcc.7b08269},
journal = {Journal of Physical Chemistry. C},
number = 45,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}

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