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Title: Spin Uncoupling in Chemisorbed OCCO and CO 2: Two High-Energy Intermediates in Catalytic CO 2 Reduction

Abstract

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an average gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [3];  [1]
  1. Stockholm Univ., Stockholm (Sweden)
  2. Univ. Federal de Minas Gerais, Minas Gerais (Brazil); Stockholm Univ., Stockholm (Sweden)
  3. 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:
1457148
Grant/Contract Number:  
348-2013-6723; 42024-1; KAW-2013.0020; KAW- 2016.0042; AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 23; 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

Hedstrom, Svante, dos Santos, Egon Campos, Liu, Chang, Chan, Karen, Abild-Pedersen, Frank, and Pettersson, Lars G. M. Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b02165.
Hedstrom, Svante, dos Santos, Egon Campos, Liu, Chang, Chan, Karen, Abild-Pedersen, Frank, & Pettersson, Lars G. M. Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction. United States. doi:10.1021/acs.jpcc.8b02165.
Hedstrom, Svante, dos Santos, Egon Campos, Liu, Chang, Chan, Karen, Abild-Pedersen, Frank, and Pettersson, Lars G. M. Tue . "Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction". United States. doi:10.1021/acs.jpcc.8b02165. https://www.osti.gov/servlets/purl/1457148.
@article{osti_1457148,
title = {Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction},
author = {Hedstrom, Svante and dos Santos, Egon Campos and Liu, Chang and Chan, Karen and Abild-Pedersen, Frank and Pettersson, Lars G. M.},
abstractNote = {Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an average gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO2– quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.},
doi = {10.1021/acs.jpcc.8b02165},
journal = {Journal of Physical Chemistry. C},
number = 23,
volume = 122,
place = {United States},
year = {Tue May 08 00:00:00 EDT 2018},
month = {Tue May 08 00:00:00 EDT 2018}
}

Journal Article:
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