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Title: Reaction of CO 2 with Groups 4 and 6 Transition Metal Oxide Clusters

Abstract

Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to research the addition of CO 2 to group 4 (MO 2) n and group 6 (MO 3) n (n = 1, 2, 3) nanoclusters. The structures and energetics arising from Lewis acid–base addition (physisorption) and formation of CO 3 2– (chemisorption) of CO 2 to these clusters were predicted. Physisorption and chemisorption of CO 2 are predicted to be thermodynamically allowed for group 4 (MO 2) n clusters, with chemisorption being more favored energetically. Correlations of the ligand binding energies (LBEs) for the group 4 clusters are made with the fluoride affinities and M–O and M=O bond strengths of the clusters. The LBEs for chemisorption on the Zr and Ti clusters are consistent with published experimental and computational studies of bulk solids. Physisorption LBEs for the Ti and Zr clusters are more exothermic than the bulk values, as the cluster models allow for better relaxation at the metal sites. Chemisorption is not predicted to occur with group 6 (MO 3) n clusters, as the larger chemisorbed structures were all found to be metastable. Furthermore, CO 2 is predicted to weakly physisorb to (WO 3) n with physisorption correlatingmore » with the Lewis acidity of the metal site.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Georgia Inst. of Technology, Atlanta, GA (United States). Energy Frontier Research Center (EFRC) Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470289
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 45; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Flores, Luis A., Murphy, Julia G., Copeland, William B., and Dixon, David A. Reaction of CO2 with Groups 4 and 6 Transition Metal Oxide Clusters. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.7b09462.
Flores, Luis A., Murphy, Julia G., Copeland, William B., & Dixon, David A. Reaction of CO2 with Groups 4 and 6 Transition Metal Oxide Clusters. United States. doi:10.1021/acs.jpca.7b09462.
Flores, Luis A., Murphy, Julia G., Copeland, William B., and Dixon, David A. Mon . "Reaction of CO2 with Groups 4 and 6 Transition Metal Oxide Clusters". United States. doi:10.1021/acs.jpca.7b09462. https://www.osti.gov/servlets/purl/1470289.
@article{osti_1470289,
title = {Reaction of CO2 with Groups 4 and 6 Transition Metal Oxide Clusters},
author = {Flores, Luis A. and Murphy, Julia G. and Copeland, William B. and Dixon, David A.},
abstractNote = {Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to research the addition of CO2 to group 4 (MO2)n and group 6 (MO3)n (n = 1, 2, 3) nanoclusters. The structures and energetics arising from Lewis acid–base addition (physisorption) and formation of CO32– (chemisorption) of CO2 to these clusters were predicted. Physisorption and chemisorption of CO2 are predicted to be thermodynamically allowed for group 4 (MO2)n clusters, with chemisorption being more favored energetically. Correlations of the ligand binding energies (LBEs) for the group 4 clusters are made with the fluoride affinities and M–O and M=O bond strengths of the clusters. The LBEs for chemisorption on the Zr and Ti clusters are consistent with published experimental and computational studies of bulk solids. Physisorption LBEs for the Ti and Zr clusters are more exothermic than the bulk values, as the cluster models allow for better relaxation at the metal sites. Chemisorption is not predicted to occur with group 6 (MO3)n clusters, as the larger chemisorbed structures were all found to be metastable. Furthermore, CO2 is predicted to weakly physisorb to (WO3)n with physisorption correlating with the Lewis acidity of the metal site.},
doi = {10.1021/acs.jpca.7b09462},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 45,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}

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