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Superoxide Radical Anions on the Surface of Zirconia and Sulfated Zirconia: Formation Mechanisms, Properties and Structure Full article

Journal PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084
Output data Year: 2005, Volume: 7, Number: 16, Pages: 3059-3069 Pages count : 11 DOI: 10.1039/b504262c
Tags ELECTRON-SPIN-RESONANCE; N-BUTANE ISOMERIZATION; METAL-OXIDES; CATALYTIC PROPERTIES; MONOCLINIC ZIRCONIA; PRESORBED MOLECULES; CATION-RADICALS; RECENT PROGRESS; ACID SITES; ADSORPTION
Authors Bedilo Alexander F. 1 , Plotnikov Mikhail A. 1 , Mezentseva Natalya V. 1 , Volodin Alexander M. 1 , Zhidomirov Georgii M. 1 , Rybkin Ilya M. 1 , Klabunde Kenneth J. 2
Affiliations
1 Boreskov Institute of Catalysis
2 Department of Chemistry, Kansas State University

Funding (3)

1 Russian Foundation for Basic Research 03-03-33178
2 Council for Grants of the President of the Russian Federation НШ-1140.2003.3
3 United States Army Research Laboratory

Abstract: In situ ESR spectroscopy has been used for direct comparison of different thermal and light-induced processes leading to generation of superoxide radical anions on the surface of various zirconia and sulfated zirconia materials. For materials of both types the magnetic resonance parameters of the radical anions were found to be practically independent of the generation method, except for oxygen coadsorption with NO that yields radicals with somewhat smaller gz values. The parameters appear to depend mostly on the state of the surface zirconia cations stabilizing the radical anions, so that the g tensor anisotropy is significantly smaller over sulfated zirconia. It is shown that light-induced formation of superoxide radical anions in the presence of coadsorbed hydrocarbons can be initiated with visible light. Original SIET reaction mechanisms are suggested for the formation of superoxide radical anions by coadsorption with hydrocarbons and illumination after such coadsorption to extend the previously known ones to account for the observed phenomena. Cluster model DFT calculations of magnetic resonance parameters of O2− radical anions stabilized on the surface of zirconium dioxide showed that the adsorption complexes have a T-shape rather than linear structure. The magnetic resonance parameters obtained by calculations practically match experimental data and adequately describe their changes after the surface modification with sulfates.
Cite: Bedilo A.F. , Plotnikov M.A. , Mezentseva N.V. , Volodin A.M. , Zhidomirov G.M. , Rybkin I.M. , Klabunde K.J.
Superoxide Radical Anions on the Surface of Zirconia and Sulfated Zirconia: Formation Mechanisms, Properties and Structure
PCCP: Physical Chemistry Chemical Physics. 2005. V.7. N16. P.3059-3069. DOI: 10.1039/b504262c WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
Submitted: Mar 24, 2005
Accepted: Jun 24, 2005
Published online: Jul 13, 2005
Identifiers:
Web of science: WOS:000230931200011
Scopus: 2-s2.0-24044531637
Elibrary: 13486197
Chemical Abstracts: 2005:687226
Chemical Abstracts (print): 143:333299
PMID: 16186911
OpenAlex: W2049263038
Citing:
DB Citing
Web of science 39
Scopus 41
Elibrary 41
OpenAlex 38
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