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Title: Effects of Vanadium Substitution on the Structure and Photocatalytic Behavior of ETS-10

Abstract

A combination of experimental and computational methods has been used to investigate the effects of vanadium doping in ETS-10. Near edge X-ray absorption fine structure (NEXAFS) spectra reveal octahedrally coordinated V{sup IV} and V{sup V} species within V-doped ETS-10 materials, confirming substitution for Ti{sup IV} sites only. Computational models, using hybrid density functional theory/molecular mechanics (DFT/MM) methods, have been developed that contain varying concentrations of V{sup IV} and V{sup V} within the O-M-O (M = Ti, V) chain. Geometry optimizations indicate that V{sup V} substitution leads to larger changes in the local chain geometry than V{sup IV} substitution. Substitution energetics for V{sup IV} and V{sup V} in different sites have been calculated to determine preferred locations of the two species, suggesting that long chains of V{sup V} are not stable and demonstrating the need for both V{sup V} and V{sup IV} within V-substituted materials. Wavefunctions for systems with an electron added or removed are used to identify electron and hole trapping sites associated with the V{sup V} and V{sup IV} doping centers respectively. An increase in photocatalytic activity is predicted at low [V] due to improved charge separation. However photocatalytic activity is expected to decrease at high [V] due tomore » increased carrier recombination. These results are consistent with recent experimental data.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930324
Report Number(s):
BNL-81034-2008-JA
Journal ID: ISSN 1932-7447; TRN: US200904%%519
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry C; Journal Volume: 111; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; PHOTOCATALYSIS; CATALYSTS; VANADIUM; MATERIAL SUBSTITUTION; DOPED MATERIALS; MORPHOLOGY; CALCULATION METHODS; CATALYTIC EFFECTS; national synchrotron light source

Citation Formats

Shough,A., Doren, D., Nash, M., and Lobo, R.. Effects of Vanadium Substitution on the Structure and Photocatalytic Behavior of ETS-10. United States: N. p., 2007. Web. doi:10.1021/jp0662247.
Shough,A., Doren, D., Nash, M., & Lobo, R.. Effects of Vanadium Substitution on the Structure and Photocatalytic Behavior of ETS-10. United States. doi:10.1021/jp0662247.
Shough,A., Doren, D., Nash, M., and Lobo, R.. Mon . "Effects of Vanadium Substitution on the Structure and Photocatalytic Behavior of ETS-10". United States. doi:10.1021/jp0662247.
@article{osti_930324,
title = {Effects of Vanadium Substitution on the Structure and Photocatalytic Behavior of ETS-10},
author = {Shough,A. and Doren, D. and Nash, M. and Lobo, R.},
abstractNote = {A combination of experimental and computational methods has been used to investigate the effects of vanadium doping in ETS-10. Near edge X-ray absorption fine structure (NEXAFS) spectra reveal octahedrally coordinated V{sup IV} and V{sup V} species within V-doped ETS-10 materials, confirming substitution for Ti{sup IV} sites only. Computational models, using hybrid density functional theory/molecular mechanics (DFT/MM) methods, have been developed that contain varying concentrations of V{sup IV} and V{sup V} within the O-M-O (M = Ti, V) chain. Geometry optimizations indicate that V{sup V} substitution leads to larger changes in the local chain geometry than V{sup IV} substitution. Substitution energetics for V{sup IV} and V{sup V} in different sites have been calculated to determine preferred locations of the two species, suggesting that long chains of V{sup V} are not stable and demonstrating the need for both V{sup V} and V{sup IV} within V-substituted materials. Wavefunctions for systems with an electron added or removed are used to identify electron and hole trapping sites associated with the V{sup V} and V{sup IV} doping centers respectively. An increase in photocatalytic activity is predicted at low [V] due to improved charge separation. However photocatalytic activity is expected to decrease at high [V] due to increased carrier recombination. These results are consistent with recent experimental data.},
doi = {10.1021/jp0662247},
journal = {Journal of Physical Chemistry C},
number = 4,
volume = 111,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}