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Dynamic Photoluminescence Studies of Vanadium Oxide Anchored On Si02 and the Effects of Added 02 and H20

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Dynamic photoluminescence studies of V-oxide anchored onto Si02 are investigated in the absence and presence of 02 or H20. It is found that the added 02 molecules interact with the charge transfer excited triplet state of tetrahedrally coordinated V-oxide species. This results in an efficient quenching of the phosphorescence due to an enhanced radiationless deactivation. On the other hand, the added H20 molecules interact with V-oxide in the ground state, resulting in the coordination change of V-species from tetrahedral to octahedral. These results obtained by dynamic photoluminescence spectroscopy are in good agreement with those obtained by ESR measurements of the photoreduced V4+ ions. From the Stern- Volmer plots for the quenching of the phosphorescence of V-oxide, the absolute quenching rate constants (reaction rate constants) of 02 for the charge transfer excited triplet state of V-oxide anchored onto Si02 is first determined to be 9.2 X 108 g-cat./mol s at 77 K and 9.3 × 1012 g-cat./mol s at 298 K.

Affiliations: 1: Department of Applied Chemistry, College of Engineering University of Osaka Prefecture, Sakai, Osaka 591, Japan; 2: Department of Industrial Chemistry, Faculty of Engineering Shinshu University, Nagano, Nagano 380, Japan; 3: Department of Chemistry, University of Maine Aubert Hall, Orono, Maine 04469, U.S.A; 4: Laboratoire de Réactivité de Surface et Structure Université P. et M. Curie, U.A. 1106-CNRS 4 Place Jussieu, Tour 54, 75252 Paris, Cedex 05, France


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