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Title: Proof of Equivalent Catalytic Functionality upon Photon-Induced and Thermal Activation of Supported Isolated Vanadia Species in Methanol Oxidation

Abstract

Here, evidence is provided that isolated surface vanadia (VO4) species on SiO2 can similarly act as a thermal heterogeneous catalyst and as a heterogeneous photocatalyst. Structurally identical surface VO4 species catalyze the selective oxidation of methanol both by thermal activation and by UV-light induction. Selectivity to formaldehyde appears to be unity. For the photocatalytic reaction at room temperature, formaldehyde desorption is rate limiting. With larger agglomerates or V2O5 nanoparticles, on the contrary, only the thermal reaction is feasible. This is tentatively attributed to the different positions of electronic states (HOMO/LUMO, valence/conduction band) on the electrochemical energy scale owing to the quantum size effect. Besides offering new fundamental insight into the mode of action of nanosized photocatalysts, our results demonstrate that tuning the photocatalytic reactivity of supported transition-metal oxides by adjusting the degree of agglomeration is feasible.

Authors:
 [1];  [2];  [3];  [4];  [4];  [5]; ORCiD logo [6]
  1. Univ. of Rostock (Germany); Ruhr Univ., Bochum (Germany)
  2. Lehigh Univ., Bethlehem, PA (United States)
  3. Max Planck Society, Ruhr (Germany)
  4. Universität Duisburg-Essen (Germany)
  5. Ruhr Univ., Bochum (Germany)
  6. Univ. of Rostock (Germany)
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:
1470292
Alternate Identifier(s):
OSTI ID: 1434221
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 11; 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 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxidation; photocatalysis; quantum size effect; structure–activity relationships; vanadium

Citation Formats

Kortewille, Bianca, Wachs, Israel E., Cibura, Niklas, Pfingsten, Oliver, Bacher, Gerd, Muhler, Martin, and Strunk, Jennifer. Proof of Equivalent Catalytic Functionality upon Photon-Induced and Thermal Activation of Supported Isolated Vanadia Species in Methanol Oxidation. United States: N. p., 2018. Web. doi:10.1002/cctc.201800311.
Kortewille, Bianca, Wachs, Israel E., Cibura, Niklas, Pfingsten, Oliver, Bacher, Gerd, Muhler, Martin, & Strunk, Jennifer. Proof of Equivalent Catalytic Functionality upon Photon-Induced and Thermal Activation of Supported Isolated Vanadia Species in Methanol Oxidation. United States. doi:10.1002/cctc.201800311.
Kortewille, Bianca, Wachs, Israel E., Cibura, Niklas, Pfingsten, Oliver, Bacher, Gerd, Muhler, Martin, and Strunk, Jennifer. Wed . "Proof of Equivalent Catalytic Functionality upon Photon-Induced and Thermal Activation of Supported Isolated Vanadia Species in Methanol Oxidation". United States. doi:10.1002/cctc.201800311. https://www.osti.gov/servlets/purl/1470292.
@article{osti_1470292,
title = {Proof of Equivalent Catalytic Functionality upon Photon-Induced and Thermal Activation of Supported Isolated Vanadia Species in Methanol Oxidation},
author = {Kortewille, Bianca and Wachs, Israel E. and Cibura, Niklas and Pfingsten, Oliver and Bacher, Gerd and Muhler, Martin and Strunk, Jennifer},
abstractNote = {Here, evidence is provided that isolated surface vanadia (VO4) species on SiO2 can similarly act as a thermal heterogeneous catalyst and as a heterogeneous photocatalyst. Structurally identical surface VO4 species catalyze the selective oxidation of methanol both by thermal activation and by UV-light induction. Selectivity to formaldehyde appears to be unity. For the photocatalytic reaction at room temperature, formaldehyde desorption is rate limiting. With larger agglomerates or V2O5 nanoparticles, on the contrary, only the thermal reaction is feasible. This is tentatively attributed to the different positions of electronic states (HOMO/LUMO, valence/conduction band) on the electrochemical energy scale owing to the quantum size effect. Besides offering new fundamental insight into the mode of action of nanosized photocatalysts, our results demonstrate that tuning the photocatalytic reactivity of supported transition-metal oxides by adjusting the degree of agglomeration is feasible.},
doi = {10.1002/cctc.201800311},
journal = {ChemCatChem},
number = 11,
volume = 10,
place = {United States},
year = {2018},
month = {2}
}

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