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

Journal Article · · ChemCatChem
 [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)
+ Show Author Affiliations

Abstract In this study, evidence is provided that isolated surface vanadia (VO 4 ) species on SiO 2 can similarly act as a thermal heterogeneous catalyst and as a heterogeneous photocatalyst. Structurally identical surface VO 4 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 V 2 O 5 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 providing 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.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012577
OSTI ID:
1470292
Alternate ID(s):
OSTI ID: 1434221
Journal Information:
ChemCatChem, Vol. 10, 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; ISSN 1867-3880
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

References (30)

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Cited By (1)

Photocatalytic Methanol Oxidation by Supported Vanadium Oxide Species: Influence of Support and Degree of Oligomerization: Photocatalytic Methanol Oxidation by Supported Vanadium Oxide Species: Influence of Support and Degree of Oligomerization journal August 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
oxidation
photocatalysis
quantum size effect
structure–activity relationships
vanadium