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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

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.

Authors:
 [1];  [2];  [3];  [4];  [4];  [5]; ORCiD logo [6]
+ Show Author Affiliations
  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)
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.
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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. https://doi.org/10.1002/cctc.201800311
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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. https://doi.org/10.1002/cctc.201800311. https://www.osti.gov/servlets/purl/1470292.
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@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 = {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.},
doi = {10.1002/cctc.201800311},
journal = {ChemCatChem},
number = 11,
volume = 10,
place = {United States},
year = {Wed Feb 28 00:00:00 EST 2018},
month = {Wed Feb 28 00:00:00 EST 2018}
}
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https://doi.org/10.1002/cctc.201800311
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Works referenced in this record:

Resolving the Atomic Structure of Vanadia Monolayer Catalysts: Monomers, Trimers, and Oligomers on Ceria
journal, October 2009

  • Baron, Martin; Abbott, Heather; Bondarchuk, Oleksandr
  • Angewandte Chemie International Edition, Vol. 48, Issue 43
  • DOI: 10.1002/anie.200903085

Formaldehyde Formation on Vanadium Oxide Surfaces V 2 O 3 (0001) and V 2 O 5 (001): How does the Stable Methoxy Intermediate Form?
journal, May 2009

  • Göbke, Daniel; Romanyshyn, Yuriy; Guimond, Sébastien
  • Angewandte Chemie International Edition, Vol. 48, Issue 20
  • DOI: 10.1002/anie.200805618

The Origin of the Ligand Effect in Metal Oxide Catalysts: Novel Fixed-Bed in Situ Infrared and Kinetic Studies during Methanol Oxidation
journal, October 2001

  • Burcham, Loyd J.; Badlani, Mohit; Wachs, Israel E.
  • Journal of Catalysis, Vol. 203, Issue 1
  • DOI: 10.1006/jcat.2001.3312

Quantitative Determination of the Speciation of Surface Vanadium Oxides and Their Catalytic Activity
journal, May 2006

  • Tian, Hanjing; Ross, Elizabeth I.; Wachs, Israel E.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 19
  • DOI: 10.1021/jp055767y

High-Visible-Light Photoactivity of Plasma-Promoted Vanadium Clusters on Nanozeolites for Partial Photooxidation of Methanol
journal, May 2017

  • El-Roz, Mohamad; Lakiss, Louwanda; Telegeiev, Igor
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 21
  • DOI: 10.1021/acsami.7b02161

Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results
journal, May 1995

  • Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T.
  • Chemical Reviews, Vol. 95, Issue 3
  • DOI: 10.1021/cr00035a013

A surface science perspective on TiO2 photocatalysis
journal, June 2011

Oligomerization of Supported Vanadia: Structural Insight Using Surface-Science Models with Chemical Complexity
journal, August 2016

  • Waleska, Philipp S.; Hess, Christian
  • The Journal of Physical Chemistry C, Vol. 120, Issue 33
  • DOI: 10.1021/acs.jpcc.6b01672

Mechanistic Studies of Methanol Oxidation to Formaldehyde on Isolated Vanadate Sites Supported on MCM-48
journal, January 2007

  • Bronkema, Jason L.; Bell, Alexis T.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 1
  • DOI: 10.1021/jp0653149

Structural Determination of Bulk and Surface Tungsten Oxides with UV−vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy
journal, September 2007

  • Ross-Medgaarden, Elizabeth I.; Wachs, Israel E.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 41
  • DOI: 10.1021/jp074219c

Mechanistic Studies of Methanol Oxidation to Formaldehyde on Isolated Vanadate Sites Supported on High Surface Area Zirconia
journal, March 2008

  • Bronkema, Jason L.; Bell, Alexis T.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 16
  • DOI: 10.1021/jp7110692

Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials
journal, February 2005

Tuning the Electronic and Molecular Structures of Catalytic Active Sites with Titania Nanoligands
journal, January 2009

  • Ross-Medgaarden, Elizabeth I.; Wachs, Israel E.; Knowles, William V.
  • Journal of the American Chemical Society, Vol. 131, Issue 2
  • DOI: 10.1021/ja711456c

In Situ Spectroscopic Investigation of the Molecular and Electronic Structures of SiO 2 Supported Surface Metal Oxides
journal, October 2007

  • Lee, Edward L.; Wachs, Israel E.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 39
  • DOI: 10.1021/jp0735482

Vanadium oxide nanostructures on another oxide: The viewpoint from model catalysts studies
journal, October 2015

  • Artiglia, Luca; Agnoli, Stefano; Granozzi, Gaetano
  • Coordination Chemistry Reviews, Vol. 301-302
  • DOI: 10.1016/j.ccr.2014.12.015

Understanding TiO 2 Photocatalysis: Mechanisms and Materials
journal, May 2014

  • Schneider, Jenny; Matsuoka, Masaya; Takeuchi, Masato
  • Chemical Reviews, Vol. 114, Issue 19
  • DOI: 10.1021/cr5001892

Formaldehydbildung auf den Vanadiumoxidoberflächen V 2 O 3 (0001) und V 2 O 5 (001): Wie bildet sich der stabile Methoxy-Zwischenzustand?
journal, May 2009

  • Göbke, Daniel; Romanyshyn, Yuriy; Guimond, Sébastien
  • Angewandte Chemie, Vol. 121, Issue 20
  • DOI: 10.1002/ange.200805618

Structure of Isolated Vanadia and Titania: A Deep UV Raman, UV–Vis, and IR Spectroscopic Study
journal, January 2016

Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes
journal, January 2013

  • Kondratenko, Evgenii V.; Mul, Guido; Baltrusaitis, Jonas
  • Energy & Environmental Science, Vol. 6, Issue 11
  • DOI: 10.1039/c3ee41272e

Photocatalytic Reduction of CO 2 on TiO 2 and Other Semiconductors
journal, June 2013

  • Habisreutinger, Severin N.; Schmidt-Mende, Lukas; Stolarczyk, Jacek K.
  • Angewandte Chemie International Edition, Vol. 52, Issue 29
  • DOI: 10.1002/anie.201207199

The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
journal, April 2012

A Theoretical Investigation of the Selective Oxidation of Methanol to Formaldehyde on Isolated Vanadate Species Supported on Titania
journal, August 2008

  • Goodrow, Anthony; Bell, Alexis T.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 34
  • DOI: 10.1021/jp801339q

Preparation and characterization of quantum size zinc oxide: a detailed spectroscopic study
journal, July 1987

  • Bahnemann, Detlef W.; Kormann, Claudius.; Hoffmann, Michael R.
  • The Journal of Physical Chemistry, Vol. 91, Issue 14
  • DOI: 10.1021/j100298a015

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR
journal, March 2017

  • Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 11
  • DOI: 10.1021/acs.jpcc.7b01658

FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces
journal, August 1987

  • Busca, Guido; Lamotte, Jean; Lavalley, Jean Claude
  • Journal of the American Chemical Society, Vol. 109, Issue 17
  • DOI: 10.1021/ja00251a025

Photokatalytische Reduktion von CO 2 an TiO 2 und anderen Halbleitern
journal, June 2013

  • Habisreutinger, Severin N.; Schmidt-Mende, Lukas; Stolarczyk, Jacek K.
  • Angewandte Chemie, Vol. 125, Issue 29
  • DOI: 10.1002/ange.201207199

Effect of water vapor on the molecular structures of supported vanadium oxide catalysts at elevated temperatures
journal, July 1996

  • Jehng, Jih-Mirn; Deo, Goutam; Weckhuysen, Bert M.
  • Journal of Molecular Catalysis A: Chemical, Vol. 110, Issue 1
  • DOI: 10.1016/1381-1169(96)00061-1

Resolving the Atomic Structure of Vanadia Monolayer Catalysts: Monomers, Trimers, and Oligomers on Ceria
journal, October 2009

  • Baron, Martin; Abbott, Heather; Bondarchuk, Oleksandr
  • Angewandte Chemie, Vol. 121, Issue 43
  • DOI: 10.1002/ange.200903085
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