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Work Function, Band Bending and Microwave Conductivity Studies on the Selective Alkane Oxidation Catalyst MoVTeNb Oxide (Orthorhombic M1 Phase) under Operation Conditions

MPS-Authors
http://pubman.mpdl.mpg.de/cone/persons/resource/persons32754

Heine,  Christian
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21590

Hävecker,  Michael
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Helmholtz-Zentrum Berlin fuer Materialien und Energy GmbH, Division Solar Energy Research, Elektronenspeicherring BESSY II;

Sanchez-Sanchez,  Maricruz
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Technische Universität München, Department Chemie;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22181

Trunschke,  Annette
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22071

Schlögl,  Robert
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21485

Eichelbaum,  Maik
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
BasCat, UniCat BASF JointLab, TU Berlin;

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Citation

Heine, C., Hävecker, M., Sanchez-Sanchez, M., Trunschke, A., Schlögl, R., & Eichelbaum, M. (2013). Work Function, Band Bending and Microwave Conductivity Studies on the Selective Alkane Oxidation Catalyst MoVTeNb Oxide (Orthorhombic M1 Phase) under Operation Conditions. The Journal of Physical Chemistry C, 117(51), 26988-26997. doi:10.1021/jp409601h.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0014-BB68-2
Abstract
A systematic gas phase-dependence of the electron work function, electron affinity, band bending and the high frequency electrical conductivity of the prospective oxidation catalyst MoVTeNbOx with orthorhombic M1 structure was identified under selective alkane oxidation conditions. The conductivity measured in a fixed bed flow reactor at 1 bar with a noncontact microwave technique and the surface electronic properties studied by in situ X-ray photoelectron spectroscopy at 0.25 mbar were determined at 400°C in 2:1 mixtures of oxygen and the alkanes ethane, propane, and n-butane, respectively. The observed modulation of the surface electron affinity is explained by a gas phase dependent modification of the dipolar structure of the active surface, while the band alignment is interpreted in terms of the formation and modification of the space charge region due to pinning of the Fermi energy to the surface state energy as defined by the vanadium(IV,V) oxide surface layer. The thus changed charge carrier density in the space charge region gives rise to the observed conductivity response. Consequently, the catalytic system and its working mode can be described as a semiconductor heterostructure comprising the semiconducting bulk phase, a vanadium oxide termination layer, and the reactive gas phase modulating the Fermi energy of the whole system.