Theoretical and Experimental Study of Light Hydrocarbon Ammoxidation and Oxidative Dehydrogenation on (110)-VSbO4 Surfaces

Density Functional Theory (DFT) calculations have been performed for ethane, ethylene, propane, and propylene adsorption on the rutile VSbO4 structure to uncover the reaction mechanism during both ODH and ammoxidation reactions. This study is complementary to a previous paper in which the adsorption of ammonia on this structure was deeply analyzed, and in addition, experimental activity results for both reactions are shown to complete the theoretical DFT calculations. These results show that ammonia, ethane, and ethylene compete for the same active sites, the former adsorbing strongly. This explains why this catalytic system is not active for ethane ammoxidation; the presence of ammonia blocks the other molecule adsorption sites and prevents ethane oxidative dehydrogenation to ethylene. Such competition does not occur with propane or propene since the adsorption of both ammonia and hydrocarbon is possible at different sites, explaining why this catalytic system is active for propane ODH reaction. During a...

[1]  M. Bañares.  Operando Spectroscopy: the Knowledge Bridge to Assessing Structure–Performance Relationships in Catalyst Nanoparticles , 2011, Advanced materials.

[2]  J. Fierro,et al.  Alumina support-stabilized nanoscaled vanadium–phosphorous mixed oxides as new catalysts for propane ammoxidation , 2011 .

[3]  M. Bañares,et al.  Correlation between theoretical and experimental investigations of the ammonia adsorption process on the (1 1 0)-VSbO4 surface , 2010 .

[4]  S. Hansen,et al.  Structural flexibility in similar to SbVO4 , 2010 .

[5]  M. Bañares,et al.  Efficient microwave-promoted acrylonitrile sustainable synthesis from glycerol , 2009 .

[6]  M. Bañares,et al.  Direct ammoxidation of ethane: An approach to tackle the worldwide shortage of acetonitrile , 2009 .

[7]  J. Fierro,et al.  Sb–V–O-based catalysts for the ammoxidation of propane with a fluidized bed reactor , 2008 .

[8]  M. Bañares,et al.  Nature of Catalytic Active Sites for Sb-V-O Mixed Metal Oxides , 2008 .

[9]  S. Larrondo,et al.  Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate , 2008 .

[10]  M. Bañares,et al.  New reaction: conversion of glycerol into acrylonitrile. , 2008, ChemSusChem.

[11]  M. Bañares,et al.  Support Effect on the Structure and Reactivity of VSbO4 Catalysts for Propane Ammoxidation to Acrylonitrile , 2007 .

[12]  F. Cavani,et al.  Oxidative dehydrogenation of ethane and propane : How far from commercial implementation? , 2007 .

[13]  J. Fierro,et al.  Selective destruction of nitrogen-containing organic volatile compounds over Sb–V–O catalysts , 2007 .

[14]  J. Fierro,et al.  Tunning the Nb addition to Sb-V-O catalysts for an efficient promotion of the ammoxidation of propane to acrylonitrile , 2006 .

[15]  J. Brazdil.  Strategies for the selective catalytic oxidation of alkanes , 2006 .

[16]  M. Bañares,et al.  A Study about the Propane Ammoxidation to Acrylonitrile with an Alumina-Supported Sb−V−O Catalyst , 2006 .

[17]  M. Bañares,et al.  Ammoxidation of propane over V-Sb and V-Sb-Nb mixed oxides , 2006 .

[18]  Guang Xiong,et al.  Effect of titanium substitution on the structure of VSbO4 catalysts for propane ammoxidation , 2005 .

[19]  M. Bañares.  Operando methodology: combination of in situ spectroscopy and simultaneous activity measurements under catalytic reaction conditions , 2005 .

[20]  M. Bañares,et al.  Operando Raman-GC studies of alumina-supported Sb-V-O catalysts and role of the preparation method , 2004 .

[21]  R. Grasselli,et al.  Fundamental Principles of Selective Heterogeneous Oxidation Catalysis , 2002 .

[22]  M. Bañares,et al.  Operando Raman study of alumina-supported Sb-V-O catalyst during propane ammoxidation to acrylonitrile with on-line activity measurement. , 2002, Chemical communications.

[23]  M. Bañares,et al.  Effect of Sb/V Ratio and of Sb + V Coverage on the Molecular Structure and Activity of Alumina-Supported Sb–V–O Catalysts for the Ammoxidation of Propane to Acrylonitrile , 2002 .

[24]  K. Takehira,et al.  Oxidation of isobutane over Mo–V–Sb mixed oxide catalyst , 2000 .

[25]  Alexis T. Bell,et al.  Kinetic Isotopic Effects in Oxidative Dehydrogenation of Propane on Vanadium Oxide Catalysts , 2000 .

[26]  M. Bañares.  Supported metal oxide and other catalysts for ethane conversion: a review , 1999 .

[27]  Kuo-Tseng Li,et al.  Catalytic Oxidation of Hydrogen Sulfide to Sulfur on Vanadium Antimonate , 1997 .

[28]  G. Centi,et al.  Effect of ammonia chemisorption on the surface reactivity of V-Sb-oxide catalysts for propane ammoxidation , 1997 .

[29]  J. Brazdil,et al.  Kinetic Isotope Effect in the Ammoxidation of Propane over an Alumina Supported Vanadium Antimony Oxide Catalyst , 1996 .

[30]  Gabriele Centi,et al.  Structure-activity relationship in Sb-V-oxide catalysts for the direct synthesis of acrylonitrile from propane , 1996 .

[31]  Hafner,et al.  Ab initio molecular dynamics for liquid metals. , 1995, Physical review. B, Condensed matter.

[32]  A. Davydov,et al.  Mechanism of Selective Paraffin Ammoxidation , 1995 .

[33]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[34]  S. Hansen,et al.  The Crystal Structure of Sb0.92V0.92O4, Determined by Neutron and Dual Wavelength X-Ray Powder Diffraction , 1993 .

[35]  G. Centi,et al.  Propane ammoxidation to acrylonitrile : an overview , 1992 .

[36]  J. Sauer,et al.  Oxidative conversion of C1–C3 alkanes by vanadium oxide catalysts. DFT results and their accuracy† , 2008 .

[37]  M. Bañares,et al.  Operando Raman−GC Study of Supported Alumina Sb- and V-Based Catalysts: Effect of Sb/V Molar Ratio and Total Sb+V Coverage in the Structure of Catalysts during Propane Ammoxidation , 2007 .

[38]  Pinliang Ying,et al.  Catalytic Performance of the Sb–V Mixed Oxide on Sb–V–O/SiO2 Catalysts in Methane Selective Oxidation to Formaldehyde , 2006 .