Aerobic Oxidations of Light Alkanes over Solid Metal Oxide Catalysts.

Heterogeneous metal oxide catalysts are widely studied for the aerobic oxidations of C1-C4 alkanes to form olefins and oxygenates. In this review, we outline the properties of supported metal oxides, mixed-metal oxides, and zeolites and detail their most common applications as catalysts for partial oxidations of light alkanes. By doing this we establish similarities between different classes of metal oxides and identify common themes in reaction mechanisms and research strategies for catalyst improvement. For example, almost all partial alkane oxidations, regardless of the metal oxide, follow Mars-van Krevelen reaction kinetics, which utilize lattice oxygen atoms to reoxidize the reduced metal centers while the gaseous O2 reactant replenishes these lattice oxygen vacancies. Many of the most-promising metal oxide catalysts include V5+ surface species as a necessary constituent to convert the alkane. Transformations involving sequential oxidation steps (i.e., propane to acrylic acid) require specific reaction sites for each oxidation step and benefit from site isolation provided by spectator species. These themes, and others, are discussed in the text.

[1]  R. M. Lambert,et al.  Critical influence of the amorphous silica-to-cristobalite phase transition on the performance of Mn/Na2WO4/SiO2 catalysts for the oxidative coupling of methane , 1998 .

[2]  H. Kung,et al.  Selective oxidative dehydrogenation of butane over VMgO catalysts , 1987 .

[3]  E. Iglesia,et al.  Kinetics and Mechanism of Oxidative Dehydrogenation of Propane on Vanadium, Molybdenum, and Tungsten Oxides , 2000 .

[4]  Edward G. Rightor,et al.  Global energy & emissions reduction potential of chemical process improvements , 2015 .

[5]  B. Grzybowska,et al.  Oxidation of C2C4 alkanes on chromium oxide/alumina and on Cr2O3: catalytic and TPD studies , 2001 .

[6]  Anders Holmen,et al.  Direct conversion of methane to fuels and chemicals , 2009 .

[7]  Hanjing Tian,et al.  Quantitative determination of the speciation of surface vanadium oxides and their catalytic activity. , 2006, The journal of physical chemistry. B.

[8]  J. Hazemann,et al.  VOx/SiO2 Catalyst Prepared by Grafting VOCl3 on Silica for Oxidative Dehydrogenation of Propane , 2015 .

[9]  Swati Rawat,et al.  Oxidation of methane by a biological dicopper center , 2010, Nature.

[10]  J. Dubois,et al.  Strategy in achieving propane selective oxidation over multi-functional Mo-based oxide catalysts , 2004 .

[11]  A. Kaddouri,et al.  The synthesis of acrolein and acrylic acid by direct propane oxidation with Ni-Mo-Te-P-O catalysts , 1999 .

[12]  Stuart H. Taylor,et al.  Continuous selective oxidation of methane to methanol over Cu- and Fe-modified ZSM-5 catalysts in a flow reactor , 2016 .

[13]  J. Watts,et al.  An Introduction to Surface Analysis by XPS and AES , 1990 .

[14]  B. Weckhuysen,et al.  In situ Raman spectroscopy studies of bulk and surface metal oxide phases during oxidation reactions , 1996 .

[15]  David Linke,et al.  Catalytic Partial Oxidation of Ethane to Acetic Acid over Mo1V0.25Nb0.12Pd0.0005Ox: II. Kinetic Modelling , 2002 .

[16]  R. Grasselli Genesis of site isolation and phase cooperation in selective oxidation catalysis , 2001 .

[17]  R. Schlögl,et al.  Dynamic surface behaviour of VPO catalysts under reactive and non-reactive gas compositions: an in-situ XAS study , 2004 .

[18]  F. Cavani,et al.  Key Aspects of Catalyst Design for the Selective Oxidation of Paraffins , 1996 .

[19]  J. Sauer,et al.  Oxidative dehydrogenation of propane by monomeric vanadium oxide sites on silica support , 2007 .

[20]  J. Weitkamp,et al.  Zeolites and catalysis , 2000 .

[21]  J. Lercher,et al.  Synthesis of single-site copper catalysts for methane partial oxidation. , 2016, Chemical communications.

[22]  Vadim V. Guliants,et al.  Recent developments in catalysis using nanostructured materials , 2009 .

[23]  G. Marin,et al.  Effect of pressure on the oxidative coupling of methane in the absence of catalyst , 1994 .

[24]  J. Coxon,et al.  Oxidation , 2018, Worked Solutions in Organic Chemistry.

[25]  W. Shim,et al.  Catalytic combustion of VOCs over a series of manganese oxide catalysts , 2010 .

[26]  W. Goddard,et al.  The critical role of phosphate in vanadium phosphate oxide for the catalytic activation and functionalization of n-butane to maleic anhydride. , 2013, Journal of the American Chemical Society.

[27]  J. Lunsford,et al.  Oxidative dehydrogenation of propane , 1996 .

[28]  A. Bell,et al.  A DFT study of the mechanism and kinetics of methane oxidation to formaldehyde occurring on silica-supported molybdena , 2007 .

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

[30]  R. Schlögl Active Sites for Propane Oxidation: Some Generic Considerations , 2011 .

[31]  K. Strohmaier Chapter 2. Synthesis Approaches , 2010 .

[32]  Zhen Zhao,et al.  Selective oxidation of ethane to acetaldehyde and acrolein over silica-supported vanadium catalysts using oxygen as oxidant , 2000 .

[33]  M. Bettahar,et al.  On the partial oxidation of propane and propylene on mixed metal oxide catalysts , 1996 .

[34]  G. Clet,et al.  Quantitative IR characterization of the acidity of various oxide catalysts , 2005 .

[35]  Keigo Kamata,et al.  Efficient Epoxidation of Olefins with ≥99% Selectivity and Use of Hydrogen Peroxide , 2003, Science.

[36]  T. Okuhara,et al.  Preparation of catalyst precursors for selective oxidation of n-butane by exfoliation–reduction of VOPO4·2H2O in primary alcohol , 2003 .

[37]  I. Wachs,et al.  In Situ Raman Spectroscopy of SiO2-Supported Transition Metal Oxide Catalysts: An Isotopic 18O−16O Exchange Study , 2008 .

[38]  许旱峤,et al.  Kirk-Othmer Encyclopedia of Chemical Technology数据库介绍及实例 , 2007 .

[39]  K. Takanabe,et al.  Methane Coupling Reaction in an Oxy‐Steam Stream through an OH Radical Pathway by using Supported Alkali Metal Catalysts , 2014 .

[40]  R. M. Lambert,et al.  New efficient catalysts for the oxidative coupling of methane , 2000 .

[41]  B. Weckhuysen,et al.  In Situ Spectroscopic Investigation of Molecular Structures of Highly Dispersed Vanadium Oxide on Silica under Various Conditions , 1998 .

[42]  R. Schlögl,et al.  High performance (VOx)n–(TiOx)m/SBA-15 catalysts for the oxidative dehydrogenation of propane , 2014 .

[43]  I. Wachs Raman and IR studies of surface metal oxide species on oxide supports: Supported metal oxide catalysts , 1996 .

[44]  V. Parmon,et al.  Iron complexes in zeolites as a new model of methane monooxygenase , 1997 .

[45]  Xiaosheng Wang,et al.  In-situ synthesis and characterization of V-MCM-41 for oxidative dehydrogenation of n-butane , 2016 .

[46]  T. Tatsumi Metals in Zeolites for Oxidation Catalysis , 2010 .

[47]  R. Schoonheydt UV-VIS-NIR spectroscopy and microscopy of heterogeneous catalysts. , 2010, Chemical Society reviews.

[48]  M. Bañares,et al.  Ethane and n-butane oxidation over supported vanadium oxide catalysts : An in situ UV-visible diffuse reflectance spectroscopic investigation , 1999 .

[49]  Gerhard Mestl,et al.  Transient behavior of vanadyl pyrophosphate catalysts during the partial oxidation of n‑butane in industrial-sized, fixed bed reactors , 2016 .

[50]  J. Millet,et al.  Optimizing the efficiency of MoVTeNbO catalysts for ethane oxidative dehydrogenation to ethylene , 2012 .

[51]  M. Anne,et al.  Structure characterization of orthorhombic phase in MoVTeNbO catalyst by powder X-ray diffraction and XANES , 2007 .

[52]  E. Hensen,et al.  Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol , 2015, Nature Communications.

[53]  T. Blasco,et al.  Oxidative dyhydrogenation of short chain alkanes on supported vanadium oxide catalysts , 1997 .

[54]  A. Galadima,et al.  Revisiting the oxidative coupling of methane to ethylene in the golden period of shale gas: A review , 2016 .

[55]  M. Bañares,et al.  An investigation on surface reactivity of Nb-doped vanadyl pyrophosphate catalysts by reactivity experiments and in situ Raman spectroscopy , 2014 .

[56]  J. Fierro,et al.  Supported Tantalum Oxide Catalysts: Synthesis, Physical Characterization, and Methanol Oxidation Chemical Probe Reaction , 2003 .

[57]  F. Cavani,et al.  Non-steady catalytic performance as a tool for the identification of the active surface in VPO, catalyst for n-butane oxidation to maleic anhydride , 2006 .

[58]  P. Larsson,et al.  Supported metal oxides for catalytic combustion of CO and VOCs emissions: preparation of titania overlayers on a macroporous support , 1997 .

[59]  F. Trifiró,et al.  Oxidative Dehydrogenation of Ethane andn-Butane on VOx/Al2O3Catalysts , 1997 .

[60]  J. Védrine,et al.  Heterogeneous partial oxidation catalysis on metal oxides , 2016 .

[61]  V. A. Kondratenko,et al.  Mechanistic aspects of the Andrussow process over Pt–Rh gauzes. Pathways of formation and consumption of HCN , 2010 .

[62]  G. Panov,et al.  Room-Temperature Oxidation of Methane by α-Oxygen and Extraction of Products from the FeZSM-5 Surface , 2011 .

[63]  Manfred Baerns,et al.  Fundamental and combinatorial approaches in the search for and optimisation of catalytic materials for the oxidative dehydrogenation of propane to propene , 2001 .

[64]  Alexis T. Bell,et al.  Isotopic Tracer and Kinetic Studies of Oxidative Dehydrogenation Pathways on Vanadium Oxide Catalysts , 1999 .

[65]  R. Schomäcker,et al.  Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor. , 2013, Dalton transactions.

[66]  M. Bañares,et al.  Comparison of Silica-Supported MoO3and V2O5Catalysts in the Selective Partial Oxidation of Methane , 1996 .

[67]  M. R. Thompson,et al.  An active site hypothesis for well-crystallized vanadium phosphorus oxide catalyst systems , 1993 .

[68]  R. Weber Effect of Local Structure on the UV-Visible Absorption Edges of Molybdenum Oxide Clusters and Supported Molybdenum Oxides , 1995 .

[69]  F. Hardcastle,et al.  The structure of surface rhenium oxide on alumina from laser raman spectroscopy and x-ray absorption near-edge spectroscopy , 1988 .

[70]  Guy Marin,et al.  Catalyst design based on microkinetic models: Oxidative coupling of methane , 2011 .

[71]  I. Hermans,et al.  Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites , 2016 .

[72]  I. Wachs Infrared spectroscopy of supported metal oxide catalysts , 1995 .

[73]  Helena Hagelin‐Weaver,et al.  Characterization of Mn–Na2WO4/SiO2 and Mn–Na2WO4/MgO catalysts for the oxidative coupling of methane , 2015 .

[74]  Pm Pieter Couwenberg,et al.  Irreducible mass-transport limitations during a heterogeneously catalyzed gas-phase chain reaction : oxidative coupling of methane , 1996 .

[75]  I. Wachs Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials , 2005 .

[76]  A. Gaffney,et al.  Techno-Economic Analysis of Oxidative Dehydrogenation Options , 2016, Topics in Catalysis.

[77]  R. Schlögl,et al.  Catalytic partial oxidation of ethane to acetic acid over Mo1V0.25Nb0.12Pd0.0005Ox. I. Catalyst performance and reaction mechanism , 2002 .

[78]  K. Takanabe,et al.  Mechanistic Aspects and Reaction Pathways for Oxidative Coupling of Methane on Mn/Na2WO4/SiO2 Catalysts , 2009 .

[79]  H. Wan,et al.  The effect of MoV0.3Te0.23PxOn catalysts with different phosphorus content for selective oxidation of propane to acrolein , 2004 .

[80]  A. Bell,et al.  Structure and Properties of Zirconia-Supported Molybdenum Oxide Catalysts for Oxidative Dehydrogenation of Propane , 2000 .

[81]  R. Schlögl,et al.  Methane Activation by Heterogeneous Catalysis , 2014, Catalysis Letters.

[82]  A. Kotarba,et al.  Effect of potassium on physicochemical properties of CrOx/Al2O3 and CrOx/TiO2 catalysts for oxidative dehydrogenation of isobutane: The role of oxygen chemisorption , 2011 .

[83]  U. Ozkan,et al.  NiMoO4 selective oxidation catalysts containing excess MoO3 for the conversion of C4 hydrocarbons to maleic anhydride: II. Selective oxidation of 1-butene , 1985 .

[84]  Qinghong Zhang,et al.  Vanadium-Containing MCM-41 for Partial Oxidation of Lower Alkanes , 2001 .

[85]  Tetsuhiko Kobayashi,et al.  Partial oxidation of ethane into acetaldehyde and acrolein by oxygen over silica-supported bismuth catalysts , 2001 .

[86]  M. Argyle,et al.  Ethane oxidative dehydrogenation pathways on vanadium oxide catalysts , 2002 .

[87]  C. Garner,et al.  X-ray absorption spectroscopy , 1979, Nature.

[88]  Robert Schlögl,et al.  Towards Physical Descriptors of Active and Selective Catalysts for the Oxidation of n‐Butane to Maleic Anhydride , 2013 .

[89]  I. Hermans,et al.  Oxidative methane upgrading. , 2012, ChemSusChem.

[90]  S. MacMillan,et al.  X-ray Spectroscopic Interrogation of Transition-Metal-Mediated Homogeneous Catalysis: Primer and Case Studies , 2017 .

[91]  J. Lunsford,et al.  Oxidative Coupling of Methane over Oxide-Supported Sodium-Manganese Catalysts , 1995 .

[92]  J. Alper,et al.  The Changing Landscape of Hydrocarbon Feedstocks for Chemical Production: Implications for Catalysis: Proceedings of a Workshop , 2016 .

[93]  Zhen Zhao,et al.  Comparative Study of Bulk and Supported V-Mo-Te-Nb-O Mixed Metal Oxide Catalysts for Oxidative Dehydrogenation of Propane to Propylene , 2003 .

[94]  H. Kung,et al.  The effect of loading of vanadia on silica in the oxidation of butane , 1993 .

[95]  A. Lemonidou,et al.  Ni–Nb–O mixed oxides as highly active and selective catalysts for ethene production via ethane oxidative dehydrogenation. Part I: Characterization and catalytic performance , 2006 .

[96]  Guy Marin,et al.  Microkinetics of methane oxidative coupling , 2008 .

[97]  J. Lunsford,et al.  Spectroscopic Characterization of Surface Oxygen Species on Barium-Containing Methane Coupling Catalysts , 1994 .

[98]  M. Roussel,et al.  MoVO-based catalysts for the oxidation of ethane to ethylene and acetic acid: Influence of niobium and/or palladium on physicochemical and catalytic properties , 2006 .

[99]  R. Grasselli,et al.  A selectivity factor in vapor‐phase hydrocarbon oxidation catalysis , 1963 .

[100]  Israel E. Wachs,et al.  In Situ Spectroscopic Investigation of the Molecular and Electronic Structures of SiO2 Supported Surface Metal Oxides , 2007 .

[101]  E. Kondratenko,et al.  Selective and stable iso-butene production over highly dispersed VO(x) species on SiO(2) supports via combining oxidative and non-oxidative iso-butane dehydrogenation. , 2010, Chemical communications.

[102]  L. Madeira,et al.  Catalytic oxidative dehydrogenation of n-butane , 2002 .

[103]  R. Schlögl,et al.  Structure sensitivity of the oxidative activation of methane over MgO model catalysts: I. Kinetic study , 2015 .

[104]  S. Sundaresan,et al.  Evolution of the active surface of the vanadyl pyrophosphate catalysts , 1995 .

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

[106]  H. Kung,et al.  The Kinetic Significance of V5+ in n-Butane Oxidation Catalyzed by Vanadium Phosphates , 1997, Science.

[107]  O. Lapina,et al.  Characterization of surface species of supported V2O5Al2O3 catalysts by 51V NMR , 1991 .

[108]  M. Nachtegaal,et al.  Catalytic conversion of methane to methanol over Cu-mordenite. , 2012, Chemical communications.

[109]  Ye Wang,et al.  Direct conversion of methane into oxygenates , 2001 .

[110]  H. Hattori,et al.  Oxide surfaces that catalyse an acid-base reaction with surface lattice oxygen exchange: evidence of nucleophilicity of oxide surfaces. , 2004, Chemphyschem : a European journal of chemical physics and physical chemistry.

[111]  J. Hagen Shape‐Selective Catalysis: Zeolites , 2006 .

[112]  N. Chen,et al.  HYDROTHERMAL SYNTHESIS OF MO-V-M-O COMPLEX METAL OXIDE CATALYSTS ACTIVE FOR PARTIAL OXIDATION OF ETHANE , 1999 .

[113]  Anthony F. Volpe,et al.  Towards an Understanding of the Reaction Pathways in Propane Ammoxidation Based on the Distribution of Elements at the Active Centers of the M1 Phase of the MoV(Nb,Ta)TeO System , 2011 .

[114]  Stuart H. Taylor,et al.  Chemically Induced Fast Solid-State Transitions of ω-VOPO4 in Vanadium Phosphate Catalysts , 2006, Science.

[115]  C. Pham‐Huu,et al.  High-yield butane to maleic anhydride direct oxidation on vanadyl pyrophosphate supported on heat-conductive materials : β-SiC, Si3N4, and BN , 2001 .

[116]  J. Dubois,et al.  Mo-V-Te-(Nb)-O mixed metal oxides prepared by hydrothermal synthesis for catalytic selective oxidations of propane and propene to acrylic acid , 2003 .

[117]  J. Védrine Heterogeneous catalytic partial oxidation of lower alkanes (C1-C6) on mixed metal oxides , 2016 .

[118]  W. Ueda,et al.  Selective oxidation of light alkanes over hydrothermally synthesized Mo-V-M-O (M=Al, Ga, Bi, Sb, and Te) oxide catalysts , 2000 .

[119]  Atsushi Urakawa,et al.  Oxidative coupling of methane—A complex surface/gas phase mechanism with strong impact on the reaction engineering , 2014 .

[120]  Alexis T. Bell,et al.  Structure and Catalytic Properties of Supported Vanadium Oxides: Support Effects on Oxidative Dehydrogenation Reactions , 1999 .

[121]  F. Rosowski,et al.  Partial oxidation of propane to acrylic acid at a Mo–V–Te–Nb-oxide catalyst , 2004 .

[122]  J. Lercher,et al.  On the Role of the Vanadium Distribution in MoVTeNbOx Mixed Oxides for the Selective Catalytic Oxidation of Propane , 2011 .

[123]  J. T. Grant,et al.  Enhanced Two-Dimensional Dispersion of Group V Metal Oxides on Silica , 2015 .

[124]  L. Madeira,et al.  Nickel Molybdate Catalysts and Their Use in the Selective Oxidation of Hydrocarbons , 2004 .

[125]  R. Lobo,et al.  Catalytic conversion of methane to methanol on Cu-SSZ-13 using N2O as oxidant. , 2016, Chemical communications.

[126]  H. Wan,et al.  Selective Oxidation of Propane to Acrolein over Ce-Doped Ag–Mo–P–O Catalysts: Influence of Ce Promoter , 2003 .

[127]  J D Lipscomb,et al.  An Fe2IVO2 Diamond Core Structure for the Key Intermediate Q of Methane Monooxygenase , 1997, Science.

[128]  A. Bell,et al.  Selective oxidation of methane over MoOx/SiO2: isolation of the kinetics of reactions occurring in the gas phase and on the surfaces of SiO2 and MoOx , 2005 .

[129]  J. Paier,et al.  Sites for methane activation on lithium-doped magnesium oxide surfaces. , 2014, Angewandte Chemie.

[130]  G. Xiao,et al.  Coking- and Sintering-Resistant Palladium Catalysts Achieved Through Atomic Layer Deposition , 2012, Science.

[131]  B. Sels,et al.  A [Cu2O]2+ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol , 2009, Proceedings of the National Academy of Sciences.

[132]  S. M. Sarathy,et al.  Integrated In Situ Characterization of a Molten Salt Catalyst Surface: Evidence of Sodium Peroxide and Hydroxyl Radical Formation , 2017, Angewandte Chemie.

[133]  J. Nieto,et al.  Kinetic Study of the Oxidation of n-Butane on Vanadium Oxide Supported on Al/Mg Mixed Oxide , 1997 .

[134]  R. Schomäcker,et al.  Investigation of the surface reaction network of the oxidative coupling of methane over Na2WO4/Mn/SiO2 catalyst by temperature programmed and dynamic experiments , 2016 .

[135]  J. Lercher,et al.  Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects , 2013 .

[136]  F. Trifiró,et al.  How the Yield of Maleic Anhydride in n-Butane Oxidation, Using VPO Catalysts, was Improved Over the Years , 2014, Topics in Catalysis.

[137]  A. Gaffney,et al.  Ethylene production via Oxidative Dehydrogenation of Ethane using M1 catalyst , 2017 .

[138]  A. Zukal,et al.  Study of vanadium based mesoporous silicas for oxidative dehydrogenation of propane and n-butane , 2012 .

[139]  Manuel Gómez,et al.  Mo/γ-Al2O3 catalysts for the oxidative dehydrogenation of propane.: Effect of Mo loading , 2001 .

[140]  S. Sundaresan,et al.  Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships☆ , 1997 .

[141]  A. Lemonidou Oxidative dehydrogenation of C4 hydrocarbons over VMgO catalyst — kinetic investigations , 2001 .

[142]  D. Su,et al.  In Situ Surface Analysis in Selective Oxidation Catalysis: n-Butane Conversion Over VPP , 2003 .

[143]  A. D. Vekki,et al.  Catalytic partial oxidation of methane to formaldehyde , 2009 .

[144]  P. Mars,et al.  Oxidations carried out by means of vanadium oxide catalysts , 1954 .

[145]  Martin Holena,et al.  Statistical Analysis of Past Catalytic Data on Oxidative Methane Coupling for New Insights into the Composition of High‐Performance Catalysts , 2011 .

[146]  G. Hutchings,et al.  Structural transformation sequences occurring during the activation of vanadium phosphorus oxide catalysts , 1996 .

[147]  S. Ishikawa,et al.  Microporous crystalline Mo–V mixed oxides for selective oxidations , 2016 .

[148]  R. Tyler,et al.  The rate controlling step in the oxidative coupling of methane over a lithium-promoted magnesium oxide catalyst , 1988 .

[149]  R. Schomäcker,et al.  Support material variation for the MnxOy-Na2WO4/SiO2 catalyst , 2014 .

[150]  R. Schomäcker,et al.  Enhanced catalytic performance of Mn(x)O(y)-Na₂WO₄/SiO₂ for the oxidative coupling of methane using an ordered mesoporous silica support. , 2014, Chemical communications.

[151]  R. Schomäcker,et al.  Mn–Na2WO4/SiO2 as catalyst for the oxidative coupling of methane. What is really known? , 2012 .

[152]  N. Foster Direct Catalytic Oxidation of Methane to Methanol , 1986 .

[153]  W. Ueda,et al.  Crystalline MoVO based complex oxides as selective oxidation catalysts of propane , 2005 .

[154]  J. M. Webster,et al.  Amorphous vanadium phosphate catalysts prepared using precipitation with supercritical CO2 as an antisolvent , 2002 .

[155]  J. Mayer,et al.  Understanding hydrogen atom transfer: from bond strengths to Marcus theory. , 2011, Accounts of chemical research.

[156]  Yuriy Román‐Leshkov,et al.  Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature , 2016, ACS central science.

[157]  R. Grasselli,et al.  Multifunctionality of Active Centers in (Amm)oxidation Catalysts: From Bi–Mo–Ox to Mo–V–Nb–(Te, Sb)–Ox , 2003 .

[158]  J. Herrmann,et al.  On the NiMoO4 oxidative dehydrogenation of propane to propene: some physical correlations with the catalytic activity , 1991 .

[159]  R. Keiski,et al.  Ethylene Oxide Formation in a Microreactor: From Qualitative Kinetics to Detailed Modeling , 2010 .

[160]  水野 哲孝 Modern heterogeneous oxidation catalysis : design, reactions and characterization , 2009 .

[161]  V. Ponec,et al.  The universal character of the Mars and Van Krevelen mechanism , 2000 .

[162]  C. Peden,et al.  Investigation of the Structure and Active Sites of TiO2 Nanorod Supported VOx Catalysts by High-Field and Fast-Spinning 51V MAS NMR , 2015 .

[163]  Avelino Corma,et al.  State of the art and future challenges of zeolites as catalysts , 2003 .

[164]  R. Schlögl,et al.  Ambient-Pressure Soft X-ray Absorption Spectroscopy of a Catalyst Surface in Action: Closing the Pressure Gap in the Selective n-Butane Oxidation over Vanadyl Pyrophosphate , 2014 .

[165]  D. Rudd,et al.  SIMULATION OF METHANE PARTIAL OXIDATION OVER SILICA-SUPPORTED MOO3 AND V2O5 , 1991 .

[166]  N. Spencer,et al.  Partial oxidation of CH to HCHO over a MoO-SiO catalyst: A kinetic study , 1987 .

[167]  R. Schlögl,et al.  Dynamics of the MoVTeNb Oxide M1 Phase in Propane Oxidation , 2010 .

[168]  J. T. Grant,et al.  Improved Supported Metal Oxides for the Oxidative Dehydrogenation of Propane , 2016, Topics in Catalysis.

[169]  Y. H. Jang,et al.  Selective oxidation and ammoxidation of propene on bismuth molybdates, ab initio calculations , 2001 .

[170]  P. Concepción,et al.  On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes , 1996 .

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

[172]  M. Vaarkamp,et al.  Ammoxidation of Propane over Catalysts Comprising Mixed Oxides of Mo and V , 1997 .

[173]  R. Schlögl,et al.  Photoelectron Spectroscopy of Catalytic Oxide Materials , 2009 .

[174]  A. Boix,et al.  Oxidative coupling of methane on Sr/La2O3 catalysts: Improving the catalytic performance using cordierite monoliths and ceramic foams as structured substrates , 2017 .

[175]  F. Arena,et al.  Working Mechanism of Oxide Catalysts in the Partial Oxidation of Methane to Formaldehyde. II. Redox Properties and Reactivity of SiO 2, MoO 3 /SiO 2, V 2O 5 /SiO 2, TiO 2, and V 2O 5 /TiO 2Systems , 1997 .

[176]  Berend Smit,et al.  Towards a molecular understanding of shape selectivity , 2008, Nature.

[177]  A. Bell,et al.  Structure and properties of oxidative dehydrogenation catalysts based on MoO3/Al2O3 , 2001 .

[178]  R. Grasselli,et al.  Propane Oxydehydrogenation over Molybdate-Based Catalysts , 1997 .

[179]  F. Cavani,et al.  VPO catalyst for n-butane oxidation to maleic anhydride: A goal achieved, or a still open challenge? , 2006 .

[180]  J. Nieto,et al.  Oxidative dehydrogenation of n-butane on MgO-supported vanadium oxide catalysts , 1998 .

[181]  P. Jacobs,et al.  Selective oxidation of methane by the bis(mu-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites. , 2005, Journal of the American Chemical Society.

[182]  P. Concepción,et al.  Preparation, characterization and reactivity of V- and/or Co-containing AlPO-18 materials (VCoAPO-18) in the oxidative dehydrogenation of ethane , 2004 .

[183]  J. Holmberg,et al.  Active centers, catalytic behavior, symbiosis and redox properties of MoV(Nb,Ta)TeO ammoxidation catalysts , 2006 .

[184]  A. Corma,et al.  Influence of the Preparation Methods of V-Mg-O Catalysts on Their Catalytic Properties for the Oxidative Dehydrogenation of Propane , 1993 .

[185]  Mark E. Davis,et al.  Comparison of Reaction Pathways for the Partial Oxidation of Propane over Vanadyl Ion-Exchanged Zeolite Beta and Mo1V0.3Te0.23Nb0.12Ox , 2001 .

[186]  A. Kozłowska,et al.  Chromium Oxide/Alumina Catalysts in Oxidative Dehydrogenation of Isobutane☆ , 1998 .

[187]  J. Fierro,et al.  Oxidative Dehydrogenation ofn-Butane over Alkali and Alkaline Earth-Promoted α-NiMoO4Catalysts☆ , 1997 .

[188]  Horia Metiu,et al.  Catalysis by doped oxides. , 2013, Chemical reviews.

[189]  H. Kung,et al.  Selectivity Patterns in Alkane Oxidation over Mg3(VO4)2-MgO, Mg2V2O7, and (VO)2P2O7 , 1993 .

[190]  A. Beale,et al.  Characterization of Solid Materials and Heterogeneous Catalysts , 2013 .

[191]  Yi-fan Han,et al.  V–Zr–P oxide catalysts for highly selective oxidation of propane to acrylic acid , 1999 .

[192]  R. Schlögl,et al.  The reaction network in propane oxidation over phase-pure MoVTeNb M1 oxide catalysts , 2014 .

[193]  H. Kung Oxidative Dehydrogenation of Light (C2 to C4) Alkanes , 1994 .

[194]  P. Concepción,et al.  Selective Oxidation of n-Butane and Butenes over Vanadium-Containing Catalysts , 2000 .

[195]  J. Lunsford CATALYTIC CONVERSION OF METHANE TO MORE USEFUL CHEMICALS AND FUELS: A CHALLENGE FOR THE 21ST CENTURY , 2000 .

[196]  M. L. Oliveira,et al.  Effect of alkali metal promoters on nickel molybdate catalysts and its relevance to the selective oxidation of butane , 1995 .

[197]  B. Weckhuysen,et al.  COMBINED DRS-RS-EXAFS-XANES-TPR STUDY OF SUPPORTED CHROMIUM CATALYSTS , 1995 .

[198]  Eleni Heracleous,et al.  Ni-Nb-O mixed oxides as highly active and selective catalysts for ethene production via ethane oxidative dehydrogenation. Part II: Mechanistic aspects and kinetic modeling , 2006 .

[199]  Jack H. Lunsford The Catalytic Oxidative Coupling of Methane , 1995 .

[200]  D. Blom,et al.  Atomic-level imaging of Mo-V-O complex oxide phase intergrowth, grain boundaries, and defects using HAADF-STEM , 2010, Proceedings of the National Academy of Sciences.

[201]  G. Hutchings,et al.  Role of the product in the transformation of a catalyst to its active state , 1994, Nature.

[202]  R. Grabowski Kinetics of Oxidative Dehydrogenation of C2‐C3 Alkanes on Oxide Catalysts , 2006 .

[203]  R. Grasselli,et al.  Catalytic Consequences of a Revised Distribution of Key Elements at the Active Centers of the M1 Phase of the MoVNbTeOx System , 2014, Topics in Catalysis.

[204]  Jeroen A van Bokhoven,et al.  The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment. , 2017, Angewandte Chemie.

[205]  A. Dalai,et al.  CORRELATION OF ELECTRICAL PROPERTIES AND PERFORMANCE OF OCM MOX/NA2WO4/SIO2 CATALYSTS , 2001 .

[206]  E. Kondratenko,et al.  Similarity and differences in the oxidative dehydrogenation of C2–C4 alkanes over nano-sized VOx species using N2O and O2 , 2009 .

[207]  P. Concepción,et al.  Reaction products and pathways in the selective oxidation of C2―C4 alkanes on MoVTeNb mixed oxide catalysts , 2010 .

[208]  Z. Liu,et al.  Synergetic effect of VOx and TeOx species in mesoporous SiO2 on selective oxidation of propane to acrolein , 2013 .

[209]  Mark E. Davis,et al.  Structure-direction in zeolite synthesis , 1995, Journal of inclusion phenomena and molecular recognition in chemistry.

[210]  A. Bell,et al.  Study of the elementary processes involved in the selective oxidation of methane over MoOx/SiO2. , 2006, The journal of physical chemistry. B.

[211]  J. Bozell,et al.  A comparative review of petroleum-based and bio-based acrolein production. , 2012, ChemSusChem.

[212]  R. Schomäcker,et al.  Li-doped MgO From Different Preparative Routes for the Oxidative Coupling of Methane , 2011 .

[213]  J. Guth,et al.  Synthesis of Aluminosilicate Zeolites and Related Silica-Based Materials , 1999 .

[214]  Frédéric Thibault-Starzyk,et al.  Analysing and understanding the active site by IR spectroscopy. , 2010, Chemical Society reviews.

[215]  J. Jehng,et al.  Determination of the chemical nature of active surface sites present on bulk mixed metal oxide catalysts. , 2005, The journal of physical chemistry. B.

[216]  Jiří Čejka,et al.  Zeolites and catalysis : synthesis, reactions and applications , 2010 .

[217]  K. A. Dubkov,et al.  Nitrous Oxide as an Oxygen Donor in Oxidation Chemistry and Catalysis , 2009 .

[218]  P. H. Kasai,et al.  The oxidative dehydrogenation of ethane over catalysts containing mixed oxides of molybdenum and vanadium , 1978 .

[219]  A. Dejoz,et al.  The effect of potassium on the selective oxidation ofn-butane and ethane over Al2O3-supported vanadia catalysts , 1995 .

[220]  I. Wachs,et al.  Structural determination of bulk and surface tungsten oxides with UV-vis diffuse reflectance spectroscopy and raman spectroscopy , 2007 .

[221]  Xiaoshu Wang,et al.  Novel modifications in preparing vanadium phosphorus oxides and their applications for partial oxidation of n-butane , 2003 .

[222]  A. Kozłowska,et al.  Oxygen adsorption and catalytic performance in oxidative dehydrogenation of isobutane on chromium oxide-based catalysts , 1999 .

[223]  Charles A. Roberts,et al.  Monitoring surface metal oxide catalytic active sites with Raman spectroscopy. , 2010, Chemical Society reviews.

[224]  R. Schlögl,et al.  XPS investigations of VPO catalysts under reaction conditions , 2005 .

[225]  J. Nørskov,et al.  Descriptor-based analysis applied to HCN synthesis from NH3 and CH4. , 2011, Angewandte Chemie.

[226]  S. Godtfredsen,et al.  Ullmann ' s Encyclopedia of Industrial Chemistry , 2017 .

[227]  M. Barteau,et al.  Differentiation of Active Oxygen Species for Butane Oxidation on Vanadyl Pyrophosphate , 2003 .

[228]  B. Weckhuysen,et al.  Recent progress in diffuse reflectance spectroscopy of supported metal oxide catalysts , 1999 .

[229]  Israel E. Wachs,et al.  The origin of the support effect in supported metal oxide catalysts : in situ infrared and kinetic studies during methanol oxidation , 1999 .

[230]  B. Grzybowska,et al.  Oxidative dehydrogenation of isobutane on supported chromia catalysts , 1996 .

[231]  W. Grünert Auger Electron, X ray and UV Photoelectron Spectroscopies , 2012 .

[232]  M. Bañares,et al.  Bulk mixed Mo–V–Te–O catalysts for propane oxidation to acrylic acid , 2004 .

[233]  M. V. Ganduglia-Pirovano,et al.  Resolving the atomic structure of vanadia monolayer catalysts: monomers, trimers, and oligomers on ceria. , 2009, Angewandte Chemie.

[234]  Arnaud Travert,et al.  Monomolecular Cracking Rates of Light Alkanes over Zeolites Determined by IR Operando Spectroscopy , 2016 .

[235]  J. T. Grant,et al.  Elucidation of Anchoring and Restructuring Steps during Synthesis of Silica-Supported Vanadium Oxide Catalysts , 2016 .

[236]  Miao Sun,et al.  Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane , 2012 .

[237]  J. Nieto,et al.  Selective oxidative dehydrogenation of ethane on MoVTeNbO mixed metal oxide catalysts , 2004 .

[238]  R. Grasselli Site Isolation and Phase Cooperation: Two Important Concepts in Selective Oxidation Catalysis: A Retrospective , 2014 .

[239]  British Petroleum , 2022, Nature.

[240]  K. P. Jong,et al.  Catalysts for Production of Lower Olefins from Synthesis Gas: A Review , 2013 .

[241]  B. Weckhuysen,et al.  Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides. , 1996, Chemical reviews.

[242]  J. Holmberg,et al.  Catalytic behaviour of M1, M2, and M1/M2 physical mixtures of the Mo-V-Nb-Te-oxide system in propane and propene ammoxidation , 2004 .

[243]  T. Vogt,et al.  Structural Characterization of the Orthorhombic Phase M1 in MoVNbTeO Propane Ammoxidation Catalyst , 2003 .

[244]  G. Hutchings Selective Oxidation of Light Alkanes , 1998 .

[245]  S. Loridant,et al.  Ni-Nb-O catalysts for ethane oxidative dehydrogenation , 2010 .

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

[247]  G. Neri,et al.  Oxidative dehydrogenation of isobutane over V2O5-based catalysts prepared by grafting vanadyl alkoxides on TiO2_SiO2 supports , 2003 .

[248]  N. Rösch,et al.  Structure and electronic properties of MoVO type mixed-metal oxides - a combined view by experiment and theory. , 2015, Dalton transactions.

[249]  J. Dubois,et al.  Propane Oxidation on MoVTeNbO Mixed Oxide Catalysts: Study of the Phase Composition of Active and Selective Catalysts , 2003 .

[250]  J. Bokhoven,et al.  Determination of the electronic and geometric structure of Cu sites during methane conversion over Cu-MOR with X-ray absorption spectroscopy , 2013 .

[251]  M. Ai Oxidation of propane to acrylic acid on V2O5&P2O5-based catalysts , 1986 .

[252]  P. Marion,et al.  Catalytic Ammoxidation of Hydrocarbons on Mixed Oxides , 2009 .

[253]  Zheng Zhai,et al.  Band-gap energy as a descriptor of catalytic activity for propene oxidation over mixed metal oxide catalysts. , 2014, Journal of the American Chemical Society.

[254]  B. Weckhuysen,et al.  Catalytic dehydrogenation of light alkanes on metals and metal oxides. , 2014, Chemical reviews.

[255]  J. Fierro,et al.  Oxidative dehydrogenation of ethane to ethylene over alumina-supported vanadium oxide catalysts: Relationship between molecular structures and chemical reactivity , 2006 .

[256]  L. Madeira,et al.  Mechanistic effects resulting from the cesium-doping of a NiMoO4 catalyst in n-butane oxidative dehydrogenation , 2005 .

[257]  F. Márquez,et al.  The Preparation, Characterization, and Catalytic Behavior of MoVTeNbO Catalysts Prepared by Hydrothermal Synthesis , 2002 .

[258]  P. Botella,et al.  The selective oxidative dehydrogenation of ethane over hydrothermally synthesised MoVTeNb catalysts. , 2002, Chemical communications.

[259]  Anthony F. Volpe,et al.  Gas phase oxidation of ethane to acetic acid using high-throughput screening in a massively parallel microfluidic reactor system , 2003 .

[260]  H. Schubert,et al.  Mn—Na2WO4/SiO2 as Catalyst for the Oxidative Coupling of Methane. What Is Really Known? , 2012 .

[261]  J. Hoebink,et al.  An Investigation of the Oxygen Pathways in the Oxidative Coupling of Methane over MgO-Based Catalysts , 1996 .

[262]  R. Schlögl,et al.  Structure sensitivity of the oxidative activation of methane over MgO model catalysts: II. Nature of active sites and reaction mechanism , 2015 .

[263]  Martin Kumar Patel,et al.  Olefins from conventional and heavy feedstocks: Energy use in steam cracking and alternative processes , 2006 .

[264]  J. Nieto,et al.  Selective oxidation of ethane: Developing an orthorhombic phase in Mo―V―X (X = Nb, Sb, Te) mixed oxides , 2009 .

[265]  Pirie,et al.  The Manufacture of Hydrocyanic Acid by the Andrussow Process , 2022 .

[266]  F. Arena,et al.  Working Mechanism of Oxide Catalysts in the Partial Oxidation of Methane to Formaldehyde. I. Catalytic Behaviour of SiO 2, MoO 3/SiO 2, V 2O 5/SiO 2, TiO 2, and V 2O 5/TiO 2Systems , 1997 .

[267]  R. Schloegl,et al.  Critical Literature Review of the Kinetics for the Oxidative Dehydrogenation of Propane over Well-Defined Supported Vanadium Oxide Catalysts , 2014 .

[268]  T. Blasco,et al.  Influence of the acid-base character of supported vanadium catalysts on their catalytic properties for the oxidative dehydrogenation of n-butane , 1995 .

[269]  S. Blanksby,et al.  Bond dissociation energies of organic molecules. , 2003, Accounts of chemical research.

[270]  Manhua Mandy Lin,et al.  Selective oxidation of propane to acrylic acid with molecular oxygen , 2001 .

[271]  Xuebing Li,et al.  Support and promoter effects in the selective oxidation of ethane to acetic acid catalyzed by Mo-V-Nb oxides , 2008 .