Abstract
Chromium, molybdenum and tungsten oxides supported on amorphous silica are catalysts for many reactions, including large-scale industrial processes. Although these systems have been extensively studied for many years, there are still a few unresolved issues, concerning mainly the nature of the active sites and mechanisms of their formation. Computational studies, using cluster or periodic models to represent the catalyst surface, are helpful in interpretation of spectroscopic data and can provide complementary information about the catalytic process. In this chapter, such computational works on CrOx/SiO2, MoOx/SiO2 and WOx/SiO2 systems are presented. It is seen that coordination environment of the transition metal, determined also by local surface properties, is a key factor influencing catalytic activity of the surface metal species. This results in complex structure–activity relationships . While a great progress has been achieved in modelling of these systems, from simple clusters to advanced periodic slabs, theoretical determination of complex reaction mechanisms using surface models with representative distribution of metal sites is still a challenge for computational catalysis.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Sautet P, Delbecq F (2010) Catalysis and surface organometallic chemistry: a view from theory and simulations. Chem Rev 110:1788–1806
Handzlik J, Kurleto K (2013) Theoretical investigations of heterogeneous olefin metathesis catalysts. Curr Org Chem 17:2796–2813
Handzlik J, Ogonowski J (2012) Structure of isolated molybdenum(VI) and molybdenum(IV) oxide species on silica: periodic and cluster DFT studies. J Phys Chem C 116:5571–5584
Handzlik J, Grybos R, Tielens F (2013) Structure of monomeric chromium(VI) oxide species supported on silica: periodic and cluster DFT studies. J Phys Chem C 117:8138–8149
Gierada M, Michorczyk P, Tielens F, Handzlik J (2016) Reduction of chromia-silica catalysts: a molecular picture. J Catal 340:122–135
Fong A, Yuan Y, Ivry SL, Scott SL, Peters B (2015) Computational kinetic discrimination of ethylene polymerization mechanisms for the Phillips (Cr/SiO2) catalyst. ACS Catal 5:3360–3374
Guesmi H, Tielens F (2012) Chromium oxide species supported on silica: a representative periodic DFT model. J Phys Chem C 116:994–1001
Guesmi H, Grybos R, Handzlik J, Tielens F (2014) Characterization of molybdenum monomeric oxide species supported on hydroxylated silica: a DFT study. Phys Chem Chem Phys 16:18253–18260
Guesmi H, Grybos R, Handzlik J, Tielens F (2016) Characterization of tungsten monomeric oxide species supported on hydroxylated silica; a DFT study. RSC Adv 6:39424–39432
Floryan L, Borosy AP, Núñez-Zarur F, Comas-Vives A, Copéret C (2017) Strain effect and dual initiation pathway in CrIII/SiO2 polymerization catalysts from amorphous periodic models. J Catal 346:50–56
Dapprich S, Komáromi I, Byun KS, Morokuma K, Frisch MJ (1999) A new ONIOM implementation in Gaussian98. Part I. The calculation of energies, gradients, vibrational frequencies and electric field derivatives. J Mol Struct THEOCHEM 461–462:1–21
Ugliengo P, Sodupe M, Musso F, Bush IJ, Orlando R, Dovesi R (2008) Realistic models of hydroxylated amorphous silica surfaces and MCM-41 mesoporous material simulated by large-scale periodic B3LYP calculations. Adv Mater 20:4579–4583
Tielens F, Gervais C, Lambert JF, Mauri F, Costa D (2008) Ab initio study of the hydroxylated surface of amorphous silica: a representative model. Chem Mater 20:3336–3344
Ewing CS, Bhavsar S, Veser G, McCarthy JJ, Johnson JK (2014) Accurate amorphous silica surface models from first-principles thermodynamics of surface dehydroxylation. Langmuir 30:5133–5141
Comas-Vives A (2016) Amorphous SiO2 surface models: energetics of the dehydroxylation process, strain, ab initio atomistic thermodynamics and IR spectroscopic signatures. Phys Chem Chem Phys 18:7475–7482
Gierada M, Petit I, Handzlik J, Tielens F (2016) Hydration in silica based mesoporous materials: a DFT model. Phys Chem Chem Phys 18:32962–32972
McDaniel MP (2010) A review of the Phillips supported chromium catalyst and its commercial use for ethylene polymerization. In: Advances in Catalysis, vol. 53, pp. 123–606
McDaniel M (2017) Manipulating polymerization chemistry of Cr/silica catalysts through calcination. Appl Catal A Gen 542:392–410
Groppo E, Lamberti C, Bordiga S, Spoto G, Zecchina A (2005) The structure of active centers and the ethylene polymerization mechanism on the Cr/SiO2 catalyst: a frontier for the characterization methods. Chem Rev 105:115–183
Weckhuysen BM, Wachs IE, Schoonheydt RA (1996) Surface chemistry and spectroscopy of chromium in inorganic oxides. Chem Rev 96:3327–3349
Hakuli A, Harlin ME, Backman LB, Krause AOI (1999) Dehydrogenation of i-butane on CrOx/SiO2 catalysts. J Catal 184:349–356
Ramani NC, Sullivan DL, Ekerdt JG, Jehng J-M, Wachs IE (1998) Selective oxidation of 1-butene over silica-supported Cr(VI), Mo(VI), and W(VI) oxides. J Catal 176:143–154
Cherian M, Rao MS, Hirt AM, Wachs IE, Deo G (2002) Oxidative dehydrogenation of propane over supported chromia catalysts: influence of oxide supports and chromia loading. J Catal 211:482–495
Michorczyk P, Pietrzyk P, Ogonowski J (2012) Preparation and characterization of SBA-1-supported chromium oxide catalysts for CO2 assisted dehydrogenation of propane. Microporous Mesoporous Mater 161:56–66
Botavina MA, Agafonov YA, Gaidai NA, Groppo E, Cortés Corberán V, Lapidus AL, Martra G (2016) Towards efficient catalysts for the oxidative dehydrogenation of propane in the presence of CO2: Cr/SiO2 systems prepared by direct hydrothermal synthesis. Catal Sci Technol 6:840–850
Kim DS, Tatibouet J-M, Wachs IE (1992) Surface structure and reactivity of CrO3/SiO2 catalysts. J Catal 136:209–221
Jehng J-M, Hu H, Gao X, Wachs IE (1996) The dynamic states of silica-supported metal oxide catalysts during methanol oxidation. Catal Today 28:335–350
Liotta LF, Venezia AM, Pantaleo G, Deganello G, Gruttadauria M, Noto R (2004) Chromia on silica and zirconia oxides as recyclable oxidizing system: structural and surface characterization of the active chromium species for oxidation reaction. Catal Today 91–92:231–236
Dines TJ, Inglis S (2003) Raman spectroscopic study of supported chromium(VI) oxide catalysts. Phys Chem Chem Phys 5:1320–1328
Groppo E, Damin A, Bonino F, Zecchina A, Bordiga S, Lamberti C (2005) New strategies in the Raman study of the Cr/SiO2 Phillips catalyst: observation of molecular adducts on Cr(II) sites. Chem Mater 17:2019–2027
Moisii C, Deguns EW, Lita A, Callahan SD, van de Burgt LJ, Magana D, Stiegman AE (2006) Coordination environment and vibrational spectroscopy of Cr(VI) sites supported on amorphous silica. Chem Mater 18:3965–3975
Lee EL, Wachs IE (2007) In situ spectroscopic investigation of the molecular and electronic structures of SiO2 supported surface metal oxides. J Phys Chem C 111:14410–14425
Lee EL, Wachs IE (2008) In situ Raman spectroscopy of SiO2-supported transition metal oxide catalysts: an isotopic 18O−16O exchange study. J Phys Chem C 112:6487–6498
Chakrabarti A, Wachs IE (2015) The nature of surface CrOx sites on SiO2 in different environments. Catal Lett 145:985–994
Peek NM, Jeffcoat DB, Moisii C, van de Burgt L, Profeta S, Scott SL, Stiegman AE (2018) Reassessment of the electronic structure of Cr(VI) sites supported on amorphous silica and implications for Cr coordination number. J Phys Chem C 122:4349–4358
Moisii C, Jeffcoat D, Peek N, van de Burgt L, Scott SL, Stiegman AE (2018) Do mono-oxo sites exist in silica-supported Cr(VI) materials? Reassessment of the resonance Raman spectra. J Phys Chem C 122:17149–17160
Gaspar AB, Martins RL, Schmal M, Dieguez LC (2001) Characterization of Cr2+ and ethylene polymerization on Cr/SiO2 catalysts. J Mol Catal A Chem 169:105–112
Groppo E, Damin A, Otero Arean C, Zecchina A (2011) Enhancing the initial rate of polymerisation of the reduced Phillips catalyst by one order of magnitude. Chem Eur J 17:11110–11114
Brown C, Krzystek J, Achey R, Lita A, Fu R, Meulenberg RW, Polinski M, Peek N, Wang Y, van de Burgt LJ, Profeta S, Stiegman AE, Scott SL (2015) Mechanism of initiation in the Phillips ethylene polymerization catalyst: redox processes leading to the active site. ACS Catal 5:5574–5583
Chakrabarti A, Gierada M, Handzlik J, Wachs IE (2016) Operando molecular spectroscopy during ethylene polymerization by supported CrOx/SiO2 catalysts: active sites, reaction intermediates, and structure-activity relationship. Top Catal 59:725–739
Barzan C, Piovano A, Braglia L, Martino GA, Lamberti C, Bordiga S, Groppo E (2017) Ligands make the difference! Molecular insights into CrVI/SiO2 Phillips catalyst during ethylene polymerization. J Am Chem Soc 139:17064–17073
Weckhuysen BM, De Ridder LM, Schoonheydt RA (1993) A quantitative diffuse reflectance spectroscopy study of supported chromium catalysts. J Phys Chem 97:4756–4763
Liu B, Nakatani H, Terano M (2002) New aspects of the induction period of ethene polymerization using Phillips CrOx/SiO2 catalyst probed by XPS, TPD and EPMA. J Mol Catal A Chem 184:387–398
Budnyk A, Damin A, Groppo E, Zecchina A, Bordiga S (2015) Effect of surface hydroxylation on the catalytic activity of a Cr(II)/SiO2 model system of Phillips catalyst. J Catal 324:79–87
Weckhuysen BM, De Ridder LM, Grobet PJ, Schoonheydt RA (1995) Redox behavior and dispersion of supported chromium catalysts. J Phys Chem 99:320–326
Weckhuysen BM, Schoonheydt RA, Mabbs FE, Collison D (1996) Electron paramagnetic resonance of heterogeneous chromium catalysts. J Chem Soc Faraday Trans 92:2431–2436
Brown C, Lita A, Tao Y, Peek N, Crosswhite M, Mileham M, Krzystek J, Achey R, Fu R, Bindra JK, Polinski M, Wang Y, van de Burgt LJ, Jeffcoat D, Profeta S, Stiegman AE, Scott SL (2017) Mechanism of initiation in the Phillips ethylene polymerization catalyst: ethylene activation by Cr(II) and the structure of the resulting active site. ACS Catal 7:7442–7455
Espelid Ø, Børve KJ (2001) Theoretical analysis of d-d transitions for the reduced Cr/silica system. Catal Lett 75:49–54
Espelid Ø, Børve KJ (2002) Theoretical analysis of CO adsorption on the reduced Cr/silica system. J Catal 205:177–190
Damin A, Vitillo JG, Ricchiardi G, Bordiga S, Lamberti C, Groppo E, Zecchina A (2009) Modeling CO and N2 adsorption at Cr surface species of Phillips catalyst by hybrid density functionals: effect of Hartree-Fock exchange percentage. J Phys Chem A 113:14261–14269
Demmelmaier CA, White RE, van Bokhoven JA, Scott SL (2008) Nature of ≡SiOCrO2Cl and (≡SiO)2CrO2 sites prepared by grafting CrO2Cl2 onto silica. J Phys Chem C 112:6439–6449
Demmelmaier CA, White RE, van Bokhoven JA, Scott SL (2009) Evidence for a chromasiloxane ring size effect in Phillips (Cr/SiO2) polymerization catalysts. J Catal 262:44–56
Zhong L, Lee M-Y, Liu Z, Wanglee Y-J, Liu B, Scott SL (2012) Spectroscopic and structural characterization of Cr(II)/SiO2 active site precursors in model Phillips polymerization catalysts. J Catal 293:1–12
Handzlik J, Kurleto K (2013) Assessment of density functional methods for thermochemistry of chromium oxo compounds and their application in a study of chromia-silica system. Chem Phys Lett 561–562:87–91
Handzlik J (2009) DFT study of molybdena-silica system—a selection of density functionals based on their performance in thermochemistry of molybdenum compounds. Chem Phys Lett 469:140–144
Cheng R, Liu X, Fang Y, Terano M, Liu B (2017) High-resolution 29Si CP/MAS solid state NMR spectroscopy and DFT investigation on the role of geminal and single silanols in grafting chromium species over Phillips Cr/silica catalyst. Appl Catal A Gen 543:26–33
Zhuravlev LT (2000) The surface chemistry of amorphous silica. Zhuravlev model. Colloids Surfaces A Physicochem Eng Asp 173:1–38
Ek S, Root A, Peussa M, Niinistö L (2001) Determination of the hydroxyl group content in silica by thermogravimetry and a comparison with 1H MAS NMR results. Thermochim Acta 379:201–212
Lillehaug S, Børve KJ, Sierka M, Sauer J (2004) Catalytic dehydrogenation of ethane over mononuclear Cr(III) surface sites on silica. Part I. C-H activation by σ-bond metathesis. J Phys Org Chem 17:990–1006
Lillehaug S, Jensen VR, Børve KJ (2006) Catalytic dehydrogenation of ethane over mononuclear Cr(III)-silica surface sites. Part 2: C-H activation by oxidative addition. J Phys Org Chem 19:25–33
Liu Z, Cheng R, He X, Wu X, Liu B (2012) DFT functional benchmarking on the energy splitting of chromium spin states and mechanistic study of acetylene cyclotrimerization over the Phillips Cr(II)/silica catalyst. J Phys Chem A 116:7538–7549
Liu Z, Cheng R, He X, Liu B (2013) Reactivity and regioselectivity of methylacetylene cyclotrimerization over the Phillips Cr/silica catalyst: a DFT study. ACS Catal 3:1172–1183
Espelid Ø, Børve KJ (2000) Theoretical models of ethylene polymerization over a mononuclear chromium(II)/silica site. J Catal 195:125–139
Espelid Ø, Børve KJ (2002) Molecular-level insight into Cr/silica Phillips-type catalysts: polymerization-active mononuclear chromium sites. J Catal 205:366–374
Espelid Ø, Børve KJ (2002) Molecular-level insight into Cr/silica Phillips-type catalysts: polymerization-active dinuclear chromium sites. J Catal 206:331–338
Potter KC, Beckerle CW, Jentoft FC, Schwerdtfeger E, McDaniel MP (2016) Reduction of the Phillips catalyst by various olefins: stoichiometry, thermochemistry, reaction products and polymerization activity. J Catal 344:657–668
Zhong L, Liu Z, Cheng R, Tang S, Qiu P, He X, Terano M, Liu B (2012) Active site transformation during the induction period of ethylene polymerization over the Phillips CrOx/SiO2 catalyst. ChemCatChem 4:872–881
Liu B, Nakatani H, Terano M (2003) Mechanistic implications of the unprecedented transformations of ethene into propene and butene over Phillips CrOx/SiO2 catalyst during induction period. J Mol Catal A: Chem 201:189–197
Conley MP, Delley MF, Siddiqi G, Lapadula G, Norsic S, Monteil V, Safonova OV, Copéret C (2014) Polymerization of ethylene by silica-supported dinuclear CrIII sites through an initiation step involving C-H bond activation. Angew Chem Int Ed 53:1872–1876
Conley MP, Delley MF, Núñez-Zarur F, Comas-Vives A, Copéret C (2015) Heterolytic activation of C-H bonds on CrIII-O surface sites is a key step in catalytic polymerization of ethylene and dehydrogenation of propane. Inorg Chem 54:5065–5078
Gierada M, Handzlik J (2017) Active sites formation and their transformations during ethylene polymerization by the Phillips CrOx/SiO2 catalyst. J Catal 352:314–328
Delley MF, Praveen CS, Borosy AP, Núñez-Zarur F, Comas-Vives A, Copéret C (2017) Olefin polymerization on Cr(III)/SiO2: mechanistic insights from the differences in reactivity between ethene and propene. J Catal 354:223–230
Fong A, Peters B, Scott SL (2016) One-electron-redox activation of the reduced Phillips polymerization catalyst, via alkylchromium(IV) homolysis: a computational assessment. ACS Catal 6:6073–6085
Kissin YV, Brandolini AJ (2008) Chemistry of olefin polymerization reactions with chromium-based catalysts. J Polym Sci Part A Polym Chem 46:5330–5347
Fong A, Vandervelden C, Scott SL, Peters B (2018) Computational support for Phillips catalyst initiation via Cr-C bond homolysis in a chromacyclopentane site. ACS Catal 8:1728–1733
Gierada M, Handzlik J (2018) Computational insights into reduction of the Phillips CrOx/SiO2 catalyst by ethylene and CO. J Catal 359:261–271
Shelimov BN, Elev IV, Kazansky VB (1986) Use of photoreduction for activation of silica-molybdena catalysts for propylene metathesis: comparison with thermal reduction. J Catal 98:70–81
Vikulov KA, Elev IV, Shelimov BN, Kazansky VB (1989) IR and UV-vis spectroscopic studies of the stable Mo=CH2 carbene complexes over photoreduced silica-molybdena catalysts with chemisorbed cyclopropane, and their role in olefin metathesis reactions. J Mol Catal 55:126–145
Zhang B, Liu N, Lin Q, Jin D (1991) The effects of Mo oxidation states on olefin metathesis. J Mol Catal 65:15–28
Handzlik J, Ogonowski J, Stoch J, Mikołajczyk M, Michorczyk P (2006) Properties and metathesis activity of molybdena-alumina, molybdena-silica-alumina and molybdena-silica catalysts—a comparative study. Appl Catal A Gen 312:213–219
Balcar H, Mishra D, Marceau E, Carrier X, Žilková N, Bastl Z (2009) Molybdenum oxide catalysts for metathesis of higher 1-alkenes via supporting MoO2(acetylacetonate)2 and MoO2(glycolate)2 on SBA-15 mesoporous molecular sieves. Appl Catal A Gen 359:129–135
Amakawa K, Wrabetz S, Kröhnert J, Tzolova-Müller G, Schlögl R, Trunschke A (2012) In situ generation of active sites in olefin metathesis. J Am Chem Soc 134:11462–11473
Amakawa K, Kröhnert J, Wrabetz S, Frank B, Hemmann F, Jäger C, Schlögl R, Trunschke A (2015) Active sites in olefin metathesis over supported molybdena catalysts. ChemCatChem 7:4059–4065
Lwin S, Wachs IE (2014) Olefin metathesis by supported metal oxide catalysts. ACS Catal 4:2505–2520
Ding K, Gulec A, Johnson AM, Drake TL, Wu W, Lin Y, Weitz E, Marks LD, Stair PC (2016) Highly efficient activation, regeneration, and active site identification of oxide-based olefin metathesis catalysts. ACS Catal 6:5740–5746
Banares MA, Fierro JLG, Moffat JB (1993) The partial oxidation of methane on MoO3/SiO2 catalysts: influence of the molybdenum content and type of oxidant. J Catal 142:406–417
Ohler N, Bell AT (2005) 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. J Catal 231:115–130
Ohler N, Bell AT (2006) Study of the elementary processes involved in the selective oxidation of methane over MoOx/SiO2. J Phys Chem B 110:2700–2709
Thielemann JP, Hess C (2012) Structure of silica-supported molybdenum oxide studied by in situ spectroscopy under reactive and non-reactive conditions. J Catal 288:124–126
Thielemann JP, Hess C (2013) Monitoring silica supported molybdenum oxide catalysts at work: a Raman spectroscopic study. ChemPhysChem 14:441–447
Ono T, Anpo M, Kubokawa Y (1986) Catalytic activity and structure of MoO3 highly dispersed on SiO2. J Phys Chem 90:4780–4784
Banares MA, Hu HC, Wachs IE (1994) Molybdena on silica catalysts: role of preparation methods on the structure-selectivity properties for the oxidation of methanol. J Catal 150:407–420
Zhang W, Desikan A, Oyama ST (1995) Effect of support in ethanol oxidation on molybdenum oxide. J Phys Chem 99:14468–14476
Biermann JJP, Janssen FJJG, Ross JRH (1992) Nitrogen containing species as intermediates in the oxidation of ammonia over silica supported molybdena catalysts. Appl Catal A Gen 86:165–179
Hu H, Wachs IE, Bare SR (1995) Surface structures of supported molybdenum oxide catalysts: characterization by Raman and Mo L3-edge XANES. J Phys Chem 99:10897–10910
Takenaka S, Tanaka T, Funabiki T, Yoshida S (1998) Structures of molybdenum species in silica-supported molybdenum oxide and alkali-ion-modified silica-supported molybdenum oxide. J Phys Chem B 102:2960–2969
Radhakrishnan R, Reed C, Oyama ST, Seman M, Kondo JN, Domen K, Ohminami Y, Asakura K (2001) Variability in the structure of supported MoO3 catalysts: studies using Raman and X-ray absorption spectroscopy with ab initio calculations. J Phys Chem B 105:8519–8530
Ohler N, Bell AT (2005) A study of the redox properties of MoOx/SiO2. J Phys Chem B 109:23419–23429
Tian H, Roberts CA, Wachs IE (2010) Molecular structural determination of molybdena in different environments: aqueous solutions, bulk mixed oxides, and supported MoO3 catalysts. J Phys Chem C 114:14110–14120
Wachs IE, Roberts CA (2010) Monitoring surface metal oxide catalytic active sites with Raman spectroscopy. Chem Soc Rev 39:5002–5017
Guo CS, Hermann K, Hävecker M, Thielemann JP, Kube P, Gregoriades LJ, Trunschke A, Sauer J, Schlögl R (2011) Structural analysis of silica-supported molybdena based on X-ray spectroscopy: quantum theory and experiment. J Phys Chem C 115:15449–15458
Thielemann JP, Kröhnert J, Hess C (2010) Nitric oxide adsorption and oxidation on SBA-15 supported molybdenum oxide: a transmission IR study. J Phys Chem C 114:17092–17098
Thielemann JP, Ressler T, Walter A, Tzolova-Müller G, Hess C (2011) Structure of molybdenum oxide supported on silica SBA-15 studied by Raman, UV-Vis and X-ray absorption spectroscopy. Appl Catal A Gen 399:28–34
Amakawa K, Sun L, Guo C, Hävecker M, Kube P, Wachs IE, Lwin S, Frenkel AI, Patlolla A, Hermann K, Schlögl R, Trunschke A (2013) How strain affects the reactivity of surface metal oxide catalysts. Angew Chem Int Ed 52:13553–13557
Louis C, Che M (1987) EPR investigation of the coordination sphere of Mo5+ ions on thermally reduced silica-supported molybdenum catalysts prepared by the grafting method. J Phys Chem 91:2875–2883
Chempath S, Zhang Y, Bell AT (2007) DFT studies of the structure and vibrational spectra of isolated molybdena species supported on silica. J Phys Chem C 111:1291–1298
Gregoriades LJ, Döbler J, Sauer J (2010) Oxidation of methanol to formaldehyde on silica-supported molybdena: density functional theory study on models of mononuclear sites. J Phys Chem C 114:2967–2979
Chempath S, Bell AT (2007) A DFT study of the mechanism and kinetics of methane oxidation to formaldehyde occurring on silica-supported molybdena. J Catal 247:119–126
Handzlik J (2005) Metathesis activity and properties of Mo-alkylidene sites differently located on silica. A density functional theory study. J Phys Chem B 109:20794–20804
Handzlik J (2007) Application of the ONIOM (QM/QM) method in the study of molybdena–silica system active in olefin metathesis. Int J Quantum Chem 107:2111–2119
Handzlik J (2007) Theoretical investigations of isolated Mo(VI) and Mo(IV) centers of a molybdena-silica catalyst for olefin metathesis. J Phys Chem C 111:9337–9348
Handzlik J, Ogonowski J (2002) DFT study of ethene metathesis proceeding on monomeric MoVI centres of MoO3/Al2O3 catalyst. The role of the molybdacyclobutane intermediate. J Mol Catal A: Chem 184:371–377
Handzlik J (2004) Metathesis activity of monomeric Mo-methylidene centres on (1 0 0) and (1 1 0)C surfaces of γ-Al2O3—a comparative DFT study. Surf Sci 562:101–112
Handzlik J, Ogonowski J, Tokarz-Sobieraj R (2005) Dependence of metathesis activity of Mo-methylidene sites on their location on (1 0 0) γ-Al2O3—a theoretical study. Catal Today 101:163–173
Handzlik J (2007) Properties and metathesis activity of monomeric and dimeric Mo centres variously located on γ-alumina—a DFT study. Surf Sci 601:2054–2065
Handzlik J, Sautet P (2008) Active sites of olefin metathesis on molybdena-alumina system: a periodic DFT study. J Catal 256:1–14
Handzlik J, Czernecki M, Shiga A, Śliwa P (2012) Paired interacting orbitals (PIO) study of Mo/SiO2 and Mo/HZSM-5 catalysts for olefin metathesis. Comput Theor Chem 991:174–181
Goldsmith BR, Sanderson ED, Bean D, Peters B (2013) Isolated catalyst sites on amorphous supports: a systematic algorithm for understanding heterogeneities in structure and reactivity. J Chem Phys 138:204105
Ewing CS, Bagusetty A, Patriarca EG, Lambrecht DS, Veser G, Johnson JK (2016) Impact of support interactions for single-atom molybdenum catalysts on amorphous silica. Ind Eng Chem Res 55:12350–12357
Mol JC (2004) Industrial applications of olefin metathesis. J Mol Catal A Chem 213:39–45
Lwin S, Li Y, Frenkel AI, Wachs IE (2016) Nature of WOx sites on SiO2 and their molecular structure-reactivity/selectivity relationships for propylene metathesis. ACS Catal 6:3061–3071
Lwin S, Wachs IE (2017) Catalyst activation and kinetics for propylene metathesis by supported WOx/SiO2 catalysts. ACS Catal 7:573–580
Howell JG, Li Y-P, Bell AT (2016) Propene metathesis over supported tungsten oxide catalysts: a study of active site formation. ACS Catal 6:7728–7738
de Lucas A, Valverde JL, Cañizares P, Rodriguez L (1999) Partial oxidation of methane to formaldehyde over W/SiO2 catalysts. Appl Catal A Gen 184:143–152
Adam F, Iqbal A (2011) The liquid phase oxidation of styrene with tungsten modified silica as a catalyst. Chem Eng J 171:1379–1386
Liu G, Wang X, Wang X, Han H, Li C (2012) Photocatalytic H2 and O2 evolution over tungsten oxide dispersed on silica. J Catal 293:61–66
Ross-Medgaarden EI, Wachs IE (2007) Structural determination of bulk and surface tungsten oxides with UV-vis diffuse reflectance spectroscopy and Raman spectroscopy. J Phys Chem C 111:15089–15099
Chauvin J, Thomas K, Clet G, Houalla M (2015) Comparative influence of surface tungstate species and bulk amorphous WO3 particles on the acidity and catalytic activity of tungsten oxide supported on silica. J Phys Chem C 119:12345–12355
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2019 Springer Nature Switzerland AG
About this chapter
Cite this chapter
Handzlik, J. (2019). Computational Modelling of Structure and Catalytic Properties of Silica-Supported Group VI Transition Metal Oxide Species. In: Broclawik, E., Borowski, T., Radoń, M. (eds) Transition Metals in Coordination Environments. Challenges and Advances in Computational Chemistry and Physics, vol 29. Springer, Cham. https://doi.org/10.1007/978-3-030-11714-6_11
Download citation
DOI: https://doi.org/10.1007/978-3-030-11714-6_11
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-030-11713-9
Online ISBN: 978-3-030-11714-6
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)