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Structure and Reactivity of sol–gel V/SiO2 Catalysts for the Direct Conversion of Methane to Formaldehyde

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Abstract

Vanadium oxide-silica catalysts prepared by the sol–gel method were characterized by different techniques (nitrogen adsorption–desorption isotherms, scanning electron microscopy, X-ray diffraction, temperature-programmed reduction, Raman spectroscopy and X-ray photoelectron spectroscopy) and applied in the direct conversion of methane to C1 oxygenates. The addition of a small amount of nitric oxide to the reaction mixture reduced the energy barrier for H-abstraction, increasing the methane conversion and formaldehyde yield. Correlations between the characterization and activity results indicate that the reaction occurs on tetrahedrally coordinated vanadium sites, as the maximum formaldehyde yield was found for the catalyst with a vanadium content of 1.5 wt%, which has a high surface density of well-dispersed tetrahedrally coordinated monomeric or slightly oligomerized VO4 species. On the other hand, a high space velocity and CH4:O2 ratio decrease the subsequent oxidation to carbon oxides, increasing oxygenate formation.

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References

  1. Houghton JT, Ding Y, Griggs DJ, Noguer M, van der Linden PJ, Dai X, Maskell K, Johnson CA (2001) Intergovernmental panel on climate change, In: Climate change 2001: the scientific basis. Cambridge University Press, Cambridge

    Google Scholar 

  2. Bergman RG (2007) Organometallic chemistry: C–H activation. Nature 446:391–393

    Article  CAS  Google Scholar 

  3. Zhang Q, He D, Zhu Q (2008) Direct partial oxidation of methane to methanol: reaction zones and role of catalyst location. J Nat Gas Chem 17:24–28

    Article  Google Scholar 

  4. Olah GO, Goeppert A, Prakash GKS (2009) Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons. J Org Chem 74(2):487–498

    Article  CAS  Google Scholar 

  5. Beznis NV, Weckhuysen BM, Bitter JH (2010) Partial oxidation of methane over Co-ZSM-5: tuning the oxygenate selectivity by altering the preparation route. Catal Lett 136:52–56

    Article  CAS  Google Scholar 

  6. Navarro RM, Peña MA, Fierro JLG (2006) in J.L.G. Fierro (ed) Metal oxides: chemistry and applications. CRC Press, Taylor and Francis Group, Boca Raton, pp 463–490

    Google Scholar 

  7. Bromly JH, Barnes FI, Muris S, You X, Haynes BS (1996) Kinetic and thermodynamic sensitivity analysis of the NO-sensitised oxidation of methane. Combust Sci Technol 115: 259–296.

    Article  CAS  Google Scholar 

  8. Alvarez-Galvan MC, Mota N, Ojeda M, Rojas S, Navarro RM, Fierro JLG (2011) Direct methane conversion routes to chemicals and fuels. Catal Today 171: 15–23

    Article  CAS  Google Scholar 

  9. Tabata K, Teng Y, Takemoto T, Suzuki E, Bañares MA, Peña MA, Fierro JLG (2002) Activation of methane by oxygen and nitrogen oxides. Catal Rev-Sci Eng 44: 1–58

    Article  CAS  Google Scholar 

  10. Irusta S, Lombardo EA, Miro EE (1994) Effects of NO and solids on the oxidation of methane to formaldehyde. Catal Lett 29:339–348

    Article  CAS  Google Scholar 

  11. Taniewski M (2004) The challenges and recent advances in C1 chemistry and technology. Polish J Appl Chem 48 (1–2):1–21

    CAS  Google Scholar 

  12. Holmen A (2009) Direct conversion of methane to fuels and chemicals. Catal Today 142 (1–2): 2–8

    Article  CAS  Google Scholar 

  13. 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(1):119–126

    Article  CAS  Google Scholar 

  14. Blasco T, Concepcion P, Nieto JML, Perez-Pariente J (1995) Preparation, characterization, and catalytic properties of VAPO-5 for the oxydehydrogenation of propane. J Catal 152:1–17

    Article  CAS  Google Scholar 

  15. de Vekki AV, Marakaev ST (2009) Catalytic partial oxidation of methane to formaldehyde. Russ J Appl Chem 82(4):521–536

    Article  CAS  Google Scholar 

  16. Ono T, Nakamura M, Unno K, Oyun A, Ohnishi J, Kataoka M, Masakazu F (2008) Partial oxidation of CH4 over Al/silica catalysts using molecular oxygen. J Mol Cat A 285:169–175

    Article  CAS  Google Scholar 

  17. Zhang H, Ying P, Zhang J, Liang C, Feng Z, Li C (2004) In: Bao X, Xu Y (eds) Natural gas conversion VII. Elsevier, Amsterdam, pp 547–552

    Google Scholar 

  18. Wang LN, Zhou ZX, Li XN, Ma TM, He SG (2015) Thermal conversion of methane to formaldehyde promoted by gold in AuNbO3(+) cluster cations. Chem Eur J 21:6957–6961

    Article  CAS  Google Scholar 

  19. Zhao YX, Li ZY, Yuan Z, Li XN, He SG (2014) Thermal methane conversion to formaldehyde promoted by single platinum atoms in PtAl2O4(−) cluster anions. Angew Chem Int Ed Engl 53:9482–9486

    Article  CAS  Google Scholar 

  20. Wang ZC, Dietl N, Kretschmer R, Ma JB, Weiske T, Schlangen M, Schwarz H (2012) Direct conversion of methane into formaldehyde mediated by [Al2O3]+ at room temperature. Angew Chem Int Ed Engl 51:3703–3707

    Article  CAS  Google Scholar 

  21. Sun Q, Jehng JM, Hu H, Herman RG, Wachs IE, Klier K (1997) In situ raman spectroscopy during the partial oxidation of methane to formaldehyde over supported vanadium oxide catalysts. J Catal 165:91–101

    Article  CAS  Google Scholar 

  22. Herman RG, Sun Q, Shi Ch, Klier K, Wang ChB, Hu H, Wachs IE, Bhasin MM (1997) Development of active oxide catalysts for the direct oxidation of methane to formaldehyde. Catal Today 37:1–14

    Article  CAS  Google Scholar 

  23. Wachs IE, Weckhuysen BM (1997) Structure and reactivity of surface vanadium oxide species on oxide supports. Appl Catal A 157:67–90

    Article  CAS  Google Scholar 

  24. Komarmeni I, Pidugu R, Menon VC (1996) Water adsorption and desorption isotherms of silica and alumina mesoporous molecular sieves. J Porous Mater 3(2):99–106

    Article  Google Scholar 

  25. Wachs IE (1996) Raman and IR studies of surface metal oxide species on oxide supports: supported metal oxide catalysts. Catal Today 27(3–4): 437–455

    Article  CAS  Google Scholar 

  26. Wang CB, Herman RG RG, Shi CS CS, Sun Q Q, Roberts JE JE (2003) V2O5–SiO2 xerogels for methane oxidation to oxygenates: preparation, characterization, and catalytic properties. Appl Catal A 247(2):321–333

    Article  CAS  Google Scholar 

  27. Arena F, Giordano N N, Parmaliana A A (1997) Working mechanism of oxide catalysts in the partial oxidation of methane to formaldehyde. II. redox properties and reactivity of SiO2, MoO3 /SiO2, V2O5 /SiO2, TiO2, and V2O5 /TiO2 systems. J Catal 167:66–76

    Article  CAS  Google Scholar 

  28. Kustrowski P, Segura Y, Chmielarz L, Surman J, Dziembaj R, Cool P, Vansant EF (2006) VOx supported SBA-15 catalysts for the oxidative dehydrogenation of ethylbenzene to styrene in the presence of N2O. Catal Today 114(2–3):307–313

    Article  CAS  Google Scholar 

  29. Gao X, Bare SR, Weckhuysen BM, Israel E, Wachs IE (1998) In situ spectroscopic investigation of molecular structures of highly dispersed vanadium oxide on silica under various conditions. J Phys Chem B 102:10842–10852

    Article  CAS  Google Scholar 

  30. Tian H, Ross EI, Wachs IE (2006) Quantitative determination of the speciation of surface vanadium oxides and their catalytic activity. J Phys Chem B 110(19):9593–9600

    Article  CAS  Google Scholar 

  31. Moisii C, van de Burgt LJ, Stiegman AE (2008) Resonance raman spectroscopy of discrete silica-supported vanadium oxide. Chem Mater 20(12):3927–3935

    Article  CAS  Google Scholar 

  32. Launay H, Loridant S, Nguyen DL, Volodin AM, Dubois JL, Millet JMM (2007) Vanadium species in new catalysts for the selective oxidation of methane to formaldehyde: activation of the catalytic sites. Catal Today 128: 176–182

    Article  CAS  Google Scholar 

  33. Launay H, Loridant S, Pigamo A, Dubois JL, Millet JMM (2007) Vanadium species in new catalysts for the selective oxidation of methane to formaldehyde: specificity and molecular structure dynamics with water. J Catal 246:390–398

    Article  CAS  Google Scholar 

  34. Du G, Lim S, Yang Y, Wang C, Pfefferle L, Haller GL (2006) Catalytic performance of vanadium incorporated MCM-41 catalysts for the partial oxidation of methane to formaldehyde. Appl Catal A 302:48–61

    Article  CAS  Google Scholar 

  35. Wallis P, Schönborn E, Kalevaru VN, Martin A, Wohlrab S (2015) Enhanced formaldehyde selectivity in catalytic methane oxidation by vanadia on Ti-doped SBA-15. RSC Adv 5:69509–69513

    Article  CAS  Google Scholar 

  36. Berndt H, Martin A, Brückner A, Schreier E, Müller D, Kosslick H, Wolf GU, Lücke B (2000) Structure and catalytic properties of VOx/MCM materials for the partial oxidation of methane to formaldehyde. J Catal 191(2):384–400

    Article  CAS  Google Scholar 

  37. Ding XL, Zhao YX, Wu XN, Wang ZC, Ma JB, He SG (2010) Hydrogen-atom abstraction from methane by stoichiometric vanadium–silicon heteronuclear oxide cluster cation. Chem-A European J 16(37):11463–11470

    Article  CAS  Google Scholar 

  38. Yu J, Scheffler M, Metiu H (2013) Oxidative dehydrogenation of methane by isolated vanadium oxide clusters supported on Au (111) and Ag (111) surfaces. J Phys Chem C 117(36):18475–18483

    Article  CAS  Google Scholar 

  39. Nguyen LD, Loridant S, Launay H, Pigamo A, Dubois JL, Millet JMM (2006) Study of new catalysts based on vanadium oxide supported on mesoporous silica for the partial oxidation of methane to formaldehyde: catalytic properties and reaction mechanism. J Catal 237:38–48

  40. Muylaert I, van der Voort P (2009) Supported vanadium oxide in heterogeneous catalysis: elucidating the structure–activity relationship with spectroscopy. Phys Chem Chem Phys 11:2826–2832

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by Najran University, Najran, The Kingdom of Saudi Arabia.

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Authors and Affiliations

  1. Institute of Catalysis and Petroleum Chemistry, CSIC, Cantoblanco, 28049, Madrid, Spain

    Cristina V. Loricera, M. Consuelo Alvarez-Galvan, Rut Guil-Lopez & Jose Luis G. Fierro

  2. Materials and Nano Research Center, Najran University, Najran, 11001, Kingdom of Saudi Arabia

    Adel A. Ismail & Saleh A. Al-Sayari

  3. Advanced Materials Department, Central Metalurgical T&D Institute, CMRDI, Helwan, 11421, Egypt

    Adel A. Ismail

Authors
  1. Cristina V. Loricera
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  2. M. Consuelo Alvarez-Galvan
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  3. Rut Guil-Lopez
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  4. Adel A. Ismail
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  5. Saleh A. Al-Sayari
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  6. Jose Luis G. Fierro
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Correspondence to M. Consuelo Alvarez-Galvan.

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Loricera, C.V., Alvarez-Galvan, M.C., Guil-Lopez, R. et al. Structure and Reactivity of sol–gel V/SiO2 Catalysts for the Direct Conversion of Methane to Formaldehyde. Top Catal 60, 1129–1139 (2017). https://doi.org/10.1007/s11244-017-0809-x

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  • DOI: https://doi.org/10.1007/s11244-017-0809-x

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