Friedel-Crafts Alkylation of o-xylene over V2O5 / ZrO2 Catalysts


  • Sreejarani K Pillai DST/CSIR Nanotechnology Innovation Centre, National Centre for Nano-Structured Materials, Council for Scientific and Industrial Research, Pretoria 0001, South Africa.
  • O Gheevarghese Department of Chemistry, Tshwane University of Technology, Pretoria 0001. South Africa.
  • I V Tleane Department of Chemistry, Tshwane University of Technology, Pretoria 0001, South Africa.



V2O5/ZrO2 catalysts, Friedel-Crafts alkylation, Lewis acidity


The present study has undertaken the Friedel-Crafts benzylation of aromatics over the V2O5/ZrO2 catalysts systems. Catalysts with different V2O5 content (0-15wt %) was prepared by wet impregnation method and characterized by XRD, BET surface area, FTIR and 5’V NMR techniques. The surface acidic properties were determined by temperature programmed desorption of NH3, cumene cracking and perylene adsorption. Under the optimized reaction conditions, these catalysts are found to be very effective and considerably more selective than the conventional homogeneous Lewis acid catalysts. The investigation of vanadia systems-catalyzed benzylation of o-xylene with benzyl chloride revealed that the catalytic activity and product selectivity are sensitive to the precise reaction parameters and can be related to the Lewis acidity of the systems. The reaction is found to be very clean and produces the desired monoalkylated product with high yield.


G. A. Olah, Friedel-Crafts Chemistry, New York: Wiley, 1973.

J. H. Clark, S. R. Cullen, S. J. Barlow and T. W. Bastock, “Environmentally friendly chemistry using supported reagent catalysts: structure–property relationships for clayzic,” J. Chem. Soc. Perkin Trans., vol. 2, pp. 1117, 1994.

B. M. Chodhary M.L. Kantam, M.Sateesh,. K.K. Rao, P.L. Santhi, ”Iron pillared clays efficient catalysts for Friedel-Crafts reactions,” Applied Catalysis A: General, Vol.149, pp. 257–264, 1997.

Y. Izumi, N. Natsume, H. Takamine, J. Tamoki and K. Urabe,”Photoelectrochemical Properties of Thin Films of Zinc Porphyrin Derivatives with Pyridyl Group,” Bull. Chem. Soc. Jpn., vol. 62, issue 2, pp. 386-391, 1989.

A. Cornelis, C. Dony, P. Lazlo and K. M. Nsunda, On the transition state for “clayzic”-catalyzed Friedel-Crafts reactions upon anisole,“ vol. 34, issue 24, pp. 3849–3852, 11 June 1993.

J. Strerte, “Synthesis and properties of titanium oxide – cross-linked montmrillonite”, Clays and Clay Minerals, vol. 34, no. 6, pp. 658-664, 1986.and

G. D. Yadav, T. S. Thorat and P. S. Kumbhar, “Inversion of the relative reactivities and selectivities of benzyl chloride and benzyl alcohol in friedel-crafts alkylation with toluene using different solid acid catalysts: An adsorption related phenomenon,” Tetrahedron Lett., vol. 34, issue 3, pp. 529–532, January 1993.

P. Lazlo and A. Mathy, “Catalysis of Friedel-Crafts Alkylation by a Montmorillonite Doped with Transition-Metal Cations,” Helvetica Chimica Acta, vol. 70, issue 3, pp. 577–586, 6 May 1987.

V. V. Rao, V. Durgakumari, S. Narayanan, “Vapour phase methylation of phenol over nanocrystalline ferrospinel system,” Appl. Catal. 49, pp. 165, 1989.

K. Tanabe, J.R. Anderson, M. Boudart (Eds.), “Iron-based catalysts for slurry-phase fischer-tropsch synthesis,“ Catalysis—Science and Technology, Springer, Berlin, vol.2, 1981.

H. Noller, J.A. Lercher, H. Vinek, “Decomposition of isopropanol on magnesium oxide/silica in relation to texture, acidity and chemical composition,” Mater. Chem. Phys., vol. 18, pp. 577, 1988.

P. Mongkolbovornkij, V. Champreda, W. Sutthisripok, N. Laosiripojana, “Production of steam cracking of feed stocks by mild cracking of plastic wastes,” Fuel Processing Technology, vol. 91, pp. 1510-1516, 2010.

Idriss Atribak, Noelia Guillén-Hurtado, Agustín Bueno-López, Avelina García-García, “Influence of the physico-chemical properties of CeO2-ZrO2 mixed oxides on the catalytic oxidation of NO to NO2,”Applied Surface Science, Vol. 256, pp. 7706-7712,Oct.2010.

Jeong Gil Seo, Min Hye Youn, Sunyoung Park, Jin Suk Chung, In Kyu Song, “Hydrogen production from glycerin by steam reforming over nickel catalysts”, International Journal of Hydrogen Energy, Vol. 34, pp. 3755-3763, May 2009.

Yue-Qin Song, De-Hua He, Bo-Qing Xu,” Study of the surface and redox properties of ceria–zirconia oxides",Applied Catalysis A: General, Vol.337, pp.19-28 ,March 2008.

Hongying Zhao, Simona Bennici, Jingxuan Cai, Jianyi Shen, Aline Auroux, “Carbon deposition on Co catalysts during Fischer–Tropsch synthesis: A computational and experimental study, Journal of Catalysis, Vol. 274, pp.259-272,September 2010.

H. Feng, J.W. Elam, J.A. Libera, M.J. Pellin, P.C. Stair, “Investigations on the properties of ceria–zirconia-supported Ni and Rh catalysts and their performance in acetic acid steam reforming”,Journal of Catalysis, Vol. 269, pp.421-431,February 2010.

Yuebing Xu, Jiangyin Lu, Mei Zhong, Jide Wang,” Natural gas pyrolysis in double-walled reactor tubes using thermal plasma or concentrated solar radiation as external heating source, Journal of Natural Gas Chemistry, Vol. 18, pp. 88-93,March 2009.

Sreejarani K. Pillai, Omanakkutty Gheevarghese, Sankaran Sugunan,” Catalytic properties of V2O5/SnO2 towards vapour-phase Beckmann rearrangement of cyclohexanone oxime”, Applied Catalysis A: General, vol. 353,pp. 130–136, 2009.

K. V.R. Chary, K. Ramesh, G. Vidyasagar, V. V. Rao,” Vapour phase alkylation of phenol with methanol over vanadium oxide supported on zirconia”, J. Mol. Catal. A: Chem.,vol. 198, pp. 195-204,2003.

P. D. I. Mercera, V. I. G. Ommen, E. B. M. Doesburg, A. J. Burgraaf and J. R. H. Ross, “Zirconia as a Support for Catalysts Evolution of the Texture and Structure on Calcination in Air,” Appl. Catal., vol. 57, pp. 127–148, 1990.

J. R. Sohn, M. Y. Park and Y. I. Pae, “Characterization by solid-state 51V NMR and X-ray Diffraction of Vanadium oxide supported on ZrO2,”Bull. Korean Chem. Soc., vol. 17 pp. 274–279, 1996.

M. A. Vuurman and I. E. Wachs, “In situ Raman spectroscopy of alumina-supported metal oxide catalysts,” J. Phys. Chem., vol. 96, pp. 5008–5016, June. 1992.

K. Jnumaru, M. Misono and T. Okuhara, “Structure and catalysis of vanadium oxide overlayers on oxide supports,” Appl. Cata. A: Gen., vol. 149, pp. 133–149, Jan. 1997.

I. E. Wachs, “Raman and IR studies of surface metal oxide species on oxide supports: Supported metal oxide catalysts,” Catal. Today, vol. 27, pp. 437–455, Feb. 1996.

L. Briand, L. Gambaro and H. Thomas, “Promotion Effects of Titanium on Partial Oxidation of Methanol over Vanadium Pentoxide Catalysts” J. Catal., vol. 161, pp. 839–860, July. 1996.

M. S. Marth, A. Wokaun and A. Baiker, “Grafting of V2O5 monolayers onto TiO2 from alkoxide precursors: A diffuse reflectance FTIR study,” J. Catal., vol. 124, pp. 86–96, July. 1990

L. J. Lakshmi, E. C. Alyea, S. T. Srinivas and P. K. Rao, “Influence of Metal Oxide Modification of Alumina on the Dispersion and Activity of Vanadia Catalysts” J. Phys. Chem. B, vol. 101, pp. 3324– 3328, Apr. 1997.

L. J. Lakshmi, T. R. B. Jones, M. Gurgi and J. M. Miller, “Synthesis, characterization and activity studies of vanadia catalysts supported on sol–gel derived Al2O3–ZrO2 mixed oxide,” J. Mol. Catal. A: Chem., vol. 152, pp. 99–110, March. 2000.

J. W. Ward, “The nature of active sites on zeolites: I. The decationated Y zeolite,” J. Catal., vol. 9, pp. 225–236, Nov. 1967.

F. Arena, R. Dario and A. Parmaliana, “A characterization study of the surface acidity of solid catalysts by temperature programmed methods,” Appl. Catal. A: Gen., vol. 170, pp. 127–137, May. 1998.

J. Le Barrs, J. C. Vedrine, A. Auroux, S. Trautman and M. Eaerns, “Microcalorimetric and infrared studies of the acid-base properties of V2O5/γ-Al2O3 catalysts,” Apppl. Catal. A. Gen., vol. 119, pp. 341– 354 Nov. 1994.

Khader, M.M., “Surface Acidity of V2O5/Al2O3 Catalysts: IR and TPD Studies”, J. Mol. Catal., 104, (1995) 87

Kijenski, J., Baiker, ”A. Acidic sites on catalyst surfaces and their determination”, Catal. Today 5,(1989),1

B. D. Flockhart, J.A.N. Scott and R.C.Pink, ”Electron-transfer at alumina surfaces. Part 1.—Electron acceptor properties of aluminas”, Trans. Faraday Soc., 62,(1966) , 730-740

H. Suja, c.s. Deepa, K. Sreeja Rani, S. Sugunan “Liquid phase benzoylation of arenes over iron promoted sulphated zirconia” Applied Catalysis A: General 230 (2002) 233.

A. Corma, and B.W Wojciechowski, “The Catalytic Cracking of Cumene”, Catal. Rev.-Sci. Eng., 24 (1982), 1– 65.

W. Przystajko, R. Fieddorow, I. G. Dalla Lana, Appl. Catal. 15 (1985) 115.

A. P. Singh et al., "Benzoylation of toluene with benzoyl chloride over zeolite catalysts", J. Mol. Catal. 102 (1995) 139-145

A. P. Singh, A.K. Pandey, "Acetylation of benzene to acetophenone over zeolite catalysts", J. Mol. Catal. 123 (1997) 141-147

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