Oxidation of geraniol using niobia modified with hydrogen peroxide





Niobium oxide, Peroxo sites, Regioselective


Nb2O5 bulk and Nb2O5 modified with H2O2 were studied in the epoxidation of geraniol at 1 bar and room temperature. The structural and morphological properties for both catalysts were very similar, indicating that the peroxo-complex species were not formed. The order of the reaction was one respect to geraniol and close to zero respect to H2O2, these values fit well with the kinetic data obtained. The geraniol epoxidation is favored by the presence of peroxo groups, which is reached using an excess of H2O2. Moreover, the availability of the geraniol to adopt the three-membered-ring transition state was found as the best form for this type of compound.

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Author Biographies

Jairo Antonio Cubillos Lobo, Pedagogical and Technological University of Colombia

Faculty of Sciences, Department of Chemistry, Catalysis Group.

José J. Martínez, Pedagogical and Technological University of Colombia

Catalysis Group, School of Chemical Sciences.

Hugo Rojas, Pedagogical and Technological University of Colombia

Catalysis Group, School of Chemical Sciences.

Norman Marín-Astorga, Eurecat U.S., Incorporated

PhD. in Chemistry.


A. Maniatakou and et al., “Synthesis, structural and DFT studies of a peroxo-niobate complex of the biological ligand 2-quinaldic acid,” Polyhedron, vol. 27, no. 16, pp. 3398–3408, Nov. 2008.

C. R. Waidmann, A. G. DiPasquale, and J. M. Mayer, “Synthesis and reactivity of oxo-peroxo-vanadium(v) bipyridine compounds,” Inorg. Chem., vol. 49, no. 5, pp. 2383–2391, Jan. 2010.

L. C. Passoni, M. R. H. Siddiqui, A. Steiner, and I. V. Kozhevnikov, “Niobium peroxo compounds as catalysts for liquid-phase oxidation with hydrogen peroxide,” J. Mol. Cat. A: Chem., vol. 153, no. 1-2, pp. 103–108, Mar. 2000.

L. C. A. Oliveira and et al., “Pure niobia as catalyst for the oxidation of organic contaminants: Mechanism study via ESI-MS and theoretical calculations,” Chem. Phys. Lett., vol. 446, no. 1-3, pp. 133–137, Sep. 2007.

L. J. Burcham, J. Datka, and I. E. Wachs, “In situ vibrational spectroscopy studies of supported niobium oxide catalysts,” J. Phys. Chem., vol. 103, no. 29, pp. 6015–6024, Jun. 1999.

D. Bayot, B. Tinant, and M. Devillers, “Water-soluble niobium peroxo complexes as precursors for the preparation of Nb-based oxide catalysts,” Catal. Today, vol. 78, no. 1-4, pp. 439–447, Feb. 2003.

M. Kantcheva, H. Budunoğlu, and O. Samarskaya, “Characterization of Zr6Nb2O17 synthesized by a peroxo route as a novel solid acid,” Catal. Commun., vol. 9, no. 5, pp. 874–879, Mar. 2008.

A. Esteves and et al., “New materials based on modified synthetic Nb2O5 as photocatalyst for oxidation of organic contaminants,” Catal. Commun., vol. 10, no. 3, pp. 330–332, Dec. 2008.

K. T. G. Carvalho, A. C. Silva, L. C. A. Oliveira, M. Gonçalves, and Z. M. Magriotis, “Nióbia sintética modificada como catalisador na oxidação de corante orgânico: utilização de H2O2 e O2 atmosférico como oxidantes,” Quím. Nova, vol. 32, no. 6, pp. 1373–1377, 2009.

T. C. Ramalho and et al., “The molecular basis for the behaviour of niobia species in oxidation reaction probed by theoretical calculations and experimental techniques,” Mol. Phys., vol. 107, no. 2, pp. 171–179, Oct. 2010.

L. C. A. Oliveira, M. Gonçalves, D. Q. L. Oliveira, A. L. N. Guarieiro, and M. C. Pereira, “Síntese e propriedades catalíticas em reações de oxidação de goethitas contendo niobio,” Quím. Nova, vol. 30, no. 4, pp. 925–929, Aug. 2007.

M. Ziolek and et al., “Catalytic performance of niobium species in crystalline and amorphous solids—gas and liquid phase oxidation,” Appl. Catal A: Gen., vol. 391, no. 1-2, pp. 194–204, Jan. 2011.

N. Marin and et al., “Control of the chemoselectivity in the oxidation of geraniol over lanthanum, titanium and niobium catalysts supported on mesoporous silica MCM-41,” Top. Catal., vol. 55, no. 7-10, pp. 620–624, Jul. 2012.

N. T. Prado and et al., “Modified niobia as a new catalyst for selective production of dimethoxymethane from methanol,” Energy & Fuels, vol. 24, no. 9, pp. 4793–4796, Aug. 2010.

N. Marin and et al., “Nb2O5 as heterogeneous catalysts for the selective oxidation of geraniol,” Curr. Org. Chem., vol. 16, no. 23, pp. 2797–2801, 2012.

X. Secordel and et al., “TiO2-supported rhenium oxide catalysts for methanol oxidation: Effect of support texture on the structure and reactivity evidenced by an operando raman study,” Catal. Today., vol. 155, no. 3-4, pp. 177–183, Oct. 2010.

C. M. de Souza, S. C. de Souza, E. Roditi, and G. Gelbard, “Oxidations of benzyl alcohol by hydrogen peroxide in the presence of complexed peroxoniobium (V) species,” J. Chem. Res, (S)., no. 3, pp. 92–93, 1997.

G. Haxhillazi, “Preparation, structure and vibrational spectroscopy of tetraperoxo complexes of CrV+, VV+, NbV+ and TaV+,” Ph.D. dissertation, Siegen Univ., Siegen, Germany, 2003.

L. Dragone, P. Moggi, G. Predieri, and R. Zanoni, “Niobia and silica–niobia catalysts from sol–gel synthesis: an X-ray photoelectron spectroscopic characterization,” Appl. Surf. Sci., vol. 187, no. 1-2, pp. 82–88, Feb. 2002.

T. C. Ramalho and et al., “The molecular basis for the behaviour of niobia species in oxidation reaction probed by theoretical calculations and experimental techniques,” Mol. Phys., vol. 107, no. 2, pp. 171–179, 2009.

F. J. Wong, N. Hong, and S. Ramanathan, “Orbital splitting and optical conductivity of the insulating state of NbO2,” Phys. Rev. B, vol. 90, no. 11, pp. 115 135–1–115 135–8, Sep. 2014.

A. Darlinski and J. Halbritter, “On angle resolved xray photoelectron spectroscopy of oxides, serrations, and protusions at interfaces,” Vac. Sci. & Technol. A., vol. 5, no. 4, pp. 1235–1240, 1987.

A. B. Posadas, A. O’Hara, S. Rangan, R. A. Bartynski, and A. A. Demkov, “Band gap of epitaxial in-plane-dimerized single-phase NbO2 films,” Appl. Phys. Lett., vol. 104, pp. 0 929 011–09 290 112, 2014.

Y. Gao, Y. Liang, and S. A. Chambers, “Synthesis and characterization of Nb-doped TiO2(110) surfaces by molecular beam epitaxy,” Surf. Sci., vol. 348, no. 1-2, pp. 17–27, Mar. 1996.

V. V. Atuchin, I. E. Kalabin, V. G. Kesler, and N. V. Pervukhina, “Nb 3d and O 1s core levels and chemical bonding in niobates,” J. Elect. Spect. Rel. Phenom., vol. 142, no. 2, pp. 129–134, Feb. 2005.

P. Chagas and et al., “A novel hydrofobic niobium oxyhydroxide as catalyst: Selective cyclohexene oxidation to epoxide,” Appl. Catal A: Gen., vol. 454, pp. 88–92, Mar. 2013.

B. X. Huang, K. Wang, J. S. Church, and Y. S. Li, “Characterization of oxides on niobium by raman and infrared spectroscopy,” Electr. Acta., vol. 44, no. 15, pp. 2571–2577, 1999.

A. A. McConnell, J. S. Aderson, and C. N. R. Rao, “Raman spectra of niobium oxides,” Spect. Acta Part A: Mol. Spect., vol. 32, no. 5, pp. 1067–1076, 1976.

F. Somma, A. Puppinato, and G. Strukul, “Niobia–silica aerogel mixed oxide catalysts: Effects of the niobium content, the calcination temperature and the surface hydrophilicity on the epoxidation of olefins with hydrogen peroxide,” Appl. Catal A: Gen., vol. 309, no. 1, pp. 115–121, Jul. 2006.

J. M. de S. e Silva, F. S. Vinhado, D. Mandelli, U. Schuchardt, and R. Rinaldi, “The chemical reactivity of some terpenes investigated by alumina catalyzed epoxidation with hydrogen peroxide and by DFT calculations,” J. Mol. Cat. A: Chem., vol. 252, no. 1-2, pp. 186–193, Jun. 2006.

A. Feliczak, A. Wawrzyńczak, and I. Nowak, “Selective catalytic oxidations of cyclohexene, thioether and geraniol with hydrogen peroxide. sensitivity to the structure of mesoporous niobosilicates,” Micropor. Mesopor. Mater., vol. 202, pp. 80–89, Jan. 2015.

M. P. Chaudhari and S. B. Sawant, “Kinetics of heterogeneous oxidation of benzyl alcohol with hydrogen peroxide,” Chem. Eng. J., vol. 106, no. 2, pp. 111–118, Feb. 2005.

A. M. Al-Ajlouni, O. Saglam, T. Diafla, and F. E. Kuhn, “Kinetic studies on phenylphosphopolyperoxotungstates catalyzed epoxidation of olefins with hydrogen peroxide,” J. Mol. Cat. A: Chem., vol. 287, no. 1-2, pp. 159–164, May 2008.




How to Cite

Cubillos Lobo, J. A., Martínez, J. J., Rojas, H. ., & Marín-Astorga, N. (2019). Oxidation of geraniol using niobia modified with hydrogen peroxide. Revista Facultad De Ingeniería Universidad De Antioquia, (91), 106–112. https://doi.org/10.17533/udea.redin.n91a10