Characterization of Tungsten-Based Catalyst Used for Selective Oxidation of Cyclopentene to Glutaraldehyde

摘要/Abstract

摘要： Tungsten-containing hexagonal mesoporous silica(W-HMS) supported tungsten oxide catalysts (WO_x/W-HMS) was prepared for the selective oxidation of cyclopentene with aqueous hydrogen peroxide to glutaraldehyde.X-ray diffraction(XRD) results indicated that the crystal form of the active phase(tungsten oxide) of the WO_x/W-HMS catalysts was dependent on the W loading and calcination temperature.X-ray photoelectron spectroscopy(XPS) analysis revealed that the dispersed tungsten oxides on the surface of W-HMS support consisted of a mixture of W(V) and W(VI).It was found that a high content of amorphous W species in(5+)oxidation state resulted in the high catalytic activity.When the Wloading was up to 12%(by mass) or the catalyst precursor was treated at temperature of 623 K,the catalytic activity decreased due to the presence of WO₃ crystallites and the oxidation of W(V) to W(VI) on the catalyst surface.Furthermore,NH₃-temperature-programmed-desorption (NH₃-TPD) analysis showed that the effects of W loading and calcination temperature on the acidity of the catalysts were related to the catalytic activity.Ahigh selectivity of 80.2% for glutaraldehyde with a complete conversion of cyclopentene was obtained over 8% WO_x/W-HMS catalyst calcined at 573 K after 14 h of reaction.

关键词: cyclopentene, glutaraldehyde, tungsten, hexagonal mesoporous silica, oxidation

Abstract: Tungsten-containing hexagonal mesoporous silica(W-HMS) supported tungsten oxide catalysts (WO_x/W-HMS) was prepared for the selective oxidation of cyclopentene with aqueous hydrogen peroxide to glutaraldehyde.X-ray diffraction(XRD) results indicated that the crystal form of the active phase(tungsten oxide) of the WO_x/W-HMS catalysts was dependent on the W loading and calcination temperature.X-ray photoelectron spectroscopy(XPS) analysis revealed that the dispersed tungsten oxides on the surface of W-HMS support consisted of a mixture of W(V) and W(VI).It was found that a high content of amorphous W species in(5+)oxidation state resulted in the high catalytic activity.When the Wloading was up to 12%(by mass) or the catalyst precursor was treated at temperature of 623 K,the catalytic activity decreased due to the presence of WO₃ crystallites and the oxidation of W(V) to W(VI) on the catalyst surface.Furthermore,NH₃-temperature-programmed-desorption (NH₃-TPD) analysis showed that the effects of W loading and calcination temperature on the acidity of the catalysts were related to the catalytic activity.Ahigh selectivity of 80.2% for glutaraldehyde with a complete conversion of cyclopentene was obtained over 8% WO_x/W-HMS catalyst calcined at 573 K after 14 h of reaction.

Key words: cyclopentene, glutaraldehyde, tungsten, hexagonal mesoporous silica, oxidation

朱志庆, 卞炜. Characterization of Tungsten-Based Catalyst Used for Selective Oxidation of Cyclopentene to Glutaraldehyde[J]. , 2008, 16(6): 895-900.

ZHU Zhiqing, BIAN Wei. Characterization of Tungsten-Based Catalyst Used for Selective Oxidation of Cyclopentene to Glutaraldehyde[J]. , 2008, 16(6): 895-900.

参考文献

1 Guo, S.Z., Xu, Z.H., Xia, R.H., Zhou, F., Fang, D.Y., “Kinetics on hydrogenation of cyclopentadiene over Pd/γ-Al₂O₃ catalyst”, Chin. J. Chem. Eng., 13(5), 623-627(2005).
2 Deng, J.F., Xu, X.H., Chen, H.Y., Jiang, A.R., “A new process for preparing dialdehydes by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide”, Tetrahedron, 48(17), 3503-3514(1992).
3 Xu, X.H., Chen, H.Y., Deng, J.F., Jiang, A.R., “Preparation of glutaraldehyde by catalytic oxidation of cyclopentene with aqueous solution of hydrogen peroxide”, Acta Chim. Sinica, 51(4), 399-403(1993).
4 Yang, X.L., Dai, W.L., Chen, H., Cao, Y., Li, H.X., He, H.Y., Fan, K.N., “Novel efficient and green approach to the synthesis of glutaraldehyde over highly active W-doped SBA-15 catalyst”, J. Catal., 229, 259-263(2005).
5 Barton, D.G., Soled, S.L., Iglesia, E., “Solid acid catalysts based on supported tungsten oxides”, Top. Catal., 6, 87-99(1998).
6 Wang, Y.D., Chen, Q.L., Yang, W.M., Xie, Z.K., Xu, W., Huang, D.Y., “Effect of support nature on WO₃/SiO₂ structure and butane-1 metathesis”, Appl. Catal. A Gen., 250, 25-37(2003).
7 Maksimov, G.M., Fedotov, M.A., Bogdanov, S.V., Litvak, G.S., Golovin, A.V., Likholobov, V.A., “Synthesis and study of acid catalyst 30% WO₃/SnO₂”, J. Mol. Catal. A Chem., 158, 435-458(2000).
8 Martin, C., Malet, P., Solana, G., Rives, V., “Structure analysis of supported tungstates”, J. Phys. Chem. B, 102, 2759-2768(1998).
9 Triwahyono, S., Yamada, T., Hattori, H., “IR study of acid sites on WO₃-ZrO₂ and Pt/WO₃-ZrO₂ ”, Appl. Catal. A Gen., 242, 101-109(2003).
10 Chen, H., Dai, W.L., Deng, J.F., Fan, K.N., “Novel heterogeneous W-doped MCM-41 catalyst for highly selective oxidation of cyclopentene to glutaraldehyde by aqueous H₂O₂”, Catal. Lett., 81(1/2), 131-136(2002).
11 Dai, W.L., Chen, H., Cao, Y., Li, H.X., Xie, S.H., Fan, K.N., “Novel economic and green approach to the synthesis of highly active W-MCM41 catalyst in oxidative cleavage of cyclopentene”, Chem. Commun., 3(7), 892-893(2003).
12 Yang, X.L., Dai, W.L., Chen, H., Xu, J.H., Cao, Y., Li, H.X., Fan, K. N., “Novel tungsten-containing mesoporous HMS material:Its synthesis, characterization and catalytic application in the selective oxidation of cyclopentene to glutaraldehyde by aqueous H₂O₂”, Appl. Catal. A Gen., 283, 1-8(2005).
13 Jin, R.H., Xia, X., Dai, W.L., Deng, J.F., Li, H.X., “An effective heterogeneous WO₃/TiO₂-SiO₂ catalyst for selective oxidation of cyclopentene to glutaraldehyde by H 2 O 2 ”, Catal. Lett., 62(2-4), 201-207(1999).
14 Yang, X.L., Dai, W.L., Xu, J.H., Chen, H., Cao, Y., Fan, K.N., “Preparation of novel WO₃/HMS catalyst and its catalytic performance for the selective oxidation of cyclopentene”, Chin. J. Catal., 26(4), 311-316(2005).(in Chinese)
15 Jin, R.H., Li, H.X., Deng, J.F., “Selective oxidation of cyclopentene to glutaraldehyde by H₂O₂ over the WO₃/SiO₂ catalyst”, J. Catal., 203(1), 75-81(2001).
16 Yang, X.L., Dai, W.L., Gao, R.H., Chen, H., Li, H.X., Cao, Y., Fan， K.N., “Synthesis, characterization and catalytic application of mesoporous W-MCM-48 for the selective oxidation of cyclopentene to glutaraldehyde”, J. Mol. Catal. A Chem., 241, 205-214(2005).
17 Zhu, Z.Q., Bian, W., Liu, L.S., Lü, Z.H., “Catalytic oxidation of cyclopentene to glutaraldehyde over WO₃/Ti-HMS catalyst”, Catal. Lett., 117(1/2), 79-84(2007).
18 Tuel, A., “Modification of mesoporous silicas by incorporation of heteroelements in the framework”, Micropor. Mesopor. Mat., 27, 151-169(1999).
19 Sun, M., Xu, N., “Nanocrystalline tungsten oxide thin film:Preparation, microstructure, and photochromic behavior”, J. Mater. Res., 15(4), 927-933(2000).
20 Valigi, M., Gazzoli, D., Pettiti, I., Mattei, G., Colonna, S., De Rossi, S., Ferraris, G., “WO_x/ZrO₂ catalysts(1) Preparation, bulk and surface characterization”, Appl. Catal. A Gen., 231, 159-172(2002).
21 Doniach, S., Sunjic, M., “Many-electron singularity in X-ray photoemission and X-ray line spectra from metals”, J. Phys. C:Solid State Phys., 3(2), 285-291(1970).
22 Le Normand, F., El Fallah, J., Hilaire, L., Lègarè, P., Kotani, A., Parlebas, J.C., “Photoemission on 3d core levels of cerium:An experimental and theoretical investigation of the reduction of cerium dioxide”, Solid State Commun., 71(11), 885-889(1989).
23 Oku, M., Wagatsurma, K., Matsuta, H., “Background subtraction from transition metal 2p XPS by deconvolution using ligand atom XPS:Study on first transition metal cyanide complexes”, J. Electron. Spectrosc., 83, 31-39(1997).
24 Sayan, S., Suzer, S., Uner, D.O., “XPS and in-situ IR investigation of Ru/SiO₂ catalyst”, J. Mol. Struct., 410/411, 111-114(1997).
25 Lok, B.M., Marcus, B.K., Angnell, C.L., “Characterization of zeolite acidity(II) Measurement of zeolite acidity by ammonia temperature programmed desorption and FT-IR spectroscopy techniques”, Zeolites, 6(3), 185-194(1986).
26 Dai, W.L., Huang, X.J., Chen, H.Y., Deng, J.F., “Kinetics and mechanism of the catalytic oxidation of cyclopentene to glutaraldehyde with aqueous hydrogen peroxide”, Indian J. Chem., 36B, 583-589(1997).
27 Yang, X.L., Dai, W.L., Guo, C.W., Chen, H., Cao, Y., Li, H.X., He, H.Y., Fan, K.N., “Synthesis of novel core-shell structured WO₃/TiO₂ spheroids and its application in the catalytic oxidation of cyclopentene to glutaraldehyde by aqueous H₂O₂”, J. Catal., 234, 438-450(2005).

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