Comparative Catalytic Behavior of Prepared Cobalt or Iron Salt of Manganese Substituted Polyoxometalate Supported on Silica in Oxidation of Benzyl Alcohol

Document Type : Research Article


1 Department of Chemistry, Faculty of Science, North Tehran Branch, Islamic Azad University, Tehran, I.R. IRAN

2 Department of Chemistry, Faculty of Science, Karaj Branch, Islamic Azad University, Karaj, I.R. IRAN


Cobalt and iron salt of mono manganese substituted Keggin polyoxometalate have been prepared and supported on silica as heterogeneous catalysts. The prepared compounds were completely characterized by conventional techniques such as FT-IR, ICP-OES, XRD, FESEM, and BET. The results indicated that the primary Keggin structure remain intact in the obtained samples and the prepared particles were in the nanoscale. The surface area of silica support decreased after loading of the cobalt or the iron salt of mono manganese substituted Keggin polyoxometalate on it. Application of the prepared compounds for demonstration of the effect of transition metals such as cobalt (or iron) combined with mono manganese substituted polyoxometalate was investigated in solvent-free oxidation of benzyl alcohol, as a test reaction, using H2O2. The results proved that the selectivity of the silica-supported cobalt salt of mono manganese substituted Keggin polyoxometalate catalyst to benzaldehyde was more than that of the other samples. The catalyst can be reused for several runs without losing significant activity.


Main Subjects

[1] Dolbecq A., Dumas E., Mayer C.R., Mialane P., Hybrid Organic-Inorganic Polyoxometalate Compounds: From Structural Diversity to Applications, Chemical Reviews, 110(10): 6009–6048 (2010).
[2] Car P.E., Patzke GR., The Fascination of Polyoxometalate Chemistry, Inorganics, 3(4): 511-515 (2015).
[6] Sang X., Wang Z., Li J., Wang H., Su F., Liu Z., Zhang L., Zhu Z., Corrosion Protection of Carbon Steel in Circulating Cooling Water by Open-Chain Carboxyethyltin and Transition Metal Co-Functionalized Tungstogermanates, Chemistry Select, 3(25): 7358-7362 (2018).
[7] Rafiee E., Eavani S., Heterogenization of Heteropoly Compounds: A Review of the Structure and Synthesis, Royal Society of Chemistry Advances, 6: 46433-46466 (2016).
[8] Wang S.S., Yang G.Y., Recent Advances in Polyoxometalate Catalyzed Reactions, Chemical Reviews, 115(11): 4893–4962 (2015).
[9] Timofeeva M.N., Acid Catalysis by Heteropoly Acids, Applied Catalysis A: General, 256: 19–35 (2003).
[10] Samadi Mollayousefi H., Fallah Shojaei A., Mahmoodi N., Preparation, Characterization, and Performance Study of PVDF Nanocomposite Contained Hybrid Nanostructure TiO2-POM Used
as a Photocatalytic Membrane
, Iran. J. Chem. Chem. Eng. (IJCCE), 40(1): 35-47 (2021).
[11] Bandyopadhyay M., Jadav D., Tsunoji N., Sano T., Sadakane M., Immobilization of Preyssler Type Heteropoly Acids on Siliceous Mesoporous Supports and their Catalytic Activities in the Dehydration of Ethanol, Reaction Kinetics, Mechanisms and Catalysis, 128: 139–147 (2019).
[12] Devassy B.M, Halligudi S.B., Zirconia Supported Heteropoly Acids: Characterization and Catalytic Behavior in Liquid-Phase Veratrole Benzoylation, Journal of Catalysis, 236: 313–323 (2005).
[13] Ghubayra R., Nuttall C., Hodgkiss S., Craven M., Kozhevnikova E.F., Kozhevnikov I.V., Oxidative Desulfurization of Model Diesel Fuel Catalyzed by Carbonsupported Heteropoly Acids, Applied Catalysis B: Environmental, 253: 309-316 (2019).
[14] Ilnickaa A.M., Bielanska E., Dobrzynska L.L, Bielanski A., Carbon Nanotubes, Silica and Titania Supported Heteropolyacid H3PW12O40 as the Catalyst for Ethanol Conversion, Applied Catalysis A: General, 421-422: 91-98 (2012).
[15] Nandiyanto A.B.D., Kim S.G., Iskandar F., Okuyama K., Synthesis of Spherical Mesoporous Silica Nanoparticles with Nanometer Size Controllable Pores and Outer Diameters, Microporous and Mesoporous Materials, 120: 447–453 (2009).
[16] Arastehnodeh A., Saghi M., Khazaei Nejad M., Preparation, Characterization and Application of Nanospherical α-Fe2O3 Supported on Silica for Photocatalytic Degradation of Methylene Blue, Iran. J. Chem. Chem. Eng. (IJCCE), 38(2): 21-28 (2019).
[17] Izumi Y., Hasebe R., Urabe K., Catalysis by Heterogeneous Supported Heteropoly Acid, Journal of   Catalysis, 84: 402-409 (1983).
[18] Heravi M.M., Sadjadi S., Hekmatshoar R., Abdi Oskooie H., Bamoharram F., Keggin-Type Heteropolyacids Catalyzed One Pot Oxidation-Trimerization of Alcohols into 2,4,6-Trisubstituted- 1,3,5-Trioxanes, Iran. J. Chem. Chem. Eng. (IJCCE), 28(2): 131-136 (2009).
[19] Macht J., Janik M.J., Neurock M., Iglesia E., Catalytic Consequences of Composition in Polyoxometalate Clusters with Keggin Structure, Angewandte Chemie, 119: 8010 –8014 (2007).
[20] Wang J.X., Zhou X.T., Han Q., Guo X.X., Liu X.H., Xue C., Ji H.B., Efficient and Selective Oxidation of Alcohols to Carbonyl Compounds at Room Temperature by a Ruthenium Complex Catalyst and Hydrogen Peroxide, New Journal of Chemistry, 43: 19415-19421 (2019).
[21] Li Z., Zhang J., Jing X., Dong J., Liu H., Lv H., Chi Y.,  Hu C., A Polyoxometalate@Covalent Triazine Framework as a Robust Electrocatalyst for Selective Benzyl Alcohol Oxidation Coupled with Hydrogen Production, Journal of Materials Chemistry A, 9(10): 6152-6159 (2021).
[22] Batalha D.C., Ferreira S.O., Da Silva R.C., Da Silva M.J., Cesium-Exchanged Lacunar Keggin Heteropolyacid Salts: Efficient Solid Catalysts for the Green Oxidation of Terpenic Alcohols with Hydrogen Peroxide, Chemistry Select, 5: 1976 –1986 (2020).
[23] Li D., Ma P., Niu J., Wang J., Recent Advances in Transition-Metal-Containing Keggin-Type Polyoxometalate-based Coordination Polymers, Coordination Chemistry Reviews, 392: 49-80 (2019).
[24] Zou Y., Li H., Zhao X., Song J., Wang Y., Ma P., Niu J., Ru(iii) -based Polyoxometalate Tetramers as Highly Efficient Heterogeneous Catalysts for Alcohol Oxidation Reactions at Room Temperature, Dalton Transactions, 50(36): 12664-12673 (2021)
[26] Reddy V.G., Jampaiah D., Chalkidis A., Sabri Y.M., Mayes E.L.H., Bhargava S.K., Highly Dispersed Cobalt Oxide Nanoparticles on Manganese Oxide Nanotubes for Aerobic Oxidation of Benzyl Alcohol, Catalysis Communications, 130: 105763 (2019).
[27] Najafpour M.M., Amini M., Bagherzadeh M., Boghaei D.M, McKee V., Synthesis, Structural Characterization and Alcohol Oxidation Activity of a New Mononuclear Manganese(II) Complex, Transition Metal Chemistry, 35: 297–303 (2010).
[29] Bhorodwaj S.H., Dutta D.K., Activated Clay Supported Heteropoly Acid Catalysts for Esterification of Acetic Acid with Butanol, Applied Clay Science, 53: 347-352 (2011).
[31] Rao P.M., Wolfson A., Kababya S., Vega S., Landau M.V., Immobilization of Molecular H3PW12O40 Heteropolyacid Catalyst in Alumina-Grafted Silica-Gel and Mesostructured SBA-15 Silica Matrices, Journal of Catalysis, 232: 210–225 (2005).
[32] Kuang W., Rives A., Fournier M., Hubaut R., Structure and Reactivity of Silica-Supported 12-Tungstophosphoric Acid, Applied Catalysis A: General, 250: 221–229 (2003).
[33] Sing K.S.W., Adsorption Methods for the Characterization of Porous Materials, Advances in Colloid and Interface Science, 76-77: 3-11 (1998).
[34] Gobara H.M., Hassan S.A. A., Comparative Study of Surface Characteristics of Nickel Supported on Silica Gel, ꝨAlumina, Aluminosilicate, Petroleum Science and Technology, 27: 1555–1571 (2009).
[35] Kanga T.H., Choi J.H., Banga Y., Yoo J., Songa J.H., Joe W., Choi J.S., Song I.K., Dehydration of Glycerin to Acrolein over H3PW12O40 Heteropolyacid Catalyst Supported on Silica-Alumina, Journal of Molecular Catalysis A: Chemical, 396: 282-289 (2015).
[36] Aghayi M., Yadollahi B., Riahi Farsani M., Zinc Substituted Keggin-Type Polyoxometalate on Dowex: a Green Heterogeneous Catalyst for Oxidation of Alcohols in Water, Journal of the Iranian Chemical Society, 17: 2895–2900 (2020).
[37] Zarnegaryan A., Salimi Beni A., Immobilization of Hexamolybdate onto Carbon-Coated Fe3O4 Nanoparticle: A Novel Catalyst with High Activity for Oxidation of Alcohols, Journal of Organometallic Chemistry, 953: 122043 (2021).
[38] Mirjalili B.F., Zolfigol M.A., Bamoniri A., Zaghaghi Z., Silica Sulfuric Acid/KClO3/wet SiO2 as an Efficient Heterogeneous Method for the Oxidation of Alcohols Under Mild Conditions, Journal of    Chemical Research, 5: 273-274 (2003).
[39] Tamiolakis I, Lykakis IN, Katsoulidis AP, Malliakas CD, Armatas GS., Ordered Mesoporous Cr2O3 Frameworks Incorporating Keggin-Type 12-Phosphotungstic Acids as Efficient Catalysts for Oxidation of Benzyl Alcohols, Journal of Materials Chemistry, 22: 6919-6927 (2012).
[40] Wang Y., Wu Z., Yu H., Han S., Wei Y., Highly Efficient Oxidation of Alcohols to Carboxylic Acids using a Polyoxometalate-Supported Chromium(III) Catalyst and CO2, Green Chemistry, 22(10): 3150-3154 (2020).