Synthesis and characterization of mono substituted polyoxometalate incorporation into amorph silica and catalytic activity of these compounds in selective oxidation of aromatic amines with hydrogen peroxide

Document Type : Original Article

Authors

1 Departement of Chemistry, Faculty of Science, Shahrekord University, Shahrekord, Iran

2 Department of Chemistry, University of Isfahan. Isfahan 81746-73441, Iran

Abstract

In this study, the selective oxidation of aromatic amines using hydrogen peroxide as an green oxidant and a polyoxometalate catalyst modified with first-row transition metals in a silica matrix was performed. Initially Mono substituted Keggin type Polyoxometalates with first row transition metals (TBA)X[PW11MO39].nH2O (M= Cr, Mn, Fe, Co, Ni, Cu, Zn) were synthesised and then incorporated into a silica matrix by using sol-gel method. The synthesized compounds were characterized using techniques such as EDAX, CHNS, XRD, SEM, and TG-DTG. For selecting the best catalyst, oxidation of aniline was performed with all catalysts and polyoxometalate substituted with Fe showed best catalytic activity. After optimization reaction conditions, oxidation of different aromatic amine was performed and Fe substituted polyoxometalates showed excellent catalytic activity for selective oxidation of different amines to corresponded nitro in heterogeneous system. The studies indicated that the catalysts have good recovery capabilities and can be reused multiple times without significant loss in activity.

Keywords

Main Subjects

References

[1] Chng, J. Y., & Sholl, D. S. (2025). Kinetic separation of siloxanes in metal–organic frameworks. The Journal of Physical Chemistry C, 129(1), 910–917.
[2] Vinayagam, V., Palani, K. N., Ganesh, S., Rajesh, S., Akula, V. V., Avoodaiappan, R., Kushwaha, O. S., & Pugazhendhi, A. (2024). Recent developments on advanced oxidation processes for degradation of pollutants from wastewater with focus on antibiotics and organic dyes. Environmental Research, 240(Part 2), 117500.
[3] Liu, Y., Zhang, B., Yan, D., & Xiang, X. (2024). Recent advances in the selective oxidation of glycerol to value-added chemicals via photocatalysis/photoelectrocatalysis. Green Chemistry, 26, 2505–2524.
[4] Blackball, J. (2004). Modern oxidation method. Wiley-VCH.
[5] Akhavan, P. F. (2005).  (Master’s thesis). Institute for Advanced Studies in Basic Sciences.
[6] Mizuno, N. (2009). Modern heterogeneous oxidation catalysis. Wiley-VCH.
[7] R. Farsani, M., Yadollahi, B., Taghiyar, H., Moghadam, AJ, Mo132-Ionic Liquid As An Effective Hybrid Catalyst For Selective Epoxidation of Different Alkenes with H2O2, Catalysis Letters 155 (2), 70.
[8] Aghayi, M., Yadollahi, B., & Farsani, M. R. (2020). 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.
[9] Wang, Y., Xu, N., Zhang, Y., Zhang, T., Zhang, Z., Li, X.-H., & Wang, X.-L. (2022). A Keggin-type polyoxometalate-based metal–organic complex as a highly efficient heterogeneous catalyst for the selective oxidation of alkylbenzenes. Dalton Transactions, 51, 2331–2337.
[10] Alizadeh, M., & Yadollahi, B. (2023). Synthesis of nanoscale surfactant-encapsulated silica-supported polyoxometalate [Si/AlO₂]@[PWZn]@CTAB and its catalytic application in the oxidation of alcohols. RSC Advances, 15(11), 8777–8783.
[11] Yekke-Ghasemi, Z., Heravi, M. M., Malmir, M., et al. (2023). Efficient oxidation of sulfides to sulfoxides catalyzed by heterogeneous Zr-containing polyoxometalate grafted on graphene oxide. Scientific Reports, 13, 16752. 
[12] Malmir, M., Heravi, M. M., Yekke-Ghasemi, Z., et al. (2022). Incorporating heterogeneous lacunary Keggin anions as efficient catalysts for solvent-free cyanosilylation of aldehydes and ketones. Scientific Reports, 12, 11573. 
[13] Yekke-Ghasemi, Z., Heravi, M. M., Malmir, M., Jahani, G., Bagheri Bisafar, M., & Mirzaei, M. (2022). Fabrication of heterogeneous-based lacunary polyoxometalates as efficient catalysts for the multicomponent and clean synthesis of pyrazolopyranopyrimidines. Inorganic Chemistry Communications, 140, 109456. 
[14] Daraie, M., Mirzaei, M., Bazargan, M., Amiri, V. S., Abdolahi Sanati, B., & Heravi, M. M. (2022). Lanthanoid-containing polyoxometalate nanocatalysts in the synthesis of bioactive isatin-based compounds. Scientific Reports, 12, 12004. 
[15] Heravi, M. M., Hosseinnejad, T., Tamimi, M., Zadsirjan, V., & Mirzaei, M. (2020). Tungstoboric acid (H₅BW₁₂O₄₀) as an efficient Lewis acid catalyst for the synthesis of chromenopyrimidine-2,5-diones and thioxochromenopyrimidin-5-ones: Joint experimental and computational study. Journal of Molecular Structure, 1205, 127598.
[16] Hosseinzadeh-Baghan, S., Mirzaei, M., Eshtiagh-Hosseini, H., Zadsirjan, V., Heravi, M. M., & Mague, J. T. (2020). An inorganic–organic hybrid material based on a Keggin-type polyoxometalate@Dysprosium as an effective and green catalyst in the synthesis of 2-amino-4H-chromenes via multicomponent reactions. Applied Organometallic Chemistry, 34(9).
[17] Samaniyan, M., Mirzaei, M., Khajavian, R., Eshtiagh-Hosseini, H., & Streb, C. (2019). Heterogeneous catalysis by polyoxometalates in metal–organic frameworks. ACS Catalysis, 9(11), 10174–10191. 
[18] Derakhshanrad, S., Mirzaei, M., Streb, C., Amiri, A., & Ritchie, C. (2021). Polyoxometalate-based frameworks as adsorbents for drug of abuse extraction from hair samples. Inorganic Chemistry, 60(3), 1472–1479. 
[19] Mirzaei, M., Eshtiagh-Hosseini, H., Alipour, M., Bauzá, A., Mague, J. T., Korabik, M., & Frontera, A. (2015). Hydrothermal synthesis, X-ray structure and DFT and magnetic studies of a (H₂SiW₁₂O₄₀)²⁻ based one-dimensional linear coordination polymer. Dalton Transactions, 44, 8824–8832.
[20] Taleghani, S., Mirzaei, M., Eshtiagh-Hosseini, H., & Frontera, A. (2016). Tuning the topology of hybrid inorganic–organic materials based on the study of flexible ligands and negative charge of polyoxometalates: A crystal engineering perspective. Coordination Chemistry Reviews, 309, 84–106.
[21] Glass, E. N., Fielden, J., Huang, Z., Xiang, X., Musaev, D. G., Lian, T., and Hill, C. L., (2016).  Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer, Inorganic Chemistry, 55(9), 4308–4319 0
[22] Patel, A., Narkhede, N., Singh, S., and Pathan, S., (2016) Keggin-type lacunary and transition metal substituted polyoxometalates as heterogeneous catalysts: A recent progress, Catalysis Reviews, 58(3), 337–370.
[23] Guo, Y., Hu, C., Jiang, C., Yang, Y., Jiang, S., Li, X., and Wang, E., (2003). Preparation and heterogeneous photocatalytic behaviors of the surface-modified porous silica materials impregnated with monosubstituted keggin units, Journal of Catalysis, 217, 141–151 (2003).
[24] Peng, G., Wang, Y., Hu, C., Wang, E., Feng, S., Zhou, Y., Ding, H., and Liu, Y., (2001). Heteropolyoxometalates which are included in microporous silica, CsxH3-xPMo12O40/SiO2 and CsyH5-yPMo10V2O40/SiO2, as insoluble solid bifunctional catalysts: synthesis and selective oxidation of benzyl alcohol in liquid–solid systems, Applied Catalysis A: General, 218, 91–99.
[25] Kozhevnikov, I. V. (1998). Catalysis by polyoxometalates. Chemical Reviews, 98, 171–198.
[26] Ward, D. A., & Ko, E. I. (1995). Preparing catalytic materials by the sol-gel method. Industrial & Engineering Chemistry Research, 34(2), 421–433.
[27] Elali, B., Brtgeault, J. M., Mercier, J., Martin, J., Martin, C., & Convert, O. (1989). The oxidation of ketones with a heteropolyacid, H5[PMo10V2O40] and dioxygen. Journal of the Chemical Society, Chemical Communications, 825.
[28] Panchenko, V. N., Borbth, L., Timofeeva, M. N., & Gobël, S. (2010). Amine-modified silica NH2–(CH2)x–SiO2 (x = 0, 2, 3) as support for cobalt-substituted polyoxometalate TBA4HPW11CoO39: Effect of the nature of the support on the oxidation activity. Molecular Catalysis A, 319, 119.
[29] Danafar, H., Yadollahi, B. (2009). (TBA)4PFeW11O39·3H2O catalyzed efficient and facile ring opening reaction of epoxides with aromatic amines. Catalysis Communications, 10, 842–847.
[30] Guo, Y., Wang, Y., Hu, C., Wang, Y., & Wang, E. (2000). Microporous polyoxometalates POMs/SiO₂: Synthesis and photocatalytic degradation of aqueous organochlorine pesticides. Chemistry of Materials, 12, 3501–3508.
[31] Assady, E., Yadollahi, B., Farsani, M. R., & Moghadam, M. (2015). Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide. Applied Organometallic Chemistry, 29, 561.
[32] Farsani, M. R., Yadollahi, B. (2014). Synthesis, characterization and catalytic performance of a Fe polyoxometalate/silica composite in the oxidation of alcohols with hydrogen peroxide. Journal of Molecular Catalysis A: Chemical, 392, 8–15.
Applied Chemistry Today
Volume 20, Issue 74
in progress ...
January 2025
Pages 195-216

Files

Share

How to cite

Statistics