Abstract

Oxidation desulfurization (ODS) is an effective method to remove sulfur compounds from fuels by converting them into more polar oxidized forms that are easier to extract. In this study, H₅PV₂Mo₁₀O₄₀/TiO₂ catalysts were synthesized and characterized using FT-IR spectroscopy. The FT-IR spectra confirmed the successful impregnation of polyoxometalate into the TiO₂ matrix, indicated by the appearance of Ti-O and O-Ti-O vibrations, while the typical H₅PV₂Mo₁₀O₄₀ peaks remained detectable. The performance of the H₅PV₂Mo₁₀O₄₀/TiO₂ catalyst in the desulfurization of 4-methyldibenzothiophene (4-MDBT) was studied based on variations in reaction time, catalyst mass, temperature, and amount of H₂O₂. The optimal conditions obtained were a reaction time of 2 hours, a catalyst mass of 0.05 g, a temperature of 60°C, and a volume of H₂O₂ of 5 mL, with a maximum sulfur conversion of 99.0%. These results indicate that H₅PV₂Mo₁₀O₄₀/TiO₂ has potential as an efficient ODS catalyst.

Keywords

References

  1. Ahmad, N., M. Badaruddin, N. Yuliasari, F. S. Arsyad, and A. Lesbani (2022). Highly Efficient Catalytic Oxidative Desulfurization of Dibenzothiophene Using Layered Double Hydroxide Modified Polyoxometalate Catalyst. Bulletin of Chemical Reaction Engineering and Catalysis, 17(4); 821–830.
  2. Ahmad, N., R. Rohmatullaili, Y. Hanifah, S. Wibiyan, A. Amri, A. Wijaya, M. Mardiyanto, R. Mohadi, I. Royani, and A. Lesbani (2023a). Recycle Performance of Heterogeneous Catalyst Metal Oxides-Based Layered Double Hydroxide for Oxidative Desulfurization Process of 4-Methyldibenzothiophene. Bulletin of Chemical Reaction Engineering and Catalysis, 18(4); 548–558.
  3. Ahmad, N., S. Wibiyan, I. Royani, R. Mohadi, and A. Lesbani (2023b). Reusable Heterogeneous Catalyst (M2+)Al-Layered Double Hydroxide Used for Oxidative Desulfurization of 4,6-Dimethyldibenzothiophene. Indonesian Journal of Material Research, 1(3); 99–105.
  4. Al-Khazaali, W. M. K. and S. A. Ataei (2023). Optimization of Biodesulfurization of Sour Heavy Crude Oil. PLOS ONE, 18(4); 1–12.
  5. Amri, A., N. Ahmad, S. Wibiyan, A. Wijaya, M. Mardiyanto, I. Royani, R. Mohadi, and A. Lesbani (2024). Optimization of Desulfurization of 4-Methyldibenzothiophene and 4,6-Dimethyldibenzothiophene Using Mg/Al Layered Double Hydroxide Equipped with ZnO/TiO2. Indonesian Journal of Chemistry, 24(4); 1011–1022.
  6. Aribike, D. S., M. A. Usman, and M. M. Oloruntoba (2020). Adsorptive Desulfurization of Diesel Using Activated Sewage Sludge: Kinetics, Equilibrium and Thermodynamics Studies. Applied Petrochemical Research, 10(1); 1–12.
  7. Artetxe, B., L. Ruiz-Rubio, J. Vilas, and J. M. Gutierrez-Zorrilla (2022). Polyoxometalates: Advances, Properties, and Applications. Jenny Stanford Publishing.
  8. Azmani, K., M. Besora, J. Soriano-López, M. Landolsi, A.-L. Teillout, P. de Oliveira, I.-M. Mbomekallé, J. M. Poblet, and J.-R. Galán-Mascarós (2021). Understanding Polyoxometalates as Water Oxidation Catalysts Through Iron vs. Cobalt Reactivity. Chemical Science, 12(25); 8755–8766.
  9. Breibeck, J., N. I. Gumerova, and A. Rompel (2022). Oxo-Replaced Polyoxometalates: There Is More than Oxygen. ACS Organic & Inorganic Au, 2(6); 477–495.
  10. Castro, G., J. Cruz-Borbolla, M. Galván, A. Guevara-García, J. Ireta, M. H. Matus, A. Meneses-Viveros, L. Ignacio Perea-Ramírez, and M. Pescador-Rojas (2024). Hydrodesulfurization of Dibenzothiophene: A Machine Learning Approach. ChemistryOpen, 13(9); e202400062.
  11. Coutinho, A. C. S. L. S., J. M. F. Barros, M. D. S. Araujo, J. B. Silva, M. J. B. Souza, R. C. O. B. Delgado, V. J. Fernandes Jr., and A. S. Araujo (2024). Hydrodesulfurization of Thiophene in n-Heptane Stream Using CoMo/SBA-15 and CoMo/AlSBA-15 Mesoporous Catalysts. Catalysts, 14(3); 198.
  12. Cui, X.-B. (2023). Special Issue: Research on Polyoxometalate Materials. Molecules, 28(12); 4662.
  13. Gooneh-Farahani, S. and M. Anbia (2023). A Review of Advanced Methods for Ultra-Deep Desulfurization under Mild Conditions and the Absence of Hydrogen. Journal of Environmental Chemical Engineering, 11(1); 108997.
  14. Gunam, I. B. W., T. Sone, and K. Asano (2021). Biodesulfurization of the Mixture of Dibenzothiophene and Its Alkylated Derivatives by Sphingomonas Subarctica T7b. Indonesian Journal of Biotechnology, 26(3); 122–127.
  15. Hanifah, Y. and A. Amri (2023). Preparation of Layered Double Hydroxide-Polyoxometalate Based Composite. Indonesian Journal of Material Research, 1(2); 68–73.
  16. Helmi, F., M. Helmi, and A. Hemmati (2022). Phosphomolybdic Acid/Chitosan as Acid Solid Catalyst Using for Biodiesel Production from Pomegranate Seed Oil via Microwave Heating System: RSM Optimization and Kinetic Study. Renewable Energy, 189; 881–898.
  17. Huo, H.-Y., Y.-W. Liu, M. Yuan, Y. Lu, J. Wang, G.-S. Zhu, and S.-X. Liu (2021). Synthesis and Characterization of H5PV2Mo10O40@Cu3(BTC)2 and Its Use as a Heterogeneous Catalyst for Oxidative Desulfurization: A Comprehensive Chemistry Laboratory Experiment. Journal of Chemical Education, 98(11); 3580–3586.
  18. Karimi, R. and B. Golmohammadi (2024). Simulation and Optimization of Heavy Fuel Oil (HFO) Refining Platform to Low Sulfur Marine Fuel (LS-FO) by Oxidative Desulfurization. Scientific Reports, 14(1); 29830.
  19. Lesbani, A., A. Marpaung, M. Verawaty, H. Rizki Amalia, and R. Mohadi (2015). Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as Catalyst. The Journal of Pure and Applied Chemistry Research, 4(1); 5–11.
  20. Liu, Q., T. Su, H. Zhang, W. Liao, W. Ren, Z. Zhu, K. Yang, C. Len, J. Yu, D. Zhao, and H. Lü (2023). Development of TiO2 Catalyst Based on Anderson-Polyoxometalates for Efficient Visible-Light-Driven Photocatalytic Oxidative Desulfurization. Fuel, 333; 126286.
  21. Mallick, L., K. Samanta, and B. Chakraborty (2024). Postsynthetic Metalation on the Ionic TiO2 Surface to Enhance Metal-CO2 Interaction During Photochemical CO2 Reduction. Chemistry – A European Journal, 30(38); e202400428.
  22. Mamuad, R. Y. and A. E. S. Choi (2023). Biodesulfurization Processes for the Removal of Sulfur from Diesel Oil: A Perspective Report. Energies, 16(6); 2738.
  23. Navarro Yerga, R. M., B. Pawelec, N. Mota, and R. Huirache-Acuña (2022). Hydrodesulfurization of Dibenzothiophene over Ni-Mo-W Sulfide Catalysts Supported on Sol-Gel Al2O3-CeO2. Materials, 15(19); 6780.
  24. Piscopo, C. G., C. M. Granadeiro, S. S. Balula, and D. Bošković (2020). Metal-Organic Framework-Based Catalysts for Oxidative Desulfurization. ChemCatChem, 12(19); 4721–4731.
  25. Saleh, T. A., S. A. Al-Hammadi, A. Tanimu, and K. Alhooshani (2018). Ultra-deep adsorptive desulfurization of fuels on cobalt and molybdenum nanoparticles loaded on activated carbon derived from waste rubber. Journal of Colloid and Interface Science, 513; 779–787.
  26. Shao, B., L. Shi, and X. Meng (2014). Deep Desulfurization of 4,6-Dimethyldienzothiophene by an Ionic Liquids Extraction Coupled with Catalytic Oxidation with a Molybdic Compound. Industrial & Engineering Chemistry Research, 53(16); 6655–6663.
  27. Shi, H., H. Zhu, T. Jin, L. Chen, J. Zhang, K. Qiao, and Z. Chen (2023a). Construction of Bi/Polyoxometalate doped TiO2 composite with efficient visible-light photocatalytic performance: Mechanism insight, degradation pathway and toxicity evaluation. Applied Surface Science, 615; 156310.
  28. Shi, N., Y. Ding, N. Li, F. Wen, and D. Liu (2023b). Polyoxometalates-modified and facets-engineered TiO2 nanocomposites for selective photocatalytic cleavage of C–C bond of lignin models. Journal of Environmental Chemical Engineering, 11(5); 110558.
  29. Tang, Q., X. An, H. Lan, H. Liu, and J. Qu (2020). Polyoxometalates/TiO2 photocatalysts with engineered facets for enhanced degradation of bisphenol A through persulfate activation. Applied Catalysis B: Environmental, 268; 118394.
  30. Tiwari, C. K., M. Baranov, A. Neyman, R. Neumann, and I. A. Weinstock (2020). Selective Oxidation by H5[PV2Mo10O40] in a Highly Acidic Medium. Inorganic Chemistry, 59(17); 11945–11952.
  31. Trisunaryanti, W., S. D. Sumbogo, S. A. Novianti, D. A. Fatmawati, M. Ulfa, and Y. L. Nikmah (2021). ZnO-activated carbon blended as a catalyst for oxidative desulfurization of dibenzothiophene. Bulletin of Chemical Reaction Engineering and Catalysis, 16(4); 881–887.
  32. Wang, H. and B. Li (2024). Recent Advances on the Functionalities of Polyoxometalate-Based Ionic Liquids. Molecules, 29(13).
  33. Wu, F., Q. Yuan, J. Wang, X. Wang, J. Luo, Y. Guo, H. Xu, and X. Wei (2025). Oxidative Desulfurization Catalyzed by Magnetically Recoverable CoFe2O4 Nano-Particles. Arabian Journal of Chemistry, 18(1); 106076.
  34. Xu, L., Q. Tong, and B. Hu (2024). Silicotungstate@ZIF-67 as an Effective Catalyst for an Extraction and Oxidative Desulfurization System. RSC Advances, 14(49); 36622–36632.
  35. Zhai, Y., J. Yu, L. Zhang, Y. Zhou, Y. Zhong, Y. Yang, and Y. A. Wang (2021). A Bifunctional Composite H5PV2Mo10O40@MOF-808(Ce): Preparation, Characterization, and Performance in the Decontamination of Chemical Warfare Agent Surrogates CEES and DMNP. Microporous and Mesoporous Materials, 322; 111163.
  36. Zhang, H. and S. Fu (2024). Polyoxometalate as an Effective Catalyst for Catalytic Lignin into Value-Added Molecules. ChemCatChem, 16(1); e202301204.
  37. Zhang, Y., G. Ji, F. Ullah, and A. Li (2023). Polyoxometalate Catalyzed Oxidative Desulfurization of Diesel Range Distillates from Waste Tire Pyrolysis Oil. Journal of Cleaner Production, 389; 136038.
  38. Zhao, J., B. Wang, R. Wang, I. V. Kozhevnikov, and K. Vladimir (2023). Efficient Diesel Desulfurization by Novel Amphiphilic Polyoxometalate-Based Hybrid Catalyst at Room Temperature. Molecules, 28(6); 2539.