Synthesis, Characterization, and Catalytic Performance of H₃[α-PMo₁₂O₄₀]·nH₂O-TiO₂ in Cyclohexane Oxidation
DOI:
https://doi.org/10.26554/ijmr.20253153Keywords:
H₃[α-PMo₁₂O₄₀].nH₂O, TiO2, Cyclohexane, cyclohexanol, cyclohexanoneAbstract
This study aims to synthesize and characterize the H₃[α-PMo₁₂O₄₀].nH₂O-TiO₂ composite as a heterogeneous catalyst for cyclohexane oxidation using H₂O₂. FT-IR and XRD characterization showed the interaction between POM and TiO₂, with an increase in TiO₂ ratio leading to a decrease in POM crystallinity. Reaction optimization showed that the POM-1.00TiO₂ catalyst gave the highest conversion of 99.95% at 80°C, 2 hours reaction time, 3 mL H₂O₂ volume, and 0.1 g catalyst mass. GC analysis confirmed the formation of cyclohexanol and cyclohexanone, with the optimized conditions resulting in a balanced selectivity of 35.51% for cyclohexanol and 34.69% for cyclohexanone, demonstrating the catalyst's effectiveness in cyclohexane oxidation.
References
Alnefaie, R. S., M. Abboud, A. Alhanash, and M. S. Hamdy (2022).
Efficient Oxidation of Cyclohexane over Bulk Nickel Oxide under Mild Conditions. Molecules, 27(10); 3145.
Chandoliya, R., S. Sharma, V. Sharma, R. Joshi, and I. Sivanesan (2024).
Titanium Dioxide Nanoparticle: A Comprehensive Review on Synthesis, Applications and Toxicity. Plants, 13(21); 2964.
Evtushok, V. Y., V. A. Lopatkin, O. Y. Podyacheva, and O. A. Kholdeeva (2022).
Immobilization of Polyoxometalates on Carbon Nanotubes: Tuning Catalyst Activity, Selectivity and Stability in H2O2-Based Oxidations. Catalysts, 12(5); 472.
Gao, Y., H. Li, N. N. Li, X. Hu, L. Feng, A. Yin, and J. Zhao (2023).
Encapsulated Peroxo-Polyoxometalates into Fe2O3/C Hybrid Material Carbonized from MIL-101(Fe) as Efficient Magnetic Catalyst for Desulfurization of Fuel. Fuel, 341; 126992.
Guangbo, C., S. Pengfei, N. Xiaoxiao, W. Li-Zhu, and Z. Tierui (2025).
Innovative and Sustainable Approaches to Aerobic Oxidation Reactions for Organics Upgrading. CCS Chemistry; 1–17.
Hanif, M. I., D. Pringgenies, and G. W. Santosa (2019).
Potential Application of Consortium Microbe from Sea Cucumber Intestinal Symbiont as Preservatives for Vaname Shrimp. Indonesian Journal of Environmental Management and Sustainability, 3(3); 106–111.
Hanifah, Y. and A. Amri (2023).
Preparation of Layered Double Hydroxide-Polyoxometalate Based Composite. Indonesian Journal of Material Research, 1(2); 68–73.
Hsu, C. Y., Z. H. Mahmoud, S. Abdullaev, F. K. Ali, Y. Ali Naeem, R. Mzahim Mizher, M. Morad Karim, A. S. Abdulwahid, Z. Ahmadi, S. Habibzadeh, and E. Kianfar (2024).
Nano Titanium Oxide (Nano-TiO2): A Review of Synthesis Methods, Properties, and Applications. Case Studies in Chemical and Environmental Engineering, 9; 100626.
Huo, H., B. Guo, G. Ma, Y. Xiang, H. Lv, S. Li, Z. Liu, F. Huang, Y. Xu, and F. Zhang (2024).
Recent Progress in Strategies to Enhance the Photocatalytic Oxidation Performance of Cyclohexane. Journal of Environmental Chemical Engineering, 12(5); 113504.
Idris, N. H. M., K. Y. Cheong, B. J. Kennedy, T. Ohno, and H. L. Lee (2022).
Buoyant Titanium Dioxide (TiO2) as High Performance Photocatalyst and Peroxide Activator: A Critical Review on Fabrication, Mechanism and Application. Journal of Environmental Chemical Engineering, 10(3); 107549.
Isahak, W. N. R. W. and A. Al-Amiery (2024).
Catalysts Driving Efficiency and Innovation in Thermal Reactions: A Comprehensive Review. Green Technologies and Sustainability, 2(2); 100078.
Jiang, Y., C.-J. Chen, K. Li, L.-P. Cui, and J.-J. Chen (2025).
Polyoxometalates for the Catalytic Reduction of Nitrogen Oxide and Its Derivatives: From Novel Structures to Functional Applications. Chemical Communications.
Kar, S. and D. Milstein (2022).
Oxidation of Organic Compounds Using Water as the Oxidant with H2 Liberation Catalyzed by Molecular Metal Complexes. Accounts of Chemical Research, 55(16); 2304–2315.
Lang, M. and H. Li (2023).
Heterogeneous Metal-Based Catalysts for Cyclohexane Synthesis from Hydrodeoxygenation of Lignin-Derived Phenolics. Fuel, 344; 128084.
Liu, G., M. Chen, X. Jin, C. Song, F. He, and Q. Huang (2021).
Combination of H3PW12O40-TiO2 Catalysts for Photo-Thermal Oxidation of Cyclohexene to Adipic Acid by 30% H2O2. Journal of Environmental Chemical Engineering, 9(4); 105422.
Mirante, F., M. Salimian, P. A. A. P. Marques, C. M. Granadeiro, and S. S. Balula (2022).
Polyoxometalate-Doped Electrospun Nanofiber Mats as Active Catalysts for the Production of Clean Fuels under Solvent-Free Systems. Sustainable Energy & Fuels, 6(20); 4681–4691.
Mouanni, S., D. Amitouche, T. Mazari, and C. Rabia (2019).
Transition Metal-Substituted Keggin-Type Polyoxometalates as Catalysts for Adipic Acid Production. Applied Petrochemical Research, 9(2); 67–75.
Mouanni, S., T. Mazari, S. Benadji, L. Dermeche, C. Marchal-Roch, and C. Rabia (2018).
Simple and Green Adipic Acid Synthesis from Cyclohexanone and/or Cyclohexanol Oxidation with Efficient (NH4)xHyMz PMo12O40 (M: Fe, Co, Ni) Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 13(2); 386–392.
Niakan, M., M. Masteri-Farahani, and H. Haidary (2024).
Catalytic Adipic Acid Production through the Cyclohexene Oxidation by a Non-HNO3 Route over SBA-16 Supported Venturello Catalyst. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 686; 133465.
Novais, H. C., B. Jarrais, I.-M. Mbomekallé, A.-L. Teillout, P. de Oliveira, C. Freire, and D. M. Fernandes (2024).
Enhanced Oxygen Reduction Reaction Activity of the Wells-Dawson Polyoxometalate P2W12Mo6 Immobilised in Nitrogen and Sulphur-Doped Carbon Nanomaterials. ChemElectroChem, 11(4); e202300622.
Palapa, N. R., T. Taher, A. Wijaya, and A. Lesbani (2021).
Modification of Cu/Cr Layered Double Hydroxide by Keggin Type Polyoxometalate as Adsorbent of Malachite Green from Aqueous Solution. Science and Technology Indonesia, 6(3); 209–217.
Pan, D., G. Li, Y. Su, H. Wei, and Z. Luo (2021).
Kinetic Study for the Oxidation of Cyclohexanol and Cyclohexanone with Nitric Acid to Adipic Acid. Chinese Journal of Chemical Engineering, 29; 183–189.
Pascual-Borràs, M., E. Arca, H. Yoshikawa, T. Penfold, P. G. Waddell, and R. J. Errington (2024).
Mechanochemical Polyoxometalate Super-Reduction with Lithium Metal. Journal of the American Chemical Society, 146(38); 26485–26496.
Peng, X., S. Zeb, J. Zhao, M. Zhang, Y. Cui, and G. Sun (2020).
Highly Selective Self-Condensation of Cyclohexanone: The Distinct Catalytic Behaviour of HRF5015: High Selectivity of Cyclohexanone Dimer. Royal Society Open Science, 7(10); 200123.
Sakthinathan, I., N. Yamasaki, D. Barreca, C. Maccato, T. Ueda, and T. McCormac (2023).
Wells-Dawson Type Polyoxometalate, [S2W18O62]4–Doped Poly(3,4-Ethylenedioxythiophene) Films: Voltammetric Behaviour and Applications to Selective Bromate Detection. Electrochimica Acta, 462; 142689.
Samaraj, E., E. Balaraman, and S. Manickam (2021).
Functional POM-Catalyst for Selective Oxidative Dehydrogenative Couplings Under Aerobic Conditions. Molecular Catalysis, 502; 111396.
Sativa, E. and A. Lesbani (2017).
Conversion of Cyclohexane to Cyclohexanol and Cyclohexanone Using H3[PMo12O40]·nH2O ZrOCl2 as Catalyst. Science and Technology Indonesia, 2(3); 59–63.
Shi, N., Y. Ding, N. Li, F. Wen, and D. Liu (2023).
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.
Trakarnpruk, W. and J. Jatupisarnpong (2013).
Acidic and Cesium Salts of Polyoxometalates with and Without Vanadium Supported on MCM-41 as Catalysts for Oxidation of Cyclohexane with H2O2. Applied Petrochemical Research, 3(1–2); 9–15.
Tubul-Sterin, T., M. Baranov, G. Gan-Or, N. Leffler, A. Neyman, and I. A. Weinstock (2023).
Polyoxometalate-Complexed Indium Hydroxide: Atomically Homogeneous Impregnation via Countercation Exchange. Inorganic Chemistry, 62(5); 1804–1812.
Wang, B., B. Wang, S. K. Shukla, and R. Wang (2023).
Enabling Catalysts for Biodiesel Production via Transesterification. Catalysts, 13(4).
Ward, T. R. and C. Copéret (2023).
Introduction: Bridging the Gaps: Learning from Catalysis Across Boundaries. Chemical Reviews, 123(9); 5221–5224.
Zhi, J., X. Xu, S. Duan, W. Chen, F. Li, X. Guo, and Y. Hou (2023).
Perovskite Films Doped with Polyoxometalate and Ionic Liquid Assisted Crystallization for Efficient Photodetectors. European Journal of Inorganic Chemistry, 26(4); e202200599.
Zhong, J., J. Pérez-Ramírez, and N. Yan (2021).
Biomass Valorisation over Polyoxometalate-Based Catalysts. Green Chemistry, 23(1); 18–36.
