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Heteropolyacids supported on hierarchically macro/mesoporous TiO2: efficient catalyst for deep oxidative desulfurization of fuel

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Abstract

The fabrication of polyoxometalates (POMs)-modified TiO2 catalysts with connected pore structure has attracted great interests due to its prominent effect on mass transfer and catalytic oxidation activity. Here, we report a series of hierarchically macro/mesoporous (M/m) phosphotungstic acid (HPW)/TiO2 composites, which are fabricated by colloidal crystal template method and applied as deep desulfurization catalyst in fuel oil. As-synthesized hierarchical HPW/TiO2 composite is interconnected by ordered macroporous channel with disordered mesoporous embedded on pore walls. Moreover, Keggin-type HPW is homogeneously dispersed on the TiO2 matrix. Hierarchical macro/mesoporous HPW/TiO2 shows an excellent catalytic performance, the removal rate for dibenzothiophene in model fuel reaches 99% under the optimum conditions. This high performance of the three-dimensional ordered macropores (3DOM) HPW/TiO2 can be attributed to its hierarchically porous which is highly beneficial for the mass transfer during the catalytic process. Moreover, the used catalyst could be regenerated by centrifugation and only slight decreasing of the catalytic activity after five cycles.

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References

  1. Xun S, Zhu W, Chang Y, Li H, Zhang M, Jiang W, Zheng D, Qin Y, Li H. Synthesis of supported SiW12O40-based ionic liquid catalyst induced solvent-free oxidative deep-desulfurization of fuels. Chem Eng J. 2016;288:608.

    Article  CAS  Google Scholar 

  2. Cheng Q, Zhang G. Enhanced photocatalytic performance of tungsten-based photocatalysts for degradation of volatile organic compounds—a review. Tungsten. 2020;2(3):240.

    Article  Google Scholar 

  3. Lü H, Ren W, Liao W, Chen W, Li Y, Suo Z. Aerobic oxidative desulfurization of model diesel using a B-type Anderson catalyst [(C18H37)2N(CH3)2]3Co(OH)6Mo6O18·3H2O. Appl Catal B. 2013;138–139:79.

    Article  Google Scholar 

  4. Abro R, Abdeltawab A, Al-Deyab S, Yu G, Qazi AB, Gao S, Chen X. A review of extractive desulfurization of fuel oils using ionic liquids. RSC Adv. 2014;4:35302.

    Article  CAS  Google Scholar 

  5. Wu P, Zhu W, Chao Y, Zhang J, Zhang P, Zhu H, Li C, Chen Z, Li H, Dai S. A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization. Chem Commun. 2016;52:144.

    Article  CAS  Google Scholar 

  6. Wang C, Zhu W, Xu Y, Xu H, Zhang M, Chao Y, Yin S, Li H, Wang J. Preparation of TiO2/g-C3N4 composites and their application in photocatalytic oxidative desulfurization. Ceram Int. 2014;40:11627.

    Article  CAS  Google Scholar 

  7. Shen C, Wang Y, Xu J, Luo G. Oxidative desulfurization of DBT with H2O2 catalysed by TiO2/porous glass. Green Chem. 2016;18:771.

    Article  CAS  Google Scholar 

  8. Ye G, Gu YL, Zhou W, Xu W, Sun YY. Synthesis of defect-rich titanium terephthalate with the assistance of acetic acid for room-temperature oxidative desulfurization of fuel oil. ACS Catal. 2020;10:2384.

    Article  CAS  Google Scholar 

  9. Ye G, Hu LL, Gu YL, Christine L, Alain R, Carole L, Nicolas N, Maya M, Xu W, Sun YY. Synthesis of polyoxometalate encapsulated in UiO-66(Zr) with hierarchical porosity and double active sites for oxidation desulfurization of fuel oil at room temperature. J Mater Chem A. 2020;8:19396.

    Article  CAS  Google Scholar 

  10. Wu N, Li B, Liu Z, Han C. Synthesis of Keggin-type lacunary 11-tungstophosphates encapsulated into mesoporous silica pillared in clay interlayer galleries and their catalytic performance in oxidative desulfurization. Catal Commun. 2014;46:156.

    Article  CAS  Google Scholar 

  11. Gómez-Paricio A, Santiago-Portillo A, Navalón S, Concepción P, Alvaro M, Garcia H. MIL-101 promotes the efficient aerobic oxidative desulfurization of dibenzothiophenes. Green Chem. 2016;18:508.

    Article  Google Scholar 

  12. Zhang M, Zhu W, Li H, Xun S, Ding W, Liu J, Zhao Z, Wang Q. One-pot synthesis, characterization and desulfurization of functional mesoporous W-MCM-41 from POM-based ionic liquids. Chem Eng J. 2014;243:386.

    Article  CAS  Google Scholar 

  13. Rezvani MA, Shojaie AF, Loghmani MH. Synthesis and characterization of novel nanocomposite, anatase sandwich type polyoxometalate, as a reusable and green nano catalyst in oxidation desulfurization of simulated gas oil. Catal Commun. 2012;25:36.

    Article  CAS  Google Scholar 

  14. Boscaro P, Cacciaguerra T, Cot D. C, N-doped TiO2 monoliths with hierarchical macro-/mesoporosity for water treatment under visible light. Micropor Mesopor Mat. 2019;280:37.

    Article  CAS  Google Scholar 

  15. Chen H, Wang J, Zhao Y, Zeng QD, Zhou GF, ** ML. Three-dimensionally ordered macro/mesoporous Nb2O5/Nb4N5 heterostructure as sulfur host for high-performance lithium/sulfur batteries. Nanomaterials. 2021;6:1531.

    Article  Google Scholar 

  16. Du Y, Zhou L, Liu Z, Guo ZR, Wang XZ, Lei JH. Designed formation of mesoscopical order of ionic liquid-based meso/macroporous Mo/TiO2 materials for high-performance oxidative desulfurization. Chem Eng J. 2020;387:124056.

    Article  CAS  Google Scholar 

  17. Huang Y, Zhou Z, Qi Y, Li X, Cheng Z, Yuan W. Hierarchically macro-/mesoporous structured Co–Mo–Ni/-Al2O3 catalyst for the hydrodesulfurization of thiophene. Chem Eng J. 2011;172:444.

    Article  CAS  Google Scholar 

  18. Yang P, Zhou S, Yue D, Li JS, Lei JH. Synthesis of ordered meso/macroporous H3PW12O40/SiO2 and its catalytic performance in oxidative desulfurization. RSC Adv. 2016;6:53860.

    Article  CAS  Google Scholar 

  19. Yan X, Mei P, Lei J, Mi Y, **ong L, Guo L. Synthesis and characterization of mesoporous phosphotungstic acid/TiO2 nanocomposite as a novel oxidative desulfurization catalyst. J Mol Catal A. 2009;304:52.

    Article  CAS  Google Scholar 

  20. Estephane G, Lancelot C, Blanchard P, Dufaud V, Chambrey S, Nuns N, Toufaily J, Hamiye T, Lamonier C. W-SBA based materials as efficient catalysts for the ODS of model and real feeds: improvement of their lifetime through active phase encapsulation. Appl Catal A-Gen. 2019;571:42.

    Article  CAS  Google Scholar 

  21. Xun S, Hou C, Li H, He MQ, Ma RL, Zhang M, Zhu WS, Li HM. Synthesis of WO3/mesoporous ZrO2 catalyst as a high-efficiency catalyst for catalytic oxidation of dibenzothiophene in diesel. J Mater Sci. 2018;53(23):15927.

    Article  CAS  Google Scholar 

  22. Witoon T, Chareonpanich M, Limtrakul J. Effect of hierarchical meso-macroporous silica supports on Fischer-Tropsch synthesis using cobalt catalyst. Fuel Process Technol. 2011;92:1498.

    Article  CAS  Google Scholar 

  23. Yang L, Qi Y, Yuan X, Shen J, Kim J. Direct synthesis, characterization and catalytic application of SBA-15 containing heteropolyacid H3PW12O40. J Mol Catal A. 2005;229:199.

    Article  CAS  Google Scholar 

  24. Kozhevnikov IV. Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions. Chem Rev. 1998;98:171.

    Article  CAS  Google Scholar 

  25. Du Y, LN Zhou, Liu ZH, Lei JH. Hierarchical porous HPW/titania–silica material with superior adsorption-catalytic oxidation activity for multi-ring thiophenic culfur compounds. New J Chem. 2020;44:4942.

    Article  Google Scholar 

  26. Collins FM, Lucy AR, Sharp C. Oxidative desulphurisation of oils via hydrogen peroxide and heteropolyanion catalysis. J Mol Catal A. 1997;117:397.

    Article  CAS  Google Scholar 

  27. Zhang J, Wang A, Li X, Ma X. Oxidative desulfurization of dibenzothiophene and diesel over [Bmim]3PMo12O40. J Catal. 2011;279:269.

    Article  CAS  Google Scholar 

  28. Granadeiro CM, Nogueira LS, Julião D, Mirante F, Ananias D, Balula SS, Silva L. Influence of a porous MOF support on the catalytic performance of Eu-polyoxometalate based materials: desulfurization of a model diesel. Catal Sci Technol. 2016;6:1515.

    Article  CAS  Google Scholar 

  29. Yang P, Zhou S, Du Y, Li J, Lei J. Influence of a porous MOF support on the catalytic performance of Eu polyoxometalate based materials: desulfurization of a model diesel. Catal Sci Technol. 2016;6:1515.

    Article  Google Scholar 

  30. Qiu J, Wang G, Zhang Y, Zeng D, Chen Y. Direct synthesis of mesoporous H3PMo12O40/SiO2 and its catalytic performance in oxidative desulfurization of fuel oil. Fuel. 2015;147:195.

    Article  CAS  Google Scholar 

  31. Zheng H, Sun Z, Chen X, Zhao Q, Wang X, Jiang Z. A micro reaction-controlled phase-transfer catalyst for oxidative desulfurization based on polyoxometalate modified silica. Appl Catal A. 2013;467:26.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by National Nature Science Foundation of China (Grant Nos. 52104254, 22008058, and 51901074).

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Author notes

  1. Gao-Chen Yang and Qi-Yun Pan contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Hubei University, Wuhan, 430070, China

    Gao-Chen Yang

  2. Institute for Advanced Materials, Hubei Normal University, Huangshi, 435002, China

    Qi-Yun Pan, Yi-Si Liu, Yue Du & Kai Wang

  3. School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, China

    Peng Yang

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  1. Gao-Chen Yang
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  2. Qi-Yun Pan
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Contributions

G-cY, QP wrote the draft; PY, Y-sL, Q-yP collected the data; YD and KW contributed to conceived the idea of the study. YD and KW revised the paper. All authors contributed to the writing and revisions.

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Correspondence to Yue Du or Kai Wang.

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Yang, GC., Pan, QY., Yang, P. et al. Heteropolyacids supported on hierarchically macro/mesoporous TiO2: efficient catalyst for deep oxidative desulfurization of fuel. Tungsten 4, 28–37 (2022). https://doi.org/10.1007/s42864-021-00125-2

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  • DOI: https://doi.org/10.1007/s42864-021-00125-2

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