{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,14]],"date-time":"2026-02-14T02:22:06Z","timestamp":1771035726865,"version":"3.50.1"},"reference-count":44,"publisher":"MDPI AG","issue":"23","license":[{"start":{"date-parts":[[2020,11,24]],"date-time":"2020-11-24T00:00:00Z","timestamp":1606176000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A peroxotungstate composite comprising the chromium terephthalate metal\u2013organic framework MIL-101(Cr) and the Venturello peroxotungstate [PO4{WO(O2)2}4]3\u2212 (PW4) has been prepared by the impregnation method. The PW4@MIL-101(Cr) composite presents high catalytic efficiency for oxidative desulfurization of a multicomponent model diesel containing the most refractory sulfur compounds present in real fuels (2000 ppm of total S). The catalytic performance of this heterogeneous catalyst is similar to the corresponding homogeneous PW4 active center. Desulfurization efficiency of 99.7% was achieved after only 40 min at 70 \u00b0C using H2O2 as an oxidant and an ionic liquid as an extraction solvent ([BMIM]PF6, 2:1 model diesel\/[BMIM]PF6). High recycling and reusing capacity was also found for PW4@MIL-101(Cr), maintaining its activity for consecutive oxidative desulfurization cycles. A comparison of the catalytic performance of this peroxotungstate composite with others previously reported tungstate@MIL-101(Cr) catalysts indicates that the presence of active oxygen atoms from the peroxo groups promotes a higher oxidative catalytic efficiency in a shorter reaction time.<\/jats:p>","DOI":"10.3390\/molecules25235494","type":"journal-article","created":{"date-parts":[[2020,11,24]],"date-time":"2020-11-24T09:06:28Z","timestamp":1606208788000},"page":"5494","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: Peroxotungstate@Metal\u2013Organic Framework"],"prefix":"10.3390","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6247-6870","authenticated-orcid":false,"given":"Yan","family":"Gao","sequence":"first","affiliation":[{"name":"REQUIMTE\/LAQV &amp; Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"},{"name":"Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry &amp; Material Science, Northwest University, Xi\u2019an 710127, Shanxi, China"}]},{"given":"F\u00e1tima","family":"Mirante","sequence":"additional","affiliation":[{"name":"REQUIMTE\/LAQV &amp; Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"}]},{"given":"Baltazar","family":"de Castro","sequence":"additional","affiliation":[{"name":"REQUIMTE\/LAQV &amp; Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"}]},{"given":"Jianshe","family":"Zhao","sequence":"additional","affiliation":[{"name":"Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry &amp; Material Science, Northwest University, Xi\u2019an 710127, Shanxi, China"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9229-1412","authenticated-orcid":false,"given":"Lu\u00eds","family":"Cunha-Silva","sequence":"additional","affiliation":[{"name":"REQUIMTE\/LAQV &amp; Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8984-0473","authenticated-orcid":false,"given":"Salete S.","family":"Balula","sequence":"additional","affiliation":[{"name":"REQUIMTE\/LAQV &amp; Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2020,11,24]]},"reference":[{"key":"ref_1","first-page":"22","article-title":"A review on fuels used for marine diesel engines","volume":"41","author":"Hoang","year":"2018","journal-title":"J. Mech. Eng. Res. Dev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"400","DOI":"10.1002\/cjoc.200790077","article-title":"Sulfur-Selective Desulfurization of Dibenzothiophene and Diesel Oil by Newly Isolated Rhodococcus erythropolisNCC-1","volume":"25","author":"Li","year":"2007","journal-title":"Chin. J. Chem."},{"key":"ref_3","unstructured":"Dnv, G., Safer, S., and Greener, D. (2018). Compliance options and implications for shipping\u2013focus on scrubbers. Global Sulphur Cap 2020, DNV-GL. Extended and Updated in 2018."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"185","DOI":"10.1016\/j.trd.2017.03.010","article-title":"The implications of the new sulphur limits on the European Ro-Ro sector","volume":"52","author":"Zis","year":"2017","journal-title":"Transp. Res. Part D Transp. Environ."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1016\/S0926-3373(02)00212-6","article-title":"New design approaches to ultra-clean diesel fuels by deep desulfurization and deep dearomatization","volume":"41","author":"Song","year":"2003","journal-title":"Appl. Catal. B Environ."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"118845","DOI":"10.1016\/j.apcatb.2020.118845","article-title":"Photocatalytic oxidative desulfurization and denitrogenation for fuels in ambient air over Ti3C2\/g-C3N4 composites under visible light irradiation","volume":"269","author":"Li","year":"2020","journal-title":"Appl. Catal. B Environ."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3454","DOI":"10.1021\/acs.nanolett.8b00472","article-title":"Engineering Ni\u2013Mo\u2013S Nanoparticles for Hydrodesulfurization","volume":"18","author":"Bodin","year":"2018","journal-title":"Nano Lett."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"312","DOI":"10.1016\/j.molliq.2018.11.051","article-title":"Deep eutectic solvents for extraction-desulphurization: A review","volume":"275","author":"Chandran","year":"2019","journal-title":"J. Mol. Liq."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"865","DOI":"10.1002\/cjce.23064","article-title":"Competitive reactive adsorption desulphurization of dibenzothiophene and hydrogenation of naphthalene over Ni\/ZnO","volume":"96","author":"Huang","year":"2018","journal-title":"Can. J. Chem. Eng."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"762","DOI":"10.1016\/j.promfg.2019.07.013","article-title":"A review of the desulphurization methods used for pyrolysis oil","volume":"35","author":"Serefentse","year":"2019","journal-title":"Procedia Manuf."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"759","DOI":"10.1039\/C1RA00309G","article-title":"An evaluation of desulfurization technologies for sulfur removal from liquid fuels","volume":"2","year":"2012","journal-title":"RSC Adv."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"590","DOI":"10.1016\/j.fuel.2014.09.083","article-title":"Temperature-responsive ionic liquid extraction and separation of the aromatic sulfur compounds","volume":"140","author":"Jiang","year":"2015","journal-title":"Fuel"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"607","DOI":"10.1016\/S0016-2361(02)00324-1","article-title":"Science and technology of novel processes for deep desulfurization of oil refinery streams: A review","volume":"82","author":"Babich","year":"2003","journal-title":"Fuel"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"8423","DOI":"10.1021\/acs.energyfuels.9b01950","article-title":"Studies on the selection of a catalyst\u2013oxidant system for the energy-efficient desulfurization and denitrogenation of fuel oil at mild operating conditions","volume":"33","author":"Subhan","year":"2019","journal-title":"Energy Fuels"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"616","DOI":"10.1016\/j.fuel.2018.11.095","article-title":"Deep oxidative desulfurization of diesel fuels using homogeneous and SBA-15-supported peroxophosphotungstate catalysts","volume":"241","author":"Mirante","year":"2019","journal-title":"Fuel"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"93","DOI":"10.1016\/j.apcata.2017.02.021","article-title":"Efficient eco-sustainable ionic liquid-polyoxometalate desulfurization processes for model and real diesel","volume":"537","author":"Ribeiro","year":"2017","journal-title":"Appl. Catal. A Gen."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1016\/j.fuel.2017.06.027","article-title":"Designation of choline functionalized polyoxometalates as highly active catalysts in aerobic desulfurization on a combined oxidation and extraction procedure","volume":"207","author":"Yu","year":"2017","journal-title":"Fuel"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1515","DOI":"10.1039\/C5CY01110H","article-title":"Influence of a porous MOF support on the catalytic performance of Eu-polyoxometalate based materials: Desulfurization of a model diesel","volume":"6","author":"Granadeiro","year":"2016","journal-title":"Catal. Sci. Technol."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.catcom.2017.10.006","article-title":"Efficient heterogeneous polyoxometalate-hybrid catalysts for the oxidative desulfurization of fuels","volume":"104","author":"Mirante","year":"2018","journal-title":"Catal. Commun."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"118089","DOI":"10.1016\/j.apcatb.2019.118089","article-title":"Construction of biomimetic catalysis system coupling polyoxometalates with deep eutectic solvents for selective aerobic oxidation desulfurization","volume":"259","author":"Chi","year":"2019","journal-title":"Appl. Catal. B Environ."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"268","DOI":"10.1016\/j.fuel.2015.10.095","article-title":"Catalytic oxidative\/extractive desulfurization of model and untreated diesel using hybrid based zinc-substituted polyoxometalates","volume":"166","author":"Ribeiro","year":"2016","journal-title":"Fuel"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4110","DOI":"10.1021\/acssuschemeng.7b00087","article-title":"Extraction coupled oxidative desulfurization of fuels to sulfate and water-soluble sulfur compounds using polyoxometalate catalysts and molecular oxygen","volume":"5","author":"Bertleff","year":"2017","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"531","DOI":"10.1016\/j.catcom.2006.02.020","article-title":"Solvent-free oxidation of alcohols catalyzed by an efficient and reusable heteropolyphosphatotungstate","volume":"8","author":"Zhang","year":"2007","journal-title":"Catal. Commun."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1016\/j.molcata.2008.04.004","article-title":"Secondary alcohols oxidation with hydrogen peroxide catalyzed by [n-C16H33N(CH3)3]3PW12O40: Transform-and-retransform process between catalytic precursor and catalytic activity species","volume":"289","author":"Zhang","year":"2008","journal-title":"J. Mol. Catal. A Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"2794","DOI":"10.1007\/s10562-019-02761-3","article-title":"Synthesis of Convertible {PO4[WO3\u21c6(O)2(O2)]4}-DMA16 in SBA-15 Nanochannels and Its Catalytic Oxidation Activity","volume":"149","author":"Jin","year":"2019","journal-title":"Catal. Lett."},{"key":"ref_26","first-page":"1","article-title":"Venturello anion immobilized on the surface of porous activated carbon as heterogeneous catalyst for the epoxidation of olefins","volume":"130","author":"Alavijeh","year":"2020","journal-title":"React. Kinet. Mech. Catal."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1205","DOI":"10.1016\/S1872-2067(15)60897-X","article-title":"Oxidative desulfurization of dibenzothiophene catalyzed by peroxotungstate on functionalized MCM-41 materials using hydrogen peroxide as oxidant","volume":"36","author":"Xie","year":"2015","journal-title":"Chin. J. Catal."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1016\/j.apcata.2013.06.026","article-title":"A micro reaction-controlled phase-transfer catalyst for oxidative desulfurization based on polyoxometalate modified silica","volume":"467","author":"Zheng","year":"2013","journal-title":"Appl. Catal. A Gen."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"70","DOI":"10.1016\/j.fuproc.2012.07.003","article-title":"Catalytic kinetics of oxidative desulfurization with surfactant-type polyoxometalate-based ionic liquids","volume":"106","author":"Zhu","year":"2013","journal-title":"Fuel Process. Technol."},{"key":"ref_30","unstructured":"Tawfik Abdo, S. (2020). Polyoxometalates-Based Nanocatalysts and Their Efficiency for Production of Sulfur-Free Diesel. Nanocomposites for the Desulfurization of Fuels, IGI Global."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"145","DOI":"10.2174\/1877944107666171102141415","article-title":"MIL-101 (Cr) MOF as a Support for Reactive Polyoxometalates (POMs) Clusters. Principles of POMs Encapsulation and Chemistry of POMs Inside MIL-101 Cavities","volume":"7","author":"Canioni","year":"2017","journal-title":"Curr. Inorg. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Sun, J., Abednatanzi, S., Voort, P.V.D., Liu, Y.-Y., and Leus, K. (2020). POM@ MOF Hybrids: Synthesis and Applications. Catalysts, 10.","DOI":"10.3390\/catal10050578"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"11950","DOI":"10.1039\/C4DT01043D","article-title":"Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal\u2013organic frameworks for catalytic oxidative desulfurization","volume":"43","author":"Wang","year":"2014","journal-title":"Dalton Trans."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2040","DOI":"10.1126\/science.1116275","article-title":"A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area","volume":"309","author":"Serre","year":"2005","journal-title":"Science"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"853","DOI":"10.1016\/j.electacta.2012.09.099","article-title":"Insights into the electrochemical behaviour of composite materials: Monovacant polyoxometalates @ porous metal-organic framework","volume":"87","author":"Grazina","year":"2013","journal-title":"Electrochim. Acta"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"316","DOI":"10.1016\/j.apcata.2012.12.039","article-title":"Monovacant polyoxometalates incorporated into MIL-101(Cr): Novel heterogeneous catalysts for liquid phase oxidation","volume":"453","author":"Granadeiro","year":"2013","journal-title":"Appl. Catal. A Gen."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"67","DOI":"10.1007\/s13203-019-0226-0","article-title":"Transition metal-substituted Keggin-type polyoxometalates as catalysts for adipic acid production","volume":"9","author":"Mouanni","year":"2019","journal-title":"Appl. Petrochem. Res."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"329","DOI":"10.1016\/j.jcat.2009.10.002","article-title":"Oxidation of dibenzothiophene to dibenzothiophene-sulfone using silica gel","volume":"268","author":"Castillo","year":"2009","journal-title":"J. Catal."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1416","DOI":"10.1039\/c3cy00853c","article-title":"Oxidative catalytic versatility of a trivacant polyoxotungstate incorporated into MIL-101(Cr)","volume":"4","author":"Granadeiro","year":"2014","journal-title":"Catal. Sci. Technol."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2404","DOI":"10.1039\/c3cy00287j","article-title":"An efficient oxidative desulfurization process using terbium-polyoxometalate@MIL-101(Cr)","volume":"3","author":"Ribeiro","year":"2013","journal-title":"Catal. Sci. Technol."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"30","DOI":"10.1016\/j.inoche.2017.11.008","article-title":"A PTA@MIL-101(Cr)-diatomite composite as catalyst for efficient oxidative desulfurization","volume":"87","author":"Sun","year":"2018","journal-title":"Inorg. Chem. Commun."},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Granadeiro, C.M., Ferreira, P.M.C., Juliao, D., Ribeiro, L.A., Valenca, R., Ribeiro, J.C., Goncalves, I.S., de Castro, B., Pillinger, M., and Cunha-Silva, L. (2018). Efficient Oxidative Desulfurization Processes Using Polyoxomolybdate Based Catalysts. Energies, 11.","DOI":"10.3390\/en11071696"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.fuproc.2014.10.030","article-title":"Desulfurization of model diesel by extraction\/oxidation using a zinc-substituted polyoxometalate as catalyst under homogeneous and heterogeneous (MIL-101 (Cr) encapsulated) conditions","volume":"131","author":"Juliao","year":"2015","journal-title":"Fuel Process. Technol."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"3587","DOI":"10.1021\/jo00250a032","article-title":"Hydrogen peroxide oxidation catalyzed by heteropoly acids combined with cetylpyridinium chloride. Epoxidation of olefins and allylic alcohols, ketonization of alcohols and diols, and oxidative cleavage of 1,2-diols and olefins","volume":"53","author":"Ishii","year":"1988","journal-title":"J. Org. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/23\/5494\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T10:36:33Z","timestamp":1760178993000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/23\/5494"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,11,24]]},"references-count":44,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2020,12]]}},"alternative-id":["molecules25235494"],"URL":"https:\/\/doi.org\/10.3390\/molecules25235494","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,11,24]]}}}