{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T00:59:44Z","timestamp":1760144384746,"version":"build-2065373602"},"reference-count":50,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2024,4,10]],"date-time":"2024-04-10T00:00:00Z","timestamp":1712707200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"CICECO-Aveiro Institute of Materials","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","POIR.04.02.00-00-D001\/20"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","POIR.04.02.00-00-D001\/20"]}]},{"name":"European Union","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","POIR.04.02.00-00-D001\/20"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","POIR.04.02.00-00-D001\/20"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>Ionic polymolybdate compounds (IPOM) possessing the anions [Mo8O26]4\u2212 and [Mo3O10]2\u2212, and cyclohexylammonium (Cy6N) or anilinium (Anil) as organic cations, namely cyclohexylammonium \u03b2-octamolybdate dihydrate (1), cyclohexylammonium trimolybdate hydrate (2), anilinium \u03b2-octamolybdate dihydrate (3), anilinium trimolybdate tetrahydrate (4) and anilinium trimolybdate dihydrate (5), were synthesized via simple, eco-friendly one-pot routes. New crystal structures of 1, 2 and 5 were discovered. IPOM compounds with different structural dimensionality, density and ratio of the number of terminal oxo groups\/molybdenum atoms (n(oxo)\/Mo) were developed. The IPOM compounds promoted the epoxidation of biobased olefins such as the fatty acid methyl esters methyl oleate and methyl linoleate with tert-butylhydroperoxide as oxidant, leading to conversions of at least 81% at 4 h, 70 \u00b0C and the corresponding epoxides. The reaction scope of applications for the IPOM catalysts covered cyclooctane oxidation.<\/jats:p>","DOI":"10.3390\/catal14040251","type":"journal-article","created":{"date-parts":[[2024,4,10]],"date-time":"2024-04-10T10:55:28Z","timestamp":1712746528000},"page":"251","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Versatile Polyoxometalates of Different Structural Dimensionalities for Liquid Phase Catalytic Oxidation"],"prefix":"10.3390","volume":"14","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1932-4975","authenticated-orcid":false,"given":"Patr\u00edcia","family":"Neves","sequence":"first","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"given":"Guilherme","family":"Sim\u00f5es","sequence":"additional","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"given":"Bogna D.","family":"Napruszewska","sequence":"additional","affiliation":[{"name":"Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krak\u00f3w, Poland"}]},{"given":"Katarzyna","family":"Pamin","sequence":"additional","affiliation":[{"name":"Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krak\u00f3w, Poland"}]},{"given":"Pawe\u0142","family":"Serda","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krak\u00f3w, Poland"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7083-1860","authenticated-orcid":false,"given":"Wieslaw","family":"\u0141asocha","sequence":"additional","affiliation":[{"name":"Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krak\u00f3w, Poland"},{"name":"Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krak\u00f3w, Poland"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3495-2133","authenticated-orcid":false,"given":"Anabela A.","family":"Valente","sequence":"additional","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2024,4,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"634","DOI":"10.1002\/pola.21201","article-title":"Synthesis and Characterization of Polyurethanes from Epoxidized Methyl Oleate Based Polyether Polyols as Renewable Resources","volume":"44","author":"Lligadas","year":"2006","journal-title":"J. Polym. Sci. A Polym. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Musik, M., Janus, E., Pe\u0142ech, R., and Sa\u0142aci\u0144ski, \u0141. (2021). Effective Epoxidation of Fatty Acid Methyl Esters with Hydrogen Peroxide by the Catalytic System H3PW12O40\/Quaternary Phosphonium Salts. Catalysts, 11.","DOI":"10.3390\/catal11091058"},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"H\u00e1jek, M., H\u00e1jek, T., Koci\u00e1n, D., Frolich, K., and Peller, A. (2023). Epoxidation of Methyl Esters as Valuable Biomolecules: Monitoring of Reaction. Molecules, 28.","DOI":"10.3390\/molecules28062819"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"469","DOI":"10.1039\/b614100e","article-title":"Oxidation, Friction Reducing, and Low Temperature Properties of Epoxy Fatty Acid Methyl Esters","volume":"9","author":"Sharma","year":"2007","journal-title":"Green Chem."},{"key":"ref_5","first-page":"1292","article-title":"Effects of Partial Hydrogenation, Epoxidation, and Hydroxylation on the Fuel Properties of Fatty Acid Methyl Esters","volume":"90","author":"Wadumesthrige","year":"2009","journal-title":"Eur. J. Lipid Sci. Technol."},{"key":"ref_6","unstructured":"(2023, December 21). Available online: https:\/\/polymer-additives.specialchem.com\/selectors\/tr-vikoflex."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1900100","DOI":"10.1002\/ejlt.201900100","article-title":"Comparison of Different Possible Technologies for Epoxidation of Cynara Cardunculus Seed Oil","volume":"122","author":"Turco","year":"2020","journal-title":"Eur. J. Lipid Sci. Technol."},{"key":"ref_8","unstructured":"(2023, December 21). Available online: https:\/\/www.fortunebusinessinsights.com\/epoxidized-soybean-oil-market-104343."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Meng, Y., Taddeo, F., Aguilera, A.F., Cai, X., Russo, V., Tolvanen, P., and Leveneur, S. (2021). The Lord of the Chemical Rings: Catalytic Synthesis of Important Industrial Epoxide Compounds. Catalysts, 11.","DOI":"10.3390\/catal11070765"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"7426","DOI":"10.1021\/acssuschemeng.2c00617","article-title":"Opportunities and Emerging Challenges of the Heterogeneous Metal-Based Catalysts for Vegetable Oil Epoxidation","volume":"10","author":"Yan","year":"2022","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"e202200783","DOI":"10.1002\/ejic.202200783","article-title":"Catalysis for Oleochemical Platforms","volume":"26","author":"Cucciolito","year":"2023","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"176","DOI":"10.1134\/S2070050420030095","article-title":"Prospects for the Development of Catalysts for the Oxidation Processes of Advanced Propylene Processing","volume":"12","author":"Pinaeva","year":"2020","journal-title":"Catal. Ind."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Shen, Y., Jiang, P., Wai, P.T., Gu, Q., and Zhang, W. (2019). Recent Progress in Application of Molybdenum-Based Catalysts for Epoxidation of Alkenes. Catalysts, 9.","DOI":"10.3390\/catal9010031"},{"key":"ref_14","first-page":"3289","article-title":"Transition-Metal Complexes for Liquid-Phase Catalytic Oxidation: Some Aspects of Industrial Reactions and of Emerging Technologies","volume":"3","year":"2003","journal-title":"J. Chem. Soc. Dalton Trans."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Pisk, J., and Agustin, D. (2022). Molybdenum, Vanadium, and Tungsten-Based Catalysts for Sustainable (Ep)Oxidation. Molecules, 27.","DOI":"10.3390\/molecules27186011"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"3500","DOI":"10.1021\/ic0255510","article-title":"Electronic Structure of the \u03b1 and \u03b2 Isomers of [Mo8O26]4\u2212","volume":"41","author":"Bridgeman","year":"2002","journal-title":"Inorg. Chem."},{"key":"ref_17","unstructured":"(2023, December 21). Available online: https:\/\/colapret.cm.utexas.edu\/courses\/320M%20Syllabus_Sp2019.pdf."},{"key":"ref_18","unstructured":"(2023, December 21). Available online: https:\/\/openstax.org\/books\/organic-chemistry\/pages\/24-4-basicity-of-arylamines?query=cyclohexylammonium."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1016\/j.apcata.2018.07.001","article-title":"Ionic Ammonium and Anilinium Based Polymolybdate Hybrid Catalysts for Olefin Epoxidation","volume":"564","author":"Neves","year":"2018","journal-title":"Appl. Catal. A Gen."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1186","DOI":"10.1039\/C4GC01411A","article-title":"Olefin Epoxidation with Hydrogen Peroxide Using Octamolybdate-Based Self-Separating Catalysts","volume":"17","author":"Zhou","year":"2015","journal-title":"Green Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"10325","DOI":"10.1021\/acs.inorgchem.7b01143","article-title":"Engineering Multifunctionality in Hybrid Polyoxometalates: Aromatic Sulfonium Octamolybdates as Excellent Photochromic Materials and Self-Separating Catalysts for Epoxidation","volume":"56","author":"Kumar","year":"2017","journal-title":"Inorg. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"841","DOI":"10.1007\/s10562-016-1702-0","article-title":"Catalytic Application of an Octamolybdate Salt (H3biim)4[\u03b2-Mo8O26] in Olefin Epoxidation (H2biim = 2,2\u2032-Biimidazole)","volume":"146","author":"Neves","year":"2016","journal-title":"Catal. Lett."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1218","DOI":"10.1007\/s10562-012-0890-5","article-title":"Molybdenum(II) Diiodo-Tricarbonyl Complexes Containing Nitrogen Donor Ligands as Catalyst Precursors for the Epoxidation of Methyl Oleate","volume":"142","author":"Gamelas","year":"2012","journal-title":"Catal. Lett."},{"key":"ref_24","unstructured":"(2023, December 21). Available online: https:\/\/www.masterorganicchemistry.com\/2017\/04\/18\/basicity-of-amines-and-pkah\/."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"698","DOI":"10.1016\/j.molstruc.2017.03.111","article-title":"Stabilization of \u03b2-Octamolybdate with Large Counterions","volume":"1141","author":"Kama","year":"2017","journal-title":"J. Mol. Struct."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"998","DOI":"10.1007\/s10562-016-1716-7","article-title":"Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen","volume":"146","author":"Szyman","year":"2016","journal-title":"Catal. Lett."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1383","DOI":"10.1039\/b515484g","article-title":"Olefin Epoxidation with Tert-Butyl Hydroperoxide Catalyzed by MoO2X2L Complexes: A DFT Mechanistic Study","volume":"11","author":"Veiros","year":"2006","journal-title":"Dalton Trans."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2147","DOI":"10.1002\/chem.200902873","article-title":"A Computational Study of the Olefin Epoxidation Mechanism Catalyzed by Cyclopentadienyloxidomolybdenum(VI) Complexes","volume":"16","author":"Poli","year":"2010","journal-title":"Chem. Eur. J."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1716","DOI":"10.1002\/ejic.200400852","article-title":"Kinetics of Cyclooctene Epoxidation with tert-Butyl Hydroperoxide in the Presence of [MoO2X2L]-Type Catalysts (L = Bidentate Lewis Base)","volume":"2005","author":"Valerie","year":"2005","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_30","first-page":"2370","article-title":"Octahedral Bipyridine and Bipyrimidine Dioxomolybdenum (VI) Complexes","volume":"8","author":"Prazeres","year":"2002","journal-title":"Chem. Eur. J."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"689","DOI":"10.1007\/s10953-008-9262-6","article-title":"Acidity of Several Anilinium Derivatives in Pure Tetrahydrofuran","volume":"37","author":"Garrido","year":"2008","journal-title":"J. Solut. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"120129","DOI":"10.1016\/j.ica.2020.120129","article-title":"Silicododecamolybdate\/Pyridinium-Tetrazole Hybrid Molecular Salt as a Catalyst for the Epoxidation of Bio-Derived Olefins","volume":"516","author":"Neves","year":"2021","journal-title":"Inorg. Chim. Acta A"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"114273","DOI":"10.1016\/j.cattod.2023.114273","article-title":"Molybdenum(VI) Complexes with Ligands Derived from 5-(2-Pyridyl)-2H-Tetrazole as Catalysts for the Epoxidation of Olefins","volume":"423","author":"Nunes","year":"2023","journal-title":"Catal. Today"},{"key":"ref_34","first-page":"269","article-title":"Catalytic Epoxidation of Methyl Linoleate-Cyclisation Products of Epoxyacid Esters","volume":"97","author":"Herman","year":"1995","journal-title":"Fat. Sci. Technol."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"113282","DOI":"10.1016\/j.mcat.2023.113282","article-title":"Catalytic Hydrolysis of Epoxyfatty Esters with Solid Sulfonic Acids","volume":"547","author":"Dorado","year":"2023","journal-title":"Mol. Catal."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"901","DOI":"10.1007\/s11746-003-0792-z","article-title":"Hydrolysis of Mono- and Diepoxyoctadecanoates by Alumina","volume":"80","author":"Piazza","year":"2003","journal-title":"J. Am. Oil Chem. Soc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2117","DOI":"10.1007\/s11746-014-2560-9","article-title":"Formation of Furan Fatty Alkyl Esters from Their Bis-Epoxide Fatty Esters","volume":"91","author":"Bantchev","year":"2014","journal-title":"J. Am. Oil Chem. Soc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1291","DOI":"10.1002\/aocs.12279","article-title":"Synthesis and Evaluation of Soy Fatty Acid Ester Estolides as Bioplasticizers in Poly(Vinyl Chloride)","volume":"96","author":"Stolp","year":"2019","journal-title":"J. Am. Oil Chem. Soc."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"261","DOI":"10.1016\/j.tet.2006.08.105","article-title":"Recent Advances in the Stereoselective Synthesis of Tetrahydrofurans","volume":"63","author":"Wolfe","year":"2007","journal-title":"Tetrahedron"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1021\/jo971147k","article-title":"Acid-Mediated Conversion of Methylene-Interrupted Bisepoxides to Tetrahydrofurans: A Biomimetic Transformation","volume":"63","author":"Capon","year":"1998","journal-title":"J. Org. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"111084","DOI":"10.1016\/j.mcat.2020.111084","article-title":"Oxidative Cyclization of Linoleic Acid in the Presence of Hydrogen Peroxide and Phosphotungstic Acid","volume":"493","author":"Araji","year":"2020","journal-title":"Mol. Catal."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"134292","DOI":"10.1016\/j.molstruc.2022.134292","article-title":"Synthesis, Crystal Structure and Selected Properties of Three New 4-Propylanilinium Polyoxomolybdates","volume":"1273","author":"Oszajca","year":"2023","journal-title":"J. Mol. Struct."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1231","DOI":"10.1107\/S0021889813013113","article-title":"EXPO2013: A Kit of Tools for Phasing Crystal Structures from Powder Data","volume":"46","author":"Altomare","year":"2013","journal-title":"J. Appl. Crystallogr."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"734","DOI":"10.1107\/S0021889802015236","article-title":"FOX, \u2018free Objects for Crystallography\u2019: A Modular Approach to Ab Initio Structure Determination from Powder Diffraction","volume":"35","year":"2002","journal-title":"J. Appl. Crystallogr."},{"key":"ref_45","unstructured":"Petricek, V., Dusek, M., and Palatinus, L. (2006). The Crystallographic Computing System, Institute of Physics."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1107\/S0108767307043930","article-title":"A Short History of SHELX","volume":"64","author":"Sheldrick","year":"2008","journal-title":"Acta Crystallogr. A"},{"key":"ref_47","unstructured":"Brandenburg, K. (2023, January 04). Diamond Version 3.2g, Crystal Impact GbR, Bonn, Germany, 1997\u20132001. Available online: http:\/\/www.crystalimpact.com\/diamond."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1107\/S002188980600731X","article-title":"Mercury: Visualization and Analysis of Crystal Structures","volume":"39","author":"Macrae","year":"2006","journal-title":"J. Appl. Crystallogr."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"713","DOI":"10.1007\/s10562-019-02935-z","article-title":"Simple Hybrids Based on Mo or W Oxides and Diamines: Structure Determination and Catalytic Properties","volume":"150","author":"Neves","year":"2020","journal-title":"Catal. Lett."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"167","DOI":"10.1007\/s10562-008-9663-6","article-title":"Electrostatic Self-Assembly of Polyoxometalates on Chitosan as Catalysts of Oxidation of Cyclic Hydrocarbons","volume":"127","author":"Pamin","year":"2009","journal-title":"Catal. Lett."}],"container-title":["Catalysts"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4344\/14\/4\/251\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T14:25:43Z","timestamp":1760106343000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4344\/14\/4\/251"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,4,10]]},"references-count":50,"journal-issue":{"issue":"4","published-online":{"date-parts":[[2024,4]]}},"alternative-id":["catal14040251"],"URL":"https:\/\/doi.org\/10.3390\/catal14040251","relation":{},"ISSN":["2073-4344"],"issn-type":[{"type":"electronic","value":"2073-4344"}],"subject":[],"published":{"date-parts":[[2024,4,10]]}}}