Rodenes-Carrillo, M.; Dhaeyere, F.; Martín, S.; Concepción Heydorn, P.; Corma Canós, A.; Sorribes-Terrés, I. (2023). Multifunctional Catalysis of Nanosheet Defective Molybdenum Sulfide Basal Planes for Tandem Reactions Involving Alcohols and Molecular Hydrogen. ACS Sustainable Chemistry & Engineering. 11(33):12265-12279. https://doi.org/10.1021/acssuschemeng.3c01489
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/201120
Título:
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Multifunctional Catalysis of Nanosheet Defective Molybdenum Sulfide Basal Planes for Tandem Reactions Involving Alcohols and Molecular Hydrogen
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Autor:
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Rodenes-Carrillo, Miriam
Dhaeyere, Frederic
Martín, Santiago
Concepción Heydorn, Patricia
Corma Canós, Avelino
Sorribes-Terrés, Iván
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Entidad UPV:
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Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química
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Fecha difusión:
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Resumen:
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[EN] Establishingtandem catalytic synthetic strategies basedon theuse of readily available, stable, and renewable feedstocks is of greatsignificant for the sustainable advancement of chemical-related industries.The key to ...[+]
[EN] Establishingtandem catalytic synthetic strategies basedon theuse of readily available, stable, and renewable feedstocks is of greatsignificant for the sustainable advancement of chemical-related industries.The key to success largely relies on applying efficient multifunctionalcatalysts that allow carrying out one-pot single-step synthesis. Inthis work, we have demonstrated that defect-engineered basal planesof a molybdenum sulfide nanomaterial ({Mo3S4}( n )) offer a multifunctional catalyticplatform for chemical process intensification. By applying this catalyst,besides borrowing hydrogen-type processes, herein exemplified forthe thioetherification of alcohols, we have also disclosed novel andrare coupling reactions requiring hydrogen activation and alcoholdehydrogenation processes in a one-pot fashion. More specifically,oxidized nucleophiles, such as o-dinitroarenes anddinitrophenyl disulfides, are reacted with alcohols in the presenceof H-2 to yield respectively benzimidazoles and benzothiazoles.The uncommon catalytic reactivity of {Mo3S4}( n ) arises from the presence of coordinativelyunsaturated molybdenum and sulfide species, which work as Lewis acidand Lewis basic sites, respectively. As suggested by in situ infrared(IR) spectroscopy investigations, the alcohol dehydrogenation involvesthe participation of both types of active sites while the H-2 dissociation takes place on coordinatively unsaturated sulfide species.
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Palabras clave:
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Molybdenum sulfide
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Defective basal planes
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Alcohols
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Borrowing hydrogen
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Coupling reactions
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Thioethers
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Benzimidazoles
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Benzothiazoles
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Derechos de uso:
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Reserva de todos los derechos
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Fuente:
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ACS Sustainable Chemistry & Engineering. (issn:
2168-0485
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DOI:
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10.1021/acssuschemeng.3c01489
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Editorial:
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American Chemical Society
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Versión del editor:
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https://doi.org/10.1021/acssuschemeng.3c01489
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Código del Proyecto:
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info:eu-repo/grantAgreement/GENERALITAT VALENCIANA//CIDEXG%2F2022%2F22//Molecularly engineering defective basal planes of molybdenum and tungsten chalcogenides-based nanomaterials for energy
conversion and storage/
info:eu-repo/grantAgreement/FEDER//E31_20R/
info:eu-repo/grantAgreement/GVA//SEJI%2F2020%2F018//Subvencions a l Excel· lencia Científica de Juniors Investigadors/
info:eu-repo/grantAgreement/MICINN//CEX2021-001230-S/
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Descripción:
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This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.3c01489.
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Agradecimientos:
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This work has been supported by the Gen-T Plan of the Generalitat Valenciana through the programs "Subvencions a l'Excel.le`ncia Cientifica de Juniors Investigadors" (SEJI/2020/018) and "Investigadors Doctors d'Exel.le`ncia" ...[+]
This work has been supported by the Gen-T Plan of the Generalitat Valenciana through the programs "Subvencions a l'Excel.le`ncia Cientifica de Juniors Investigadors" (SEJI/2020/018) and "Investigadors Doctors d'Exel.le`ncia" (CIDEXG/2022/22). Financial support by the Severo Ochoa Center of Excellence program (CEX2021-001230-S) is gratefully acknowledged. S.M. thanks DGA/fondos FEDER (construyendo Europa desde Aragon) for funding the research group Platon (E31_20R). M.R. acknowledges the Vice-Rectorate for Research, Innovation and Transfer of the Universitat Polite`cnica de Vale`ncia (UPV) for a pre-doctoral fellowship. F.D. thanks the ERASMUS+ program. The authors also thank the Electron Microscopy Service of the UPV for TEM and STEM facilities and Dr. G. Antorrena for technical support in XPS studies.
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Tipo:
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Artículo
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