Selective Dehydrogenation of Formic Acid Catalyzed by Air-Stable Cuboidal PN Molybdenum Sulfide Clusters
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Otros documentos de la autoría: Gutiérrez-Blanco, María; Stein, Carolin A. M.; Alfonso, Carmina; Guillamón, Eva; Safont Villarreal, Vicent Sixte; Sorribes, Iván; Junge, Henrik; Beller, matthias; Llusar, Rosa
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Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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Título
Selective Dehydrogenation of Formic Acid Catalyzed by Air-Stable Cuboidal PN Molybdenum Sulfide ClustersAutoría
Fecha de publicación
2023-09-13Editor
WileyCita bibliográfica
GUTIÉRREZ-BLANCO, María, et al. Selective dehydrogenation of formic acid catalyzed by air‐stable cuboidal PN molybdenum sulfide clusters. ChemCatChem, p. e202300740.Tipo de documento
info:eu-repo/semantics/articleVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Formic acid is considered as a promising hydrogen storage material in the context of a green hydrogen economy. In this work, we present a series of aminophosphino and imidazolylamino Mo3S4 cuboidal clusters which are ... [+]
Formic acid is considered as a promising hydrogen storage material in the context of a green hydrogen economy. In this work, we present a series of aminophosphino and imidazolylamino Mo3S4 cuboidal clusters which are active and selective for formic acid dehydrogenation (FAD). Best results are obtained with the new [Mo3S4Cl3(ediprp)3](BPh4) (4(BPh4)) (ediprp=(2-(diisopropylphosphino)ethylamine)) cluster, which is prepared through a simple ligand exchange process from the Mo3S4Cl4(PPh3)3(H2O)2 precursor. Under the conditions investigated, complex 4+ showed significantly improved performance (TOF=4048 h−1 and 3743 h−1 at 120 °C in propylene carbonate using N,N-dimethyloctylamine as base after 10 min and 15 min, respectively) compared to the other reported molybdenum compounds. Mechanistic investigations based on stoichiometric and catalytic experiments show that cluster 4+ reacts with formic acid in the presence of a base to form formate substituted species [Mo3S4Cl3-x(OCOH)x(ediprp)3]+ (x=1–3) from which the catalytic cycle starts. Subsequently, formate decarboxylation of the partially substituted [Mo3S4Cl3-x(OCOH)x(ediprp)3]+ (x=1, 2, 3) catalyst through a β-hydride transfer to the metal generates the trinuclear Mo3S4 cluster hydride. Dehydrogenation takes place through protonation by HCOOH to form Mo−H⋅⋅⋅HCOOH dihydrogen adducts, with regeneration of the Mo3S4 formate cluster. This proposal has been validated by DFT calculations. [-]
Entidad financiadora
Spanish Ministerio de Economía y Competitividad | Generalitat Valenciana | Universitat Jaume I | State of Mecklenburg and Western Pomerania | European Union
Código del proyecto o subvención
PID2019-107006GB-C22 | CIAICO/2021/122 | UJI-B2021-29 | UJI-B2022-56 | project“h2cycle” | PRE2019-088511
Derechos de acceso
© 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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