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Selective Dehydrogenation of Formic Acid Catalyzed by Air-Stable Cuboidal PN Molybdenum Sulfide Clusters
dc.contributor.author | Gutiérrez-Blanco, María | |
dc.contributor.author | Stein, Carolin A. M. | |
dc.contributor.author | Alfonso, Carmina | |
dc.contributor.author | Guillamón, Eva | |
dc.contributor.author | Safont Villarreal, Vicent Sixte | |
dc.contributor.author | Sorribes, Iván | |
dc.contributor.author | Junge, Henrik | |
dc.contributor.author | Beller, matthias | |
dc.contributor.author | Llusar, Rosa | |
dc.date.accessioned | 2023-11-08T13:17:55Z | |
dc.date.available | 2023-11-08T13:17:55Z | |
dc.date.issued | 2023-09-13 | |
dc.identifier.citation | GUTIÉRREZ-BLANCO, María, et al. Selective dehydrogenation of formic acid catalyzed by air‐stable cuboidal PN molybdenum sulfide clusters. ChemCatChem, p. e202300740. | ca_CA |
dc.identifier.uri | http://hdl.handle.net/10234/204783 | |
dc.description.abstract | 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. | ca_CA |
dc.description.sponsorShip | Funding for open access charge: CRUE-Universitat Jaume I | |
dc.format.extent | 11 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | Wiley | ca_CA |
dc.rights | © 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH | ca_CA |
dc.rights.uri | http://creativecommons.org/licenses/by-nc/4.0/ | ca_CA |
dc.subject | dehydrogenation | ca_CA |
dc.subject | formic acid | ca_CA |
dc.subject | homogeneous catalysis | ca_CA |
dc.subject | hydrogen | ca_CA |
dc.subject | molybdenum sulfide | ca_CA |
dc.title | Selective Dehydrogenation of Formic Acid Catalyzed by Air-Stable Cuboidal PN Molybdenum Sulfide Clusters | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | https://doi.org/10.1002/cctc.202300740 | |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | ca_CA |
dc.type.version | info:eu-repo/semantics/publishedVersion | ca_CA |
project.funder.name | Spanish Ministerio de Economía y Competitividad | ca_CA |
project.funder.name | Generalitat Valenciana | ca_CA |
project.funder.name | Universitat Jaume I | ca_CA |
project.funder.name | State of Mecklenburg and Western Pomerania | ca_CA |
project.funder.name | European Union | ca_CA |
oaire.awardNumber | PID2019-107006GB-C22 | ca_CA |
oaire.awardNumber | CIAICO/2021/122 | ca_CA |
oaire.awardNumber | UJI-B2021-29 | ca_CA |
oaire.awardNumber | UJI-B2022-56 | ca_CA |
oaire.awardNumber | project“h2cycle” | ca_CA |
oaire.awardNumber | PRE2019-088511 | ca_CA |
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