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- Title
Selective Dehydrogenation of Formic Acid Catalyzed by Air‐Stable Cuboidal PN Molybdenum Sulfide Clusters.
- Authors
Gutiérrez‐Blanco, María; Stein, Carolin A. M.; Alfonso, Carmina; Guillamón, Eva; Safont, Vicent S.; Sorribes, Iván; Junge, Henrik; Beller, Matthias; Llusar, Rosa
- 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.
- Subjects
FORMIC acid; MOLYBDENUM sulfides; DEHYDROGENATION; HYDROGEN economy; MOLYBDENUM compounds; PROPYLENE carbonate
- Publication
ChemCatChem, 2023, Vol 15, Issue 20, p1
- ISSN
1867-3880
- Publication type
Article
- DOI
10.1002/cctc.202300740