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Catalyst accessibility to chemical reductants in metal–organic frameworks

A molecular H(2)-evolving catalyst, [Fe(2)(cbdt)(CO)(6)] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are forme...

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Detalles Bibliográficos
Autores principales: Roy, Souvik, Pascanu, Vlad, Pullen, Sonja, González Miera, Greco, Martín-Matute, Belén, Ott, Sascha
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5836565/
https://www.ncbi.nlm.nih.gov/pubmed/28261731
http://dx.doi.org/10.1039/c7cc00022g
Descripción
Sumario:A molecular H(2)-evolving catalyst, [Fe(2)(cbdt)(CO)(6)] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that large proportions of the [FeFe] catalysts within the MOF engage in photochemical hydrogen production and the amount of produced hydrogen is proportional to the catalyst loading.