Catalyst accessibility to chemical reductants in metal–organic frameworks. Issue 22 (6th March 2017)

• Record Type: Journal Article
• Authors: Roy, Souvik; Pascanu, Vlad; Pullen, Sonja; González Miera, Greco; Martín-Matute, Belén; Ott, Sascha
• Is Part Of: Chemical communications. Volume 53:Issue 22(2017)
• Page Start: 3257
• Page End: 3260
• Publication Date: 2017-03-06
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c7cc00022g
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : This study of catalyst accessibility inside metal–organic frameworks demonstrates that pore dimensions, catalyst loadings, concentration of reductant, and reaction times all influence the proportion of catalysts within MOFs that engage in redox chemistry. Abstract : A molecular H2 -evolving catalyst, [Fe2 (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.