Cargando…

Enhanced Photochemical Hydrogen Production by a Molecular Diiron Catalyst Incorporated into a Metal–Organic Framework

[Image: see text] A molecular proton reduction catalyst [FeFe](dcbdt)(CO)(6) (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal–organic framework (MOF) by postsynthetic exchan...

Descripción completa

Detalles Bibliográficos
Autores principales: Pullen, Sonja, Fei, Honghan, Orthaber, Andreas, Cohen, Seth M., Ott, Sascha
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2013
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3829681/
https://www.ncbi.nlm.nih.gov/pubmed/24116734
http://dx.doi.org/10.1021/ja407176p
Descripción
Sumario:[Image: see text] A molecular proton reduction catalyst [FeFe](dcbdt)(CO)(6) (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal–organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)(3)](2+) as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)(6) catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1(–) and 1(2–) from undesirable charge recombination with oxidized ascorbate.