Visible-light-harvesting basolite-A520 metal organic framework for photocatalytic hydrogen evolution

A heterogeneous photosensitizer Ru@dpdhpzBASF-A520 has been successfully synthesized following an unprecedented strategy based on the incorporation of surface dipyridyl-dihydropyridazine adducts by Diels–Alder reaction on the aluminum fumarate units of the highly porous metal-organic framework (MOF) BASF-A520 and their further coordination to ruthenium metal centers. The characterization of the resulting metal-organic framework, including the ruthenium bipyridine-like photosensitizer moieties attached to its linkers, has been carried out by a wide variety of techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance (13C CP/MAS NMR), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–vis) spectroscopy. The light absorption in the visible region shown by the resulting material, Ru@dpdhpzBASF-A520, has allowed its application as a single-site solid photosensitizer for photochemical reactions of hydrogen evolution in conjunction with Pt nanoparticles as catalyst, EDTA as sacrificial electron donor and MV as electron carrier. A remarkable photocatalytic activity after 72 h was achieved, with a TON of 1157 based on the heterogeneous ruthenium photosensitizer, in aqueous solution at pH 5.0, which confirmed the effective stabilization of the ruthenium dipyridyl-dihydropyridazine adducts on the MOF surface and the efficient electron injection from the photoexcited Ru@dpdhpzBASF-A520 to Pt nanoparticles mediated by MV electron carrier for hydrogen generation from water. [Display omitted] •Fumarate linkers in MOF BASF-520 can be functionalized by a Diels-Alder reaction.•Surface dipyridyl-dihydropyridazine adducts were incorporated onto BASF-A520.•Bipyridine-like ruthenium complexes were formed on MOF linkers.•Ru-complexes-tethered MOF and Pt acted as artificial photosynthesis systems.•High photocatalytic performance was achieved for light-driven hydrogen production.