Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) Metal–Organic Framework

The present article describes the hydrogen production from an aqueous medium over amino-functionalized Ti­(IV) metal–organic framework (Ti-MOF-NH<sub>2</sub>) under visible-light irradiation. Ti-MOF-NH<sub>2</sub>, which employs 2-amino-benzenedicarboxylic acid as an organic linker, has been synthesized by a facile solvothermal method. Pt nanoparticles as cocatalysts are then deposited onto Ti-MOF-NH<sub>2</sub> via a photodeposition process (Pt/Ti-MOF-NH<sub>2</sub>). The XRD and N<sub>2</sub> adsorption measurements reveal the successful formation of a MOF framework structure and its remaining structure after deposition of Pt nanoparticles. The observable visible-light absorption up to ∼500 nm can be seen in the DRUV–vis spectrum of Ti-MOF-NH<sub>2</sub>, which is associated with the chromophore in the organic linker. Ti-MOF-NH<sub>2</sub> and Pt/Ti-MOF-NH<sub>2</sub> exhibit efficient photocatalytic activities for hydrogen production from an aqueous solution containing triethanolamine as a sacrificial electron donor under visible-light irradiation. The longest wavelength available for the reaction is 500 nm. The results obtained from wavelength-dependent photocatalytic tests and photocurrent measurements as well as in situ ESR measurements demonstrate that the reaction proceeds through the light absorption by its organic linker and the following electron transfer to the catalytically active titanium-oxo cluster.