The present article describes the hydrogen production
from an aqueous
medium over amino-functionalized Ti(IV) metal–organic framework
(Ti-MOF-NH2) under visible-light irradiation. Ti-MOF-NH2, 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-NH2 via a
photodeposition process (Pt/Ti-MOF-NH2). The XRD and N2 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-NH2, which is associated with the chromophore in the organic
linker. Ti-MOF-NH2 and Pt/Ti-MOF-NH2 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.
A new class of macrocyclic metal-N(4) complexes [MN(4)](n) (M = Co and Fe) were designed and synthesized based on a triangular ligand. Their unique triangular trinuclear structure provides a high density of active sites and facilitates the reduction of dioxygen via a four-electron pathway. Among them, a [CoN(4)](3)/C catalyst (20 wt %) exhibits high catalytic activity and long-time stability for the oxygen reduction reaction (ORR) in alkaline conditions, superior to the commercial Pt/C catalyst. Such structurally well-defined [MN(4)](n) complexes provide a platform for a new generation of nonprecious metal catalysts (NPMCs) for fuel cell applications.
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