Three-in-one: achieving a robust and effective hydrogen-evolving hybrid material by integrating polyoxometalate, a photo-responsive metal–organic framework, and in situ generated Pt nanoparticles

Abstract

A Wells–Dawson-type polyoxometalate ([P₂W₁₈O₆₂]⁶⁻, denoted as P₂W₁₈), a photo-responsive Zr-based metal–organic framework (MOF, NU-1000), and in situ generated Pt nanoparticles were successfully integrated into a three-in-one hybrid material (P₂W₁₈@NU-1000-Pt) using a facile impregnation and subsequent photoreduction method. The resulting three-in-one hybrid material exhibits effective and robust activity towards photocatalytic hydrogen production in a water-compatible system under Xe-lamp irradiation, achieving a hydrogen production of 35 100 μmol g⁻¹ and a turnover number (TON) of 5484 versus moles of Pt after 5 days of reaction. The post-catalysis three-in-one hybrid composite could be easily recycled at least 5 times without declining catalytic activity. Moreover, such a water-compatible photocatalytic system also reveals potential practical applications for catalyzing hydrogen production under natural sunlight irradiation. A possible photocatalytic mechanism was elucidated based on various photophysical and spectroscopic analyses, proving the importance of synergistic cooperation of the NU-1000 MOF, the P₂W₁₈ cluster, and in situ generated Pt NPs in such a three-in-one P₂W₁₈@NU-1000-Pt hybrid photocatalyst.