Photocatalytic water splitting is a natural but challenging chemical way of harnessing renewable solar power to generate clean hydrogen energy. Here we report a potential hydrogen-evolving photochemical molecular device based on a self-assembled ruthenium–palladium heterometallic coordination cage, incorporating multiple photo- and catalytic metal centres. The photophysical properties are investigated by absorption/emission spectroscopy, electrochemical measurements and preliminary DFT calculations and the stepwise electron transfer processes from ruthenium-photocentres to catalytic palladium-centres is probed by ultrafast transient absorption spectroscopy. The photocatalytic hydrogen production assessments reveal an initial reaction rate of 380 μmol h−1 and a turnover number of 635 after 48 h. The efficient hydrogen production may derive from the directional electron transfers through multiple channels owing to proper organization of the photo- and catalytic multi-units within the octahedral cage, which may open a new door to design photochemical molecular devices with well-organized metallosupramolecules for homogenous photocatalytic applications.
Thermo-sensitive hydrogels based on different polymers have been broadly used in the pharmaceutical fields. In this review, the state-of-the-art thermo-sensitive hydrogels for drug delivery are elaborated
Phase isomerism is a common and important phenomenon in inorganic materials, but the molecular isomerism of their nanocluster models is still rare. In this work, we report the first pair of isomeric titanium‐oxo clusters. Through combining pentagonal {Ti(Ti5)} building units in corner‐sharing or edge‐sharing forms, the two obtained Ti20‐oxo clusters take vertical and horizontal core configurations, respectively, which are both functionalized by the same organic ligands. More interestingly, the vertical type Ti20‐oxo core contains an identical {Ti8O14} moiety as anatase, making it the first molecular model of anatase TiO2. As a result, the vertical type cluster exhibits better photocatalytic H2 evolution activity, higher photocurrent response and faster charge transfer to external acceptors than its horizontal isomer. Thus, this work provides a cluster isomer method to understand the structure–property relationship of import titanium oxide materials.
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