Engineering Cu/TiO₂@N-Doped C Interfaces Derived from an Atom-Precise Heterometallic Cu^II₄Ti^IV₅ Cluster for Efficient...

Engineering interfaces is an effective method to create efficient photocatalysts by reducing the recombination of photogenerated carriers. Still, there is a lack of proficient strategies to construct suitable interfaces. In this work, we design and synthesize an atom-precise heterometallic Cu^II₄Ti^IV₅ cluster, [Ti₅Cu₄O₆(ba)₁₆]·2CH₃CN (1, Hba = benzoic acid), which is used as a precursor for fabricating efficient photocatalytic interfaces. The cluster has a precise composition and structure with hierarchical bimetal atom distribution and favorable binding properties. The resulting Cu/TiO₂@N-doped C interfaces are obtained via the thermal treatment. Combined Cu/TiO₂ with N-doped C interfaces provide multiple channels for the transmission of photogenerated carriers and effectively reduce the recombination probability of photogenerated charge carriers. Consequently, the novel interface structure exhibits an excellent hydrogen evolution rate via the photocatalytic water splliting. Density functional theory calculations also support high activity of the interfaces toward hydrogen evolution. As a proof-of-concept application, we show that choosing well-defined metal clusters as precursors can offer a valuable method for engineering photocatalytically efficient interfaces.