Pt Nanoparticles@Photoactive Metal–Organic Frameworks: Efficient Hydrogen Evolution via Synergistic Photoexcitation and Electron Injection

Pt nanoparticles of 2–3 nm and 5–6 nm in
diameter
were loaded into stable, porous, and phosphorescent metal–organic
frameworks (MOFs 1 and 2) built from [Ir­(ppy)2(bpy)]+-derived dicarboxylate ligands (L1 and L2) and Zr6(μ3-O)4(μ3-OH)4(carboxylate)12 secondary building
units, via MOF-mediated photoreduction of K2PtCl4. The resulting Pt@MOF assemblies serve as effective photocatalysts
for hydrogen evolution by synergistic photoexcitation of the MOF frameworks
and electron injection into the Pt nanoparticles. Pt@2 gave a turnover number of 7000, approximately five times the value
afforded by the homogeneous control, and could be readily recycled
and reused.

直径为2~3 nm与5~6 nm的铂（Pt）纳米颗粒，通过金属有机框架介导的氯铂酸钾（K₂PtCl₄）光还原反应，被负载于由[Ir(ppy)₂(bpy)]⁺衍生的二羧酸配体（L1与L2）以及Zr₆(μ₃-O)₄(μ₃-OH)₄(羧酸根)₁₂次级结构单元所构筑的稳定、多孔且具有磷光性能的金属有机框架（metal–organic frameworks，MOFs）1和2中。所得的Pt@MOF组装体可作为高效产氢光催化剂，通过金属有机框架骨架的协同光激发以及向铂纳米颗粒的电子注入实现催化过程。其中Pt@2的周转数可达7000，约为均相对照体系的五倍，且可便捷回收复用。