Controlled Partial Linker Thermolysis in Metal-Organic Framework UiO-66-NH2 to Give a Single-Site Copper Photocatalyst for the Functionalization of Terminal Alkynes.

Metal-organic frameworks (MOFs) with expanding porosity and tailored pore environment are intriguing towards catalytic application. We report herein the straightforward method of controlled partial linker thermolysis to introduce desirable mesopores in monoligand MOF, which is different from the classical thermolyzing method that starts from mixed-linker MOF. UiO-66-NH2 after partial ligand thermolysis exhibits significant mesoporosity, retained crystal structure, improved charge photogeneration and abundant anchoring sites, which is ideal to explore single-site photocatalysis. Atomically dispersed Cu is then accommodated in the tailored pore. The resulting single-site Cu catalyst exhibits excellent performance to accomplish photocatalytic reactions of alkylation and oxidation coupling for terminal alkynes functionalization. The study highlights the advantage of controlled partial linker thermolysis to synthesize hierarchical MOF to achieve the advanced single-site photocatalysis.