Utilizing Metal‐Thiocatecholate Functionalized UiO‐66 Framework for Photocatalytic Hydrogen Evolution Reaction

Abstract Exploiting clean energy is essential for sustainable development and sunlight‐driven photocatalytic water splitting represents one of the most promising approaches toward this goal. Metal‐organic frameworks (MOFs) are competent photocatalysts owing to their tailorable functionality, well‐defined structure, and high porosity. Yet, the introduction of the unambiguous metal‐centered active site into MOFs is still challenging since framework motifs capable of anchoring metal ions firmly are lacking. Herein, the assembly using 1,4‐dicarboxylbenzene‐2,3‐dithiol (H 2 dcbdt ) and Zr‐Oxo clusters to give a thiol‐functionalized UiO‐66 type framework, UiO‐66‐dcbdt, is reported. The thiocatechols on the struts are allowed to capture transition metal (TM) ions to generate UiO‐66‐dcbdt‐M ( M = Fe, Ni, Cu) with unambiguous metal‐thiocatecholate moieties for photocatalytic hydrogen evolution reaction (HER). UiO‐66‐dcbdt‐Cu is found the best catalyst exhibiting an HER rate of 4.18 mmol g −1 h −1 upon irradiation with photosensitizing Ru‐polypyridyl complex. To skip the use of the external sensitizer, UiO‐66‐dcbdt‐Cu is heterojunctioned with titanium dioxide (TiO 2 ) and achieves an HER rate of 12.63 mmol g −1 h −1 (32.3 times that of primitive TiO 2 ). This work represents the first example of MOF assembly employing H 2 dcbdt as the mere linker followed by chelation with TM ions and undoubtedly fuels the rational design of MOF photocatalysts bearing well‐defined active sites.