Utilizing Metal‐Thiocatecholate Functionalized UiO‐66 Framework for Photocatalytic Hydrogen Evolution Reaction. Issue 17 (24th January 2023)

• Record Type: Journal Article
• Authors: Zhong, Hao; Chen, Song; Jiang, Zhixin; Hu, Jieying; Dong, Jiale; Chung, Lai‐Hon; Lin, Qia‐Chun; Ou, Weihui; Yu, Lin; He, Jun
• Is Part Of: Small. Volume 19:Issue 17(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-01-24
• Subjects: metal thiocatecholate -- metal‐organic frameworks -- photocatalytic hydrogen evolution reaction -- post‐synthetic modification; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.202207266
• Languages: English
• ISSNs: 1613-6810

Abstract

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 (H2 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 (TiO2 ) and achieves an HER rate of 12.63 mmol g −1 h −1 (32.3 times that of primitive TiO2 ). This work represents the first example of MOF assembly employing H2 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. Abstract : Thiocatecholates occupying the same side of the struts on the UiO‐66 framework capture Cu ions to construct structurally robust and unambiguous Cu‐thiocatecholato active sites for photocatalytic hydrogen evolution reaction.