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 (H2dcbdt) 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 H2dcbdt as the mere linker followed by chelation with TM ions and undoubtedly fuels the rational design of MOF photocatalysts bearing well‐defined active sites.

GSH-depleting metal–polyphenol-network nanoparticles with dual enzyme activities induce enhanced ferroptosis

“…The surface area of Ce-aMOFs was derived to be ca. 6.69 m 2 g −1 , which was significantly smaller than that reported in the references for normal MOFs 40,41 (Fig. 1C), due to the non-porous feature of aMOFs.…”

Structure–property–performance relationship of vanadium- and manganese-based metal–organic frameworks and their derivatives for energy storage and conversion applications

“…43,44 The easy post-synthesis surface functionalization of organic moieties provided a great chance to design organic-inorganic hybrids with a high porosity used in various energy applications. 45,46 On the other hand, it is possible to transform MOFs into their derivatives, which possess signicant electro-catalytic activities, mainly found in bimetallic MOFs. 47 The optimal structural stability of MOFs for various energy applications can be achieved by modifying their pathways as single MOFs, composites, and derivatives (Fig.…”

Thiol and thioether-based metal–organic frameworks: synthesis, structure, and multifaceted applications

“…Metalloporphyrin (MTFPP) guest also acts as a robust anchor of the photocatalyst, preventing the catalyst's leaching and increasing recyclability. UiO-66-DCBDT-M (M = Fe, Ni, Cu) synthesized by Zhong et al 112 were examined for the photocatalytic H 2 evolution reaction, where UiO-66-DCBDT-Cu shows the best result. The noble metal free heterojunction UiO-66-DCBDT-Cu@TiO 2 shows the HER rate of 12.63 mmol g −1 h −1 (Table 16, entry no.…”

“…6) synthesized from thiol-based ligand L 3 with UiO-66 topology. 112 The presence of the thiol group in the 2,3 position of the ligand allows the incorporation of a transition metal by chelation (M = Fe, Ni or Cu) to synthesize UiO-66-DCBDT-M photocatalyst. Gui et al reported ZrDMTD (Fig.…”