Incorporation of iron hydrogenase active sites into a stable photosensitizing metal-organic framework for enhanced hydrogen production

• Published in: Applied catalysis. B, Environmental Vol. 258; p. 117979
• Main Authors: Wang, Wenjing, Song, Xiao-Wei, Hong, Zixiao, Li, Beibei, Si, Yanan, Ji, Chunqing, Su, Kongzhao, Tan, Yanxi, Ju, Zhanfeng, Huang, Yiyin, Chen, Chang-Neng, Yuan, Daqiang
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 05.12.2019; Elsevier BV
• Subjects: [FeFe]-hydrogenases; Catalysts; Catalytic activity; Chemical reactions; Covalent bonds; Electron transfer; Hydrogen; Hydrogen evolution; Hydrogen production; Hydrogenase; Iron; Ligands; Metal-organic framework; Metal-organic frameworks; Photocatalysis; Photosensitization; Reaction synthesis; Visible-light catalysis; Metal-organic framework; Hydrogen evolution; Visible-light catalysis; [FeFe]-hydrogenases
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2019.117979

[Display omitted] •Constructing a photosensitizable UiO-MOF from mixed functional dicarboxylate ligands.•Integrating a covalently bonded hydrogen evolving catalyst (Complex A) into a highly stable photosensitizable UiO-MOF.•Improving the electron transfer efficiency between the photosensitizer and the Fe2S2 catalytic site.•The photocatalytical mechanism was investigated and well supported by fluorescent spectra and cyclic voltammetry data. We have successfully integrated a covalently bonded hydrogen evolving catalyst (Complex A) into a highly stable photosensitizable UiO-MOF by a facile click reaction synthesis. The UiO-MOF was constructed from mixed functional dicarboxylate ligands, in which a [Ru(bpy)3]2+-derived dicarboxylate ligand (H2L1) acts as a photosensitizer and an azide-modified dicarboxylate ligand (H2L2) allows the catalyst Complex A to be firmly bound to the framework by covalent bonds. The integration of the photosensitizer and catalyst molecules together into the same UiO-MOF decreases the distance between them, and leads to improvement of the electron transfer efficiency between the photosensitizer and the Fe2S2 catalytic site. Reference experiments show that the resultant UiO-MOF-Fe2S2 exhibits exponentially enhanced photocatalytic activity and stability in a visible-light driven hydrogen process. The excellent performance of the UiO-MOF-Fe2S2 indicates that incorporation of the Fe2S2 catalytic center into UiO-MOF is a promising strategy with which to stabilize Fe2S2 catalyst in water and improve the photocatalytic efficiency of hydrogen evolution.