Post-synthetic exchange (PSE) of UiO-67 frameworks with Ru/Rh half-sandwich units for visible-light-driven H2 evolution and CO2 reduction. Issue 24 (4th June 2018)

• Record Type: Journal Article
• Authors: Liao, Wei-Ming; Zhang, Jian-Hua; Wang, Zheng; Yin, Shao-Yun; Pan, Mei; Wang, Hai-Ping; Su, Cheng-Yong
• Is Part Of: Journal of materials chemistry. Volume 6:Issue 24(2018)
• Page Start: 11337
• Page End: 11345
• Publication Date: 2018-06-04
• Subjects: Materials -- Research -- Periodicals; Chemistry, Analytic -- Periodicals; Environmental sciences -- Research -- Periodicals; 543.0284
• DOI: 10.1039/c8ta02962h
• Languages: English
• ISSNs: 2050-7488

Abstract

Abstract : Four Ru/Rh half-sandwich units are incorporated into UiO-67 frameworks by post-synthetic exchange (PSE) method, and employed for photocatalytic H2 evolution and CO2 reduction. Abstract : Electron-deficient Ru/Rh half-sandwich units are optoelectronical, stereochemical, and redox and catalytically active in nature. Four different species of these units were designed and successfully incorporated into UiO-67 frameworks by post-synthetic exchange (PSE) method and employed for photocatalytic H2 evolution and CO2 reduction. Among them, the PSE-MOF catalysts containing [M–OH2 ] (M = Rh or Ru) groups show higher photocatalytic activity than those with [M–Cl], providing a new example of the exploitation of H2 O molecules as small ancillary ligands for the construction of Ru/Rh half-sandwich units and subsequent incorporation into MOFs as photocatalytic centers. The application of TEOA (triethanolamine) and DMA ( N, N -dimethylaniline) as sacrificial agents leads to different catalytic mechanisms and durations. A long-term hydrogen evolution lasting for 174 h without significant decrease in efficiency was achieved in the RhOH2 @UiO-DMA system, showing the advantage of PSE-MOFs as highly stable photocatalytic platforms with superior self-protective properties.