title: Photoactive Metal-Organic Framework and Its Film for Light-Driven Hydrogen Production and Carbon Dioxide Reduction.
abstract: The design of a new photocatalytic system and integrating the essential components in a structurally controlled manner to create artificially photosynthetic systems is high desirable. By incorporating a photoactive triphenylamine moiety to assemble a Gd-based metal-organic framework as a heterogeneous photosensitizer, new artificial systems were constructed for the proton and carbon dioxide reduction under irradiation. The assembled MOFs exhibited a one-dimensional metal-oxygen pillar that was connected together by the depronated TCA(3-) ligands to form a three-dimensional noninterpenetrating porous framework. The combining of proton reduction and/or the carbon dioxide reduction catalysts, i.e., the Fe-Fe hydrogenase active site models and the Ni(Cyclam) complexes, initiated a photoinduced single electron transfer from its excited state to the substrate. The system exhibited an initial TOF of 320 h(-1) of hydrogen per catalyst and an overall quantum yield of about 0.21% and is able to reduce carbon dioxide under irradiation. The deposit of the photoactive Gd-TCA into the film of an α-Al2O3 plate provided a platform for the practical applications through prolonging the lifetime of the artifical system and allowed the easily operated devices being recyclable as a promising photocatalytic system.
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian, 116024, China.
authors.forename: Pengyan
authors.initials: P
authors.lastname: Wu
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian, 116024, China.
authors.forename: Xiangyang
authors.initials: X
authors.lastname: Guo
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian, 116024, China.
authors.forename: Linjuan
authors.initials: L
authors.lastname: Cheng
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian, 116024, China.
authors.forename: Cheng
authors.initials: C
authors.lastname: He
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian, 116024, China.
authors.forename: Jian
authors.initials: J
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian, 116024, China.
authors.forename: Chunying
authors.initials: C
authors.lastname: Duan