title: Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water.
abstract: Achieving highly efficient hydrogen (H2) evolution via artificial photosynthesis is a great ambition pursued by scientists in recent decades because H2 has high specific enthalpy of combustion and benign combustion product. [FeFe]-Hydrogenase ([FeFe]-H2ase) mimics have been demonstrated to be promising catalysts for H2 photoproduction. However, the efficient photocatalytic H2 generation system, consisting of PAA-g-Fe2S2, CdSe QDs and H2A, suffered from low stability, probably due to the hole accumulation induced photooxidation of CdSe QDs and the subsequent crash of [FeFe]-H2ase mimics. In this work, we take advantage of supramolecular interaction for the first time to construct the secondary coordination sphere of electron donors (HA(-)) to CdSe QDs. The generated secondary coordination sphere helps realize much faster hole removal with a ~30-fold increase, thus leading to higher stability and activity for H2 evolution. The unique photocatalytic H2 evolution system features a great increase of turnover number to 83600, which is the highest one obtained so far for photocatalytic H2 production by using [FeFe]-H2ase mimics as catalysts.
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Min
authors.initials: M
authors.lastname: Wen
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Xu-Bing
authors.initials: XB
authors.lastname: Li
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Jing-Xin
authors.initials: JX
authors.lastname: Jian
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Xu-Zhe
authors.initials: XZ
authors.lastname: Wang
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Hao-Lin
authors.initials: HL
authors.lastname: Wu
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Bin
authors.initials: B
authors.lastname: Chen
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Chen-Ho
authors.initials: CH
authors.lastname: Tung
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Li-Zhu
authors.initials: LZ
authors.lastname: Wu