title: Self-Assembled Framework Enhances Electronic Communication of Ultrasmall-Sized Nanoparticles for Exceptional Solar Hydrogen Evolution.
abstract: Colloidal quantum dots (QDs) have demonstrated great promise in artificial photosynthesis. However, the ultrasmall size hinders its controllable and effective interaction with cocatalysts. To improve the poor interparticle electronic communication between free QD and cocatalyst, we design here a self-assembled architecture of nanoparticles, QDs and Pt nanoparticles, simply jointed together by molecular polyacrylate to greatly enhance the rate and efficiency of interfacial electron transfer (ET). The enhanced interparticle electronic communication is confirmed by femtosecond transient absorption spectroscopy and X-ray transient absorption. Taking advantage of the enhanced interparticle ET with a time scale of ∼65 ps, 5.0 mL of assembled CdSe/CdS QDs/cocatalysts solution produces 94 ± 1.5 mL (4183 ± 67 μmol) of molecular H2in 8 h, giving rise to an internal quantum yield of ∼65% in the first 30 min and a total turnover number of >1.64 × 107per Pt nanoparticle. This study demonstrates that self-assembly is a promising way to improve the sluggish kinetics of the interparticle ET process, which is the key step for advanced H2photosynthesis.
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: Yu-Ji
authors.initials: YJ
authors.lastname: Gao
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: Yang
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, the Chinese Academy of Sciences Beijing 100049, P.R. China.
authors.forename: Fei
authors.initials: F
authors.lastname: Zhan
authors.affiliation: X-ray Sciences Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60430, United States.
authors.forename: Xiao-Yi
authors.initials: XY
authors.lastname: Zhang
authors.affiliation: Synchrotron Soleil, L'Orme des Merisiers St-Aubin, 91192 Gif-sur-Yvette Cedex, France.
authors.forename: Qing-Yu
authors.initials: QY
authors.lastname: Kong
authors.affiliation: Department of Chemistry, Renmin University of China , Beijing 100872, P.R. China.
authors.forename: Ning-Jiu
authors.initials: NJ
authors.lastname: Zhao
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: Qing
authors.initials: Q
authors.lastname: Guo
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: Zhi-Jun
authors.initials: ZJ
authors.lastname: Li
authors.affiliation: Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, the Chinese Academy of Sciences Beijing 100049, P.R. China.
authors.forename: Ye
authors.initials: Y
authors.lastname: Tao
authors.affiliation: Department of Chemistry, Renmin University of China , Beijing 100872, P.R. China.
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Zhang
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.identifier: 0000-0003-0437-1442
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.identifier: 0000-0001-9999-9755
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.identifier: 0000-0002-5561-9922
authors.initials: LZ
authors.lastname: Wu
mesh_terms: D000179:Acrylates; D003102:Colloids / Q000737:chemistry; D004579:Electron Transport; D006859:Hydrogen / Q000737:chemistry*; D053758:Nanoparticles / Q000737:chemistry*; D010316:Particle Size; D010984:Platinum / Q000737:chemistry; D045663:Quantum Dots; D013499:Surface Properties
chemical_list: D000179:Acrylates; D003102:Colloids; D010984:Platinum; D006859:Hydrogen