JACS: Su Chengyong / Shi Jianying research group, Sun Yat sen University, progress in coordination supramolecular self-assembly series: heterogeneous study of molecular based photocatalytic hydrogen production devices

It is an ideal way to transform solar energy into clean chemical energy and to solve the energy crisis and environmental pollution problems faced by human society The research group of Professor Su Chengyong and Associate Professor Shi Jianying, School of chemistry, Sun Yat sen University, early developed a metal organic molecular cage hydrogen production device [PD 6 (rul 3) 8] 28 + (moc-16), which is spatially independent and functionally equivalent, and integrates 8 photosensitive metal organic ruthenium centers and 6 catalytic PD 2 + centers ）The initial hydrogen production rate of 380 μ mol · H-1 and 635 ton (48 h) were obtained (nature communications, 2016, 7:13169) Although metal organic molecular cages improve the hydrogen production performance of molecular based catalysts, the stability under light conditions is still the decisive factor for their further application Recently, based on the coordination and assembly strategy, they have realized the controllable assembly of Au 25 (SG) 18 nanoclusters on the inner and outer surfaces of the main frame of the metal organic zif-8 (advanced materials, 2018, 30, 1704576) Using a similar strategy, they implanted moc-16 into the main body of zif-8, further transformed zif-8 into Zn x (MEIM) x (CO 3) x (czif), and obtained moc-16 @ czif catalyst The catalyst retains the inherent picosecond time scale characteristic of moc-16, and the lifetime of the triplet excited by moc-16 is extended from nanosecond to microsecond due to the support effect In addition, the unique hydrophilicity of czif promotes the transfer of H 2O as a proton source to PD catalytic site, while the addition of BIH sacrificial reagent with free carrier induction ability and reduction ability significantly improves the conductivity of moc-16 @ czif, further promoting the process of photocatalytic electron transfer Finally, the moc-16 @ czif showed a 50 times higher activity (TOF ~ 0.4s-1) than that of homogeneous catalyst, and had a high stability A Structure diagram of moc-16 assembled in zif-8 and its derivative czif; B accumulation of ton and TOF values based on PD catalytic center (visible light irradiation, λ > 420 nm, light intensity: 100 MW / cm 2) (source: J am Chem SOC.) Based on the construction of hydrogen generating devices with multiple photosensitive centers and multiple catalytic centers, the research work further implanted them into the metal organic framework materials to simulate the proton and electron transport and transfer in the natural enzyme catalytic environment While avoiding the poor stability of molecular based catalysts, the hydrogen production performance of photocatalysts is greatly improved, which provides a new idea for the design and construction of artificial photocatalysts Relevant research results were published in Journal of the American Chemical Society (Yucheng Luo, Kunlin Chu, Jianying Shi, * Dongjun Wu, Xudong Wang, Marcel mayor, and  Cheng-Yong Su* Heterogenization of Photochemical Molecular Devices: Embedding a Metal−Organic Cage into a ZIF-8-Derived Matrix To Promote Proton and Electron Transfer J Am Chem Soc   2019 ,  141 , 13057-13065）。 The research work has been supported by the National Natural Science Foundation, the local innovation team of the Pearl River talent program, the Guangdong Provincial Natural Science Fund, the Guangzhou science and technology planning project, and the basic research business fees of the Central University, as well as the strong support of the Key Laboratory of Bioinorganic and synthetic chemistry of Zhongshan University and the Institute of functional materials of Lehn.