Characterization and manipulation of the photosystem Ⅱ-semiconductor interfacial molecular interactions in solar-to-chemical energy conversion  

作　　者：Min He Wangyin Wang Zheyi Liu Wenxiang Zhang Jinan Li Wenming Tian Ye Zhou Yan Jin Fangjun Wang Can Li 

机构地区：[1]CAS Key Laboratory of Separation Sciences for Analytical Chemistry,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian National Laboratory for Clean Energy,Dalian 116023,Liaoning,China [4]State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China

出　　处：《Journal of Energy Chemistry》2022年第7期437-443,I0012,共8页能源化学（英文版）

基　　金：the financial supported by National Key R&D Program of China,China(2019YFE0119300);the National Natural Science Foundation of China,China(32088101,91853101,and 22075280);the Original Innovation Project of CAS,China(ZDBSLY-SLH032);the Excellent Young Scientist Grant of Liaoning Province,China(2019-YQ-07);the grant from DICP(DICPI202007)。

摘　　要：Semi-artificial photosynthesis interfacing catalytic protein machinery with synthetic photocatalysts exhibits great potential in solar-to-chemical energy conversion. However, characterizing and manipulating the molecular integration structure at the biotic-abiotic interface remain a challenging task. Herein,the biointerface molecular integration details of photosystem II(PSII)-semiconductor hybrids, including the PSII orientation, interfacial microdomains, and overall structure modulation, are systematically interrogated by lysine reactivity profiling mass spectrometry. We demonstrate the semiconductor surface biocompatibility is essential to the PSII self-assembly with uniform orientation and electroactive structure.Highly directional localization of PSII onto more hydrophilic Ru/Sr Ti O_(3):Rh surface exhibits less disturbance on PSII structure and electron transfer chain, beneficial to the high water splitting activity.Further, rational modification of hydrophobic Ru_(2)S_(3)/Cd S surface with biocompatible protamine can improve the hybrid O_(2)-evolving activity 83.3%. Our results provide the mechanistic understanding to the structure–activity relationship of PSII-semiconductor hybrids and contribute to their rational design in the future.

关 键 词：PSII-semiconductor hybrids Biointerface molecular interaction Solar-to-chemical energy conversion Mass spectrometry Lysine reactivity profiling 

分 类 号：TK519[动力工程及工程热物理—热能工程] O657.63[理学—分析化学] Q945.11[理学—化学]