An integrated photocatalytic redox architecture for simultaneous overall conversion of CO_(2)and H_(2)O toward CH_(4)and H_(2)O_(2)  

一体化集成式人工光合成架构将CO_(2)和H_(2)O同时转化为CH_(4)和H_(2)O_(2)

作　　者：Muhammad Salman Nasir Bowen Sheng Ying Zhao Haotian Ye Jun Song Jinglin Li Ping Wang Tao Wang Xinqiang Wang Zhen Huang Baowen Zhou Muhammad Salman Nasir;盛博文;赵瀛;叶昊天;宋俊;李景林;王平;王涛;王新强;黄震;周宝文

机构地区：[1]Key Laboratory for Power Machinery and Engineering of Ministry of Education,Research Center for Renewable Synthetic Fuel,School of Mechanical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China [2]State Key Laboratory of Artificial Microstructure and Mesoscopic Physics,School of Physics,Nano-Optoelectronics Frontier Center of Ministry of Education(NFC-MOE),Peking University,Beijing 100871,China [3]Department of Mining and Materials Engineering,McGill University,Montreal,H3A 0G4,Canada [4]Electron Microscopy Laboratory,School of Physics,Peking University,Beijing 100871,China [5]Peking University Yangtze Delta Institute of Optoelectronics,Nantong 226010,China [6]Collaborative Innovation Center of Quantum Matter,School of Physics,Peking University,Beijing 100871,China

出　　处：《Science Bulletin》2025年第3期373-382,共10页科学通报(英文版)

基　　金：supported by the National Key Research and Development Program of China(2023YFB4004900);Shanghai Pilot Program for Basic Research-Shanghai Jiao Tong University(21TQ1400211);the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2022MS007);the National Natural Science Foundation of China(22109095);the National Natural Science Foundation of China(62305005,62321004,and 62227817);Beijing Natural Science Foundation(z200004);the Natural Sciences and Engineering Research Council of Canada Discovery Grant(RGPIN-2017-05187);McGill Engineering Doctoral Award(MEDA),and Digital Alliance of Canada-computational resources.

摘　　要：Solar-driven overall conversion of CO_(2)and H_(2)O into fuels and chemicals shows an ultimate strategy for carbon neutrality yet remains a huge challenge.Herein,an integrated photocatalytic redox architecture of Zn NPs/GaN Nanowires(NWs)/Si is explored for light-driven overall conversion of CO_(2)and H_(2)O into CH_(4)and H_(2)O_(2)simultaneously without any external sacrificial agents and additives.The as-designed architecture affords a benchmark CH_(4)activity of 189 mmol gcat^(-1)h^(-1)with a high selectivity of 93.6%,in the synchronized formation of H_(2)O_(2)at a considerable rate of 25 m g^(-1)h^(-1).Moreover,a considerable turnover number of 27,280 mol CH_(4)per mol Zn was achieved over a long-term operation of 80 h.By operando spectroscopic characterizations,isotope experiments,and density functional theory calculations,it is unraveled that Zn sites are synergetic with GaN to drive CO_(2)-to-CH_(4)conversion with a lowered energy barrier of 0.27 eV while inhibiting hydrogen evolution reaction with a relatively high energy barrier of 0.93 eV.Notably,owing to the unique surface properties of GaN,water is split into*OH and*H,followed by the formation of H_(2)O_(2)because of the alleviated adsorption strength of*OH by Zn NPs.Together,the hierarchical architecture enables the achievement of high activity and high selectivity of CH_(4)from CO_(2)reduction in distilled water along with the generation of H_(2)O_(2).This work provides an integrated photocatalytic redox architecture for the synchronized production of CH_(4)and H_(2)O_(2)with the only inputs of CO_(2),distilled water,and light.

关 键 词：Zn nanoparticles GaN nanowires/Si Integrated redox architecture Artificial photosynthesis CH_(4)and H_(2)0_(2) 

分 类 号：TQ221.11[化学工程—有机化工] TQ123.6