High-rate CH_(4)-to-C_(2)H_(6) photoconversion enabled by Au/ZnO porous nanosheets under oxygen-free system  

作　　者：Kai Zheng Xiaojing Zhang Jun Hu Chengbin Xu Juncheng Zhu Jing Li Mingyu Wu Shan Zhu Li Li Shumin Wang Yumei Lv Xin He Ming Zuo Chengyuan Liu Yang Pan Junfa Zhu Yongfu Sun Yi Xie 

机构地区：[1]Hefei National Laboratory for Physical Sciences at Microscale,National Synchrotron Radiation Laboratory,University of Science and Technology of China,Hefei 230026,China [2]Key Laboratory of Photochemical Conversion and Optoelectronic Materials,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences,Beijing 100190,China [3]State Grid Anhui Electric Power Research Institute,Hefei 230601,China

出　　处：《Science China Chemistry》2024年第3期869-875,共7页中国科学（化学英文版）

基　　金：supported by the National Key R&D Program of China(2019YFA0210004,2022YFA1502904,2021YFA1501502);the National Natural Science Foundation of China(22125503,21975242,U2032212,21890754,22002148);2023 Synchrotron Radiation Joint Fund of USTC;the Youth Innovation Promotion Association of CAS(CX2340007003)。

摘　　要：Photocatalytic CH_(4) coupling into high-valued C_(2)H_(6) is highly attractive,whereas the photosynthetic rate,especially under oxygen-free system,is still unsatisfying.Here,we designed the negatively charged metal supported on metal oxide nanosheets to activate the inert C-H bond in CH_(4)and hence accelerate CH_(4) coupling performance.As an example,the synthetic Au/ZnO porous nanosheets exhibit the C_(2)H_(6) photosynthetic rate of 1,121.6μmol g^(-1)_(cat)h^(-1)and the CH_(4) conversion rate of 2,374.6μmol g^(-1)_(cat)h^(-1) under oxygen-free system,2 orders of magnitude higher than those of previously reported photocatalysts.By virtue of several in situ spectroscopic techniques,it is established that the generated Au^(δ-)and O^-species together polarized the C-H bond,while the Au^(δ-)and O^-species jointly stabilized the CH_(3) intermediates,which favored the coupling of CH_(3) intermediate to photosynthesize C_(2)H_(6) instead of overoxidation into CO_(x).Thus,the design of dual active species is beneficial for achieving high-efficient CH_(4)-to-C_(2)H_(6) photoconversion.

关 键 词：dual surface-active sites selective methane coupling ETHANE room temperature 

分 类 号：O644.1[理学—物理化学] TB383.1[理学—化学] O643.36[一般工业技术—材料科学与工程]