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作者:

Xu Ruinian (Xu Ruinian.) | Liu Ning (Liu Ning.) | Dai Chengna (Dai Chengna.) | Li Yan (Li Yan.) | Zhang Jie (Zhang Jie.) | Wu Bin (Wu Bin.) | Yu Gangqiang (Yu Gangqiang.) | Chen Biaohua (Chen Biaohua.) (学者:陈标华)

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摘要:

Direct oxidation of methane to methanol (DMTM) constitutes a big challenge in C 1 chemistry. Herein, we present a continuous N 2 O-DMTM investigation by simultaneously introducing 10 vol% H 2 O into the reaction system over Cu-BEA zeolites. Combining a D 2 O isotopic tracer technique and ab initio molecular dynamics (AIMD) simulation, we for the first time demonstrate that the H 2 O molecules can participate in the reaction through a proton transfer route, wherein the H 2 O molecules can build a high-speed proton transfer bridge between the generated moieties of CH 3 - and OH - over the evolved mono(μ-oxo) dicopper ([Cu-O-Cu] 2+ ) active site, thereby pronouncedly boosting the CH 3 OH selectivity (3.1 → 71.6%), productivity (16.8 → 242.9 μmol g cat -1 h -1 ) and long-term reaction stability (10 → 70 h) relative to the scenario of absence of H 2 O. Unravelling the proton transfer of H 2 O over the dicopper [Cu-O-Cu] 2+ site would substantially contribute to highly efficient catalyst designs for the continuous DMTM.

关键词:

H2O proton transfer Ab initio molecular dynamics Cu-BEA zeolite Continuous Methane Oxidation to Methanol DFT simulation

作者机构:

  • [ 1 ] [Xu Ruinian]Beijing University of Technology, Faculty of Environment and Life, CHINA
  • [ 2 ] [Liu Ning]Beijing University of Technology, College of Environmental and Energy Engineering, 100 Ping Le Yuan, Chaoyang District, Beijing, CHINA
  • [ 3 ] [Dai Chengna]Beijing University of Technology, Faculty of Environment and Life, 100124, Beijing, CHINA
  • [ 4 ] [Li Yan]Beijing University of Chemical Technology, State Key Laboratory of Chemical Resource Engineering, CHINA
  • [ 5 ] [Zhang Jie]Beijing University of Chemical Technology, State Key Laboratory of Chemical Resource Engineering, CHINA
  • [ 6 ] [Wu Bin]Beijing University of Technology, Faculty of Environment and Life, CHINA
  • [ 7 ] [Yu Gangqiang]Beijing University of Technology, Faculty of Environment and Life, CHINA
  • [ 8 ] [Chen Biaohua]Beijing University of Technology, Faculty of Environment and Life, CHINA

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来源 :

Angewandte Chemie

ISSN: 1521-3773

年份: 2021

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WoS核心集被引频次: 0

SCOPUS被引频次: 44

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