中国科学院机构知识库网格
Chinese Academy of Sciences Institutional Repositories Grid
Reactivity descriptors of diverse copper-oxo species on ZSM-5 zeolite towards methane activation

文献类型:期刊论文

作者Wang, Guiru1,3; Chen, Wei1,3; Huang, Ling3; Liu, Zhiqiang3; Sun, Xianyong3; Zheng, Anmin2,3
刊名CATALYSIS TODAY
出版日期2019-11-01
卷号338页码:108-116
ISSN号0920-5861
关键词Cu-oxo-species Zeolite Spin density Methane activation Descriptors
DOI10.1016/j.cattod.2019.05.007
英文摘要Copper-containing ZSM-5 zeolite can facilitate the direct oxidation of methane to form methanol under mild condition with high selectivity. However, due to the limitation of the experimental characterization, the identification of the catalytic sites in Cu-exchanged zeolites still remains unclear. Herein, the reactivity of different [CuxOy] (x = 1, 2, 3; y = 1, 2, 3)- and [CuOH](+)-ZSM-5 active sites towards methane partial oxidation process has been elucidated by using density functional theory (DFT) calculations. It is indicated that i) C-H activation over five different active sites obeys the radical mechanism, and the reactivity follows the sequence: copper-oxyl [CuO](+) (S = 1) > tricopper [Cu3O3](2+) (S = 3/2) > bis-(mu-oxo)-dicopper [Cu2O2](2+) (S = 1) > mono-(mu-oxo)-dicopper [CuOCu](2+) (S = 1) > mono-copper [CuOH](1)(+) (S = 1/2); ii) The rate constants for C-H bond cleavage of methane at the reaction temperature are faster at the higher temperature; iii) The descriptors for C-H activation of methane on [CuxOy] (x = 1(similar to)3, y = 1 3)- and [CuOH](+)-ZSM-5 have been established, for which the active site with more spin density and less negative charge will induce the lower activation barriers for C-H activation of methane. Meanwhile, the stronger hydrogen affinity of the active site is, the lower the activation barriers of methane C-H activation will be. Taken the stability and activation barrier together, the catalytic performance of copper-oxyl site has been enhanced by the presence of water.
WOS关键词COMBINED QUANTUM-MECHANICS ; GENERALIZED GRADIENT APPROXIMATION ; H BOND ACTIVATION ; DIRECT CONVERSION ; HYDROGEN-ATOM ; ACTIVE-SITE ; CATALYTIC CONVERSION ; MONONUCLEAR COPPER ; AB-INITIO ; OXIDATION
资助项目National Natural Science Foundation of China[21522310] ; National Natural Science Foundation of China[21473244] ; National Natural Science Foundation of China[91645112] ; Natural Science Foundation of Hubei Province of China[2014CFA043] ; Key Research Program of Frontier Sciences, CAS[QYZDB-SSW-SLH026] ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase)[U1501501] ; Sinopec Corp.[417012-4]
WOS研究方向Chemistry ; Engineering
语种英语
出版者ELSEVIER
WOS记录号WOS:000483921400012
资助机构National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Sinopec Corp. ; Sinopec Corp. ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Sinopec Corp. ; Sinopec Corp. ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Sinopec Corp. ; Sinopec Corp. ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) ; Sinopec Corp. ; Sinopec Corp.
源URL[http://ir.wipm.ac.cn/handle/112942/14868]  
专题中国科学院武汉物理与数学研究所
通讯作者Zheng, Anmin
作者单位1.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
2.Huazhong Univ Sci & Technol, Wuhan Natl Lab Optoelect, Wuhan 430074, Hubei, Peoples R China
3.Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Natl Ctr Magnet Resonance,Wuhan Key Lab Magnet Re, Wuhan 430071, Hubei, Peoples R China
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GB/T 7714
Wang, Guiru,Chen, Wei,Huang, Ling,et al. Reactivity descriptors of diverse copper-oxo species on ZSM-5 zeolite towards methane activation[J]. CATALYSIS TODAY,2019,338:108-116.
APA Wang, Guiru,Chen, Wei,Huang, Ling,Liu, Zhiqiang,Sun, Xianyong,&Zheng, Anmin.(2019).Reactivity descriptors of diverse copper-oxo species on ZSM-5 zeolite towards methane activation.CATALYSIS TODAY,338,108-116.
MLA Wang, Guiru,et al."Reactivity descriptors of diverse copper-oxo species on ZSM-5 zeolite towards methane activation".CATALYSIS TODAY 338(2019):108-116.

入库方式: OAI收割

来源:武汉物理与数学研究所

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