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 |
DOI | 10.1016/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 |
推荐引用方式 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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