CO2 Chemisorption and Its Effect on Methane Activation in La2O3-Catalyzed Oxidative Coupling of Methane

doi:10.1021/acs.jpcc.5b10457

	CO2 Chemisorption and Its Effect on Methane Activation in La2O3-Catalyzed Oxidative Coupling of Methane
	Chu, Changqing 1; Zhao, Yonghui 1; Li, Shenggang1,2 ; Sun, Yuhan1,2
	2016-02-11
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY C (IF:3.3[JCR-2023],3.5[5-Year])
ISSN	1932-7447
卷号	120 期号:5 页码:2737-2746
发表状态	已发表
DOI	10.1021/acs.jpcc.5b10457
摘要	Density functional theory and coupled cluster theory calculations were carried out to study the formation of the carbonate species on La2O3 catalyst using the cluster model and its effect on subsequent CH4 activation. Physisorption and chemisorption energies as well as energy barriers for the reaction of CO, and La2O3 clusters, and the reaction of CH4 with the CO32- site on the resulting clusters, were predicted. Our calculations show that CO, chemisorption at the La3+-C-3(2-) pair sites is thermodynamically and kinetically very favorable due to the strong basicity of the O2- site on La2O3, which leads to the formation of the La3+CO32- pair sites. In addition, CH4 activation at the La3+-C-3(2-) pair sites is similar to that at the La3+-C-3(2-) pair sites, which results in the formation of the bicarbonate species and the La-CH3 bond, although the La3+-C-3(2-) pair sites are much less reactive with CH4 in terms of both thermodynamics and kinetics. Further thermodynamical calculations show that the CO32- species in these clusters dissociate between 500 to 1250 K, with half of them completely dissociated at 873 K, consistent with the experimental observation. Our studies suggest that the CO32- site is unlikely to be the active site in La2O3-catalyzed oxidative coupling of methane, and CO, as a major byproduct is likely to act as a poison to the (LaO3)-O-2-based catalysts especially at modest reaction temperature.
收录类别	SCI ; EI
语种	英语
资助项目	"Frontier Science" program of Shell Global Solutions International B.V.[PT32281]
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
WOS类目	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:000370210400028
出版者	AMER CHEMICAL SOC
EI入藏号	20160801962893
EI主题词	Alkalinity ; Catalysis ; Catalyst activity ; Catalysts ; Chemical activation ; Chemisorption ; Density functional theory ; Methane ; Numerical methods ; Thermodynamics
EI分类号	Thermodynamics:641.1 ; Chemistry, General:801.1 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Numerical Methods:921.6 ; Probability Theory:922.1
WOS关键词	BASIS-SETS ; GEOMETRY OPTIMIZATION ; STRUCTURE SENSITIVITY ; LA2O3 CATALYSTS ; SURFACE ; MODEL ; PERFORMANCE ; STABILITY ; BASICITY ; ACIDITY
原始文献类型	Article
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/1925
专题	物质科学与技术学院_特聘教授组_李圣刚组物质科学与技术学院_特聘教授组_孙予罕组
通讯作者	Li, Shenggang
作者单位	1.Chinese Acad Sci, Shanghai Adv Res Inst, CAS Key Lab Low Carbon Convers Sci & Engn, 100 Haike Rd, Shanghai 201210, Peoples R China 2.ShanghaiTech Univ, Sch Phys Sci & Technol, 319 Yueyang Rd, Shanghai 200031, Peoples R China
通讯作者单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Chu, Changqing,Zhao, Yonghui,Li, Shenggang,et al. CO2 Chemisorption and Its Effect on Methane Activation in La2O3-Catalyzed Oxidative Coupling of Methane[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2016,120(5):2737-2746.
APA	Chu, Changqing,Zhao, Yonghui,Li, Shenggang,&Sun, Yuhan.(2016).CO2 Chemisorption and Its Effect on Methane Activation in La2O3-Catalyzed Oxidative Coupling of Methane.JOURNAL OF PHYSICAL CHEMISTRY C,120(5),2737-2746.
MLA	Chu, Changqing,et al."CO2 Chemisorption and Its Effect on Methane Activation in La2O3-Catalyzed Oxidative Coupling of Methane".JOURNAL OF PHYSICAL CHEMISTRY C 120.5(2016):2737-2746.