A computational study on the hydrogenation of CO2 catalyzed by a tetraphos-ligated cobalt complex: monohydride vs. dihydride

doi:10.1039/c4cy01031k

GIEC OpenIR > 中国科学院广州能源研究所

	A computational study on the hydrogenation of CO2 catalyzed by a tetraphos-ligated cobalt complex: monohydride vs. dihydride
	Gao, Hui 1,2; Chen, Limin 2; Chen, Jinzhu1,3 ; Guo, Yuanyuan 1; Ye, Daiqi 2
	2015
发表期刊	CATALYSIS SCIENCE & TECHNOLOGY
卷号	5 期号:2 页码:1006-1013
摘要	Density functional theory (DFT) calculations were used to study the mechanisms of hydrogenation of carbon dioxide catalyzed by the tetraphos-ligated (PP3: P.CH2CH2PPh2)(3)) cobalt complexes. We investigated the binding modes between CO2 and the cobalt metal center to determine whether the CO2 coordinated to the metal center in the catalytic processes. The monohydride catalytic pathway (Path I) and the dihydride catalytic pathway (Path II) for the hydrogenation of CO2 have been explored. In these two cases, a weak H. CO2 interaction leads to cleavage of the Co-H bond and subsequent formation of the formate ligand. Moreover, the transformation from the dihydride to the monohydride is endergonic by 9.2 kcal mol(-1) and the relevant free energy barrier is about 20.9 kcal mol(-1). However, the largest free energy barrier of 19.1 kcal mol(-1) in Path II is significantly lower than that in Path I (22.8 kcal mol(-1)), which corresponds to the hydride transfer from the cobalt center to CO2. The detailed comparisons of the possible pathways suggest that Path II is much more favoured than Path I and that it is not necessary to form the monohydride species in the whole catalytic cycle. Our results, which unambiguously demonstrate that the active catalyst is the dihydride rather than the monohydride, are consistent with the experimental observations and, most importantly, provide detailed mechanistic insight.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1039/c4cy01031k
研究领域[WOS]	Chemistry
关键词[WOS]	SUPERCRITICAL CARBON-DIOXIDE ; FORMIC-ACID ; MECHANISTIC INSIGHT ; STORAGE MATERIAL ; METAL CATALYSTS ; FE HYDROGENASES ; ALKYL FORMATES ; IRON CATALYST ; REDUCTION ; MODELS
收录类别	SCI
语种	英语
WOS类目	Chemistry, Physical
WOS记录号	WOS:000348937900042
引用统计	被引频次：23[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.giec.ac.cn/handle/344007/10795
专题	中国科学院广州能源研究所
作者单位	1.Chinese Acad Sci, Guangzhou Inst Energy Convers, CAS Key Lab Renewable Energy, Guangzhou 510640, Guangdong, Peoples R China 2.S China Univ Technol, Coll Environm Sci & Engn, Guangdong Prov Key Lab Atmospher Environm & Pollu, Guangzhou 510006, Guangdong, Peoples R China 3.Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China
第一作者单位	中国科学院广州能源研究所
推荐引用方式 GB/T 7714	Gao, Hui,Chen, Limin,Chen, Jinzhu,et al. A computational study on the hydrogenation of CO2 catalyzed by a tetraphos-ligated cobalt complex: monohydride vs. dihydride[J]. CATALYSIS SCIENCE & TECHNOLOGY,2015,5(2):1006-1013.
APA	Gao, Hui,Chen, Limin,Chen, Jinzhu,Guo, Yuanyuan,&Ye, Daiqi.(2015).A computational study on the hydrogenation of CO2 catalyzed by a tetraphos-ligated cobalt complex: monohydride vs. dihydride.CATALYSIS SCIENCE & TECHNOLOGY,5(2),1006-1013.
MLA	Gao, Hui,et al."A computational study on the hydrogenation of CO2 catalyzed by a tetraphos-ligated cobalt complex: monohydride vs. dihydride".CATALYSIS SCIENCE & TECHNOLOGY 5.2(2015):1006-1013.