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A computational study on the hydrogenation of CO2 catalyzed by a tetraphos-ligated cobalt complex: monohydride vs. dihydride
Gao, Hui1,2; Chen, Limin2; Chen, Jinzhu1,3; Guo, Yuanyuan1; Ye, Daiqi2
2015
Source PublicationCATALYSIS SCIENCE & TECHNOLOGY
Volume5Issue:2Pages:1006-1013
AbstractDensity 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.
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
DOI10.1039/c4cy01031k
WOS Subject ExtendedChemistry
WOS KeywordSUPERCRITICAL CARBON-DIOXIDE ; FORMIC-ACID ; MECHANISTIC INSIGHT ; STORAGE MATERIAL ; METAL CATALYSTS ; FE HYDROGENASES ; ALKYL FORMATES ; IRON CATALYST ; REDUCTION ; MODELS
Indexed BySCI
Language英语
WOS SubjectChemistry, Physical
WOS IDWOS:000348937900042
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Document Type期刊论文
Identifierhttp://ir.giec.ac.cn/handle/344007/10795
Collection中国科学院广州能源研究所
Affiliation1.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
First Author AffilicationGuangZhou Institute of Energy Conversion,Chinese Academy of Sciences
Recommended Citation
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.
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