title: Theoretical study of the geometries and decomposition energies of CO₂ on Al₁₂X: doping effect of Al₁₂X.
abstract: The adsorption and decomposition of CO₂ molecule on X-centered icosahedronal Al₁₂X clusters (doping atom X=Al, Be, Zn, Fe, Ni, Cu, B, C, Si, P) were investigated by the DFT methods of PW91 and PWC. Adsorption energies, chemisorption energies and energy barriers of physic- and chemisorptions for CO₂ were determined. It was found that the doping atoms and spin states have important influences on the Al₁₂X geometries, electronic properties and energies of the adsorption processes. CO₂ chemisorption on the Al₁₂C cluster is energetically and kinetically unfavorable. CO₂ decomposition on the metallic doping Al₁₂X (X=Fe, Ni, Cu) clusters has relatively low energy barriers. On contrary, the barriers are large when X=B, C, Si and P. The energy barriers for CO₂ chemisorption and decomposition on the Al₁₂Fe cluster are 5.23 kJ/mol and 38.53 kJ/mol, respectively. These values are the lowest among all the clusters being discussed. The adsorption and decomposition of CO₂ on the Al₁₂X cluster can be tuned by X doping.
authors.affiliation: Key Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, PR China; School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, PR China.
authors.forename: Jian-Ying
authors.initials: JY
authors.lastname: Zhao
authors.affiliation: Laboratory of Science and Technology on Combustion and Explosion, Xi'an Modern Chemistry Research Institute, Xi'an 710065, PR China.
authors.forename: Feng-Qi
authors.initials: FQ
authors.lastname: Zhao
authors.affiliation: Laboratory of Science and Technology on Combustion and Explosion, Xi'an Modern Chemistry Research Institute, Xi'an 710065, PR China.
authors.forename: Si-Yu
authors.initials: SY
authors.lastname: Xu
authors.affiliation: Key Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, PR China. Electronic address: xhju@njust.edu.cn.
authors.forename: Xue-Hai
authors.initials: XH
authors.lastname: Ju
mesh_terms: D000327:Adsorption; D000535:Aluminum / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D013499:Surface Properties; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D002245:Carbon Dioxide; D000535:Aluminum
keywords: Adsorption and decomposition; Carbon dioxide; DFT; Doping effect; X-centered Al(12)X cluster