title: The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface.
abstract: CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2(-) anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process.
authors.affiliation: Beijing Computational Science Research Center, Beijing 100084, China.
authors.forename: Wen-Jin
authors.initials: WJ
authors.lastname: Yin
authors.affiliation: Beijing Computational Science Research Center, Beijing 100084, China.
authors.forename: Bo
authors.initials: B
authors.lastname: Wen
authors.affiliation: Beijing Computational Science Research Center, Beijing 100084, China.
authors.forename: Sateesh
authors.initials: S
authors.lastname: Bandaru
authors.affiliation: Paul Scherrer Institute, CH-5232 Villigen-PSI, Switzerland.
authors.forename: Matthias
authors.initials: M
authors.lastname: Krack
authors.affiliation: Beijing Computational Science Research Center, Beijing 100084, China.|Chengdu Green Energy and Green Manufacturing Technology R&D Center, Chengdu, Sichuan, 610207, China.
authors.forename: M W
authors.initials: MW
authors.lastname: Lau
authors.affiliation: Beijing Computational Science Research Center, Beijing 100084, China.
authors.forename: Li-Min
authors.initials: LM
authors.lastname: Liu