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.
Highlights
Than the TiO2 conduction band minimum (CBM) about 0.4 eV above the Fermi level[28]
Our results show that the CO2 activation and reduction processes on the rutile (110) surface are greatly affected by the excess electrons and holes
We examine the effect of excess electrons on the CO2 adsorption and activation on the perfect/reduced rutile (110) surfaces
Summary
Than the TiO2 conduction band minimum (CBM) about 0.4 eV above the Fermi level[28]. such relatively high potential prevents the efficient electron transfer process from TiO2 to CO2, which is a necessary for the photo-catalytic reduction reaction. Spin moment and density calculations show that the CO2 anion can exist in the TiO2 (110) containing excess electrons, and a new configuration of CO2 cation exists in the hole system. Our results show that the CO2 activation and reduction processes on the rutile (110) surface are greatly affected by the excess electrons and holes.
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