Reduction of CO2 with Water on Pt-Loaded Rutile TiO2(110) Modeled with Density Functional Theory

详细信息    查看全文

• 作者：Naoto Umezawa ; Henrik H. Kristoffersen ; Lasse B. Vilhelmsen ; Bjørk Hammer
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：May 5, 2016
• 年：2016
• 卷：120
• 期：17
• 页码：9160-9164
• 全文大小：342K
• 年卷期：0
• ISSN：1932-7455

文摘

Photoreduction of CO₂ for fuel production is considered to be an ultimate solution to today’s energy crisis. Platinum (Pt) particles are known to promote photocatalysis reactions when loaded on the surface of titanium dioxide (TiO₂). In this study, we investigate the initial step of the reduction process of CO₂ with water, i.e., the formation of formate, HCOO^–, from surface bound CO₂ and H₂O on rutile TiO₂(110) in terms of energetics of initial and final states using density functional theory calculations. To understand the role of a Pt cocatalyst, chemisorption energies of HCOO and OH on TiO₂(110) are investigated with and without a Pt cluster. It is revealed that free electrons provided by the Pt cluster dramatically decrease the chemisorption energy thanks to the electron transfer from high-lying Pt states to unoccupied valence states induced by the adsorbates, which facilitates ionization of HCOO^– and OH^– on the TiO₂ surface near the Pt cluster. Direct adsorption of HCOO and OH on the surface of the Pt cluster is also energetically favored.