A Density Functional Theory and Experimental Study of CO2 Interaction with Brookite TiO2

作者：Rodriguez Monique M; Peng Xihong; Liu Lianjun; Li Ying; Andino Jean M^*

来源：Journal of Physical Chemistry C, 2012, 116(37): 19755-19764.

DOI：10.1021/jp302342t

The interactions of CO2 with the (210) surface of brookite TiO2 were studied using first-principle calculations on cluster and periodic slab systems. Charge and spin density analyses were implemented to determine if charge transfer to the CO2 molecule occurred and whether this charge transfer was comparable to that seen with the anatase TiO2 (101) surface. Although the brookite (210) surface provided energetically similar CO2 interactions as compared to the anatase (101) surface, the brookite surface had negligible charge transfer to the CO2 molecule. This result suggests that unmodified brookite is not a suitable catalyst for the reduction of CO2. However, the results also suggest that modification of the brookite surface through the creation of oxygen vacancies may lead to enhancements in CO2 reduction. The computational results were supported with laboratory data for CO2 interaction with perfect brookite and oxygen-deficient brookite. The laboratory data, generated using diffuse reflectance Fourier transform infrared spectroscopy, confirms the presence of CO2- at significant levels on the oxygen-deficient brookite.

• 出版日期2012-9-20