(769b) The Role of Surface Deposited Pt on the Photoactivity of TiO2

Zhou, Y., University of Colorado, Boulder
Weimer, A. W., University of Colorado at Boulder

The role of Pt clusters on defect free anatase TiO2 (101) surfaces has been studied using ab initio pseudopotential calculations based on density functional theory. The calculated electronic structure of Pt clusters supported on (101) anatase shows that excited electrons and holes are trapped by Pt nearly equally (upon addition of an extra electron 0.57 e- localizes on the Pt cluster, while the addition of a hole causes the loss of 0.59 e- from the Pt cluster). Furthermore, Pt states completely bridge the band gap and act as  electron-hole recombination centers, which is deleterious to the photoactivity of TiO2. In addition, calculations show that O2 will not adsorb on the TiO2 surface unless an extra electron or subsurface defect exists. On the other hand, the Pt cluster was found to significantly enhance the adsorption of O2, stemming from the high O2 adsorption energy of -1.69 eV and the many adsorption sites a Pt cluster presents. This results in enhanced photocatalytic performance because O2 can scavenge electrons more efficiently from Pt than from TiO2, which increases the interfacial electron transfer rate. The initial increase and subsequent decrease in TiO2’s photoactivity with increasing Pt loading can be explained by the competition between increased O2 adsorption and electron-hole recombination. At Pt loadings above the optimum level the increased electron-hole recombination outweighs the increased O2 adsorption, which is limited by its concentration and diffusion in solution.