Carboxylate Adsorption on Rutile TiO2(100): Role of Coulomb Repulsion, Relaxation, and Steric Hindrance

Understanding the adsorption and photoactivity of acetic acid and trimethyl acetic acid on TiO 2 surfaces is important for improving the performance of photocatalysts and dye-sensitized solar cells. Here we present a structural study of adsorption on rutile TiO 2 (100)-1 × 1 and -1 × 3 using Scanning Tunnelling Microscopy and Density Functional Theory calculations. Exposure of both terminations to acetic acid gives rise to a ×2 periodicity in the [001] direction (i.e., along Ti rows), with a majority ordered c(2 × 2) phase in the case of the 1 × 1 termination. The DFT calculations suggest that the preference of c(2 × 2) over the 2 × 1 periodicity found for TiO 2 (110)-1 × 1 can be attributed to an increase in interadsorbate Coulomb repulsion. Exposure of TiO 2 (100)-1 × 1 and -1 × 3 to trimethyl acetic acid gives rise to largely disordered structures due to steric effects, with quasi-order occurring in small areas and near step edges where these effects are reduced.