How TiO2 crystallographic surfaces influence charge injection rates from a chemisorbed dye sensitiser

High-energy metal oxide surfaces are considered to be promising for applications involving surface-adsorbate electron transfer, such as photocatalysis and dye-sensitised solar cells. Here, we compare the efficiency of electron injection into different TiO(2) anatase surfaces. We model the adsorption of a carboxylic acid (formic acid) on anatase (101), (001), (100), (110) and (103) surfaces using density functional theory calculations, and calculate electron injection times from a model dye into these surfaces. We find that the different positions of the conduction band edge of these surfaces determine the rate of electron injection (which is faster for the surfaces with lower-lying conduction band, among them the most stable (101) surface). However, if the dye's injection energy is enforced to be at a fixed energy deep inside each surface's conduction band, then several anatase surfaces, such as the synthetically achievable (001) surface, show rates of injection comparable or faster than the (101) surface. Moreover, because of their higher-lying conduction bands, these minority surfaces are likely to offer higher open-circuit voltages in dye-sensitised solar cells. Therefore, synthetically accessible high-energy anatase surfaces, such as (001)-oriented nanostructures, may be promising candidates for use in dye-sensitised solar cells.