Observation of Molecular Hydrogen Produced from Bridging Hydroxyls on Anatase TiO2(101).

Anatase TiO2 is used extensively in a wide range of catalytic and photocatalytic processes and is a promising catalyst for hydrogen production. Here, we show that molecular hydrogen was produced from bridging hydroxyls (HOb) on the (101) surface of single-crystal anatase (TiO2(101)). This stands in contrast to rutile TiO2(110), where HOb pairs react to form H2O. Electron bombardment at 30 K produced bridging oxygen vacancies in the surface. Deuterated bridging hydroxyls (DOb) were subsequently formed via dissociation of adsorbed D2O and confirmed by infrared reflection-absorption spectroscopy. During temperature-programmed desorption (TPD) spectroscopy, D2 desorption was observed at 520 K. Density functional theory calculations show that both H2 and H2O production from HOb are endothermic at 0 K on TiO2(101), but H2 (H2O) desorption is entropically driven above 230 K (800 K). The calculated activation barrier for H2 desorption is 1.40 eV, which is similar to the desorption energy obtained from analysis of the D2 TPD spectra. The H2 desorption likely proceeds in two steps: H atom diffusion on the surface and then recombination.