Site-specific photocatalytic splitting of methanol on TiO2(110)†

Clean hydrogen production is highly desirable for future energy needs, making the understanding of molecular-level phenomena underlying photocatalytic hydrogen production both fundamentally and practically important. Water splitting on pure TiO2 is inefficient, however, adding sacrificial methanol could significantly enhance the photocatalyzed H2 production. Therefore, understanding the photochemistry of methanol on TiO2 at the molecular level could provide important insights to its photocatalytic activity. Here, we report the first clear evidence of photocatalyzed splitting of methanol on TiO2 derived from time-dependent two-photon photoemission (TD-2PPE) results in combination with scanning tunneling microscopy (STM). STM tip induced molecular manipulation before and after UV light irradiation clearly reveals photocatalytic bond cleavage, which occurs only at Ti surface sites. TD-2PPE reveals that the kinetics of methanol photodissociation is clearly not of single exponential, an important characteristic of this intrinsically heterogeneous photoreaction.