Hydrogen-Bond Network Promotes Water Splitting on the TiO₂ Surface

Abstract

Breaking the strong covalent O–H bond of an isolated H2O molecule is difficult, but it can be largely facilitated when the H2O molecule is connected with others through hydrogen-bonding. How a hydrogen-bond network forms and performs becomes crucial for water splitting in natural photosynthesis and artificial photocatalysis and is awaiting a microscopic and spectroscopic understanding at the molecular level. At the prototypical photocatalytic H2O/anatase-TiO2(001)-(1×4) interface, we report the hydrogen-bond network can promote the coupled proton and hole transfer for water splitting. The formation of a hydrogen-bond network is controlled by precisely tuning the coverage of water to above one monolayer. Under ultraviolet (UV) light irradiation, the hydrogen-bond network opens a cascaded channel for the transfer of a photoexcited hole, concomitant with the release of the proton to form surface hydroxyl groups. The yielded hydroxyl groups provide excess electrons to the TiO2 surface, causing the reduction of Ti4+ to Ti3+ and leading to the emergence of gap states, as monitored by in situ UV/X-ray photoelectron spectroscopy. The density functional theory calculation reveals that the water splitting becomes an exothermic process through hole oxidation with the assistance of the hydrogen-bond network. In addition to the widely concerned exotic activity from photocatalysts, our study demonstrates the internal hydrogen-bond network, which is ubiquitous at practical aqueous/catalyst interfaces, is also indispensable for water splitting.