Heterogeneous photocatalysis is vital in solving energy and environmental issues that this society is confronted with. Although photocatalysts are often operated in the presence of water, it has not been yet clarified how the interaction with water itself affects charge dynamics in photocatalysts. Using water-coverage-controlled steady and transient infrared absorption spectroscopy and large-model (∼800 atoms) ab initio calculations, we clarify that water enhances hole trapping at the surface of TiO2 nanospheres but not of well-faceted nanoparticles. This water-assisted effect unique to the nanospheres originates from water adsorption as a ligand at a low-coordinated Ti–OH site or through robust hydrogen bonding directly to the terminal OH at the highly curved nanosphere surface. Thus, the interaction with water at the surface of nanospheres can promote photocatalytic reactions of both oxidation and reduction by elongating photogenerated carrier lifetimes. This morphology-dependent water-assisted effect provides a novel and rational basis for designing and engineering nanophotocatalyst morphology to improve photocatalytic performances.

Charge carrier trapping plays a vital role in heterogeneous photocatalytic water splitting because it strongly affects the dynamics of photogenerated charges and hence the photoconversion efficiency. Although hole trapping by water at water/photocatalyst interface is the first step of oxygen evolution in water splitting, little has been known on how water adsorbate itself is involved in hole trapping dynamics. To clarify this point, we have performed infrared transient and steady-state absorption spectroscopy of anatase TiO2 nanoparticles as a function of the number of water adsorbate layers. Here, we demonstrate that water molecules reversibly adsorbed in the first layer on TiO2 nanoparticles are capable to trap photogenerated holes, while water in the second layer hydrogen bonding to the first-layer water makes hole trapping less effective.

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