Light-Induced Proton Pumping with a Semiconductor: Vision for Photoproton Lateral Separation and Robust Manipulation.

Energy-transfer reactions are the key for living open systems, biological chemical networking, and the development of life-inspired nanoscale machineries. It is a challenge to find simple reliable synthetic chemical networks providing a localization of the time-dependent flux of matter. In this paper, we look to photocatalytic reaction on TiO ₂ from different angles, focusing on proton generation and introducing a reliable, minimal-reagent-consuming, stable inorganic light-promoted proton pump. Localized illumination was applied to a TiO ₂ surface in solution for reversible spatially controlled "inorganic photoproton" isometric cycling, the lateral separation of water-splitting reactions. The proton flux is pumped during the irradiation of the surface of TiO ₂ and dynamically maintained at the irradiated surface area in the absence of any membrane or predetermined material structure. Moreover, we spatially predetermine a transient acidic pH value on the TiO ₂ surface in the irradiated area with the feedback-driven generation of a base as deactivator. Importantly we describe how to effectively monitor the spatial localization of the process by the in situ scanning ion-selective electrode technique (SIET) measurements for pH and the scanning vibrating electrode technique (SVET) for local photoelectrochemical studies without additional pH-sensitive dye markers. This work shows the great potential for time- and space-resolved water-splitting reactions for following the investigation of pH-stimulated processes in open systems with their flexible localization on a surface.