Layer-by-Layer Assembly of Polyoxometalates for Photoelectrochemical (PEC) Water Splitting: Toward Modular PEC Devices

Artificial photosynthesis is considered one of the most promising solutions to modern energy and environmental crises. Considering that it is enabled by multiple components through a series of photoelectrochemical processes, the key to successful development of a photosynthetic device depends not only on the development of novel individual components but also on the rational design of an integrated photosynthetic device assembled from them. However, most studies have been dedicated to the development of individual components due to the lack of a general and simple method for the construction of the integrated device. In the present study, we report a versatile and simple method to prepare an efficient and stable photoelectrochemical device via controlled assembly and integration of functional components on the nanoscale using the layer-by-layer (LbL) assembly technique. As a proof of concept, we could successfully build a photoanode for solar water oxidation by depositing a thin film of diverse cationic polyelectrolytes and anionic polyoxometalate (molecular metal oxide) water oxidation catalysts on the surface of various photoelectrode materials (e.g., Fe₂O₃, BiVO₄, and TiO₂). It was found that the performance of photoanodes was significantly improved after the deposition in terms of stability as well as photocatalytic properties, regardless of types of photoelectrodes and polyelectrolytes employed. Considering the simplicity and versatile nature of LbL assembly techniques, our approach can contribute to the realization of artificial photosynthesis by enabling the design of novel photosynthetic devices.