Modular Layer‐by‐Layer Assembly of Polyelectrolytes,Nanoparticles, and Molecular Catalysts into Solar‐to‐Chemical Energy Conversion Devices

The design and fabrication of solar‐to‐chemical energy conversion devices are enabled through interweaving multiple components with various morphologies and unique functions using a versatile layer‐by‐layer assembly method. Cationic and anionic polyelectrolytes are used as an electrostatic adhesive to assemble the following functional materials: plasmonic Ag nanoparticles for improved light harvesting, upconversion nanoparticles for utilization of near‐infrared light, and polyoxometalate water oxidation catalysts for enhanced catalytic activity. Polyelectrolytes also have an additional function of passivating the surface recombination centers of the underlying photoelectrode. These functional components are precisely assembled on a model photoanode (e.g., Fe₂O₃ and BiVO₄) in a desired order and various combinations without degradation of their intrinsic properties. As a result, the performance of water oxidation photoanodes is synergistically enhanced. This study can enable the design and fabrication of novel solar‐to‐chemical energy conversion devices.