Unassisted Photoelectrochemical Cell with Multimediator Modulation for Solar Water Splitting Exceeding 4% Solar-to-Hydrogen Efficiency

Photoelectrochemical overall water splitting has been considered as a promising approach for producing chemical energy from solar energy. Although many photoelectrochemical cells have been developed for overall water splitting by coupling two semiconductor photoelectrodes, inefficient charge transfer between the light-harvesters and electron acceptor/donor severely restricts the solar energy conversion efficiency. Inspired by natural photosynthesis, we assembled a photoelectrochemical platform with multimediator modulation to achieve unassisted overall water splitting. Photogenerated electrons are transferred in order through multimediators driven by the electrochemical potential gradient, resulting in efficient charge separation and transportation with enhanced charge transfer rate and reduced charge recombination rate. The integrated system composed of inorganic oxide-based photoanode (BiVO₄) and organic polymer-based photocathode (PBDB-T:ITIC:PC₇₁BM) with complementary light absorption, exhibits a solar-to-hydrogen conversion efficiency as high as 4.3%. This work makes a rational design possible by constructing an efficient charge-transfer chain in artificial photosynthesis systems for solar fuel production.