Thermoelectric-Photoelectrochemical Water Splitting under Concentrated Solar Irradiation

Photoelectrochemical devices could play a crucial role toward fuel production in a circular economy. Yet, light absorption suffers losses from thermalization and the inability to use low-energy photons. Here, we demonstrate that photoelectrochemical reactors can utilize this waste heat by integrating thermoelectric modules, which provide additional voltage under concentrated light irradiation. While most single semiconductors require external bias, we already accomplish unassisted water splitting under 2 sun irradiation by wiring a BiVO₄ photoanode to a thermoelectric element, whereas the photocurrent of a perovskite-BiVO₄ tandem system is enhanced 1.7-fold at 5 sun. This strategy is particularly suitable for photoanodes with more positive onset potentials like hematite, with thermoelectric-perovskite-Fe₂O₃ systems achieving a 29.7× overall photocurrent increase at 5 sun over conventional perovskite-Fe₂O₃ devices without light concentration. This thermal management approach provides a universal strategy to facilitate widespread solar fuel production, as light concentration increases output, reduces the reactor size and cost, and may enhance catalysis.