Photocatalytic water splitting is attracting enormous interest for the storage of solar energy but no practical method has yet been identified. In the past decades, various systems have been developed but most of them suffer from low activities, a narrow range of absorption and poor quantum efficiencies (Q.E.) due to fast recombination of charge carriers. Here we report a dramatic suppression of electron-hole pair recombination on the surface of N-doped TiO₂ based nanocatalysts under enhanced concentrations of H⁺ and OH⁻, and local electric field polarization of a MgO (111) support during photolysis of water at elevated temperatures. Thus, a broad optical absorption is seen, producing O₂ and H₂ in a 1:2 molar ratio with a H₂ evolution rate of over 11,000 μmol g⁻¹ h⁻¹ without any sacrificial reagents at 270 °C. An exceptional range of Q.E. from 81.8% at 437 nm to 3.2% at 1000 nm is also reported.

Photocatalytic splitting of seawater for hydrogen evolution has attracted a great deal of attention in recent years. However, the poor energy conversion efficiency and stability of photocatalysts in a salty environment have greatly hindered further applications of this technology. Moreover, the effects of electrolytes in seawater remain controversial. Here we present electrolyte-assisted charge polarization over an N-doped TiO₂ photocatalyst, which demonstrates the stoichiometric evolution of H₂ and O₂ from the thermo-assisted photocatalytic splitting of seawater. Our extensive characterizations and computational studies show that ionic species in seawater can selectively adsorb on photo-polarized facets of the opposite charge, which can prolong the charge-carrier lifetime by a factor of five, leading to an overall energy conversion efficiency of 15.9 ± 0.4% at 270 °C. Using a light-concentrated furnace, a steady hydrogen evolution rate of 40 mmol g⁻¹ h⁻¹ is demonstrated, which is of the same order of magnitude as laboratory-scale electrolysers.

A local-magnetic-field-promoted photocatalytic overall water splitting system is developed for the Fe ₃ O ₄ /N-TiO ₂ catalyst, and an unprecedented solar-to-hydrogen efficiency of 11.9 ± 0.5% is achieved at 270 °C.