High-temperature isothermal chemical cycling for solar-driven fuel production

Abstract

The possibility of producing chemical fuel (hydrogen) from the solar-thermal energy input using an isothermal cycling strategy is explored. The canonical thermochemical reactive oxide, ceria, is reduced under high temperature and inert sweep gas, and in the second step oxidized by H₂O at the same temperature. The process takes advantage of the oxygen chemical potential difference between the inert sweep gas and high-temperature steam, the latter becoming more oxidizing with increasing temperature as a result of thermolysis. The isothermal operation relieves the need to achieve high solid-state heat recovery for high system efficiency, as is required in a conventional two-temperature process. Thermodynamic analysis underscores the importance of gas-phase heat recovery in the isothermal approach and suggests that attractive efficiencies may be practically achievable on the system level. However, with ceria as the reactive oxide, the isothermal approach is not viable at temperatures much below 1400 °C irrespective of heat recovery. Experimental investigations show that an isothermal cycle performed at 1500 °C can yield fuel at a rate of ∼9.2 ml g⁻¹ h⁻¹, while providing exceptional system simplification relative to two-temperature cycling.