Efficiency maximization in solar-thermochemical fuel production: challenging the concept of isothermal water splitting.

Widespread adoption of solar-thermochemical fuel production depends on its economic viability, largely driven by the efficiency of use of the available solar resource. Herein, we analyze the efficiency of two-step cycles for thermochemical hydrogen production, with emphasis on efficiency. Owing to water thermodynamics, isothermal H2 production is shown to be impractical and inefficient, irrespective of reactor design or reactive oxide properties, but an optimal temperature difference between cycle steps, for which efficiency is the highest, can be determined for a wide range of other operating parameters. A combination of well-targeted pressure and temperature swing, rather than either individually, emerges as the most efficient mode of operation of a two-step thermochemical cycle for solar fuel production.