Abstract
Splitting CO(2) with a thermochemical redox cycle utilizes the entire solar spectrum and provides a favorable path to the synthesis of solar fuels at high rates and efficiencies. However, the temperature/pressure swing commonly applied between reduction and oxidation steps incurs irreversible energy losses and severe material stresses. Here, we experimentally demonstrate for the first time the single-step continuous splitting of CO(2) into separate streams of CO and O(2) under steady-state isothermal/isobaric conditions. This is accomplished using a solar-driven ceria membrane reactor conducting oxygen ions, electrons, and vacancies induced by the oxygen chemical potential gradient. Guided by the limitations imposed by thermodynamic equilibrium of CO(2) thermolysis, we operated the solar reactor at 1,600°C, 3·10(-6) bar [Formula: see text] and 3,500 suns radiation, yielding total selectivity of CO(2) to CO + ½O(2) with a conversion rate of 0.024 μmol·s(-1) per cm(2) membrane. The dynamics of the oxygen vacancy exchange, tracked by GC and XPS, further validated stable fuel production.