Solar-driven co-thermolysis of CO2 and H2O promoted by in situ oxygen removal across a non-stoichiometric ceria membrane

We report on the first ever experimental demonstration of simultaneous thermolysis of CO2 and H2O with in situ separation of fuel and oxygen in a solar-driven membrane reactor. Gaseous CO2/H2O mixtures at molar ratios from 3 : 4 to 2 : 1 were fed to a mixed ionic-electronic conducting non-stoichiometric ceria (CeO2-delta) membrane enclosed in a solar cavity receiver and exposed to simulated concentrated solar radiation of up to 4200 suns. Reaction rates were measured under isothermal and isobaric conditions in the range of 1723-1873 K and 0.2-1.7 Pa O-2, yielding a maximum combined CO and H-2 fuel production rate of 2.3 mu mol cm(-2) min(-1) at 1873 K and 0.2 Pa O-2 at steady state, which corresponded to a conversion of reactants of 0.7%. Under all conditions tested, CO production was favored over H-2 production, as expected from theory. Experimental results followed the same trends as the thermodynamic equilibrium limits of membrane-assisted thermochemical fuel production.