Particulate photocatalytic reactors with spectrum-splitting function for artificial photosynthesis.

We have applied spectrum splitting, which is the most reliable way for highly efficient solar energy utilization, to particulate photocatalytic reactors. We have elucidated that the spectrum splitting is feasible using plural cells/compartments, in which photocatalyst particles of different bandgaps are suspended respectively, arranged optically in series. When the particles are sufficiently small (≤20 nm in diameter), high-energy photons are absorbed in the wide-gap cell/compartment on the solar illumination side while low-energy photons reach the backside narrow-gap cell/compartment with being scarcely diffuse-reflected. We have proposed two concrete configurations of the reactors: wide-gap cell/narrow-gap Z-scheme cell (WG/Z), and wide-gap cell/two-compartment cell of middle-gap and narrow-gap (WG/MG-NG), based on the previous configuration of a two-compartment cell of wide-gap and narrow-gap (WG-NG). We have constructed a new model of the carrier supply process from the semiconductor photocatalysts to the active sites, and calculated the practical upper limits of the carrier supply rates and solar-to-chemical conversion efficiencies. The spectrum-splitting reactors can yield higher efficiencies of artificial photosynthetic H2 and CO production by up to 1.5-1.6 times than the conventional Z-scheme reactors. The newly proposed WG/Z reactor widens the room of the material developments and improves the robustness against solar spectrum variation, and hence would be a promising practical solution, although the efficiency is slightly lower than that for the ideal WG-NG reactor. The WG/MG-NG reactor yields the highest efficiency among the three configurations, with high spectral robustness.