Hot-carrier photocatalysts for artificial photosynthesis

Abstract

We applied hot-carrier extraction to particulate photocatalysts for artificial photosynthetic reactions including water splitting for H2 production and CO2 reduction to CO and HCOOH, and elucidated promising features of hot-carrier photocatalysts (HC-PCs). We designed a specific structure of the HC-PC; a semiconductor core in which thermalization of photo-generated carriers is significantly suppressed is surrounded by a shell whose bandgap is wider than that of the core. Among the photo-generated hot carriers in the core, only carriers whose energies are larger than the shell bandgap are extracted passing through the shell to the active sites on the shell surface. Thus, the shell functions as an energy-selective contact. We calculated the upper bounds of the rates of the carrier supply from the core to the active sites using a newly constructed detailed-balance model including partial thermalization and nonradiative recombination of the carriers. It has been revealed that the HC-PCs can yield higher carrier-supply rates and thus potentially higher solar-to-chemical energy conversion efficiencies for H2 and CO production than those of conventional photocatalysts with the assistance of intraband transition and Auger recombination/impact ionization. It should be noted, however, that one of the necessary conditions for efficient hot-carrier extraction is sufficiently large carrier density in the core, which, in turn, requires concentrated solar illumination by several hundreds. This would raise rate-limiting problems of activities of the chemical reactions induced by the photo-generated carriers and material-transfer properties.