Anomalous Photoinduced Hole Transport in Type I Core/Mesoporous-Shell Nanocrystals for Efficient Photocatalytic H2 Evolution.

Controlling the carrier dynamics in a semiconductor nanoparticulate photocatalyst is the key to developing catalytic activity. Generally, type I band alignment is unsuitable for photocatalysts because the photoinduced carriers accumulate in the narrow bandgap semiconductor. To avoid the termination of reactions and/or photocorrosion of materials caused by carrier accumulation, it is common to employ type II band alignment for photoenergy conversion systems instead of type I. However, CdS/ZnS core/mesoporous-shell heterostructures show superior photocatalytic activity despite having type I band alignment that is generally unfavorable for photocatalytic reactions. Transient absorption spectroscopy and time-resolved microwave conductivity revealed efficient photoinduced hole transfer from the CdS phase to the ZnS phase. The defect-mediated hole transfer from the CdS to the ZnS phase resulted in long-lived charge separation (>2.4 ms) leading to high photocatalytic performance. This study provides insight into defect-mediated carrier transfer in nanoparticulate photocatalysts, which could be used as a guideline for the design of highly active and stable nanoparticulate photocatalysts.