Cocatalyst activity mapping for photocatalytic materials revealed by the pattern-illumination time-resolved phase microscopy.

Abstract

Photocatalytic water-splitting represents a promising avenue for clean hydrogen production, necessitating an in-depth understanding of the photocatalytic reaction mechanism. The majority of the photocatalytic materials need cocatalysts to enhance the photo-oxidation or reduction reactions. However, the working mechanism, such as collecting charge carriers or reducing the reaction barrier, is not clear because they disperse inhomogeneously on a surface, and it is difficult to follow the local charge carrier behavior. This study employs the pattern-illumination time-resolved phase microscopy (PI-PM) method to unravel the spatial charge carrier behavior in photocatalytic systems, utilizing time-resolved microscopic image (refractive index change) sequences and their clustering analyses. This approach is robust for studying the change in local charge carrier behavior. We studied two major cocatalyst effects on photocatalysts: TiO2 with/without Pt and hematite with/without CoPi. The PI-PM method, supported by charge type clustering and the effects of scavengers, allowed for the analysis of local activity influenced by cocatalysts. This approach revealed that the introduction of cocatalysts alters the local distribution of charge carrier behavior and significantly impacts their decay rates. In TiO2 systems, the presence of Pt cocatalysts led to a local electron site on the micron scale, extending the lifetime to a few tens of microseconds from a few microseconds. Similarly, in hematite films with CoPi, we observed a notable accumulation of holes at cocatalyst sites, emphasizing the role of cocatalysts in enhancing photocatalytic efficiency. The study's findings highlight the complexity of charge carrier dynamics in photocatalytic processes and the significant influence of cocatalysts.