Abstract

Transition-metal doping has been demonstrated to be effective for tuning the photocatalytic activity of semiconductors. Nonetheless, the impact of doping-induced trap states on the concentration of surface-reaching photoexcited charges remains a topic of debate. In this study, through time-resolved spectroscopies and kinetic analysis, we found that the concentration of surface-reaching photoholes (Ch+(surf)) in doped TiO2 nanoparticles sensitively relies on the type of dopants and their associated trap states. Among the studied dopants (Fe, Cu, and Co), Fe doping resulted in the most significant increase in Ch+(surf), nearly double that of Co or Cu doping. Fe-doping induced more effective hole trap states, acting as the mediator for interfacial charge transfer, thus accelerating charge separation and consequently enriching Ch+(surf). This work provides valuable insight into understanding and controlling Ch+(surf) in transition-metal-doped TiO2 materials.

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