Correlation between Dynamics of Polaronic Photocarriers and Photoelectrochemical Performance in Mo-Doped Bismuth...

Bismuth vanadate (BiVO₄) has received intense research interest due to its outstanding performance for solar water splitting, and doping it with molybdenum (Mo) ions can effectively boost photoelectrochemical performance. In this material, highly localized polarons play a key role in the photoconversion process. Herein, we uncovered the influence of Mo dopants on the dynamics of polaronic transient species using transient absorption spectroscopy. We find that the preexisting electron small polarons stemming from the thermal ionization of dopants provide additional centers to capture itinerant holes, which significantly decrease the hole lifetime. However, the introduction of dopants increases the lifetime of self-trapped excitons that arise from the binding of electron polarons and holes. The dependence of the photoelectrochemical performance of BiVO₄ photoelectrodes on doping levels can be well explained by combining the dopant effects on the lifetimes of delocalized and self-trapped transient species. Our findings provide guidance for rational optimization of dopant concentration to maximize the PEC efficiency.