A limiting factor to the efficiency of water Oxygen Evolution Reaction (OER) in metal oxide nanoparticle photocatalysts is the rapid recombination of holes and electrons. Facet-engineering can effectively improve charge separation and, consequently, OER efficiency. However, the kinetics behind this improvement remain poorly understood. This study utilizes photoinduced absorption spectroscopy to investigate the charge yield and kinetics in facet-engineered BiVO₄ (F-BiVO₄) compared to a non-faceted sample (NF-BiVO₄) under operando conditions. A significant influence of preillumination on hole accumulation is observed, linked to the saturation and, thus, passivation of deep and inactive hole traps on the BiVO₄ surface. In DI-water, F-BiVO₄ shows a 10-fold increase in charge accumulation (∼5 mΔOD) compared to NF-BiVO₄ (∼0.5 mΔOD), indicating improved charge separation and stabilization. With the addition of Fe(NO₃)₃, an efficient electron acceptor, F-BiVO₄ demonstrates a 30-fold increase in the accumulation of long-lived holes (∼45 mΔOD), compared to NF-BiVO₄ (∼1.5 mΔOD) and an increased half-time, from 2 to 10 s. Based on a simple kinetic model, this increase in hole accumulation suggests that facet-engineering causes at least a 50-100 meV increase in band bending in BiVO₄ particles, thereby stabilizing surface holes. This energetic stabilization/loss results in a retardation of OER relative to NF-BiVO₄. This slower catalysis is, however, offset by the observed increase in density and lifetime of photoaccumulated holes. Overall, this work quantifies how surface faceting can impact the kinetics of long-lived charge accumulation on metal oxide photocatalysts, highlighting the trade-off between lifetime gain and energetic loss critical to optimizing photocatalytic efficiency.

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