In this section
@article{Li:2026:10.1021/jacs.6c05776,
author = {Li, L and Wang, T and Hu, B and Oldham, LI and Chen, Q and Li, K and Yang, C and Alimard, P and Meng, Z and Ning, H and Durrant, JR and Kafizas, A and Bakulin, AA},
doi = {10.1021/jacs.6c05776},
journal = {J Am Chem Soc},
title = {Fast Interfacial Hole Consumption Suppresses Space-Charge Layer Trap Filling in BiVO4 Photoanodes.},
url = {http://dx.doi.org/10.1021/jacs.6c05776},
year = {2026}
}
TY - JOUR
AB - Photoelectrochemical (PEC) oxidation of biomass-derived organics (e.g., glycerol) can outperform water oxidation while coproducing value-added chemicals. However, the kinetic basis of this enhanced performance, such as hole consumption dynamics and space-charge-layer (SCL) trap filling under PEC operating conditions, remains poorly understood. Using BiVO4 as a model photoanode, we combine operando optical and photocurrent spectroscopies, including trap-selective pump-push photocurrent (PPPC) mapping, to track bulk and interfacial charge-carrier dynamics over the femtosecond-to-second (fs-s) time scale. Overall, we show that glycerol oxidation accelerates interfacial hole consumption, lowering the surface-hole density required to sustain a given photocurrent, thereby suppressing SCL trap filling and trap-mediated recombination. Glycerol increases the per-hole turnover frequency 32-fold (∼3.5 to ∼113.2 s-1) and the photocurrent density at 1.23 VRHE from ∼0.5 to ∼1.3 mA cm-2, while formic acid and dihydroxyacetone are the dominant quantified liquid products. Spatially resolved PPPC mapping (over ∼20 mm2) shows that glycerol also suppresses localized trap-filled hot spots. Glycerol leaves the dominant early time bulk carrier dynamics largely unchanged while suppressing the microsecond buildup of trapped electrons in the SCL. These results highlight microsecond time-scale kinetic competition between interfacial hole consumption and SCL trap filling as a key design principle for PEC oxidation of renewable organics.
AU - Li,L
AU - Wang,T
AU - Hu,B
AU - Oldham,LI
AU - Chen,Q
AU - Li,K
AU - Yang,C
AU - Alimard,P
AU - Meng,Z
AU - Ning,H
AU - Durrant,JR
AU - Kafizas,A
AU - Bakulin,AA
DO - 10.1021/jacs.6c05776
PY - 2026///
TI - Fast Interfacial Hole Consumption Suppresses Space-Charge Layer Trap Filling in BiVO4 Photoanodes.
T2 - J Am Chem Soc
UR - http://dx.doi.org/10.1021/jacs.6c05776
UR - https://www.ncbi.nlm.nih.gov/pubmed/42319808
ER -
Dr. Andreas Kafizas
Leader - Solar Coatings Group
e-mail: a.kafizas@imperial.ac.uk
tel: +44(0)20 7594 6752
twitter: @CoatingsSolar