@article{He:2026:10.1021/jacs.5c18734,
author = {He, T and Benetti, D and Tseng, C and Moss, B and Teschner, D and Jones, TE and Kafizas, A and Grätzel, M and Piccinin, S and Durrant, JR},
doi = {10.1021/jacs.5c18734},
journal = {J Am Chem Soc},
pages = {4833--4838},
title = {Observation of Transition from Rate Law to Butler-Volmer Controlled Water Oxidation Kinetics on Hematite Photoanodes.},
url = {http://dx.doi.org/10.1021/jacs.5c18734},
volume = {148},
year = {2026}
}

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TY  - JOUR
AB  - Despite its central role in photoelectrochemical (PEC) water splitting, the mechanistic pathway of water oxidation on metal oxides remains unresolved, with population-based and Butler-Volmer (BV) models offering distinct views on how surface valence band holes drive the reaction. Here, we bring together these two perspectives by combining operando photoinduced absorption (PIA) spectroscopy with photocurrent analyses on α-Fe2O3 (hematite) photoanodes as a function of light intensity. We find a crossover from population-controlled, rate law water oxidation at low hole densities to a BV-like, potential driven regime at high densities, triggered by band edge unpinning once surface M-OH species are fully oxidized, and excess holes accumulate without compensation. This mechanistic transition unifies competing models of interfacial charge transfer and reveals design principles for optimizing water oxidation in metal oxide photoelectrodes.
AU  - He,T
AU  - Benetti,D
AU  - Tseng,C
AU  - Moss,B
AU  - Teschner,D
AU  - Jones,TE
AU  - Kafizas,A
AU  - Grätzel,M
AU  - Piccinin,S
AU  - Durrant,JR
DO  - 10.1021/jacs.5c18734
EP  - 4838
PY  - 2026///
SP  - 4833
TI  - Observation of Transition from Rate Law to Butler-Volmer Controlled Water Oxidation Kinetics on Hematite Photoanodes.
T2  - J Am Chem Soc
UR  - http://dx.doi.org/10.1021/jacs.5c18734
UR  - https://www.ncbi.nlm.nih.gov/pubmed/41607339
VL  - 148
ER  - 

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