BibTex format
@article{Benetti:2026:10.1021/jacs.6c11949,
author = {Benetti, D and Scott, SB and Yu, S and Murawski, J and Liang, C and Winiwarter, A and Yang, G and Kafizas, A and Hankin, A and Stephens, IEL and Durrant, JR and Eisner, F},
doi = {10.1021/jacs.6c11949},
journal = {J Am Chem Soc},
pages = {41739--41744},
title = {Linking Oxygen Evolution Selectivity to Water Oxidation Reaction Order on Hematite Photoanodes by Operando Photoelectrochemical Mass Spectrometry.},
url = {http://dx.doi.org/10.1021/jacs.6c11949},
volume = {148},
year = {2026}
}
RIS format (EndNote, RefMan)
TY - JOUR
AB - Water oxidation on metal-oxide (photo)anodes is often assumed to yield molecular oxygen. Here, we combine operando photoelectrochemical mass-spectrometry oxygen detection with spectroelectrochemical rate law analyses to link oxygen selectivity to surface-hole density on hematite photoanodes. At low current and hole densities, where first-order kinetics dominate, a near-zero Faradaic efficiency for oxygen evolution is observed, revealing that isolated single-hole water oxidation is poorly coupled to molecular oxygen formation. Increasing surface-hole density sharply increases O2 Faradaic efficiency, showing that the kinetic crossover to cooperative third-order water oxidation is also a selectivity switch toward O2 evolution. Equivalent behavior under dark electrochemical operation shows that multihole chemistry is intrinsic to hematite and governs selective oxygen evolution, likely representing a general feature of semiconducting metaloxides.
AU - Benetti,D
AU - Scott,SB
AU - Yu,S
AU - Murawski,J
AU - Liang,C
AU - Winiwarter,A
AU - Yang,G
AU - Kafizas,A
AU - Hankin,A
AU - Stephens,IEL
AU - Durrant,JR
AU - Eisner,F
DO - 10.1021/jacs.6c11949
EP - 41744
PY - 2026///
SP - 41739
TI - Linking Oxygen Evolution Selectivity to Water Oxidation Reaction Order on Hematite Photoanodes by Operando Photoelectrochemical Mass Spectrometry.
T2 - J Am Chem Soc
UR - http://dx.doi.org/10.1021/jacs.6c11949
UR - https://www.ncbi.nlm.nih.gov/pubmed/42937982
VL - 148
ER -