Khurana, DivyanshDivyanshKhuranaPlankensteiner, NinaNinaPlankensteinerVermang, BartBartVermangVereecken, PhilippePhilippeVereecken2025-05-062024-11-262025-05-0620251433-7851WOS:001357989100001https://imec-publications.be/handle/20.500.12860/44848Knowing the exact location of the semiconductor band-edges is key for mechanistic insights into their use for water and CO2 photo/electrocatalysis. In this regard, a reliable strategy for nano-semiconductors did not exist yet. We demonstrate the use of reversible redox probes on nano-semiconductor electrodes to determine their band-edge locations in aqueous solutions. Rectifying current-potential (i-U) characteristics with the high work function (i.e. more positive formal potential) Fe(CN)63−/Fe(CN)64− redox couple yielded the exact flatband potential at various pH whereas the reversible i-U characteristics with the low work function (i.e. more negative formal potential) Ru(NH3)63+/Ru(NH3)62+ redox couple provided the conduction band-edge location and dopant concentration for a 30 nm thin-film n-TiO2. The methodology can be extended to other nano-semiconductors and serves as an alternative to and goes beyond the capabilities of the Mott-Schottky procedure for bulk semiconductor electrodes.Journal article10.1002/anie.202415857WOS:001357989100001ANATASE TIO2ENERGETICSRUTILEGAASMEDLINE:39504260