Rapid Determination of the Optimum Thickness of Doped TiO2 Nanotubes Layer by Local Photoelectrochemistry and Operando Properties Extraction by Data Modeling.

Abstract

In this work, the optimal thickness of TiO2, M‐doped, N‐doped, and (M:N) codoped TiO2 (with M = Nb or Ta) nanotubes (NTs) for photoelectrochemical (PEC) water splitting is determined, in one step through local photoelectrochemical analysis of electrodes with variable thickness of the photoactive material. A simple anodization method allows the growth, on a single electrode, of aligned doped TiO2 nanotubes whose length gradually changes from 0 to 15 μm. The external quantum efficiency (EQE) as a function of the NTs film thickness is measured using a small beam of UV or visible light to scan the surface and locally trigger the oxygen evolution reaction (OER). The results provide the optimal NT layer thickness for each type of doped TiO2‐NTs and demonstrate that if the (M:N) codoped TiO2‐NTs have the best activity in the visible region, the optimal layer thickness is reduced compared to TiO2 or M:doped TiO2‐NTs. Additionally, by fitting the data with a model that incorporates charge carrier transfer and light absorption mechanisms in the film, it becomes possible to evaluate in operando the interfacial charge transfer, absorption coefficient or majority carrier mean path which are important properties of semiconducting (SC) materials for PEC applications.This article is protected by copyright. All rights reserved.