Photoanodes Based on TiO$_2$ and $\alpha$-Fe$_2$O$_3$ for Solar Water Splitting Superior Role of 1D Nanoarchitectures and of Combined Heterostructures

Abstract

Solar driven photoelectrochemical water splitting (PEC-WS) using semiconductor photoelectrodes represents a promising approach for a sustainable and environmentally friendly production of renewable energy vectors and fuel sources, such as dihydrogen (H2). In this context, titanium dioxide (TiO$_2$) and iron oxide (hematite, $\alpha$-Fe$_2$O$_3$) are among the most investigated candidates as photoanode materials, mainly owing to their resistance to photocorrosion, non-toxicity, natural abundance, and low production cost. Major drawbacks are, however, an inherently low electrical conductivity and a limited hole diffusion length that significantly affect the performance of TiO$_2$ and $\alpha$-Fe$_2$O$_3$ in PEC devices. To this regard, one-dimensional (1D) nanostructuring is typically applied as it provides several superior features such as a significant enlargement of the material surface area, extended contact between the semiconductor and the electrolyte and, most remarkably, preferential electrical transport that overall suppress charge carrier recombination and improve TiO$_2$ and $\alpha$-Fe$_2$O$_3$ photo-electrocatalytic properties. The present review describes various synthetic methods, properties and PEC applications of 1D-photoanodes (nanotubes, nanorods, nanofibers, nanowires) based on titania, hematite, and on $\alpha$-Fe$_2$O$_3$/TiO$_2$ heterostructures. Various routes towards modification and enhancement of PEC activity of 1D photoanodes are also discussed including doping, decoration with co-catalysts and heterojunction engineering. Finally, the challenges related to the optimization of charge transfer kinetics in both oxides are highlighted.