Enhanced Electrocatalytic Oxygen Reduction Reaction of TiO2 Nanotubes by Combining Surface Oxygen Vacancy Engineering and Zr Doping

This work examines the cooperative effect between Zr doping and oxygen vacancy engineering in anodized TiO2 nanotubes (TNTs) for enhanced oxygen reduction reactions (ORRs). Zr dopant and annealing conditions significantly affected the electrocatalytic characteristics of grown TNTs. Zr doping results in Zr4+ substituted for Ti4+ species, which indirectly creates oxygen vacancy donors that enhance charge transfer kinetics and reduce carrier recombination in TNT bulk. Moreover, oxygen vacancies promote the creation of unsaturated Ti3+(Zr3+) sites at the surface, which also boosts the ORR interfacial process. Annealing at reductive atmospheres (e.g., H2, vacuum) resulted in a larger increase in oxygen vacancies, which greatly enhanced the ORR activity. In comparison to bare TNTs, Zr doping and vacuum treatment (Zr:TNT–Vac) significantly improved the conductivity and activity of ORRs in alkaline media. The finding also provides selective hydrogen peroxide production by the electrochemical reduction of oxygen.