The relationship between microstructure and photocatalytic behavior in lanthanum-modified 2D TiO2 nanosheets upon annealing of a freeze-cast precursor

Abstract

Titanium dioxide modified with 3 wt% La was prepared via a green freeze-casting method, and its photocatalytic activity was tested in terms of its ability to degrade 4-chlorophenol (4-CP) and remove total organic carbon (TOC). Under annealing conditions, the freeze-cast precursor was transformed into an La-modified anatase with a well-defined 2D TiO₂ nanosheet morphology. Rietveld refinement of the X-ray diffraction patterns confirmed the substitutional nature of the La cation that induced local structural variations and involved subtle ion displacement in the TiO₂ lattice due to the ionic size effect. Despite nearly identical tetragonal structures, replacement of Ti with La alters the photocatalytic activity through a reduction in band gap energies and an increase in charge carrier mobility. Material annealed at 650 °C exhibited the highest photocatalytic performance and achieved efficient TOC removal. Upon annealing at 800 °C, nanoscale lanthanum-enriched regions were generated due to the diffusive migration of La cations and phase transition from anatase to rutile. The La³⁺ cation, acting as a structural promoter, supported 2D TiO₂ growth with well controlled crystallite size, surface area and porosity. La³⁺ could be regarded as a potential electronic promoter that can reduce the band gap of 2D TiO₂ nanosheets and can provide a signature of the electron transfer and carrier charge separation. Both methods, kinetics of degradation of 4-CP and TOC, provided similar results, revealing that the photocatalytic activity under UV light irradiation increased in the order 950C < 500 °C < 800 °C < 650 °C < TiO₂-P25.