Experimental and theoretical investigations of the influence of carbon on a Ho3+-TiO2 photocatalyst with Vis response

Abstract

Due to their photon up-converting capability, lanthanide ions are ideal candidates dopants for semiconductors for developing visible light-driven photocatalytic activity. Of particular relevance, the low luminescence efficiency of Ln-based nanoparticles is one of the main factors that limits their further applications. Carbon, which is present on the surface of all TiO2 photocatalysts, can be responsible for luminescence quenching processes and, thus, decreasing the photocatalytic activity of TiO2. This article presents a systematic experimental and theoretical study of the effects of carbon on the photocatalytic performance of Ho3+-modified TiO2. Ho3+-TiO2 photocatalysts modified with various carbon contents (from 0.5 to 20 mol.%) were successfully prepared using a simple hydrothermal method. As-obtained samples were characterized by UV–Vis diffuse reflectance spectroscopy (DRS/UV–Vis), X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), N2 adsorption measurements, photoluminescent spectroscopy (PL), field-emission scanning electron microscopy (FE-SEM) and scanning transmission microscopy (STEM). The photodegradation efficiency of phenol was estimated for visible light (λ > 420 nm and λ > 455 nm). The XPS and XRD analyses and theoretical calculations revealed that the substitutional doping of holmium and carbon in the TiO2 anatase structure resulted in the appearance of a new sub-band-gap. Changes in the material texture, BET surface area and pore volume can be easily controlled via carbon content in samples. Doping of the Ho3+-TiO2 photocatalysts with carbon resulted in quenching of the emission of Ho3+ and, thus, the photodegradation of phenol, was observed in samples containing smaller amounts of carbon. Sixty minutes of irradiation resulted in 89% of phenol degradation under visible light (λ > 420 nm).