Kinetic study of adsorption and photocatalytic degradation of methylene blue dye using TiO₂ nanoparticles with activated carbon

Abstract

Activated carbon (AC) exhibits limited adsorption capacity for pollutants. Conversely, titanium dioxide (TiO2) demonstrates excellent photocatalytic performance, making it a popular choice for pollutant removal. This study investigates the removal of methylene blue (MB) dye from wastewater using AC, TiO2@AC-2, and TiO2@AC-10 samples via adsorption and photocatalysis. The Energy Dispersive analysis of X-rays (EDAX) has confirmed the presence of Ti, C and O in the prepared samples without any impurities. All the diffraction peaks in X-ray diffractograms indicated the presence of pure anatase TiO2 (tetragonal phase) with no evidence of any other phase. Fourier transform infrared spectroscopy (FTIR) analysis identified a peak around 545 cm⁻¹ in the TiO2@AC-2 sample, indicative of O-Ti-O stretching vibrations. This peak shifted to 602 cm⁻¹ in the TiO2@AC-10 sample. Raman spectroscopy confirmed the presence of carbon (D and G bands) at 1310-1347 cm⁻¹ and 1582-1597 cm⁻¹. Additionally, characteristic Raman active bands for anatase TiO2 were observed at 154 cm⁻¹ (Eg), 204 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 508 cm⁻¹ (A1g), and 628 cm⁻¹ (Eg). N2 adsorption-desorption isotherms revealed a mesoporous structure for all samples (AC, TiO2@AC-2, and TiO2@AC-10) with hysteresis loops, indicating pores ranging from 2 nm to 50 nm in diameter. Reflectance spectra of TiO2@AC-2 and TiO2@AC-10 displayed absorption edges at 368 nm and 385 nm, respectively, corresponding to a direct band gap of approximately 3.22 eV. Subsequently, these prepared samples were effectively employed for the removal of methylene blue (MB) dye from wastewater utilizing both adsorption and photocatalysis method. Under dark conditions, 20 mg/L doses of TiO2@AC-2 and TiO2@AC-10 resulted in 60% and 36% dye adsorption within 60 minutes respectively. In the presence of UV radiation, the degradation of dye was observed to be 74% and 95% by TiO2@AC-2 and TiO2@AC-10 respectively. This observation indicates that TiO2 nanoparticles along with AC leads to enhanced photocatalytic activity. The Langmuir-Hinshelwood model reveals lower rate constants for AC compared to the composite samples. This is likely because AC lacks inherent catalytic activity, requiring UV light to trigger adsorption. Conversely, TiO2@AC-10 exhibits the highest rate constants (K1 = 24.25 × 10-3 min⁻¹ and K2 = 82.71 × 10-3 min⁻¹), aligning with its higher TiO2 content confirmed by EDAX analysis. This suggests a significantly faster photocatalytic rate and superior degradation efficiency, even at a low sample concentration (20 mg/L).