Ionic liquid/TiO₂ nanoparticles doped with non-expensive metals: new active catalyst for phenol photodegradation

TiO₂ nanoparticles were synthesized using 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI·BF₄) ionic liquid and doped with non-expensive metals Cu²⁺ and Fe³⁺ by the sol-gel method. The new generated photocatalysts had their morphological, textural and structural characteristics analysed by scanning electron microscopy and dispersive X-ray spectroscopy (SEM/EDS), transmission electron microscopy (TEM), Brunauer-Emmett-Teller analysis (BET), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and diffuse reflectance spectroscopy (DRS). The results showed two phases by XRD analysis, anatase (majority) and rutile (minority). The SEM micrographs exposed spherical TiO₂ NPs/BMI·BF₄ IL and compact layers for Cu²⁺ and Fe³⁺-doped TiO₂ NPs in BMI·BF₄ IL, the EDX confirmed only the presence of Ti, O, Fe and Cu. The BET and BJH analyses exhibited high porous TiO₂ NPs/BMI·BF₄ IL. The BET and BJH analyses confirmed that the pore diameter of mesoporous materials was between 12 and 16 nm with similar values for surface area (55-63 m² g^-1). The TEM images exhibited spherical shape nanoparticles with mean diameter of 20-22 nm. The DRS analysis and Tauc equation were applied to estimate the optical energy band gap of the photocatalysts. The energy band gap values of 3.1 eV, 3.32 eV, and 2.78 eV were obtained for TiO₂ NPs/BMI·BF₄ IL, 1% Fe³⁺-doped TiO₂ NPs/BMI·BF₄ IL and 1% Cu²⁺-doped TiO₂ NPs/BMI·BF₄ IL, respectively. Phenol photodegradation was realized using Cu²⁺ and Fe³⁺-doped TiO₂ NPs/BMI·BF₄ IL under UV/visible irradiation and quantified by HPLC-FLD. The phenol photodegradation was investigated by different concentrations of metal-doped TiO₂ NPs/BMI·BF₄ IL. The new active photocatalysts 1% Cu²⁺-doped TiO₂ NPs and 1% Fe³⁺-doped TiO₂ NPs/BMI·BF₄ IL exhibited high catalytic activity (99.9% and 96.8%, respectively). The photocatalysts 1% Cu²⁺ and 1% Fe³⁺-doped TiO₂ NPs/BMI·BF₄ IL were also evaluated using industrial wastewater from the tobacco industry. The results showed 56.7% phenol photodegradation, due to the complexity of the tobacco matrix wastewater.