This study investigated the synthesis of two different types of photocatalysts, namely, boron/sodium fluoride co-doped titanium dioxide (B/NaF-TiO2), and its analogue, a dye-sensitized form of silicon-based axial methoxy substituted phthalocyanine (B/NaF-TiO2SiPc). Structural and morphological characterizations were performed via X-ray diffraction (XRD); Fourier transform infra-red (FTIR); N2 adsorption–desorption at 77 K by Brunauer–Emmett–Teller (BET) and Barrett, Joyner, and Halenda (BJH) methods; transmission electron microscopy (TEM); X-ray photoelectron spectroscopy (XPS); and UV–visible absorption spectroscopy. The estimated crystallite size of pure TiO2 and pure B/NaF-TiO2 was 24 nm, and that of B/NaF-TiO2SiPc was 29 nm, whereas particle sizes determined by TEM were 25, 28, and 31 nm for pure TiO2, B/NaF-TiO2 and B/NaF-TiO2SiPc respectively. No significant differences between B/NaF-TiO2 and B/NaF-TiO2SiPc were observed for surface area by (BET) analysis (13 m2/g) or total pore volume by the BJH application model (0.05 cm3/g). Energy band gap values obtained for B/NaF-TiO2 and B/NaF-TiO2SiPc were 3.10 and 2.90 eV respectively, lower than pure TiO2 (3.17 eV). The photocatalytic activity of the synthesized materials was tested using carbamazepine (CBZ) as the model substrate. Carbamazepine removal after 4 h of irradiation was almost 100% for B/NaF-TiO2 and 70% for B/NaF-TiO2SiPc; however, the substrate mineralization proceeded slower, suggesting the presence of organic intermediates after the complete disappearance of the pollutant.

Photocatalytic coatings of TiO2/ZnO/CuPc were developed on stainless steel substrates by subsequent sol gel dip coating for TiO2, spray pyrolysis for ZnO, and spin coating for copper (ii) phthalocyanine (CuPc) deposition. The latter compound was successfully prepared using a Schiff-based process. The materials and coatings developed were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy with attached energy dispersive spectroscopy (SEM-EDS), UV-Vis spectroscopy, room temperature photoluminescence (RTPL) spectroscopy, H1-nuclear magnetic resonance (1H-NMR) spectroscopy, C13-nuclear magnetic resonance (13C-NMR) spectroscopy, and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS). The as-deposited TiO2/ZnO/CuPc on stainless steel retained in pristine state the structural and morphological/spectroscopic characteristics of its respective components. Estimated energy band gap values were 3.22 eV, 3.19 eV, 3.19 eV for TiO2, ZnO, TiO2/ZnO respectively and 1.60 eV, 2.44 eV, and 2.92 eV for CuPc. The photocatalytic efficiency of the fabricated TiO2/ZnO/CuPc coatings was tested toward ibuprofen (IBF). After 4 h irradiation under 365 nm UV, an increased degradation of about 80% was achieved over an initial 5 mg/L ibuprofen (IBF). This was much higher compared to about 42% and 18% IBF degradation by TiO2/ZnO and TiO2 thin film, respectively. In all cases, the stability of the best-performing photocatalyst was investigated showing a small decline to 77% of IBF degradation after the 5th cycle run. The effect of pH, reactive oxygen species (ROS) probe, shed light on a possible catalytic mechanism that was suggested.

Contaminants of emerging concerns (CECs) spread across a wide range of organic product compounds. As biorecalcitrants, their removal from conventional wastewater treatment systems remains a herculean task. To address this issue, heterogenous solar driven advanced oxidation process based-TiO2 and other semiconductor materials has been extensively studied for their abatement from wastewater sources. In this study, we have synthesized by hydrothermal assisted co-precipitation Ag doped ZnSnO3. Structural and morphological characterizations were performed via X-ray diffraction (XRD), Fourier transform infra-red (FTIR), N2 adsorption-desorption at 77 K by Brunauer-Emmet-Teller (BET) and Barrett, Joyner, and Halenda (BJH) methods, Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy coupled with Energy dispersive spectroscopy (SEM-EDS), and UV-visible absorption in Diffuse reflectance spectroscopy (UV-vis/DRS) mode. Crystallite size estimate for Ag-ZnSnO3 and undoped form was 19.4 and 29.3 nm, respectively, while respective TEM particle size estimate was 79.0 nm and 98.2 nm. BET surface area and total pore volume by BJH for Ag-ZnSnO3 were estimated with respective values of 17.2 m2/g and 0.05 cm3/g in comparison to 18.8 m2/g and 0.06 cm3/g for ZnSnO3. Derived energy band gap (Eg) values were 3.8 eV for Ag-ZnSnO3 and 4.2 eV for ZnSnO3. Photocatalytic performance of Ag-ZnSnO3 was tested towards caffeine achieving about 68% removal under (natural) unmodified pH = 6.50 and almost 100% removal at initial pH around 7.5 after 4 h irradiation. The effect of initial pH, catalyst dosage, pollutant concentration, charge scavengers, H2O2, contaminant inorganic ions (anions) as well as humic acid (HA) on the photocatalyst activity over caffeine degradation were assessed. In accordance with the probation test of the reactive species responsible for photocatalytic degradation process, a reaction mechanism was deduced.