Graphitic carbon nitride (g-C3N4) has proved to be a promising heterogeneous photocatalyst in the visible range. It can be used, among others, for the oxidative conversion of environmentally harmful nitrophenols occurring in wastewater. However, its photocatalytic activity needs to be enhanced, which can be achieved by modification with various dopants. In our work, copper-modified g-C3N4 was prepared by ultrasonic impregnation of the pristine g-C3N4 synthesized from thiourea. The morphology, microstructure, and optical properties of the photocatalysts were characterized by XRD, FT-IR, DRS, SEM, XPS, and TEM. DRS analysis indicated a slight change in both the CB and the VB energies of Cu/g-C3N4 compared to those of g-C3N4. The efficiency of the photocatalysts prepared was tested by the degradation of nitrophenols. Copper modification caused a sevenfold increase in the rate of 4-nitrophenol degradation in the presence of H2O2 at pH = 3. This dramatic enhancement can be attributed to the synergistic effect of copper and H2O2 in this photocatalytic system. A minor Fenton reaction role was also detected. The reusability of the Cu/g-C3N4 catalyst was demonstrated through five cycles. Copper-modified g-C3N4 with H2O2 proved to be applicable for efficient visible-light-driven photocatalytic oxidative degradation of nitrophenols.
Catalysts for visible-light-driven oxidative cleaning processes and antibacterial applications (also in the dark) were developed. In order to extend the photoactivity of titanium dioxide into the visible region, nitrogen-doped TiO2 catalysts with hollow and non-hollow structures were synthesized by co-precipitation (NT-A) and sol–gel (NT-U) methods, respectively. To increase their photocatalytic and antibacterial efficiencies, various amounts of silver were successfully loaded on the surfaces of these catalysts by using a facile photo-deposition technique. Their physical and chemical properties were evaluated by using scanning electron microscopy (SEM), transmission electron microscopy–energy dispersive X-ray spectroscopy (TEM–EDS), Brunauer–Emmett–Teller (BET) surface area, X-ray diffraction (XRD), and diffuse reflectance spectra (DRS). The photocatalytic performances of the synthesized catalysts were examined in coumarin and 1,4-hydroquinone solutions. The results showed that the hollow structure of NT-A played an important role in obtaining high specific surface area and appreciable photoactivity. In addition, Ag-loading on the surface of non-hollow structured NT-U could double the photocatalytic performance with an optimum Ag concentration of 10−6 mol g−1, while a slight but monotonous decrease was caused in this respect for the hollow surface of NTA upon increasing Ag concentration. Comparing the catalysts with different structures regarding the photocatalytic performance, silverized non-hollow NT-U proved competitive with the hollow NT-A catalyst without Ag-loading for efficient visible-light-driven photocatalytic oxidative degradations. The former one, due to the silver nanoparticles on the catalyst surface, displayed an appreciable antibacterial activity, which was comparable to that of a reference material practically applied for disinfection in polymer coatings.
Graphitic carbon nitride (g-C3N4) proved to be a promising semiconductor for the photocatalytic degradation of various organic pollutants. However, its efficacy is limited by a fast electron hole recombination, a restricted quantity of active sites, and a modest absorption in the visible range. To overcome these limitations, g-C3N4-Bi2S3 and g-C3N4-ZnS composites were effectively produced utilizing a starch-assisted technique. The findings from FT-IR, XRD, EDX, XPS, BET, SEM, and TEM demonstrated that the enhanced photocatalytic activity of g-C3N4-Bi2S3 and g-C3N4-ZnS composites was primarily due to their improved photocarrier separation and transfer rates. The photocatalyst facilitated the aerobic photocatalytic degradation of colorless contaminants such as coumarin and para-nitrophenol (4-NP). For the decomposition of 4-NP, g-C3N4-Bi2S3 exhibited a maximum efficiency of 90.86% in UV light and 16.78% in visible light, with rate constants of 0.29 h−1 and 0.016 h−1, respectively. In contrast, g-C3N4-ZnS demonstrated a maximum efficiency of 100% in UV light and 15.1% in visible light, with rate constants of 0.57 h−1 and 0.018 h−1, respectively. The bioinspired synthesis combined with the modification with metal sulfides proved to considerably enhance the photocatalytic activity of g-C3N4, increasing its potential for practical applicability in environmentally friendly water treatment systems for the efficient removal of recalcitrant organic contaminants.
It is well known that surfactants increase the solubility of hydrophobic organic compounds and cause adverse environmental effects. The removal of these compounds from the contaminated soil or ground-water is particularly difficult due to their water soluble feature. In this work, an ultra-high performance hydrophilic interaction liquid chromatographic method was developed for the separation of oligomers of Triton X-100 octylphenol-polyethoxylate non-ionic surfactant. Liquid chromatography-mass spectrometry (LC-MS) was used to identify the Triton X-100 compounds. There was a 44 mass unit difference between two adjacent peaks that is the molar mass of one ethylene oxide group (–CH CH O–). A quadratic retention model was applied for the estimation of retention of the examined non-ionic surfactant and the optimization of gradient elution conditions. The optimized method was suitable for the baseline separation of 28 Triton X-100 oligomers in five minutes.
The synthesis and structural characterization of synthetic zinc oxide and halloysite-based zinc oxide nanocomposites (with 2–28 m/m% ZnO content) are presented. The chemical precipitation of zinc hydroxide precursors and its subsequent drying at 80 °C yielded dominantly zinc oxide (zincite). Thermal treatment at 350 °C completely transformed the remaining precursor to ZnO without causing structural dehydroxylation of the halloysite support. The procedure yielded zinc oxide nanoparticles with 10–22 nm average size having quasi-spherical scale-like morphology. The specific surface area of the synthetic zinc oxide was found to be low (13 m2/g), which was significantly enhanced after nanocomposite preparation (27–47 m2/g). The photocatalytic activity of the prepared nanocomposites was probed by the degradation of a phenolic compound (4-nitrophenol) upon UV irradiation in liquid phase. Compared to their individual constituents, an increased activity of the nanocomposites was observed, while the SSA-normalized photocatalytic activity revealed a synergic effect in nanocomposites above 9 m/m% ZnO content. The nanocomposites were found to be stable at pH = 5.6, with a minor and major mobilization of zinc ions at pH = 12.4 and pH = 1.9, respectively. The toxicity of leachates in different pH environments by Vibrio fischeri bioluminescence indicated low toxicity for ZnO nanoparticles and insignificant toxicity for the nanocomposites. The enhanced photocatalytic activity together with the lower toxicity of the halloysite-ZnO nanocomposites highlight their application potential in water treatment.