Enhanced activity of ZnS (111) by N/Cu co-doping: Accelerated degradation of organic pollutants under visible light.

High-efficiency photocatalysts are of great significance for the application of photocatalytic technology in water treatment. In this study, N/Cu co-doped ZnS nanosphere photocatalyst (N/Cu-ZnS) is synthesized by a hydrothermal method for the first time. After doping, the texture of nanosphere becomes loose, the nanometer diameter is reduced, making the specific surface area of catalyst increased from 34.73 to 101.59 m2/g. The characterization results show that more ZnS (111) crystal planes are exposed by N/Cu co-doping; the calculations of density functional theory show that N/Cu co-doping can increase the catalytic activity of the ZnS (111) crystal plane, enhance the adsorption capacity of (111) crystal plane to O2, and promote the generation of •O2-. The energy levels of the introduced impurities can be hybridized with the energy levels of S and Zn at the top of valence band and the bottom of conduction band, which makes the band gap narrower, thus enhancing the absorption of visible light. Compared with pure ZnS, the degradation rates of 2,4-dichlorophenol (2,4-DCP) and tetracycline (TC) by N/Cu-ZnS under visible light (>420 nm) are increased by 83.7 and 51 times, respectively. In this research, a promising photocatalyst for photocatalytic degradation of organic pollutants in wastewater is provided.

Photocatalytic degradation of organic pollutants in water by N-doping ZnS with Zn vacancy: enhancement mechanism of visible light response and electron flow promotion.

In order to improve the visible light response, N-doping ZnS (N-ZnS) nanospheres with Zn vacancy and porous surface were prepared by a simple one-pot hydrothermal method. Characterizations and density functional theory simulations showed excellent visible light response of N-ZnS. N-doping introduced impurity energy levels, which led to orbital hybridization and changed the original dipole moment. The presence of ortho Zn vacancy (O-Znv) can effectively reduce e--h+ recombination and photocorrosion. Furthermore, O-Znv caused lattice distortion (twisted the -S-Zn-N-(O-Znv)-S-Zn-S- chemical bond chain), resulting in "vacancy effect" to accelerate e- flow. Under visible light, the photocatalytic degradation efficiency of tetracycline (TC) and 2,4-dichlorophenol (2,4-DCP) was 90.31% and 60.84%, respectively. TOC degradation efficiency was 31.4% and 25.6%, respectively. Combined with Fukui index and LC-MS methods, it was found that TC and 2,4-DCP were degraded under the constant attack of active substances such as ·OH. This work can provide a reference for the application of catalytic materials in the field of visible light photocatalysis.

Antibacterial properties of recoverable CuZnO@Fe3O4@GO composites in water treatment.

The growth of bacteria will lead to water quality deterioration and equipment damage. Therefore, it is necessary to control the growth and reproduction of microorganisms in water treatment. A new type of magnetic recoverable CuZnO@Fe3O4@GO composites was prepared by ultrasonic method, and the composites were characterized and analyzed by SEM, TEM, XPS, and other methods. The optimum mass ratio of composites was determined by orthogonal experiment, and the antibacterial properties and mechanism of the composite were investigated by gram-positive bacteria Staphylococcus aureus and gram-negative bacteria Escherichia coli. Finally, the antibacterial properties of the composites in the effluent of the secondary sedimentation tank were researched. It was shown that the optimum mass ratio of the composites was GO:Fe3O4:CuZnO =1:2:3. When the dosage of composites was 180 mg L-1 and the action time was 100 min, the antibacterial rate against S. aureus and E. coli reached more than 99.5%. The composites could destroy the cell structure of two kinds of bacteria, increase the content of active oxygen in bacteria cells, and enhance the leakage rate of protein by more than 9 times in 150 min, thereby causing the death of the bacteria. And the antibacterial rate of the composites in effluent of the secondary sedimentation tank could reach 99%, and the magnetic recovery rate could reach more than 98%. After 5 cycles of use, the antibacterial rate could still exceed 90%.