Fabrication of 0D/1D S-scheme CoO-CuBi2O4 heterojunction for efficient photocatalytic degradation of tetracycline by activating peroxydisulfate and product risk assessment.

The step-scheme (S-scheme) heterojunction has excellent redox capability, effectively degrading organic pollutants in wastewater. Combining S-scheme heterojunction with activated persulfate advanced oxidation process reasonably can further enhance the degradation of Emerging Contaminants. Herein, a novel zero-dimensional/one-dimensional (0D/1D) CoO-CuBi2O4 (CoO-CBO) photocatalyst with S-scheme heterojunction was designed by hydrothermal and solvothermal methods. The band structure and electron and hole transfer pathway of CoO-CBO were analyzed using the ex-situ and in-situ X-ray photoelectron spectroscopy (XPS), Ultraviolet and Visible Spectrophotometer (UV-Vis) and optical radiation Kelvin probe force microscope (KPFM), and the formation of S-scheme heterojunction was demonstrated. The photocatalytic activity of ·S-scheme CoO-CBO heterojunction was carried out by degrading tetracycline (TC) with activating potassium monopersulfate triple salt under visible light. Compared with pure CuBi2O4 and pure CoO, 30%CoO/CuBi2O4 catalyst exhibited the highest TC degradation performance after activating persulfate, degrading 89.5% of TC within 90 min. On the one hand, the S-scheme heterojunction formed between CoO and CBO had a high redox potential. On the other hand, the activation of persulfate by Co and Cu could accelerate redox cycles and facilitate the generation of active radicals such as SO4-, O2- and OH, promoting the separation of the photogenerated e- and h+ in the composite, enhancing the peroxydisulfate (PDS) activation performance and improving the degradation effect of TC. Then, a gradual decrease in the toxicity of the intermediates in the TC degradation process was detected by ECOCER. In all, this study provided an S-scheme CoO/CuBi2O4 heterojunction that can activate PDS to degrade TC efficiently, which provided a new idea for the study of novel pollutant degradation and environmental toxicology.

Construction of a floating photothermal-assisted photocatalytic system with a three-dimensional hollow porous network structure.

Solar energy is the inevitable choice to achieve the low-carbon, green, and circular development of society, and photocatalysis technology is one of the shining pearls. To make full use of the solar spectrum and solve the shortcomings of the recovery difficulty of powdery materials and the loss of activity due to the influence of the external environment, it is possible to construct floating materials using melamine sponges to recover photocatalytic materials quickly. At the same time, floating materials can absorb oxygen in the air for the generation of active groups, effectively solving the problem of less O2 in the water. The carbon-based materials have excellent light absorption properties, high thermal conductivity, and excellent photothermal conversion efficiency and are ideal for constructing floating photothermal photocatalytic systems. As an example, we combined a cheap melamine sponge with urea, prepared a hollow porous network structure g-C3N4 (HPNCN) with a high specific surface area by direct thermal shrinkage method, and then attached the CoO to its surface by hydrothermal method to form a heterojunction with a suitable band gap. Various characterization tests verified the photothermal-photocatalytic properties. Among them, 30% CoO/HPNCN has the best photocatalytic degradation effect on tetracycline (TC), and the removal rate is 88.1%. After five cycles, the removal rate is only 5% lower than the initial, indicating that it has good stability and recyclability. We conducted an active ingredient capture experiment, ESR, and LC-MS analysis to clarify the intermediates and reaction mechanism of TC photocatalytic degradation. On this basis, the ECOSAR program and QSAR method were used to analyze the environmental toxicity of TC and its intermediate products. These results provide a broad prospect for the potential application of the floating photothermal-photocatalysis system in antibiotic pollution control and its application in other fields.

Boosted Tetracycline and Cr(VI) Simultaneous Cleanup over Z-Scheme WO3/CoO p-n Heterojunction with 0D/3D Structure under Visible Light.

In this study, a Z-Scheme WO3/CoO p-n heterojunction with a 0D/3D structure was designed and prepared via a simple solvothermal approach to remove the combined pollution of tetracycline and heavy metal Cr(VI) in water. The 0D WO3 nanoparticles adhered to the surface of the 3D octahedral CoO to facilitate the construction of Z-scheme p-n heterojunctions, which could avoid the deactivation of the monomeric material due to agglomeration, extend the optical response range, and separate the photogenerated electronhole pairs. The degradation efficiency of mixed pollutants after a 70 min reaction was significantly higher than that of monomeric TC and Cr(VI). Among them, a 70% WO3/CoO heterojunction had the best photocatalytic degradation effect on the mixture of TC and Cr(VI) pollutants, and the removing rate was 95.35% and 70.2%, respectively. Meanwhile, after five cycles, the removal rate of the mixed pollutants by the 70% WO3/CoO remained almost unchanged, indicating that the Z-scheme WO3/CoO p-n heterojunction has good stability. In addition, for an active component capture experiment, ESR and LC-MS were employed to reveal the possible Z-scheme pathway under the built-in electric field of the p-n heterojunction and photocatalytic removing mechanism of TC and Cr(VI). These results offer a promising idea for the treatment of the combined pollution of antibiotics and heavy metals by a Z-scheme WO3/CoO p-n heterojunction photocatalyst, and have broad application prospects: boosted tetracycline and Cr(VI) simultaneous cleanup over a Z-scheme WO3/CoO p-n heterojunction with a 0D/3D structure under visible light.

Rational Design of Monolithic g-C3N4 with Floating Network Porous-like Sponge Monolithic Structure for Boosting Photocatalytic Degradation of Tetracycline under Simulated and Natural Sunlight Illumination.

In order to solve the problems of powder g-C3N4 catalysts being difficult to recycle and prone to secondary pollution, floating network porous-like sponge monolithic structure g-C3N4 (FSCN) was prepared with a one-step thermal condensation method using melamine sponge, urea, and melamine as raw materials. The phase composition, morphology, size, and chemical elements of the FSCN were studied using XRD, SEM, XPS, and UV-visible spectrophotometry. Under simulated sunlight, the removal rate for 40 mg·L-1 tetracycline (TC) by FSCN reached 76%, which was 1.2 times that of powder g-C3N4. Under natural sunlight illumination, the TC removal rate of FSCN was 70.4%, which was only 5.6% lower than that of a xenon lamp. In addition, after three repeated uses, the removal rates of the FSCN and powder g-C3N4 samples decreased by 1.7% and 2.9%, respectively, indicating that FSCN had better stability and reusability. The excellent photocatalytic activity of FSCN benefits from its three-dimensional-network sponge-like structure and outstanding light absorption properties. Finally, a possible degradation mechanism for the FSCN photocatalyst was proposed. This photocatalyst can be used as a floating catalyst for the treatment of antibiotics and other types of water pollution, providing ideas for the photocatalytic degradation of pollutants in practical applications.