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Heavy metal pollution treatment in industrial wastewater is crucial for protecting biological and environmental safety. However, the highly efficient and selective removal of heavy metal ions from multiple cations in wastewater is a significant challenge. This work proposed a pulse electrochemical method with a low-/high-voltage periodic appearance to selectively recover heavy metal ions from complex wastewater. It exhibited a higher recovery efficiency for heavy metal ions (100% for Pb2+and Cd2+, >98% for Mn2+) than other alkali and alkaline earth metal ions (Na+, Ca2+, and Mg2+were kept below 3.6, 1.3, and 2.6%, respectively) in the multicomponent solution. The energy consumption was only 34–77% of that of the direct current electrodeposition method. The results of characterization and experiment unveil the mechanism that the low-/high-voltage periodic appearance can significantly suppress the water-splitting reaction and break the mass-transfer limitation between heavy metal ions and electrodes. In addition, the plant study demonstrates the feasibility of treated wastewater for agricultural use, further proving the high sustainability of the method. Therefore, it provides new insights into the selective recovery of heavy metals from industrial wastewater.

Herein, we developed an unmodified hexagonal boron nitride (h-BN) photoelectrochemical (PEC) biosensing platform with a low background signal and high sensitivity based on CuS quantum dots (QDs)/Co3O4polyhedra-driven multiple signal amplifications. The prepared porous h-BN nanosheets with large specific surface areas, as the photoelectric substrate material, can provide extensive active reaction sites. Meanwhile, the CuS QDs/Co3O4polyhedra were synthesized by the zeolitic imidazolate framework (ZIF-67) and utilized as a multiple signal amplifier, which can not only drive the p-n semiconductor quenching effect to compete with the h-BN photoelectrode for the consumption of electron donors and exciting light but also trigger a mimetic enzymatic catalytic precipitation effect to inhibit electron transfer. The quenching ability and peroxidase-like activity of CuS QDs/Co3O4polyhedra were evaluated to prove its superiority, and the possible mechanisms of electron transfer and enzymatic catalytic were further analyzed in detail. The developed PEC biosensing platform for the chlorpyrifos assay presented outstanding performance with a wide linear range from 1 × 10–1to 1 × 107ng mL–1and a low detection limit of 0.34 pg mL–1and exhibited excellent selectivity, reproducibility, and stability. In addition, the CuS QDs/Co3O4polyhedra-activated h-BN PEC biosensing platform may exhibit universality for various analytes via replacing the corresponding target aptamer sequence. This work provides a remarkable inspiration and valuable reference for the development of the PEC biosensor, and the signal amplifier-enabled unmodified PEC biosensing platform strategy has a bright application in early safety warning, bioanalysis and clinical diagnosis.

The good performance of base metal catalysts for the electrooxidation of organic pollutants has attracted great attention. However, base metal phosphides for electrooxidation are seldom studied owing to the sluggish water adsorption and dissociation dynamics, which will hinder the production of the sorbed hydroxyl radicals (M(•OH)) and thus inhibit the electrooxidation of organic pollutants. Herein, we proposed a universal strategy to improve the electrooxidation capability of metal phosphides by modulating the surface electron densities. The electron interactions between cobalt (Co) and phosphorus (P) are modulated after iron doping, resulting in more positively charged Co and more negatively charged P, which can promote the adsorption and activation of water molecules and produce large quantities of M(•OH). Meanwhile, the experimental results show that the iron-modulated Fe0.53Co0.47P nanosheet arrays exhibit higher removal efficiency of tetracycline than the boron-doped diamond and Pt anode at low current intensity. Based on experimental results and density functional theory + Ucalculations (DFT + U), it is found that Fe0.53Co0.47P has lower barrier (0.45 eV) to form the sorbed hydroxyl radicals (M(•OH)) and higher overpotential to produce O2than its counterparts, suggesting that Fe0.53Co0.47P can produce more M(•OH) instead of O2. The above results highlighted the feasibility of these base metal phosphides for electrooxidation for advanced water purification.

Studies on the removal of As(iii) by Fe-based materials have been carried out for decades, but the time-consuming process and low removal capacity are obstacles for large-scale practical applications. Here, a rapid and efficient technique was proposed for the removal of As(iii) using Cu-doped Fe@Fe2O3core–shell nanoparticles (CFF) synthesized by a facile two-step reduction method and aging process, which realized a thorough removal of As(iii) from smelting wastewater at neutral pH within 30 min. The copper doped in CFF not only provided two extra oxygen reduction pathways to enhance the molecular oxygen activation, but also improved the electron transfer ability and removal efficiency of As(iii). The existence of copper contributed to the rapid oxidization and adsorption of As(iii), and the removal rate increased nearly 10-times in the aerobic system. Meanwhile, the proposed Cu-doped Fe@Fe2O3core–shell nanoparticles and shifted oxygen reduction pathway could be easily scaled up for other transition metals, such as Ni. Molecular dynamics (MD) simulations based on the large-scale atomic/molecular massively parallel simulator (LAMMPS) were also employed to investigate the formation process of CFF. Furthermore, the removal efficiency of arsenic in smelting wastewater remained to be 90% after 6 times of cycling. Therefore, the distinctive oxidation activities of CFF hold great promise for applications in arsenic removal.

The utilization of solar energy based on semiconductor photocatalysts for pollutant removal and environmental remediation has become a research hot spot and attracted great attention. In this study, a novel ternary BiVO4/Ag/Cu2O nanocomposite has been successfully synthesized viasimple wet impregnation of Cu2O particles coupled with a subsequent photo-reduction pathway for the deposition of metallic Ag on the surface of BiVO4. The resulting BiVO4/Ag/Cu2O photocatalyst was used for the degradation of tetracycline (TC) under visible light irradiation (λ> 420 nm). Results showed that the coating contents of the Cu2O and Ag particles presented a great effect on the eventual photocatalytic activity of the photocatalysts, and the optimum coating contents of Cu2O and Ag were obtained with their mass ratios of 3% and 2%, respectively. Under optimum conditions, nearly 91.22% TC removal efficiency was obtained based on ternary BiVO4/Ag/Cu2O nanocomposites, higher than that of pure BiVO4(42.9%) and binary BiVO4/Cu2O (65.17%) and BiVO4/Ag (72.63%) nanocomposites. Meanwhile, the enhanced total organic carbon (TOC) removal efficiency also indicated the excellent photocatalytic degradation ability of the BiVO4/Ag/Cu2O nanocomposites. As for their practical application, the effects of initial TC concentration, various supporting electrolytes and different irradiation conditions were investigated in detail. Three-dimensional excitation–emission matrix fluorescence spectroscopy (3D EEMs) was used to show the by-products of TC molecule degradation. Cycling experiments indicated the high stability of the as-prepared photocatalysts. Furthermore, the results obtained from radical trapping experiments and ESR measurements suggested that the photocatalytic degradation of TC in the BiVO4/Ag/Cu2O based photocatalytic system was the joint action of the photogenerated holes (h+), superoxide radical (O2−) and hydroxyl radical (OH). The enhanced photocatalytic activity of BiVO4/Ag/Cu2O was attributed to the synergistic effect of Cu2O, Ag and BiVO4, especially the surface plasmon resonance effect and the established local electric field brought about by metallic Ag. Additionally, to deeply understand the reaction mechanism, a dual Z-scheme charge transfer pathway has been proposed.

Sulfate radicals have been increasingly used for the pathogen inactivation due to their strong redox ability and high selectivity for electron-rich species in the last decade. The application of sulfate radicals in water disinfection has become a very promising technology. However, there is currently a lack of reviews of sulfate radicals inactivated pathogenic microorganisms. At the same time, less attention has been paid to disinfection by-products produced by the use of sulfate radicals to inactivate microorganisms. This paper begins with a brief overview of sulfate radicals’ properties. Then, the progress in water disinfection by sulfate radicals is summarized. The mechanism and inactivation kinetics of inactivating microorganisms are briefly described. After that, the disinfection by-products produced by reactions of sulfate radicals with chlorine, bromine, iodide ions and organic halogens in water are also discussed. In response to these possible challenges, this article concludes with some specific solutions and future research directions.

Antibiotic residues in the environment and in foods pose a serious threat to ecosystems and human health. Developing sensitive and on-site detection methods is therefore in high demand. In this work, a portable paper-based colorimetric sensor with a smartphone platform with an ultrahigh sensitivity has been designed for on-site and quantitative analysis of antibiotic residues based on aptamer-regulated nanozyme activity. The developed excellent peroxidase-like nanozymes, carbon-protected NiCo bimetal oxides with a unique hollow nanocage structure (NiCo@C HCs), could effectively catalyze the oxidation of chromogenic substrates by H2O2. Once bound to a specific aptamer, the enzyme-mimicking activity of NiCo@C HCs is obviously inhibited as a result of the masking of active sites but could be restored via the target-aptamer recognition. Herein, the aptamer-modified NiCo@C HCs are embedded on paper pieces to construct paper-based biochips for visual detection. Meanwhile, a smartphone platform is integrated for the signal readout. Using enrofloxacin (ENR) as an analyte model, the proposed paper-based analysis platform shows a reliable and sensitive detection of ENR with an ultralow detection limit of 0.029 ng/mL. The platform also works well in various real samples. This analysis method is facile in design, showing a great application potential for on-site and mass screening of antibiotic residues in the environment and in foods.

The good performance of base metal phosphides as alternative catalysts for hydrogen evolution has attracted great attention. However, phosphorus-hydrogen bonds (P-Hads) are easily formed on the surface of metal phosphides, which will severely inhibit hydrogen evolution reaction (HER). Herein, we propose a universal strategy to improve the HER activity of metal phosphides by modulating the surface electron densities. The iron modulated Fe0.29Co0.71P nanosheet arrays exhibit an overpotential of 74 mV at 10 mA cm−2and a Tafel slope of 53.56 mV dec−1, which are close to the performance of noble metal catalysts in alkaline condition. The electronic interactions between cobalt and phosphorus are modulated after iron doping, resulting in more positively charged Co, which can promote adsorption and activation of H2O molecules and will weaken P-Hadsbonds formed on the catalyst surfaces. Therefore, Fe0.29Co0.71P can optimize the adsorption and desorption of H atoms, and can promote both Volmer and Heyrovsky steps of HER. In addition, the electron density modulation of catalytic sites also improves the OER catalytic performance of Fe0.29Co0.71P. The overall water splitting electrolyzer assembled by Fe0.29Co0.71P/Ni-foam exhibits a lower cell voltage (1.59 V/10 mA cm−2), compared to that (1.61 V/10 mA cm−2) of the IrO2//Pt/C electrolyzer.