a b s t r a c tFe 3 O 4 magnetic nanoparticles (MNPs) with diameters about 10 nm were synthesized successfully and used to remove phenol and aniline from aqueous solution. The results showed that phenol and aniline could be eliminated easily from solution under acidic and neutral conditions in the presence of MNPs and H 2 O 2 . When the concentrations of Fe 3 O 4 MNPs and H 2 O 2 were 5 g L −1 and 1.2 M, respectively, phenol and aniline could be removed completely after 6 h of reaction at 308 K, and the total organic carbon (TOC) abatement efficiency for phenol and aniline were 42.79% and 40.38%. Some intermediates such as formic acid, acetic acid, fumaric acid and hydroquinone were detected during reaction. Fe 3 O 4 MNPs exhibited good stability and reusability, also showed excellent catalysis ability to eliminate some substituted phenolic and aniline compounds from solution. Fe 3 O 4 MNPs had good superparamagnetism and was readily separated from solution by applying an external magnetic field. Finally we proposed that phenol and aniline might be degraded by the hydroxyl free radicals (·OH) released from H 2 O 2 in the presence of Fe 3 O 4 MNPs as catalysts.

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ABSTRACT:We here first proposed a yolk−shell Co 3 O 4 @ metal−organic frameworks (MOFs) nanoreactor via a facile method to accommodate sulfate radical-based advanced oxidation processes (SR-AOPs) into its interior cavity. The mesoporous and adsorptive MOFs shells allow the rapid diffusion of reactant molecules to the encapsulated Co 3 O 4 active sites, and the confined high instantaneous concentration of reactants in the local void space is anticipated to facilitate the SR-AOPs. As a proof of concept, the nanoreactor was fully characterized and applied for catalytic degradation of 4-chlorophenol (4-CP) in the presence of peroxymonosulfate (PMS). The enhancement of SR-AOPs in the nanoreactor is demonstrated by the result that degradation efficiency of 4-CP reached almost 100% within 60 min by using the yolk−shell Co 3 O 4 @MOFs catalysts as compared to only 59.6% under the same conditions for bare Co 3 O 4 NPs. Furthermore, the applicability of this nanoreactor used in SR-AOPs was systematically investigated in terms of effect of reaction parameters and identification of intermediates and primary radical as well as mineralization of the reaction and stability of the composite. The findings of this study elucidated a new opportunity for improved environmental remediation.

A facile strategy for the fabrication of novel bouquet-shaped magnetic porous nanocomposite via grafting a covalent organic framework (COF, TpPa-1) onto the surface-modified FeO nanoparticles (FeO NPs) was reported. The magnetic TpPa-1 (a COF synthesized from 1,3,5-triformylphloroglucinol (Tp) and p-phenylenediamine (Pa-1)) contains clusters of core-shell magnetic nanoparticles and interconnected porous TpPa-1 nanofibers. Thus, it possesses larger specific surface area, higher porosity, and supermagnetism, making it an ideal sorbent for enrichment of trace analytes. Its performance was evaluated by the magnetic solid-phase extraction (MSPE) of trace polycyclic aromatic hydrocarbons (PAHs) from environmental samples prior to high-performance liquid chromatographic analysis. The results indicated that the magnetic TpPa-1 possessed superior enrichment capacity of such organic compounds.

A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52 m2 g−1), excellent magnetic response (14.89 emu g−1), and large mesopore volume (0.09 cm3 g−1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting π–π stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84 mg MB g−1 at an initial MB concentration of 30 mg L−1, which increased to 245 mg g−1 when the initial MB concentration was 300 mg L−1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles.

A facile, economical, and low-toxicity approach was proposed to coat gold nanoparticles (Au NPs) on the surface of graphene-encapsulated magnetic microspheres. The current method makes it possible to integrate Fe 3 O 4 NPs and metal NPs with graphene without any interference or site competition. Dopamine serves as a reducing agent as well as a coupling agent for the assembly of reduced graphene oxide (RGO) and Au NPs on magnetic cores, so that no additional chemicals and thermal treatments are needed. The X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) results demonstrate that GO is successfully deoxygenated by the reduction of the PDA layer, while transmission electron microscopy (TEM), scanning electron microscopy (SEM), and inductively coupled plasma mass spectrometry (ICP-MS) results indicate that plenty of Au NPs (about 7.3 nm in diameter) are homogeneously distributed onto the surface of RGO and the Au content of the composite is 13.58 wt%. The high Au content endows the nanocatalyst with great catalytic performance towards the reduction of o-nitroaniline to benzenediamine by NaBH 4 (completely transformation within 4 min). Furthermore, the as-prepared catalyst can be easily recovered and reused at least ten times due to the high magnetization and stability.

a b s t r a c tThe occurrence, removal efficiency and seasonal variation of 22 antibiotics, including eight fluoroquinolones, nine sulfonamides and five macrolides, were investigated in eight sewage treatment plants (STPs) in Beijing, China. A total of 14 antibiotics were detected in wastewater samples, with the maximum concentration being 3.1 lg L À1 in the influent samples and 1.2 lg L À1 in the effluent samples. The most frequently detected antibiotics were ofloxacin, norfloxacin, sulfadiazine, sulfamethoxazole, erythromycin and roxithromycin; of these, the concentration of ofloxacin was the highest in most of the influent and effluent samples. Eighteen antibiotics were detected in the sludge samples, with concentrations ranging from 1.0 Â 10 À1 to 2.1 Â 10 4 lg kg À1. The dominant antibiotics found in the sludge samples were the fluoroquinolones, with ofloxacin having the highest concentration in all the sludge samples. The antibiotics could not be removed completely by the STPs, and the mean removal efficiency ranged from À34 to 72%. Of all the antibiotics, the fluoroquinolones were removed comparatively more efficiently, probably due to their adsorption to sludge. Seasonal variation of the antibiotics in the sludge samples was also studied. The concentrations of antibiotics in winter were higher than in spring and autumn. Since the total levels of the fluoroquinolones detected in the influent samples were lower than the predicted no-effect concentration (PNEC) of 8.0 lg L À1 , the residues of these antibiotics would be unlikely to have adverse effects on microorganisms involved in sewage treatment processes.

In this work, we propose a simple, sensitive and reliable assay for melamine in raw milk with dopaminestabilized silver nanoparticles (AgNPs) as a colorimetric reader. Dopamine can reduce Ag + and functionalize the produced AgNPs to form monodispersed AgNPs. The coexisting melamine in reaction solution could bind dopamine through Michael addition and Schiff base reactions, which leads to the aggregation of AgNPs and induces a colorimetric response. The one-step assay is simple, rapid and highly sensitive. The color-change is quantitatively correlated with the concentration of melamine in the range of 10 ppb to 1.26 ppm, which is below the safety limit in China (1.0 ppm) and EU (2.0 ppm). The coexisting substances including phenylalanine, DL-leucine, L-glutamate, sulfanilic acid, Mg 2+ , galactose, lysine, urea and glucose do not affect the determination of melamine. The colorimetric sensor can be used for rapid monitoring of raw milk quality.