Xiaole Zhang

Chitosan-Coated Octadecyl-Functionalized Magnetite Nanoparticles: Preparation and Application in Extraction of Trace Pollutants from Environmental Water Samples

In the present study, chitosan-coated octadecyl-functionalized magnetite nanoparticles (Fe(3)O(4)-C(18)-chitosan MNPs) are synthesized and used as an adsorbent to extract trace analytes from environmental water samples. The magnetic nanoparticles, 20 nm in diameter, are of uniform size and have a high magnetic saturation value of 52 emu g(-1), which endue the adsorbent with a large surface area and convenience of isolation. The anionic pollutants, perfluorinated compounds (PFCs), are trapped by the octadecyl group of the interior hydrophobic layer. The positively charged chitosan polymer coating also contributes to PFC enrichment. At the same time, the coating improves the dispersibility of MNPs in aqueous solution and enhances the anti-interference ability of the adsorbent to natural organic macromolecules in complex samples by size exclusion or electrostatic repulsion. A liquid chromatography-tandem mass spectrometry system is employed in the determination of PFCs after preconcentration with the MNP adsorbent. The predominant factors affecting preconcentration are investigated and optimized. Under the selected conditions, concentration factors of 1000 are achieved by extracting the analytes from 500 mL of several environmental water samples and concentrating the eluants to 0.5 mL with a nitrogen flow. The method detection limits obtained for perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorononanoic acid (PFNA), perluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and perfluorotetradecanoic acid (PFTA) in Gaobeidian wastewater are 0.24, 0.093, 0.24, 0.14, 0.075, 0.24, and 0.17 ng L(-1), respectively. Recoveries of PFOA, PFOS, PFNA, PFDA, PFUnDA, PFDoDA, and PFTA are in the ranges of 88-108%, 63-112%, 79-109%, 56-107%, 66-106%, 56-106%, and 66-103% for four spiked water samples with low relative standard deviation (2-8%), which indicates good method precision. The advantages of this novel adsorbent are high extraction efficiency, anti-interference, and convenient operation.

Humic acid coated Fe3O4 magnetic nanoparticles as highly efficient Fenton-like catalyst for complete mineralization of sulfathiazole

Humic acid coated Fe(3)O(4) magnetic nanoparticles (Fe(3)O(4)/HA) were prepared for the removal of sulfathiazole from aqueous media. Fe(3)O(4)/HA exhibited high activity to produce hydroxyl (OH) radicals through catalytic decomposition of H(2)O(2). The degradation of sulfathiazole was strongly temperature-dependent and favored in acidic solution. The catalytic rate was increased with Fe(3)O(4)/HA dosage and H(2)O(2) concentration. When 3 g L(-1) of Fe(3)O(4)/HA and 0.39 M of H(2)O(2) were introduced to the aqueous solution, most sulfathiazole was degraded within 1h, and >90% of total organic carbon (TOC) were removed in the reaction period (6h). The major final products were identified as environmentally friendly ions or inorganic molecules (SO(4)(2-), CO(2), and N(2)). The corresponding degradation rate (k) of sulfathiazole and TOC was 0.034 and 0.0048 min(-1), respectively. However, when 3 g L(-1) of bare Fe(3)O(4) were used as catalyst, only 54% of TOC was eliminated, and SO(4)(2-) was not detected within 6h. The corresponding degradation rate for sulfathiazole and TOC was 0.01 and 0.0016 min(-1), respectively. The high catalytic ability of Fe(3)O(4)/HA may be caused by the electron transfer among the complexed Fe(II)-HA or Fe(III)-HA, leading to rapid regeneration of Fe(II) species and production of OH radicals.

Spatial confinement of a Co3O4 catalyst in hollow metal-organic frameworks as a nanoreactor for improved degradation of organic pollutants.

We here first proposed a yolk-shell Co3O4@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 Co3O4 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 Co3O4@MOFs catalysts as compared to only 59.6% under the same conditions for bare Co3O4 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 novel Fe3O4–graphene–Au multifunctional nanocomposite: green synthesis and catalytic application

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 Fe3O4 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 NaBH4 (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.

One-step synthesis of silver/dopamine nanoparticles and visual detection of melamine in raw milk.

In this work, we propose a simple, sensitive and reliable assay for melamine in raw milk with dopamine-stabilized 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.

Polydopamine-Coated Magnetic Nanoparticles for Enrichment and Direct Detection of Small Molecule Pollutants Coupled with MALDI-TOF-MS

Polydopamine-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@PDA NPs) were synthesized and applied as matrix for the detection of pollutants by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The synthesis of Fe(3)O(4)@PDA NPs was accomplished in 30 min by in situ polymerization of dopamine without any toxic reagent. Using Fe(3)O(4)@PDA NPs as matrix of MALDI-TOF, eleven small molecule pollutants (molecular weight from 251.6 to 499.3), including Benzo(a)pyrene (BaP), three perfluorinated compounds (PFCs), and seven antibiotics, were successfully detected in either positive or negative reflection mode without background interference. Furthermore, the Fe(3)O(4)@PDA NPs can also enrich trace amounts of hydrophobic target, such as BaP, from solution to nanoparticles surface. Then the Fe(3)O(4)@PDA-BaP can be isolated through magnetic sedimentation step and directly spotted on the stainless steel plate for MALDI measurement. With Fe(3)O(4)@PDA NPs as adsorbent and matrix, we also realized the analysis of BaP in tap water and lake water samples. Thus, a magnetic solid-phase extraction (MSPE)-MALDI-TOF-MS method was established for the measurement of BaP.

Modifying the surface of Fe3O4/SiO2 magnetic nanoparticles with C18/NH2 mixed group to get an efficient sorbent for anionic organic pollutants

In this article, C(18)/NH(2) mixed group modified Fe(3)O(4)/SiO(2) magnetic nanoparticles (Fe(3)O(4)/SiO(2)/C(18)+NH(2) MNPs) were successfully synthesized and used for the extraction of perfluorinated compounds (PFCs) from large volume of water solution. The Fe(3)O(4)/SiO(2)/C(18)+NH(2) MNPs, about 25 nm in diameter, possess high extraction ability to the anionic organic pollutants due to the dual function of hydrophobic octadecyl group and cationic aminopropyl groups at low pH. More than 90% of the targets can be extracted from 500 mL of water solution with 0.1g of the MNP sorbent at pH 3. Twenty min is sufficient to reach adsorption equilibrium, and the targets can be desorbed from the sorbent readily with 12 mL of alkalized methanol after magnetic separation. Simplified extraction procedure could be achieved because of the superparamagnetism and high saturation magnetization of the sorbent (44 emu g(-1)). Therefore, preconcentration of trace level of PFCs from water solution can be performed by using this Fe(3)O(4)/SiO(2)/C(18)+NH(2) MNP sorbent which are stable for multiple reuses.

Easy Synthesis of Surface-Tunable Carbon-Encapsulated Magnetic Nanoparticles: Adsorbents for Selective Isolation and Preconcentration of Organic Pollutants

We have prepared core/shell structured carbon-encapsulated magnetic nanoparticles (CMNPs) with a simple method by using inorganic iron salt and glucose solution as precursor substance. The synthetic procedure does not require the use of organic solvents. We have utilized X-ray photoelectron spectroscopy, infrared spectroscopy, X-ray diffraction, and Raman analysis to examine the surface properties of CMNPs prepared at different temperature. The specific surface areas, magnetization and contents of graphitized carbon on carbon shell of CMNPs increase with heat treatment temperature. The obtained CMNPs are used to adsorb or preconcentrate bisphenol A (BPA), 4-n-nonylphenol (4-NP), 4-tert-octylphenol (4-OP), diethyl phthalate (DEP), dipropyl phthalate (DPP), dibutyl phthalate (DBP) dicyclohexyl phthalate (DCHP), dioctyl phthalate (DOP), sulfonamide, tetracyclines, and quinolones antibiotics organic compounds from water samples. The adsorption of analytes is mainly based on π-π stacking interaction, hydrophobic interaction and hydrogen bonds between analytes and graphitic carbon. As a result, the adsorption or extraction behaviors of CMNPs to analytes are controlled by the content of oxygen-containing species and graphitized carbon on carbon shell of CMNPs. CMNPs prepared at 200 °C have ample oxygen-containing species (80%) on surface and favor the adsorption and extraction of quinolones antibiotics. CMNPs heated at 300-500 °C with the graphitization efficiency of carbon shell lower than 50% exhibit great preconcentration performance to BPA, 4-NP, 4-OP, DBP, DCHP, DOP, tetracyclines, and quinolones antibiotics. CMNPs prepared at 850 °C are highly graphitized (80%) and have strong adsorption affinity to all model analytes; however, they can quantitatively extract only highly polar sulfonamide antibiotics and moderately polar DEP, DPP because of hard desorption of other model analytes. We suggest that the appropriate adsorbent to certain organic contaminants can be obtained with this technique just by tuning the heat temperature without any post-treatment.

Assembly of a Nanoreactor System with Confined Magnetite Core and Shell for Enhanced Fenton‐Like Catalysis

Conventional solid catalysts for heterogeneous Fenton-like reactions in bulk solution usually suffer from aggregation and vulnerability, which greatly lower the catalytic efficiency and hamper their practical application. Herein, we demonstrate a promising yolk-shell nanostructure with both the core and the shell composed of magnetite (designated as yolk-like Fe3O4@Fe3O4/C) as a nanoreactor capable of accommodating the Fenton-like reaction into its void space. Benefiting from the mesoporous shell and perfect interior cavity of this composite, reactants can access and be abundantly confined within the microenvironment where Fe3O4 sites are dispersed on the entire cavity surfaces, thus leading to a higher catalytic efficiency compared with the conventional solid catalysts in bulk solution. The chosen model reaction of chlorophenols degradation in the presence of the as-prepared materials as well as hydrogen peroxide (H2O2) confirms this assumption. Under the optimal reaction conditions, more than 97 % 4-chlorophenol (4-CP) can be degraded in the Fe3O4@Fe3O4/C nanoreactor, whereas only 28 % can be achieved by using bare Fe3O4 particles within 60 min. Furthermore, owing to the existence of the outermost carbon layer and high-magnetization properties, the nanoreactor can be re-used for several runs. The synthesized nanoreactor displays superior catalytic activity toward the Fenton-like reaction compared with the bare solid catalysts, and thereby holds significant potential for practical application in environmental remediation.

Biocompatible phosphatidylcholine bilayer coated on magnetic nanoparticles and their application in the extraction of several polycyclic aromatic hydrocarbons from environmental water and milk samples

In this work, phosphatidylcholine (PC) was coated on magnetic nanoparticles to form lipid bilayer as solid-phase extraction (SPE) sorbents for the enrichment of polycyclic aromatic hydrocarbons (PAHs) from environmental water and milk samples. The lipid bilayer was coated on Fe(3)O(4) nanoparticles using a modified dry lipid film hydration method. The resulted Fe(3)O(4)/PC could be readily isolated from solution with a magnet, and exhibited excellent adsorption performance to organic pollutants. Only 0.1g of sorbents was enough to extract PAHs from 500 mL aqueous solution, and 6 mL of acetonitrile was required to desorb them. The method was fast and relied on 10 min extraction time and 5 min magnetic separation. The proposed method was successfully applied to determine PAHs in some environmental water and milk samples. The detection limit was in the range of 0.2-0.6 ng L(-1). The recoveries of the spiked water samples ranged from 89% to 115% with relative standard deviations (RSD) varying from 1% to 8%. For spiked milk samples, RSD was satisfactory (1-9%), but the recoveries were relatively low (42-62%). We show the potentials of Fe(3)O(4)/PC sorbents in environmental water and biological sample analyses.