Xiaona Li

Adsorption of ionizable organic contaminants on multi-walled carbon nanotubes with different oxygen contents.

Multi-walled carbon nanotubes (MWNTs), which are considered to be promising candidates for the adsorption of toxic organics, are released into aqueous environment with their increasing production and application. In this study, the adsorption behaviors of five structurally related ionizable organic contaminants namely perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonamide (PFOSA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-n-nonylphenol (4-NP) onto MWNTs with different oxygen contents (3.84-22.85%) were investigated. The adsorption kinetics was investigated and simulated with pseudo-second-order model. The adsorption isotherms were found to be fitted with Freundlich model and influenced by both the properties of organic chemicals and the oxygen contents of MWNTs. As adsorption capacity decreases dramatically with the increasing of oxygen contents, the MWNTs with the lowest oxygen contents possess the highest adsorption capacity among four MWNTs. For the MWNTs with the oxygen contents of 3.84%, the adsorption affinity related with hydrophobic interaction and π-electron polarizability decreased in the order of 4-NP>PFOSA>PFOS>2,4-D>PFOA. Furthermore, the adsorption characters of five contaminants were affected by solution pH and solute pK(a) considering electrostatic repulse force and hydrogen bonding, which showed the adsorption of MWNTs with lower oxygen content is much sensitive to solution chemistry.

Preparation and evaluation of molecularly imprinted solid-phase microextraction fibers for selective extraction of bisphenol A in complex samples.

Molecular imprinted polymer (MIP) as solid-phase microextraction (SPME) fibers coating has gained great attention in recent years. In this study, a simple preparation approach for bisphenol A (BPA) MIP coating with controlled thickness on fused-silica capillaries was developed. A capillary was inserted into a larger bore capillary to form a sleeve as mold. The prepolymer solution containing the template BPA was introduced into the interspace between the two capillaries for polymerization under photoirradiation. The larger bore capillary was removed away after the polymerization, and MIP coating with certain thickness on the surface of the inserted capillary was obtained. SPME conditions based on the MIP-coated fibers were optimized, and the extraction performance of the fibers with different thickness coating was compared. Finally, the MIP fibers were used for selective extraction of BPA spiked in tap water, human urine, and milk samples. The average recoveries of spiked BPA in the three samples were 92.5%, 81.6%, and 87.5%, respectively. The present analytical performance is not up to par for applicability to real environmental matrices. Further improvement will be necessary for analysis of real complex samples.

Enhanced adsorption of PFOA and PFOS on multiwalled carbon nanotubes under electrochemical assistance.

Removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from aqueous solution has attracted wide attention in light of their environmental persistence, bioaccumulation, and potential toxicity. Although various destructive technologies were developed, removal of PFOX (X = A and S) under mild conditions are still desirable. In this work, multiwalled carbon nanotubes (MWNTs) were applied to remove PFOX in electrochemically assistant adsorption. Electrosorption kinetics and isotherms were investigated relative to open circuit (OC) adsorption and adsorption on powder MWNTs. Compared with powder MWNTs adsorption, the initial adsorption rate (υ(0)) of 100 μg/L PFOX at 0.6 V increased 60-fold (PFOA) and 41-fold (PFOS) according to pseudosecond-order kinetics model and the maximum electrosorption capacity (q(m)) of PFOX (50 μg/L to 10 mg/L) increased 150-fold (PFOA) and 94-fold (PFOS) simulated with Langmuir model. These significant improvements were assumed to benefit from enhanced electrostatic attraction under electrochemical assistance. Furthermore, the used MWNTs were found to be regenerative and reusable. This work provides not only a new approach to effective removal of perfluorochemicals from aqueous solution but also a low energy-consumption and environmentally-friendly strategy for application of carbon nanotubes in water treatment.

Adsorption of ciprofloxacin, bisphenol and 2-chlorophenol on electrospun carbon nanofibers: in comparison with powder activated carbon.

Carbon nanofibers (CNFs) were prepared by electrospun polyacrylonitrile (PAN) polymer solutions followed by thermal treatment. For the first time, the influence of stabilization procedure on the structure properties of CNFs was explored to improve the adsorption capacity of CNFs towards the environmental pollutants from aqueous solution. The adsorption of three organic chemicals including ciprofloxacin (CIP), bisphenol (BPA) and 2-chlorophenol (2-CP) on electrospun CNFs with high surface area of 2326m(2)/g and micro/mesoporous structure characteristics were investigated. The adsorption affinities were compared with that of the commercial powder activated carbon (PAC). The adsorption kinetics and isotherms showed that the maximum adsorption capacities (qm) of CNFs towards the three pollutants are sequenced in the order of CIP>BPA>2-CP, which are 2.6-fold (CIP), 1.6-fold (BPA) and 1.1-fold (2-CP) increase respectively in comparison with that of PAC adsorption. It was assumed that the micro/mesoporous structure of CNFs, molecular size of the pollutants and the π electron interaction play important roles on the high adsorption capacity exhibited by CNFs. In addition, electrostatic interaction and hydrophobic interaction also contribute to the adsorption of CNFs. This study demonstrates that the electrospun CNFs are promising adsorbents for the removal of pollutants from aqueous solutions.

Selective detection of nanomolar Cr(VI) in aqueous solution based on 1,4-dithiothreitol functionalized gold nanoparticles

The determination of trace Cr(vi) is very important because of its highly carcinogenic and mutagenic effects. In this study, a colorimetric detection method based on 1,4-dithiothreitol functionalized gold nanoparticles (DTT-AuNPs) for nanomolar Cr(vi) in aqueous solution is reported. The method principle was based on the aggregation of DTT-AuNPs induced by Cr(vi), which led to red-shift of the surface plasmon resonance (SPR) peak of DTT-AuNPs. UV-vis absorption spectra, Zeta potentials, and transmission electron microscopy (TEM) images were used to demonstrate the aggregation of DTT-AuNPs. Some parameters affecting the detection including solution pH and DTT concentration were optimized. Under the optimized conditions, a good linear relationship (correlation coefficient r = 0.997 5) was obtained between the ratio (A650/520) of the absorbance at 650 nm to that at 520 nm and the concentration of Cr(vi) over the range of 100-600 nM, and the limit of detection (LOD) for Cr(vi) at a signal-to-noise ratio of 3 was 20 nM. The method showed selective detection toward Cr(vi) against other common metal ions in waters. Furthermore, the method developed was applied for detecting trace Cr(vi) in real water samples, with recoveries of 95%-115%.

Evaluation of a novel microextraction technique for aqueous samples: Porous membrane envelope filled with multiwalled carbon nanotubes coated with molecularly imprinted polymer

A novel microextraction technique based on membrane-protected multiwalled carbon nanotubes coated with molecularly imprinted polymer (MWCNTs-MIP) was developed. In this technique, MWCNTs-MIP were packed inside a polypropylene membrane envelope, which was then clamped onto a paper clip. For extraction, the packed membrane envelope was first impregnated with toluene and then placed in sample solutions. Target analytes in the solutions were first extracted into toluene in the membrane envelope, and were then extracted specifically onto the MWCNTs-MIP. After the extraction, target analytes were desorbed in methanol for liquid chromatography analysis. MWCNTs-MIP of prometryn were used as a model to demonstrate the feasibility of this novel microextraction technique. Factors affecting the extraction including organic solvent, stirring rate, extraction time, salt concentration, and pH were investigated. Under the optimized conditions, the limits of detection (a signal-to-noise ratio of 3) for the selected triazine herbicides were 0.08-0.38 μg/L. The prepared membrane envelope could be used at least 50 times. The developed method was used for the analysis of the triazines spiked in river water, wastewater, and liquid milk, with recoveries ranging from 79.3-97.4, 58.9-110.3 and 76.2-104.9%, respectively.

An electrochemically reduced graphene oxide chemiresistive sensor for sensitive detection of Hg 2+ ion in water samples

Divalent mercuric (Hg2+) ion is one of the most prevalent forms of mercury species in waters with high toxicity and bioaccumulation in the human body, for which sensitive and selective detection methods are highly necessary to carry out its recognition and quantification. Here an electrochemically reduced graphene oxide (RGO) based chemiresistive sensor was constructed and used for the detection of Hg2+ ion in various water samples. Monolayer GO sheets were assembled onto interdigitated electrodes, followed by reduction through linear sweep voltammetry and then modification with a single-stranded DNA aptamer. The electrochemically derived RGO based sensor showed selective response to as low as 0.5nMHg2+ ion in presence of other metal ions and matrices. A comparison between chemiresistive sensors prepared with electrochemically and chemically derived RGO showed that the former had better response performance for sensing Hg2+ ion. The proposed method provides a simple tool for rapid, selective and sensitive monitoring of Hg2+ ion in environmental samples.

Azide-functionalized hollow silica nanospheres for removal of antibiotics.

Antibiotics, which are hardly removed from polluted water by conventional water-treatment technologies, adsorption has been deemed as one of the efficient and promising method to resolve the problems of antibiotics pollution. Herein, we reported a synthesis of filtration separable hollow nanostructured silicas (HNSs) with efficient click functionalization property for antibiotics adsorption. The clickable HNSs were synthesized by the co-condensation and assembling of tetramethoxysilane (TMOS) and 3-azidopropyltrimethoxysilane (AzPTMS) around F127 single micelle template. Alkynyl compounds such as phenylacetylene (Ph), propargyl alcohol (PA), 1-heptyne (Hep), and 2-butyne-1,4-diol (BD) have been linked to the materials through click reaction with high efficiency. Antibiotic adsorption results reveal that functional groups play an important role in adsorption properties of adsorbents and phenyl was found to be the optimal functional group due to the π-π stacking effect. Excellent adsorption capacity and recyclability indicate that the clickable hollow nanostructured silicas exhibit potential application for antibiotics removal.

ELECTROCHEMICALLY ENHANCED ADSORPTION OF NONYLPHENOL ON CARBON NANOTUBES: KINETICS AND ISOTHERMS STUDY

Removal of nonylphenol (NP) from aqueous solution has attracted widely attention due to its aquatic toxicity and potential to disrupt the endocrine system. In an effort to develop the effective and environment-friendly treatment method for NP, adsorption of 4-n-nonylphenol (4-NP) on multi-walled carbon nanotubes (MWCNTs) under electrochemical assistance was studied. The adsorption kinetics and isotherms were investigated at different polarization potentials and compared with those of open circuit (OC) and powder MWCNTs adsorption. The adsorption kinetics was simulated by the model including pseudo-first-order model, pseudo-second-order model and intraparticle diffusion model. The isotherm was simulated with Langmuir model and Freudlich model, respectively. Experimental results indicated that 4-NP is able to be efficiently removed at a potential of -0.6V. Comparing with that of powder MWCNTs adsorption, the initial adsorption rate υ0 at -0.6V increased 7.9-fold according to pseudo-second-order model and the maximum adsorption capacity qm improved 1.7-fold according to Langmuir model. The improved adsorption effect at negative potential was ascribed to enhanced π-π electron-donor-acceptor (EDA) interaction between 4-NP and MWCNTs under electrochemical assistance.

Determination and prediction of octanol-air partition coefficients of hydroxylated and methoxylated polybrominated diphenyl ethers.

The octanol-air partition coefficient (K(OA)) of 19 hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and 10 methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were measured as a function of temperature using a gas chromatographic retention time technique. At room temperature (298.15K), log K(OA) ranged from 8.30 for monobrominated OH/MeO-PBDEs to 13.29 for hexabrominated OH/MeO-PBDEs. The internal energies of phase change from octanol to air (Delta(OA)U) for 29 OH/MeO-PBDE congeners ranged from 72 to 126 kJ mol(-1). Using partial least-squares (PLS) analysis, a statistically quantitative structure-property relationship (QSPR) model for logK(OA) of OH/MeO-PBDE congeners was developed based on the 16 fundamental quantum chemical descriptors computed by PM3 Hamiltonian, for which the Q(cum)(2) was about 0.937. The molecular weight (Mw) and energy of the lowest unoccupied molecular orbital (E(LUMO)) were found to be main factors governing the log K(OA).