Lu-Bin Zhong

Synthesis of Fe3O4/Polyacrylonitrile Composite Electrospun Nanofiber Mat for Effective Adsorption of Tetracycline.

Novel Fe3O4/polyacrylonitrile (PAN) composite nanofibers (NFs) were prepared by a simple two-step process, an electrospinning and solvothermal method. Characterization by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) demonstrated formation of a uniform nanoparticles coating (about 20 nm in thickness) on the PAN nanofiber backbone. The coating was constructed by well-crystallized cubic phase Fe3O4 nanoparticles as examined by X-ray diffraction spectroscopy (XRD). The coating doubled the specific surface area of NFs, from 8.4 to 17.8 m2 g(-1), as confirmed by nitrogen sorption isotherm analysis. To evaluate the feasibility of Fe3O4/PAN composite NFs as a potential adsorbent for antibiotic removal, batch adsorption experiments were conducted using tetracycline (TC) as the model antibiotic molecule. The results showed that Fe3O4/PAN composite NFs were effective in removing TC with no impactful loss of Fe in the pH regime of environmental interest (5-8). The adsorption of TC onto Fe3O4/PAN composite NFs better fitted the pseudo-second-order kinetics model, and the maximum adsorption capacity calculated from Langmuir isotherm model was 257.07 mg g(-1) at pH 6. The composite NFs also exhibited good regenerability over repeated adsorption/desorption cycles. Surface complexation between TC and the composite NFs contributed most to the adsorption as elucidated by X-ray photoelectron spectroscopy (XPS). This highly effective and novel adsorbent can be easily modularized and separated, promising its huge potential in drinking and wastewater treatment for antibiotic removal.

Self-assembly of Au nanoparticles on PMMA template as flexible, transparent, and highly active SERS substrates.

We report a simple and rapid method for fabricating a surface-enhanced Raman scattering (SERS) substrate, which offers good flexibility, excellent optical transparency, and high SERS activity. Specifically, the SERS substrate (AuNPs/PMMA film) was obtained through self-assembly of gold nanoparticles (AuNPs) on newborn poly(methyl methacrylate) (PMMA) template. The UV-vis spectroscopy analysis and scanning electron microscopy observation revealed that the gold nanoparticles were closely assembled on the flexible and transparent PMMA template. The fabricated AuNPs/PMMA film SERS substrate allowed detection of model molecule, malachite green isothiocyanate, at a concentration as low as 0.1 nM, and exhibited good reproducibility in the SERS measurement. The Raman enhancement factor (EF) of the AuNPs/PMMA film was found to be as high as (2.4 ± 0.3) × 10(7). In addition, measure of residual malachite green on fish surface was carried out, and the result indicated that the AuNPs/PMMA film had great potential in the in situ ultrasensitive detection of analyte on irregular objects.

Removal of tetracycline from aqueous solution by a Fe3O4 incorporated PAN electrospun nanofiber mat

Pollution of antibiotics, a type of emerging contaminant, has become an issue of concern, due to their overuse in human and veterinary application, persistence in environment and great potential risk to human and animal health even at trace level. In this work, a novel adsorbent, Fe3O4 incorporated polyacrylonitrile nanofiber mat (Fe-NFM), was successfully fabricated via electrospinning and solvothermal method, targeting to remove tetracycline (TC), a typical class of antibiotics, from aqueous solution. Field emission scanning electron microscopy and X-ray diffraction spectroscopy were used to characterize the surface morphology and crystal structure of the Fe-NFM, and demonstrated that Fe-NFM was composed of continuous, randomly distributed uniform nanofibers with surface coating of Fe3O4 nanoparticles. A series of adsorption experiments were carried out to evaluate the removal efficiency of TC by the Fe-NFM. The pseudo-second-order kinetics model fitted better with the experimental data. The highest adsorption capacity was observed at initial solution pH4 while relative high adsorption performance was obtained from initial solution pH4 to 10. The adsorption of TC on Fe-NFM was a combination effect of both electrostatic interaction and complexation between TC and Fe-NFM. Freundlich isotherm model could better describe the adsorption isotherm. The maximum adsorption capacity calculated from Langmuir isotherm model was 315.31 mg/g. Compared to conventional nanoparticle adsorbents which have difficulties in downstream separation, the novel nanofiber mat can be simply installed as a modular compartment and easily separated from the aqueous medium, promising its huge potential in drinking and wastewater treatment for micro-pollutant removal.

Functionalized chitosan electrospun nanofiber for effective removal of trace arsenate from water.

An environment-friendly iron functionalized chitosan elctrospun nanofiber (ICS-ENF) was synthesized for trace arsenate removal from water. The ICS-ENF was fabricated by electrospinning a mixture of chitosan, PEO and Fe3+ followed by crosslinking with ammonia vapor. The physicochemical properties of ICS-ENF were characterized by FESEM, TEM-EDX and XRD. The ICS-ENF was found to be highly effective for As(V) adsorption at neutral pH. The As(V) adsorption occurred rapidly and achieved equilibrium within 100 min, which was well fitted by pseudo-second-order kinetics model. The As(V) adsorption decreased with increased ionic strength, suggesting an outer-sphere complexation of As(V) on ICS-ENF. Freundlich model well described the adsorption isotherm, and the maximum adsorption capacity was up to 11.2 mg/g at pH 7.2. Coexisting anions of chloride and sulfate showed negligible influence on As(V) removal, but phosphate and silicate significantly reduced As(V) adsorption by competing for adsorption sites. FTIR and XPS analysis demonstrated –NH, –OH and C–O were responsible for As(V) uptake. ICS-ENF was easily regenerated using 0.003 M NaOH, and the removal rate remained above 98% after ten successively adsorption-desorption recycles. This study extends the potential applicability of electrospun nanofibers for water purification and provides a promising approach for As(V) removal from water.

Facile one-pot synthesis of urchin-like Fe–Mn binary oxide nanoparticles for effective adsorption of Cd(II) from water

The development of efficient and low-cost adsorbent is critical for water treatment, but still presents great challenges. Herein, we report the synthesis of three-dimensional (3D) hierarchical nanostructured adsorbent, urchin-like Fe–Mn binary oxides (UFMBO), by simple heating without any template/surfactant. The surface morphology, crystalline and pore structure were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and nitrogen adsorption–desorption isotherm, respectively. Results revealed that the UFMBO had a 3D hierarchical nanostructure with a high specific surface area of 142 m2 g−1, which was conducive to pollutant adsorption and adsorbent separation. Cd(II) removal using the UFMBO was evaluated by batch adsorption experiments. The adsorption equilibrium was established within 3 h, and the adsorption process was better described by pseudo second-order kinetics model. The adsorption isotherm data fitted well to Langmuir model, and the maximum adsorption capacity was 74.76 mg g−1 at pH 6.0. Influence by ionic strength on the adsorption was significant, implying that Cd(II) may form outer-sphere complexes on the adsorbent surface. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analysis suggested hydroxyl group played an important role in Cd(II) uptake. The highly effective 3D UFMBO adsorbent can be easily separated and regenerated, demonstrating its great potential in cadmium removal from contaminated water source.

Electrospun Chitosan Nanofiber Membrane for Adsorption of Cu(II) from Aqueous Solution: Fabrication, Characterization and Performance

The preparation, characterization and application of chitosan (CS) based electrospun nanofiber membrane for the adsorptive removal of Cu(II) from water were systematically investigated. Homogeneous, porous polyvinyl alcohol (PVA)/CS nanofiber membrane with amorphous structure, and average fiber diameter of 49 nm was successfully fabricated. The adsorption of Cu(II) onto the positively charged PVA/CS nanofiber membrane (pH < 6) was due to chemisorption rather than electrostatic adherence, and was highly pH-dependent. The adsorption equilibrium of Cu(II) by the PVA/CS nanofiber was established within 120 min, which was much faster than that by CS beads, and the adsorption kinetics followed pseudo-second-order model well (r 2 > 0.995). The adsorption isotherm data were well fitted with Langmuir model, and the maximum Cu(II) adsorption capacity of PVA/CS nanofiber membrane was 90.3 mg·g-1, which was much higher than that of CS beads. The adsorbed Cu(II) formed strong inner-sphere complex with the adsorbent. Coexisting cations of iron, lead, cadmium, nickel, calcium, and magnesium have insignificant effect on the Cu(II) adsorption, indicating the adsorbent has good selectivity for Cu(II) adsorption. FTIR and XPS analysis reveal amine, hydroxyl and ether groups are responsible for the Cu(II) adsorption. This work demonstrates the electrospun PVA/CS nanofiber membrane is a promising adsorbent for heavy metal removals.

Enhanced adsorption of arsenite from aqueous solution by an iron-doped electrospun chitosan nanofiber mat: Preparation, characterization and performance

A novel iron-doped chitosan electrospun nanofiber mat (Fe@CTS ENM) was synthesized, which was proven to be effective for the removal of arsenite (As(III)) from water at neutral pH condition. The physiochemical properties and adsorption mechanism were explored by SEM-EDS and X-ray photoelectron spectroscopy (XPS). Batch adsorption experiments were carried out to evaluate the As(III) adsorption performance of the Fe@CTS ENM with various process parameters, such as adsorbent dose, solution pH, initial As(III) concentration, contact time, ionic strength, coexisting anions, and natural organic matter. The experimental results indicated that the maximum adsorption capacity was up to 36.1 mg g-1. Especially, when the adsorbent dosage was higher than 0.3 g L-1, the As(III) concentration was reduced from 100 µg L-1 to less than 10 µg L-1, which indicated the Fe@CTS ENM could effectively remove trace As(III) from water over a wide pH range (from 3.3 to 7.5). Kinetics study demonstrated that the adsorption equilibrium was achieved within 2.0 h, corresponding to a fast uptake of As(III). The presence of common co-ions and humic acid had little effect on the As(III) adsorption. XPS analysis suggested that the FeO, COH, COC and CN groups on the adsorbent surface play dominant roles in the adsorption of As(III). Adsorption-desorption regeneration test further demonstrated that no appreciable loss in the adsorption capacities was observed, which confirmed that the Fe@CTS ENM maintained a desirable life cycle that was free of complex synthesis processes, expensive and toxic materials, qualifying it as an efficient and low-cost As(III) adsorbent.

Preparation, characterization and performance of an electrospun carbon nanofiber mat applied in hexavalent chromium removal from aqueous solution

Hexavalent chromium, Cr(VI), a highly toxic oxyanion known as a carcinogen and mutagen, is an issue of concern due to its adverse impact on human health. Therefore, development of effective technologies and/or materials for Cr(VI) removal from water has been of great interest for researchers. In this study, an electrospun carbon nanofiber (CNF) mat was prepared via electrospinning polyacrylonitrile (PAN), followed by thermal pre-oxidation and carbonization. Scanning electron microscopy (SEM) observation showed that the fiber diameter of the CNF with carbonization temperature of 950°C (CNF950) was about 266 nm. Potentiometric titration analysis demonstrated that the point of zero charge pH (pHpzc) of CNF950 was around 7.93. CNF950 demonstrated high adsorption capacity and fast adsorption kinetics for Cr(VI) at pH < 3. Langmuir isotherm calculations showed that the maximum adsorption capacity of Cr(VI) on CNF950 was 118.8 mg/g at pH 2. The adsorption isotherm of Cr(VI) on CNF950 was well described by the Redlich-Peterson model, revealing that Cr(VI) adsorption was the result of a combination of monolayer and multilayer adsorption, depending on the initial Cr(VI) concentration. Solution pH greatly affected Cr(VI) adsorption onto CNF950 due to the electrostatic interaction, and the adsorption capacity was relatively high when pH was below 3. X-ray photoelectron spectroscopy (XPS) analysis revealed that the removal of Cr(VI) might be the result of a combination of redox reaction and electrostatic adsorption. The adsorption-saturated CNF950 could be regenerated by NaOH solution. This study extends the potential applicability of electrospun CNF mats for Cr(VI)-contaminated water purification.

Facile On-Site Aqueous Pollutant Monitoring Using a Flexible, Ultralight, and Robust Surface-Enhanced Raman Spectroscopy Substrate: Interface Self-Assembly of Au@Ag Nanocubes on a Polyvinyl Chloride Template

Aquatic ecosystems and human health have been seriously threatened by illegal discharge of wastewater, while simple and effective monitoring methods are still sparse. Here, we propose a facile method for on-site pollutant monitoring by surface-enhanced Raman spectroscopy with a novel substrate. This substrate is fabricated by interface self-assembly of Au@Ag nanocubes (NCs) on a simultaneously formed polyvinyl chloride (PVC) template, followed by coating with a thin Au film. The Au@Ag@Au-NCs/PVC film is flexible, ultralight, and robust and could float on the surface of water and firmly contact with water even under harsh environmental conditions. Moreover, the Au@Ag@Au-NCs/PVC film is translucent, allowing penetration of laser beams and enhancement of Raman signals. When thiram was used as a model contaminant in aqueous solution, a good linear relationship ( R2 = 0.972) was obtained over the range of 0.1-50 ppb with a detection limit of 0.1 ppb. Raman signals of thiram can be instantly and consecutively detected with the enhancement of the film in the simulated experiments, suggesting its possible use in the long run. Furthermore, the film can be easily regenerated by NaBH4 solution washing, which could reduce the operating cost. In summary, the Au@Ag@Au-NCs/PVC film has great potential in on-site pollutant monitoring in aqueous environments with a portable Raman spectrometer.