Functionalized Nanoparticles as Sorbents for Removal of Toxic Species

Removal of various toxic species from aqueous streams is of great importance. Sorption is one of the important remediation procedures as it involves the use of cheap and easily available materials. Also the advantage of regeneration of the sorbent involves the possibility of using novel sorbents. Nanosorbents are very important as the removal is based on the surface phenomena and this is greatly affected by surface charge and area. Functionalization has been very important to bring about the removal of metal ions with greater selectivity.

Functionalized PU Foam for Water Filtration

Polyurethane foam is functionalized with Sulfonic acid groups to remove lead ions (Pb2+) from drinking water through a cation exchange process. The synthesis is based on addition polymerization of the -NCO groups of an isocyanate with the –OH groups of a polyol to form the urethane. Toluene-diisocyanateis reacted with Polypropylene glycol to form a linear pre-polymer, which is further polymerized using a chain extender, N, N-bis(2-hydorxyethyl)-2-aminoethane-sulfonic acid (BES). BES acts as a functional group site to exchange Pb2+ ions. A set of experiments was designed to study the effect of various processing parameters on the performance of the synthesized foam. The maximum Pb2+ ion exchange capacity of the foam was found to be 47ppb/g from a 100ppb Pb2+ solution over a period of 60 minutes. A multistage batch filtration process increased the lead removal to 50-54ppb/3g of foam over a period of 90 minutes.

Extraction of Polystyrene from Styrofoam Waste: Synthesis of Novel Chelating Resin for the Enrichment and Speciation of Cr(III)/Cr(VI) Ions in Industrial Effluents

Polystyrene (PS) was extracted from Styrofoam (expanded polystyrene foam) waste, so called white pollutant. The PS was functionalized with N,N- Bis(2-aminobenzylidene)benzene-1,2-diamine (ABA) ligand through an azo spacer. The resin was characterized by FT-IR spectroscopy and elemental analysis. The PS-N=N-ABA resin was used for the enrichment and speciation of Cr(III)/Cr(VI) ions and total Cr determination in aqueous samples by flame atomic absorption spectrometry (FAAS). The separation of Cr(III)/Cr(VI) ions was achieved at pH 2. The recovery of Cr(VI) ions was achieved ≥ 95.0% at optimum parameters: pH 2; resin amount 300mg; flow rates 2.0mL min-1 of solution and 2.0mL min-1 of eluent (2.0mol L-1 HNO3). Total Cr was determined by oxidation of Cr(III) to Cr(VI) ions using H2O2. The limit of detection (LOD) and quantification (LOQ) of Cr(VI) were found to be 0.40 and 1.20μg L-1, respectively with preconcentration factor of 250. Total saturation and breakthrough capacitates of the resin for Cr(IV) ions were found to be 0.181 and 0.531mmol g-1, respectively. The proposed method was successfully applied for the preconcentration/speciation of Cr(III)/Cr(VI) ions and determination of total Cr in industrial effluents.

Green-Reduction of Covalently Functionalized Graphene Oxide with Varying Stoichiometry

Graphene-based materials were prepared by chemical reduction of covalently functionalized graphene oxide with environmentally friendly agents. Two varying stoichiometry of graphene oxide (GO) induced by using different chemical preparation conditions, further covalent functionalization of the GO materials with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride / N-hydroxysuccinimide and ascorbic acid and sodium bisulfite as reducing agents were exploited in order to obtain controllable properties of the final solution-based graphene materials. The obtained materials were characterized by thermo-gravimetric analysis, Fourier transform infrared and Raman spectroscopy and X-ray diffraction. The results showed successful functionalization of the GO materials, while a comparison of the deoxygenation efficiency of the two-type functionalized graphene oxide suspensions by the different reducing agents has been made, revealing the strong dependence of their properties on the GO structure and reducing agents.

A Finite Element Model for Estimating Young-s Modulus of Carbon Nanotube Reinforced Composites Incorporating Elastic Cross-Links

The presence of chemical bonding between functionalized carbon nanotubes and matrix in carbon nanotube reinforced composites is modeled by elastic beam elements representing covalent bonding characteristics. Neglecting other reinforcing mechanisms in the composite such as relatively weak interatomic Van der Waals forces, this model shows close results to the Rule of Mixtures model-s prediction for effective Young-s modulus of a Representative Volume Element of composite for small volume fractions (~1%) and high aspect ratios (L/D>200) of CNTs.

Carbon Nanotubes with Magnetic Particles

Magnetic carbon nanotubes composites were obtained by filling carbon nanotubes with paramagnetic iron oxide particles. Detailed investigation of magnetic behaviour of resulting composites was done at different temperatures. Measurements indicate that these functionalized nanotubes are superparamagnetic at room temperature; however, no superparamagnetism was observed at 125 K and 80 K. The blocking temperature TB was estimated at 145 K. These magnetic carbon nanotubes have the potential of being used in a wide range of applications, in particular, the production of nanofluids, which can be controlled and steered by appropriate magnetic fields.

Preparation and Characterization of Self Assembled Gold Nanoparticles on Amino Functionalized SiO2 Dielectric Core

Wet chemistry methods are used to prepare the SiO2/Au nanoshells. The purpose of this research was to synthesize gold coated SiO2 nanoshells for biomedical applications. Tunable nanoshells were prepared by using different colloidal concentrations. The nanoshells are characterized by FTIR, XRD, UV-Vis spectroscopy and atomic force microscopy (AFM). The FTIR results confirmed the functionalization of the surfaces of silica nanoparticles with NH2 terminal groups. A tunable absorption was observed between 470-600 nm with a maximum range of 530-560 nm. Based on the XRD results three main peaks of Au (111), (200) and (220) were identified. Also AFM results showed that the silica core diameter was about 100 nm and the thickness of gold shell about 10 nm.

Functionalization and Characterization of Carbon Nanotubes/ Polypropylene Nanocomposite

Chemical and physical functionalization of multiwalled carbon nanotubes (MWCNT) has been commonly practiced to achieve better dispersion of carbon nanotubes (CNTs) in polymer matrix. This work describes various functionalization methods (acidtreatment, non-ionic surfactant treatment with TritonX-100), fabrication of MWCNT/PP nanocomposites via melt blending and characterization of mechanical properties. Microscopy analysis (FESEM, TEM, XPS) showed effective purification of MWCNTs under acid treatment, and better dispersion under both chemical and physical functionalization techniques combined, in their respective order. Tensile tests showed increase in tensile strength for the nanocomposites that contain MWCNTs up to 2 wt%. A decrease in tensile strength was seen in samples that contain 4 wt% of MWCNTs for both raw and Triton X-100 functionalized, signifying MWCNT degradation/rebundling at composition with higher content of MWCNTs. For the acid-treated MWCNTs, however, the tensile results showed slight improvement even at 4wt%, indicating effective dispersion of MWCNTs.

Synthesis and Characterization of Surface Functionalized Nanobiocomposite by Nano Hydroxyapatite

In this study, synthesis of biomemitic patterned nano hydroxyapatite-starch biocomposites using different concentration of starch to evaluate effect of polymer alteration on biocomposites structural properties has been reported. Formation of hydroxyapatite nano particles was confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Size and morphology of the samples were characterized using scanning and transmission electron microscopy (SEM and TEM). It seems that by increasing starch content, the more active site of polymer (oxygen atoms) can be provided for interaction with Ca2+ followed by phosphate and hydroxyl group.

Synthesis, Characterization and PL Properties of Cds Nanoparticles Confined within a Functionalized SBA-15 Mesoprous

A simple and dexterous in situ method was introduced to load CdS nanocrystals into organofunctionalized mesoporous, which used an ion-exchange method. The products were extensively characterized by combined spectroscopic methods. X- ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) demonstrated both the maintenance of pore symmetry (space group p6mm) of SBA-15 and the presence of CdS nanocrystals with uniform sizes of about 6 - 8 nm inside the functionalized SBA-15 channels. These mesoporous silica-supported CdS composites showed room temperature photoluminescence properties with a blue shift, indicating the quantum size effect of nanocrystalline CdS.

Synthesis and Characterization of PEG-Silane Functionalized Iron Oxide Nanoparticle as MRI T2 Contrast Agent

Iron oxide nanoparticle was synthesized by reactive-precipitation method followed by high speed centrifuge and phase transfer in order to stabilized nanoparticles in the solvent. Particle size of SPIO was 8.2 nm by SEM, and the hydraulic radius was 17.5 nm by dynamic light scattering method. Coercivity and saturated magnetism were determined by VSM (vibrating sample magnetometer), coercivity of nanoparticle was lower than 10 Hc, and the saturated magnetism was higher than 65 emu/g. Stabilized SPIO was then transferred to aqueous phase by reacted with excess amount of poly (ethylene glycol) (PEG) silane. After filtration and dialysis, the SPIO T2 contrast agent was ready to use. The hydraulic radius of final product was about 70~100 nm, the relaxation rates R2 (1/T2) measured by magnetic resonance imaging (MRI) was larger than 200(sec-1).

Removal of Ciprofloxazin and Carbamazepine by Adsorption on Functionalized Mesoporous Silicates

Ciprofloxacin (CIP) and Carbamazepine (CBZ), nonbiodegradable pharmaceutical residues, were become emerging pollutants in several aquatic environments. The objectives of this research were to study the possibility to recover these pharmaceuticals residues from pharmaceutical wastewater by increasing the selective adsorption on synthesized functionalized porous silicate, comparing with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS), functionalized HMSs (3- aminopropyltriethoxy, 3- mercaptopropyltrimethoxy and noctyldimethyl) were synthesized and characterized physico-chemical characteristics. Obtained adsorption kinetics and isotherms showed that 3-mercaptopropyltrimethoxy functional groups grafted on HMS provided highest CIP and CBZ adsorption capacities; however, it was still lower than that of PAC. The kinetic results were compatible with pseudo-second order. The hydrophobicity and hydrogen bonding might play a key role on the adsorption. Furthermore, the capacities were affected by varying pH values due to the strength of hydrogen bonding between targeted compounds and adsorbents. Electrostatic interaction might not affect the adsorption capacities.

Comparative Kinetic Study on Alkylation of p-cresol with Tert-butyl Alcohol using Different SO3-H Functionalized Ionic Liquid Catalysts

Ionic liquids are well known as green solvents, reaction media and catalysis. Here, three different sulfonic acid functional ionic liquids prepared in the laboratory are used as catalysts in alkylation of p-cresol with tert-butyl alcohol. The kinetics on each of the catalysts was compared and a kinetic model was developed based on the product distribution over these catalysts. The kinetic parameters were estimated using Marquadt's algorithm to minimize the error function. The Arrhenius plots show a curvature which is best interpreted by the extended Arrhenius equation.

Investigation of Shear Thickening Liquid Protection Fibrous Material

The stab resistance performance of newly developed fabric composites composed of hexagonal paper honeycombs, filled with shear thickening fluid (STF), and woven Kevlar® fabric or UHMPE was investigated in this study. The STF was prepared by dispersing submicron SiO2 particles into polyethylene glycol (PEG). Our results indicate that the STF-Kevlar composite possessed lower penetration depth than that of neat Kevlar. In other words, the STF-Kevlar composite can attain the same energy level in stab-resistance test with fewer layers of Kevlar fabrics than that of the neat Kevlar fabrics. It also indicates that STF can be used for the fabrication of flexible body armors and can provide improved protection against stab threats. We found that the stab resistance of the STF-Kevlar composite increases with the increase of SiO2 concentration in STF. Moreover, the silica particles functionalized with silane coupling agent can further improve the stab resistance.

Amberlite XAD-4 Functionalized with 1-amino-2-naphthole for Determination and Preconcentration of Copper (II) in Aqueous Solution by Flame Atomic Absorption Spectrometry

A new chelating resin is prepared by coupling Amberlite XAD-4 with 1-amino-2-naphthole through an azo spacer. The resulting sorbent has been characterized by FT-IR, elemental analysis and thermogravimetric analysis (TGA) and studied for preconcentrating of Cu (II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The optimum pH value for sorption of the copper ions was 6.5. The resin was subjected to evaluation through batch binding of mentioned metal ion. Quantitative desorption occurs instantaneously with 0.5 M HNO3. The sorption capacity was found 4.8 mmol.g-1 of resin for Cu (II) in the aqueous solution. The chelating resin can be reused for 10 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 99% was obtained the metal ions with 0.5 M HNO3 as eluting agent. The method was applied for metal ions determination from industrial waste water sample.

Polyethylenimine Coated Carbon Nanotube for Detecting Rancidity in Frying Oil

Chemical detection is still a continuous challenge when it comes to designing single-walled carbon nanotube (SWCNT) sensors with high selectivity, especially in complex chemical environments. A perfect example of such an environment would be in thermally oxidized soybean oil. At elevated temperatures, oil oxidizes through a series of chemical reactions which results in the formation of monoacylglycerols, diacylglycerols, oxidized triacylglycerols, dimers, trimers, polymers, free fatty acids, ketones, aldehydes, alcohols, esters, and other minor products. In order to detect the rancidity of oxidized soybean oil, carbon nanotube chemiresistor sensors have been coated with polyethylenimine (PEI) to enhance the sensitivity and selectivity. PEI functionalized SWCNTs are known to have a high selectivity towards strong electron withdrawing molecules. The sensors were very responsive to different oil oxidation levels and furthermore, displayed a rapid recovery in ambient air without the need of heating or UV exposure.

Low Temperature Ethanol Gas Sensor based on SnO2/MWNTs Nanocomposite

A composite made of plasma functionalized multiwall carbon nanotubes (MWNTs) coated with SnO2 was synthesized by sonochemical precipitation method. Thick layer of this nanocomposite material was used as ethanol sensor at low temperatures. The composite sensitivity for ethanol has increased by a factor of 2 at room temperature and by a factor of 13 at 250°C in comparison to that of pure SnO2. SEM image of nanocomposite material showed MWNTs were embedded in SnO2 matrix and also a higher surface area was observed in the presence of functionalized MWNTs. Greatly improved sensitivity of the composite material to ethanol can be attributed to new gas accessing passes through MWNTs and higher specific surface area.

Computational Studies of Binding Energies and Structures of Methylamine on Functionalized Activated Carbon Surfaces

Empirical force fields and density functional theory (DFT) was used to study the binding energies and structures of methylamine on the surface of activated carbons (ACs). This is a first step in studying the adsorption of alkyl amines on the surface of functionalized ACs. The force fields used were Dreiding (DFF), Universal (UFF) and Compass (CFF) models. The generalized gradient approximation with Perdew Wang 91 (PW91) functional was used for DFT calculations. In addition to obtaining the aminecarboxylic acid adsorption energies, the results were used to establish reliability of the empirical models for these systems. CFF predicted a binding energy of -9.227 (kcal/mol) which agreed with PW91 at - 13.17 (kcal/mol), compared to DFF 0 (kcal/mol) and UFF -0.72 (kcal/mol). However, the CFF binding energies for the amine to ester and ketone disagreed with PW91 results. The structures obtained from all models agreed with PW91 results.

Study of Encapsulation of Quantum Dots in Polystyrene and Poly (E-Caprolactone)Microreactors Prepared by Microvolcanic Eruption of Freeze Dried Microspheres

Polymeric microreactors have emerged as a new generation of carriers that hold tremendous promise in the areas of cancer therapy, controlled delivery of drugs, for removal of pollutants etc. Present work reports a simple and convenient methodology for synthesis of polystyrene and poly caprolactone microreactors. An aqueous suspension of carboxylated (1μm) polystyrene latex particles was mixed with toluene solution followed by freezing with liquid nitrogen. Freezed particles were incubated at -20°C and characterized for formation of voids on the surface of polymer microspheres by Field Emission Scanning Electron Microscope. The hollow particles were then overnight incubated at 40ºC with unfunctionalized quantum dots (QDs) in 5:1 ratio. QDs Encapsulated polystyrene microcapsules were characterized by fluorescence microscopy. Likewise Poly ε-caprolactone microreactors were prepared by micro-volcanic rupture of freeze dried microspheres synthesized using emulsification of polymer with aqueous Poly vinyl alcohol and freezed with liquid nitrogen. Microreactors were examined with Field Emission Scanning Electron Microscope for size and morphology. Current study is an attempt to create hollow polymer particles which can be employed for microencapsulation of nanoparticles and drug molecules.

Determination and Preconcentration of Iron (II) in Aqueous Solution with Amberlite XAD-4 Functionalized with 1-amino-2-naphthole by Flame Atomic Absorption Spectrometry

A new chelating resin is prepared by coupling Amberlite XAD-4 with 1-amino-2-naphthole through an azo spacer. The resulting sorbent has been characterized by FT-IR, elemental analysis and thermogravimetric analysis (TGA) and studied for preconcentrating of Fe (II) using flame atomic absorption spectrometry (FAAS) for metal monitoring. The optimum pH value for sorption of the iron ions was 6.5. The resin was subjected to evaluation through batch binding of mentioned metal ion. Quantitative desorption occurs instantaneously with 0.5 M HNO3. The sorption capacity was found 4.1 mmol.g-1 of resin for Fe (II) in the aqueous solution. The chelating resin can be reused for 10 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 97% was obtained the metal ions with 0.5 M HNO3 as eluting agent. The method was applied for metal ions determination from industrial waste water sample.