Green Synthesis of Fe and Fe/Pd Bimetallic Nanoparticles in Membranes for Reductive Degradation of Chlorinated Organics

Membranes containing reactive nanoparticles (Fe and Fe/Pd) immobilized in a polymer film (polyacrylic acid, PAA-coated polyvinylidene fluoride, PVDF membrane) are prepared by a new method. In the present work a biodegradable, non-toxic -"green" reducing agent, green tea extract was used for nanoparticle (NP) synthesis, instead of the well-known sodium borohydride. Green tea extract contains a number of polyphenols that can act as both chelating/reducing and capping agents for the nanoparticles. Therefore, the particles are protected from oxidation and aggregation, which increases their stability and longevity. The membrane supported NPs were successfully used for the degradation of a common and highly important pollutant, trichloroethylene (TCE). The rate of TCE degradation was found to increase linearly with the amount of Fe immobilized on the membrane, the surface normalized rate constant (k(SA)) being 0.005 L/m(2)h. The addition of a second catalytic metal, Pd, to form bimetallic Fe/Pd increased the k(SA) value to 0.008 L/m(2)h. For comparison purposes, Fe and Fe/Pd nanoparticles were synthesized in membranes using sodium borohydride as a reducing agent. Although the initial k(SA) values for this case (for Fe) are one order of magnitude higher than the tea extract synthesized NPs, the rapid oxidation reduced their reactivity to less than 20 % within 4 cycles. For the green tea extract NPs, the initial reactivity in the membrane domain was preserved even after 3 months of repeated use. The reactivity of TCE was verified with "real" water system.     

On the electrochemical characterization of ion-selective cellulose acetate membranes with and without stigmasterol liquid membranes

Stigmasterol, a plant product, has been used as a surfactant to generate liquid membranes supported on a cellulose acetate matrix. Electrochemical characterization of the membrane has been attempted with a view to simulating its behavior with natural membranes by measuring membrane potentials and membrane conductance. The selectivity of cellulose acetate membrane kept in contact with magnesium chloride solutions of different mean concentrations has been found to change from anion to cation. Transport numbers have been estimated from membrane potential data. Permselectivity and fixed charge density values for the cellulose acetate membrane with and without stigmasterol have been determined from transport numbers. The variation of these parameters with concentration and pH has also been examined.     

Modified cellulose acetate flat membranes for desalination

In this article, the radiation grafting of acrylamide on to cellulose acetate flat membranes using UV-irradiation on the initiator is described. The modified membranes thus obtained have been characterized by IR, DSC, and TGA. Their transport properties have been studied. The modified membranes exhibit higher salt rejection with slightly reduced water flux as compared with cellulose acetate membrane. The work is further extended to study the thermal stability of these modified membranes in a dry state. These modified membranes up to 330°C are stable.     

Determination of the pore radius of regenerated cellulose membranes by a dyeing technique

Membrane structure strongly affects the transport of solutes through dialysis membranes. This suggests that knowledge of membrane structure and its effects on permeability is required in order to improve the membranes. Solute transport in membrane pores is limited by steric hindrance at the pore entrances, frictional resistance of the pore walls, and the tortuosity of the pores. Differences in dyeing properties are found among the various tubular dialysis membranes made of regenerated cellulose (RC) that are commercially available. The objective of the present study is to determine intramembrane diffusivity for dyes, and from this the pore radius of RC membranes based on pore model calculations. Values of the pore radius of RC membranes obtained from intramembrane diffusivity data are in disagreement with our previously reported values obtained from solute and pure water permeability data. This indicates that RC membranes are of asymmetrical structure and slightly tight near the outside surfaces.     

Hollow-fiber-type pore-filling membranes made by plasma-graft polymerization for the removal of chlorinated organics from water

Hollow-fiber-type pore-filling membranes were prepared to reduce the emission of toxic chlorinated organics into the environment. These membranes can remove 1,1,2-trichloroethane (TCE) or dichloromethane (DM) from water, and concentrate them in the permeate. The pore-filling membrane can efficiently remove organics from water because of the suppression of the membrane swelling by the porous substrate matrix, and the fact that it can maintain a high solute diffusivity, because of the linear graft chains that fill the substrate pores. Laurylacrylate (LA) or n-butylacrylate (BA) grafted layers were formed inside the porous hollow-fiber substrate, and the pores were filled with the grafted chains formed from plasma-initiated graft polymerization. The hollow-fiber-type LA-grafted membranes showed extremely high separation properties: a 0.09 wt.% TCE aqueous solution was condensed to 99 wt.% TCE in the permeate. The membrane can remove TCE from a water stream, and at the same time, the membrane can purify the TCE for re-use. The membrane also showed high separation performance for an aqueous DM solution. The mass transfer resistance outside the membrane was estimated by using a concentration polarization model. When the mass transfer coefficient at the membrane and feed stream boundary layer was below 10⁻⁴ m/s, the boundary layer resistance affected the membrane performance. This needs to be taken into account when designing the membrane module and operating conditions.     

Improved Membranes for Hemodialysis

Asymmetric membranes of cellulose acetate and cellulose acetate modified with pendant amino groups have been evaluated for ultrafiltration and dialysis properties. Ultrafiltration rates from 4 to 30 times that of Cuprophan were obtained. During the ultrafiltration test, up to 89% of inulin in the test solution permeated with the ultrafitrate in contrast to the 14% permeation of inulin through a Cuprophan membrane. In spite of the apparently facile permeation of high molecular weight species (e.g., inulin) through the experimental membranes, human albumin was quantitatively reflected. Dialysis tests indicate that cellulose acetate membranes 38 μ or less in thickness should surpass 23-μ-thick (wet) Cuprophan in purely diffusional transport of blood solutes of low molecular weight.

In addition to their promising ultrafiltration and dialysis properties, membranes made from a blend of cellulose acetate and N,N-diethylaminoethylcellulose acetate were found to sorb heparin strongly. The clotting time of rabbit blood in contact with the heparinized membranes was extended, in some cases indefinitely.     

Influence of Composition of Nickel-Iron Nanoparticles for Abiotic CO2 Conversion to Early Prebiotic Organics

Abiotic synthesis of formate and short hydrocarbons takes place in serpentinizing vents where some members of vent microbial communities live on abiotic formate as their main carbon source. To better understand the catalytic properties of Ni−Fe minerals that naturally exist in hydrothermal vents, we have investigated the ability of synthetic Ni−Fe based nanoparticular solids to catalyze the H₂-dependent reduction of CO₂, the first step required for the beginning of pre-biotic chemistry. Mono and bimetallic Ni−Fe nanoparticles with varied Ni-to-Fe ratios transform CO₂ and H₂ into intermediates and products of the acetyl-coenzyme A pathway—formate, acetate, and pyruvate—in mM range under mild hydrothermal conditions. Furthermore, Ni−Fe catalysts converted CO₂ to similar products without molecular H₂ by using water as a hydrogen source. Both CO₂ chemisorption analysis and post-reaction characterization of materials indicate that Ni and Fe metals play complementary roles for CO₂ fixation.     

Sorption and permeation behaviour of metal thiocyanate complexes on cellulose acetate polymers

Various metal thiocyanate complexes in aqueous solution were sorbed on solid cellulose acetate polymers. The sorption selectivity increased in the order Zn(2+) > Fe(3+) > Cu(2+) > Co(2+) > Ni(2+). The sorption behaviour followed a Langmuir-type adsorption isotherm, and the maximum adsorption capacity was 6.1 x 10(-5) mole of complex per g of polymer under optimum conditions. The zinc species sorbed appear to be NH(4)Zn(H(2)O)(SCN)(3) or (NH(4))(2)Zn(SCN)(4) according to analysis of the sorption equilibrium. The ion-association species formed by the complex zinc anion and the ammonium ion was supposed to be sorbed (or "extracted") onto the polymer matrix. As an application of sorption of metal complexes, a new hyperfiltration process was proposed for selective separation of metal ions. Thus, a mixture of metal thiocyanate complexes was hyperfiltered through cellulose acetate membranes. Permeation of certain metal complexes was preferred, and the selectivity was found to be similar to the sorption selectivity. These findings lead to a generalized idea that hyperfiltration separation of ionic species, particularly anionic metal complexes, can be attained by using polymer membranes which selectively adsorb or extract such ionic species as ion-association complexes onto the polymer matrix.     

Catalytic dechlorination of Aroclor 1242 by Ni/Fe bimetallic nanoparticles

Ni/Fe bimetallic nanoparticles were synthesized for treatment of Aroclor 1242, in order to evaluate their applicability for in situ remediation of groundwater and soil contaminated by polychlorinated biphenyls (PCBs). Our experimental results indicate that the total PCB concentration changed during the reduction of 3,5-dichlorobiphenyl (PCB 14), and biphenyl was produced as the final product. Initially, the concentration of 3-chlorobiphenyl (PCB 2) was increased in the prophase reaction and then slowly decreased, suggesting that Aroclor 1242 was first adsorbed by Ni/Fe nanoparticles, and then, the higher chlorinated congeners were converted gradually to the lower chlorinated congeners, and finally to biphenyl. The dechlorination efficiency of Aroclor 1242 reached approximately 80% at 25°C in just 5h, then 95.6% and 95.8% in 10h and 24h, respectively. The study revealed that high Ni/Fe nanoparticle dosage and high Ni content in Ni/Fe nanoparticles favor the catalytic dechlorination reaction. Moreover, a comparison of different types of catalysts on the dechlorination of Aroclor 1242 indicated that Ni/Mg and Mg powders showed a greater reactivity than Ni/Fe and Fe nanoparticles, respectively.     

Removal of aromatic compounds in the aqueous solution via micellar enhanced ultrafiltration: Part 1. Behavior of nonionic surfactants

The effects of nonionic surfactants having different hydrophilicity and membranes having different hydrophobicity and molecular weight cut-off on the performance of micellar-enhanced ultrafiltration (MEUF) process were examined. A homologous series of polyethyleneglycol (PEG) alkylether having different numbers of methylene groups and ethylene oxide groups was used for nonionic surfactants. Polysulfone membranes and cellulose acetate membranes having different molecular cut-off were used for hydrophobic membranes and hydrophilic membranes, respectively. The concentration of surfactant added to pure water was fixed at the value of 100 times of critical micelle concentration (CMC). The flux through polysulfone membranes decreased remarkably due to adsorption mainly caused by hydrophobic interactions between surfactant and membrane material. The decline of solution flux for cellulose acetate membranes was not as serious as that for polysulfone membranes because of hydrophilic properties of cellulose acetate membranes. The surfactant rejections for the cellulose acetate membranes increased with decreasing membrane pore size and with increasing the hydrophobicity of surfactant. On the other hand the surfactant rejections for polysulfone membranes showed totally different rejection trends with those for cellulose acetate membranes. The surfactant rejections for the polysulfone membranes depend on the strength of hydrophobic interactions between surfactant and membrane material and molecular weight of surfactants.     

Polymeric membranes based on cellulose acetate loaded with candle soot nanoparticles for water desalination

This study is concerned with modifying cellulose acetate (CA)/polyethylene glycol (PEG) membranes prepared via phase inversion technique in the presence of carbon nanoparticles; candle soot (CS) resulting from combusted candle. CS nanoparticles were analyzed via Fourier transform infrared spectroscopy and transmission electron microscopy. The developed membranes were characterized for their surface morphology, mechanical properties as well as thermal stability. CS nanoparticles contributed in improving the salt rejection % with a slight reduction in the water flux behavior. Employing the annealed cellulose acetate/polyethylene glycol membranes loaded with candle soot nanoparticles provides an adequate approach towards water desalination implementations.     

Aqueous-phase synthesis of PAA in PVDF membrane pores for nanoparticle synthesis and dichlorobiphenyl degradation

This paper deals with bimetallic (Fe/Pd) nanoparticle synthesis inside the membrane pores and application for catalytic dechlorination of toxic organic compounds form aqueous streams. Membranes have been used as platforms for nanoparticle synthesis in order to reduce the agglomeration, encountered in solution phase synthesis which leads to a dramatic loss of reactivity. The membrane support, polyvinylidene fluoride (PVDF) was modified by in situ polymerization of acrylic acid in aqueous phase. Subsequent steps included ion exchange with Fe²⁺, reduction to Fe⁰ with sodium borohydride and Pd deposition. Various techniques, such as STEM, EDX, FTIR and permeability measurements, were used for membrane characterization and showed that bimetallic (Fe/Pd) nanoparticles with an average size of 20–30 nm have been incorporated inside of the PAA-coated membrane pores. The Fe/Pd-modified membranes showed a high reactivity toward a model compound, 2,2′-dichlorobiphenyl and a strong dependence of degradation on Pd (hydrogenation catalyst) content. The use of convective flow substantially reduces the degradation time: 43% conversion of dichlorobiphenyl to biphenyl can be achieved in less than 40 s residence time. Another important aspect is the ability to regenerate and reuse the Fe/Pd bimetallic systems by washing with a solution of sodium borohydride, because the iron becomes inactivated (corroded) as the dechlorination reaction proceeds.     

Optimization of profenofos organophosphorus pesticide degradation by zero-valent bimetallic nanoparticles using response surface methodology

This study synthesized bimetallic Fe/Ni nanoparticles and used them for catalytic degradation of profenofos, an organophosphorus pesticide. This novel bimetallic catalyst (Fe/Ni) was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray analysis spectroscopy (EDAX) and X-ray diffraction (XRD). The bimetallic nano-catalyst was prepared at diameters of 20–50 nm and was shown to effectively degrade profenofos. A three-factor central composite design combined with response surface methodology was used to maximize profenofos removal using the bimetallic system. A quadratic model was built to predict degradation efficiency. ANOVA was used to determine the significance of the variables and interactions between them. Good correlation between the experimental and predicted values was confirmed by the high F-value (16.38), very low P-value (<0.0001), non-significant lack of fit, an appropriate coefficient of determination (R² = 0.936) and adequate precision (14.75). The highest removal rate attained was 94.51%.     

Impurity partitioning in Nafion and ceramic separators used for purification of spent chromium plating solutions

Cationic partitioning (Cu(II), Ni(II), and Fe(III)) into Nafion and ceramic membranes equilibrated with different salt solutions was investigated in this study. Both single-ion and multicomponent partitioning in a Nafion-117 membrane in a 2.12 M chromic acid solution was well characterized with the Freundlich isotherm. The affinity for the Nafion membrane was Fe(III)>Ni(II)>Cu(II). The partition coefficients of the divalent cations in multicomponent partitioning experiments were similar to those in single-ion experiments whereas the partition coefficients of the trivalent cation decreased. Among the factors investigated, pH had the most significant influence on the partition coefficients, especially in the pH range of about 0.5–1.5. In contrast, temperature in the range of 25–55 °C had an insignificant effect. The ceramic diaphragm had partition coefficients equal to the porosity (0.4) of the ceramic for all of the species implying that cations were not adsorbed to its surface.     

Role of membrane surface morphology in colloidal fouling of cellulose acetate and composite aromatic polyamide reverse osmosis membranes

Laboratory-scale colloidal fouling tests, comparing the fouling behavior of cellulose acetate and aromatic polyamide thin-film composite reverse osmosis (RO) membranes, are reported. Fouling of both membranes was studied at identical initial permeation rates so that the effect of the transverse hydrodynamic force (permeation drag) on the fouling of both membranes is comparable. Results showed a significantly higher fouling rate for the thin-film composite membranes compared to that for the cellulose acetate membranes. Addition of an anionic surfactant (sodium dodecyl sulfate, SDS) to mask variations in chemical and electrokinetic surface characteristics of the cellulose acetate and aromatic polyamide membranes resulted in only a small change in the fouling behavior. The higher fouling rate for the thin-film composite membranes is attributed to surface roughness which is inherent in interfacially polymerized aromatic polyamide composite membranes. AFM and SEM images of the two membrane surfaces strongly support this conclusion. These surface images reveal that the thin-film composite membrane exhibits large-scale surface roughness of ridge-and-valley structure, while the cellulose acetate membrane surface is relatively smooth.     

CHARACTERIZATION OF REGENERATED CELLULOSE MEMBRANES HYDROLYZED FROM CELLULOSE ACETATE

A series of cellulose acetate membranes were prepared by using formamide as additive, and then were hydrolyzedin 4 wt% aqueous NaOH solution for 8 h to obtain regenerated cellulose membranes. The dependence of degree ofsubstitution, structure, porous properties, solubility and thermal stability on hydrolysis time was studied by chemical titration,Fourier transform infrared spectroscopy, scanning electron microscopy, wide-angle X-ray diffraction, and differentialscanning calorimetry, respectively. The results indicated that the pore size of the regenerated cellulose membranes wasslightly smaller than that of cellulose acetate membrane, while solvent-resistance, crystallinity and thermostability weresignificantly improved. This work provides a simple way to prepare the porous cellulose membranes, which not only kept thegood pore characteristics of cellulose acetate membranes, but also possessed solvent-resistance, high crystallinity andthermostability. Therefore, the application range ofcellulose acetate membranes can be expanded.     

Studies on cellulose acetate-carboxylated polysulfone blend ultrafiltration membranes--Part I

Hydrophilic polysulfone ultrafiltration (UF) membranes were prepared from blends of cellulose acetate with carboxylated polysulfone of 0.14 degree of carboxylation. The effects of blend polymer composition on compaction, pure water flux, water content and membrane hydraulic resistance (R_m), have been investigated to evaluate the performance of the membranes. The performance of the blend membranes of various blend polymer compositions were compared with that of membranes prepared from pure cellulose acetate and blends of cellulose acetate and pure polysulfone. The hydrophilic cellulose acetate-carboxylated polysulfone blend UF membranes showed better performance compared to membranes prepared from pure cellulose acetate and blends of cellulose acetate and pure polysulfone.     

尺寸比例可调的Au-Ni双金属纳米颗粒的制备

本文采用贵金属诱导还原法制备了一种Ni端尺寸可调的Au-Ni双金属纳米颗粒.该反应以十八胺为还原剂,硝酸镍和氯金酸为反应物,反应中Au3+首先被还原成Au0,随着温度上升,Ni2+从Au0获得电子而被还原成Ni0,十八胺持续提供电子,得到了雪人状的Au-Ni双金属纳米颗粒.采用I2/KI水溶液和0.5%(质量分数)盐酸分别对Au端和Ni端进行择性蚀刻,通过调节蚀刻时间,连续调控两端尺寸,可以达到完全刻蚀,最终制备了一种两端尺寸比例连续可调的Au-Ni双金属纳米颗粒.蚀刻后得到的新鲜表面为进一步功能复合提供了反应场所.     

Sorption and diffusion of VOCs in DAY zeolite and silicalite-filled PDMS membranes

The sorption and diffusion properties of ethanol, 1,1,1-trichloroethane (TCA) and trichloroethylene (TCE) were determined in silicalite-filled and dealuminized-Y-zeolite (DAY)-filled poly[dimethylsiloxane] (PDMS) membranes at 25, 100 and 150°C. Zeolite filling results in increased solubility coefficients (S) for polar solvents like ethanol over pure PDMS. No significant increase in S is observed in case of TCA and TCE which act as good solvents for PDMS. However, at higher temperatures, the sorption is higher in zeolite-filled membranes even for the good solvents. The VOC diffusivity decreases with increasing degree of zeolite filling because of higher characteristic diffusion time in zeolites (for ethanol) and increasing tortuosity of the diffusion path (for TCA). Due to the presence of carbon=carbon double bond, TCE exhibits marginal diffusivity drop in zeolite-filled membranes. The specific zeolite-polymer interactions, that is, tendency of zeolite pore blocking by polymer chains or the formation of voids on zeolite-polymer interface are influenced by the zeolite pore size and type of VOC permeating through the composite membrane. The variation in experimentally observed ethanol permeability due to zeolite filling could be qualitatively estimated from the sorption-diffusion data.     

Characterization of magnetic nanoparticles using energy-selected transmission electron microscopy.

Fe, Co, and Ni magnetic nanoparticles have been characterized using energy-selected imaging in a high-resolution transmission electron microscope. The samples comprised Fe/FeO x and Co/CoO x nanoparticles synthesized by inert gas evaporation and a Ni/C nano-composite prepared by a sonochemical method. All of the particles examined were found to be between 5 and 30 nm in size, with the Fe and Co crystals coated in 5-10 nm of metal oxide layer and the Ni metallic crystallites embedded in an amorphous carbon spherical matrix.