Nanocomposite membranes containing positively polarized gold nanoparticles for facilitated olefin transport

Positively polarized gold nanoparticles have been demonstrated for use as stable olefin carriers for facilitated olefin transport membranes. The formation and size of gold nanoparticles stabilized by 4-dimethylaminopyridine (DMAP) were monitored using X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–visible spectroscopy. Nanocomposite membranes that deliver high separation performance for olefin/paraffin mixtures were prepared by dispersing gold nanoparticles stabilized by DMAP in a polymer matrix, poly(vinyl pyrrolidone) (PVP). X-ray photoelectron spectroscopy (XPS) and zeta potential measurements revealed that gold nanoparticles stabilized by DMAP exhibited a high positive polarity, which is responsible for the reversible interaction between the gold nanoparticles and olefin molecules. Compared to neat PVP membranes, the composite membranes consisting of PVP and the polarized gold nanoparticles showed stable and enhanced separation of olefin/paraffin mixtures.     

A Simple and Fast Aqueous‐Phase Synthesis of Ultra‐Highly Concentrated Silver Nanoparticles and Their Catalytic Properties

A simple and fast synthetic route to ultra‐highly concentrated silver nanoparticles with long‐term stability by reducing AgNO₃ with ascorbic acid in the presence of polyethyleneimine (PEI) as a stabilizer in an aqueous phase is reported. The concentration of silver precursor was as high as 2000 mm (200 g of Ag nanoparticle per liter of water) and the reaction time was less than 10 min. The resulting silver nanoparticles show long‐term stability after two months of storage at room temperature without any signs of particle aggregation or precipitation in an aqueous phase. The successful ligand exchange of PEI‐stabilized silver nanoparticles to polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) without particle aggregation is also demonstrated. In addition, the catalytic activities of silver nanoparticles stabilized by various stabilizers prepared by the ligand exchange method was investigated. The PEI‐stabilized silver nanoparticles exhibited a higher stability than those of PEG‐ and PVP‐stabilized silver nanoparticles in the diffusion‐controlled catalytic reduction of 4‐nitrophenol to 4‐aminophenol by NaBH₄.     

Effective chemical route for the synthesis of silver nanostructures in formamide

Poly(N-vinyl-2-pyrrolidone) (PVP) and gelatin protected silver nanostructures are prepared in formamide by simple chemical route. Both PVP and gelatin stabilized silver nanoparticles in formamide lead to the formation of nanostructures of various definite geometric shapes and sizes. The effect of anisotropy on the surface plasmon absorption band is analyzed by monitoring the UV-Visible absorption spectra of gelatin stabilized silver nanoparticles. The particles were characterized by UV-Visible absorption spectra and TEM.     

Effect of the polymer matrix on the formation of silver nanoparticles in polymer–silver salt complex membranes

When polymer–silver salt complex membranes were exposed to UV irradiation, the separation performances of both the permeance and selectivity for propylene–propane decreased, which was primarily attributed to the reduction of the silver ions in the membranes to silver nanoparticles. Here, the effect of the polymer matrix on the formation of silver nanoparticles in the polymer–silver salt complex membranes was investigated. This effect was assessed for the complexes of two kinds of silver salts (AgBF₄ and AgCF₃SO₃) with several polymeric ligands containing three different carbonyl groups, including poly(vinyl pyrrolidone) (PVP) with an amide group, poly(vinyl methyl ketone) (PVMK) with a ketone group, and poly(methyl methacrylate) (PMMA) with an ester group. UV–vis spectra and transmission electron microscopy (TEM) images clearly indicated that the reduction rate of the silver ions has the following order in the various polymer matrices: PVP > PVMK > PMMA, whereas the size and the distribution of the nanoparticles exhibited the reverse order. The tendency to form silver nanoparticles was explained in terms of the differences between the comparative strengths of the interactions of the silver ions with the different carbonyl oxygens in the matrices, as well as that of the silver ions with counteranions, which was characterized by X‐ray photoelectron spectroscopy (XPS) and FT‐Raman spectroscopy. It was concluded that when the concentration of free silver ions was low due to weak polymer–silver ion and strong silver ion–anion interactions, as found with PMMA, the reduction rate of silver ions to silver nanoparticles was slow. Therefore, the PMMA–silver complex membranes were less sensitive to decreases in separation performance upon UV irradiation than compared to the PVP membranes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1168–1178, 2006     

Role of anions for the reduction behavior of silver ions in polymer/silver salt complex membranes

The reduction of silver ions to silver nanoparticles is an essential issue in polymer/silver salt complex membranes for facilitated olefin transport, because it has a critical influence on the long-term stability of membrane performance. In this study, the role of anions for the formation of silver nanoparticles in polymer/silver salt complexes was investigated. This role was assessed for the complexes of poly(N-vinyl pyrrolidone) (PVP) with three silver salts including AgBF₄, AgCF₃SO₃, and AgNO₃. Especially, UV irradiation to the membranes was used to clearly investigate the reduction behavior of silver ions. Separation performance test, UV–vis spectroscopy and transmission electron microscopy (TEM) clearly show that the reduction rate of silver ions strongly depends on the counteranions of salt, and has the following order: AgBF₄ > AgCF₃SO₃ > AgNO₃. This behavior of the formation of silver nanoparticles in polymer/silver salt complex membranes is explained in terms of the interaction strength of silver ions with the carbonyl oxygens of polymer, and that of silver ions with counteranions. It is concluded that when the former interaction is strong and the latter one is weak, the reduction rate of silver ions to silver nanoparticles is fast, and vice versa. These interactions were characterized using FT-IR, FT-Raman spectroscopy, and theoretical ab initio calculation.     

Structural changes of silver polymer electrolytes: Comparison between poly(2‐ethyl‐2‐oxazoline) and poly(N‐vinyl pyrrolidone) complexes with silver salt

The difference between the polymer matrices of poly(2‐ethyl‐2‐oxazoline) (POZ) and poly(N‐vinyl pyrrolidone) (PVP) does not have a significant effect on the facilitated propylene transport and propylene solubility in 1:1 polymer/silver salt complex membranes, according to our previous work. In this article, its origin is investigated in terms of both microstructures of silver polymer electrolytes and the coordinative interaction of silver ion with polymer and with the counteranion. Initially different microstructures of POZ and PVP become similar to each other upon dissolving a large amount of silver salt, as evidenced by propane transport properties, specific volume, and Bragg d‐spacing. The dissolution of the silver salt in the polymer solvent strongly depends on the coordinative interaction between silver ion and carbonyl oxygen of POZ and PVP. Thus, the structural similarity upon dissolving silver salts in POZ and PVP is primarily determined by the coordinative interaction between silver ion and carbonyl oxygen, which was confirmed by theoretical structure calculation based on density functional theory and by IR and Raman spectroscopy. Therefore, facilitated olefin transport for silver polymer electrolyte membranes does not strongly depend on the polymeric matrix at high silver concentrations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 232–237, 2004     

Complexation mechanism of olefin with silver ions dissolved in a polymer matrix and its effect on facilitated olefin transport

Remarkable separation performance of olefin/paraffin mixtures was previously reported by facilitated olefin transport through silver-based polymer electrolyte membranes. The mechanism of facilitated olefin transport in solid membranes of AgCF3SO3 dissolved in poly(N-vinyl pyrrolidone) (PVP) is investigated. In silver polymer electrolyte membranes, only free anions are present up to the 2:1 mole ratio of [C=O]:[Ag], and ion pairs start to form at a ratio of 1:1, followed by higher-order ionic aggregates above a ratio of 1:2. At silver concentrations above 3:1, the propylene permeance increases almost linearly with the total silver concentration, unexpectedly, regardless of the silver ionic constituents. It was also found that all the silver constituents, including ion pairs and higher order ionic aggregates, were completely redissolved into free anions under the propylene environment; this suggests that propylene can be a good ligand for the silver cation. From these experimental findings, a new mechanism for the complexation reaction between propylenes and silver salts in silver-polymer electrolytes was proposed. The new mechanism is consistent with the linearity between the propylene permeance and the total silver concentration regardless of the kind of the silver constituents. Therefore, the facilitated propylene transport through silver-polymer electrolytes may be associated mainly with the silver cation weakly coordinated with both carbonyl oxygen atoms and propylene.     

Mechanism of growth of colloidal silver nanoparticles stabilized by polyvinyl pyrrolidone in gamma-irradiated silver nitrate solution

Silver nanoparticles were prepared by using polyvinyl pyrrolidone (PVP) as a stabilizer and gamma-irradiation. Transmission electron microscopy (TEM) results showed that both the amount and the molecular weight of PVP in the irradiated solution considerably affect the average size of the silver nanoparticles. The average size of the silver nanoparticles decreases with increasing the amount of PVP in the solution, but increases with increasing its molecular weight. Further, TEM showed that the silver nanoparticles become disassembled into smaller nanoparticles after dilution with distilled water and sonication. Since the processes of dilution and sonication are not expected to result in chemical reactions or to split the silver nanoparticles, we conclude that each silver nanoparticle prepared by [Formula: see text] -irradiation consists of several smaller nanoparticles surrounded by PVP. Thus, based on these observations, we propose a three-step mechanism for the growth of the silver nanoparticles under the conditions considered here. In the first step, the silver ions interact with PVP, then in the second step the silver ions that are exposed to gamma-irradiation are reduced to silver atoms; nearby silver atoms then aggregate at close range. These aggregates are the primary nanoparticles. Finally, these primary nanoparticles coalesce with other nearby primary nanoparticles or interact with PVP to form larger aggregates which are the secondary (final) nanoparticles.     

溶剂热法制备银纳米晶

以聚乙烯吡咯烷酮(PVP)作为表面活性剂,利用乙二醇溶剂热法成功制备了银纳米颗粒;利用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)分析了样品的形貌和晶体结构,并考察了溶剂组成等因素对银纳米颗粒形貌的影响.研究结果表明所得银纳米晶粒径均一,直径约为90nm;增大PVP的加入量会降低产物的粒径,溶剂中水的引入会影响银纳米晶的形貌.     

Structure and separation properties of π‐complex membranes comprising poly(hexamethylenevinylene) and silver tetrafluoroborate

Polymer/silver‐ion π‐complex membranes consisting of poly(hexamethylenevinylene) (PHMV) and silver tetrafluoroborate exhibit unusually high separation performance for olefin/olefin and olefin/paraffin mixtures. The formation of π complexes between silver ions and unsaturated C?C bonds of PHMV has been confirmed with wide‐angle X‐ray scattering, differential scanning calorimetry, and X‐ray photoelectron spectroscopy. Fourier transform infrared and ultraviolet spectroscopy studies have revealed that silver ions make π complexes with olefins such as 1,3‐butadiene, propylene, and ethylene. Of these three olefins, 1,3‐butadiene has the highest binding affinity with silver ions in dissolved in PHMV, and this results in its higher solubility and permeance. Therefore, the π‐complex membranes exhibit unusually high separation performance for olefin/olefin and olefin/paraffin mixtures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1434–1441, 2006     

Catalytic activation of nitrobenzene on PVP passivated silver cluster: A DFT investigation

Poly(N‐vinyl‐2‐pyrrolidone) (PVP) has been used extensively to stabilize the surface of noble metal nanoparticles against aggregation and also to produce anisotropic nanostructures. Naturally, it is very important to understand the effect of such surface stabilization by PVP on the catalytic activity of these nanoparticles. This communication investigates through DFT calculations the electronic properties of PVP stabilized 13‐atom Ag cluster for catalytic activation of nitrobenzene (NB). These computations suggest that poly(N‐vinyl‐2‐pyrrolidone) (PVP) interact with silver (Ag) cluster mainly through oxygen atom and acts not only as a stabilizer to prevent the aggregation of Ag clusters but also as an electron donor to activate the Ag clusters for further reaction. Natural Bonding Orbital (NBO) calculations show that catalytic activation of NB by PVP passivated Ag cluster occurs due to interaction of the oxygen of the nitro group with the Ag cluster. Weak back donation of electrons from M(dπ) orbital of Ag to antibonding σ* of one of the N O bond, facilitates the formation of the nitroso intermediate. To understand the extent and the nature of this interaction better, vibrational frequency calculation of nitrobenzene association with Ag13‐2PVP cluster is carried out. Red shift in the frequencies is consequence of strong interaction with that of silver cluster present in Ag13‐2PVP‐NB model.     

Interactions of Ag Particles Stabilized by 7,7,8,8-Tetracyanoquinodimethane with Olefin Molecules in Poly(ether-block-amide)

In this study, to use a stabilized carrier, silver nanoparticles (AgNPs) were used as carriers and electron acceptors were added to activate the surface of AgNPs as olefin carriers. In addition, poly(ether-block-amide) (PEBAX), consisting of polyamide (hard segments) and polyether (soft segments), was investigated for the correlation of the between-segments ratio related to the stability of AgNPs and separation performance. As a result, contrary to the expectation that high permeance would be observed in PEBAX-1657/AgNPs/7,7,8,8-tetracyanoquinodimethane (TCNQ) membrane, which had a higher ratio of polyether soft segment, the PEBAX-5513/AgNPs/TCNQ membrane, which had a relatively high proportion of polyamide, showed a higher permeance without difference in selectivity. These unexpected data were attributable to the fact that the relatively abundant amount of PA groups in PEBAX-5513 was able to stabilize and positively polarize the surface of AgNPs, resulting in the stabilized and high performance of olefin separation.     

同轴静电纺丝法在纳米中空Ti02纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶,钛酸四正丁酯和PVP溶胶,银颗粒为前驱体,以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维.将双组分纤维在200℃下热处理去除乙醇与表面吸附水后,继而在空气气氛中焙烧至600℃.可以得到在内表面上沉积银颗粒的TiO2纳米管,银颗粒的直径为5-40 nm,TiO2纳米管的外径150-300 nm.管臂厚10-20 nm.用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征.中空纤维的直径和管壁可以通过改变电纺参数来调节.与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较,Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

同轴静电纺丝法在纳米中空TiO2纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶/钛酸四正丁酯和PVP溶胶/银颗粒为前驱体, 以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维. 将双组分纤维在200 ℃下热处理去除乙醇与表面吸附水后, 继而在空气气氛中焙烧至600 ℃, 可以得到在内表面上沉积银颗粒的TiO2纳米管, 银颗粒的直径为5-40 nm, TiO2纳米管的外径150-300 nm, 管臂厚10-20 nm. 用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征. 中空纤维的直径和管壁可以通过改变电纺参数来调节. 与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较, Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

Colloidal gold nanoparticles as catalyst for carbon-carbon bond formation: application to aerobic homocoupling of phenylboronic acid in water

Gold nanoparticles (<2 nm) stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP NPs) were prepared by reduction of AuCl4- with NaBH4 in the presence of PVP and characterized via an array of methods including optical absorption spectroscopy, transmission electron microscopy, X-ray diffraction, X-ray absorption near-edge structure, extended X-ray absorption fine structure, and X-ray photoelectron spectroscopy. We demonstrate for the first time that the Au:PVP NPs act as catalyst toward homocoupling of phenylboronic acid in water under aerobic conditions. Suppression of biphenyl formation under anaerobic conditions indicates that molecular oxygen dissolved in water is intimately involved in the coupling reactions. A mechanism of the aerobic homocoupling catalyzed by the Au:PVP NPs is proposed on the basis of a crucial role of dissolved oxygen, steric effects on the product yields, and the well-established mechanism for the Pd(II)-based catalysts.     

First successful design of semi-IPN hydrogel-silver nanocomposites: a facile approach for antibacterial application

Semi-IPN hydrogels in which poly(vinyl pyrrolidone) (PVP) chains were physically dispersed throughout poly(acrylamide) (PAM) gel networks were synthesized. These semi-IPN hydrogel networks can act as excellent nanoreactors for producing and stabilizing metal nanoparticles. The current methodology allows us to entrap metal nanoparticles throughout hydrogel networks via PVP chains. An optimized semi-IPN hydrogel formulation was found to produce silver nanoparticles, ca. 3-5 nm. The synthesized semi-IPN hydrogel-silver nanocomposites were fully characterized by using UV-vis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The developed semi-IPN hydrogel-silver nanocomposite (SHSNC) was evaluated for preliminary antibacterial applications.     

Solvent-induced shape evolution of PVP protected spherical silver nanoparticles into triangular nanoplates and nanorods

The reaction between silver nitrate and poly(N-vinyl-2-pyrrolidone) (PVP) in pyridine at ambient conditions could lead to the formation of spherical nanoparticles or quadrilateral and triangular silver nanoplates, depending on the silver-to-PVP ratio used. It is proposed that the spherical Ag nanoparticles, which were formed early in the reaction, were transformed into nanoplates through an Ostwald ripening process driven by the bridging flocculation of small spherical Ag nanoparticles. This unique and hitherto unreported shape evolution process was carefully followed by a combination of techniques, viz., UV-visible spectroscopy, TEM, and powder X-ray diffraction.     

Preparation of silver nanoparticles with controlled particle size

Silver colloids show different colors due to light absorption and scattering in the visible region based on plasmon resonance. The resonance wavelength depends on particle size and shape. Here we report chemical reduction methods for preparation of silver nanoparticles exhibiting multicolor in aqueous solutions. Depending on chemical conditions the obtained nanoparticles are different regarding size and morphology.In order to investigate the relationship between size, stability and color of silver colloids we obtained silver nanoparticles in aqueous solutions using different reducing agents. The effect of polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA) on stabilization of obtained silver colloids was investigated. We have also studied the effect of silver precursor and its concentration on the formation of stable silver colloids.UV-VIS spectrum for silver colloids contains a strong plasmon band near 410 nm, which confirms silver ions reduction to Ag° in the aqueous phase. The formation of metal silver was also confirmed by powder X-ray diffraction (XRD) analysis. The diameter size of silver nanoparticles was in the range from 5 nm to 100 nm     

Laser-induced silver nanocrystal formation in polyvinylpyrrolidone solutions

We report unusual laser-induced shape conversions of silver nanoparticles dispersed in polyvinylpyrrolidone (PVP) aqueous solutions. Silver nanocrystals such as nanoplates and nanorods were formed using laser irradiation for colloidal silver nanoparticles prepared using laser ablation in aqueous solutions of PVP. Differing from the nanocrystal formation observed in neat water and halide solutions, which were induced by weak laser or fluorescent-light irradiation, the nanocrystal formation in PVP solutions was induced by strong laser irradiation. On the other hand, nanocrystal formation was not observed in polyvinylalcohol (PVA) solutions, in which fusion of nanoparticles were prominent. It is proposed that the nanocrystals were formed from fragmented nanoparticles protected by PVP via a ripening process.     

Biosynthesis of silver nanocrystals by Bacillus licheniformis

The use of microorganisms for the synthesis of nanoparticles is in the limelight of modern nanotechnology. Using the bacterium Bacillus licheniformis, the biosynthesis of silver nanoparticles was investigated. These silver nanoparticles were characterized by means of UV-vis spectroscopy, scanning electron microscopy (SEM), electron diffraction spectroscopy (EDX) and X-ray diffraction (XRD). The nanoparticles exhibited maximum absorbance at 440 nm in UV-vis spectroscopy. The XRD spectrum of silver nanoparticles exhibited 2theta values corresponding to the silver nanocrystal. SEM micrographs revealed the formation of well-dispersed silver nanoparticles of 50 nm, and the presence of silver was confirmed by EDX analysis.