反相微乳液中AgCl纳米粒子的可控合成与AgCl/GMA-MMA-AMPS共聚物有机-无机杂化膜的研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为表面活性剂,在甲基丙烯酸缩水甘油酯(GMA)和甲基丙烯酸甲酯(MMA)混合物为油相的反相微乳液体系中合成了AgCl纳米粒子,然后通过微乳液聚合制备了AgCl/GMA-MMA-AMPS共聚物有机-无机杂化膜,并用于苯/环己烷混合物的渗透气化分离.利用紫外-可见光谱及透射电子显...     

Recovery of nanoparticles produced in phosphatidylcholine-based template phases

This paper focuses on the characterization and use of polymer-modified phosphatidylcholine (PC)/sodium dodecyl sulfate (SDS)-based inverse microemulsions as a template phase for BaSO4 nanoparticle formation. The area of the optically clear inverse microemulsion phase in the isooctane/hexanol/water/PC/SDS system is not significantly changed by adding polyelectrolytes, i.e., poly(diallyldimethylammonium chloride) (PDADMAC), or amphoteric copolymers of diallyldimethylammonium chloride and maleamid acid to the SDS-modified inverse microemulsion. Shear experiments show non-Newtonian flow behavior and oscillation experiments show a frequency-dependent viscosity increase (dilatant behavior) of the microemulsions. Small amounts of bulk water were identified by means of differential scanning calorimetry. One can conclude that the macromolecules are incorporated into the individual droplets, and polymer-filled microemulsions are formed. The polymer-filled microemulsions were used as a template phase for the synthesis of BaSO4 nanoparticles. After solvent evaporation the nanoparticles were redispersed in water and isooctane, respectively. The polymers incorporated into the microemulsion are involved in the redispersion process and influence the size and shape of the redispersed BaSO4 particles in a specific way. The crystallization process mainly depends on the type of solvent and the polymer component added. In the presence of the cationic polyelectrolyte PDADMAC the crystallization to larger cubic crystals is inhibited, and layers consisting of polymer-stabilized spherical nanoparticles of BaSO4 (6 nm in size) will be observed.     

A new and simple method for sulfur nanoparticles synthesis

Sulfur nanoparticles were successfully synthesized via novel water-in-oil microemulsion system. The microemulsion system contained cyclohexane as an oil phase, Triton X-100 as a surfactant, butanol as a co-surfactant and sodium polysulfide solution or hydrochloric acid solution as aqueous phase, respectively. The sulfur nanoparticles were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and Fourier transform infrared spectroscopy. The results showed that the as-prepared monoclinic sulfur nanoparticles exhibited high purity and spherical shape with an average size of about 22 nm.     

新型双链表面活性剂DDOBA的合成与高单分散性憎水纳米金的制备

自行设计合成了新颖的苄胺型双链表面活性剂3,4-双十二烷氧基苄胺(DDOBA). 利用DDOBA/正丁醇/正庚烷/甲酸/HAuCl₄·4H₂O自发形成的水/油(W/O)型微乳液作为微反应器, 通过微波辐射下的甲酸还原法成功制备了DDOBA保护的憎水性金纳米粒子, 并通过紫外-可见(UV-Vis)光谱、透射电镜(TEM)、高分辨透射电镜(HR-TEM)和X射线衍射(XRD)等方法进行了表征和分析. 结果显示, DDOBA既可参与形成稳定的W/O型(油包水型)微乳液, 又可作为金纳米粒子的良好保护剂. 在合适的微乳液体系组成范围内, 用本实验方法可以获得高单分散性的憎水性金纳米粒子, 并能在空气/水界面上自动形成大面积短程有序的纳米金二维自组装膜.     

反相微乳液介质中纳米Sm2O3的制备

用十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/钐盐水溶液(氨水)所形成的反相微乳液体系, 控制合成Sm2O3球形纳米粒子. 绘制出25 ℃下CTAB/正丁醇/正辛烷/钐盐水溶液(氨水)体系的拟三元相图, 得到了反相微乳液区.在此反相微乳区内合成了Sm2O3的前驱体, 对前驱体进行热分析(TG-DSC), 确定了得到纳米Sm2O3产物的适宜焙烧温度为900 ℃, 并考察了微乳液中反应物浓度、反应时间等因素对合成产物的影响. 采用X射线衍射(XRD)、透射电镜(TEM)、激光粒度仪(NSA)、荧光光谱(FS)仪等分析方法对Sm2O3产物的形貌、晶形、粒径及荧光性质进行了表征. 结果表明, 25 益下利用反相微乳液法, 成功地制备了粒径分布较窄、分散性良好的球形纳米Sm2O3粒子, 粒径约20 nm左右, 且表现出较强的荧光性质.     

Novel Synthesis of CeO2 Nanoparticles Within Formamide/Tri(ethyleneglycol)monododecyl Ether/n-Octane Nonaqueous Microemulsion Systems

The present study evaluates a new method to prepare Cerium oxide (CeO₂) nanoparticles by formamide/tri(ethyleneglycol)monododecyl ether (C₁₂E₃)/n-octane oil-continuous nonaqueous microemulsion. The effect of the polar phase (formamide/water) on the phase behavior, drop size, and conductivity behavior of the reverse microemulsion were investigated. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the phase and morphology of synthesized CeO₂ nanoparticles. It was found that the CeO₂ powders synthesized within nonaqueous microemulsions and aqueous microemulisons had an average particle size of 30–50 nm and 15–40 nm, respectively. The experimental results indicate the formation mechanism of CeO₂ nanoparticles in formamide nonaqueous microemulsion and aqueous microemulsion is similar, and the formamide nonaqueous microemulsion can be used as nanoreactors for preparation of nanoparticles.     

Formation of organically and inorganically passivated CdS nanoparticles in reverse microemulsions

This paper is focused on the formation of organically and inorganically passivated cadmium sulfide (CdS) nanoparticles in two different types of microemulsions. On the one hand, we used a ternary inverse microemulsion consisting of water, heptanol, and 3-(N,N-dimethyldodecylammonio)propanesulfonate and on the other hand, a poly(ethyleneimine)-based quaternary microemulsion containing water, toluene, pentanol, and sodium dodecylsulfate. UV-vis measurements confirm the formation of CdS-ZnS core-shell nanoparticles in the ternary microemulsion. Using the quaternary microemulsion template phase, polymer capped luminescent CdS nanoparticles can be formed. After a complete solvent evaporation, the nanoparticles are redispersed in water and characterized by means of dynamic light scattering and transmission electron microscopy. From the ternary microemulsion, well-stabilized CdS-ZnS core-shell nanoparticles with diameters of about 5 nm can be redispersed, but from the quaternary microemulsion, only nanoparticle aggregates of about 100 nm.     

微乳液体系相图的研究及其在纳米氟化物制备中的应用

绘制了十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C₄H₉OH)/正辛烷(n-C₈H₁₈)/水[或NH₄F溶液、或Ba(NO₃)₂溶液、或KNO₃-Mg(NO₃)₂混合溶液]四组分微乳体系的拟三元相图.观察了电导率随水(或盐溶液)含量变化的规律,很好地印证了微乳液体系的相行为.选取相图中微乳区点作为最佳条件,制备了KMgF₃纳米粒子.     

Preparation of nanosize silica in reverse micelles: ethanol produced during TEOS hydrolysis affects the microemulsion structure

Microemulsions have been widely used as microreactors for the synthesis of nanoparticles and mesoporous materials. The correlation between the microstructure of a microemulsion and the features of the obtained materials is the most intriguing problem. On this point, many investigations have their ground on the structure of the precursor microemulsion, i.e., the system before the reaction takes place. Nevertheless, any reactions usually involve the formation of byproducts (aside from the nanoparticles). Several of these byproducts (e.g., ions, amphiphilic molecules) could modify the microemulsion structure during the course of the reaction. Here we examine the hydrolysis of tetraethoxysilane (TEOS) in the water-in-oil microemulsion hexadecyl-trimethylammonium bromide (CTAB)/pentanol/hexane/water. Conductivity and NMR measurements performed during the course of the reaction, in combination with dynamic light scattering and pulsed field gradient spin-echo NMR investigation performed on the microemulsion upon the addition of ethanol, indicate that a byproduct (ethanol) modifies the microreactor structure. The ethanol produced by the TEOS hydrolysis drives the microemulsion structure from small disconnected reverse micelles toward large connected aggregates until (for high enough ethanol loading) the system phase separates into two coexisting liquid phases (a dense interconnected network and a dilute reverse micellar phase).     

Magnesium hydroxide nanoparticles synthesized in water-in-oil microemulsions

Well-dispersed magnesium hydroxide nanoplatelets were synthesized by a simple water-in-oil (w/o) microemulsion process, blowing gaseous ammonia (NH(3)) into microemulsion zones solubilized by magnesium chloride solution (MgCl(2)). Typical quaternary microemulsions of Triton X-100/cyclohexane/n-hexanol/water were used as space-confining microreactors for the nucleation, growth, and crystallization of magnesium hydroxide nanoparticles. The obtained magnesium hydroxide was characterized by field-emission scanning electron microscopy (FESEM), high-resolution transmission election microscopy (HRTEM), X-ray powder diffraction (XRD), laser light scattering, Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis-differential scanning calorimetry (TGA-DSC). The mole ratio of water to surfactant (omega(0)) played an important role in the sizes of micelles and nanoparticles, increasing with the increase of omega(0). The compatibility and dispersibility of nanoparticles obtained from reverse micelles were improved in the organic phase.     

Recycling nanoparticles stabilized in water-in-CO2 microemulsions for catalytic hydrogenations

Catalytic hydrogenations of olefins took place effectively in supercritical CO2 with Pd0 nanoparticles dispersed in the fluid phase using a water-in-CO2 microemulsion consisting of water, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as a surfactant, and 1-octanol as a cosolvent. The hydrogenated products dissolved in supercritical CO2 can be separated from the octanol solution containing AOT microemulsions with Pd0 nanoparticles by phase separation (upper phase, supercritical CO2 with hydrogenated products; lower phase, 1-octanol containing AOT microemulsions with Pd0 nanoparticles) accompanied by reduction of CO2 pressure. After collecting the hydrogenated products by flowing the upper CO2 phase to a collection vessel, the Pd0 nanoparticles remaining in the lower phase can be redispersed into supercritical CO2 by pressurizing the system to a pressure where a homogeneous phase is attained. The redispersed nanoparticles can be reused as catalysts for the next runs of the hydrogenations. Triphenylethylene was hydrogenated to 1,1,2-triphenylethane at conversions of 100% (1st-3rd runs), >99% (4th run), and >96% (5th run) using the recycled Pd0 nanoparticles. The feasibility of using other organic solvents as cosolvents is also studied in the present paper.     

In situ formation of dispersed palladium nanoparticles in microemulsion: efficient reaction system for ligand-free Heck reaction

The ligand-free Heck reaction catalyzed by Pd(OAc)2 performed well in a TX10 oil-in-water microemulsion. TEM proved in situ formation distributed palladium nanoparticles in the microemulsion. The role of TX10 in the reaction system is the palladium nanoparticles reducing agent and stabilizer. The effect of reaction parameters on the Heck reaction conversion were discussed. The results indicated that the aqueous phase concentration, the base concentration, and the temperature played key roles in the conversion of the reaction. Iodobenzene was converted to the corresponding trans-stilbene quantitatively within 90-150 min. Therefore, the heptane/TX 10/butanol/water/propylene glycol microemulsion containing in situ formed palladium nanoparticles was a very efficient catalyst system for the ligand-free Heck reaction.     

Polyelectrolyte-modified microemulsions as new templates for the formation of nanoparticles

The paper is focused on the formation and redispersion of monodisperse BaSO₄ nanoparticles in polyelectrolyte-modified microemulsions. It is shown that a cationic polyelectrolyte of low molar mass, e.g. poly(diallyldimethylammonium chloride) (PDADMAC), can be incorporated into the individual inverse microemulsion droplets (L2 phase) consisting of heptanol, water, and an amphoteric surfactant with a sulfobetaine head group. These PDADMAC-filled microemulsion droplets can be successfully used as a template phase for the nanoparticle formation. The monodisperse BaSO₄ nanoparticles are produced by a simple mixing procedure and can be redispersed after solvent evaporation without a change in particle dimensions. Dynamic and electrophoretical light scattering in combination with sedimentation experiments in the analytical ultracentrifuge of the redispersed powder show polyelectrolyte-stabilized nanoparticles with diameters of about 6 nm. The polyelectrolyte shows a “size control effect”, which can be explained by the polyelectrolyte–surfactant interactions in relation to the polyelectrolyte–nanoparticle interactions during the particle growth, solvent evaporation and redispersion process. However, the approach used here opens a way to produce different types of polyelectrolyte-stabilized nanoparticles (including rare metals, semiconductors, carbonates or oxides) of very small dimensions.     

Tunable synthesis of hierarchical mesoporous silica nanoparticles with radial wrinkle structure

We studied the formation mechanism of hierarchical mesoporous silica nanoparticles with a wrinkle structure (wrinkled silica nanoparticles, WSNs), and a method for substructure control of silica nanoparticles was proposed. We confirmed that WSNs were generated in the bicontinuous microemulsion phase of the Winsor III system. By using the phase behavior of the Winsor III system, which depends on the water-surfactant-oil mixing ratio, and by adding various cosolvents, we could precisely control the structure of silica nanoparticles from the mesoporous to the wrinkle form; furthermore, we could control the interwrinkle distance.     

Span/Tween混合表面活性剂微乳液制备纳米铁及脱硝研究

研究了以Span 80和Tween 60为混合表面活性剂的微乳液的形成。以电导率及目测法为表征手段,利用正交试验,分析了多因素对W/O型微乳液最大增容水量的影响,探明了该乳液形成的适宜条件。     

Poly(ethyleneimine) as reducing and stabilizing agent for the formation of gold nanoparticles in w/o microemulsions

This paper is focused on the use of branched poly(ethyleneimine) (PEI) as reducing as well as stabilizing agent for the formation of gold nanoparticles in different media. The process of nanoparticle formation was investigated, in the absence of any other reducing agents, in microemulsion template phase in comparison to the nucleation process in aqueous polymer solution.

On the one hand, it was shown that the polyelectrolyte can be used for the controlled single-step synthesis and stabilization of gold nanoparticles via a nucleation reaction and particles with an average diameter of 7.1 nm can be produced.

On the other hand, it was demonstrated that the polymer can also act as reducing and stabilizing agent in much more complex systems, i.e. in water-in-oil (w/o) microemulsion droplets. The reverse microemulsion droplets of the quaternary system sodium dodecylsulfate (SDS)/toluene–pentanol (1:1)/water were successfully used for the synthesis of gold nanoparticles. The polymer, incorporated in the droplets, exhibits reducing properties, adsorbs on the surface of the nanoparticles and prevents their aggregation. Consequently, nanoparticles of 8.6 nm can be redispersed after solvent evaporation without a change of their size.

Nevertheless, the polymer acts already as a “template” during the formation of the nanoparticles in water and in microemulsion, so that an additional template effect of the microemulsion is not observed.

The particle formation for both methods is checked by means of UV–vis spectroscopy and the particle size and size distribution are investigated via dynamic light scattering and transmission electron microscopy (TEM).     

Stability and optical properties of dispersions of CdS,ZnS, and Ag<Subscript>2</Subscript>S nanoparticles synthesized in microemulsion

CdS, ZnS, and Ag₂S nanoparticles have been synthesized in microemulsion. The synthesis of nanoparticles depend on the composition of the reaction medium and on the proportions of the precursors. The phase diagram for sedimentation stable dispersion of the nanoparticles synthesized in microemulsion has been determined. The region of the stable nanoparticle dispersion is much smaller than the region of the inverse microemulsion in the n-heptane-AOT-H₂O system. The UV-vis absorption and photoluminescence spectra of the CdS, ZnS, and Ag₂S nanoparticles have been investigated. The size of the nanoparticles increases with an increase in droplet size in the microemulsion, and this shifts the exciton peaks.     

SDS/正戊醇-二甲苯-水(盐水)拟三元体系相图和电导研究及纳米ZnO的制备

实验绘制了十二烷基硫酸钠(SDS)/正戊醇(n-C₅H₁₀OH)-二甲苯[C₆H₄(CH₃)₂]-水[或Zn(NO₃)₂溶液]四组分微乳液体系在不同温度时的拟三元相图. 测定了电导率随水(或盐溶液)含量变化的规律, 电导的规律与相图吻合. 依据电解质理论探讨了微乳液的微观结构, 研究表明, 温度对油包水(W/O)反相微乳液区域影响不大, 电解质的加入对油包水(W/O)反相微乳液区域影响较大. 通过SDS/正戊醇-二甲苯-H₂O及SDS/正戊醇-二甲苯-盐水的拟三元体系的相图观察及实验研究, 选择乳化剂(SDS/正戊醇)与二甲苯质量比为4:6的微乳液作为最佳条件, 制备出了ZnO纳米粒子.     

壳聚糖/聚丙烯酸纳米粒子对蛋白质的吸附行为

以马来酸酐改性的壳聚糖(MAH-chitosan)和丙烯酸(AA)为单体,采用反相微乳液聚合法制备了AA含量分别为77%(AA-Cs)和29%(Cs-AA)壳聚糖/聚丙烯酸复合纳米粒子。TEM结果表明,该复合纳米粒子平均粒径为125~150nm,进而研究了其对牛血红蛋白(Hb)、牛血清白蛋白(BSA)和溶菌酶(Ly)吸附和脱附行为。AA-Cs对各种蛋白的吸附量均较高;而Cs-AA对3种蛋白的吸附则具有一定选择性。AA-Cs对等电点低于脱附pH值的Hb的脱附量较大。Cs-AA粒子在较低pH值(pH=3.4)时对吸附有利,但在高pH值(pH=6.6)进行吸附时,对脱附更为有利。     

微乳液聚合耦合共混法构建聚偏氟乙烯共混杂化膜

以苯乙烯和甲基丙烯酸甲酯混合物作为油相, 采用反相微乳液法制备了AgCl纳米粒子; 通过微乳液原位聚合油相单体得到包含AgCl纳米粒子的聚合乳液; 将聚合乳液与聚偏氟乙烯(PVDF)通过共混法构建了包含AgCl纳米粒子的PVDF共混杂化膜. 紫外-可见光谱、 透射电子显微镜(TEM)及扫描电子显微镜(SEM)等表征结果和超滤实验结果表明, 聚合乳液加入的同时引入了亲水性聚合物和表面亲水的AgCl纳米粒子, 不仅改善了PVDF共混杂化膜的孔隙率和平均孔径, 还显著增强了PVDF共混杂化膜的极性和亲水性, 最终提升了膜的水通量和抗污染性能; 过量聚合乳液加入后不能与PVDF材料均匀共混, 而且AgCl纳米粒子也会在膜中形成团聚物堵塞膜孔隙, 从而削弱了膜的水通量和抗污染性能.