微乳技术制备纳米催化剂的研究进展

综述了微乳技术制备纳米催化剂的基本原理和影响因素以及在催化剂制备中的应用。该方法所采用装置简单、操作方便,制备的催化剂具有粒径小、粒径可调、分布均匀、催化反应活性高等优点。微乳体系的构成是多种多样的,讨论了各种因素对制备纳米催化剂的影响,指出了该技术存在的问题和发展趋势。     

微乳法制备纳米催化剂研究进展

微乳法作为制备纳米微粒的有效方法,具有操作简单、制备粒子尺寸均匀、颗粒大小及形状可控等优点,在纳米催化剂制备领域具有广阔的应用前景。综述了近年来采用微乳法制备纳米催化剂的研究状况,尤其是对利用微乳法制备金属纳米粒子、金属氧化物及负载型金属催化剂进行了综述。     

纳米硫酸钡制备过程中的蒸馏法破乳和微孔液的循环使用

以硫酸钠和氯化钡的W／O型微乳液反应制备纳米硫酸钡为实验体系,利用微乳液中各组分沸点的差异,提出了利用蒸馏法破坏微乳液,实现纳米颗粒与微乳液体系的分离以及微乳液循环利用的新工艺。研究了破乳时蒸馏温度、循环使用时体系中的盐浓度、含水量等因素对纳米颗粒品质的影响,比较了蒸馏法破乳和加高浓度盐、升高温度等方法破乳对纳米颗粒回收率的影响。实验结果表明,蒸馏温度升高不会导致纳米颗粒的团聚,随着循环次数的增加,粒径从第一次制备的14nm增加到第五次制备的25nm,但单分散性和分布仍然良好;体系中水含量过大,制备出的纳米颗粒粒径不均一;此外蒸馏法破乳回收纳米颗粒的收率可以达到82％,高于加盐破乳和升温破乳的回收率。     

胶体体系中合成纳米胶囊的研究进展

综述了在不同胶体体系(乳液、双重乳液、微乳等)中合成纳米胶囊的研究工作，介绍了纳米胶囊新型的合成手段，包括界面聚合法、界面沉积法、复相乳液溶剂挥发法、聚电解质的逐步沉积法和微乳聚合法等不同的制备方法。并从纳米胶囊的粒径、包裹率、Zeta电位、热敏性和酸碱敏感性等方面分析了纳米胶囊的物理化学性能。     

微乳液法制备纳米催化剂的应用研究进展

介绍了微乳液法制备纳米催化剂的工艺过程,阐述了微乳液法制备负载型纳米催化剂、无载体型纳米催化剂、分子筛及载体的研究进展,分析了制备过程中影响催化剂粒径大小及分布的因素,评述了微乳液法制备纳米催化剂的特点及发展方向.     

热处理对微乳液法制备纳米氧化镍的影响

微乳液法是近年来制备纳米颗粒的有效方法之一，具有装置简单，操作容易，微粒可控等优点。以氯化镍和氨水为原料，以Triton X-100／环己彬正己醇／水为反相微乳体系，成功制备出纳米氧化镍前驱体，然后对前驱体进行热处理，得到纳米氧化镍粉末，系统考察了热处理对纳米氧化镍颗粒形貌、粒径分布的影响。结果显示，利用微乳液法制备的氧化镍纳米颗粒大小、形态及分散性优于经热处理后的粉末；X射线衍射谱及透射电镜显示，热处理后的氧化镍粉末粒径随着热处理温度的升高而增大。     

反相微乳液法制备甲醇合成的铜基催化剂

反相微乳液法是一种合成金属纳米颗粒的有效方法,以十六烷基三甲基溴化铵(CTAB)、正戊醇、环己烷、金属盐溶液构建反相微乳液体系,制备了一系列用于合成甲醇的纳米铜基催化剂,并分别对其结构、形貌和活性进行了表征。结果表明,催化剂制备过程中的老化温度、碱浓度、H2O/CTAB的摩尔比以及盐溶液的浓度对催化剂的粒径和活性均有一定的影响,为甲醇合成催化剂的新型制备方法提供了借鉴。     

微乳法制备Pd-Cu双金属催化剂

选择Cu为助剂,采用微乳法分别优选具有较好稳定性的Cu和Pd微乳液体系,并将Cu和Pd依次负载于Al_2O_3载体上,经干燥、活化和还原制备了Pd-Cu/Al_2O_3催化剂。采用原位IR、CO化学吸附和HRTEM等对催化剂进行表征,结果表明,与常规溶液负载法制备的Pd-Ag/Al_2O_3催化剂相比,采用微乳法降低了催化剂表面酸性,提高了活性组分Pd分散度,Pd粒径分布更为均匀。在750 mL加氢反应器中,采用C_2后加氢原料对催化剂性能进行评价,结果表明,与常规溶液负载法相比,微乳法制备的催化剂在反应温度低4℃条件下,乙炔转化率相当,选择性高9.9个百分点,绿油生成量较低。微乳法制备Pd-Cu双金属催化剂具有良好的工业应用前景。     

微乳液法制备纳米TiO2/活性炭复合体的研究

纳米TiO2是一种高效的光催化剂,而光催化剂的制备和固化是光催化技术应用的关键。采用油酸/正丁醇/NaOH溶液制备了纳米TiO2/活性炭复合材料。用微乳体系制备出纳米二氧化钛前驱体,然后由表面活性剂稳定和保护的纳米粒子在氢键吸附等作用力下包覆于活性炭载体的表面。用热重-差热分析、扫描电镜、红外光谱法对其结构进行分析。结果表明:所制得TiO2粒径为20 nm左右,呈球形分布于活性炭表面。用分光光度法测得TiO2的包覆率为28.2%。     

纳米金属催化剂的制备方法及其比较

纳米金属催化剂的制备方法包括化学法和物理法。化学法中主要有溶胶-凝胶法、沉淀法、溶剂热合成法、微乳法和水解法等;物理法主要有气相凝聚法、溅射法和机械研磨法等。其中化学法中的溶胶-凝胶法及沉淀法应用最广。对纳米金属催化剂的制备方法进行了比较,并简要论述了制备及应用过程中存在的主要问题。     

Sulfur Nanoparticles Synthesis and Characterization from H2S Gas, Using Novel Biodegradable Iron Chelates in W/O Microemulsion

Sulfur nanoparticles were synthesized from hazardous H₂S gas using novel biodegradable iron chelates in w/o microemulsion system. Fe³⁺–malic acid chelate (0.05 M aqueous solution) was studied in w/o microemulsion containing cyclohexane, Triton X-100 and n-hexanol as oil phase, surfactant, co-surfactant, respectively, for catalytic oxidation of H₂S gas at ambient conditions of temperature, pressure, and neutral pH. The structural features of sulfur nanoparticles have been characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive spectroscopy (EDS), diffused reflectance infra-red Fourier transform technique, and BET surface area measurements. XRD analysis indicates the presence of α-sulfur. TEM analysis shows that the morphology of sulfur nanoparticles synthesized in w/o microemulsion system is nearly uniform in size (average particle size 10 nm) and narrow particle size distribution (in range of 5–15 nm) as compared to that in aqueous surfactant systems. The EDS analysis indicated high purity of sulfur (>99%). Moreover, sulfur nanoparticles synthesized in w/o microemulsion system exhibit higher antimicrobial activity (against bacteria, yeast, and fungi) than that of colloidal sulfur.     

不饱和聚酯树脂微乳液的研究(Ⅲ) 磺酸盐不饱和聚酯树脂微乳化的表征

研究了4种正构醇(正丙醇、正丁醇、正戊醇和正己醇)对磺酸盐不饱和聚酯树脂的粘度和电导率的影响,聚酯树脂中醇含量增加,溶液的电导率增大,粘度下降;聚酯树脂中的醇含量相同时,醇的碳链越短,溶液的粘度越低,电导率越大。在一定的温度和搅拌速度下,将含有一定量醇的磺酸盐不饱和聚酯树脂加水微乳化,用微乳化过程中体系粘度和阻抗的变化表征了微乳化相反转过程,发现粘度比电导表征相转变更好。用差示扫描量热法的吸收热焓和吸收峰的温度判断了不同含水量时体系的相态。     

乐果无水微乳剂的研究

无水微乳化是解决硫代磷酸酯类农药有水微乳剂分解的一种行之有效的方法。试验利用热贮试验过程中的酸度变化筛选了表面活性剂和助表面活性剂，成功地制备了乐果的无水微乳剂；它的各项理化指标达到40％乐果乳油国标，证实了农药无水微乳剂的可行性。对无水微乳化的理论基础、配方组成进行了探讨，认为无水微乳剂是一种具有广阔应用前景的农药新剂型。     

Preparation and investigation of sodium alginate nanocapsules by different microemulsification devices

Numerous techniques of preparation have been reported for the encapsulation of the core material, but the microemulsion technique is the most effective and commonly used for encapsulation. In this article, three microemulsification devices including ultrasonic stirrer, labo ratory reactor, and mechanical stirrer were used to produce the alginate nanocapsules containing peppermint oil. The effect of different parameters on surface morphology, mean particle size, and size distributions were investigated. The results indicated that the ultrasonic stirrer is the best device to make the nanocapsules containing essential oils prepared by microemulsion method, so that the size of nanocapsules prepared by ultrasonic stirrer was about 56 nm. Also, the results of GC‐MS, FTIR, and TGA show that quantities of the remaining compounds in nanocapsules prepared by ultrasonic stirrer are higher than other devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41904.     

十二烷基三甲基溴化铵/醇/庚烷/水微乳化作用研究

以铁氰化钾为电化学探针,用循环伏安法测定了十二烷基三甲基溴化铵(DTAB)/醇/庚烷/水体系微乳液的扩散系数,同时用电导率法研究了微乳液的结构及结构转变。绘制了不同条件下DTAB微乳体系的拟三元相图,探讨了体系的微乳化作用规律,考察了醇的种类、含量对微乳区形成的影响。结果表明,当醇(正丁醇)固定时,随着醇含量增加,微乳区面积先增大后减小;醇的链长不同,体系的微乳区类型及面积分数均不同,随着醇碳链的增长,微乳区面积先增大后减小。     

Fe3O4纳米晶表面裹负SiO2的制备研究

纳米材料又称超微颗粒材料,是由纳米粒子组成,具有纳米尺寸效应。纳米材料用于化学反应会呈现出不同寻常的反应性能。磁性纳米材料作为一种新型的纳米材料,具有不同于常规材料的独特效应,如量子尺寸效应、表面效应、小尺寸效应、宏观量子隧道效应及顺磁效应等,这些效应使磁性纳米粒子具有不同于常规材料的光、电、声、热、磁敏感特性。近年来有关磁性纳米材料的研究备受瞩目。特别是Fe3O4纳米晶,由于其优异的磁性和表面活性及其在磁流体、微波吸收材料、水处理、催化、生物医药、生物分离等方面的应用前景,正在成为众多领域研究的热点。基于Fe3O4纳米晶的磁性纳米催化剂兼有了磁性纳米材料的所有独特性能,将其应用于催化领域,会呈现出常规催化材料所不具备的催化性能。目前液相制备Fe3O4纳米晶的液相方法主要有沉淀法、水热法、溶胶-凝胶法、微乳液法、微波超声法等。这几种方法制得的Fe3O4纳米晶有较大的差异,往往因其在不同领域的应用而采用不同的方法制备Fe3O4纳米晶。结合前人研究成果,笔者采用共沉淀法在无氮气保护的条件下制备出了粒径分布在15 nm±4 nm之间的Fe3O4纳米晶。考察了n(Fe^2+)/n(Fe^3+)、晶化时间、晶化温度、pH值对Fe3O4纳米颗粒粒径分布的影响,并在Fe3O4纳米晶表面裹负SiO2,提高了其抗氧化性能并增强其表面修饰性能,为进一步表面裹负金属活性组分制备磁性纳米催化剂打下基础。     

Structure of reverse microemulsion-templated metal hexacyanoferrate nanoparticles

The droplet phase of a reverse microemulsion formed by the surfactant cetyltrimethylammonium ferrocyanide was used as a matrix to synthesize nanoparticles of nickel hexacyanoferrate by adding just a solution of NiCl₂ to the microemulsion media. Dynamic light scattering and small-angle neutron scattering measurements show that the reverse microemulsion droplets employed have a globular structure, with sizes that depend on water content. Transmission electron microscopy and electron diffraction are used to obtain information about the structure of the synthesized nanoparticles. The results show that the size and shape of the coordination compound nanoparticles correspond with the size and shape of the droplets, suggesting that the presented system constitutes an alternative method of the synthesis of metal hexacyanoferrate nanoparticles.     

Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H₂O₂ detected.