十二烷基硫酸钠辅助下低温合成碱式碳酸镁微球

在SDS辅助下,利用氯化镁和碳酸钠溶液在较低温度下(<55℃)反应结晶直接合成碱式碳酸镁微球。利用XRD、FTIR,SEM等技术研究了SDS加入量,反应温度,反应物浓度以及NaCl浓度等合成条件对产物的影响。结果表明:在反应温度低于55℃时,控制反应物浓度小于0.20 mol.L-1,加入一定量的SDS,可以有效抑制无定形颗粒向MgCO3.3H2O生长,促使无定形纳米颗粒通过相转移与自组装直接向碱式碳酸镁4MgCO3.Mg(OH)2.4H2O转变。SDS加入量,反应温度,反应物浓度以及NaCl浓度对碱式碳酸镁微球尺寸和微观形貌均起到调节作用。     

球状、立方状及空心立方状PbS纳米晶的控制合成及其形成机理

以醋酸铅为铅源,硫代乙酰胺为硫源,在表面活性剂十二烷基硫酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)共同作用下,通过简单地调节水热反应的反应温度控制合成出球状、立方状和空心立方状PbS纳米晶。利用XRD、TEM对合成产物的结构和形貌进行了表征,发现合成的球状、立方状和空心立方状PbS纳米晶尺寸均一,直径为100 nm左右。对球状、立方状和空心立方状PbS纳米晶的形成机理进行了初探,结果表明反应温度较低时,水热反应初始阶段形成的PbS小颗粒呈球形,在表面活性剂SDS的烷基链模板和CTAB微胶束软模板共同作用下生成球状PbS纳米晶;反应温度较高时,水热反应初始阶段形成的PbS小颗粒由于自身的立方相岩盐晶体结构的影响有呈立方状趋势,在SDS和CTAB共同作用下产物堆积成空心立方体状或立方状。     

SrTiO3纳米四方片状晶体的自组装行为及向立方晶体的转变

采用复合氢氧化物媒介法(CHM), 以SrCO₃和TiO₂为原料在200 ℃、48 h的生长条件下合成了立方相SrTiO₃纳米晶体, 它由大量的平行四方片层自组装成为长约500-800 nm、宽约100-150 nm的弯曲条状. 生长时加入少量水可以改变晶体的形状得到尺寸略大的立方SrTiO₃颗粒. 探讨了CHM法制备纳米SrTiO₃粉体的形成机理, 指出SrTiO₃纳米条的生长经过了“溶解→均相成核→片状晶体的生长→片层自组装”四个过程, 此外分析了水在CHM方法中对晶体生长产生的影响.     

微波固相法合成层状磷锑酸钾化合物

应用微波合成技术, 以石墨或三氧化二铁为加热介质, 合成了两种新的层状磷锑酸钾: KSbP2O8, K3Sb3P2O14。与传统固相反应相比较(典型合成条件为:950~1000℃下、24h), 微波法可在微波辐射下(2.45 GHz), 仅在40~90分钟内使反应完成。在详细研究相转变的同时, 对微波在固相合成中的作用进行了初步的讨论。     

微波干法催化醛酮与胺的缩合反应

利用微波辐射和固体中性Al2 O3 载体催化醛酮与胺的缩合反应的方法合成了十六种亚胺 ,研究了微波功率、作用时间、产物提取方式等因素对反应的影响 ;与无微波作用的一般合成方法相比 ,该法明显地提高反应速度及产率 ;文中用低极性熔点递变物质灌装毛细管的方法观测微波作用下反应温度 ,探讨微波作用化学反应的机理 ,其机理除与微波加热作用有关外还与分子间氢键及分子的缔合性有关。     

交联聚苯乙烯树脂固载甲酰基的微波辅助还原

在微波照射的相转移催化(MI-PTC)条件下,3种甲酰基功能化的交联聚苯乙烯树脂——对甲酰基苯氧基甲基树脂、对甲酰基-2-甲氧基苯氧基甲基树脂和对甲酰基-3-甲氧基苯氧基甲基树脂固载的甲酰基被NaBH4还原,得到相应的3种苄羟基功能化的树脂——Wang树脂、Sasrin树脂和新型的对苄羟基-3-甲氧基苯氧基甲基树脂.考察了溶剂、相转移催化剂等因素对反应的影响,优化的反应介质为THF/H2O混合溶剂,相转移催化剂为苄基三羟乙基氯化铵(BTHAC).然而,在传统加热和微波辐射条件下,最有效混合溶剂的配比有所不同.在水浴加热条件下,最有效的反应溶剂为12 mL THF+3 mL H2O;而在微波加热的条件下,最有效的反应溶剂却是3 mL THF+12 mL H2O.在优化的溶剂、催化剂条件下,微波功率为60 W时,高分子固载的甲酰基30 min之内几乎被定量地还原成羟基.与传统加热方式比较,MI-PTC还原聚苯乙烯固载甲酰基可以大大缩短反应时间,提高反应效率,是一种进行高分子化合物官能团转化的良好方法.     

高温高压Li3N-hBN体系cBN转变的热力学分析

以经典热力学第二定律ΔG<0为依据,分析了静态高温高压触媒法合成立方氮化硼(cBN)过程中发生的可能反应.考虑温度和压强对反应物相体积的影响,计算了六方氮化硼(Li3N-hBN)体系中hBN+Li3N→Li3BN2,h BN→cBN及Li3BN2→Li3N+cBN反应在高温高压条件下的ΔG.结果证实,Li3BN2由Li3N与hBN在高温高压(T>1300 K,P>3.0 GPa)条件下反应得到,在cBN的合成(T=1600～1800 K,P=4.6～6.0 GPa)条件下,hBN和Li3BN2都有向cBN转化的倾向,但由hBN向cBN直接转变的反应自由能比Li3BN2分解生成cBN的反应自由能更负,反应的可能性更大.探讨了高温高压条件下立方氮化硼的转变机理。     

微波场对SrTiO3化学合成中热过程的影响

在分析微波场中SrTiO3化学合成体系与电磁场相互作用的基础上,探讨合成体系在微波场中的加热机制和影响升温的主要因素（如合成体系的介电性质、保温材料的结构、生还的致密度等）,结果表明,TiO2和SrCO3在低温阶段对体系的升温速率的贡献相接近;高温阶段体系升温主要是TiO2的贡献,同时产物对升温有较大的影响。微波合成与常规合成再加热方式上的明显不同,对合成过程、合成时间等影响较大。     

单分散钛酸锶纳米晶体的形成机理

采用水热法,利用乙醇和水的混合溶剂合成了单分散钛酸锶纳米晶体.X射线衍射(XRD)结果显示该晶体为立方相,延长反应时间其结晶性增强.扫描电子显微镜(SEM)、透射电子显微镜(TEM)结果显示样品为70 nm左右的均匀立方块晶体.利用SEM、TEM、高分辨透射电子显微镜(HRTEM)和电子衍射(ED)谱研究了该纳米晶体的生长过程,结果表明：前驱体经过扩散反应生成钛酸锶晶核,晶核之间由于定向生长作用而团聚连接形成颗粒球,最后颗粒球在缓慢的奥斯特瓦尔德熟化作用下转化为钛酸锶晶体.这一“扩散反应定向生长奥斯特瓦尔德熟化”的生长过程揭示了钛酸锶纳米晶体的生长机理.利用Johnson-Mehl-Avrami(JMA)方程模拟证实了其初始阶段的扩散反应机理,并得出反应活化能为15.79 kJ·mol^-1.     

单分散钛酸锶纳米晶体的形成机理

采用水热法,利用乙醇和水的混合溶剂合成了单分散钛酸锶纳米晶体。X射线衍射(XRD)结果显示该晶体为立方相,延长反应时间其结晶性增强。扫描电子显微镜(SEM)、透射电子显微镜(TEM)结果显示样品为70nm左右的均匀立方块晶体。利用SEM、TEM、高分辨透射电子显微镜(HRTEM)和电子衍射(ED)谱研究了该纳米晶体的生长过程,结果表明:前驱体经过扩散反应生成钛酸锶晶核,晶核之间由于定向生长作用而团聚连接形成颗粒球,最后颗粒球在缓慢的奥斯特瓦尔德熟化作用下转化为钛酸锶晶体。这一“扩散反应、定向生长、奥斯特瓦尔德熟化”的生长过程揭示了钛酸锶纳米晶体的生长机理。利用Johnson-Mehl-Avrami(JMA)方程模拟证实了其初始阶段的扩散反应机理,并得出反应活化能为15.79kJ·mol^-1。     

Fast synthesis of temperature-sensitive PNIPAAm hydrogels by microwave irradiation

A novel method, microwave irradiation synthesis, is proposed for the preparation of thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogels. The PNIPAAm hydrogels were separately synthesized by using microwave irradiation method and water-bath heating method. Chemical groups, lower critical solution temperature (LCST) and surface morphology of these PNIPAAm hydrogels were characterized by FT-IR, DSC and SEM. Swelling ratios of the gels were measured gravimetrically in the temperature range from 10.0 to 60.0 °C. Results showed that (1) the use of microwave irradiation can greatly shorten the reaction time required for PNIPAAm hydrogel synthesis from several hours to several minutes in comparison with water-bath heating method, and obviously improve the yields of the PNIPAAm gels, which were up to 99% after a short reaction time; (2) SEM micrographs and textural measurement revealed that the gels synthesized using microwave irradiation had more porous structure, and their average pore sizes and specific surface areas were larger than those of the gels synthesized using water-bath heating method; and (3) the PNIPAAm hydrogels synthesized using microwave irradiation had much higher swelling ratios at 10.0 °C below the LCST, and had lower swelling ratio at 60.0 °C above the LCST compared to the hydrogels synthesized by water-bath method.     

Kinetics study on the dissolution of UO<Subscript>2</Subscript> particles by microwave and conventional heating in 4 mol/L nitric acid

The dissolution of UO₂ particles in 4 mol·L⁻¹ nitric acid medium at temperatures of 90–110°C by microwave heating and conventional heating has been investigated, respectively. It is found that the dissolution ratios of UO₂ particles by microwave heating were 10%–40% higher than that by conventional heating. Kinetics research shows that the dissolution of UO₂ particles in 4 mol·L⁻¹ nitric acid is controlled by the diffusion control model for microwave heating and by the surface reaction control model for conventional heating. The diffusion control model for the dissolution of UO₂ particles by microwave heating could be explained by the diffuseness on the surface of UO₂ particles.     

超微镍粉的微乳液法制备研究

采用水（溶液）／二甲苯／SDS／正戊醇反相微乳液体系,用水合肼还原硫酸镍制备了纳米级（15－100nm)镍微粒,采用XRD、TEM等法对产物进行了鉴定与表征,考察了微乳液体系诸构成因素对纳米级镍制备的影响规律。     

Preparation of uniform and nano‐sized NaA zeolite using silatrane and alumatrane precursors

Nano‐sized Na A zeolite was successfully synthesized via the sol–gel process and microwave techniques. The synthesis parameters, such as hydroxide ion concentration, seed amount, as well as heating time and temperature, were studied to obtain the most uniform and very small sized NaA zeolite using the composition of SiO₂:Al₂O₃:xNa₂O:410H₂O; 3 ≤ x ≤ 6. It was found that hydroxide ion concentration affects the crystal size and heating time, whereas a higher amount of seed provides smaller sized NaA zeolite. The zeolite product can be synthesized using a higher temperature for a shorter time or lower temperature for a longer time. The best conditions for synthesizing the smallest size, 0.1–0.2 µm, and the most homogeneous NaA zeolite is to use the composition of SiO₂:Al₂O₃:3Na₂O:410H₂O and 3 wt% crystal seed at 80 °C microwave heating for 6 h. The synthesized NaA zeolite was characterized using XRD and SEM. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis of 2-Substitued Indoles via Pd-Catalysed Cyclization in an Aqueous Micellar Medium

The synthesis of 2-substituted indoles starting from the corresponding unprotected 2-alkynylanilines was made possible in 3% TPGS-750-M water using Pd(OAc)₂ alone as the catalyst. The reaction was sensitive to the heating mode respect to the nature of the starting material as, in many cases, convectional heating was better than microwave dielectric heating. The MW (microwave) delivery mode had also an influence in the formation of by-products and, consequently, product yields. A tandem Sonogashira-cyclisation reaction was also accomplished using Pd(OAc)₂/Xphos in the nanomicellar water environment.     

A Microwave-Assisted Boudouard Reaction: A Highly Effective Reduction of the Greenhouse Gas CO2 to Useful CO Feedstock with Semi-Coke

The conversion of CO₂ into more synthetically flexible CO is an effective and potential method for CO₂ remediation, utilization and carbon emission reduction. In this paper, the reaction of carbon-carbon dioxide (the Boudouard reaction) was performed in a microwave fixed bed reactor using semi-coke (SC) as both the microwave absorber and reactant and was systematically compared with that heated in a conventional thermal field. The effects of the heating source, SC particle size, CO₂ flow rate and additives on CO₂ conversion and CO output were investigated. By microwave heating (MWH), CO₂ conversion reached more than 99% while by conventional heating (CH), the maximum conversion of CO₂ was approximately 29% at 900 °C. Meanwhile, for the reaction with 5 wt% barium carbonate added as a promoter, the reaction temperature was significantly reduced to 750 °C with an almost quantitative conversion of CO₂. Further kinetic calculations showed that the apparent activation energy of the reaction under microwave heating was 46.3 kJ/mol, which was only one-third of that observed under conventional heating. The microwave-assisted Boudouard reaction with catalytic barium carbonate is a promising method for carbon dioxide utilization.     

Microwave Effects Due to Anionic or Cationic Initiators in Emulsion Polymerization Reactions

Summary: Emulsion polymerization reactions were performed under microwave irradiation and conventional heating using anionic or cationic initiators and surfactants. Microwave irradiation promoted higher reaction rates for both initiators and surfactants, in comparison with the conventional heating. The effect of high power microwave irradiation was studied using a method of cycles of heating and cooling, where rapid polymerization reactions were obtained. In the reactions with anionic initiator and surfactant, a decrease in the particle diameters was observed with microwave heating, and even smaller particles were obtained using high power microwave irradiation. Moreover, the decrease in the particle size was acompanied by an increase in the polymer molecular weight. On the other hand, these effects were not observed for reactions with cationic initiator and surfactant.     

Stabilization of Titanium Dioxide Nanoparticles at the Surface of Carbon Nanomaterials Promoted by Microwave Heating

TiO₂ is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO₂@C, and that microwave irradiation can be advantageous for the synthesis of carbon‐based materials. Composites of TiO₂ with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO₂ nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO₂ is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance.     

Effect of Microwave Activation on Polymerization Rate and Molecular Weight Development in Emulsion Polymerization of Methyl Methacrylate

Polymerization rate and molecular weight development experimental results for the emulsion polymerization of methyl methacrylate (MMA), in the presence of potassium persulphate (PPS) as initiator, and activated with a 50 W microwave source, are reported. The polymerization kinetics of the microwave activation experiment (MA) was compared against a traditional conductive heating (CH) polymerization reaction. The number average molecular weights, M_n, of the polymer samples obtained with microwave activation were significantly higher than those obtained from conductive heating. These high values of M_n were obtained from the beginning of the polymerization reaction. Polydispersity index (PDI) values in the range of 1.18 to 1.83 were obtained in the microwave irradiated samples. These values are lower than those produced by conventional emulsion polymerization of styrene and other vinyl monomers, and resemble the PDI values obtained in controlled‐radical polymerization processes. Polymer particles of submicron size (60 to 100 nm) were obtained.     

Nanosized SrTiO<Subscript>3</Subscript> powder from oxalate precursor microwave aided synthesis and thermal characterization

Nanosized strontium titanate (SrTiO₃) was synthesized from strontium titanyl oxalate hydrate, SrTiO(C₂0₄)₂4H₂0 (STO) precursor employing microwave heating technique. STO precursor was characterized by Thermogravimetry (TG) and differential thermal analysis (DTA) techniques prior to the heat treatment in conventional and microwave heating system. STO precursor heated in microwave heating system in air at 773 K for 30 min yielded pure cubic SrTiO₃. The product obtained by heating of STO precursor in the same system at 973 K for same duration was, however, much more crystalline. Experiments repeated in conventional furnace showed that SrTiO₃ was formed above 973 K. SrTiO₃ powder obtained was characterized by X-ray diffraction (XRD) and Transmission electron microscopy (TEM) techniques. TEM study shows that the particles of SrTiO₃ are nearly spherical in shape and the particle size of SrTiO₃ powder varies between 28 and 68 nm.