三维有序大孔聚苯乙烯的制备及表征

采用播种生长法制备了粒径为330 nm的单分散胶体二氧化硅（SiO2），并对单分散的SiO2颗粒表面进行改性，以提高颗粒对苯乙烯单体的亲和力.然后通过垂直沉积法组装出SiO2胶粒晶体模板.依靠毛细管力将苯乙烯前驱物快速填充进模板颗粒的间隙，加热原位聚合 ，用氢氟酸去除模板后制得三维有序大孔聚苯乙烯.扫描电子显微镜结果显示，所合成的孔材料高度有序，孔腔尺寸约为210 nm，孔腔之间由较小孔窗连接，形成非常开放的通道网络 . 关键词： 三维有序大孔材料(3DOM) 聚苯乙烯 模板 二氧化硅     

掺溴聚-4-甲基-1-戊烯的合成研究

 液溴与聚-4-甲基-1-戊烯（PMP）的四氯化碳溶液反应，在光照条件下得到溴代PMP，通过红外与元素分析确证了其结构。并通过热重分析对其性能进行了初步的研究。研究发现，在光照条件下溴原子很容易与PMP中叔丁基上的氢原子发生取代反应，得到化学掺杂溴原子的聚合物。该聚合物在150℃以下比较稳定，在150℃以上就会失去HBr。采用此种方法，可得到掺杂均匀的低密度材料。     

Mesoporous Silica Materials Synthesized via Sol-Gel Methods Modified with Ionic Liquid and Surfactant Molecules

采用离子液体1-甲基-3-丁基咪唑四氟硼酸盐改性的溶胶-凝胶法以及表面活性剂十六烷基三甲基溴化铵进一步改性的溶胶-凝胶法制备介孔二氧化硅. 通过X射线衍射、氮气吸附脱附和扫描电子显微镜对所制备的样品进行表征. 结果表明,与仅用离子液体为模板制备的介孔二氧化硅相比,采用表面活性剂和离子液体的混合物为模板制备的介孔二氧化硅具有较小的孔径和较规则的孔结构. 说明利用该方法制备介孔二氧化硅,表面活性剂的加入会在一定程度上影响所制介孔二氧化硅的微结构.     

介孔二氧化硅双重孔隙的导热特性研究

介孔二氧化硅颗粒的双重孔隙分布特征对材料的导热性能具有显著影响。本文通过微观形态表征分析了介孔二氧化硅的复合孔道，并基于受限空间内的气体分子动力学理论，构建了双重孔隙结构的热导率关联模型。为了验证理论模型的合理性与准确性，采用瞬态热带法测量了介孔二氧化硅材料(MCM-41和SBA-15)在0～30 MPa和20～550℃的环境压力及温度变化下的有效热导率。实验测量结果表明，本文理论模型可以有效预测介孔二氧化硅颗粒热导率的变化规律。进一步根据模型分析可知，材料热导率随着环境温度及压力的升高而增长，表现出明显的正相关性，同时其微观结构的差异也是热导率变化的决定性因素。     

“瓶中造船”法合成银/空心介孔SO2蛋黄壳纳米结构

通过一种简单有效的“瓶中造船”的方法成功合成了银/空心介孔二氧化硅的蛋黄-蛋壳结构的纳米反应器,通过透射电镜证实这种结构的银/空心介孔SO2结构在SO2介孔空腔内含有一个银纳米颗粒,颗粒的平均尺寸约为43 nm,介空SO2空心球的平均壁厚约为14 nm. 通过ICP表征证实这种反向合成的方法得到银的质量比高达10.29%. 这种结构相比于裸露的银纳米颗粒在硼氢化钠做还原剂催化还原4-硝基苯酚到4-氨基苯酚的时候表现出了良好的催化性能.     

纳米SiO2形成柯石英的p-T相图

 使用纳米SiO₂粉体为原料,在2.0～4.2 GPa、150～1200 ℃范围内进行了一系列的高压高温实验研究,得到了该压力温度范围内晶化产物α-石英与柯石英的p-T相图,而且该相图中的相边界在650 ℃以下斜率为负,在650 ℃以上基本水平。通过X射线衍射仪（XRD）、Raman光谱仪（Raman）、傅立叶红外光谱仪（FT-IR）、DSC-TGA差热分析仪（TG-DTA）-等表征手段,发现纳米SiO₂原粉中水分（包含Si－OH和吸附水）的存在能显著降低合成柯石英的温度和时间,在4.2 GPa压力下得到了目前合成柯石英的最低温度190 ℃。常压下,合成的柯石英在800 ℃以下能够稳定存在,在1 000 ℃以上转化为α-方石英。     

R相C_(60)聚合物的磁性研究

在高温高压条件下利用高压合成装置合成了二维R相C60聚合物,并利用X射线衍射(XRD)和超量子干涉(SQUID)对合成的样品进行了研究.X射线衍射(XRD)数据表明,在6 Gpa压力和700℃-725℃的温度条件下合成的聚合物为纯度较高的二维R相C60聚合物,当温度升高至800℃时,富勒烯的笼状结构塌陷,样品全部变为无定形碳结构.超量子干涉(SQUID))数据表明,在富勒烯笼状结构出现破缺或共价键结构出现断裂的边界条件下制备的二维R相C60聚合物具有铁磁性,样品的磁性来源于破缺的C60分子笼和断裂的共价键.     

火焰原子光谱法分析有机功能试剂改性纳米SiO2对水中Cr2072-的吸附行为

以纳米二氧化硅(Nano-SiO2)为原料,硅烷偶联剂(KH-550)作为交联剂首先合成了氨丙基纳米二氧化硅(Nano-APSG),然后加入有机功能试剂季磷盐(COOH-Ph-CH2-P(C6H5)3Br)通过有机合成反应合成有机功能试剂改性纳米二氧化硅材料(Si|(CH2)3-NH-CO-Ph-CH2-P(C6H5)3Br),利用红外、粒径、热重分析等对结构进行了表征.通过火焰原子吸收光谱法研究此有机功能试剂改性纳米二氧化硅材料对水中Cr2O12-离子的吸附行为,考察了吸附的最佳pH、震荡时间、吸附剂用量等因素的影响,实验结果表明,在pH1,吸附剂用量为0.1 g,震荡时问为30 min时吸附剂对Cr2O72-离子的吸附效率可达95%以上,实验结果表明这种新型的功能材料可实现对废水中Cr2O72离子的分离与处理.     

一种ICF靶用智能靶涂层的结构和性能表征

 合成了一种材料N,N′-二苯并咪唑-苝二酰亚胺(PV),经多次真空升华提纯,产率为68%,纯度达95%以上。利用傅里叶变换红外光谱（FTIR）、紫外/可见吸收光谱（UV/Vis）、元素分析、热失重分析（TG）对该产物的结构和性能进行了表征。结果表明:苝四甲酸二酐（PTCDA）与邻苯二胺反应,易转化成二苯并咪唑苝类衍生物。该PV材料在450～750 nm范围内有两个强的吸收峰,其初始热分解温度约为510 ℃,热稳定性较好。     

含N、O和S的Schiff碱配体与铜(Ⅱ)、锌(Ⅱ)配合物的合成及红外光谱研究

本文在40℃条件下制得了5-氯水杨醛,使其与硫脲缩合合成出了一种含N、O、S的新型Schiff碱配体,该配体与铜(Ⅱ)、锌(Ⅱ)能形成稳定的配合物,其组成、结构已由元素分析和红外光谱所表征.     

Preparation and characterization of montmorillonite-silica nanocomposites: A sol-gel approach to modifying clay surfaces

Montmorillonite-silica nanocomposites were prepared by a sol-gel approach involving hydrolysis reaction of alkoxysilanes (TEOS) and subsequent condensation reaction with hydroxyl groups of the clay, resulting in the formation of the mesoporous silica network and silica nanoparticles covered or attached on the clay surfaces. According to X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and nitrogen adsorption isotherms, the structure and surface properties of the sol-gel-modified clay can be controlled by varying the TEOS/clay mass ratio and/or adding trace amounts of acid as catalyst. In the case of acid-catalyzed procedures, large continuous mesoporous silica was covered on the clay surfaces, resulting in delamination of clay platelets in silica matrix at higher TEOS/clay ratio, and attaching of isolated mesoporous silica on the clay surface at lower TEOS/clay ratio, respectively. In the case of non-catalyzed procedures, silica nanoparticles were attached on the two-dimensional (2D) clay platelets, while the stack order of the clay was maintained regardless of the TEOS/clay ratios. This sol-gel modification approach combines the surface properties of mesoporous silica and nanoparticles with layered clay, while inheriting the structural properties of the pristine clay such as further intercalation with organic compounds and polymers.     

Synthesis of porous hollow silica spheres using polystyrene-methyl acrylic acid latex template at different temperatures

Porous hollow silica spheres were prepared by using polystyrene-methyl acrylic acid latex as a template and cetyltrimethylammonium bromide as a wall structure-directing agent starting from tetraethoxysilane. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), FT-infrared spectroscopy (FT-IR) and nitrogen adsorption/desorption were used to characterize the hollow silica spheres. When silica-coated latex composites were prepared at room temperature, hollow silica spheres with micropores in the walls were formed after removing the latex templates by calcination. When silica-coated latex composites were aged at a higher temperature of 150 °C, intact mesoporous hollow silica spheres were formed after calcination treatment.     

溶剂热再结晶合成由纳米颗粒自组装成的一维CdS纳米棒

采用两种不同的溶剂热路径合成出了不同形貌和尺寸的CdS纳米晶, 一种是以无水乙二胺(en) 为溶剂, CdCl₂·2.5H₂O和硫脲(H₂NCSH₂N) 为镉源和硫源, 在不同反应温度(160 ℃-220 ℃ 下制备出了CdS纳米晶, 讨论温度对CdS纳米晶生长的影响; 另一种是以en为溶剂, 将在160 ℃下合成的产物在200 ℃下原位再结晶生长2-8 h, 分析原位生长时间对CdS纳米晶生长的影响. 通过X射线衍射(XRD)、 扫描电子电镜(SEM) 和透射电子电镜(TEM) 等表征产物的物相、 形貌和微结构, 分析可知: 两种路线合成的产物均为六方相CdS; 当温度为160 ℃时, 产物形貌为纳米颗粒状, 当温度高于160 ℃时, 产物为CdS纳米棒状; 同时, 在200 ℃下原位再结晶生长不同时间后发现产物形貌由纳米颗粒转变为纳米棒, 通过场发射扫描电镜(HRTEM) 分析可知: 纳米棒是由零维纳米颗粒自组装而成. 最后, 讨论了影响产物CdS纳米晶形貌转变的因素和纳米棒的生长机理.     

Surface-modified mesoporous silica with ferrocene derivatives and its ultrasound-triggered functionality

Novel ferrocene derivatives designed as gatekeepers were successfully composed on the pore outlet of amino-functionalized mesoporous silica by post-synthesis grafting where the peptide bond of the amine group (-NH₂) of mesoporous silica was linked with the carboxylic acid group (-COOH) of both ends of the ferrocene derivatives. The materials of the amine-functionalized mesoporous silica (NH₂-MS) and ferrocene-functionalized mesoporous silica (Fc-CONH-MS) were characterized using X-ray diffractions (XRD), Fourier-transform infrared (FT-IR), N₂ sorption isotherms, solid-state NMR spectra, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), transmission electron microscopy (TEM), and UV-vis absorption spectra. The ferrocene attached to the mesoporous silica pore outlet was cleavaged by ultrasound irradiation, which opened the closed-pore outlets, suggesting a possible application for controlled release drug carrier.     

Thermal stability of second generation carbosilane dendrimers with peripheral ammonia groups

Spinel nickel zinc ferrite nanowires were successfully prepared in mesoporous silica SBA-15 as a host matrix. The powder was annealed at a range of temperatures (500–900 °C) with heating rate 0.5 °C/min. The required NiZnFe₂O₄ phase was obtained at 700 °C. The specific surface area S_BET data revealed that the surface area of the mesoporous silica after annealing was decreased from 821 to 90 m²/g which indicated that the spinal ferrite fills the channels of mesoporous materials. The one-dimensional spinel nanostructures were characterized by X-ray diffraction, infrared spectroscopy, vibrating sample magnetometer, and transmission electron microscopy before and after a selective removal of the silica template in aqueous solution of NaOH or HF. The presence of SBA-15 lowers the formation temperature of nickel zinc ferrite nanowires compared to the corresponding bulk material. The magnetic properties revealed a high saturation magnetization level (~43 emu/g) for the Ni–Zn nanowires at 900 °C.     

铜膜和铁膜污染物诱导熔石英表面损伤行为的对比研究

采用人工溅射的方式分别在熔石英基片上镀制了光学厚度相近的铜膜和铁膜污染物。研究了熔石英基底在355nm波长的激光损伤阈值。分别采用透射式光热透镜技术、椭偏仪、原子力显微镜和光学显微镜研究了两类薄膜的热吸收、膜层厚度、表面微观形貌以及激光辐照后薄膜的损伤形貌。实验结果表明：熔石英表面的金属膜状污染物均导致基片损伤阈值下降,位于前表面的污染物引起的损伤阈值下降更为严重,约为23％。两种污染物薄膜引起基底的损伤形貌、基底损伤阈值的下降幅度与薄膜的热吸收系数与微观结构有关。从热力学响应角度,结合损伤形貌对污染物诱导熔石英表面形貌的损伤机理进行了讨论。     

Structural change of mesoporous silica with sonochemically prepared gold nanoparticles in its pores

Ultrasonic irradiation of mesoporous silica soaked in a mixture of chloroauric acid and isopropanol for 120 min in Ar atmosphere at room temperature yielded Au/SiO₂ mesoporous composite, which was characterized by high resolution transmission electron microscopy and optical absorption measurement. The structure of mesoporous silica after sonochemical preparation of gold (Au) nanoparticles within its pores was studied by nitrogen adsorption technique. It has been shown that the structural parameters, such as specific surface area (SSA), porosity (P), the mean pore diameter (l_p) were increased significantly after ultrasonic irradiation. It is suggested that the collision of Au nanoparticles with pore walls and localized erosion induced by the asymmetric implosive collapse of cavities on the extensive liquid–solid interface that are responsible for the structural change in the mesoporous solid.     

Effect of drying technique on the physicochemical properties of sodium silicate-based mesoporous precipitated silica

The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m²/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N₂ physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed.     

Wide range humidity sensing of LiCl incorporated in mesoporous silica circular discs

Lithium chloride (LiCl) incorporated MCM-41 has been synthesised by sol-gel method using tetraethyl orthosilicate as a precursor in basic medium. 5, 10, 15, 20, 25, 30 and 35 wt% of LiCl were incorporated in mesoporous silica to investigate the humidity sensing. With increasing wt% of LiCl broadening of O–H peak is observed in the Fourier Transform Infrared spectra, indicating greater adsorption of hydroxyl groups on porous silica. The surface area of the MCM-41 circular discs was determined by Brunauer?Emmett?Teller (BET). Scanning electron microscopy images suggest that incorporation of LiCl leads to coalescence of grains in mesoporous silica. 25 wt% LiCl incorporated MCM-41 showed a wide range linear response of impedance change for 11%–90% RH exhibiting 3.5-order drop in impedance at a 1 kHz frequency. The Nyquist plots for all compositions showed increased ionic conduction with increasing relative humidity.