添加三甲基乙氧基硅烷制备耐高温硅/铝复合气凝胶

以仲丁醇铝(ASB)和三甲基乙氧基硅烷(TMEO)为前驱体,采用溶胶-凝胶法,经乙醇超临界干燥制备了耐温高、成型性好的硅/铝复合气凝胶。用透射电子显微镜、N2吸附分析仪、红外光谱仪、X射线衍射仪、hot disk热分析仪等仪器表征了气凝胶的形貌、孔结构、表面基团、晶相、热学等性能。在溶胶-凝胶过程中,通过添加TMEO在氧化铝纳米颗粒表面引入了-Si-(CH_3)_3基团,该基团经高温热处理后会在Al_2O_3表面形成SiO_2纳米颗粒,有效地抑制了Al_2O_3纳米颗粒在高温下的晶体生长,使得该复合气凝胶具有优异的耐温性能。在1 200℃高温处理后,线性收缩低至16%,比表面积可达141 m~2·g~(-1),这将进一步促进气凝胶材料在高温保温隔热、吸附、催化等领域的广泛应用。     

乙炔和三乙氧基硅烷的硅氢加成反应研究

制备了氯铂酸-异丙醇、氯铂酸-聚甲基乙烯基硅氧烷和氯铂酸-三苯基膦三种催化剂,评价了它们在乙炔与三乙氧基硅烷的硅氢加成反应中的催化活性及选择性;并考察了反应温度、乙炔流量、氯铂酸-聚甲基乙烯基硅氧烷与三乙氧基硅烷摩尔比、PPh3/H2PtCl6摩尔比等因素对产物收率的影响.结果表明,氯铂酸-聚甲基乙烯基硅氧烷对该反应表现出较高的催化活性,在催化剂与三乙氧基硅烷摩尔比为1.2×10-4∶1,T=80℃,乙炔流量=120 mL/min的条件下反应,产物乙烯基三乙氧基硅烷的选择性为100%,收率可达97.5%.     

耐高温核/壳结构TiO2/SiO2复合气凝胶的制备及其光催化性能

以钛酸四丁酯为源, 采用苯胺-丙酮原位生成水溶胶-凝胶法, 在乙醇超临界干燥过程中用部分水解的钛醇盐和硅醇盐对TiO₂凝胶进行超临界修饰制备了具有核/壳纳米结构的块体TiO₂/SiO₂复合气凝胶. 制备的复合气凝胶具有优异的机械性能, 其杨氏模量可达4.5 MPa. 复合气凝胶同时具有极好的高温热稳定性. 经过1000 ℃热处理后, 线性收缩由纯TiO₂气凝胶的31%降至复合气凝胶的10%, 且比表面积由纯TiO₂气凝胶的31 m²·g^-1提升至复合气凝胶的143 m²·g^-1. 此外, 该复合气凝胶经1000 ℃热处理后具有优异的光催化降解亚甲基蓝的性能. 其优异的光催化性能得益于TiO₂/SiO₂复合气凝胶1000 ℃处理后高的比表面积和小的颗粒尺寸. 优良的耐热性能、力学性能和光催化性能使获得的具有核/壳纳米结构的TiO₂/SiO₂复合气凝胶在光催化领域具有良好的应用前景.     

γ-脲丙基三乙氧基硅烷的制备及表征

采用γ-氨丙基三乙氧基硅烷与尿素进行亲核取代反应,合成了γ-脲基丙基三乙氧基硅烷;通过对工艺条件的优化制备得到了纯度高达99%以上的产品并采用红外光谱及核磁进行了表征。     

3-氨丙基三乙氧基硅烷对溶胶-凝胶法苯乙烯-顺丁烯二酸酐共聚物/SiO_2杂化材料的制备与性能的影响

用３ 氨丙基三乙氧基硅烷（ＡＰＴＥＳ）作为偶联剂，通过溶胶 凝胶（Ｓｏｌ Ｇｅｌ）过程制得两相以共价键结合的透明苯乙烯 顺丁烯二酸酐共聚物／ＳｉＯ２杂化材料．通过ＦＴＩＲ分析等证实了材料有机相与无机相间是以共价键结合的．分析了材料热处理温度和分别用盐酸或氨水作催化剂时对材料溶胶分数的影响、偶联剂及其用量对溶胶 凝胶体系凝胶时间的影响、并研究了杂化材料中无机含量对材料折射率和Ｔｇ的影响     

铈锰/硅基气凝胶载体的制备及其在合成碳酸二苯酯中的应用

分别采用原位合成法、浸渍法制备不同组成的铈锰/硅基气凝胶载体,利用XRD、BET、TEM、EDS、FT-IR等手段对其结构进行表征.结果表明:采用浸渍法制备的铈锰/复合硅基气凝胶,铈锰金属氧化物为纳米尺寸颗粒,孔道保留较为完整.以苯酚催化氧化羰基化合成碳酸二苯酯反应,考察了铈锰/硅基复合气凝胶载体载钯催化剂的催化性能,结果表明以浸渍法制备组分为m(Ce+Mn)/m(SiO_2)=20%载钯催化剂,在反应压力5 MPa、反应温度75℃、反应时间6 h时,碳酸二苯酯单程收率可达21.58%,选择性为99.27%.     

多孔硅的模板限制镁热还原法制备及性能

采用一种基于气-固反应机制的模板限制镁热还原法,以SiO2气凝胶为模板在低温(650℃)下制备出一种高比表面积纳米多孔硅材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和比表面积(BET)分析等表征手段对样品的成分、物相结构、微观形貌和孔结构进行分析,并初步研究了材料的光学特性和电化学性能.结果表明,产物为纳米硅晶体颗粒组成的多孔结构,保留了与原始气凝胶模板相似的微观形貌,比表面积高达602 m2·g-1.该材料在室温下表现出显著的红光光致发光特性,且具有较高的储锂容量和较好的嵌入/脱出锂性能.     

快速制备高掺杂CuO/SiO2复合气凝胶

通过环氧丙烷预反应法, 以乙腈为溶剂快速制备了高掺杂的氧化铜/二氧化硅复合气凝胶. 在典型的合成过程中, 将正硅酸甲酯(TMOS)、乙腈、去离子水和环氧丙烷混合进行预反应, 然后将该溶液与氯化铜的乙腈-水溶液混合并添加环氧丙烷, 在35℃烘箱中静置0.5 h 后转化为湿凝胶, 再经过CO₂超临界流体干燥和热处理即可获得黑色块状CuO/SiO₂复合气凝胶. 最终气凝胶样品密度约为180 mg·cm^-3, 比表面积高达625 m2·g^-1, 平均掺杂比为19.91%±2.42% (Cu:Si 摩尔比), 压缩模量为1.639 MPa, 具有成型性好、分散均匀等优点,是良好的背光源靶材料. 本论文还通过对比实验对凝胶化过程的机理进行分析, 结果表明, 通过改变溶剂和采用环氧丙烷预催化均衡了两种不同前驱体的反应速率, 实现了共凝胶的目的. 此外, 该方法还有望为其它金属氧化物/二氧化硅复合气凝胶的制备提供新思路.     

无皂乳液聚合制备硅铝氧烷/PMMA复合体系

硅铝氧烷溶胶;聚甲基丙烯酸甲酯复合体系;无皂乳液聚合制备硅铝氧烷/PMMA复合体系     

溴二氟甲基三甲基硅烷的合成及其在有机合成中的应用

溴二氟甲基三甲基硅烷(TMSCF₂Br)自2011年首次被作为二氟卡宾前体报道以来,已发展成为一种重要的二氟甲(烷)基化试剂,并在有机合成中得到了广泛应用.在简要介绍TMSCF₂Br合成方法的基础上,重点阐述了利用TMSCF₂Br作为二氟卡宾前体或三甲基硅基二氟甲基自由基前体实现不同底物的系列二氟甲基或氟烷基化反应的研究进展.藉此对TMSCF₂Br在有机合成反应的活化方式和机理及其应用优势与不足等进行分析讨论,为从事有机合成和有机氟化学相关的科研人员提供一些参考与启发.     

Characterization and Catalytic Properties of Aerogel Chromium Oxide Supported by Alumina or Silica

Alumina or silica supported chromium oxide catalysts prepared by sol-gel technique have been investigated by X-ray diffraction, BET analysis, combined diffuse reflectance spectroscopy, EPR and reduction-extraction by ethane 1,2 diol. The results reveal the presence of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions. Chromium species Cr⁶⁺ are isolated and atomically dispersed on the alumina support as free chromate CrO ₄ ^2– while on silica, dichromate or polychromate species like Cr₂O ₇ ^2– or Cr₃O ₁₀ ^2– predominate. Chromium oxide exhibits a better catalytic properties for paraxylene partial oxidation, when it is supported on alumina. The difference of oxidation states and degree of oligomerisation of chromium on the two supports affects the catalytic properties.     

增强体复合SiO2气凝胶的研究进展

SiO_2气凝胶是一种具有纳米结构的多孔材料,在声学、光学、热学、电学等领域有着广阔的应用前景,但是脆弱的力学性能严重限制了其实际应用。目前,在SiO_2气凝胶中引入增强体是改善其力学性能最为有效的方法,常用的增强体根据类别可分为纤维、聚合物、纳米材料等。本文综述了增强体复合SiO_2气凝胶的最新研究进展,对复合气凝胶的制备方法、增强机理进行分析并对未来提高气凝胶力学性能的方法发展重点进行了展望。     

低密度、块状氧化铝气凝胶制备

研究了工艺参数对氧化铝溶胶及气凝胶的影响。结果表明,稳定的氧化铝溶胶优化制备工艺为：仲丁醇铝为前驱体,水解温度60 ℃,仲丁醇铝、乙醇、水的物质的量之比为1∶(8～16)∶1.2;螯合剂乙酰乙酸乙酯能有效控制仲丁醇铝水解缩聚速率,提高溶胶的稳定性;块状氧化铝气凝胶主要成份为多晶勃姆石相,比表面积为447 m²·g^-1,其强度和密度随乙醇量的增加而降低,密度最低为0.040 g·cm^-3。氧化铝气凝胶微观结构由许多片叶状颗粒堆积形成,经1 200 ℃热处理后仍保持原有的微观形貌,比表面积为73 m²·g^-1。     

块状石英纤维/Al_2O_3气凝胶复合材料的非超临界干燥法制备及表征

采用溶胶-凝胶法和常压干燥法以N,N′-二甲基甲酰胺(DMF)作为干燥控制化学添加剂制备了低密度石英纤维增强Al2O3气凝胶复合材料.通过氮气吸附-脱附实验比较研究了石英纤维对氧化铝气凝胶孔结构参数的影响;采用X射线衍射技术表征了在升温过程中石英纤维/Al2O3气凝胶复合材料的相结构变化;利用扫描电子显微镜和透射电子显微镜观察了Al2O3气凝胶基体及其石英纤维复合材料的微观形貌;初步探讨了DMF对Al2O3气凝胶形貌和密度的影响.研究结果表明石英纤维/Al2O3气凝胶复合材料成块性好,纤维与气凝胶基体结合紧密,石英纤维提高了Al2O3相转变温度,适量的DMF有利于形成均匀凝胶网络结构,减小干燥收缩压力.     

Preparation of Alumina Aerogel Films by Low Temperature CO2 Supercritical Drying Process

Alumina aerogel thin films were formed by a new synthesis route. Sols were prepared by the Yoldas process. Gels were formed by sol evaporation in a few hours. Films were prepared by dip coating glass or alumina substrates into both the sols and the gels. Aerogel films with special morphology were produced for the first time by exchanging the film solvent with acetone after the dip coating, followed by supercritical drying. The morphology of the films, studied by SEM and TEM, consists of fiber-like network of round chains (≈0.1 μm thick), and pores (0.1–0.5 μm in diameter). It is shown that the fibers contain a homogeneous arrangement of sol particles, 2–4 nm in size. Formation of this microstructure can be attributed to phase separation in the alumina-water-acetone system in a 2D film geometry. A conceptual model for the film development is proposed.     

高比表面积窄孔分布氧化铝的制备研究 Ⅱ.加硅的影响

 采用pH摆动法，以硫酸铝为铝源，以氢氧化钠为碱沉淀剂，考察了添加SiO2对沉淀氧化铝物性的影响．通过孔结构分析、粒度测定和电镜观察等证实，加入少量SiO2可使沉淀粒子分散、变小，颗粒相对均匀，从而提高了氧化铝的比表面积和孔集中的程度．当加入2．5％的SiO时，pH仅摆动2次，即可使氧化铝粉体的孔体积高达1．2ml／g，比表面积达380m2／g．这类氧化铝的孔结构适宜，粒子小，易直接成型为孔径集中和耐压强度好的载体，故用于重油高压加氢脱氮反应具有较好的性能．沉淀时酸侧pH值降低，尽管沉淀氧化铝的孔径向较小的方面集中，但此时沉淀粒子呈紧密堆积，颗粒变大，比表面积下降，氧化铝沉淀粒子的结构发生改变．不同结构的氧化铝表现出不同的催化活性．     

Effects of Ti Addition on Alumina/Titania Composite Aerogels Synthesized by Sol–Gel Process and Supercritical Ethanol Drying

Alumina/titania composite aerogels with different titania contents were synthesized by the sol–gel process and supercritical ethanol drying. The structures and morphologies of synthesized aerogels were analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and N₂ adsorption–desorption tests. Supercritical ethanol drying induced the crystallization of titania, which prompted the transformation of the structure from pseudoboehmite to γ‐Al₂O₃ . Reversely, alumina retarded the anatase‐to‐rutile transformation of titania. The content of titania significantly affected the structure and morphology of alumina/titania composite aerogels. A high content of titania (≥40%) resulted in the phase separation of titania particles, which grew to form the anatase phase octahedral particles with well‐developed facets. When the titania content was low, titania particles could be homogeneously dispersed in alumina particles to form spherical clusters with the poor crystallinity. Titania particles were in the anatase phase, and no rutile phase was formed until the temperature rose to 1000°C. In addition, titania addition resulted in a decrease in the specific surface area (SSA) of alumina aerogels because the SSA of titania was lower than that of alumina aerogels.     

Preparation of Silica Aerogel/Resin Composites and Their Application in Dental Restorative Materials

As the most advanced aerogel material, silica aerogel has had transformative industrial impacts. However, the use of silica aerogel is currently limited to the field of thermal insulation materials, so it is urgent to expand its application into other fields. In this work, silica aerogel/resin composites were successfully prepared by combining silica aerogel with a resin matrix for dental restoration. The applications of this material in the field of dental restoration, as well as its performance, are discussed in depth. It was demonstrated that, when the ratio of the resin matrix Bis-GMA to TEGDMA was 1:1, and the content of silica aerogel with 50 μm particle size was 12.5%, the composite achieved excellent mechanical properties. The flexural strength of the silica aerogel/resin composite reached 62.9546 MPa, which was more than five times that of the pure resin. Due to the presence of the silica aerogel, the composite also demonstrated outstanding antibacterial capabilities, meeting the demand for antimicrobial properties in dental materials. This work successfully investigated the prospect of using commercially available silica aerogels in dental restorative materials; we provide an easy method for using silica aerogels as dental restorative materials, as well as a reference for their application in the field of biomedical materials.     

介孔氧化铝的制备及应用

本文介绍了介孔氧化铝(MA)的各种制备方法,概括了MA制备的分析表征方法,如TEM、SAED、XRD、LAXRD、气体吸附-脱附、DT-TGA等。通过平均孔径、比表面积、MA形貌等因素,讨论和总结了制备方法、铝源、模板剂、反应物配比、pH值和后处理方法等对MA制备和热稳定性的影响,综述了近年来MA的研究和应用进展,并对今后的研究方向进行了展望。