氧化铁气凝胶的制备及其表征

气凝胶是由纳米量级超细微粒或高聚物分子构成的多孔性固态材料^[1,2],其杨氏模量、声传播速率、折射率、热导率和电导率等均与其宏观密度成标度关系.它拥有反常输运特性、动力学性质和低温热学性质.     

块状TiO2气凝胶的制备及其表征

随着以溶胶-凝胶法和超临界干燥技术为基础的气凝胶制备方法的逐步完善,已不断制备出多种气凝胶[1～3].由于TiO2具有半导体特性,它常被作为光催化剂而受到重视,但是TiO2气凝胶的结构强度远比SiO2气凝胶小,在制备过程中极易碎裂粉化,所以至今未见制备块状TiO2气凝胶的报道.Dagan等[4]曾用异钛酸丁酯为母体制得TiO2气凝胶,并发现水杨酸在TiO2气凝胶存在下的光解速率是一般TiO2粉末的10倍,但获得的仅为TiO2气凝胶粉末.张敬畅等[5]以无机盐为原料,采用溶胶-凝胶法结合超临界干燥技术制备了纳米级TiO2气凝胶,也未能得到块状TiO2气凝胶材料. 本文报道以正钛酸丁酯为原料制备块状TiO2气凝胶的方法,并用TEM,SEM,XRD和IR等手段对所获得的气凝胶进行了结构表征.     

碳化硅块状气凝胶的制备及应用

碳化硅气凝胶具有高温稳定性、低热膨胀系数、良好的抗热震性以及抗氧化和耐腐蚀等优异的性质,在高温和高腐蚀性环境下的隔热、电磁吸波、过滤和吸附等领域具有较大的应用潜力。然而,块状碳化硅气凝胶的可控制备一直是一项较大的挑战。本文综述了块状碳化硅气凝胶在制备工艺和应用两个方面的研究进展,首先分析总结了各种制备工艺及其优缺点,包括有机/SiO₂复合气凝胶碳热还原法、预陶瓷化聚合物裂解法、化学气相沉积法、高温气相渗硅法和碳化硅纳米线组装法;然后,详细介绍了碳化硅气凝胶在高温隔热和电磁吸波两个领域的应用研究进展;最后,展望了碳化硅气凝胶未来的若干发展方向。     

An Easy Way To Prepare Monolithic Inorganic Oxide Aerogels

Inorganic oxide aerogels have unique thermal, optical, electrical, magnetic, and chemical properties, which result in them potentially having a broad range of applications. However, their preparation is commonly based on a supercritical drying method, which greatly limits real applications of aerogels and their commercialization. Here we demonstrate a general method for drying wet gels to form aerogels that is based on the sublimation of organic solvent. The organic solvent must have a low surface tension, undergo sublimation easily, and have a high freezing point to allow the rapid synthesis of monolithic inorganic oxide aerogels under vacuum conditions. This cost‐effective process will facilitate application of aerogel materials. This approach may also be used for the preparation of other porous materials, whose theoretical and practical applications should be investigated.     

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TiO2/SiO2气凝胶的非超临界干燥法制备及其表征

分别通过TiO2和SiO2的单独溶胶和TiO2/SiO2复合凝胶,并添加干燥控制化学添加剂甲酰胺,形成比较完善的凝胶网络结构,同时通过正硅酸乙酯的乙醇溶液浸泡,低表面张力溶剂替换和分级陈化以及干燥等步骤,实现了块状TiO2/SiO2复合气凝胶的非超临界干燥制备.所得TiO2/SiO2气凝胶为无色或乳白色轻质块状多孔固体,表观密度约0.4～0.9g/cm3,孔隙率约80%～95%.它由直径约10nm的TiO2和SiO2微粒相互分散复合而成,孔洞直径约几十纳米.其相态SiO2为无定形,TiO2为锐钛矿晶型.随着焙烧温度的升高,直到800℃不发生相变化.     

Characterization of Silica-Containing Aluminum Hydroxide and Oxide Aerogels

Pure and silica-containing Al hydroxide aerogels were prepared by the supercritical drying method. The samples were later calcined, giving rise to alumina and Si–Al mixed oxides. The materials were characterized from the points of view of their bulk and surface structures. The Si-free material before calcination is well-crystallized boehmite that converts to γ-alumina by calcination. The silica-containing hydroxides are composed of boehmite layers with silicates in the interlayer region. The resulting mixed oxides present silica essentially in the bulk. The surface structure of alumina seems poorly sensitive to silica addition. Surface silanol groups appear only for SiO₂more than 4%. No Brønsted acidity appears. Silica addition allows mixed oxides with higher surface areas to be obtained.     

Monolithic Nanoporous Crystalline Aerogels

Monolithic aerogels can be easily obtained by drying physical gels formed by linear uncross‐linked polymers. Preparation methods, structure, and properties of these physically cross‐linked polymeric aerogels are reviewed, with particular emphasis to those whose cross‐linking knots are crystallites and, more in particular, crystallites exhibiting nanoporous‐crystalline forms. The latter aerogels present beside disordered amorphous micropores (typical of all aerogels) also all identical nanopores of the crystalline phases. Their outstanding guest transport properties combined with low material cost, robustness, durability, and ease of handling and recycle make these aerogels suitable for applications in chemical separations, purification, and storage as well as in biomedicine. Scientific, technological, and industrial perspectives for monolithic nanoporous‐crystalline polymeric aerogels are also discussed.

     

β-FeOOH气凝胶的制备及表征

用氯化铁和氢氧化钠溶液为原料制得了块状β－ＦｅＯＯＨ气凝胶,构成气凝胶的基本粒子为长约１８ｎｍ、直径约５ｎｍ的棒状粒子,制备过程包括聚合铁水凝胶的制备和超临界干燥两部分。初步研究了溶液羟铁摩尔比（ＯＨ＾－／Ｆｅ＾３＋对气凝胶密度和比表面的影响,应用ＢＥＴ、ＴＥＭ、ＸＲＤ和Ｍｏｓｓｂａｕｅｒ谱等手段对气凝胶样品进行了表征。结果表明,气凝胶样品是由β－ＦｅＯＯＨ超细微粒构成的具有连续网络结构的多孔性块     

硫铁矿烧渣制备氧化铁黄和氧化铁红

对利用硫铁矿烧渣制备氧化铁黄和氧化铁红进行了研究。考察了影响硫铁矿烧渣还原、酸溶、中和、氧化等过程的各种因素。结果表明,在适宜的条件下,利用烧渣可以制备出用做颜料的氧化铁黄和氧化铁红。     

Preparation and Characterization of Mg‐Zr Mixed Oxide Aerogels and Their Application as Aldol Condensation Catalysts

A series of Mg‐Zr mixed oxides with different nominal Mg/ (Mg+Zr) atomic ratios, namely 0, 0.1, 0.2, 0.4, 0.85, and 1, is prepared by alcogel methodology and fundamental insights into the phases obtained and resulting active sites are studied. Characterization is performed by X‐ray diffraction, transmission electron microscopy, X‐ray photoelectron spectroscopy, N₂ adsorption–desorption isotherms, and thermal and chemical analysis. Cubic Mg_xZr_1?xO_2?x solid solution, which results from the dissolution of Mg²⁺ cations within the cubic ZrO₂ structure, is the main phase detected for the solids with theoretical Mg/ (Mg+Zr) atomic ratio ≤0.4. In contrast, the cubic periclase (c‐MgO) phase derived from hydroxynitrates or hydroxy precursors predominates in the solid with Mg/(Mg+Zr)=0.85. c‐MgO is also incipiently detected in samples with Mg/(Mg+Zr)=0.2 and 0.4, but in these solids the c‐MgO phase mostly arises from the segregation of Mg atoms out of the alcogel‐derived c‐Mg_xZr_1?xO_2?x phase during the calcination process, and therefore the species c‐MgO and c‐Mg_xZr_1?xO_2?x are in close contact. Regarding the intrinsic activity in furfural–acetone aldol condensation in the aqueous phase, these Mg? O? Zr sites located at the interface between c‐Mg_xZr_1?xO_2?x and segregated c‐MgO display a much larger intrinsic activity than the other noninterface sites that are present in these catalysts: Mg? O? Mg sites on c‐MgO and Mg? O? Zr sites on c‐Mg_xZr_1?xO_2?x. The very active Mg? O? Zr sites rapidly deactivate in the furfural–acetone condensation due to the leaching of active phases, deposition of heavy hydrocarbonaceous compounds, and hydration of the c‐MgO phase. Nonetheless, these Mg‐Zr materials with very high specific surface areas would be suitable solid catalysts for other relevant reactions catalyzed by strong basic sites in nonaqueous environments.     

氧化钇掺杂块状SiO_2气凝胶的制备与表征

以正硅酸四乙酯(TEOS)为前驱体,YCl3·6H2O为掺杂剂,采用溶胶-凝胶法并结合CO2超临界干燥工艺得到了块状Y2O3-SiO2气凝胶,其中Y2O3掺杂含量控制在5wt%~30wt%范围内。利用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、比表面积测定(BET)、X射线荧光分析(XRF)等测试手段对样品进行表征。结果表明:经过氧化钇掺杂后得到的Y2O3-SiO2气凝胶,不仅维持了SiO2气凝胶原有的空间网络结构,而且具有更高的热稳定性,经过900℃热处理2 h后,10wt%Y2O3(0.447 g的YCl3·6H2O)掺杂的Y2O3-SiO2气凝胶仍然处于无定形态,平均孔径约为21.3 nm,比表面积高达643.8 m2·g-1。     

氧化钇掺杂块状SiO2气凝胶的制备与表征

以正硅酸四乙酯（TEOS）为前驱体,YCl₃·6H₂O为掺杂剂,采用溶胶-凝胶法并结合CO₂超临界干燥工艺得到了块状Y₂O₃-SiO₂气凝胶,其中Y₂O₃掺杂含量控制在5wt%~30wt%范围内。利用扫描电镜（SEM）、透射电镜（TEM）、X射线衍射（XRD）、比表面积测定（BET）、X射线荧光分析（XRF）等测试手段对样品进行表征。结果表明：经过氧化钇掺杂后得到的Y₂O₃-SiO₂气凝胶,不仅维持了SiO₂气凝胶原有的空间网络结构,而且具有更高的热稳定性,经过900℃热处理2h后,10wt%Y₂O₃（0.447g的YCl₃·6H₂O）掺杂的Y₂O₃-SiO₂气凝胶仍然处于无定形态,平均孔径约为21.3nm,比表面积高达643.8m₂·g^-1。     

块体溶胶-凝胶生物活性玻璃的制备与表征

由于溶胶-凝胶工艺和玻璃组分的限制,从凝胶制备块体生物玻璃有一定难度.获得块体凝胶的关键步骤是干燥工艺,其中毛细管压力起决定作用.用一种简便可靠的方法,制备了均匀、透明、无裂纹的块体溶胶-凝胶生物玻璃585.选用合适的干燥添加剂(DCCA),结合准平衡干燥可以有效防止干燥过程中的凝胶开裂.体外浸泡试验表明,该样品具有优良的生物活性,但是机械强度不高.在玻璃组分中引入TiO₂后,选择合适的DCCA制得的块体材料保持一定的生物活性,同时抗压强度明显提高.讨论了不同的DCCA对干燥过程的不同作用机理和对材料的介孔结构特征的影响,以及TiO₂对提高凝胶骨架和材料整体强度的贡献,还有对体外生物活性的影响.     

氧化铁纳米线阵列的溶胶-凝胶模板法制备与表征

0引言氧化铁在颜料、磁记录材料和催化剂等方面具有广泛的应用[1,2]。尤其是纳米氧化铁在纳米尺度具有良好的气敏特性[3]。纳米材料可以分为零维、一维、二维纳米材料,一维材料是纳米材料的重要组成部分,是纳米组装的基础。一维纳米材料的制备方法中氧化铝模板法占有极其重要的     

Preparation and Characterization of a Low-Density Imprinted Monolithic Column

This work is a first effort to prepare a low-density imprinted monolithic column for LC. The new molecularly imprinted polymer monolith was prepared with 30% (w/w) monomers in the pre-polymerization mixture while general high-density monoliths are prepared with 40% monomers. The resulting low-density (S)-naproxen-imprinted monolith produced better chiral resolution of rac-naproxen (R _s = 1.55) and column efficiencies of imprinted molecules up to 2,860 plates m^?1. Morphological characteristics of low density imprinted monolith was further studied by mercury intrusion porosimetry, scanning electron microscopy (SEM) and nitrogen sorption method. The experiments demonstrated that the strategy of low-density column may be one of a potential approach to the improvement of column efficiency of an imprinted stationary phase.     

铁的氧化物纳米颗粒及其组装体的化学制备

铁的氧化物纳米颗粒作为一种重要的磁性纳米颗粒在磁记录材料、磁性液体、催化、尤其是生物医用领域有着广泛的应用前景,因而受到了研究者们极大的关注。本文对铁的氧化物磁性纳米颗粒的化学制备方法进行了综述,将其归结为复分解和热分解两种策略;总结了近期含铁的氧化物纳米颗粒组装体的研究进展,并对未来的发展做了展望。     

溶剂热法制备纳米氧化镍及其表征

以乙酰丙酮镍、油酸、油胺为原料，十八烯为溶剂，聚乙烯吡咯烷酮为表面活性剂，采用溶剂热法，在不同反应条件制备了纳米级氧化镍材料.通过X射线衍射（X-ray diffraction，XRD）、透射电子显微镜（Transmission electron microscope，TEM）、紫外-可见光吸收光谱（Ultraviolet-visible spectroscopy，UV-Vis）光谱分析以及塔菲尔（Tafel）测试考察了反应物比例、保温时间、表面活性剂（PVP）、油胺的量对产物微结构、粒径、形貌、光学以及电化学活性性能的影响.实验结果表明：在反应物n[Ni（acac）₂]∶n（OA）=1∶2、添加剂PVP质量分数为1.66%、油胺物质的量为30 mmol、200℃下保温8 h时，可获得粒径约为30～40 nm纯相氧化镍，具有最佳电化学活性，交换电流密度为J₀=1.23×10^-2 mA·cm^-2.     

Preparation,Characterization and Applications of Electron-Beam Curing-Derived Monolithic Materials

Summary: Acrylate/methacrylate-based monoliths have been prepared via electron- beam (EB) initiated polymerization. These monolithic columns were found suitable for application in the analytical scale separation of various analytes such as proteins. Functionalization of the monolithic columns was accomplished via copolymerization of functional monomers. Selected examples of both synthesis and application will be summarized.