CuO(CoO,MnO)/SiO_2纳米复合气凝胶催化剂载体的制备及其在合成碳酸二苯酯中的应用

以正硅酸乙酯为硅源,以乙酸铜、乙酸钴和乙酸锰的水溶液为前驱体,采用溶胶–凝胶法和CO2超临界干燥工艺制备了CuO(CoO,MnO)/SiO2纳米复合气凝胶。采用场发射扫描电镜、透射电镜和电子散射能谱分析等对纳米复合气凝胶的微观结构和组成进行了表征。采用Brunauer–Emmett–Teller法测定了纳米复合气凝胶的比表面积、孔径及孔径分布。以纳米复合气凝胶为载体制备了负载型催化剂,用于催化合成碳酸二苯酯(diphenyl carbonate,DPC),并用气相色谱仪对反应液进行了分析。结果表明:纳米复合气凝胶的粒径为20～100nm,孔径为2～8nm,平均孔径为3.16nm,比表面积为664.4m2/g;过渡金属的摩尔含量为13.77%;催化合成DPC的质量收率达27.14%。     

疏水性SiO2气凝胶常压干燥制备与表征

以正硅酸乙酯(TEOS)为硅源,以NH4F为催化剂,实现了纳米多孔SiO2气凝胶材料的常压干燥制备,采用三甲基氯硅烷(TMCS)进行疏水改性,以减少样品在使用过程中的收缩和塌陷.结果表明:TMCS疏水改性的SiO2气凝胶样品的表观密度为0.191 g/cm3,导热系数为0.031 W/(m· K),比表面积为667 m2/g.SEM和TEM的测试结果表明,所得样品为纳米介孔材料.接触角的测定分析表明,TMCS疏水改性的SiO2气凝胶样品与水的接触角为147°,表现出良好的疏水性.400 ℃热处理后,气凝胶因失去大量的甲基基团,由疏水性变为亲水性.     

厘米级SiO2气凝胶球体的制备及表征

以正硅酸乙酯(TEOS)为硅源,采用酸碱两步催化溶胶-凝胶法和CO2超临界干燥技术成功制备出完整的厘米级SiO2气凝胶球体.当配比条件为TEOS∶ EtOH∶ H2O=1∶10∶4时制备的SiO2气凝胶球体具有典型的纳米多孔网络结构.采用扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外光谱仪(FT-IR)、孔径分布及比表面积测试仪(BET)、纳压痕技术对SiO2气凝胶球体的表面形貌、内部结构、化学成分、比表面积、孔径分布及力学性能进行研究分析.研究表明:低温有利于制备出完整的厘米级SiO2气凝胶球体.随着凝胶温度的增加,SiO2气凝胶球体样品的收缩率逐渐增加,而孔隙率和比表面积逐渐减小.当凝胶温度为-5℃时,厘米级SiO2气凝胶球体样品的平均孔径为24.8 nm,孔体积为4.9 m3/g,比表面积高达1004.38 m2/g,密度为0.104g/cm3,收缩率约为16.2％,孔隙率约为95.3％,弹性模量和硬度最大分别为8.79 MPa与5.24 MPa.     

石棉绒增强SiO2气凝胶隔热材料常压工艺研究

气凝胶是一种优质隔热材料.本文以石棉绒纤维作为气凝胶的增强材料,以水玻璃为硅源,通过常压干燥工艺进行SiO2气凝胶块体保温隔热材料的制备.研究了湿凝胶制备工艺流程及洗涤工艺对气凝胶材料结构及性能的影响.研究发现,以石棉绒为增强材料常压制备SiO2湿凝胶的最佳制备工艺为:在水、纤维和分散剂配制的纤维分散悬浮液中首先加入乙醇搅拌均匀,然后与水玻璃和氟硅酸钠配制的水玻璃凝胶液搅拌混合,再注模固化;在固化湿凝胶的洗涤和溶剂置换工艺中,以水为洗涤溶剂效果好,产品性能高.以石棉绒为增强材料,采用常压干燥工艺制备的SiO2气凝胶隔热材料具有收缩率小,产品规整,密度小,孔隙率高,及较好的强度和隔热性能.     

莫来石纤维增强SiO2气凝胶隔热材料的制备

以正硅酸乙酯（TEOS）为硅源,采用溶胶-凝胶及超临界干燥技术制备了莫来石纤维增强SiO2气凝胶隔热材料,并系统地研究了HF催化剂以及溶剂等制备因素对气凝胶品质的影响。结果表明：HF催化剂、H2O、乙醇和甲酰胺用量对TEOS的水解缩聚反应有较大影响,调节其配比可以制备具有不同密度的SiO2气凝胶隔热材料;添加甲酰胺可以调节凝胶内部网络结构,防止干燥时由于应力不均而开裂或破裂。     

疏水SiO2气凝胶的制备及表征

以正硅酸乙酯(TEOS)为硅源,三甲基氯硅烷(TMCS)为改性剂,经老化、表面疏水改性,常压干燥制备了高比表面积疏水SiO2气凝胶.用傅立叶变换红外光谱仪(FT-IR)、扫描电镜(SEM)、比表面及孔径分布仪、热重分析仪(TG-DSC)对其疏水特性及结构进行表征.结果表明:疏水SiO2气凝胶与水的接触角达145°,在空气中的热稳定温度为269 ℃;且比表面积达1035 m2/g,具有典型的气凝胶结构特征,孔径尺寸和密度分别达9.7 nm和0.129 g/cc,骨架颗粒尺寸小于30 nm.     

内疏外亲SiO_2气凝胶的制备及表征

以正硅酸乙酯(TEOS)为硅源,无水乙醇为溶剂,硝酸为催化剂,氨水为凝胶剂,经溶胶-凝胶过程制备块状湿凝胶。再以三甲基氯硅烷(TMCS)为疏水改性剂,3-氨丙基三羟基硅烷为亲水改性剂对制备的湿凝胶进行改性处理,最后经超临界CO2干燥得到块体SiO2气凝胶。考察了亲水改性剂加入量分别为0、0.15、0.75、1.5、2.70 mL时对块体SiO2气凝胶亲水性的影响,并通过扫描电子显微镜(SEM)、接触角、吸水率、红外光谱(FT-IR)等对气凝胶进行表征。结果表明:所得气凝胶块体具有纳米多孔结构,内部疏水(最大接触角可达123°),表面亲水,试样亲水性随亲水剂用量的增加而增大;同一试样亲水性存在一定的梯度变化,亲水性由内到外逐渐增强。     

疏水型SiO2气凝胶

以多聚硅为硅源，通过溶胶-凝胶、表面修饰及超临界干燥过程制备出了疏水型SiO2气凝胶，表面修饰后SiO2气凝胶洞由修饰前的23．1nm减小到18．2nm，比表面积由修饰前的477m^2g^-1增加到563m^2g^-1，骨架颗粒比修饰前略大，饱和水蒸汽吸附量由吸附前的0．04(重量比)降低到0．0012，且与水不浸润。     

热塑性聚氨酯中空纤维/SiO2气凝胶隔热材料的制备及性能研究

以热塑性聚氨酯中空纤维为增韧材料,正硅酸乙酯为硅源,采用溶胶-凝胶技术制备了热塑性聚氨酯中空纤维/SiO2气凝胶隔热材料.考察了纤维类型、中空纤维铺设方式、中空纤维规格对SiO2气凝胶隔热性能的影响.结果表明:中空纤维增韧SiO2气凝胶的隔热性能略低于纯SiO2气凝胶,但其韧性有了显著提高.中空纤维垂直铺设,采用合适的内径及壁厚的中空纤维能获得较好隔热性能的SiO2气凝胶隔热材料.     

甲基三乙氧基硅烷改性制备疏水SiO2气凝胶

采用原位聚合法结合超临界干燥工艺,以正硅酸四乙酯为硅源、甲基三乙氧基硅烷为改性剂制备出疏水型SiO2气凝胶．采用比表面积及微孔物理分析仪、接触角分析仪、热分析仪和红外光谱仪对其性能和结构进行表征．结果表明：所制备出的SiO2气凝胶是接触角为160°、比表面积为674．47m^2／g和孔体积为4．13cm^3／g@疏水型气凝胶．疏水SiO2气凝胶的热稳定温度为244．5℃．     

Porous YSZ ceramics with unidirectionally aligned pore channel structure: Lowering thermal conductivity by silica aerogels impregnation

The previous report of this work has demonstrated the fabrication and properties of porous yttria-stabilized zirconia (YSZ) ceramics with unidirectionally aligned pore channels. As a follow-up study, the present work aims at lowering the thermal conductivity of the porous YSZ ceramics by silica aerogels impregnation. The porous YSZ ceramics were immersed in an about-to-gel silica sol. Both the unidirectionally aligned pore channels and the inter-grain pores by grain stacking in the channel-pore wall of the porous YSZ ceramics were impregnated with the silica sol. After aging and supercritical drying, silica aerogels formed in the macroporous network of the porous YSZ ceramics with unidirectionally aligned pore channels. The influences of silica aerogel impregnation on the microstructure and properties of porous YSZ ceramics with unidirectional aligned pore channels were investigated. The porosity decreased after impregnation with silica aerogels. Both microstructure observation and pore size distribution indicated that both channel-pore size and inter-grain pore-size decreased significantly after impregnation with silica aerogels. Impregnating porous YSZ ceramics with silica aerogels remarkably lowered the room-temperature thermal conductivity and enhanced the compressive strength. The as-fabricated materials are thus suitable for applications in bulk thermal isolators.     

超临界干燥制备疏水型二氧化硅气凝胶

文章以正硅酸乙酯为原料,经溶胶-凝胶过程制备二氧化硅醇凝胶,采用三甲基氯硅烷作为表面改性剂,对醇凝胶进行化学表面修饰,超临界干燥,制备了疏水性二氧化硅气凝胶粉末。运用红外光谱、BET、扫描电镜、XRD对其结构、形貌及化学组成进行了分析。结果表明：该样品是表面连有疏水基团-CH3的疏水性SiO2气凝胶,呈连续网络结构的球状纳米粒子,孔径分布主要集中在2～4nm,是热稳定性较高的非晶、多孔、轻质介孔材料。     

Surface Modification of Silica Aerogels Dried with 2-Methyl-1-Propanol in the Sub-Critical Pressure

Silica aerogels were made by sol-gel techniques using industrial silicon derivatives (polyethoxydisiloxanes, E-40), followed by drying under sub-critical pressure with iso-butanol. The shrinkage (linear), specific surface area, S_BET, SEM, TEM and the pore size distribution of the silica aerogels were investigated. The results show that the shrinkage (linear) is below 5%, diameter of the silica particles is about 6 nm and the pore size of the silica aerogels is 10 nm. The specific surface area of the silica aerogel is 559.2 m²/g. IR and NMR techniques were used to determine the organic groups on the silica matrix, GC/MS was also introduced to analyse the composition of the recycled iso-butanol. The surface modification and the reactions of iso-butanol to the silica aerogel are also discussed.     

Influence of Catalyst (Citric Acid) Concentration on the Physical Properties of TEOS Silica Aerogels

In the present paper, the experimental results on the influence of catalyst (citric acid) concentration on the physical properties of TEOS silica aerogels, are reported. The aerogels have been prepared by hydrolysis and polycondensation of tetraethoxysilane (TEOS) using citric acid (CTA) as a new catalyst followed by supercritical drying in an autoclave. In order to obtain the best quality silica aerogels in terms of monolithy, high transparency, low density, large surface area and high porosity with uniform pore size distribution, the catalyst concentrations were varied from 0.0005 M to 0.1 M by keeping the molar ratio of TEOS : EtOH : H₂O constant at 1 : 5 : 7, respectively. It has been found that the lower (<0.001) CTA concentration resulted in low density, smaller surface area but opaque aerogels whereas higher (>0.005 M) CTA concentration resulted in high density, large surface area, highly transparent but cracked aerogels. On the other hand, medium (between 0.001 and 0.005 M) CTA concentration resulted in monolithic, low density, large surface area and highly transparent silica aerogels. The pore size distribution (PSD) for higher (0.1 M) and lower (0.0005) CTA concentrations shifted towards smaller and larger pore radii respectively, whereas for medium (0.001 M) CTA concentration, the PSD is narrow and uniform, which reduces the differential pressure during supercritical solvent extraction leading to monolithic silica aerogels. These results have been supported and discussed by considering the particle and pore sizes observed by Scanning Electron Microscopy (SEM). The surface area was measured by BET analysis.     

Synthesis and characterization of a xonotlite fibers–silica aerogel composite by ambient pressure drying

Xonotlite fibers (XFs) reinforced silica aerogel composites were prepared by a sol–gel method under ambient pressure drying. XFs were synthesized through a dynamic hydrothermal route and had a noodle-like structure with length of 5–10 μm and average diameter of 150–200 nm. The microstructure analysis showed that XFs were inlaid in silica aerogel matrix by physical combination which contributed to restrict the volume shrinkage of alcogels and maintain the integrality aerogels during drying process. The physical, naonporous and thermal properties of the as prepared aerogel composites were investigated and discussed in detail. The new aerogel composites possessed porous nanostructure, which exhibited typical properties of 0.126 g/cm³ density, 4.132 cm³/g pore volume, and thermal conductivity of 0.0285 W/(m K). The results indicated that the introduced XFs didn’t significantly alter the porosity, hydrophobicity or thermal conductivity of aerogel matrix. It was also found that the aerogel composites had much more outstanding porosity than that of pure aerogel upon calcinations at 800 °C. This study fabricated XFs–silica aerogel composites and explored a new way for silica aerogels to endure and remain monolithic under ambient pressure drying.     

微波辅助溶胶-凝胶法制备高比表面积SiO2气凝胶

以四甲氧基硅烷(TMOS)为原料,三甲基氯硅烷(TMCS)为疏水改性剂,通过微波辅助溶胶-凝胶法制备高比表面积SiO2气凝胶,用FTIR、SEM、XRD、BET以及TG-DSC对其结构进行表征。结果表明,微波辅助溶胶-凝胶法制得的SiO2气凝胶比表面积达1 096 m2/g,SiO2气凝胶颗粒呈均匀分布,孔径主要分布在2～10 nm;与水的接触角为141°,表现出良好的疏水性;在空气中的耐温点达543℃,具有良好的热稳定性。     

常压干燥法制备SiO2气凝胶粉体

以工业硅溶胶为原料,通过凝胶过程与干燥条件的控制,采用常压干燥法制备了SiO2 气凝胶粉体,并考察了老化液中正硅酸乙脂(TEOS)含量和干燥控制化学添加荆甲酰胺的添加对气凝胶粉体堆积密度、比表面积和孔径分布的影响.结果表明:所得气凝胶粉体具有纳米多孔结构,组成气凝胶结构的基本粒子呈圆球形,粒径为10～25 nm,由基本粒子连接而成的网络结构具有5～50 nm的孔径分布;随着热处理温度从常温升至1 100℃,SiO2气凝胶从最初的无定形态转化为方石英;在,TEOS的醇溶液中老化,有利于增强凝胶骨架的强度;添加甲酰胺可以改善气凝胶粉体的孔径分布,提高其比表面积.     

MTMS基SiO_2气凝胶的制备及其影响因素

以甲基三甲氧基硅烷(MTMS)为前驱体,通过酸碱两步溶胶凝胶法,常压干燥制备了SiO2气凝胶,综合研究了反应条件对气凝胶导热系数,堆积密度,比表面积和孔径的影响,利用FT-IR分析了SiO2气凝胶的化学结构。     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase, photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.     

常压干燥法制备疏水性SiO2气凝胶

利用正硅酸乙酯做先躯体,盐酸与氨水做催化剂,通过二步法制备了二氧化硅气凝胶,并利用三甲基氯硅烷和正己烷做表面改性剂采用共沸法逐级对湿凝胶进行表面改性.测试分析了气凝胶的密度、表观、疏水性、比表面积、孔径分布和热稳定性.结果表明:气凝胶的物理特性及其疏水性受到三甲基氯硅烷与正己烷的体积比(ψ)的影响,其密度随着ψ增大而减小,当ψ=3%时,气凝胶的疏水性最好;所制得的SiO2在350℃仍具有良好的热稳定性,并且具有高比表面积(838.6 m2/g)和孔体积(2.10cm3/g).