常压干燥法制备Al2O3块状气凝胶

以无机铝盐Al(H2O)9(NO3)3为前驱体，甲酰胺作为干燥控制化学添加剂(DCCA)，1,2-环氧丙烷作为凝胶网络诱导剂，通过溶胶-凝胶法制备氧化铝凝胶；在常压条件下对凝胶进行干燥，得到乳白色、半透明、轻质、块状氧化铝气凝胶.初步探讨了在凝胶制备和陈化过程中增强凝胶网络结构强度的途径和机理.     

离子液体辅助水热法合成六方片状γ-Al_2O_3

采用离子液体辅助水热法,以氯化铝为铝源,正丁胺为沉淀剂,离子液体1-丁基-3-甲基咪唑四氟硼酸盐([Bmim]BF4)为模板,合成了具有特殊晶面取向的六方片状γ-Al_2O_3介孔材料,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)以及N2等温吸-脱附等方法对产物进行了表征.结果表明,离子液体的加入改变了前驱体的晶相组成,通过调节[Bmim]BF4的用量能够促使前驱体从γ-Al OOH向三水铝石与督三水铝石混合晶相进行相转变,经过高温焙烧形成相应的氧化铝产物,最终实现氧化铝从菱形纳米片向六方纳米片的结构转变.当[Bmim]BF4与铝源的摩尔比为0. 15时,160℃下反应24 h能够获得形貌均匀且规整的六方片状γ-Al_2O_3,其平均粒径约为600 nm,厚度为200 nm,上下基底面为{111}晶面族,侧面由{110}晶面族组成.相比于无模板作用下得到的菱形纳米片,六方片状γ-Al_2O_3具有更大的比表面积(203 m2/g)和孔径更为均一(4. 2 nm)的介孔孔道.本文还对离子液体控制合成介孔氧化铝的模板机理进行了研究.     

高比表面积有序介孔氧化铝的制备与表征

采用溶胶-凝胶法以非离子表面活性剂PEO-PPO-PEO三嵌段共聚物F127为模板剂, 以异丙醇铝为铝源, 以异丙醇为溶剂, 成功地制备出比表面积为485 m2/g、孔径分布窄(2~20 nm)、孔容在1.2 cm3/g以上和孔道呈蠕虫状且具有一定有序性的介孔氧化铝. 采用BET, TEM, XRD和TG多种测试技术对产物性能进行了表征. 探讨了水铝比、醇水混合溶液的滴加速度、反应时间、水浴温度、陈化温度及陈化时间等条件对合成的有序介孔氧化铝结构的影响.     

以离子液体为铝源和模板合成氧化铝纳米纤维

以咪唑类氯铝酸盐离子液体(x Al Cl_3-[C_(10)mim]Cl)为模板和铝源,采用溶胶-凝胶法合成了氧化铝纳米纤维.考察了氯铝酸盐离子液体中Al Cl_3的摩尔分数以及焙烧温度对纤维状氧化铝合成的影响,通过X射线衍射仪(XRD)、场发射透射电子显微镜(TEM)和物理吸附仪对样品进行了表征.研究结果表明,氯铝酸盐离子液体可以同时作为模板剂和铝源合成具有一定形貌的氧化铝.当Al Cl_3的摩尔分数x(Al Cl_3)=0.5时,可以合成出纳米纤维状氧化铝,纳米纤维直径约为2 nm,长度约为200 nm,比表面积为238.38 m~2/g,孔容为0.54 cm~3/g,平均孔径为8.43 nm.合成的氧化铝具有高的热稳定性,在900℃下焙烧依然能够很好地保持其形貌结构和γ晶型.此外,提出了氢键共π-π键堆积机理来解释超细纤维氧化铝的合成过程.     

一种新型介孔磷酸硅铝(SAPO)分子筛的合成及表征

以Silicate-1晶种为硅源,水热合成了一种新型介孔磷酸硅铝(SAPO-1)分子筛,并且通过X射线粉末衍射、红外光谱、透射电镜、扫描电镜、热重分析、N2吸附/脱附和氨气程序升温脱附(NH₃-TPD)等多种手段对产物进行了表征.红外光谱表明,Silicate-1导向剂成功地引入了介孔骨架;氨气程序升温脱附(NH₃-TPD)结果表明,SAPO-1具有较强的酸性.催化结果表明,SAPO-1在大分子催化反应中有较高的活性.     

阶层多孔二氧化硅块体材料的制备与表征

以正硅酸甲酯(TMOS)为前驱体、0.01 mol·L-1盐酸为催化剂、聚环氧乙烷(PEO,分子量为10 000)为相分离剂、环氧丙烷(PO)为凝胶促进剂、十二烷基硫酸钠(SDS)为造孔剂,采用溶胶-凝胶伴随相分离制备阶层多孔二氧化硅块体材料,利用差热分析(DTA)、热重分析(TG)、傅里叶变换红外(FT-IR)光谱、扫描电镜(SEM)、X射线衍射(XRD)、N2吸附/脱附装置等测试技术对所制得的阶层多孔块体进行了表征,探究造孔剂SDS对大孔和介孔结构的影响机理。研究表明:SDS在凝胶过程中以胶束的形式进入到骨架中形成介孔孔道;当SDS为0.21 g时,块体材料的阶层多孔结构最优,大孔孔径为1~3μm,介孔孔径为4~5 nm,比表面积为650 m2·g-1;800℃热处理后,大孔结构和骨架上的介孔基本保持,比表面积仍能达到421 m2·g-1,体现出良好的热稳定性。     

基于聚肽和海藻酸钠自交联水凝胶的制备与表征

首先以正己胺为引发剂,引发肌氨酸-N-羧酸内酸酐(Sar-NCA)和谷氨酸苄酯-N-内酸酐(BLG-NCA)进行开环聚合制备共聚物,该共聚物经水合肼改性得到无规共聚物聚肌氨酸-co-聚谷氨酸酰肼(PSar-co-PGH);然后用高碘酸钠氧化海藻酸钠制备了氧化海藻酸钠(ALG-CHO);最后将不同浓度的PSar-co-PGH溶液和ALG-CHO溶液进行物理混合,制备了水凝胶。聚合物结构分别采用傅里叶红外光谱(FT-IR)和核磁共振氢谱(1 H-NMR)进行表征;采用扫描电镜、红外光谱和旋转流变仪分别对其凝胶机理和力学性能进行表征。探讨了pH对水凝胶形成的影响。结果表明:成功制备了基于PSar-co-PGH/ALG-CHO的pH响应性水凝胶,水凝胶的储能模量随着PSarco-PGH浓度的增大而增大。     

添加环氧丙烷法常压干燥制备ZrO2气凝胶

以无机锆盐硝酸氧锆(ZrO(NO3)2·5H2O)为前驱体,1,2-环氧丙烷(PO)为凝胶促进剂,甲酰胺(FA)为干燥控制化学添加剂(DCCA),采用溶胶-凝胶法并通过常压干燥制备了轻质二氧化锆(ZrO2)气凝胶,利用差热分析(DTA)、扫描电镜(SEM)、N2吸附/脱附等测试技术对所制得的ZrO2气凝胶进行了表征.结果表明:添加环氧丙烷常压干燥制得的ZrO2气凝胶具有纳米尺寸的多孔网络结构,表观密度可低至202.08 kg·m-3,比表面积可高达645.0 m2·g-1,与超临界干燥效果相当.环氧丙烷因其环氧原子的强亲核性和不可逆的开环反应,可促进凝胶化,并通过环氧丙烷的量控制反应过程和凝胶状态.     

负载Ni金属有序介孔氧化铝催化剂的制备及表征

采用原位合成法和传统浸渍法以价格低廉的硝酸铝作为铝源, 聚乙二醇1540为模板剂, 硝酸镍为镍源, 制备出负载Ni金属有序介孔氧化铝催化剂, 并采用BET、TEM、XRD、TG多种测试技术对合成催化剂的物理化学性质和结构特征进行了表征. 实验结果表明, 两种方法均能制备出比表面积大(＞210 m2·g-1)、孔径分布窄(4 nm左右)的负载Ni金属介孔氧化铝催化剂. 与浸渍法相比, 原位合成法所制备的负载Ni金属有序介孔氧化铝镍离子与载体具有更强的相互作用力, 且孔结构具有一定的有序性.     

聚乙二醇/四氢呋喃三臂嵌段共聚醚的合成研究

以三臂聚乙二醇、四氢呋喃为主要原料,在三氟化硼乙醚的催化作用下进行阳离子开环聚合反应,合成了聚乙二醇-四氢呋喃三臂嵌段共聚醚.通过正交试验考察了反应时间、配料比、催化剂用量和助开环剂用量等因素对所合成的嵌段共聚醚羟值的影响,得到了合成较大相对分子质量三臂嵌段共聚醚的较佳合成条件,并采用红外光谱法、凝胶渗透色谱法、核磁共振测试对所合成的共聚醚进行了表征.     

负载型氧化锆催化剂上甲醇脱氢制甲醛

甲醇在无氧条件下脱氢,可以制得含水量极低的甲醛。在上述反应中,主要采用以硅胶为载体的负载型氧化物催化剂,其中以周期表ⅠB和ⅡB族金属,如铜、银或锌为主要组分。这些金属的氧化物在高温下易还原、烧结和表面积炭而使催化剂失活。添加P,S,Se或Te等组分作为助催化剂,在一定程度上可以改善催化性能。最近的发展倾向是采用非负载的碱金属盐作为催化剂,如Na_2CO_3,Na_2MoO_4,或Na_xLi_(1-x)AlO_2(0≤x≤1)。这类催化剂要求过高的反应温度,如高于650℃,甚至900℃条件下使用。     

What controls the pore spacing in porous anodic oxides?

In this paper, we use energy-based perturbation criteria to examine whether strain or electrostatic energy acts as a driving force for porosity initiation in anodic oxides. By doing so, we also succeeded to rationalise the dependence of pore spacing on anodising conditions. Our experimental approach consists of measuring in-situ the internal stress in anodic oxide films grown galvanostatically on aluminium in phosphoric acid, and to correlate these data with the measured pore spacing of the obtained porous films. Our results indicate that the possibility of a strain energy-induced surface instability is unlikely, as for this case the constitutive dependence of pore spacing on internal stress was not verified. Instead, the measured pore spacing, electric field and barrier oxide thickness obtained on our anodic alumina films indicate that electrostatic energy is the main driving force for pore initiation, as well as the factor controlling the pore spacing. Corroborative quantitative evidence for this novel electrostatic-based scaling law is provided by data compiled from the literature for a range of other anodic oxide systems, including nanoporous alumina and nanotubular titania films.     

High surface area, mesoporous, glassy alumina with a controllable pore size by nanocasting from carbon aerogels

A strategy to synthesize amorphous, mesoporous alumina by nanocasting has been developed, involving carbon aerogel as a hard template and aluminum nitrate solution as an alumina precursor. The alumina generated exhibits small, transparent granules with a 3-6 mm diameter and has inherited the three-dimensional network structure of the carbon template. The mesopore surface area of the alumina can be as high as 365 m2 g(-1), and the pore volume reaches 1.55 cm3 g(-1) after calcination at 600 degrees C in air for 8 h. The pore parameters can be varied within a certain range by variation of the carbon aerogel template and the loading amount of the alumina precursor. At high loadings, the obtained glassy alumina clearly has a bimodal pore size distribution in the mesopore range.     

负载型聚酰亚胺-二氧化硅-银杂化膜的制备和表征

采用溶胶凝胶法制备了硅藻莫来石负载的SiO2(SiO2KM)负载的聚酰亚胺二氧化硅银杂化膜,采用IR、TGA、SEM、XRD、氮吸附、气体渗透性能测量等方法对膜的性能进行了表征.银的加入使杂化溶胶的粘度增大,膜孔径增大,孔径分布弥散;二氧化硅在杂化膜中以无定型存在,银以氯化银的形式存在;Ag+和聚酰亚胺中的氮以配位键络合在一起,丙烯通过双键吸附在Ag+上;杂化膜热稳定性随二氧化硅的加入而增加,随银的加入而降低.丙烯丙烷在杂化膜上的分离因子为3.54～4.1,银的加入对丙烯的传输有明显的促进作用.     

Using Polymer-Colloid Complexes for Obtaining Mesoporous Aluminium Oxide by the Template Sol-Gel Method

The paper reports the results of using polymer-colloid complexes in solutions in order to control textural properties of mesoporous aluminium oxide in the sol–gel synthesis process. Polyethyleneimine, cetyltrimethylammonium chloride, as well as a polymer-colloid complex formed by their interaction in the solution were used as pore-forming templates. The mesoporous aluminium oxides synthesized in this work had a narrow pore size distribution and a large surface area. The application of different templates made it possible to affect the mechanism of supramolecular self–assembly of materials, namely by controlling the pore sizes. When the polymer-colloid complex was used as the template for the formation of aluminium oxide nanostructures, 6 nm cylindrical pores were formed, while using individual templates led to the formation of 8–13 nm mesopores. Identifying the formation mechanism of a certain pore type will make it possible to use these materials in specific reactions.     

Mesostructured gamma-Al(2)O(3) with a lathlike framework morphology

A novel three-step assembly pathway is reported for the formation of a mesostructured alumina with framework pore walls made of crystalline, lathlike gamma-Al(2)O(3) nanoparticles. In the initial supramolecular assembly step of the pathway a mesostructured alumina with a wormhole framework morphology and amorphous pore walls is assembled through the hydrolysis of Al(13) oligocations and hydrated aluminum cations in the presence of a nonionic diblock or triblock poly(ethylene oxide) surfactant as the structure-directing porogen. The walls of the initial mesostructure are then transformed in a second hydrolysis step at a higher temperature to a surfactant-boehmite mesophase, denoted MSU-S/B, with a lathlike framework made of boehmite nanoparticles. A final thermal reaction step topochemically converts the intermediate boehmitic mesophase to a mesostructure with crystalline gamma-Al(2)O(3) pore walls, denoted MSU-gamma, with retention of the lathlike framework morphology. The boehmitic MSU-S/B intermediates formed from the chloride salts of aluminum incorporate chloride anions into the mesostructure. Chloride ion incorporation tends to disorder the nanoparticle assembly process, leading to a broadening of the slit-shaped framework pores in the final MSU-gamma phases and to the introduction of intra- and interparticle textural mesopores. However, the well-ordered MSU-gamma phases made from aluminum nitrate as the preferred aluminum reagent exhibit narrow framework pore size distributions and average pore sizes that are independent of the surfactant size and packing parameter, in accord with a lathlike framework assembled from nanoparticles of regular size and connectivity. The high surface areas ( approximately 300-350 m(2)/g) and pore volumes ( approximately 0.45-0.75 cm(3)/g) provided by these mesostructured forms of gamma-Al(2)O(3) should be useful in materials and catalytic applications where the availability of surface Lewis acid sites and the dispersion of supported metal centers govern reactivity.     

Influence of different templates on the morphology of mesoporous aluminas

Mesoporous alumina has many environmental applications as catalysts support and adsorption or separation material. We studied the synthesis conditions for the mesoporous alumina formation from aluminum isopropoxide in the presence of anionic (lauric and stearic acid), cationic (cetyltrimethylammonium bromide, CTAB) and non-ionic (triblock poly(ethylene oxide)-poly(propylene oxide)-polyethyleneoxide, P123) templates. The X-ray diffraction data show that the alumina mesophases obtained at 550°C in the presence of fatty acids or P123 have amorphous walls, whereas the samples prepared at 500°C by using CTAB, in alkaline medium are crystalline with a γ-alumina structure. The solvothermal treatment caused the alumina mesophase with crystalline walls to be obtained at 550°C. The samples were investigated by nitrogen adsorption-desorption isotherms and scanning electron microscopy. The obtained alumina mesophases have specific surface areas in the range of 300–450 m² g⁻¹, narrow pore size distribution, and different morphology depending on the template used in the synthesis.      

Preparation of mesoporous alumina with large pore size and their supported rhenium oxide catalysts in metathesis of 1-butene and 2-butene to propene

Mesoporous γ-aluminas with large pore size(up to 19 nm,denoted as MA19) are prepared from dispersed pseudo-boehmite using pluronic P123 as template.It is found that these mesoporous alumina supported rhenium oxide catalysts were more active and have far longer working life-span in gas-phase metathesis of 1-butene and 2-butene to propene than rhenium oxide on conventional alumina with small pore size(5 nm).At 60°C and atmospheric pressure with WHSV = 1 h-1,the similar stable conversions of butene(ca.55%) for all the 13 wt% Re 2 O 7 /alumina catalysts were obtained near the chemical equilibrium,and the stable working life-spans of Re 2 O 7 /MA19 were far longer than that of Re 2 O 7 /Al 2 O 3,being about 70 h and 20 h,respectively.     

Turkish perlite supported nickel oxide as the heterogeneous acid catalyst for a series of Claisen–Schmidt condensation reactions

Potentially active and eco-friendly solid acid catalysts have been synthesized by loading different weight percentages (10, 15, and 50) of nickel oxide on thermally activated Turkish perlite through the deposition-precipitation method. Structural features of prepared catalysts were analyzed using BET surface area analysis, X-ray diffraction, scanning electron microscope (SEM), SEM-EDX, transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR), pyridine adsorbed FT-IR, UV-Vis diffuse reflectance spectroscopy (DRS), and thermogravimetric analysis (TGA) techniques. Pyridine adsorbed FT-IR analysis confirmed the presence of the optimum amount of Bronsted acidic sites in a catalyst having 15 wt. % loading of nickel oxide, which was tested for catalyzing a series of Claisen–Schmidt condensation of cyclohexanone and aromatic aldehydes to produce good isolated yield (90%–93%) of 2,6-bis(substituted benzylidene)cyclohexanones, significantly used in anti-tumor and cytotoxic activities. The high catalytic efficiency of the chosen catalyst remains almost intact up to six reaction cycles. On higher wt. % loading of nickel oxide, crystallite size increases along with agglomeration of larger nickel oxide particles on catalyst surface resulting in pore blockage and poor catalytic activity. Loading of NiO on the surface of thermally activated Turkish perlite was confirmed by SEM-EDX analysis, and TEM observations show that the particle size of the preferred catalyst was less than 50 nm. Based on results drawn from XRD, FT-IR, pyridine adsorbed FT-IR, UV-Vis DRS studies, model structures were proposed for Turkish perlite and all prepared catalysts. During this work, the catalytic potential of the preferred catalyst was compared with other previously reported catalysts, and it showed appreciable results. The formed products were further confirmed by their melting point and ¹H-NMR analysis.     

Silica–silver nanostructured spheres prepared by spray pyrolysis of sol containing silver precursor

Silver–silica nanostructured composites were prepared by spray pyrolysis of aqueous sols of silica nanoparticles containing silver nitrate. The physical and chemical characteristics of the composites prepared at different Ag/Si atomic ratio in the sols and temperatures of pyrolysis were examined by TEM, SEM, XRD, FT-IR and UV-visible spectra. For the low silver ratios up to 0.2, well-dispersed silver particles were produced in the pore of the silica agglomerates with their size and surface plasmon resonance depending on the pore size and silver mobility, in addition to the loading and temperature. The formation of silver silicate and new-phase silica as well as crystallinity of the silver prepared was discussed. There was also explained how the temperature of preparation affected the morphologies of the composites produced with higher Ag/Si ratios greater than 1. Mechanism on the formation of silver–silica composites was proposed for the wide range of the ratios from 0.01 to 3.