Different Synthesis Methods for Ordered Mesoporous Silicas And Their Characteristics Comparison

1　IntroductionInorganicmesoporousmaterialshaveahighpotentialforapplicationsinthefieldsofcatalysis,adsorption ,sepa rationprocesses,biologymaterials,novelopticalmaterialsetc.Mesoporousmaterialshaverapidlyattractedresearchinterestsinthefieldofphysics,chemistryandmaterialssince 1 990s.Oneofthemostrepresentativemesoporousmaterialsismesoporoussilicapreparedbyusingalkylquaternaryammoniumcationicsurfactantsastemplate[1 3 ].Recently ,themesoporoussilicahasbecomeoneofthemostactivefieldsofhost guestass…     

渝东南地区海相页岩有机质孔隙发育特征

有机质孔隙是高—过成熟海相页岩主要的气体储集空间。基于四川盆地东南部(渝东南地区)五峰组—龙马溪组页岩研究,将有机质划分为干酪根和沥青两种基本类型,其中,干酪根可进一步划分为无结构型干酪根和结构型干酪根两种类型,沥青可划分为固体沥青和复合有机质; 根据有机质孔隙的分布和发育特征,将其划分为干酪根内孔隙、海绵状孔隙和气泡状孔隙3种类型。通过扫描电镜实验和ImageJ软件提取有机质孔隙,结合圆度、凸性、伸长率、分形维数等孔隙形态参数分析不同类型有机质孔隙发育特征。结果表明:①随总有机碳的增加,有机质面孔率逐渐增加; ②当总有机碳低于2%时,随总有机碳的增加,平均孔径、分形维数逐渐减小,有机质孔隙趋于均一; 当总有机碳高于2%,随总有机碳的增加,平均孔径、分形维数逐渐增大,有机质孔隙趋于复杂; ③无结构型干酪根有机质孔隙以微孔(孔径小于25 nm)和小孔(孔径为25～100 nm)为主,发育少量中孔(孔径为100～1 000 nm); 结构型干酪根有机质孔隙以微孔为主,小孔其次,中孔发育较少; 沥青有机质孔隙以小孔为主,发育部分中孔和大孔(孔径大于1 000 nm); ④与沥青有机质孔隙相比,干酪根有机质孔隙圆度、凸性较大,伸长率较低; 但由于干酪根有机质孔隙的平均孔径较小,小孔含量高,分形维数相较于沥青偏高。     

Preparation and characterization of 3-dimensionally ordered macroporous SiC

Compared with the non-ordered macroporous materials, 3D long range ordered macroporous materials exhibit many advanced properties, such as the uniform pore size and the high permeability, etc. Nowadays, many kinds of 3D ordered macroporous (3DOM) materials, such as oxide ceramics[1―4], carbon[5] and polymers[6,7], have been successfully fabricated. However, the developed porous materials have some drawbacks that the porous carbon and polymer cannot be used in air at high temperatures, and o…     

Synthesis and Characterization of Carboxyl-terminated Polyethylene Glycol Functionalized Mesoporous Silica Nanoparticles

Colloidal mesoporous silica nanoparticles functionalized with carboxy-terminated polyethylene glycol(CMS-PEG-COOH) were successfully synthesized by covalently grafting dicarboxy-terminated polyethylene glycol(HOOC-PEG-COOH) on the surface of the amino functionalized CMS nanoparticles with amide bond as a cross linker. Moreover, the structural and particle properties of CMS-PEG-COOH were characterized by nuclear magnetic resonance spectroscopy(1 H-NMR), transmission electron microscopy(TEM), dynamic light scattering(DLS), nitrogen adsorption-desorption measurements, X-ray diffraction(XRD), and Fourier transform infrared spectroscopy(FT-IR). The nanomaterials presented a relatively uniform spherical shape morphology with diameters of about 120 nm,and favorable dispersibility in weak acid solution. The CMSPEG-COOH exhibited no changes in the state of amorphous, while the mesopores sizes of 5.25 nm might provide the nanomaterials with large capacity for the loading and releasing of drugs. So the results indicated that CMSPEG-COOH might be a critical nanomaterial for drug delivery system in the future.     

介孔氧化铟纳米粒子的制备及其气敏性质

以介孔氧化硅KIT-6为硬模板制备了介孔氧化铟纳米粒子,并对其进行了X射线粉末衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、氮气物理吸附分析。介孔氧化铟纳米粒子具有高的结晶度和有序介观结构,其尺寸为100 nm左右,比表面积为82 m2/g,孔径为4.5 nm左右,孔体积为0.42cm3/g。气敏性能测试结果表明介孔氧化铟纳米粒子对乙醇具有较好的敏感度,优于体相的氧化铟颗粒,在乙醇气体检测方面有潜在的应用。     

Size determination of ultramicropores and small mesopores using a calculation procedure based on the tangents of comparison plot

Pore size distribution (PSD) curves of synthesized hollow silica spheres with ultrmicropores and small mesopores were obtained from calculations based on the BJH, KJS, SF, MP, NLDFT models and Prof. Zhu’s method. Comparisons indicate that Zhu’s method not only gives reasonable small mesopore size but also could be further extended to the ultramicropores region for the PSD evaluation.     

离子液体[C_6mim]Br中TiO_2气凝胶的制备

以钛酸四丁酯为前驱体,离子液体[C6mim]Br为催化剂及模板剂,在低温、常压条件下制备了TiO2气凝胶。利用扫描电子显微镜(SEM)、X射线衍射(XRD)及N2吸附/脱附法对结构进行了分析。结果表明,TiO2气凝胶为锐钛矿晶体结构,平均孔径为9.7nm,比表面积为264.3m2/g,孔体积为0.513cm3/g。以活性蓝为模拟污染物,紫外汞灯为光源,研究了TiO2气凝胶的光催化活性。结果表明,TiO2气凝胶具有优于P25的光催化活性。     

离子交换法合成L/MCM-41复合分子筛

以十六烷基三甲基溴化铵(CTAB)为模板剂,分别采用包埋法和离子交换法,两步晶化都合成了L/MCM-41复合分子筛,并通过XRD、SEM、TEM和BET等测试手段对合成样品进行表征,检测结果表明用离子交换法合成的复合分子筛孔径为3.04 nm.与水热晶化法合成的MCM-41相比:(1)壁厚由0.55 nm增大到1.81 nm;(2)水热稳定性也明显提高,在100℃沸腾状态下结构保持时间由原来的低于2 h增大到8 h.与L沸石相比,K+含量降低为0.26%.     

Synthesis of mesoporous carbon as electrode material for supercapacitor by modified template method

The pore structures and electrochemical performances of mesoporous carbons prepared by silica sol template method as electrode material for supercapacitor were investigated. The mean pore size and mass specific capacitance of the mesoporous carbons increase with the increase of mass ratio of silica sol to carbon source （glucose）. A modified template method, combining silica sol template method and ZnCl2 chemical activation method, was proposed to improve the mass specific capacitance of the mesoporous carbon with an improved BET surface area. The correlation of rate capability and pore structure was studied by constant current discharge and electrochemical impedance spectroscopy. A commercially available microporous carbon was used for comparison. The result shows that mesoporous carbon with a larger pore size displays a higher rate capability. Mesoporous carbon synthesized by modified template method has both high mass specific capacitance and good rate capability.     

Preparation and Characterization of Carboxyl Functionalized Fluorescent Mesoporous Silica Nanoparticles Containing 8-Hydroxyquinolinate Zinc Complexes

Fluorescent mesoporous silica nanoparticles functionalized with carboxyl group(Znq-CMSCOOH) were successfully synthesized by in situ formation route of 8-hydroxyquinolinate zinc complexes in channels of mesoporous silica nanoparticles and post-grafting of carboxyl group on the surface. Moreover,the particle size and structural properties of Znq-CMS-COOH were characterized by transmission electron microscopy(TEM), field emission scanning electron microscopy(FE-SEM), dynamic light scattering(DLS),Fourier transform infrared spectroscopy(FT-IR), UV-vis spectrometer, fluorescence spectrometer and nitrogen adsorption-desorption measurements. The obtained results suggest that the Znq-CMS-COOH presents the uniform spherical shape with the mean diameter of about 85 nm and the obvious wormhole arrangement mesoporous. In addition, the Znq-CMS-COOH possesses green fluorescence with the emission peaks at 495 nm. So the Znq-CMS-COOH, which is beneficial to further modification and tracing, might be a great potential carrier for applying in drug delivery system in the future.     

二氧化硅中空微球的制备与表征

以正硅酸乙酯为硅源,聚乙二醇为软模板,氨水为沉淀剂,室温下采用沉淀法制备出二氧化硅空心微球。通过扫描电子显微镜(SEM)和透射电子显微镜(TEM)对其进行表征,结果表明,制备的二氧化硅空心球粒径100～250nm,壳层厚度10nm,表面光滑,球形规整度好。     

Structrue and Characteristics of Mesoporous Silica Synthesized in Acid Medium and Its Reaction Mechanism

Structrue and pore characteristics of the mesoporous silica synthesized in acid medium were studied by means of XRD, HRTEM, BET, FT-IR, DSC-TGA, and the reaction mechanism was also investigated deeply. The results show that mesopores in the sample possess hexagonal arrays obviously, whereas the structure of silica matrix is amorphous. The results also show that the acting mode of silica and CTMA^ inside the mesopores was chemical bonding force. The structure of rnesoporous silica was mainly dependent on the aggregational condition of micelle of CTMA^ as well as their liquid- crystallized status. In addition, condensation and dehydration of silicate radicals were accompanied in the process of calcination, which resulted in the mesoporous structure ordered in local range and the pore sizes largening.     

琼脂糖凝胶中树枝状银的生长研究

以琼脂糖凝胶作为模板、还原剂和稳定剂,通过溶胶-凝胶法制备琼脂糖/纳米银复合凝胶,对所得到的银纳米粒子进行了表征. 在复合凝胶外侧使用铝箔破坏凝胶中银纳米粒子的平衡状态,实现银纳米粒子在凝胶中的聚集并生成三维树枝状结构,并对树枝状银进行了表征. 结果表明,银纳米粒子为球形,粒径在20 nm左右,分散性好. 以琼脂糖凝胶为模板生长的树枝状银形状完整,尺寸与复合凝胶的样品大小有关,可达厘米级. 树枝状银的形貌可通过改变硝酸银浓度进行调控. 树枝状银结构的形成是扩散限制凝聚的结果. 关键词:琼脂糖;银纳米粒子;树枝状银;复合凝胶;可控制备     

模板剂结构和合成温度对两步法制备介孔硅结构的影响

以F108和F127为模板剂,在不添加无机盐或辅助剂情况下,采用两步法在弱酸性体系中分别制备了具有Im3m结构的SBA．16及Fm3m结构的FDU-12硅基介孔材料．采用X射线衍射（XRD）、透射电子显微镜（TEM）及氮气吸附-脱附对其进行了表征,结果显示：在此条件下制备的两种不同结构的立方介孔硅均为典型的小孔（3．57～4．26nm）厚壁（9．68～9．81nm）型硅基介孔材料．结合制备过程中反应物组成及合成温度对形成小孔厚壁型介孔材料的过程进行了讨论．对体系合成温度变化的研究表明：温度的微小变化对最终产物有序性有着很大的影响,而最终产物的结构则是由所用的模板剂结构决定的．     

介孔碳片的合成及吸附脱硫性能

采用溶胶-凝胶法,以三嵌段共聚物聚氧化乙烯氧化丙烯氧化乙烯EO27- PO61-EO27 (P104)为模板剂,蔗糖为共模板,正硅酸乙酯(TEOS)为硅源,在强酸性及无机盐存在条件下制备出介孔硅片,并以此为硬模板,通过浓硫酸处理的方法成功制备了介孔碳片.并采用扫描电子显微镜、N2吸附-脱附实验对合成的介孔碳片进行了表征...     

工业钛液制备介孔TiO2及其催化性能研究

以工业钛液为钛源,通过CTAB/P123复合模板剂形成的超分子自组装结构诱导钛的水解、缩聚得介孔TiO2前驱体,经臭氧氧化、多次萃取、分步焙烧脱模后得介孔TiO2。采用XRD、粒度分布、等温N2吸附及FT-IR等对样品进行表征。前驱体、脱模中间物及产物均为比表面积大、六方排列的锐钛型介孔结构。随着模板剂的脱除,样品的总钛含量增大,结晶度提高,产物介孔TiO2的孔径分布窄,平均孔径为3.23nm,SBET为281.5m2/g。比表面积的提高,锐钛晶型的改善及表面吸附键合的少量硫酸根等强化了介孔TiO2的催化性能,其对亚甲基蓝光催化氧化降解及乙酸乙酯酯化反应均表现出高的活性。     

Pore structure of new composite adsorbent SiO<Subscript>2</Subscript>·<Emphasis Type="Italic">x</Emphasis>H<Subscript>2</Subscript>O· <Emphasis Type="Italic">y</Emphasis>CaCl<Subscript>2</Subscript> with high uptake of water from air

A new composite adsorbent SiO₂·xH₂O·yCaCl₂ which is composed of macro-porous silica gel and calcium chloride is introduced. In order to analyze its adsorption theory, adsorption and desorption isotherms, BET surface areas, pore volumes and average pore diameters of macro-porous silica gel and four composite adsorbent samples with different CaCl₂ content are measured using SEM and Asap2010 apparatus. From the adsorption isotherms, desorption isotherms and lag loops, it can be deduced that the main pore structure in macro-porous silica gel and the new composite adsorbent have two shapes: taper with one top open and taper or hyperbolic taper with both ends open. Based on the analysis of pore diameter distribution and lag loop, a sketch map showing calcium chloride filled in pore of macro-porous silica gel is presented. The adsorption isotherms at 25°C are measured. Experimental results show that the new composite adsorbent can adsorb more water than common adsorbents (macro-porous silica gel, micro-porous silica gel and synthetic zeolite 13X). In the light of the results of pore structure, adsorption isotherms and lyolysis phenomenon are analyzed.     

Preparation and characterization of the system SiO2-CaO-P2O5 bioactive glasses by microemulsion approach

The system of SiO₂-CaO-P₂O₅ bioactive glasses (BG) were successfully synthesized by microemulsion approach. X-ray diffraction (XRD),scanning electron micro scopy(SEM) and energy dispersive X-ray (EDX) analyses, transmission electron microscopy(TEM),Fourier transform infrared spectroscopy (FTIR), BET N₂ gas adsorption analysis techniques were utilized in order to evaluate the phase composition, dimension, morphology, interconnectivity of pores and particle size of the synthesized BG respectiveely. The biocompatibility of BG was assessed by using dimethylthiazol diphenyl tetrazolium bromide (MTT).The BG scaffolds were implanted in rabbit mandibles and studied histologically. The results showed that the BG with a particle size less than 100 nm was prepared successfully. The measured BET specific surface area and pore volume was 113.9 m²/g and 0.28 cm³/g respectively. Cell cultures revealed that BG has been shown to have good biocompatibility and is also beneficial to the survival of Schwann cells, which can promote cell proliferation in vivo assay indicating that the BG can promote osteoconductivity.     

基于PVP模板剂水热法制备TiO_2纳米管

以聚乙稀吡咯烷酮(PVP)为模板剂,钛酸四正丁酯为钛源,水热法制备TiO2纳米管.分别采用X射线粉末衍射仪(XRD)、红外光谱仪(FT-IR)、透射电子显微镜(TEM)和比表面积孔径分析仪对产物的晶相、结构、形貌、比表面积和孔径分布进行了表征.考察了所制备TiO2纳米管的水热稳定性和热稳定性.结果表明:用PVP为模板剂能制得高比表面积的TiO2纳米管,其管径约在6～8 nm之间.所制备的TiO2纳米管,100℃水热处理7 d,500℃焙烧3 h后,TiO2纳米管的结构没有被破坏,说明制备出了具有较高的热稳定性和水热稳定性的TiO2纳米管.     

仿生合成SiO2载体及其固定脂肪酶的条件研究

采用L-脯氨酸为模板,仿生制备用于固定脂肪酶的二氧化硅载体．SEM、IR表征得知,制备的仿生载体为粒径约3um的SiO2微球,氮气吸附表征得知,SiO2微球内部孔径大小约16．8nm．载体固定脂肪酶的实验结果表明,固定化脂肪酶的相对最佳条件：酶液质量浓度5mg／mL,反应温度40℃,反应时间7h,pH=8,最高固载率可达82．3％,酶活1067U／g载体．