一种合成六方板状Zr-Ce-SBA-15介孔材料的新方法

以P123为模板剂, 正硅酸乙酯为硅源, 氯化氧锆和硝酸亚铈为无机前驱盐, 在不外加无机酸的条件下, 利用无机前驱盐自身水解产生的弱酸性环境, 通过水热合成路线一步合成了具有大的径轴比、短孔道、六方板状形貌的Zr-Ce-SBA-15介孔材料. 利用粉末X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、电感耦合等离子体原子发射光谱(ICP-AES)和氮气吸附等手段对所合成的样品进行了表征. 结果表明, 合成的材料具有类似于SBA-15的二维六方介孔结构, 孔径、孔容和比表面积分别为5.6 nm, 0.96 cm3/g和776 m2/g. 与常规SBA-15相比, 这种短孔道、大径轴比的六方板状介孔材料在吸附、分离及催化等领域中能更有效地促进分子的扩散传递.     

TEPA功能化SBA-15的CO_2吸附性能

以正硅酸乙酯(TEOS)为硅源,P123为模板剂,通过加入适量HAc及调整反应体系pH方式,采用水热及萃取法合成表面羟基含量较高的介孔SBA-15材料.以不同含量四乙烯五胺(TEPA)对SBA-15进行功能化,获得氨基功能化介孔SBA-15材料.利用X射线衍射(XRD)、N2吸-脱附、傅里叶红外光谱(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、元素分析等手段对材料结构性能进行表征.以不同含量TEPA功能化介孔SBA-15为吸附剂,对CO_2进行吸附,考察了吸附温度、CO_2浓度、水等对吸附效率的影响.实验结果表明,常温、常压下30%TEPA功能化介孔SBA-15的CO_2吸附量最高,且重复使用性能良好.     

磁性功能介孔材料固相萃取-气相色谱法测定水中的多氯联苯

采用一锅法合成Fe₃O₄纳米粒子,并利用溶胶-凝胶法制备了SBA-15@Fe₃O₄磁性介孔复合材料。以介孔二氧化硅材料(SBA-15)的表面硅羟基为靶位,借助苯基三氯硅烷与硅羟基的硅烷化反应将苯基基团接枝到材料表面,得到苯基功能化磁性介孔材料Ph-SBA-15@Fe₃O₄,该材料有良好的疏水性,并保留了SBA-15的有序二维六方孔道结构。将其用于磁性固相萃取(MSPE)吸附水样中的多氯联苯(PCBs),建立了气相色谱-电子捕获检测法(GC-ECD)检测PCBs。在优化条件下,7种PCBs在0.025～50μg/L范围内呈良好线性关系,线性相关系数(R²)均大于0.9999,方法回收率为89.8%～108%。该方法可用于实际水样中痕量PCBs的高效快速检测。     

介孔材料氨基表面修饰及其对CO2的吸附性能

采用接枝方法在介孔材料MCM-41和SBA-15的孔道内表面进行氨基化修饰, XRD、29Si-NMR、FT-IR、TGA、BET等测试结果表明, 氨丙基三乙氧基硅烷(APTS)和氨乙基氨丙基甲基二甲氧基硅烷(AEAPMDS)都分别接枝在介孔材料的孔道内, 表面氨基修饰量约为1.5-2.9 mmol·g-1. 表面修饰后介孔材料的孔道仍高度有序, 但比表面积减小. 表面修饰前后介孔材料对CO2的吸附性能发生显著变化, 由于物理吸附转化为以氨基为活性中心的化学吸附, 吸附量从修饰前的0.67 mmol·g-1提高到2.20 mmol·g-1.     

片/板状短孔道SBA-15的控制合成及应用

有序介孔材料家族中,SBA-15因具有较大的孔径尺寸、规则可调的孔道结构以及卓越的机械和水热稳定性而备受关注。最近,片/板状短孔道SBA-15由于更有利于分子快速扩散和质量传递成为介孔材料研究领域的热点。目前合成片/板状短孔道SBA-15的主要方法有有机物辅助、金属离子诱导及多重模板剂协同效应。根据不同类别添加剂的作用机制,本文综述了片/板状短孔道SBA-15的控制合成方法及其在催化、吸附和生物分子固定等不同领域的最新进展,并对其应用前景进行了展望。     

有序介孔胺化的聚合物材料的合成及在Knoevenagel缩合反应中的催化性能

通过氯化和胺化等手段对有序介孔聚合物材料(FDU-16)进行功能化, 成功地将胺基引入到介孔聚合物骨架中, 制备出新型有序介孔固体碱催化材料. X射线衍射(XRD)、 氮气吸附-脱附及透射电子显微镜(TEM)表征结果表明, 功能化后的固体碱材料依然保持高度有序性; 红外表征结果表明, 大量的胺基被引入到材料的骨架中. 在Knoevenagel缩合中, 这种新型有序介孔固体碱材料表现出比功能化的介孔二氧化硅等材料更高的催化活性, 这主要归因于其具有较高的比表面积、较强的碱性以及较多的活性中心.     

金在氨基硅烷修饰SBA-15上的巴豆醛选择加氢性能

采用三种氨基硅烷试剂(APTS: 3-氨丙基三甲氧基硅烷, TPED: N-(2-氨乙基)-3-氨丙基三甲氧基硅烷, TPDT: 3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷)对介孔SBA-15分子筛进行后嫁接表面功能化(分别记为APTS-SBA-15, TPED-SBA-15和TPDT-SBA-15), 然后利用氨基与氯金酸之间的静电作用及化学还原法, 将金纳米粒子引入分子筛的介孔孔道. 采用N₂物理吸附、X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等手段对催化剂的结构和电子性质进行了系统表征; 以巴豆醛液相加氢制巴豆醇反应比较了氨基硅烷的种类对催化性能的影响. 结果表明, 氨基硅烷的给电子能力是决定金催化剂上C＝O键加氢选择性的主要因素, 氨基硅烷的给电子能力越强, 金活性位上的电子密度越高, 则巴豆醇的选择性和收率就越高.     

功能化有序介孔碳对重金属离子Cu(Ⅱ)、Cr(Ⅵ)的选择性吸附行为

以三嵌段共聚物F127为模板剂,酚醛树脂为碳源,正硅酸乙酯为硅源,三组分共组装合成介孔碳-氧化硅纳米复合物,再经HF去除氧化硅,得到有序介孔碳(OMC).X射线衍射(XRD)、透射电子显微镜(TEM)、低温N2吸脱附(BET)等测试表明,所得样品具有高度有序的介孔结构,比表面积和孔容分别为1330m2·g-1和2.13cm3·g-1,平均孔径6.4nm.对其先氧化、后氯化、再胺化,得到不同胺基接枝量的胺化介孔碳(C-NH2(m),m为加入的乙二胺的质量(g)).傅里叶变换红外(FT-IR)光谱表征结果证实,胺基官能团成功接枝到有序介孔碳表面.TEM测试表明介孔碳的有序孔道结构得到了较好的保持.以有序介孔碳、胺化介孔碳作吸附剂对Cu(Ⅱ)、Cr(Ⅵ)进行选择性吸附研究.结果表明:功能化修饰前,样品对Cu(Ⅱ)、Cr(Ⅵ)饱和吸附量分别为213.33、241.55mg·g-1;修饰后饱和吸附量可分别达到495.05、68.21mg·g-1.功能化介孔碳表现了较强的选择性吸附Cu(Ⅱ)的能力.     

酸诱导介观相转变硅基介孔材料的合成机理及其改性

采用两步法以三嵌段共聚物P104(PEO27-PPO61-PEO27)为模板剂合成介孔材料, 研究了介孔材料结构随体系pH 值的变化, 探讨了体系中介观相转变的机理. 研究表明,随着pH 的升高, 发现体系中无机物种和模板剂所组成的介观相发生了转变,由P6mm 的SBA-15(pH=1.51-2.67)2D六角孔道结构转变为3D 蠕虫状孔道的MSU-X(pH=3.93-4.56)结构. 对所得的两种不同种类的硅基材料以γ-胺丙基三乙氧基硅烷(APTES: NH2(CH2)3Si(C2H5O)3)进行表面烷基化改性结果表明, 在同样的条件下, 经过改性后MSU-X类介孔材料孔壁上接枝的烷基数目要远超过SBA-15 类介孔材料.     

共聚法和嫁接法制备二茂铁杂化介孔材料及其催化性能

 以桥联硅氧烷 1,1'-双[(2-三乙氧基硅基) 乙基]二茂铁 (BTEF) 和正硅酸乙酯为前驱体, 以十六烷基三甲基溴化铵为结构导向剂, 采用共聚法制备了二茂铁功能化的周期介孔有机硅烷材料 (PMO-Fc). 同时以 BTEF 为修饰剂, 以甲苯为分散剂, 采用嫁接法制备了 Fc-MCM-41 杂化介孔材料. 采用 N2 物理吸附、X 射线衍射、透射电镜和红外光谱等手段对材料进行了表征, 评价了其催化苯羟化反应活性. 结果表明, PMO-Fc 具有有序的二维六方形孔道结构, 较大的比表面积和孔体积, 在苯羟化反应中表现出比 Fc-MCM-41 更高的催化活性, 苯酚的选择性和收率分别为 65.3% 和 20.2%.     

Amino-functionalized SBA-15 type mesoporous silica having nanostructured hexagonal platelet morphology

Amino-functionalized SBA-15 type mesoporous silicas having unique hexagonal platelet morphologies with short channels (100-300 nm) running parallel to the thickness of the nanostructured hexagonal platelet type morphologies have been directly synthesized by co-condensation of aminopropyltriethoxysilane (APTES) and sodium metasilicate as a silica source in the presence of Pluronic P123 triblock copolymer as a structure directing agent.     

富含羧基的球形介孔分子筛SBA-15的合成及药物释放性能

本文采用原位合成法合成了富含羧基的SBA-15球形介孔分子筛. 研究了修饰剂（三烷氧基氰乙基硅烷 CTES）的用量对介孔分子筛SBA-15形貌、孔径及BET比表面积的影响. 用粉末X射线衍射(XRD)、扫描电镜(SEM)、红外（IR）和氮气吸附/脱附对样品进行了详细的表征. 该材料展示了尺寸在0.5-1 μm规则的球形形貌、有序的二维六方相介孔结构、较大的比表面积和孔容、并且随着修饰剂用量的增加, SBA-15的孔径变小, 比表面积下降. 药物组装及缓释性能测试表明, 该材料具有较好的药物组装及缓释释放性能. 该材料在催化、药物载体和色谱分析填料等领域将具有潜在的应用.     

六方平板状氨基-甲基双官能化SBA-15的合成及对胆红素的吸附

以氨丙基甲基二乙氧基硅烷和正硅酸乙酯为硅源,三嵌段共聚物P123为模板剂,无机盐KCl为助剂,酸性条件下一步法合成了氨基-甲基双官能化SBA-15（AMS）. XRD,FTIR,BET,29Si MAS NMR,SEM及HRTEM等表征结果表明：无机盐不仅提高了AMS材料的介孔有序度,而且控制样品形貌从六方平板状向纤维状转变. 胆红素吸附实验表明：六方平板状AMS比纤维状AMS和纯SBA-15具有更快的吸附速率和更大的吸附容量,这可能是六方平板状形貌易于胆红素扩散以及双官能基团（甲基,氨基）增加了对胆红素吸附作用力的结果.     

SBA-15负载CeO2纳米晶的溶胶-凝胶一步合成

以P123为模板剂, 正硅酸乙酯和硝酸铈为前驱体, 通过溶胶-凝胶路线在酸性条件下合成了SBA-15负载氧化铈(CeO2与SiO2质量比为28.7%)有序介孔材料. 采用热重/差热分析(TGA/DTA)、X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明, 合成的材料具有类似于SBA-15的结构, 孔径、孔容和比表面积分别为38.7 Å, 0.46 cm3/g和570 m2/g. X射线衍射(XRD)、透射电镜(TEM)、X射线能谱(EDS)和选区电子衍射花样联合表征证实了铈物种以高分散的CeO2纳米晶的形式分布在介孔基体中.     

Synthesis of carboxyl-modified rod-like SBA-15 by rapid co-condensation

Carboxyl-modified SBA-15 rod-like mesoporous materials have been synthesized by a facile rapid co-condensation of tetraethylorthosilicate (TEOS) and 2-cyanoethyltriethoxysilane (CTES), followed by hydrolysis of cyanide groups in sulfuric acid. The concentration of carboxylic groups was varied by changing the silica source ratio of CTES/TEOS from 0.05 to 0.3. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the uniform ordered mesoporous structure and rod-like morphology of SBA-15 have been preserved even at the high concentration of carboxylic groups employed. Characterization by Fourier transformed infrared spectroscopy (FTIR), solid-state NMR investigation indicated that carboxylic groups have been successfully grafted onto the surface of SBA-15 through siloxane bonds [(O(3))SiCH(2)CH(2)COOH. The negative charges of the modified SBA-15 materials were enhanced by the presence of the carboxylic groups on the surface. The capacity of lysozyme adsorption of the modified SBA-15 materials were found to be significantly improved as compared with pure silica SBA-15. The maximum amount of lysozyme adsorption on carboxyl-modified was increased with the pH of solution increased from 5.5 to 9.0.     

Synthesis, characterization, and catalytic performance of copper-containing SBA-15 in the phenol hydroxylation

A series of copper-containing SBA-15 samples were successfully synthesized via evaporation-induced self-assembly route. The resulting materials were characterized by X-ray diffraction (XRD), (29)Si MAS NMR spectroscopy, transmission electron microscopy (TEM), N(2) sorption, inductively coupling plasma-atomic emission spectrometer (ICP-AES), thermogravimetry, and differential thermal analysis (TG-DTA), Fourier-transform infrared spectroscopy (FT-IR), UV-vis diffuse reflectance spectra (UV-vis) and X-ray photoelectron spectroscopy (XPS). The results indicated that: (1) all the samples exhibited typical hexagonal arrangement of mesoporous structure; (2) copper ions could be incorporated into the framework of SBA-15; (3) the addition of urea in the hydrothermal stage efficiently reduced the leaching of copper and improved the thermal stability of the mesoporous materials. Catalytic performances of the obtained materials were evaluated in the hydroxylation of phenol with H(2)O(2). The catalytic tests showed that the synthesized materials exhibited high activity for this reaction and copper ions in the framework were more active than copper species in the extra-framework position. The nitric acid treatment on the samples removed the bulk CuO species, which resulted in a dramatic increase in the catalytic activity.     

CeO_2/Ni/Mo/SBA-15甲烷二氧化碳重整催化剂的表征和催化性能(英文)

考察了CeO2修饰及未修饰的Ni/Mo/SBA-15催化剂在CH4-CO2重整上的催化性能并采用N2吸脱附、CO2程序升温脱附、H2程序升温还原、傅里叶红外光谱、X射线衍射、扫描电子显微镜和X射线光电子能谱对催化剂进行了表征.结果表明,在常压,800oC条件下,经过100h在线评价后,Ni/Mo/SBA-15和CeO2/Ni/Mo/SBA-15催化剂仍具有高的反应活性和规整的六方介孔结构,其中CeO2修饰的CeO2/Ni/Mo/SBA-15催化剂表面没有积炭形成,表明CeO2的加入促进了Ni物种在SBA-15介孔分子筛表面的分散,从而阻止了Ce/Ni/Mo/SBA-15催化剂上Ni的烧结和积炭.     

SBA-15表面改性及其对介孔La0.8Sr0.2CoO3钙钛矿型催化剂结构和性能的影响

Mesoporous SBA-15 with mesopore diameter up to 10.1 nm was prepared by a hydrothermal method, and was further functionalized to obtain different surface properties. Thus-prepared SBA-15 was employed as a template to synthesize rhombohedrally crystallized mesoporous La_0.8Sr_0.2CoO₃ perovskite via a nanocasting method. The surface properties of the SBA-15 were adjusted by treatment with concentrated hydrochloric acid, trimethylchlorosilane (TMCS), and 3-aminopropyltriethoxysilane (APTES). A series of characterization techniques verified that all the synthesized templates possessed ordered two-dimensional hexagonal mesoporous structure, and the surface was successfully modified with methyl and amino groups. The mesoporous perovskite structure was formed in the samples and the surface properties of SBA-15 significantly influenced the structure and properties of La_0.8Sr_0.2CoO₃ perovskite oxides. Wide-angle X-ray diffraction patterns suggested that the modified silica templates were conducive to the formation of pure perovskite frameworks with good crystallinity. The catalysts also possessed mesoporous structure, as confirmed by small-angle XRD patterns, high-resolution transmission electron microscopy images, and nitrogen adsorption analysis. Moreover, the La_0.8Sr_0.2CoO₃ materials synthesized using surface-functionalized templates exhibited relatively higher catalytic activity and stability in CO oxidation. Complete CO conversion could be achieved at 140℃ using the thus-prepared La_0.8Sr_0.2CoO₃ materials, and no significant loss in catalytic activity was observed after 100 h of on-stream reaction experiments. X-ray photoelectron spectroscopy, H₂ temperature-programmed reduction, and O₂ temperature-programmed desorption experiments revealed that the existence of Co⁴⁺, Sr enrichment in the perovskite structure, and high content of adsorbed oxygen species play a critical role in the enhanced catalytic activity of the catalysts. We also proposed the possible reasons for the effect of surface properties of the silica templates on the structure and properties of the La_0.8Sr_0.2CoO₃ nanomaterials.     

有序介孔二氧化硅对正丁醛的吸附性能

合成了一系列具有不同孔结构与性质的有序介孔二氧化硅材料SBA-15、MCM-41、SBA-16、KIT-6,同时通过改变水热温度制备了不同孔径大小的SBA-15,并利用小角X射线散射、透射电镜、扫描电镜和氮气吸附-脱附等手段,对其介孔结构进行了表征.以正丁醛为探针分子,考察了其对有机醛的吸附,并与Y-沸石的吸附性能做了对比.结果表明,材料的介孔比表面积与其对正丁醛的吸附量成正比,吸附等温线符合Langmuir模型,属于单层吸附,具有最大介孔比表面积的MCM-41对正丁醛的吸附量最大(484 mg·g-1).最后将SBA-15添加到卷烟滤嘴中,实验结果表明,SBA-15能显著降低卷烟烟气中巴豆醛的释放量.     

有序介孔二氧化硅对正丁醛的吸附性能

合成了一系列具有不同孔结构与性质的有序介孔二氧化硅材料SBA-15、MCM-41、SBA-16、KIT-6, 同时通过改变水热温度制备了不同孔径大小的SBA-15, 并利用小角X射线散射、透射电镜、扫描电镜和氮气吸附-脱附等手段, 对其介孔结构进行了表征. 以正丁醛为探针分子, 考察了其对有机醛的吸附, 并与Y-沸石的吸附性能做了对比. 结果表明, 材料的介孔比表面积与其对正丁醛的吸附量成正比, 吸附等温线符合Langmuir 模型, 属于单层吸附, 具有最大介孔比表面积的MCM-41对正丁醛的吸附量最大(484 mg·g^-1). 最后将SBA-15添加到卷烟滤嘴中, 实验结果表明, SBA-15能显著降低卷烟烟气中巴豆醛的释放量.