铈在六方介孔氧化硅中的液相移植及原子荧光特性

采用液相移植法制备了Ce掺杂六方介孔氧化硅材料,并用X射线衍射、透射电镜、Fourier变换红外光谱、N2吸附、热失重-差热分析、X射线光电子能谱和原子荧光光谱等测试手段研究了合成材料的介孔结构、Ce的化学态及原子荧光特征.结果表明:Ce引入后的介孔氧化硅材料仍保持了六方介孔结构.合成材料中的Ce4 经Si-O-Ce键合于介孔氧化硅的孔表面,进而引发绿色荧光发射强度显著增强且明显蓝移.红外光谱中,在960cm-1处的谱带强度相对于800cm-1处的增强证明了Ce的成功引入.     

高铈含量的MCM-48介孔分子筛的合成与表征

以十六烷基三甲基溴化铵(hexadecyl trimethyl ammonium bromide,CTAB)和曲拉通(Triton,TX-100)混合表面活性剂作为模板剂,在水热晶化过程中引入铈源,合成了铈含量高达12%(摩尔分数)的Ce-MCM-48,借助X射线衍射、N2吸附-脱附等温分析、透射电镜、紫外可见漫反射吸收光谱分析了产物结构和性能.结果表明:所合成的材料在较高掺杂量时仍保持立方有序介孔结构和较高的比表面积(1 185～331 m2/g),掺杂的铈以Ce4+形式进入孔道骨架或孔道内壁.     

介孔SAPO-11分子筛的制备及应用

综述了介孔SAPO-11分子筛的合成机理、制备方法及应用。介绍了介孔SAPO-11分子筛的合成机理,液晶模板机理和协同作用机理,在不同模板剂与无机硅源的静电作用或相互作用下形成液晶结构,移除液晶后,形成介孔孔道。SAPO-11分子筛属于微孔型(<2 nm)磷酸硅铝分子筛,通过模板法、后处理法和分子筛硅源法等制备方法得到的介孔SAPO-11分子筛结晶度良好,孔径和比表面积均增大,有利于大分子反应物进入其孔道和产物溢出。     

介孔SAPO-11分子筛的制备及应用

综述了介孔SAPO-11分子筛的合成机理、制备方法及应用。介绍了介孔SAPO-11分子筛的合成机理,液晶模板机理和协同作用机理,在不同模板剂与无机硅源的静电作用或相互作用下形成液晶结构,移除液晶后,形成介孔孔道。SAPO-11分子筛属于微孔型(<2 nm)磷酸硅铝分子筛,通过模板法、后处理法和分子筛硅源法等制备方法得到的介孔SAPO-11分子筛结晶度良好,孔径和比表面积均增大,有利于大分子反应物进入其孔道和产物溢出。     

自组装法合成介孔铝酸锌尖晶石陶瓷纳米粉

采用硝酸铝和硝酸锌为无机原料,以嵌段聚合物P123为表面活性剂,自组装法合成了介孔结构的铝酸锌尖晶石纳米粉体。利用X射线衍射、透射电镜、氮气吸附-脱附比表面测定仪对铝酸锌样品进行表征,样品为单一尖晶石相,而且具有介孔结构,500℃焙烧的铝酸锌样品比表面积最大,比表面积为98.4m2·g-1。     

硅基纳米材料用于阿司匹林长效缓释的研究

表面活性剂采用十六烷基三甲基溴化铵为活性成分,硅源采用正硅酸乙酯,利用低温水热法合成了MCM-4l介孔分子筛,采用动态吸附法将阿司匹林药物吸附到分子筛MCM-41的孔道中,吸附前后的介孔分子筛分别利用傅里叶红外光谱(IR)、紫外光谱(UV)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)等对吸附前后的分子筛进行了表征;借助紫外-可见吸收光谱(UV)研究了分子筛的最大吸附量、吸附时间、体外释放等。结果显示,所合成的分子筛MCM-41有序的介孔材料;MCM-4l用于药物阿司匹林的载体最大载药量为:45mg·g-1(m(药物)/m(载体))和良好的缓释效果。     

大黄药渣制备超级活性炭

以大黄药渣为原料,磷酸为活化剂制备了超级活性炭,考察了浸渍磷酸质量分数、活化温度和时间对活性炭织构的影响;采用N2吸附、SEM、XRD、FT-IR对活性炭进行了表征。结果表明:制备超级活性炭的条件为浸渍磷酸质量分数50%~80%、活化温度400~450℃、活化时间40~180 min;活化温度和浸渍磷酸质量分数对活性炭织构的影响较大,时间影响较小;用60%磷酸浸渍,在400℃活化60 min生产的活性炭表面积达到2 413 m2·g-1,相应的微孔和介孔体积分别为0.91 cm3·g-1和0.93cm3·g-1;活性炭孔道由多种结构的孔构成,除介孔和微孔外,最大的方形孔道中还分布着椭圆形的小孔,微孔则主要集中在0.6 nm和1.0 nm,而介孔在5.0 nm以下;此外,在600℃下活化有石墨微晶产生。     

二氧化钛介孔材料的制备

基于溶胶-凝胶过程,以十六烷基溴化铵为模板剂,合成了TiO2以及V/Ce/F-TiO2 介孔材料。利用XRD、Ｎ２吸附、TEM、TG-DTA和UV-Vis DRS等手段表征了材料的晶相组成、晶粒尺寸、介孔结构、热稳定性及吸光性能。通过系统研究表明,延长凝胶时间和优化陈化工艺可以得到TiO2介孔材料。TiO2和V/Ce/F/TiO2的平均孔径为3.1～5.1 nm,最大比表面积可达189 m2/g。焙烧温度大于450 ℃脱除模板剂时可引起孔道的塌陷,而掺杂V/Ce/F后可稳定材料的介孔结构。相对于纯TiO2光催化剂,掺杂V/F的TiO2吸光带边红移至可见光区。     

基于氨基功能化介孔硅的pb2＋选择性吸附剂

采用后接枝法将氨丙基三乙氧基硅烷接枝到二氧化硅网络中,合成了氨丙基功能化的MCM-41介孔硅.FTIR结果显示,氨基被共价键键合到了介孔硅基体上.实验结果表明,所制备的功能化材料可以选择性吸附水溶液中的Pb2+,最大吸附量为193 mg·g-1.     

碱性水热环境下制备MCM-41介孔材料的分形表征

分别以硅酸钠和正硅酸乙脂为原料,采用碱性溶液环境在水热条件下成功合成了MCM-41系列的SiO2介孔材料.以小角X射线衍射(SAXRD)、透射电子显微镜(TEM)、N2等温吸-附脱附曲线、傅立叶变换红外吸收光谱(FTIR)表征了所获得的产品,并以FHH计算法对所获得的介孔样品进行了分形特性分析.结果表明:产物为具有短程有序的六方堆积介孔材料,具有明显的MCM-41系列材料的特征,比表面积高达l100 m2/g以上,孔容高达1.0cm3/g以上,以硅酸钠为原料合成的产物的孔容和比表面积更大.产物的表面分形维数分别为2.9491和2.9632,充分说明了产物中具有粗糙的表面和丰富的内部孔道,验证了以分形维数方法表征介孔材料的独特技术优势.     

Effect of the cerium loading on the HMS structure. Preparation,characterization and catalytic properties

Ce–HMS mesoporous materials were prepared by incipient wetness method starting from HMS synthesized in acid condition. The effect of cerium quantity, in the range of Ce/Si atomic ratio 0.02–0.3, on its structure and properties was investigated. Results showed that the HMS hexagonal structure was maintained after the cerium adding. Furthermore, the surface area and the pore volume were reduced. The presence of the cerianite nanoparticles located within the HMS channels up to 0.05, thus covering the HMS surface at higher Ce/Si atomic ratio, was observed. The catalytic performances of the materials were tested in ethanol partial oxidation reaction.     

铈在介孔氧化锆中的液相移植

利用Ce(NO3) 3·6H2 O溶液与介孔氧化锆原粉在一定pH值的液相中反应 ,将Ce/CeO2 催化剂移植到多孔氧化锆材料中 .用XRD ,TEM ,N2 吸附 -脱附及UV -VIS吸收光谱等手段对产物进行表征 ,结果表明 :铈经Zr—O—Ce键成功地负载于多孔ZrO2 骨架中 ,并且分散于孔表面及孔道中 ,同时保持孔道的有序性及多孔氧化锆较高的比表面积 .     

Highly active methanol decomposition catalyst derived from Pd‐hydrotalcite dispersed on mesoporous silica

Pd‐hydrotalcite (abbreviated as Pd(HT)) was dispersed on HMS (hexagonal mesoporous silica) by synthesizing Pd(HT) in an HMS suspension, and the resultant product (Pd(HT)/HMS) was used as a catalyst precursor for methanol decomposition to synthesis gas. The IR spectra of Pd(HT)/HMS showed all the bands of Pd(HT) and HMS with little shift, which indicated that Pd(HT) was synthesized in the Pd(HT)/HMS. Pd(HT)/HMS did not show the XRD pattern of Pd(HT) when the mass ratio of Pd(HT) to HMS was from 2/1 to 1/2. This indicated that Pd(HT) was formed in very small particles in the Pd(HT)/HMS after dispersion. Two endothermic peaks of Pd(HT) in the DTA curve shifted to lower temperatures in the Pd(HT)/HMS because the small Pd(HT) particles formed in the Pd(HT)/HMS were easily collapsed by heat treatment. Pd(HT)/HMS was thermally decomposed and reduced to form a supported Pd catalyst (abbreviated Pd(Mg(Al)O)/HMS) for methanol decomposition. Pd(Mg(Al)O)/HMS at 3.6 wt% showed a 52.5% conversion which was much higher than those over 3.6 wt% Pd(Mg(Al)O) (34.7%) and 3.6 wt% Pd/HMS (13.7%) for methanol decomposition at 523 K. The conversions of methanol over Pd(Mg(Al)O) and Pd/HMS increased with the increase in Pd loadings from 3.6 to 15 wt% and decreased when the Pd loadings were over 15 wt%. In contrast, the conversion over Pd(Mg(Al)O)/HMS increased with the increase in Pd loading even when the Pd loading was up to 30%. 30 wt% Pd(Mg(Al)O)/HMS showed a 91.7% conversion which was about twice that over 15 wt% Pd(Mg(Al)O) (47.1%) at 523 K. The Pd(Mg(Al)O)/HMS catalyst showed a larger BET surface area and Pd metal surface area than those of Pd(Mg(Al)O). By characterization using XPS analyses, the metal–support interaction between small Pd and small Mg(Al)O became stronger in the Pd(Mg(Al)O)/HMS catalyst. Large surface area, high Pd dispersion and strong metal–support interaction caused the high catalytic activity for methanol decomposition to synthesis gas over the Pd(Mg(Al)O)/HMS catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of the Novel Mesoporous Solid Acid Catalyst UDCaT‐4 via Synergism of Persulfated Alumina and Zirconia into Hexagonal Mesoporous Silica for Alkylation Reactions

A novel mesoporous solid acid catalyst named UDCaT‐4 was designed by loading persulfated alumina and zirconia (PAZ) into highly oredered, hexagonal mesoporous silica (HMS). UDCaT‐4 was characterized by XRD, BET surface area and pore size analysis which revealed that neither pore blocking nor structure collapse of HMS had occurred. NH₃‐TPD and FTIR were used to determine the acid strength and nature of the sulfate ion retained on the surface of UDCaT‐4. It is known that HCl and water have detrimental effects on the activity of the zirconia‐based catalyst. Hence, the activity of UDCaT‐4 was evaluated in comparsion with that of bulk PAZ in the liquid‐phase alkylation of toluene with benzyl chloride and also in the vapour‐phase alkylation of mesitylene with isopropanol, where acid and water are generated in‐situ, respectively, as co‐products. The superior catalytic acivity of UDCaT‐4 is atributed to the uniform dispersion of the superacidic centers of PAZ into HMS vis‐à‐vis bulk PAZ. Reusability and time on‐stream studies reveal that UDCaT‐4 is a robust and reusable catalyst even in the presence of HCl and H₂O.     

Ti-HMS合成、表征及其催化氧化性能研究

以有机金属二氯二茂钛为钛源,六方介孔二氧化硅分子筛(HMS)为载体,采用嫁接法合成了含钛量(mol)分别为2.8%、3.8%和4.8%的Ti-HMS,HMS合成原料组成中H2O/EtOH(v/v)分别为0.5、1、2、5、9.合成材料用X射线粉末衍射(XRD)、N2吸附-脱附等温线、漫反射紫外可见光谱(UV-VIS)进行了表征,并考察了它们以叔丁基过氧化物(TBHP)为氧化剂在对叔丁基甲苯液相氧化中的催化性能.结果表明,表面钛嫁接后的HMS介孔结构有所损失,比表面积和孔体积减少.载体HMS合成原料中的H2O/EtOH(v/v)影响介孔织构和钛的配位环境.UV-VIS资料表明,H2O/EtOH(v/v)=0.5和9时不利于钛着床于分子筛骨架,H2O/EtOH(v/v)=1、2和5的HMS适合作为嫁接钛的载体.催化剂的活性主要受四配位Ti、介孔织构的影响.钛嫁接的HMS在氧化反应中表现出较好的催化活性,载钛量为4.8%Ti、H2O/EtOH(v/v)=1的Ti-HMS显示最好催化活性,对叔丁基甲苯转化率为21.8%.     

六方介孔氧化硅负载磷钨酸的催化性能

采用浸渍法将磷钨酸(HPW)负载于六方介孔氧化硅(HMS)上,制备HPW改性HMS介孔材料HPW/HMS,对其进行了表征;以HPW/HMS为催化剂,催化2-萘甲醚(2-MN)与乙酸酐(AA)的酰化反应,考察了各因素对催化反应的影响. 结果表明,HPW高度分散在HMS上,HPW/HMS的酸量和酸强度随HPW负载量增加而增加. 在温度120℃、时间4 h、催化剂用量0.3 g及2-萘甲醚/乙酸酐摩尔比1:2条件下,2-萘甲醚转化率为75.3%(mol),目标产物2-甲氧基-1-萘乙酮的选择性达83.0%(mol). 催化剂可回收再利用,催化活性略有降低.     

Direct synthesis of CeO2/SiO2 mesostructured composite materials via sol–gel process

A series of CeO₂/SiO₂ mesostructured composite materials was synthesized by sol–gel process using Pluronic P123 as template, tetraethylorthosilicate as silica source and hexahydrated cerium nitrate as precursor under acid condition. The as-synthesized materials with Ce/Si molar ratio ranging from 0.03 to 0.3 were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), laser Raman spectroscopy (LRS), and N₂ adsorption. Characterization revealed that all samples possess ordered hexagonal mesoporous structure similar to SBA-15 and possess high surface area, large pore volume and uniform pore size. The fact that cerium species are present as highly dispersed CeO₂ nanocrystals in hexagonal matrix was confirmed by XRD combined with high-resolution TEM and selected area electron diffraction (SAED) analysis. Introduction of ceria to silica matrix can cause a distortion of hexagonal ordering structure and decrease pore diameter and increase the wall thickness of mesopores. Moreover, it can be found that this sol–gel route is a feasible, effective and simple method for templating synthesis of CeO₂/SiO₂ composite materials.     

One-pot synthesis of wormhole-like mesostructured silica with a high amine loading for enhanced adsorption of clofibric acid

A series of ordered amine-functionalized hexagonal mesoporous silicas (HMS-NH₂) were synthesized successfully via direct co-condensation using dodecylamine as a structure-directing agent in the presence of 3-aminopropyltrimethoxysilane (APS), [aminoethylamino]propyltrimethoxysilane or [(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEEA) as amine group precursors. Tetrahydrofuran was used as the organic solvent to control the interaction and sol–gel reaction of the silica source and aminosilanes. The effect of the type and concentration of the added aminosilanes on the physicochemical properties of the resulting HMS-NH₂ materials were investigated. Thermogravimetric analysis, Fourier-transform infrared spectroscopy and solid-state ²⁹Si nuclear magnetic resonance spectroscopy confirmed a successful functionalization of the HMS surface with different amine groups. X-ray diffraction and transmission electron microscopy indicated that their wormhole-like mesostructured framework was retained after functionalization at a high APS loading level (15 mol%) or using AEEA as the aminosilane precursor. A high degree (88–98%) of aminosilanes was incorporated into the HMS framework, corresponding to an amine concentration of 0.72–2.16 mmol g^?1. The HMS-NH₂ materials had a high surface area (272–627 m² g^?1), a large total pore volume (0.48–1.92 cm³ g^?1) and exhibited an enhanced adsorption capacity for clofibric acid in aqueous solution.     

Characteristics of Gallium-Substituted Hexagonal Mesoporous Silica: Effects of Gallium Content

Gallium-substituted hexagonal mesoporous silicas (Ga-HMS) with various Si/Ga ratios in the range of 15 and 200 were prepared at ambient temperature by neutral surfanctant templating pathway. The materials were synthesized by using dodecylamine as a template and tetraethylorthosilicate as a silicon source. They were characterized by energy dispersive X-ray spectroscopy, powder X-ray diffraction (XRD), N₂ adsorption-desorption, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared absorption spectroscopy and ultraviolet-visible absorption spectroscopy. Ga-HMS samples had high surface areas and uniform mesoporous channels, which are similar to MCM-41. However, they differed from MCM-41 in presenting only a single peak in XRD patterns. They also possessed other characters of larger framework wall thickness, small crystallite domain sizes, and complementary textural mesoporosities in comparison with M41S materials. Ga-HMS materials had micropores and the hysteresis loops were obvious. These small crystallite size and complementary textural mesoporosity provided better access of the framework-confined mesopores. These mesoporous Ga-HMS samples exhibited irregularly shaped mesoscale fundamental particles which aggregated into larger particles. They also demonstrated better thermal stability than MCM-41. The textural pore volumes of Ga-HMS specimens could be up to 20 times as large as the framework volumes. The surfactant could be removed completely by calcination at 650^∘C. An absorption band of FT-IR at ca. 960 cm^–1 was assigned to the vibration of Si–O–Ga linkages. These samples also showed an absorbance band at 255 nm and 250 nm in UV-vis spectra. The results show that gallium was incorporated into the structure of HMS. The efforts in preparing Ga-HMS specimens by neutral-template synthesis route had led to new mesoporous silica molecular sieves with catalytically active gallium centers.     

Propane oxidative dehydrogenation over vanadia catalysts supported on mesoporous silicas with varying pore structure and size

The structural characteristics and the performance of vanadia catalysts (0.7–8 wt.% V) supported on mesoporous (MCM-41, HMS, MCF, SBA-15), microporous (silicalite) and non-porous (SiO₂) silicas in oxidative dehydrogenation of propane were investigated. The structure of vanadia species, the redox and the acidic properties of the catalysts were studied using in situ Raman spectroscopy, TPD- NH₃ and H₂-TPR. The only vanadia species detected on the surface of HMS and MCM-41 for V loadings up to 8 wt.% were isolated monovanadates indicating high vanadia dispersion. Additional bands ascribed to V₂O₅ nanoparticles were evidenced in the case of SBA-15 and MCF supported catalysts while these bands were the only ones identified on the surface of the catalysts supported on silicalite and non-porous silica. The catalysts supported on mesoporous HMS and MCM-41 materials showed the best performance achieving high propane conversions (35–40%) with relatively high propene selectivities (35–47%). Lower activity due to the lower degree of vanadia dispersion, caused by the partial destruction of the pore structure was observed for the SBA-15 and MCF supported catalysts. The degree of dispersion of the V species on the catalyst surface and not the pore size and structure of the mesoporous support or the acidity/reducibility characteristics mainly determine the catalytic activity towards propene production. In addition, it was shown that the pore structure and size of the mesoporous supports did not have any significant effect in the turnover rates (TOF values) of propane conversion (and propene formation at low propane conversion, below ca. 10%). However, the highest propene yield (up to 19%) and stable catalytic behavior was attained for catalysts supported on HMS mesoporous silica, and especially for those combining framework mesoporosity and textural porosity (voids between primary nanoparticles).