ZSM-5@Mesoporous Silica核壳复合结构分子筛的制备及其甲苯甲醇烷基化择形催化性能的研究

采用阳离子表面活性剂模板法在ZSM-5晶体颗粒表面外延生长介孔氧化硅壳层来调变其外表面酸性, 制备了具有高择形催化性能的介孔氧化硅包裹ZSM-5分子筛的微孔-介孔核壳结构复合材料ZSM-5@mesosilica. 扫描电镜和高分辨透射电镜表征显示, 具有无序孔道结构的介孔壳层均匀包覆于ZSM-5晶粒的外表面, 而且壳层的厚度在一定范围内可调变; 另外, 壳层介孔的孔道走向垂直于分子筛核, N₂吸附曲线表明复合材料的微孔和介孔具有互通性. 吡啶吸附和氨吸脱附实验结果证明这些分子可以自由扩散进入分子筛的微孔道, 并且介孔壳层包覆以后ZSM-5分子筛内的酸性位和强度基本没有变化. 用固定床评价了该复合分子筛对甲苯甲醇烷基化反应的催化性能, 结果表明, 与常规ZSM-5相比, ZSM-5@mesosilica核壳材料表现出了较高的对位选择性. 核壳材料独特的择形催化性能归因于介孔氧化硅壳层将ZSM-5非择形性的外表面酸性位部分覆盖, 从而抑制了对二甲苯在外表面的二级异构化反应.     

介孔/大孔Al2O3-SiO2复合氧化物的制备与表征

 以正硅酸甲酯和硝酸铝为硅和铝的前驱体,以非离子表面活性剂C16EO10为结构导向剂,采用溶胶-凝胶法制备了双孔结构硅铝复合氧化物材料. 扫描电镜和N2吸附/脱附分析表明,材料具有三维连续大孔和骨架介孔的双孔分布结构. 微米范围的连续大孔结构是由于溶胶-凝胶过程中诱发了Spinodal相分离所致,而骨架介孔的形成则可能是由于表面活性剂分子进入凝胶骨架中,起到构建介孔结构的模板作用. 骨架元素分析结果表明,制备过程中添加的铝大部分进入了凝胶骨架中,取代部分硅而形成酸性硅铝复合氧化物. 采用Hammett指示剂法和吡啶吸附红外光谱法分析了材料的表面固体酸性,结果显示,硅铝复合氧化物属于中强酸,酸强度H0在-5.6～-3.0 之间的酸中心数约为0.35 mmol/g, 并且材料表面的L酸位较为丰富, B酸位相对较少.     

磷酸盐辅助一步合成介孔Beta分子筛

在合成纳米Beta分子筛的体系中添加磷酸二氢钠等无机盐,通过一步晶化制备介孔Beta分子筛.纳米分子筛组装形成的二次粒子克服了传统纳米粒子难以过滤分离的问题,同时所形成的粒间介孔改善了分子在催化剂内的扩散从而提高催化反应效率.采用X射线衍射、扫描电镜、氮吸附-脱附和氨程序升温脱附等表征方法对材料进行表征,结果表明磷酸二氢钠的用量对介孔体积有很大影响.当NaH2PO4/SiO2摩尔比为0.1时,合成的材料具有较好的孔结构和酸性,并在叔丁醇与苯酚的液相烷基化反应中表现出最好的催化活性.     

具有介孔结构的ZSM-12分子筛的制备、表征及催化性能

采用碱脱硅法制备了具有介孔结构的ZSM-12分子筛,并运用X射线衍射、N2吸附-脱附、固体核磁共振和氨程序升温脱附等方法对碱处理前后的ZSM-12分子筛进行了表征,并考察了碱脱硅改性对分子筛的孔结构、酸性以及催化萘的烷基化反应性能的影响.结果表明,通过改变NaOH溶液的浓度可以在保持ZSM-12分子筛骨架结构的同时,有效地调变介孔的分布,随着碱处理浓度的提高,ZSM-12分子筛的介孔孔容增加,孔径分布范围变宽,产生的二次介孔改善了反应产物的扩散性能,有效地提高了对萘和甲醇烷基化反应的催化性能,萘转化率和2,6-二甲基萘选择性均得到提高.     

双模板法合成介孔/大孔二级孔道碳材料

以酚醛树脂低聚物为前驱物, 利用双模板法制备了具有介孔/大孔双孔结构的碳材料. 其中以二氧化硅蛋白石为大孔模板, 以嵌段共聚物自组装结构为介孔模板. 对样品进行了扫描电子显微镜(SEM), 透射电子显微镜(TEM), X射线衍射(XRD)和氮气吸附-脱附实验表征. 结果表明所制备的双孔碳材料大孔直径约为230 nm, 介孔直径10 nm.     

介孔SBA-15的形貌控制合成及负载染料后其光学性能研究

采用水热-组装法、溶剂挥发法等材料合成方法制备了不同形貌(粉末棒状、单块、薄膜)负载染料的介孔SBA-15复合材料, 并开展光学性质研究. 通过TEM, XRD, N₂吸附-脱附表征证明所合成的各种形貌SBA-15材料均具有规则有序介孔结构, 组装染料后复合材料的形貌及结构保持完整|Uv-vis, PL表征表明染料在SBA-15孔道中呈单分散状态, 负载染料后的复合材料具有发光特性.     

具有结晶孔壁介孔镁锌氧复合物(英文)

以介孔碳为硬模板经过二次填充制备了介孔镁锌氧复合物.采用X射线衍射(XRD),透射电镜(TEM),扫描电镜(SEM),N2吸附脱附等手段对材料的结构及形貌进行了表征.结果表明,所制备的材料在具有高有序介孔结构的同时还具有结晶的孔壁.孔径尺寸均为4.0nm,比表面积均为114.5m2.g-1.广角XRD结果初步表明,材料中氧化镁和氧化锌复合形成了固溶体.该材料作为一种半导体材料有望在光学器件领域获得新的应用价值.     

以微孔沸石MCM-49和MCM-56为硅铝源合成强酸性介孔分子筛

以相同硅铝比的微孔沸石MCM-49 和MCM-56为硅铝源, 通过碱处理和十六烷基三甲基溴化铵模板剂, 合成了具有较强酸性的六方结构介孔分子筛材料MM-49和MM-56, 并采用XRD、红外光谱、氮气吸附-脱附等方法对其进行了结构表征, 采用NH3-TPD和IR-吡啶吸附方法对其进行了酸性表征. 实验结果表明, MM-56和MM-49具有明显强于常规介孔分子筛酸性的特点, 在苯酚与叔丁醇的烷基化反应中表现了良好的催化性质.     

氨基功能化SBA-15介孔分子筛的制备与表征

以3-氨丙基三乙氧基硅烷为偶联剂,采用后合成法对介孔分子筛(SBA-15)的表面进行改性,制得氨基功能化的介孔NH<,2>-SBA-15材料(简称NH<,2>-SBA-15),其结构和性能经FT-IR,元素分析,XRD,SEM及低温N<,2>吸附-脱附表征.结果表明,氨基成功地嫁接到SBA-15表面,含量高达3.47 ...     

可用于色谱固定相的介孔氧化硅球材料的合成

采用非离子型嵌段高分子表面活性剂EO₂₀PO₃₀EO₂₀ (P65)为结构导向剂, 正硅酸乙酯为硅源, 在酸性介质中, 静置法制备了微米级介孔氧化硅球. 通过改变合成温度、反应时间或者无机盐KCl的加入量, 可以调节介孔氧化硅球的直径(9.0～17.6 μm); 加入1,3,5-三甲苯(TMB)或者调节水热温度, 可以调节介孔氧化硅球的孔径(2.3～4.8 nm). 采用X射线衍射(XRD)、N₂吸附-脱附、扫描电镜(SEM)、激光散射粒度分布和对溶菌酶的吸附等方法, 对介孔氧化硅球的结构、孔性质、形貌、吸附性质等进行了表征. 实验发现, 孔径较小的介孔氧化硅球(≤4.3 nm)对溶菌酶的吸附不明显(≤42 mg/g), 而孔径(4.8 nm)大于溶菌酶直径的材料对溶菌酶有较大的吸附量(192 mg/g), 说明孔径均匀可调的介孔氧化硅球材料可以很好地用作体积排阻色谱柱的固定相.     

Textural and structural properties and surface acidity characterization of mesoporous silica-zirconia molecular sieves

Homogeneous mesoporous zirconium-containing MCM-41 type silica were prepared by supramolecular templating and their textural and structural properties were studied using powder X-ray diffraction, N₂ porosimetry, atomic force microscopy, EXAFS, XPS, and UV-VIS-NIR diffuse reflectance spectroscopy. Their acid properties were also studied by using IR spectroscopy and by the use of catalytic tests such as the decomposition of isopropanol and the isomerization of 1-butene. The materials prepared show a good degree of crystallinity with a regular ordering of the pores into a hexagonal arrangement and high thermal stability. The specific surface area of the prepared materials decreases as the zirconium content rises. Zirconium atoms are in coordination 7 to 8 and located at the surface of the pores such that a high proportion of the oxygen atoms bonded to zirconium corresponds to surface non-condensed oxygen atoms. Both facts are responsible for the acid properties of the solids that show weak Brønsted and medium strong Lewis acidity.     

Synthesis of Superacid‐Functionalized Mesoporous Nanocages with Tunable Pore Diameters and Their Application in the Synthesis of Coumarins

Here we demonstrate for the first time the preparation of a triflic acid (TFA)‐functionalized mesoporous nanocage with tunable pore diameters by the wet impregnation method. The obtained materials have been unambiguously characterized by XRD, N₂ adsorption, FTIR spectroscopy, and NH₃ temperature‐programmed desorption (TPD). From the characterization results, it has been found that the TFA molecules are firmly anchored on the surface of the mesoporous supports without affecting their acidity. We also demonstrate the effect of the pore and cage diameter of the KIT‐5 supports on the loading of TFA molecules inside the pore channels. It has been found that the total acidity of the materials increases with an increase in the TFA loading on the support, whereas the acidity of the materials decreases with an increase in the pore diameter of the support. The acidity of the TFA‐functionalized mesoporous nanocages is much higher than that of the zeolites and metal‐substituted mesoporous acidic catalysts. The TFA‐functionalized materials have also been employed as the catalysts for the synthesis of 7‐hydroxy‐4‐methylcoumarin by means of the Pechmann reaction under solvent‐free conditions. It has been found that the catalytic activity of the TFA‐functionalized KIT‐5 is much higher than that of zeolites and metal‐substituted mesoporous catalytic materials in the synthesis of coumarin derivatives. The stability of the catalyst is extremely good and can be reused several times without much loss of activity in the above reaction.     

柠檬酸配合法制备CuMnCeOx催化剂及常温催化氧化性能研究

摘要：常温催化氧化是消除室内HCHO污染最可行的方法之一,其中以过渡金属氧化物为代表的催化剂因性能优异、成本低廉而备受广泛关注。采用柠檬酸络合法和水热法制备了一系列CuMnCeOx催化剂,研究考察制备方法及载体对催化剂氧化性能的影响,并利用XRD、SEM、BET、H2-TPR、XPS和IR等对催化剂进行微观表征与分析。研究发现,制备方法及载体类型对催化剂的表面结构形貌、氧化性能产生显著影响,其中采用柠檬酸络合法所制的CuMnCeOx-C催化剂性能最佳,48h的HCHO去除率达98.6%,完全满足GB50325-2001标准要求,其介孔结构,晶体粒径及所形成的铈基铜锰固溶体均利于形成大量氧空位及催化氧化反应,且展示出良好的抗水蒸气和稳定性能,其在常温催化氧化VOCs方面具有重要应用前景。     

ZrO2-TiO2-CeO2的制备及其在NH3选择性催化还原NO中的应用

采用共沉淀法制备了载体材料TiO2、ZrO2-TiO2及ZrO2-TiO2-CeO2, 并利用X射线衍射(XRD)实验、比表面积测定(BET)、程序升温脱附(NH3-TPD)、储氧性能测定(OSC)及程序升温还原(H2-TPR)等方法对三种载体材料进行了表征. 结果表明, ZrO2-TiO2-CeO2具有较多的表面强酸位, 并具有一定的储氧性能和较强的氧化还原性能. 以三种材料为载体, 制备了质量分数分别为1%、9%的V2O5、WO3的整体式催化剂. 研究了三种催化剂在富氧条件下用NH3选择性催化还原NO的催化性能. 结果表明, 以ZrO2-TiO2-CeO2为载体的催化剂在反应空速为10000 h-1, 275 ℃时, NO的转化率接近100%, 具有最好的催化活性,并有良好的应用前景。     

含锌尖晶石型ZnM_2O_4(M=Cr,Al,Fe)催化剂上二氯甲烷高效催化燃烧

采用溶胶凝胶法制备出一系列的含锌尖晶石型ZnM_2O_4(M=Cr,Al,Fe)催化剂并测试其对二氯甲烷催化燃烧性能,并对催化剂进行了XRD,H_2-TPR,NH_3-TPD和XPS等表征.制备出的催化剂都具有较高的反应活性,其中ZnCr_2O_4尖晶石活性最佳,其T50为277℃.表征结果表明,催化剂的性能受到表面酸性和氧化还原性的协同作用.ZnCr_2O_4尖晶石催化剂具有较小的中等酸强度的表面酸性和最佳的低温还原性能,因此反应性能最佳.     

Al2O3 Effect on the Catalytic Activity of Cu-ZnO-Al2O3-SiO2 Catalysts for Dimethyl Ether Synthesis from CO2 Hydrogenation

The effect of Al2O3 on the Cu-ZnO-Al2O3-SiO2 catalysts prepared by a pseudo sol-gel method has been investigated and these catalysts were characterized by XRD, H2-TPR, XPS, NH3-TPD and CO2- TPD techniques. As revealed by XRD and H2-TPR, the added alumina produces high dispersion of CuO and makes the reduction of CuO difficult. XPS analysis detects a remarkably high Al^3＋ enrichment at the surface of calcined samples, along with a decrease of Eb of Cu 2p3/2, which confirms the Cu-Al interaction. Another important role of Al203 would be to incorporate into the SiO2 structure to form the acid-base sites for ether formation. The reaction results shows that the addition of Al2O3 exhibits a promoting effect on the CO2 conversion only when its content is below 1.4%, and an optimal DME selectivity is obtained when 4.0%Al2O3 is added, indicating a better ＇synergistic effect＇ is present between the methanol forming component and the acidic component in bifunctional catalysts. Possible relationship between the catalytic activity and the Cu-Al interaction as well as the surface acidity is discussed.     

A1_2O_3 Effect on the Catalytic Activity of Cu-ZnO-Al_2O_3-SiO_2 Catalysts for Dimethyl Ether Synthesis from CO_2 Hydrogenation

1. Introduction Dimethyl ether (DME) has received more and more attention as a clean alternative diesel fuel since it has higher cetane value, lower NOx emission, lesser carbon particulates and near-zero smoke compared with those for the traditional diesel fuels [1,2]. So far DME has been produced from methanol dehydra- tion over solid-acid catalysts [2,3] or from syngas over bifunctional catalysts [1,4-7]. Recently, great efforts have been emphasized on the direct synthesis of DME from C…     

Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica

A series of Al-containing SBA-15 type materials with different Si/Al ratio, were prepared by post-synthesis modification of a pure highly ordered mesoporous silica SBA-15 obtained by using sodium silicate as silica source, and amphiphilic block copolymer as structure-directing agent. A high level of aluminum incorporation was achieved, reaching an Si/Al ratio of up to 5.5, without any significant loss in the textural properties of SBA-15. These materials were fully characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ²⁷Al NMR spectroscopy, and N₂ adsorption at 77 K. The acid properties of these materials have been evaluated by NH₃-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FTIR spectroscopy. The effective acidity of these materials was evaluated using two catalytic reactions: 2-propanol dehydrogenation and 1-butene isomerization. The adsorption of basic probe molecules and the catalytic behavior revealed an evolution of the acid properties with the Al content. These studies have shown that the Al-SBA-15 materials contain Brønsted and Lewis acid sites with medium acidity which makes them appropriate to be used as acid catalysts in heterogeneous catalysis, catalytic supports, and adsorbents.     

新型有序介孔磺酸化酚醛树脂FDU-16-SO3H的合成与酸催化性能

通过氯磺酸磺化有序介孔酚醛树脂(FDU-16)制备了新型有序介孔固体酸催化剂FDU-16-SO₃H. X射线衍射(XRD)、氮气吸附以及透射电镜(TEM)等表征结果表明, 经过磺化后的固体酸催化剂依然保持了高度有序性, 大量的磺酸根基团存在于材料的骨架之中. 在酯化反应和酰基化反应中, 这种新型有序介孔固体酸催化剂表现出比工业树脂和磺酸化介孔二氧化硅等材料更高的催化活性, 这主要归因于它具有较大的比表面积、较强的酸性以及骨架的疏水性.     

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.