负载Co介孔分子筛催化热解乙醇制备纳米碳管

以硅酸钠为原料,CTAB为模板剂,水热法合成MCM-41介孔分子筛,采用浸渍法制备负载钴的介孔分子筛(Co/MCM-41),并将其作为催化剂,CVD法热解无水乙醇制备CNTs.利用XRD、TEM、比表面积和孔径分布测定和Raman光谱等方法对所合成的介孔分子筛和纳米碳管进行了表征.结果表明:所制备的Co/MCM-41样品具有典型的MCM-41的介孔结构;当热解反应温度为750℃下所制备出的纳米碳管的品质最好.     

不同钴含量CoAPO-5分子筛的合成、表征及其催化环己烷氧化性能

用水热法合成了一系列不同含量钴掺杂的磷酸铝分子筛CoAPO-5. 合成的样品用X射线衍射(XRD), 扫描电镜(SEM), 紫外可见漫反射光谱(UV-Vis DRS), 热重分析(TG)仪和电感耦合等离子体发射光谱(ICP-AES)等进行了表征. XRD表征显示, 合成的CoAPO-5分子筛具有较高的结晶度, 分子筛晶胞参数与Co含量之间存在较好的对应关系. UV-Vis漫反射光谱显示合成的CoAPO-5分子筛具有骨架钴的特征三重峰; 焙烧后峰的强度降低, 表明分子筛骨架中Co2+可被氧化成Co3+. SEM表明该分子筛具有典型的AlPO4-5分子筛形貌特征. TG结果也表明Co2+进入了分子筛骨架, 分子筛具有较好的稳定性. 在环己烷氧化反应中CoAPO-5具有较好的催化性能, 环己烷转化率与环己酮选择性均较高; 随着分子筛中钴含量的增加, 环己烷的转化率增加.     

含钴介孔分子筛催化热解乙醇制备纳米碳管

以CTAB为模板剂,硅酸钠、氯化钴为原料,通过水热法合成含钴介孔分子筛(Co-MCM-41)。以所合成的Co-MCM-41做催化剂,采用化学气相沉积(CVD)法催化热解乙醇制备纳米碳管。通过XRD、FT-IR、TEM、N2吸附-脱附和Raman光谱等分析手段对所合成的介孔分子筛和纳米碳管进行了表征。结果表明:合成的Co-MCM-41样品具有MCM-41的介孔结构,比表面积较大且介孔有序性较好。以所合成的含钴介孔分子筛催化热解乙醇制备出管径均匀、管壁较厚、顶端开口的多壁纳米碳管。     

Cr-HMS合成、表征及其在催化氧化反应中的应用

合成了一系列不同Cr含量的CrHMS介孔分子筛,并对其物化性质进行了表征.结果表明,Cr的引入降低了介孔分子筛骨架结构的规整度和孔径的均一程度.CrHMS对苯羟基化和环己烷氧化反应均表现出良好的催化活性,并且随Cr含量的增加,催化活性呈火山型分布.对于较易进行的环己烷氧化反应,将CrHMS在H₂气氛中预先还原处理,可使催化剂既能保持较高的催化氧化活性,又能获得较好的稳定性.     

钴分子筛催化剂的制备及其分子筛载体对环己烷氧化选择性的影响

为了考察催化剂载体的孔道结构和择形性能对环己烷部分氧化反应的影响,采用直接水热法制备出了Co/S-1,Co/TS-1以及Co/MCM-41分子筛催化剂.XRD,FT-IR和SEM结果表明合成的样品具有较高的结晶度,晶粒大小均匀,其活性组分钴进入了分子筛骨架.采用氧气为氧化剂,考察了合成的钴催化剂样品对环己烷部分氧化的催化性能,并与CoAPO-5、Co/A l2O3、均相Co(OAc)2.4H2O催化剂以及无催化氧化的结果进行了比较.实验结果表明:分子筛载体能利用其孔道结构和择形性能,降低环己醇(酮)选择性对环己烷转化率的依赖性,且反应的选择性随分子筛载体孔径的增加而下降.孔道较小的Co/TS-1和Co/S-1做催化剂时,过氧化物含量低,环己烷转化率可达5%以上,同时反应总选择性为95%左右.     

模板剂对全硅MCM-41介孔分子筛结构的影响

分别采用十六烷基三甲基溴化铵和十六烷基三乙基溴化铵作为模板剂,硅溶胶为硅源,用水热晶化法在碱性（NaOH）介质中合成了MCM-41介孔分子筛样品.通过XRD、N2吸附-脱附、TG-DTA、IR等测试手段对这两种样品进行了对比表征分析.考察了两种不同模板剂对其晶体结构、比表面及孔径大小的影响.实验结果表明,相对于十六烷基三甲基溴化铵做模板剂,采用大头基的十六烷基三乙基溴化铵可以合成较大孔径和孔容（分别为4.72 nm和1.14 cm3•g-1）的MCM-41介孔分子筛,而且具有较窄的孔径分布,因此对于合成大孔径的介孔分子筛MCM-41,十六烷基三乙基溴化铵是一种很好的模板剂.     

海泡石制备HMS和AlSBA介孔分子筛的研究

通过酸浸和模板合成处理，海泡石直接合成有序介孔二氧化硅和含铝的介孔二氧化硅. 海泡石用盐酸处理后120 ℃下在NaOH溶液中处理72 h, 得到具有HMS结构特征的介孔分子筛；在含铝的碱性溶液中处理后得到具有AlSBA结构的介孔分子筛. 并用SAXRD、BET、TPD表征了介孔分子筛的物相结构、比表面积、孔径分布和表面酸性. 两种介孔分子筛的比表面积分别为508 m2•g^-1和946 m2•g^-1，孔径分别为3.4 nm和3.9 nm，且孔径分布窄. NH3-TPD结果表明分子筛表面都有两个酸中心，随着Al原子的引入，表面酸性增强.     

利用ＳＢＡ-１５介孔内纳米碳合成含介孔的ＺＳＭ-５分子筛

SBA-15介孔分子筛内填充蔗糖并炭化后, 分别在碱性和弱酸性条件下, 用含铝源及TPABr的溶液浸渍,将SBA-15分子筛孔壁的无定形结构转化成ZSM-5分子筛的晶体结构, 除碳后得到含介孔的ZSM-5分子筛. 用X射线衍射、 N_2吸附-脱附、 ~(27)Al MAS NMR、 NH_3-TPD、 TEM、 SEM等对样品进行了表征, 考察了晶化时间等参数对样品的影响. 结果表明, 碱性条件下合成的ZSM-5分子筛晶体中含有少量孔径约3.2～4.2 nm的介孔孔道, 其酸强度接近与常规ZSM-5分子筛的酸强度;弱酸性条件下合成的ZSM-5分子筛晶体中含有大量孔径约1.4～1.6 nm的孔道, 其酸强度明显低于常规ZSM-5分子筛的酸强度.     

新型介孔分子筛Sn-SBA-1的合成与表征

在强酸性条件下沿“S X-I ”路线合成了具有立方结构(空间点群为Pm3n)的含Sn介孔分子筛SBA-1,并通过多种手段对其进行表征:XRD显示合成的介孔材料具有良好有序的立方结构,N2吸脱附测得样品有大的孔径(≈2nm)和比表面积(>1100m2g-1),UV-vis和FT-IR证明杂原子Sn替代S i进入分子筛骨架,并且以高分散四面体配位形式存在于分子筛骨架中,SEM则确定合成出来的材料为球形颗粒,粒径在2-4μm之间.     

甲基接枝化HMS介孔分子筛的制备、表征与吸附性能

以工业级正十六胺为模板剂合成纯硅HMS介孔分子筛,用液相沉积法、以环己烷为溶剂对其进行表面接枝改性,并用简单的热失重分析法确定了最佳的硅烷浓度:通过IR、29SiCP-MAS NMR、XRD和N2吸附等手段对样品进行表征,考察了样品的吸附性能.结果表明,甲基成功接枝于HMS表面,最佳的硅烷用量为0.23mol/L,甲基接枝后HMS的孔径和比表面有所降低;接枝后HMS的吸附水性能(亲水性)大幅度降低,而吸附环己烷性能(亲油性)大幅增加.     

中孔硅酸盐材料MCM-41的合成与表征研究(英文)

以十六烷基三甲基溴化铵为模板剂,硅酸钠为硅源,铝酸钠为铝源,在水热条件下成功地合成出了ＭＣＭ－４１中孔硅酸盐材料。采用ＸＲＤ、低温Ｎ２吸附脱附等测试手段对合成的ＭＣＭ－４１样品进行了表征。通过优化合成条件,合成出孔径３.２ ｎｍ、比表面９０４ｍ２／ｇ和孔壁厚约１.４６ ｎｍ的ＭＣＭ－４１分子筛。催化活性测定采用微反应活性实验来评价其活性和选择性。     

X-ray diffraction structure analysis of MCM-48 mesoporous silica

The structure of MCM-48 mesoporous silicate materials has been fully characterized from X-ray diffraction data by applying recently developed methods of mesostructure analysis and full-profile refinement. The pore wall thickness of both as-made and calcined MCM-48 was determined with high precision to be 8.0(1) Angstrom. No regular variations of the wall thickness were detected, but its density was found to be ca. 10% higher in the low-curvature regions. The surfactant density in the pores was assessed around 0.6-0.7 g/cm(3) and was found to have a distinct minimum in the pore center similar to that detected previously in MCM-41. A new extended model function of the density distribution in MCM-48 is proposed on the basis of the structural features that were revealed.     

Pore curvature effect on the stability of Co-MCM-41 and the formation of size-controllable subnanometer Co clusters

Samples of Co-MCM-41 with different pore diameters have been synthesized using organic templates with different alkyl chain lengths. The reducibility of cobalt in these highly stable samples was investigated by TPR and X-ray absorption spectroscopy. We have found that the reducibility correlates strongly with the pore diameter of the MCM-41, with the cobalt incorporated in the smaller pore MCM-41 being more resistant to complete reduction. It is proposed that the distribution of cobalt ions in the pore wall is affected by both the preparation procedure and the pore diameter. The size of the metallic Co clusters formed after different reducing treatments correlates linearly with the pore size, giving direct evidence for the effect of the radius of curvature on reducibility. Complete cobalt reduction after TPR causes an inverse variation of the cluster size with the pore size, resulting from differences in the density of Co clusters and from differences in the rate of Co migration and aggregation outside the pores of MCM-41 with different pore sizes.     

氮气在MCM－41分子筛中的吸附：实验和分子模拟

用美国Micromeritics公司生产的ASAP2010物理吸附仪测定了低温（77 K） N_2在MCM-41分子筛中的吸附等温线，获得了表征MCM-41特征的BET比表面、BJH孔 容和平均孔径。同时用巨正则Monte Carlo（GCMC）模拟方法考究了N_2在MCM-41中 的吸附，得到了N_2在MCM-41中的模拟吸附等温线，分析了流体在MCM-41分子筛中 的微观结构。GCMC模拟中MCM-41介孔材料模型化为圆柱孔，N_2模型化为Lennard- Jones（LJ）球。N_2和MCM-41介孔墙壁间的相互作用采用Tjatjopoulos-Feke- Mann（TFM）势能模型进行表征。通过使模拟和实验结果有一个好的吻合，确定了 一组有效的MCM-41分子筛的势能参数（σ_(ww) = 0.265 nm，∈_(ww)/k = 190 K ）。这为以后其他吸附质在MCM-41中吸附的预测奠定了基础、提供了依据。     

Cerium modified MCM-41 nanocomposite materials via a nonhydrothermal direct method at room temperature

Ce-containing MCM-41 materials were prepared via a direct, nonhydrothermal method at room temperature from tetra-ethoxysilane, n-hexadecyl trimethyl ammonium bromide, ammonia solution, and cerium(IV) ammonium nitrate precursors. Composite materials containing the nominated ratios of 5 and 10% (w/w) CeO2/MCM-41 were targeted. The obtained materials were investigated by TGA, DSC, FTIR, diffuse reflectance UV-vis, XRD, N2 adsorption/desorption isotherms, and SEM. Results indicated the insertion of cerium ions in tetrahedral environment in the framework of MCM-41. BET surface area amounting to 824 and 726 m2/g; total pore volume amounting to 0.427 and 0.515 cm3/g; and narrow pore size distribution maximizing at 22.5 and 23.7 A, respectively were obtained for the 5 and 10% CeO2/MCM-41 calcined composites. SEM showed a spherical type morphology for the composites which is rather similar to their blank MCM-41, and no clear ceria aggregates were observed on the external surfaces of composites spherical particles. Thus, the adopted method allows the persistence of MCM-41 texture with cerium inserts in the framework of MCM-41 and/or forms finely divided ceria nanoparticles on the wall of MCM-41 materials. Moreover, stabilization of any formed ceria nanoparticles was attributed to the short nonintersecting porous nature of MCM-41 matrix, which hinders their aggregation upon calcinations.     

用实验吸附等温线和计算机分子模拟表征中孔分子筛MCM-41

首先比较了表征MCM-41的两个势模型对吸附等温线的影响。发现在一维势模型 中,低压部分的吸附应与选用的势模型的势阱深度有关,而毛细凝聚发生的位置与 孔壁在离壁面较远处与流体分子的相互作用的强弱有关。然后作者使用了一个“混 合”的势模型,即采用作者提出的势函数表征孔壁中氧原子对MCM-41中流体分子的 作用,而采用Tjatjopoulos等提出的势函数近似地表征MCM-41表面硅醇基团以及一 些未知因子对流体分子的作用。虽然这种势模型仍然是一维的,但这种势模型将孔 壁内氧原子的作用和表面上非均匀性分开考虑,具有较明确的物理意义。通过计算 机模拟与实验数据的比较发现,这种势模型可以较好地拟合氮气在MCM-41中的吸附 等温线。     

以离子液体为模板剂合成MCM-41的研究——不同扩孔剂对介孔分子筛MCM-41孔径结构的影响

以离子液体为模板剂, 正硅酸乙酯为硅源, 研究了扩孔剂三甲苯, 癸烷, 以及三甲苯与癸烷1∶1的混合物对介孔分子筛MCM-41结构的影响, 采用XRD以及氮吸附-脱附分析技术对合成的介孔分子筛MCM-41进行了表征.结果表明: 三种扩孔剂中以三甲苯与癸烷1∶1的混合物效果最优, MCM-41的孔径可达到4.5 nm, 并且可以提高介孔分子筛的比表面积与结晶度.扩孔剂的最佳添加量为: 扩孔剂与模板剂之比等于1.0;最佳晶化温度120 ℃.     

Nitrogen adsorption on silica surfaces of nonporous and mesoporous materials

We present an accurate comparative analysis of N 2 adsorption at 77 K on nonporous silica and the pore wall surface of MCM-41 materials. The analysis shows that in the low-pressure region of N 2 adsorption obeys a peculiar mechanism governed by short-ranged forces, which makes the surface curvature effect on the N 2 adsorption in mesopores nearly negligible. We used this observation to define more exactly compared to the BET technique the specific surface area of the reference adsorption isotherm on nonporous silica basing on XRD data and linear sections of t-plots. Calculation of the capillary evaporation and condensation pressures seems to confirm our previous finding that the capillary condensation pressure corresponds to the equilibrium transition rather than spinodal condensation at least for pore sizes less than 7 nm. It allowed us to provide more reliable pore size distribution (PSD) analysis of mesoporous silica materials. For example, the PSDs of MCM-41 samples do not show artificial peaks in the micropore range that we obtained in our earlier publications.     

The Synthesis and Application of the Mesoporous Molecular Sieves MCM-41 — A Review

We report a “delayed neutralization” process for the preparation of highly-ordered aluminosilicate MCM-41 molecular sieves with high thermal and hydrothermal stability, and sharp pore size distribution. However, the structural order and pore size are dependent on the carbon chain length. In the mixture surfactant systems, the pore size of the MCM-41 materials could be fine-tuned. The pore size can be extended from 2.5 to 4.5 nm by adding a suitable amount of hydrocarbons. The tubular morphology of the MCM-41 material of 0.3 to 10 micrometers diameter, where the wall consists of coaxial cylindrical pores of nanometers MCM-41, can be obtained by careful control of the surfactant-water content and the rate of condensation of silica. An optimum condition for automatic synthesis of the hierarchical TWT structure has been accomplished. The addition of 1-alkanols as cosurfactant would not only improve the order of the MCM-41 hexagonal structure but also promote the formation of micrometer-sized hierarchical materials, for example: tubules-within-tubule and uniform-sized hollow spheres of diameter 5.0 ± 1.0 μm. However, the inside of the micron spheres has intricate structures possessing various topological genus ranks. The MCM-41 is a good supporter for Molybdenum oxide catalysts. The rate of deactivation in the catalytic reaction of ethyl-benzene dehydrogenation to styrene increases in the order: M_T < M_P < SiO₂. The physically mixed samples have higher catalytic activity than impregnated ones.     

An analytical approach to determine the pore shape and size of MCM-41 materials from X-ray diffraction data

The pore shape and size of MCM-41 were studied analytically by comparing the observed powder X-ray diffraction intensities with that derived from the MCM-41 crystal structure models, with two different pore shapes, a hexagon and a circle. The powder diffraction patterns from the as-synthesized and the calcined MCM-41 were measured by a synchrotron radiation at SPring-8, Japan. The MCM-41 structure with circular and hexagonal pore shapes explains well for the as-synthesized and the calcined MCM-41 crystals, respectively. The pore size and boundary obtained by this approach agree with those obtained from an N2 gas adsorption measurement combined with the Fourier synthesized density map.