间歇式水热合成制备丝光沸石膜及其异丙醇脱水应用

采用市售廉价大孔α-Al₂O₃管作为基质材料，通过热浸渍法在管外表面涂敷晶种，随后在无模板剂体系下，利用新型的间歇式水热合成法制备丝光沸石膜。对比了传统加热和间歇式加热对丝光沸石膜形貌、结构及渗透蒸发异丙醇脱水分离性能的差异。考察了合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比在间歇式水热合成下对丝光沸石膜的影响。研究结果表明，当合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比分别为0.24、16.7和0.25时，制备的丝光沸石膜渗透蒸发异丙醇脱水分离性能最佳，在75℃下，对异丙醇/水(9∶1，w/w)的渗透通量达5.60 kg·m^-2·h^-1，水对异丙醇的分离因数大于10 000。     

硅源量和晶化时间对SAPO-34分子筛结构和性能的影响

以吗啡啉为模板剂合成了SAPO-34分子筛，研究了晶化液SiO₂/Al₂O₃比(硅源量)的影响。当SiO₂/Al₂O₃ ≥ 0.6时，能合成出纯净的SAPO-34分子筛;SiO₂/Al₂O₃=1.0时，分子筛骨架中出现“硅岛”结构，此时合成的分子筛样品具有最高的(乙烯+丙烯)选择性。继续增大硅铝比对(乙烯+丙烯     

晶种协同廉价有机模板导向合成高纯度MCM-49沸石

采用廉价低毒性的环己胺（CHA）作为有机模板剂,并合理添加少量MCM-49沸石晶种,在静态水热条件下成功合成了高纯度MCM-49沸石.研究了起始凝胶组成（如Al₂O₃/SiO₂,H₂O/SiO₂,CHA/SiO₂,晶种/SiO₂,Na₂O/SiO₂）、晶化温度和时间等因素对合成MCM-49沸石的影响.通过XRD、SEM、N₂吸附、固体²⁷Al和²⁹Si MAS NMR等手段表征产物,结果表明合成的MCM-49沸石具有良好的结晶度、均匀的晶体尺寸、高比表面积和纯的四配位Al³⁺物种.热重差热分析（TG-DTA）和固体¹³C MAS NMR表征结果证实CHA是作为模板剂填充在沸石产物的孔道内.这种合成MCM-49的方法具有廉价和低毒性的特点,对其产业应用有潜在的重要价值.     

微波场中T型分子筛的合成及晶化研究

研究了微波场中T型分子筛的结晶过程。考察了微波加热体系中合成参数如合成时间、溶胶组成、反应压力和模板剂用量对分子筛晶化的影响。微波加热的主要优点是减少合成时间,无模板剂的溶胶在普通加热条件下的晶化时间需要120 h,而在微波场中则仅需要20～25 h。另一方面,由于微波的快速加热特性促进了稳定相钙十字沸石的生成,从而减小了次稳定相T型分子筛的结晶区间。在未添加模板剂条件时,100 ℃下微波水热合成T型分子筛的结晶区间为：20≤n_SiO2/n_Al2O3≤22和0.31≤ n_M2O/n_SiO2≤0.33(其中M₂O=Na₂O+K₂O, n_Na/n_K=3和n_M2O/n_SiO2=11.70)。在普通加热和微波加热合成体系中,添加模板剂均能扩大结晶区间,同时还可以进一步减少合成时间。     

厚度可控薄板形Silicalite-1的制备

通过精细调整控制合成条件, 在SiO₂-TPAOH-H₂O-NH₄F (TPAOH: 四丙基氢氧化铵)体系中制备出了厚度可控的薄板型Silicalite-1 分子筛材料, 并利用扫描电镜(SEM)、高分辨透射电镜(HRTEM)、粉末X射线衍射(XRD)及差热-热重分析(TG-DTA)对样品的结构信息、样品形貌及物理化学性质进行了表征. 研究表明, NH₄F浓度和反应体系pH 值对Silicalite-1 分子筛的形貌起着重要的导向作用. 随着NH₄F/SiO₂的摩尔比(n(NH₄F)/n(SiO₂))由0 增加到0.18, 分子筛形貌由交互生长的椭圆形变为板形, 其厚度也逐渐变薄; 当n(NH₄F)/n(SiO₂)=0.4 时, 厚度达到最薄. 继续增加NH₄F/SiO₂的摩尔比, 其厚度增加, 这是由于F^-提高了样品结晶度. HRTEM研究表明b轴垂直于平面, 由于在MFI 结构的材料中, b轴方向是其直孔道方向, 这种材料有利于客体分子的进出. 还研究了样品的热稳性, 所有样品在1100℃焙烧2 h后, 其形貌和结构不发生变化.     

粉煤灰基NaA/NaX双晶型沸石分子筛构建及其协同吸附氨氮性能

以粉煤灰为原料,采用“联合改性三步合成法”——超声辅助碱熔微波晶化法联合废旧玻璃/13X晶种/NaH₂PO₄浸渍三阶段改性合成沸石分子筛(GFS);作为对比,采用传统碱熔水热法合成沸石分子筛(FS);采用“三步合成法”——超声辅助碱熔微波晶化法合成沸石分子筛(WFS)。并采用X射线衍射(XRD)、扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)、能量色散光谱(EDS)、N₂吸附-脱附等方法对材料的组成、形貌和结构进行了表征。结果表明,WFS和GFS较FS具有更高的比表面积和发达的介孔、微孔,且沸石分子筛晶型从NaA单晶型转为NaA/NaX双晶型。氨氮吸附实验结果表明,GFS (56.01 mg·g^-1)较WFS (49.17 mg·g^-1)和FS (39.75 mg·g^-1)吸附性能更优,吸附动力学和热力学数据符合二级动力学模型和Langmuir模型,氨氮吸附过程为以离子交换为主的吸附,且为自发放热过程,低温促进氨氮吸附。     

模板剂在分子筛合成过程中的作用机理

启用分子模拟途径,通过Lennard-Jones势对模板剂分子与分子筛骨架间非成键作用的能学分析,论证n=5、6的双季铵盐［(CH₃)₃N(CH₂)_nN(CH₃)₃］Br₂在ZSM-50分子筛骨架合成过程中所起的模板作用。     

高硅无铝Mo-Beta沸石的合成与结构表征

用水热晶化法合成了无铝Mo-Beta沸石,讨论了合成条件对无铝Mo-Beta沸石晶化的影响,通过化学分析、XRD、IR、DTA/TGA、TEM、NMR、ICP和UV-Vis紫外漫反射光谱测定了样品的n(SiO₂)/n(MoO₃)比,并对其结构进行了表征,结果表明,所合成的Mo-Beta沸石晶粒均匀,Mo存在于沸石骨架中,由于Mo的掺入,引起Beta沸石红外光谱、差热分析曲线及晶胞参数, ²⁹SiMASNMR谱等发生变化。     

Cr-β沸石的合成与催化性能研究

在SiO₂-Cr₂O₃-(TEA)₂O-Na₂O-H₂O体系中，以四乙基氢氧化铵(TEAOH)为模板剂合成了Cr-β沸石，用XRD、IR、SEM及DTA-TGA等方法对样品进行了表征，探讨了反应混合物组成对Cr-β沸石晶化的影响，初步考查了Cr-β沸石催化苯酚与过氧化氢的羟基化反应活性。     

EU-1分子筛的合成及其在正己烷异构化反应中的催化性能

在不同硅铝比(n_SiO2/n_Al2O3)的合成凝胶(含纯硅凝胶)中引入晶种,合成了纯相的EU-1分子筛。研究了铝源、模板剂和晶种添加量对EU-1分子筛的结晶度、形貌尺寸等的影响;重点研究了不同硅铝比对样品结晶度、晶粒尺寸、酸性、比表面积和孔容等的影响。将合成结果绘制成了纯相EU-1分子筛的合成条件三元图,从三元图可看出,晶种法可显著扩大纯相EU-1分子筛的合成区域。将Pt/H-EU-1用于正己烷异构化反应,结果表明,该催化剂具有优异的正己烷异构化活性及稳定性,对异构烷烃有较高的选择性。     

氟离子对无胺法合成高硅丝光沸石的结构导向作用

 在含氟无胺体系中合成了高硅丝光沸石，研究了合成条件对丝光沸石产物的影响．结果表明，投料n（SiO2）／n（Al2O3）＝20～200时，控制晶化条件可得到高硅丝光沸石纯相．由含氟无胺体系中丝光沸石的热力学稳定相区可见，氟离子的引入对方沸石的生成的相区无影响，ZSM－5和镁碱沸石生成的相区消失，丝光沸石生成的相区扩大，石英生成的相区缩小，且基本上变为两相共存区．合成产物丝光沸石的硅铝比随着氟硅比的升高同步增大，证明氟离子在无胺合成高硅丝光沸石时具有结构导向作用．     

高负载量丝光沸石/堇青石整体式催化剂的原位合成和表征

采用原位合成法制备了高负载量的丝光沸石/堇青石整体式催化剂，考察了晶种添加、晶化方式(静/动态)和投料硅铝比等因素的影响，通过称重计算了丝光沸石负载量，并结合XRD，SEM等表征手段对其结晶状况和形貌进行了分析。结果表明，原位合成可有效制备高负载量(最高可达47.4%)的丝光沸石/堇青石整体式催化剂。晶种添加有利于提高丝光沸石负载量。静态晶化负载量一般高于动态晶化，但动态晶化方式则有利于更高水硅比条件下丝光沸石的生成。投料硅铝比和晶化方式的协同作用，共同影响分子筛负载量和形貌。     

Synthesis of High-Ratio Mordenite

Synthesis of a mordenite-like zeolite from reaction mixtures of composition 2.5R ·. (2.2-7.3)Na₂O · Al₂O₃ · (12-40)SiO₂ · (300-1200)H₂O, where R is monoethanolamine, was studied. The crystallization conditions under which mordenite with a SiO₂/Al₂O₃ ratio of 13 to 22 can be synthesized were determined.     

Zur Synthese von kristallinen Metallsilicathydraten mit Schichtstruktur

Synthesis of Crystalline Metal Silicate Hydrates of Layer Structure The purpose of this paper is the synthesis of m etal s ilicate h ydrates by means of hydrothermal crystallization from the ternary systems M_2/nO? SiO₂? H₂O (M = Li, Na, K, Ca, Mg). The prepared products, the sodium silicates ilerite, magadiite, and kenyaite and a potassium silicate hydrate, are species of crystallization sequences of a hydrothermal quartz formation process at low temperatures. The product sequences, obtained under different crystallization conditions are given and discussed.     

Synthesis of a gallosilicate analogue of high silica,large Port Mordenitel

A high silica (SiO₂/Ga₂O₃ = 42) crystalline mordenite containing gallium (III) in framework positions has been prepared by hydrothermal crystallization at 413 K in the presence of tetraethylammonium bromide. Evidence for the presence of framework gallium in the mordenite lattice is obtained from chemical analysis, XRD, framework IR, solid state MASNMR, thermoanalytical studies, sorption and catalytic activity studies. Chemical analysis and NMR data indicate the absence of significant amounts of aluminium (SiO₂/Al₂O₃ > 2400). An increase in the interplanar spacing and unit cell volume as well as a shift to lower wavenumbers of framework vibrations occurs on gallium incorporation in the mordenite lattice. Ga-mordenite exhibited significant ion exchange capacity. The gallium analogue of mordenite exhibited significant catalytic activity and shape selectivity in the isomerization reaction ofm-xylene.NCL communication No. 5317.     

ZSM-5、ZSM-57分子筛和丝光沸石间的转晶规律

考察了硅铝比、碱度、有机胺模板剂、晶化时间及温度等合成条件对ZSM-5、ZSM-57 分子筛和丝光沸石之间相互转晶的影响. 发现较高的碱度、较长的晶化时间有利于合成丝光沸石；较低的碱度、较高的诱导晶化温度、较长的晶化时间有利于合成低硅铝比的ZSM-57 分子筛；合成低硅铝比的ZSM-5分子筛则需要在能合成丝光沸石和ZSM-57 分子筛的碱度区间内精确调节碱度, 缩短晶化时间、降低诱导晶化温度、加入适当晶种, 有利于合成低硅铝比的ZSM-5 分子筛. 合成条件稍微改变, 会导致各种沸石之间发生转晶, 晶化产物出现两种或两种以上的晶型.     

Fischer–Tropsch reaction over a Co<Subscript>2</Subscript>-Ni-Mn/SiO<Subscript>2</Subscript> nanocatalyst prepared by thermal decomposition of a new precursor

This study was prepared for the first time the trimetallic nanocatalyst Co₂-Ni-Mn/SiO₂ by thermal decomposition of) [Ni(H₂O)₅Co(dipic)₂].2H₂O + [Mn(H₂O)₅Co(dipic)₂] 2H₂O)/SiO₂, to study the Fischer–Tropsch reaction for conversion of the synthesis gas to light olefins. The catalytic performance of Co₂-Ni-Mn/SiO₂ as a nanocatalyst prepared by thermal decomposition of an inorganic precursor was compared to that of the trimetallic nanocatalysts Co₂-Ni-Mn/SiO₂ as reference nanocatalysts prepared by impregnation and co-precipitation. The characterization of precursor and nanocatalyst were confirmed by thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) specific surface area, and X-ray diffraction (XRD). The Fischer–Tropsch reaction for all nanocatalysts of Co₂-Ni-Mn/SiO₂ was studied at 280–360 °C at a gas hourly space velocity of 3600 h^?1, and a H₂/CO molar ratio of 1:1 at atmospheric pressure. The results showed that the Co₂-Ni-Mn/SiO₂ nanocatalyst prepared by thermal decomposition of an inorganic complex exhibited the higher activity than the other nanocatalysts and showed maximum selectivity to light olefins at 360 °C.     

Study of crystallization process of soda lead silicate glasses by thermal and spectroscopic methods

The crystallization process of some glasses in the ternary Na₂O–SiO₂–PbO system with good chemical stability that can be used for waste inertization was studied using X-ray diffraction (XRD), infrared spectroscopy (FT-IR), differential thermal analysis (DTA) and scanning electron microscopy. The parent glasses were characterized by XRD and FT-IR, and their vitreous state was determined. DTA measurements evidenced glass transition (T _g) and crystallization temperatures (T _c). The thermal treatments were conducted at vitreous transition temperature (400 °C) and at highest effect of crystallization (650 °C). XRD evidenced the lead and sodium silicate crystalline phases in samples treated at 650 °C for 12 h. Micrometer crystallites dispersed in the glass matrices have affected the transparence of glasses and made them opaque after treatment at 650 °C. The influence of oxide quantities in compositions on the crystallization tendency was revealed. A PbO higher content than that of SiO₂ as well as lower Na₂O content decreased the tendency of crystallization.     

SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES WITH AMPICILLIN

Abstract

The reaction, in water, of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with sodium ampicillinate at room temperature has allowed isolation of dimers with the following general formula [M(amp)Cl]₂ × nH₂O (n = 1.5?3.2). The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibilities and spectroscopic methods (IR, Raman, EPR and UV-Visible). A dinuclear structure based on octahedrally coordinated metal ions is proposed.     

Hydrothermal Synthesis,Solid State Structure,and Thermal Properties of a Family of Isomorphous 1‐D Coordination Polymers Aggregated by Extensive Hydrogen Bonding: {[M(3,3′‐bpy)(H2O)4](SO4)·2H2O} (M = Co,Ni, Zn)

Hydrothermal synthesis has afforded a family of new coordination polymers incorporating 3,3′‐bipyridine (3,3′‐bpy), {[M(3,3′‐bpy)(H₂O)₄](SO₄)·2H₂O} (M = Co, Ni, Zn). The crystal structures revealed 1‐D undulating cationic ribbons of formulation {[M(3,3′‐bpy)(H₂O)₄]}_n²ⁿ⁺ with both unligated charge‐balancing sulfate anions and water molecules of crystallization entrapped by hydrogen bonding. The 1‐D ribbons run along the (101) crystal direction and further aggregate via extensive hydrogen bonding patterns. Thermal decomposition data were consistent with stepwise loss of water molecules of crystallization and aquo ligands followed by decomposition due to ligand removal.