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1.
TS-1分子筛在H_2O_2参与的有机物分子选择氧化及环氧化反应中具有优异的催化性能,一直广受关注.目前,随着精细化工反应中大分子及液相反应的增多,目前工业上使用的微米级尺寸的沸石晶粒催化材料因其狭窄的孔道和较大的扩散阻力而越来越不能满足工业的实际生产需求与应用.小晶粒纳米沸石由于具有较大的外比表面积和较高的晶内扩散速率,因而在提高催化剂的利用率、增强大分子转化能力、减小深度反应、提高选择性以及降低结焦失活等方面均表现出优越的性能.然而,尺寸低于100 nm的沸石又存在着分离问题.因此,具有高催化活性、又能一步实现分离与回收的纳米沸石聚集体的合成,引起了人们的研究兴趣.目前可以通过使用聚苯乙烯球,球型阴离子交换树脂,硅烷化聚合物,聚合诱导胶体聚集(PICA)等实现纳米沸石聚集体材料的合成.其中采用有机硅烷化试剂来制备多级孔纳米沸石聚集体材料提供了一种新的路线.在沸石晶体表面修饰上有机硅烷化试剂,含Si–C键的有机硅烷化物种可以有效地阻止沸石颗粒的晶体生长,抑制形成大的沸石晶体,从而得到纳米粒子聚集体;同时有机硅烷化物种也对纳米沸石进行了表面改性,提高了其疏水性.特别是在有机相中硅烷化沸石可以形成小的、均匀的、聚集的疏水性的纳米沸石.同时,硅烷化试剂的本质和分子大小是沸石聚集体中多级孔大小的决定性因素.具有可调结构的多级孔沸石晶体可以通过在常规的碱性沸石合成混合物溶液中添加一个两性有机硅表面活性剂而合成.研究发现,固定在沸石纳米晶表面的机硅烷物种Si–C键能部分抑制纳米颗粒进一步聚集成较大的晶体,使用硅烷化晶种的方法可以合成具有高比表面的多级孔ZSM-5等沸石.然而,目前已报道的通过硅烷化晶种方法中得到的多级孔TS-1沸石材料的尺寸仅有100–150 nm,仍不利于分离和回收.近来桥联有机硅烷试剂进入人们的视野——通过干胶法合成多级孔β沸石,然而它们的尺寸也只有300–500 nm,反应分离和回收仍然非常困难.本文采用有机桥联硅烷化合物作为硅烷化试剂,将TS-1纳米沸石晶种或者晶体组装聚集成大的沸石聚集体.TEM和SEM结果表明,桥联有机硅烷在沸石晶体的聚集和后续的晶体生长中起到了非常有效的作用,成功地将100 nm左右的纳米沸石晶种或晶体桥联/组装成宏观大尺寸(5–40μm)的沸石聚集体.这些TS-1聚集体具有较好的机械强度,即使连续超声1 h也不会毁坏其结构,表明所得到的沸石材料可以在制备上解决分离困难并且在催化应用上容易回收.XRD,BET以及UV-Vis分析结果表明,引入在TS-1沸石晶种或者晶体溶液中有机硅烷试剂不会影响沸石的晶体结构、微孔体积以及Ti的配位状态.将H_2O_2作为氧化剂评价TS-1沸石聚集体和传统的纳米TS-1在烯烃环氧化反应中的催化性能,结果表明,硅烷化步骤对小分子己烯氧化的活性和选择性的影响不大,在环己烯大分子的氧化反应里表现出了较高的活性和选择性. 相似文献
2.
Novel method for synthesis of titanium silicalite-1 (TS-1) 总被引:2,自引:0,他引:2
Titanium silicalite-1 (TS-1) was easily synthesized using inorganic silicon and titanium source, tetrapropylammonium bromide (TPABr) or TPAOH as templating molecule, NH3· H2O, HDA or TEAOH etc. as base sources. In this system, TPA cations (come from TPABr or TPAOH) served as tern-plating agents to direct the MFI structure. NH3H2O, TEAOH or HDA etc. provides the alkalinity necessary for crystallization. X-ray diffraction, UV-Vis, ER spectroscopies, SEM, 29 Si MAS NMR showed that the zeolites obtained possessed all the structural characteristics of TS-1, and titanium atoms were introduced into the framework in TS-1. This material was proved to have high crystallinity and high catalytic activity to allyl chloride epoxidation and propylene epoxidation. All the samples synthesized had similar catalytic properties with a standard TS-1 through compared inorganic reactant system with organic synthesis system using propylene epoxidation. The effects of silicon source and TPABr/SiO2 ratio were discussed. 相似文献
3.
采用微波加热技术法合成TS-1分子筛, 以30%的H2O2水溶液为氧化剂, 考察了所合成的TS-1分子筛在苯乙烯和1-己烯环氧化反应中的催化性能, 并与传统水热法合成的TS-1进行了比较. 结果表明, 由微波合成TS-1的催化性能比传统水热法合成的TS-1更为优异. 采用XRD, FT-IR, UV-vis, SEM等手段对二者进行表征, 发现微波合成的TS-1晶粒与晶粒之间存在“粘连”现象, 这种现象降低了分子筛表面硅羟基含量, 增加了TS-1分子筛的疏水性, 使得分子筛对反应底物苯乙烯和1-己烯的吸附能力增强, 从而导致催化性能显著提高. 相似文献
4.
表面活性剂Tween对TS-1合成及催化性能影响的研究 总被引:3,自引:3,他引:3
以添加吐温的少量四丙基氢氧化铵(TPAOH)为模板剂,水热下合成了钛硅分子筛(TS-1)。采用FTIR、XRD、SEM、BET、UV-Vis等手段对分子筛进行表征。XRD结果表明,所得样品完全晶化,具有典型的MFI拓扑学结构;FTIR结果表明,样品在960 cm-1处出现了强吸收峰,表明钛已进入骨架;UV-Vis谱图表明,所合成样品在330 nm附近没有电子跃迁信号,表明其中没有锐钛矿型TiO2;SEM结果表明所合成样品的晶粒大小均匀。在添加适量吐温所得的胶团溶液中,模板剂分子与吐温之间的协同作用有助于TPAOH与硅、钛源定向反应,避免非骨架TiO2的生成,减少了TPAOH的用量,丙烯环氧化反应结果表明,吐温20、吐温40、吐温60及吐温80等非离子表面活性剂的添加都有助于降低模板剂(TPAOH)的用量和提高TS-1的催化活性,其中吐温40的影响尤为显著,吐温40/TPAOH摩尔比为0.02时,过氧化氢转化率达98.1%,环氧丙烷选择性和收率分别可达96.1%和94.3%。 相似文献
5.
Maria Crisan Maria Zaharescu A. Jitianu D. Crisan Maria Preda 《Journal of Sol-Gel Science and Technology》2000,19(1-3):409-412
Nano-sized, amorphous and monodispersed poly-component powders in the Al2O3–TiO2–MgO and Al2O3–TiO2–SiO2 systems have been obtained by the sol-gel method. These powders have been characterized by XRD, IR spectroscopy, DTA/TGA and EDAX spectrometry. This last method confirmed the composition of the ternary powders, which are formed during the gelation process.The powders were tested as precursors for obtaining advanced ceramics, as tialite, Al2TiO5. The samples prepared with powders obtained by sol-gel method have shown a high reactivity, and the formation of tialite was improved. 相似文献
6.
Jijian Cheng Wen Liang Yingjie Hu Qi Chen G.H. Frischat 《Journal of Sol-Gel Science and Technology》2003,27(3):309-313
The effect of different new sol-gel BaO—TiO2—SiO2 and CaO—BaO—TiO2—SiO2 coatings on long-term durability of glass fiber reinforced cement (GRC) was examined. Flexural strength of GRC was measured after curing for 7 to 150 days. Significant improvement was observed for coated GRC in this study and discussed in terms of the hydrate formation at interface. Concerned with the alkali resistance, CaO—BaO—TiO2—SiO2 coating was more effective than BaO—TiO2—SiO2 coating. In special, the 10CaO—10BaO—60TiO2—20SiO2 coating, prepared by sol-gel method, was recommended for the highest flexural strength of GRC and least corrosion at surface of E-glass fiber. 相似文献
7.
Won Young Jung Seung Hee Baek Seong Soo Park Gun-Dae Lee Euh Duck Jeong Hyun Gyu Kim Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2007,91(2):233-240
The nanosized titania and TiO2/SiO2 particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination
temperature has been investigated. The major phase of the pure TiO2 particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO2/SiO2 particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for
the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO2/SiO2 particles decreases as compared to pure TiO2 at high calcination temperatures. The TiO2/SiO2 particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO2 particles. 相似文献
8.
Hongye Zhang Yun Xie Zhimin Liu Ranting Tao Zhenyu Sun Kunlun Ding Guimin An 《Journal of colloid and interface science》2009,338(2):468-473
Monodispersed TiO2 hybrid microspheres were prepared via the hydrolysis of titanium isopropoxide (TTIP) in ethanol solution containing p-aminophenylacetic acid (APA). The effects of the APA:TTIP molar ratio, water content, reaction time and reaction temperature on the morphology of the resultant spheres were investigated. The products were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. It was demonstrated that the diameters of the resultant TiO2 spheres could be tuned in the range of 380–800 nm by changing the APA:TTIP molar ratio (1:3 to 3:1) and water content (1–3 v/v%) in the reaction medium, and that increasing the APA:TTIP molar ratio led to larger TiO2 hybrid spheres while increasing the water content decreased their size. The loading content of APA in the hybrid spheres could reach 20 wt.% as they were prepared with the APA:TTIP ratio of 3:1. The possible formation mechanism of the hybrid spheres was also investigated. It was found that APA slowed down the hydrolysis rate of the titanium precursor so that resulted in the formation of the TiO2 spheres. In addition, the APA present in TiO2 spheres acted as a reducing agent to in situ convert HAuCl4 into metallic Au on the surface of the TiO2 spheres. The catalytic activity of the resultant Au/APA–TiO2 composite was examined using transfer hydrogenation of phenylacetone with 2-propanol, and it was indicated that the catalyst displayed high efficiency for this reaction. 相似文献
9.
在不同硅铝比(nSiO2/nAl2O3)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。 相似文献
10.
A new one-pot, efficient three-component condensation of benzaldehydes, 2-naphthol, and carbamates in the presence of silica supported sodium hydrogen sulfate as an effective heterogeneous catalyst for the synthesis of novel 1-carbamato-alkyl-2-naphthol derivatives under solvent-free conditions is described. The present methodology offers several advantages, such as high yields, short reaction times, and very easy workup. 相似文献
11.
在不同硅铝比(nSiO2/nAl2O3)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。 相似文献
12.
A simple and green method has been developed for the synthesis of 2-aminocyclohex-1-ene-1-carboxylic esters through a one-pot three-component condensation reaction of primary amines, ethyl acetoacetate and chalcones using FeCl3/SiO2 nanoparticles in ethanol. This method has several advantages such as high to excellent product yields in short time, using an inexpensive and reusable catalyst and available starting material. 相似文献
13.
An ultra-low hydrolysis sol-gel route for titanosilicate xerogels and their characterization 总被引:1,自引:0,他引:1
Toney Fernandez Gijo Jose Siby Mathew Rejikumar PR Unnikrishnan NV 《Journal of Sol-Gel Science and Technology》2007,41(2):163-168
In this work TiO2-SiO2 xerogels were prepared through an ultra low hydrolysis method using titanium and silicon alkoxide. The samples were heat
treated to 500°C. The xerogels were characterized using TGA/DTA, FTIR, XRD and TEM. The samples showed the formation of Si–O–Ti
bridges by its characteristic vibration within 925–960 cm−1 range. Si–O–Si bond angles were calculated using the central force network model. The TiO2 in all the samples crystallized on heat treatment to 500°C. The crystallite size calculated using the Scherer formula from
the XRD was verified from the Transmission Electron Micrograph. Samples heat treated to 350°C remained amorphous and hence
could be used as hosts for biomaterials and organic optical materials. 相似文献
14.
Nikolai Bazhin 《Reaction Kinetics and Catalysis Letters》2007,90(2):401-404
ATP synthesis assisted by the F1F0-ATP synthase enzyme is considered in the context of chemical thermodynamics. It is shown that the proton gradient itself
has no energy. For this reason, ATP synthesis with the participation of protons’ gradient has no privileges in comparison
with direct ATP synthesis. 相似文献
15.
Statistical designs were used to investigate the effects of various processing conditions on the fissuring and/or fragmentation of sol–gel catalytic materials. Three types of sol–gel materials were studied: SiO2, TiO2-doped SiO2 and CeO2-doped SiO2. Five processing variables were investigated: the quantity of water included in the sol–gel preparation, the amount of TiO2 or CeO2 precursors, the mixing time, the gelation time and the influence of treatment in an oven at 40C prior to the heating treatment (pre-heating time). Processing variables were set at high and low limits in three different 24 full-factorial designs. As notable results, the water content appeared to be a critical processing variable in every studied factorial designs. Pre-heating time was also significant for SiO2 gels. Finally the amount of CeO2 precursor and the gelation time were found to be influential for the synthesis of non-cracked CeO2-doped SiO2 sol–gel monoliths. 相似文献
16.
Aerogels are extremely porous high-tech materials based on inorganic oxides, especially silica. The paper describes synthesis and properties of SiO2-aerogel, and changes occurring during heating of SiO2-aerogel in the temperature range from 20 to 1000°C. Four thermoanalytical methods were used: Thermodilatometry, Differential thermal analysis, Thermogravimetry and Derivative thermogravimetry. 相似文献
17.
Young Bok Ryu Won Young Jung Man Sig Lee Euh Duck Jeong Hyun Gyu Kim Seong-Soo Park Gun-Dae Lee Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2008,93(2):333-341
Nanosized TiO2 particles were prepared by the hydrothermal method from the amorphous powders which were precipitated in an aqueous peroxotitanate
solution. The physical properties of the nanosized TiO2 particles prepared were investigated. We also examined the activity of TiO2 particles as a photocatalyst on the decomposition of orange II. The titania sol can be successfully crystallized to the anatase
phase through hydrothermal aging at temperatures higher than 160°C. The particle size increases from 18 to 26 nm as the synthesis
temperature increases from 140 to 200°C. Titania particles prepared at 180°C show the highest activity, and titania particles
calcined at 400°C show also the highest activity on the photocatalytic decomposition of orange II. 相似文献
18.
The present paper reviews in detail the different studies now being conducted by our research team concerning the ultradeep hydrodesulfurization (HDS) of dibenzothiophene (DBT) derivatives over Mo/TiO2 and Mo/TiO2–Al2O3 catalysts. First, a detailed characterization of Mo/TiO2 (P-25 Degussa, 50 m2/g) catalysts prepared by equilibrium adsorption technique shows that Mo- species are highly and uniformly dispersed on the surface of titania up to 6.6 wt% MoO3 loading. Above this value, some aggregation of Mo occurs, leading to the formation of bulk MoO3. Below 6.6 wt% MoO3 loading, the Raman spectroscopy data of the calcined samples show that the supported Mo-species possess a highly distorted octahedral MoO6 structure. TiO2–Al2O3 composites were prepared by chemical vapor deposition (CVD) using TiCl4 as a precursor. Using several characterization techniques, we demonstrated that the support composite presents a high dispersion of TiO2 over -Al2O3 without forming precipitates up to ca. 11 wt% loading. Moreover, the textural properties of the composite support are comparable to those of alumina. Under the present sulfidation conditions (673 K, 5%H2S/95%H2), Mo-species supported on TiO2 are better sulfided than on alumina, as demonstrated using XPS. This can be attributed to the relatively lower interaction between Mo-species and titania. The state of sulfide species supported on the composite support can be considered as a transition state between TiO2 and Al2O3. However, at relatively higher TiO2 loadings (ca. 11 wt%), Mo/TiO2–Al2O3 catalysts exhibit sulfidability similar to that of Mo/TiO2. The HDS tests conducted in both the laboratory and in industry show that sulfide catalysts supported on TiO2–Al2O3 (ca. 11 wt% TiO2) are more active than those supported on TiO2 or Al2O3. 相似文献
19.
Yong Yang Yuming Zhou Jianhua Ge Yongjuan Wang Yunxia Zhu 《Journal of solid state chemistry》2011,184(10):2617-2622
Optically active polyurethane/titania/silica (LPU/TiO2/SiO2) multilayered core–shell composite microspheres were prepared by the combination of titania deposition on the surface of silica spheres and subsequent polymer grafting. LPU/TiO2/SiO2 was characterized by FT-IR, UV–vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), SEM and TEM, and the infrared emissivity value (8–14 μm) was investigated in addition. The results indicated that titania and polyurethane had been successfully coated onto the surfaces of silica microspheres. LPU/TiO2/SiO2 exhibited clearly multilayered core–shell construction. The infrared emissivity values reduced along with the increase of covering layers thus proved that the interfacial interactions had direct influence on the infrared emissivity. Besides, LPU/TiO2/SiO2 multilayered microspheres based on the optically active polyurethane took advantages of the orderly secondary structure and strengthened interfacial synergistic actions. Consequently, it possessed the lowest infrared emissivity value. 相似文献
20.
Hiroaki Imai Koichi Awazu Masarux Yasumori Hideo Onuki Hiroshi Hirashima 《Journal of Sol-Gel Science and Technology》1997,8(1-3):365-369
Structural changes in SiO2 and TiO2 gel films were investigated using ultraviolet (UV) and vacuum ultraviolet (VUV) irradiations. A significant compaction with dehydration of SiO2 gel films was induced by irradiation of photons in the range of 9–18 eV. The refractive index and the shrinkage of the irradiated SiO2 gel films were comparable to those obtained by sintering at 1000°C. Densification of TiO2 gel films was also observed with irradiation of 5–14 eV photons. However, effects of the irradiation on TiO2 gel were smaller that those on SiO2 gel. The structural changes in the gel films are attributed to electronic excitations which are induced by irradiation with photons having higher energies than the bandgap of the oxides. The photo-induced effects are presumed to depend on the optical properties and structure of the gels. 相似文献