Ti接枝MCM-48对苯羟化反应的化学亲和选择性及化学稳定性研究

合成了具有较好长程结构和孔结构的Si MCM - 48,以合成后表面接枝改性的方法制备了表面Ti含量不同的Ti接枝MCM - 48催化剂 ,通过X射线衍射 (XRD)、低温N2 吸 -脱附、X射线光电子能谱 (XPS)及原子吸收光谱等对催化剂作了表征 ,Ti接枝MCM - 48仍具有良好的长程有序结构和孔结构 ,其比表面积高于 95 0m2 ·g-1,孔径分布窄 ,随Ti接枝量提高 ,最可几孔径由 2 5nm逐渐降低至 1 9nm。将Ti接枝MCM - 48催化剂用于苯羟化反应 ,研究了其苯羟化性能和结构稳定性 ,结果发现 :Ti接枝MCM - 48对苯羟化反应具有一定活性 ,苯酚选择性高于80 % ,且随表面Ti含量增加 ,苯转化率和苯酚选择性提高。反应后催化剂的孔结构、比表面及孔径分布未受到影响 ,长程有序结构稍有改变     

Ti-containing MCM-41 catalysts for liquid phase oxidation of cyclohexene with aqueous H2O2 and tert-butyl hydroperoxide

Framework Ti-substituted and Ti-grafted MCM-41 mesoporous material has been prepared by direct hydrothermal synthesis and a post-synthesis grafting method. The materials have been tested as catalysts for cyclohexene oxidation with aqueous H₂O₂ and tert-butyl hydroperoxide (TBHP). With aqueous H₂O₂ in methanol, the major products were cyclohexene diol and its methyl ethers. No cyclohexene oxide was produced. Titanium leaching was a serious problem, and the catalyst lost its activity irreversibly after only one cycle of reaction. With TBHP, the selectivity for cyclohexene oxide was near 100%, titanium leaching was negligible, and the catalyst could be repeatedly used after regeneration without suffering significant activity loss. However, the reaction rate was lower than when H₂O₂ was used. Framework substituted material and catalysts prepared by Ti-grafting onto a MCM-41 support behaved similar, but the Ti-grafted MCM-41 is somewhat more active. The turnover frequency (TOF) per mole of Ti decreases with an increase of Ti content in the catalyst. This is caused by a reduced Ti dispersion within the silica matrix. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mono (V, Nb) or bimetallic (V–Ti, Nb–Ti) ions modified MCM-41 catalysts: synthesis, characterization and catalysis in oxidation of hydrocarbons (aromatics and alcohols)

Mesoporous MCM-41 molecular sieves modified by single (V and Nb) or bimetal (Nb–Ti and V–Ti) ions with highly ordered hexagonal arrangement of their cylindrical channels were prepared by direct synthesis with two different silica sources (sodium silicate and TEOS) and characterized (as-synthesized samples and those used after reaction) by XRD, N₂ adsorption–desorption, TEM, SEM and FTIR techniques. Niobium and titanium were stabilized in the autoclavized gel by complexation with a ligand (acetylacetone and oxalic acid, respectively). V modified MCM-41 catalysts gave a very high activity in hydroxylation reaction of benzene and toluene and a low conversion in oxidation of styrene while Nb-modified MCM-41 samples showed very high conversion in oxidation of styrene but low oxidation conversion of benzene and toluene. Further introduction of titanium in V- and Nb-modified MCM-41 materials conducted to the less well-ordered hexagonal arrangement and gave very different effect on activity in oxidation of aromatics. Introduction of Ti into V-MCM-41 solids led to an increase in activity in oxidation of styrene and benzene but a decrease in conversion in oxidation of toluene. While the addition of Ti in Nb-MCM-41 resulted in a slight increase in conversion of styrene oxidation but a significant decrease in activity of benzene and toluene oxidation. It reveals that the introduction mode of oxidant in the reactors can also influence the activity and selectivity of reaction. An increase in reaction rate of oxidation, in the first 20 h, was obtained by introduction of H₂O₂ step by step during the reaction. The present paper evidenced that the side chain oxidation is main reaction of styrene oxidation while the hydroxylation is main reaction of benzene and toluene. That is why these two reactions need different catalytic centers as revealed by this paper. The oxidation of alcohols using V-modified MCM-41 as catalysts has also been explored and these catalysts showed a very low catalytic activity which increases in the order: hexanol相似文献   

Vanadium-containing ordered mesoporous silicas: Synthesis, characterization and catalytic activity in the hydroxylation of biphenyl

A series of vanadium-containing ordered mesoporous MCM-41 materials (V-OMS) have been synthesized by direct hydrothermal (V-MCM-41) and grafting (V/MCM-41) methods using hexadecyl trimethyl ammonium bromide (HDTMABr) as the structure-directing agent. The physico-chemical properties of the vanadium-containing materials were characterized in detail by ICP-OES, XRD, FT-IR, N₂ adsorption–desorption, DRUV-VIS, TPR, XPS and SEM techniques. The redox performances of the vanadium-modified mesoporous materials were tested in the hydroxylation of biphenyl using aqueous H₂O₂ (30 wt.%) as oxidant. For a better exploitation of the catalytic activity, the reaction parameters are optimized in terms of temperature, solvent, oxidant, etc. A comparison between the catalytic activity values of the vanadium-containing mesoporous materials prepared by the two routes shows that vanadium-substituted (V-MCM-41) materials had increased activity and improved selectivity for mono hydroxyl products in the hydroxylation reaction of biphenyl compared to the V/MCM-41 catalysts. The heterogenity of the catalysts was verified by a series of leaching studies. Both the catalysts enhance the leaching of active vanadia species during the reaction; among them, V/MCM-41 shows the least heterogenity.     

Competent,selective and high yield of 7-hydroxy-4-methyl coumarin over sulfonated mesoporous silica as solid acid catalysts

Highly ordered mesoporous MCM-41 and SBA-15 have been synthesized and functionalized with different amounts of propyl sulfonic acid groups using 3-mercaptopropyltrimethoxysilane as sulfur source. The synthesized catalysts have been well-characterized by different techniques such as XRD, FTIR and BET surface area and pore size distribution by BJH method. FTIR spectra of chemisorbed pyridine and temperature programmed desorption of NH₃ techniques have been successfully used to characterize the acidic sites. The results showed that, both surface area, mean pore diameter and pore volume decrease as the extent of sulfonation increase. XRD results and TEM images confirm the stability of mesoporous long range order even after sulfonation process done. In addition, the study also showed that, sulfonation enhances the surface acidity and new moderate and strong acid sites were created. All the sulfonated catalysts under investigations have been found to be highly active and selective for the Pechmann condensation reaction of resorcinol with ethyl acetoacetate. More than 98% yield of 7-hydroxy-4-methyl coumarin was obtained with 100% selectivity. Presence of high number of moderate and strong Brönsted acid sites in sulfonated catalysts help in achieving high yields. Furthermore, the MCM-41 sulfonated catalysts showed higher catalytic performance due to their higher surface acidities.     

Photocatalytic decomposition of 4-nitrophenol on Ti-containing MCM-41

A series of Ti-containing MCM-41 samples, such as Ti-MCM-41 with variable Si/Ti ratios and Cr–Ti-substituted TiO₂-loaded MCM-41 having different TiO₂ loading, were prepared and studied for the photocatalytic decomposition of 4-nitrophenol in UV and visible light. The samples were characterized using surface area measurement, XRD, FT-IR, and UV–vis DRS techniques. In the case of the Ti-MCM-41 samples with Si/Ti ratios higher than 20 which were found to have typical mesoporous structure, the framework incorporation of Ti into MCM-41 increased with decreasing Si/Ti ratio. On the contrary, the Ti-MCM-41 with lower Si/Ti ratio (Si/Ti = 10) shows low structural integrity and the formation of Ti-oxide species, leading to a considerable decrease in surface area. In the case of Cr–Ti-substituted TiO₂-loaded MCM-41 samples, significant absorption occurs in visible light and the absorption in both UV and visible region increases with increasing TiO₂ loading. However, when the amount of TiO₂ loaded on Cr–Ti-MCM-41 increased above 33 wt.%, the absorption in visible light increased slightly. Thus, it seems that, at higher TiO₂ loading, some TiO₂ particles are not closely bound to the wall of Cr–Ti-MCM-41. The photocatalytic activities of Ti-containing MCM-41 samples were strongly influenced by the amount of Ti. Under UV illumination, the highest photocatalytic activity for photocatalytic decomposition of 4-NP was observed for the Ti-MCM-41 having Si/Ti ratio of 20. Among various Ti-containing MCM-41 materials prepared in this work, only Cr–Ti-substituted TiO₂-loaded MCM-41 catalysts exhibited discernable photocatalytic activities in visible light, and their photocatalytic activities increased considerably with increasing TiO₂ loading up to 33 wt.%. Further increase in TiO₂ loading enhanced photocatalytic activity slightly.     

Characteristics of Ti-MCM-41 and its Catalytic Properties in Oxidation of Benzene

A series of mesoporous titanosilicate Ti-MCM-41 molecular sieves with various Si/Ti ratios have been hydrothermally synthesized using hexadecyl-trimethylammonium bromide as the organic surfactant. These materials were characterized with powder X-ray diffraction (XRD), framework FTIR, diffuse reflectance UV-visible spectroscopy, nitrogen sorption measurements, differential thermal analysis (DTA), and transmission electron microscopy (TEM). The crystallinity of Ti-MCM-41 after calcination was almost two-fold higher than that of the as-synthesized one. The crystallinity and surface area of Ti-MCM-41 both decrease with an increase of titanium content. The results of XRD and FTIR show that the solid products have the MCM-41 structure and contained only atomically dispersed titanium, consistent with framework titanium in Ti-MCM-41. All of the materials had a uniform pore size distribution with pore size of around 3.0 nm. The hexagonal array structure of uniform pore size was observed by TEM. It proved that the pores were highly aligned. The catalytic activities of Ti-MCM-41 were tested in the partial oxidation of benzene by diluted hydrogen peroxide in a batch reactor. Ti-MCM-41 had a higher activity than TiO₂ and Ti/NaY. The activity of Ti-MCM-41 increased with titanium content. The activity of Ti-MCM-41 prepared with hydrothermal synthesis was higher than that of the sample prepared with impregnation. The high activity in Ti-MCM-41 can be attributed to its hydrohobicity and large pore size. Phenol was the only liquid phase product on all of the samples.     

Catalytic epoxidation of unsaturated alcohols on Ti-MCM-41

The catalytic epoxidation of a series of unsaturated terpenic alcohols was carried out on titanium-containing MCM-41 mesoporous materials with tert-butylhydroperoxide. A direct comparison between in-framework Ti-MCM-41 and Ti-grafted MCM-41 showed a better performance of the latter, even if the difference between them becomes lower as the alcoholic group approaches the C=C double bond. At 358 K and in both acetonitrile and ethyl acetate, the epoxidation rate of the double bond is ruled, on these catalysts, mainly by electronic factors, which cause the preferential oxidation of internal unsaturations instead of the terminal ones. It is also governed by the OH-function position, so that, particularly in ethyl acetate, the closer the hydroxyl group to the unsaturation, the higher is the conversion rate of the terpene.     

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study, various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5. The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied. The results of XRD, TEM N₂-adsorption-desorption, NH₃-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals, and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5. Catalytic cracking of n-dodecane (550 ℃, 4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance, with the improvement higher than 87% in the catalytic activities and 21% in the deactivation rate compared with untreated zeolites. This could be ascribed to their suitable pore structure, which enhanced the diffusion of reactant molecules in pores of catalysts.     

Acidity and catalytic activity of the mesoporous aluminosilicate molecular sieve MCM-41

The acidity and catalytic properties of aluminosilicate mesoporous molecular sieves with the MCM-41 structure and bulk Si/Al ratios in the 10–60 range have been investigated. The incorporation of 4-coordinate aluminium into the structure of MCM-41 generates both BrØnsted and Lewis acid sites in amounts increasing with the degree of incorporation. However, the BrØnsted/Lewis acid population ratio is independent of the content of aluminium. The number and strength of acid sites generated are comparable to those of a pillared acid-activated clay and lower than in zeolite H-Y with Si/Al=3.65. Aluminosilicate MCM-41 is a moderate catalyst for the conversion of cumene which proceeds predominantly via catalytic cracking to propene and benzene. The sample of MCM-41 with the highest content of framework aluminium (Si/Al=10) has the largest number of BrØnsted acid sites and exhibits highest catalytic activity.     

Thermoporometry as a new tool in analyzing mesoporous MCM-41 materials

Thermoporometry, a calorimetric procedure, is applied for measuring the pore size distribution, pore volume and surface area of mesoporous MCM-41 molecular sieves using water as the adsorbate. A series of MCM-41 materials with various pore diameters was synthesized and subjected to the new method. The results are compared with nitrogen physisorption. Both methods are complementary, whereby the former provides also information about the pore shape. MCM-41 materials with pores wider than 50 Å also allow the use of benzene as the adsorbate in thermoporometry.     

Characterisation and catalytic properties of MCM-41 and Pd/MCM-41 materials

Pure silica MCM-41 mesoporous molecular sieve material was synthesised and characterised by in situ synchrotron XRD, TEM, TGA/DTA and DRIFTS techniques. In situ energy dispersive XRD (EDXRD) confirmed the exact nature of the pore diameter of MCM-41 and the change in crystal structure on calcination. The IR band at 1057 cm^-1 of as-synthesised MCM-41 was shifted by 14 cm^-1 on heating to 673 K due to increased condensation of silanol groups to form Si-O-Si bridges. Calcined MCM-41 materials were used to support Pd, and the catalytic activities for 1-hexene and benzene selective hydrogenation were investigated. The Pd/MCM-41 catalyst showed high activity in hydrogenation of 1-hexene at an inlet reaction temperature of 298 K, but did not show any activity in hydrogenation for benzene. TEM results for the reduced Pd/MCM-41 catalysts revealed that the average Pd particle size was around 2-2.5 nm and these particles were located in the pores of MCM-41 and showed good distribution. TPR measurements showed that about 70% of palladium oxide (PdO) loading in the calcined catalysts was reduced at sub-ambient temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of mesoporous MCM-41 from natural sepiolite and its catalytic activity of cracking waste polystyrene plastics

Mesoporous MCM-41 was prepared by leaching of sepiolite and sequent hydrothermal synthesis in NaOH solution with hexadecyltrimethylammonium bromide as template. Small-angle X-ray diffraction patterns, Scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller were performed to characterize the resulting compounds. The results showed that the crystallinity and pore size of MCM-41 increased with increase of crystallization time, ratios of surfactant to SiO₂ and decrease of Mg content. The experimental results of catalytic cracking of polystyrene waste showed that the MCM-41 with MgO from natural sepiolite had high catalytic activity and good selectivity to monomer styrene for the catalytic cracking of polystyrene when the ratio of waste plastics to MCM-41 was 200. The side reactions yielded ethylbenzene, isopropylbenzene, isopropenylbenzene and secondary cross-linking were suppressed by basic species MgO in MCM-41.     

不同碱介质对合成硅基MCM-41的影响

研究了在较高的硅与表面活性剂摩尔比(10)体系中,采用不同的碱介质(氨水、乙二胺、三乙醇胺／NaOH)来合成MCM-41。通过XRD,N2吸附-脱附等表征手段,分析了不同碱介质体系对制备MCM-41的影响,并分别与NaOH介质中合成的MCM-41进行比较。结果显示,弱碱介质(NH3,EDA)有利于提高MCM-41的热稳定性;而采用混合碱介质(三乙醇胺／NaOH),则可在一定程度上改善MCM-41的水热稳定性,但随着三乙醇胺量的增加,材料的孔径会相应的减小。     

Pyrolysis of an LDPE-LLDPE-EVA copolymer mixture over various mesoporous catalysts

The aim of the present work was to study the performance of mesoporous catalysts in the catalytic cracking of an LDPE+LLDPE+EVA copolymer. Mesoporous catalysts, including MCM-41, Nano-MCM-41, Al-Nano-MCM-41, MMZ-ZSM-5 and Meso-MFI, were applied for this reaction. Also, microporous HZSM-5 was used for a comparison. All of the catalysts showed higher decomposition abilities than thermal decomposition. The catalytic conversion of the LDPE+LLDPE+EVA copolymer was highest with the use of Meso-MFI due to its pore size and strong Br?nsted acidity, with high selectivity for lower olefin and gasoline range hydrocarbon. Both MMZ-ZSM-5 and Al-Nano-MCM-41 have an acid site that induced the decomposition reactions, and thus, produced compounds with lower carbon numbers in liquid products. MCM-41, which exhibits no acidity, showed a similar distribution of liquid products to that via thermal cracking, while Nano-MCM-41 showed better catalytic cracking ability due to its high surface area.     

苯加氢催化剂Pd/MCM—41催化性能的研究

对负载型催化剂Pd/MCM—41进行了透射电镜及N2吸附表征。结果表明,金属Pd主要以纳米粒子的形式负载在分子筛表面,MCM—41的基本结构未被破坏。将Pd/MCM—41用于苯加氢反应,研究了反应温度和反应压力对催化活性的影响。结果表明,随着反应温度、反应压力的增加,苯的转化率得到有效提高。     

Co掺杂对Ce/MCM-41和Ce/SBA-15催化剂催化氧化甲苯性能的影响

以分子筛为载体,采用等体积浸渍法制备Ce/SBA-15、Ce/MCM-41、Ce Co/SBA-15和Ce Co/MCM-41催化剂。用N2吸附-脱附、X射线衍射、扫描电子显微镜、H2程序升温还原、X射线光电子能谱和傅立叶变换红外光谱等对载体和催化剂进行表征,并考察催化剂催化氧化甲苯的活性。结果表明,与载体相比,随着Ce和Co的浸渍,催化剂的比表面积和孔容下降,但仍然保持了载体的有序介孔结构。引入的Ce和Co没有进入分子筛骨架,而是以立方相固溶体形式存在于分子筛表面和孔道中。催化剂催化氧化甲苯活性顺序依次为:Ce Co/SBA-15>Ce Co/MCM-41>Ce/MCM-41>Ce/SBA-15。共浸渍Ce和Co的催化剂活性明显优于只浸渍Ce的催化剂,活性与其还原性能直接相关,Ce Co/SBA-15催化剂具有最低的还原温度和最好的供氧能力,从而表现出最优的催化性能。     

Stability of MCM-41-Supported CoMo Hydrotreating Catalysts

The performance of sulfided CoMo hydrotreating catalysts supported on MCM-41 has been evaluated using hydrodesulfurization of 4-ethyl, 6-methyl- dibenzothiophene (4E,6M-DBT) model compound in n-hexadecane and of 4-methyl, 6-methyl-dibenzothiophene (4,6-DMDBT) in a commercial feed as a test reaction. Although the performance of CoMoS/MCM-41 is high for the model feed reaction as compared to commercial CoMoS/alumina, for the commercial feed reaction the performance of the commercial catalyst is much better. Model feed reaction with the addition of carbazole shows that, although this nitrogen-containing compound has a strong inhibiting effect, the lower catalytic performance of CoMoS/MCM-41 in the commercial feed test is probably not solely due to the presence of nitrogen. TEM investigations show that the decrease in activity of the CoMoS/MCM-41 in the nitrogen-containing and commercial feed reactions is not due to sintering of the sulfidic phase. However, it appears that the MCM-41 collapses during the catalytic reactions, and this effect is most pronounced for the commercial feed test. The degradation of the MCM-41 support material does not affect the dispersion of the CoMoS, but induces increased coking.     

Basic Cs-Pt/MCM-41 Catalysts: Synthesis, Characterization and Activity in n-Hexane Conversion

Cs-Pt/MCM-41 catalysts with basic character have been prepared by selective adsorption of Pt(NH₃)₄(OH)₂ at pH = 8 on pure silica MCM-41 followed by incipient-wetness impregnation of CsNO₃, then oxidation and reduction. The influence of the amount of Cs (0, 2 and 4 wt%) on the size of the reduced Pt particles and on their catalytic behavior in the conversion of n-hexane has been investigated. Whatever the Pt content (0.7 or 2.0 wt% Pt), the addition of Cs results in a higher Pt dispersion, a higher initial activity and a higher selectivity for aromatization. On the more basic Pt-richest MCM-41 sample (4 wt% Cs, 2 wt% Pt) the selectivity to benzene reaches values close to those obtained on Cs-enriched Pt/Cs-BEA zeolite. However, the catalytic stability is lower. The catalytic trends are discussed in view of the physicochemical properties of the solids determined by chemical analysis, N₂ physisorption, XRD and TEM before and after catalytic test.     

Effect of pore size on the performance of mesoporous material supported chiral Mn(III) salen complex for the epoxidation of unfunctionalized olefins

A series of mesoporous MCM-41 and MCM-48 materials with different pore sizes were synthesized and used as supports to immobilize chiral Mn(III) salen complex. The heterogeneous catalysts were characterized by XRD, FT-IR, DR UV–vis, and N₂ sorption, and the results indicated the successful immobilization of chiral Mn(III) salen complex. The confinement effect of pore size on the catalytic performance of the heterogeneous catalysts was studied for the asymmetric epoxidation of unfunctionalized olefins with m-chloroperoxybenzoic acid as an oxidant. It was found that the conversions and enantiomeric excess (ee) values were closely correlated with the pore sizes of parent supports. The catalysts immobilized on the large-pore mesoporous supports exhibited higher conversions, and for the catalysts immobilized on MCM-41 materials, the ee values improved with increasing pore size. However, for the MCM-48 material-supported catalysts, the compatible pore size of the support with the substrate was beneficial for obtaining higher enantioselectivity in olefin epoxidation.