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1.
首次研究了含羟基的HMS(c)和含十四胺模板剂的HMS(u)以及用3-氨丙基三乙基氧基硅烷改性的HMS(m)三种中孔载体与Ti(OPr)4的交换反应规律,发现载体表面官能团对交换反应有明显影响,对HMS(c),在低温交换下可获得更高的钛交换量,提高交换温度钛交换量反而下降;对HMS(u)和HMS(m),则是随交换温度的升高,钛交换量增加,这表明含羟基的载休比含氨基的载体更易与Ti(OPr)4交换,交换温度会影响Ti(OPr)4与HMS(c)表面羟基作用的数目,对含氨基载体则无此影响,苯乙烯环氧化结构表明,用HMS(c)组装的钛催化剂氧化活性最高,以HMS)u)组装的钛催化剂环氧化选择性最好,氨基和酒石酸二乙酯(DET)配体对钛活性中心的调变作用会造成其活性下降,而选择性上升。  相似文献   

2.
实验研究结果表明双核金属酞菁类化合物MPc-PcM(M=V、Cr、Mn、Fe、Co、Ni、Cu)是催化H_2S液相氧化反应的良好催化剂,且其催化活性顺序为Co>Ni>V>Fe>Cu>Cr>Mn.采用量子化学理论计算方法(INDO/S)分析了其前线分子轨道的构成特征,结果表明这几种MPc-PcM的LUMO轨道皆为有金属离子参与形成的π轨道,但HOMO轨道间的差异却很大.M=Co、Ni、Cu、Cr时,其HOMO为π轨道;而M=Fe、Mn时,其HOMO却为σ轨道.正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下,才导致MPc-PcM的催化活性顺序并非按中心金属离子价电子层d电子数的递变而呈现出规律性的变化.  相似文献   

3.
CO2部分氧化乙烷制乙烯Pd—Cu/MoO3—SiO2催化剂的研究   总被引:7,自引:0,他引:7  
李青  钟顺和 《应用化学》1998,15(6):49-52
用化学吸附-红外光谱、化学吸附-程序升温脱附(TPD)和微型反应技术研究了Pd-Cu/MoO3-SiO2(MoSO)催化剂对CO2和乙烷的吸附活化和部分氧化反应性能.结果表明,乙烷以C—H键中的H吸附于MoSO载体表面MoO键的端基氧上;Pd-Cu/MoSO催化剂对CO2有良好的化学吸附活化性能,CO2的吸附除有线式吸附态和剪式吸附态外,还有一种新的卧式吸附态;Pd-Cu/MoSO催化剂的晶格氧参与了化学反应.探讨了在Pd-Cu/MoSO催化剂上CO2的部分氧化乙烷反应机理  相似文献   

4.
采用XRD,顺磁共振(ESR),Mossbauer和或温还原(TPR)技术对负截型Cu-Fe-O(Ⅰ),Cu-Fe-Co-O(Ⅱ)催化剂的固相结构及热稳定性进行了研究。结果发现,(Ⅰ)中主要存在Fe2CuO4,CuO和颗粒度小于13nm的Fe2O3相。随着焙烧温度的升高,CuO晶相逐渐消失,Fe2CuO4的晶相长大。(Ⅱ)中Ce的存在,能提高Cu^2+的浓度,抑制CuO和Fe2CuO4晶相的生成,  相似文献   

5.
通过η5-R~1C_5H_4(CO)_3MNa与η~5-R~2C_5H_4(CO)_3MNa(M=Mo,W)以及η~5-R~1C_5H_4(CO)_3MoNa与η~5-R~2C_5H_4(CO)_3WNa在Fe_2(SO_4)_3醋酸水溶液作用下的交叉氧化偶联反应,合成了7个新的非对称型金属单键化合物η~5-R~1C_5H_4(CO)-3Mo─Mo(CO)_3C_5H_4R~2-η~5(R~1,R~2:C(O)Me,CO2Et),η5-R1C5N4(CO)3W─W(CO)3C5H4R2-η5(R1,R2:C(O)Me,CO2Et;H,CO2Et)和η5-R1C5H4(CO)3Mo─W(CO)3C5H4R2-η5(R1,R2:C(O)Me,H;Et,C(O)Me;C(O)Me,n-Bu;CO2Me,n-Bu).用C/N分析、IR、1HNMR和MS表征了它们的结构,并对该氧化偶联反应的特点进行了讨论.  相似文献   

6.
宋礼成  伍伯牧 《结构化学》1995,14(5):393-398
通过η^5-CH3COC5H4(CO)3MoNa与(μ3-S)FeCo2(CO)9的反应俣成了(μ3-S)FeMoCo(η^5-CH3COC5H4(CO)81,1进一步(η^5-C5H5)Ni的反应合成了(μ3-S)-FeMoNi(η^5-CH3COC5H4)(CO)52,(μ3-S)FeMoNi(η^5-C5H5(η^5-C5H5)-(CO)53及(μ3-S)FeMoCo(η5-C5H5)(CO  相似文献   

7.
作为甲醇氧化制甲醛、甲醇氨氧化制HCN反应的催化剂,其活性组分钼的流失是导致催化剂失活的主要原因。本文结合程序升温脱附(TPD)及X-光衍射(XRD)等测试手段,对Mo-Fe/SiO_2催化剂及工业实际用多元复合钼催化剂中钼的流失动力学和机理进行了研究。在HCN合成过程中,水能引起活性组分钼的流失,而水又是反应产物。对工业用多元复合钼催化剂的流失情况进行了动力学考察,实验发现,催化剂中的钼是较难流失的,XRD测试结果表明,Mo-Fe/SiO_2催化剂中的钼是以Fe_2(MoO_4)_3晶体形式存在的,而反应后催化剂中Mo为MoO_3晶体状态。与其它催化剂比较,MoO_3/SiO_2催化剂中的钼难流失,而较Bi-Mo/SiO_2催化剂中的钼易流失。其中工业用催化剂是最为稳定的。根据实验结果,结合我们以前的工作,证明Mo-Fe/SiO_2催化剂中,由于钼组分和铁组分的相互作用,使得Mo-Fe/SiO_2中的Mo的流失难于单组分的MoO_3/SiO_2催化剂,此外钼流失过程中MoO_2(OH)_2与催化剂中铁组分反应生成钼酸盐的倾向也是Mo难于流失的原因之一。而Mo-Fe/SiO_2和Mo-Bi/SiO_2催化剂中钼流失速度的差异  相似文献   

8.
对比考察了Mo/CuH-ZSM-5和Mo/H-ZSM-5催化剂的甲烷无氧芳构化性能,并用XRD,XPS,ESR等多种测试手段对反应前后催化剂上的Mo物种及铜助剂的价态变化进行了详细研究,发现Cu(Ⅱ)部分取代H-ZSM-5变换位上的H^+后,抑制了活性组分MoO2的还原,而Cu物种自身被还原,进而将这种价态变化与催化剂的活性进行了关联。  相似文献   

9.
超大孔Fe和V—Ti分子筛的合成   总被引:1,自引:0,他引:1  
袁忠勇  刘述全 《分子催化》1995,9(6):457-463
水热法合成了具有超大孔MCM-41分子筛结构的含Fe和V-Ti分子筛,通过XRD,骨架IR,ESR,^29SiMAS NMR,紫外漫反射等测试表征证实,Fe原子在FeMCM-41分子筛骨架上,V和Ti同是进入V-TiMCM-41分子筛骨架。  相似文献   

10.
应用INDO/S半经验量子化学方法,对簇合物离子Mo3S和Mo3S4Mn+(M=Fe、Ni,n=4;M=Cu,n=5)分别进行分子轨道计算。根据计算得到的簇离子中的原子表观电荷和成键指标,说明Fe、Ni、Cu+与Mo3S成键作用的相对强度依次是Fe-Mo>Ni-Mo>Cu+-Mo。比较了用含组态作用的INDO/S方法计算得到的电子跃迁能与实验得到的电子吸收光谱值,并讨论了吸收峰归属情况。对于M为Fe、Ni的簇离子Mo3S4M4+,最低能量的电子跃迁吸收峰起源于异金属间电荷转移跃迁(MM’CT);而Mo3S4Cu(5+)簇离子观察到的吸收峰主要是Mo3S芯的局域内电荷转移跃迁。根据理论计算结果,由Cu+离子到Mo3S的电荷转移跃迁谱线,大约在46000cm-1以上才能观察到吸收峰。从Mo3S4Fe4+次低能量吸收峰的实验值16600cm-1和理论值16500cm-1与Mo3S的最低能量吸收峰的实验值16600cm-1和理论值16900cm-1比较,表明无论从理论上或实验上都能证实簇离子Mo3S4Fe4+在能量为16600cm-1处的吸收峰是起因于Mo3S芯的局域内电荷转移跃迁。  相似文献   

11.
An effective method for dispersing NiO onto ordered mesoporous silica, SBA-15, is described. The procedure involves the use of polyethylene oxide (PEO) as an encapsulating agent. It can be expected that encapsulation between PEO and Ni2+ ions mainly involves complexes between PEO and Ni2+ ions. Both N2 adsorption/desorption isotherm and TEM analyses indicate that a 2-dimensionally hexagonal pore structure with a distinct pore symmetry (space group P6mm) is maintained throughout the procedure, even though both Ni2+ ions and PEO are present in the middle of the self-assembly of mesostructured silica. The particle size of the NiO increases slightly as a function of PEO concentration. When the ratio of PEO to the templating agent (triblock copolymer, polyethylene oxide-polypropylene oxide-polyethylene oxide) reaches a value of 4.5, ordered mesoporous silica with NiO is hardly formed.  相似文献   

12.
模板剂对全硅MCM-41介孔分子筛结构的影响   总被引:10,自引:0,他引:10  
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.  相似文献   

13.
Supramolecular structures of lecithin occurred to be the template in the synthesis of mesoporous aluminosilicates; using of various combinations of lecithin and cetyltrimethyl-ammonium bromide or octadecylamine as templating agents allowed to obtain mesoporous substances with pores up to 100 Å, as well as biporous materials in aluminosilicate system. In the presence of glucose oxidase and cetyltrimethyl-ammonium bromide combinations aluminosilicate substances with complex porous structure were shown to be formed (pore size distributions exhibited 3 peaks, corresponding 3 effective size of mesopores in the 30–100 Å range). The investigation of sorption of glucose oxidase on obtained aluminosilicate mesoporous substances was carried out, the results obtained allowus to consider such materials as prospect for creation high capable and selective sorbents for biomolecules sorption, as well as active elements of chemical and biosensors.  相似文献   

14.
Unusual partially crystalline ordered mesoporous zirconosilicate doughnuts with Si/Zr ratio as low as 1.5 were synthesized from the aqueous polymerisation of a single source molecular precursor Zr[OSi(Ot-BuO)(3)](4) without the use of any templating agent. A radial homogenous mesoporosity (4 nm) was observed inside these very regular sub-micrometric (600 nm) doughnuts. These structures were partially crystallized in hydrothermal conditions (100°C) into an analogous zircon (ZrSiO(4)) framework. The formation mechanism has been investigated. It is evidenced that chlorine anions Cl(-) concentration and pH value are essential to achieve the process, even if their role is still a matter of investigations. The obtained materials demonstrated even higher catalytic activity, selectivity and stability in the liquid oxidative dehydrogenation of hydroquinone to 1,4-benzoquinone compared to TS-1 zeolite catalysts and amorphous highly ordered mesoporous zirconosilicate materials.  相似文献   

15.
By adjusting the local effective surfactant packing parameter through synthesis temperature, highly ordered SBA-16-type mesoporous silica materials have been synthesized by templating with a nonionic triblock copolymer Pluronic F68 in strongly acidic conditions at temperature 30~40°C with the addition of K2SO4. The prepared SBA-16-type mesoporous silica materials having Im3m cubic mesostructure were proved by the well-defined x-ray diffraction patterns combined with transmission electron microscopy. Scanning electron microscopy indicated that a transformation from faced-sphere to faced-polyhedron shape morphologies could be induced with increasing of the synthesis temperature. The nitrogen adsorption–desorption analysis revealed that the mean pore size (5.50~6.13 nm) of the prepared materials increased with increasing synthesis temperature. However, when the synthesis temperature exceeded 46°C, only disordered mesoporous silca was obtained. Our synthesis strategies by adjusting the local effective surfactant packing parameter through synthesis condition, even in a narrow range, would be used not only to optimize the synthesis conditions of reported mesoporous silca, but also to fabricate new mesoporous silica materials with well-ordered channel and anticipated morphologies.  相似文献   

16.
以廉价国产化试剂合成大孔径高度有序介孔氧化硅分子筛   总被引:4,自引:0,他引:4  
王丽敏  范杰  屠波  赵东元 《无机化学学报》2002,18(10):1053-1056
新一代大孔径(1~30nm)介孔分子筛在大分子转化、吸附、生物大分子分离以及电磁、传感器、光电子等领域均具有广泛的应用前景犤1~4犦。由昂贵的长链有机季铵盐阳离子表面活性剂为模板合成的MCM-41介孔分子筛,由于其孔径小,水热稳定性差,受到了较大的限制。与其相比,以嵌段高分子共聚物为模板剂合成的介孔分子筛SBA-15具有孔径均一,有序度高,并且其孔径大以及水热性能良好等优点,近年来得到了广泛的研究犤5~9犦。其骨架上修饰有机硅烷,可用于重金属的分离、回收,以及蛋白质的控释与分离。利用主-客体方法在SB…  相似文献   

17.
A repeating template method is presented for the synthesis of mesoporous metals with 2D hexagonal mesostructures. First, a silica replica (i.e., silica nanorods arranged periodically) is prepared by using 2D hexagonally ordered mesoporous carbon as the template. After that, the obtained silica replica is used as the second template for the preparation of mesoporous ruthenium. After the ruthenium species are introduced into the silica replica, the ruthenium species are then reduced by a vapor‐infiltration method by using the reducing agent dimethylamine borane. After the ruthenium deposition, the silica is chemically removed. Analysis by transmission and scanning electron microscopies, a nitrogen‐adsorption–desorption isotherm, and small‐angle X‐ray scattering revealed that the mesoporous ruthenium had a 2D hexagonal mesostructure, although the mesostructural ordering is decreased compared to that of the original mesoporous carbon template. This method is widely applicable to other metal systems. By changing the metal species introduced into the silica replica, several mesoporous metals (palladium and platinum) can be synthesized. Ordered mesoporous ruthenium and palladium, which are not easily attainable by the soft‐templating methods, can be prepared. This study has overcome the composition variation limitations of the soft‐templating method.  相似文献   

18.
Transition-metal-oxide materials possessing ordered mesoporosity have recently attracted significant research interest due to their numerous potential applications. Among them, ordered mesoporous zinc oxide (ZnO) is a very tempting material because of the importance of ZnO in heterogeneous catalysis. Here, first results of the preparation of ordered mesoporous ZnO materials by using different templates are reported. Porous materials with high surface area, different pore sizes, and nanocrystalline ZnO walls were obtained. Furthermore, we compare the two fundamental templating techniques, involving liquid crystals or ordered mesoporous carbon materials as templates. Regarding the formation of mesoporous ZnO, it was evident that the hard-matter carbon template is superior.  相似文献   

19.
Synthesis of a novel thermally stable mesoporous ceria-titania phase using a neutral templating route is reported. The as-made inorganic-template hybrid mesostructured matrix showed a broad low-angle XRD peak characteristic of mesoporous materials. Careful thermal treatment of the matrix allowed the subsequent densification (of the pore walls) of the inorganic component and removal of the organic component so that a high-quality mesoporous ceria-titania was formed as observed by TEM analysis. The calcined material showed the formation of fluorite type structure of CeO(2) but no crystalline titania phase was observed. The mesoporous structure remained even after high-temperature treatment. The material had high surface area after calcination up to the temperature of 973 K, with well-dispersed ceria and titania components and negligible bulk oxide formation (from XRD, UV-vis, and XPS analysis). These novel mesoporous ceria-titania materials showed high performance for the removal of volatile organic compound (toluene). The toluene removal performance was further enhanced for Pt impregnated mesoporous ceria-titania.  相似文献   

20.
New hybrid organic–inorganic materials exhibiting ordered mesoporous structures have been synthesized by co-condensation of tetraethoxysilane and various alkyltrimethoxysilanes with increasing length of the hydrocarbon chain (propyl, octyl, hexadecyl), in water–ethanol solution containing ammonia, in the presence of a cationic surfactant (cetyltrimethylammonium bromide) as templating agent. The obtained hybrid materials were characterized by using several physico-chemical techniques, such as X-ray diffraction, N2 adsorption, 29Si MAS NMR, SEM and elemental analysis. It was shown that the direct synthesis procedure allows obtaining ordered hybrid mesoporous silica with various contents of organic functions, from 5 to 20 %. Moreover, increasing the chain length of the organic group, from propyl to octyl and hexadecyl leads to a change of the pore structure from hexagonal p6mm MCM-41 type architecture to cubic Ia3d MCM-48 type mesostructure.  相似文献   

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