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1.
利用二维多量子魔角旋转(2D MQ MAS)技术并结合量子化学计算,研究了铝在MCM-22分子筛骨架上的分布,并对铝的不等价四面体位进行了归属.在27Al 2D 5Q MAS NMR谱中骨架四配位铝的范围内观察到3个信号,证明MCM-22分子筛有3种骨架铝.经计算这3种骨架四配位铝的各向同性化学位移和四极作用常数分别为:δ 50.5、δ 57.3、δ 62.4和1.74、1.68、1.92 MHz. MCM-22分子筛结构中有8种结晶学不等价四面体(T)位.我们通过模拟MCM-22分子筛的27Al 2D 5Q MAS NMR谱,认为8种不等价T位分为3组. T2、T6位上的铝分别与δ 61、δ 49处的信号相关, T1、T3、T4、T5、T7、T8位上的铝对δ 56处的共振峰有贡献.当硅铝原子数比(Si/Al)在10~15之间变化时,铝在MCM-22分子筛的骨架上是无规占据的.  相似文献   

2.
27Al spin-echo, high-speed MAS (nu(rot) = 30 kHz), and MQMAS NMR spectroscopy in magnetic fields of B0 = 9.4, 14.1, and 17.6 T were applied for the study of aluminum species at framework and extra-framework positions in non-hydrated zeolites Y. Non-hydrated gamma-Al2O3 and non-hydrated aluminum-exchanged zeolite Y (Al,Na-Y) and zeolite H,Na-Y were utilized as reference materials. The solid-state 27Al NMR spectra of steamed zeolite deH,Na-Y/81.5 were found to consist of four signals. The broad low-field signal is caused by a superposition of the signals of framework aluminum atoms in the vicinity of bridging hydroxyl protons and framework aluminum atoms compensated in their negative charge by aluminum cations (delta(iso) = 70 +/- 10 ppm, C(QCC) = 15.0 +/- 1.0 MHz). The second signal is due to a superposition of the signals of framework aluminum atoms compensated by sodium cations and tetrahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 65 +/- 5 ppm, C(QCC) = 8.0 +/- 0.5 MHz). The residual two signals were attributed to aluminum cations (delta(iso) = 35 +/- 5 ppm, C(QCC) = 7.5 +/- 0.5 MHz) and octahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 10 +/- 5 ppm, C(QCC) = 5.0 +/- 0.5 MHz). By chemical analysis and evaluating the relative solid-state 27Al NMR intensities of the different signals of aluminum species occurring in zeolite deH,Na-Y/81.5 in the non-hydrated state, the aluminum distribution in this material was determined.  相似文献   

3.
Guest(metal)-zeolite interactions in a two component heterogeneous catalyst have been investigated by high-field and high-speed (27)Al MAS NMR, and two-dimensional (27)Al MQ MAS NMR experiments as well as ab initio DFT methods. It was established that strong interactions between guest and zeolite occur in a metal/zeolite system, with the metal anchored to the tetrahedral aluminum framework site through two oxygen bridges. It disturbs the tetrahedral environment of associated aluminum framework, changing AlO(4) geometry from near T(d) to C(2v); this enables us to resolve this species from the undisturbed aluminum framework species in high-field (27)Al MAS NMR and two-dimesional (27)Al MQ MAS NMR experiments.  相似文献   

4.
The effect of adsorbate molecules on the quadrupolar interaction of framework aluminum atoms with the electric field gradient in dehydrated zeolite H,Na-Y has been studied by (27)Al MAS NMR and (27)Al MQMAS NMR spectroscopy at magnetic fields of 9.4 and 17.6 T. Upon adsorption of molecules interacting with bridging OH groups by hydrogen bonds (acetonitrile and acetone), the quadrupole coupling constant of framework aluminum atoms was found to decrease from 16.0 MHz (unloaded zeolite) to 9.4 MHz. Adsorption of molecules, which cause a proton transfer from the zeolite framework to the adsorbates (ammonia and pyridine), reduces the quadrupole coupling constant to 3.8 MHz for coverages of 0.5-2 molecules per bridging OH group. The experiments indicate that the quadrupole coupling constant of framework aluminum atoms in dehydrated zeolite H,Na-Y reflects the chemical state of adsorbate complexes formed at bridging OH groups. In agreement with earlier investigations it was found that a proton affinity of the adsorbate molecules of PA = 812-854 kJ/mol is necessary to induce a proton transfer from the zeolite framework to the adsorbed compounds. This proton transfer is accompanied by a strong improvement of the tetrahedral symmetry of zeolitic framework AlO(4) tetrahedra and a decrease of the electric field gradient.  相似文献   

5.
By using a high-resolution solid state nuclear magnetic resonance spectrometer with 27Al and 29Si probes, the interaction between Mo species and HZSM-5 of frsol|Mo/HZSM-5 catalysts has been studied. The results show that there is a strong interaction between Mo species and HZSM-5 zeolite. The framework aluminum in the zeolite can be easily extracted by the introduction of Mo species. The extractability of framework aluminum by Mo species increases with increasing Mo loading and the calcination temperature. The extraction process leads to the formation of non-framework Al at first and then a new crystalline phase of Al2(MoO4)3. The dealumination of the catalyst having a Mo loading of 15% and had been calcined at 973 K is so severe that all the aluminum in the framework are extracted and no framework Al could be detected by 27Al MAS NMR. The catalyst, therefore, lost its catalytic activity for methane dehydrogenation and aromatization in the absence of oxygen. The Si/Al ratio measured from 29Si MAS NMR further confirms the dealumination process observed by 27Al MAS NMR. The MAS NMR results give us an evidence that Al2(MoO4)3 crystallites are much less active for the reaction.  相似文献   

6.
Various boron only ([B]-BEA) as well as aluminum- and boron-containing beta zeolites ([Al,B]-BEA) have been prepared and modified by ion exchange of ammonium, sodium, and nickel ions. The zeolite samples have been characterized by 11B, 27Al, and 29Si MAS as well as three of them by 11B and 27Al 3Q-MAS NMR spectroscopy. The quantitative contributions of defect-free Si(nX) (n = 2, 1, 0; X = Al, B) and Si(OH)x (x = 2, 1) sites to the NMR signal intensities were calculated from the various Si/(Al + B) ratios and relative 11B, 27Al, and 29Si NMR signal intensities using the special distribution of aluminum and boron in different periodical building units of the zeolite framework. The boron atoms are sitting exclusively in diagonal positions in the four-membered rings of [B]-BEA zeolites, while the aluminum atoms are situated both in diagonal and lone positions in the four-membered rings of [Al,B]-BEA zeolites. A higher part of boron atoms are positioned in framework-related deformed tetrahedral boron species than in lattice positions in the [B]-BEA than in the [Al,B]-BEA zeolites. All extraframework octahedral aluminum species are transformed back to lattice positions due to ion exchange from the protonated form to ammonium-, sodium-, or nickel-ions containing zeolites. Oppositely, trigonal boron leaves the zeolite structure completely during ion exchange.  相似文献   

7.
The calcium silicate hydrate (C-S-H) phase resulting from hydration of a white Portland cement (wPc) in water and in a 0.3 M NaAlO(2) solution has been investigated at 14 and 11 hydration times, respectively, ranging from 6 h to 1 year by (27)Al and (29)Si MAS NMR spectroscopy. (27)Al MAS NMR spectra recorded at 7.05, 9.39, 14.09, and 21.15 T have allowed a determination of the (27)Al isotropic chemical shift (delta(iso)) and quadrupolar product parameter (P(Q) = C(Q)) for tetrahedrally coordinated Al incorporated in the C-S-H phase and for a pentacoordinated Al site. The latter site may originate from Al(3+) substituting for Ca(2+) ions situated in the interlayers of the C-S-H structure. The spectral region for octahedrally coordinated Al displays resonances from ettringite, monosulfate, and a third aluminate hydrate phase (delta(iso) = 5.0 ppm and P(Q) = 1.20 MHz). The latter phase is tentatively ascribed to a less-crystalline aluminate gel or calcium aluminate hydrate. The tetrahedral Al incorporated in the C-S-H phase has been quantitatively determined from (27)Al MAS spectra at 14.09 T and indirectly observed quantitatively in (29)Si MAS NMR spectra by the Q(2)(1Al) resonance at -81.0 ppm. A linear correlation is observed between the (29)Si MAS NMR intensity for the Q(2)(1Al) resonance and the quantity of Al incorporated in the C-S-H phase from (27)Al MAS NMR for the different samples of hydrated wPc. This correlation supports the assignment of the resonance at delta(iso)((29)Si) = -81.0 ppm to a Q(2)(1Al) site in the C-S-H phase and the assignment of the (27)Al resonance at delta(iso)((27)Al) = 74.6 ppm, characterized by P(Q)((27)Al) = 4.5 MHz, to tetrahedrally coordinated Al in the C-S-H. Finally, it is shown that hydration of wPc in a NaAlO(2) solution results in a C-S-H phase with a longer mean chain length of SiO(4) tetrahedra and an increased quantity of Al incorporated in the chain structure as compared to the C-S-H phase resulting from hydration of wPc in water.  相似文献   

8.
何秋平  程晓维  鄢浩  龙英才 《化学学报》2009,67(18):2067-2073
在前文研究天然Stilbite沸石(CXN沸石)水热稳定性影响因素的基础上, 以27Al与29Si MAS NMR, NH3-TPD和低温氮吸附等详细研究了铵型CXN沸石骨架铝配位状态和硅配位状态, 表面酸性与孔性质等与水蒸汽处理温度的关系. 随温度升高, 沸石骨架硅铝比逐渐提高, 并伴随硅羟基缺陷增多. 经750 ℃水蒸汽处理3 h后沸石骨架硅铝比可达到21.3. 沸石总酸量随水蒸汽处理温度的提高而降低, 沸石骨架铝脱除造成沸石孔道部分被堵塞, 但同时形成有利于分子扩散的介孔.  相似文献   

9.
以拟薄水铝石为铝源、水玻璃为硅源、十六烷基三甲基溴化铵为模板剂,在110℃时水热晶化合成了含Al的MCM-41介孔分子筛.采用X射线衍射(XRD)、N2吸附-脱附、固体29Si、27Al魔角旋转核磁共振技术(MASNMR)、扫描电镜(SEM)及吡啶吸附傅里叶变换红外(FTIR)光谱技术对AlMCM-41分子筛进行了表征.结果表明:AlMCM-41分子筛具有六方排列的孔道结构,同时具有很高的相对结晶度、比表面积和孔容,且孔分布单一;AlMCM-41分子筛中Si原子在骨架内键合的程度更高,使AlMCM-41分子筛具有更好的骨架晶化程度;同时具有四配位骨架铝,使AlMCM-41介孔分子筛具有适当的酸性.  相似文献   

10.
喻志武  王强  陈雷  邓风 《催化学报》2012,(1):2140-2150
采用各种固体核磁共振 (NMR) 技术详细研究了 H-MCM-22 分子筛中 Brnsted/Lewis 酸的协同效应. 二维 1H 双量子魔角旋转 (DQ-MAS) NMR 结果表明, 在脱铝 H-MCM-22 分子筛中 Brnsted 酸位 (骨架桥式羟基) 和 Lewis 酸位 (非骨架铝羟基) 之间是空间邻近的, 暗示着可能存在 B/L 酸协同效应. 二维 27Al DQ-MAS NMR 结果揭示了各种铝物种之间的空间邻近性, 表明 B/L 酸协同效应优先发生在 H-MCM-22 分子筛超笼中的骨架 T6 位铝和非骨架铝物种之间. 2-13C-丙酮探针分子实验发现, 因 B/L 酸协同效应而导致脱铝 H-MCM-22 分子筛酸性明显增强, 氘代吡啶探针分子实验也证实在 H-MCM-22 分子筛的超笼中发生了 B/L 酸协同效应. 上述结果将有助于我们理解在脱铝 H-MCM-22 分子筛上发生的多相催化机理.  相似文献   

11.
HZSM-5分子筛焙烧脱铝的27Al MQMAS NMR研究   总被引:1,自引:0,他引:1  
用29Si、27Al魔角旋转固体核磁共振(MAS NMR)结合二维多量子魔角旋转(2D MQMAS)技术对焙烧脱铝的HZSM-5分子筛中铝的配位状态进行了研究.结果表明,HZSM-5分子筛经焙烧后,在化学位移(δ)45处出现一宽峰信号,其主要来自扭曲四配位铝.通过二维三量子铝谱计算出扭曲四配位铝的四极作用常数约为5.2 MHz.对700和750 ℃焙烧样品的铝谱进行分峰拟合,发现在δ 30处又出现一个小峰,归属为非骨架五配位铝.同时,在750 ℃焙烧样品的二维多量子铝谱中直接观察到非骨架五配位铝的信号.焙烧温度低于700 ℃,脱铝不明显;高于700 ℃,引起分子筛骨架的显著脱铝.焙烧还造成部分骨架铝的信号变得“不可观测”.  相似文献   

12.
Multinuclear (1)H, (19)F, and (27)Al MAS (magic angle spinning) and corresponding 2D HETCOR (heteronuclear correlation) NMR spectroscopy, in combination with powder XRD measurements, provide the direct evidence for the NH(4)AlF(4) crystalline phase, which was formed from zeolite HY dealuminated with an aqueous (NH(4))(2)SiF(6) solution at 80 degrees C. The NH(4)AlF(4) crystalline phase exhibits a characteristic second-order quadrupolar-induced (27)Al NMR line shape spreading from 0 to -90 ppm (in a magnetic field of 11.7 T) and two (19)F resonances at -151 and -166 ppm in the (19)F NMR spectrum. An( 27)Al quadrupolar coupling constant (C(Q)) of 9.5 MHz and an asymmetry parameter (eta) of 0.1 were identified, for the first time, for the NH(4)AlF(4) crystalline phase observed. On the basis of the (19)F{(27)Al} TRAPDOR (transfer population in double resonance) NMR results, the (19)F resonances at -151 and -166 ppm are therefore assigned to (19)F spins associated with the fluorines in the terminal Al-F and the bridging Al-F-Al groups, respectively.  相似文献   

13.
采用不同浓度硝酸对斜发沸石(HEU)进行改性处理,结合元素分析(ICP-AES)、N2物理吸附、X射线粉末衍射(XRD)、魔角旋转固体核磁(MAS NMR)等测试手段及DFT理论计算,研究了酸处理对斜发沸石结构的影响。结果表明,硝酸处理对不同平衡阳离子的HEU(Na-K-HEU、NH4-HEU、H-HEU)具有不同的脱铝效果。酸处理后Na-K-HEU和NH4-HEU的硅铝比、比表面积均显著升高。随硝酸浓度增大两个沸石样品的脱铝程度逐渐增加,同时骨架结构也逐渐破坏,硝酸浓度达到4 mol/L时其相对结晶度已低于50%。而H-HEU样品的骨架结构稳定,随硝酸浓度的增大铝含量轻微降低,硝酸浓度达到6 mol/L时相对结晶度仍高达94.8%。阳离子反交换实验结果证明,平衡阳离子的类型不是影响HEU骨架稳定性的主要因素。Na-K-HEU和经硝酸铵交换后的NH4-HEU中铝都以骨架铝的形式存在,而在后者焙烧成为H-HEU时出现部分非骨架铝,伴随了骨架的稳定化过程。  相似文献   

14.
焙烧对HZSM-5分子筛结构的影响   总被引:3,自引:0,他引:3  
运用魔角自转固态核磁共振谱(MAS-NMR),研究了焙烧对HZSM-5分子筛结构的影响.结果表明,高温焙烧将引起HZSM-5分子筛骨架的脱铝,当焙烧温度从500℃增加到700℃时,HZSM-5的骨架Si/Al比由16.7增加至22.7;而当焙烧温度由700℃到800℃时,骨架Si/Al比则由22.7增加到了48.5.27Al-MASNMR结果表明,从骨架上脱下来的铝,部分地形成了NMR不可见的无定形态.随着焙烧温度的升高,NMR不可见铝增多  相似文献   

15.
27Al和29Si MAS-NMR对Mo/HZSM-5催化剂的研究   总被引:3,自引:0,他引:3  
使用^29Al固体离分辨核磁技术对甲烷无氧芳构化催化剂Mo/HZSM-5分子筛进行了研究,发现HZSM-5分子筛本体中仅含有少量非骨架Al,Mo物种与分子筛骨架Al的相互作用随Mo担载量以及焙烧的温度的升高而增加,在高温焙烧下,Mo物种会使分子筛骨架严重脱铝,并且生成Al2(MoO4)3新相,最终导致分子筛骨架塌陷,催化性能下降。  相似文献   

16.
A series of vanadoaluminosilicate MCM-41 mesoporous molecular sieves with various compositions have been hydrothermally synthesized. Hexadecyltrimethylammonium bromide was used as a surfactant in the synthesis. The samples were characterized with nitrogen sorption, X-ray diffraction, differential thermal analysis, thermogravimetric analysis, Fourier transform-Infrared spectroscopy, UV-visible spectroscopy, scanning electron microscopy, transmission electron microscopy, and solid state NMR. The solid products had the MCM-41 structure and contained only atomically dispersed vanadium and aluminum consistent with framework vanadium and aluminum. The samples were hydrophobic and contained large amount of surfactant in the as-synthesized samples. The surfactant could be removed upon calcination at 450°C. N2 sorption measurements and TEM demonstrate the high mesoporosity of [V, Al]-MCM-41. The incorporation of vanadium and aluminum into MCM-41 decreased the surface area to some extent. The morphologies of all the samples were the agglomerate of plates. 29Si MAS NMR shows that the pore wall is amorphous. 27Al MAS NMR shows that all of aluminum species were tetrahedrally coordinated even after calcination at 550°C.  相似文献   

17.
采用硝酸回流和水蒸气两种处理方法对用动态水热法合成的纳米MCM-49分子筛进行脱铝改性. 用XRD、氮气吸附-脱附、NH3-TPD、FTIR和NMR等技术进行了表征, 并考察了脱铝前后MCM-49分子筛在苯与丙烯液相烷基化反应中的催化性能. 27Al核磁共振谱表明, 硝酸回流和水蒸气处理能有效地脱除MCM-49分子筛的部分骨架铝和非骨架铝. NH3-TPD和FTIR表征结果表明, 脱铝降低了MCM-49分子筛的Brönsted酸和Lewis酸的酸量. 硝酸脱铝未改变分子筛的酸强度分布, 而在600 ℃水蒸气脱铝则造成酸强度的降低. 实验条件下, MCM-49分子筛的丙烯转化率为99.5%, 异丙苯的选择性为73.6%. 脱铝改性降低了烷基化反应活性和异丙苯的选择性, 提高了收率. 与脱铝前MCM-49分子筛相比, 常温下经硝酸处理5 h的脱铝MCM-49分子筛在保持催化活性相当的情况下, 异丙苯收率提高了5.3%.  相似文献   

18.
凝胶制备对气相合成MCM-22沸石的影响   总被引:2,自引:0,他引:2  
以硅酸钠为硅源、硫酸铝为铝源制备硅铝干凝胶,六亚甲基亚胺(HMI)为模板剂,采用气相法合成MCM-22沸石。对硅铝干凝胶进行了29 Si MAS NMR、27 Al MAS NMR、红外以及透射电镜表征,讨论了pH值对硅铝干凝胶及合成MCM 22沸石的影响。结果表明,pH值的改变影响硅铝聚集态、干凝胶的结构及其粒径等物理性质,合成时硅铝干凝胶解聚、气固间传质及固相溶解速度不一致,影响产物MCM-22的结晶度。当制备干凝胶的pH值为8.7~10.7时,得到结晶度高的MCM-22沸石;当pH值增大到11.1时,产物出现杂晶丝光沸石;pH为11.6时只能得到丝光沸石。  相似文献   

19.
A natural CXN zeolite (stilbite, type code-STI) discovered in China was modified with NH4^ exchange by using ammonium salt and calcinations (procedure Ⅰ), or with NH4 exchange followed by treatment with acid (procedure Ⅱ). The coordination state of Si and A1 atoms in the framework, the property of ion exchange, and the adsorption of the H-STI zeolite samples prepared by different modification procedure were investigated with XRD,EDX,^29Si and ^27Al MAS NMR, Ag^ ion exchange and Ne adsorption. The results of the investigations indicate that different procedure of the modification made variety on the distribution of the framework Si atoms and A1 atoms,the content of non-framework aluminum, and the blocking channels and the shielding effect to the positions of the exchangeable cations. The H-STI zeolite prepared by the procedure Ⅱ possesses high ion exchange capacity, open and perfect pore system, and high thermal stability.  相似文献   

20.
两步法合成中孔Al-MSU-X   总被引:3,自引:0,他引:3  
翟尚儒  魏伟  吴东  孙予罕 《化学学报》2004,62(4):442-444
以预先制备的Al-O-Si纳米粒子为前驱物和非离子型表面活性剂聚乙二醇辛基苯基醚(TX-100)为中孔导向剂两步合成了孔道形状为"wormhole-like"的含铝MSU-X介孔材料,并用XRD, HRTEM, N2吸附-脱附,27Al MAS NMR, NH3-TPD和催化裂化异丙苯对其结构和催化性能进行了表征;结果证明铝原子已被有效地引入了该中孔材料的骨架结构内,从而使得其在异丙苯裂解反应中显示出较高的催化活性.  相似文献   

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