不同镧含量LaNaY沸石的^129Xe NMR研究

用＾１２９ＸｅＮＭＲ技术研究了ＬａＮａＹ沸石在不同镧含量时的离子定位情况，发现经３５０℃抽真空预处理后，即使在低镧含量时也有部分镧离子留在超笼内，其数目取决于沸石中总的镧含量，当平均每单胞内镧离子数达到８个后，在３５０℃下方钠石笼中出现镧离子对，不可逆地形成桥式镧氧（氢氧）化物；但低于此含量时，镧离子处于不同方钠石笼中，面成对发生反应，通常认为Ｎａ＾＋离子与Ｘｅ的化学位移无关，但＾１２９ＸｅＮＭＲ     

^29Si,^27AIMASNMR研究不同脱铝深度稀土 超稳Y沸石中Si、Al的分布

本文应用^29Si,^27AIMASNMR和XRD技术,测量了四种不同脱铝深度的稀土超稳Y沸石的骨架硅铝比,得到了一致的结果,并研究了稀土超稳Y沸石的脱铝过程和稀土离子和Y沸石骨架铝的机理.发现稀土离子存在时,Y沸石骨架中Si、Al的分布与相同硅铝比的ＨＹ不同,在浅、中度脱铝时,主要脱除的是Si(2Al)和Si(3Al)中的铝,深度脱铝时,主要是Si(1Al)和少量Si(2Al)中的铝,而Si(3Al)几乎不变,提出稀土离子最可能是位于方钠的Si(3Al)附近,平衡三个AlO 四面体上的负电荷,起到稳定Si(3Al)结构单元的作用.其次,稀土超稳Y沸石中总的非骨架铝(N~Al)~EF,随脱铝深度的增加而增加,仅只在REUSY-38的^27AIMAS NMR谱中观察到Al^3+非骨架铝的存在.^29Si,^27AIMASNMR     

铝在MCM-22分子筛骨架上分布的27Al MQ MAS NMR研究

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.     

沸石结构中骨架铝、非骨架铝固体~(27)Al NMR研究

应用乙酰丙酮络合沸石结构中非骨架铝的性质。建立了固体静态~(27)Al NMR定量测定沸石结构中骨架铝、非骨架铝比率的方法。论证了小角度脉冲和自旋晶格弛豫时间是准确定量的重要条件。同时还考察了水和乙酰丙酮对沸石骨架铝、非骨架铝结构的影响,认为干燥沸石中骨架铝存在于不对称结构中,水分子可以改变其周围电荷分布,提高其结构对称性。非骨架铝存在于极端不对称结构中,其与乙酰丙酮的络合物溶于乙醇溶液中,并具有液体核磁共振行为,因而在计算骨架铝信号强度时须乘上35/9换算因子。     

IR. MAS NMR法研究富硅超稳镨氢Y沸石

制备了NH_4Y、USY、PrHY、USPrHY、F8Y及FSPrHY催化剂, 测定其组成和物性. 于红外光谱装置上比较了上述催化剂羟基峰的异同, 通过对吡啶的吸脱附测定了诸催化剂的酸强度. B 酸强度顺序为: FSPrHY>FSY>USPrHY>USY>PrHY>NH_4Y. ~(29)Sit MAS NMR谱表明, 在USPrHY 及FSPrHY 的Si(0Al)%甚多于PrHY 和NH_4Y中的Si(0Al)%. IR、~(29)Si MAS NMR及活性测试等结果说明: 沸石中0NNN铝位的存在, 是达到强酸性的必要条件. 高价稀土阳离子形成(?)及Pr(OH)~(2+)抵消了方钠石笼中AlO_4~-上的电荷, 增强了剩余铝位上羟基酸强度; 且从骨架羟基上吸引电子, 因而使质子酸性更强, 从而提高了裂解、岐化、脱烷基活性.     

~(29)Si,~(27)AlMASNMR研究不同脱铝深度稀土超稳Y沸石中Si、Al的分布

本文应用~(29)Si,~(27)Al MAS NMR和XRD技术,测量了四种不同脱铝深度的稀土超稳Y沸石的骨架硅铝比,得到了一致的结果,并研究了稀土超稳Y沸石的脱铝过程和稀土离子稳定Y沸石骨架铝的机理.发现稀土离子存在时,Y沸石骨架中Si、Al的分布与相同硅铝比的HY不同,在浅、中度脱铝时,主要脱除的是Si(2Al)和Si(3Al)中的铝,深度脱铝时,主要是脱除Si(1Al)和少量Si(2Al)中的铝,而Si(3Al)几乎不变,提出稀土离子最可能是位于方钠石笼的Si(3Al)附近,平衡三个AlO_4~-四面体上的负电荷,起到稳定Si(3Al)结构单元的作用.其次,稀土超稳Y沸石中总的非骨架铝(N_(Al))_EF,随脱铝深度的增加而增加,仅只在REUSY-38的~(27)Al MAS NMR谱中观察到Al~(a+)非骨架铝的存在.     

羟基自由基在沸石分子筛合成中的作用

沸石分子筛由于具有独特的形选催化作用及可调的酸性, 已成为化学工业中最重要的固体催化材料. 沸石分子筛的合成主要基于碱性条件下的水热晶化, OH^?被认为起到催化硅铝物种的解聚及聚合作用. 近年来, 研究者发现了羟基自由基加速分子筛的水热晶化机制. 通过利用紫外光照射或芬顿反应等物理或化学方法向分子筛合成体系引入羟基自由基, 可以实现沸石分子筛的加速晶化及高硅沸石分子筛的合成. 理论计算结果表明, 羟基自由基可以促进Si—O—Si 键的断裂和重新生成, 从而显著加快分子筛成核并促进硅原子进入骨架. 本综述介绍了羟基自由基在沸石分子筛晶化方面的最新研究进展, 探讨了羟基自由基的主要作用和优势, 并对沸石分子筛合成的羟基自由基路线发展前景进行了展望.     

硅铝酸钠溶液中27Al和29Si的核磁共振研究

本文采用原位核磁共振方法检测不同碱度硅铝酸钠溶液中²⁷Al的信号, 在比较了文献实验结果的基础上, 明确了体系中的不同铝物种的化学位移, 进一步提出了硅铝酸钠溶液中的硅铝物种的归属.     

聚酰亚胺／SiO_2杂化材料的硅核磁共振波谱和电光性质的研究

以含氟的二胺5,5’-(六氟异丙基)-二-(2-氨基苯酚)(6FHP)及二酐4, 4’-(六氟异丙基)-苯二酸酐(6FDA)或均苯四甲酸酐(PMDA)为单体,以分散红 1(DR1)为活性生色分子合成具有非线性光学特性的含氟聚酰亚胺,并采用溶胶-凝胶(Sol-Gel)法合成相应的聚酰亚胺／SiO2杂化材料．采用固态29 Si MAS NMR谱研究了含氟聚酰亚胺／SiO2杂化材料的交联结构,结果表明杂化材料中是以T3、Q3、Q4结构为主,说明在杂化材料中形成了交联网状结构．采用衰减全反射(ATR)测定了聚酰亚胺和杂化材料在832 nm处的电光系数,其值分别为 32、28、34和29 pm／V,结果表明具有较高的电光系数．     

29Si spin-lattice NMR relaxation in microporous silica-based materials with high Mn2+ concentrations

The 29Si T1 time measurements have been performed under magic angle spinning for supermicroporous Si/Mn materials 1-6 containing Mn2+ in concentrations of 0 (1), 1.2 (2), 2.5 (3), 3.8 (4), 15 (5) and 19.8 wt% (6). It has been found that the central lines, corresponding to isotropic chemical shifts, and their sidebands relax differently in samples 2-4 with relatively small Mn2+ contents. Because the relaxation curves for 1-6 are nonexponential and identical for 6 at spinning rates of 5, 10 and 12 kHz, dipolar relaxation via the paramagnetic centers is dominant. The relaxation data have been interpreted as a function of Mn2+ concentrations in terms of incorporation of the Mn2+ ions into the silica lattice when their concentration is small (相似文献   

New synthesis of mullite. Structural evolution study by 17O, 27Al and 29Si MAS NMR spectroscopy

Mullite has been prepared from a new combination of precursors. An aluminum alkoxide, aluminium isopropoxide, and silicon tetrachloride, are hydrolysed in tetrahydrofuran solution by ¹⁷O enriched water. The resulting powder is chemically homogeneous, crystallizing into mullite at 980°C. The structural evolution has been studied by DTA, TGA, XRD and ¹⁷O, ²⁷Al and ²⁹Si MAS NMR spectroscopy.     

Solid-state NMR spectra of paramagnetic silica-based materials: observation of 29Si and 27Al nuclei in the first coordination spheres of manganese ions

Some silica-based solids, prepared by the sol/gel method in the presence of high Mn2+ concentrations, have been characterized by the 29Si, 27Al MAS NMR spectra and 29Si T1 measurements. The single-pulse 29Si and 27Al MAS NMR spectra have shown broad spinning sideband patterns that are interpreted in terms of anisotropic bulky magnetic susceptibility (BMS) and dipole-field effects. In the absence of paramagnetic isotropic shifts, the 29Si and 27Al nuclei observed in the single-pulse NMR spectra have been assigned to nuclei remote from paramagnetic centers. It has been demonstrated that the 29Si and 27Al nuclei, which are in the vicinity of the manganese ions, can be detected by the Hahn-echo MAS NMR experiments at different carrier frequencies.     

Direct Observation of Various Al Sites in SAPO-34by ^27Al Multiquantum(MQ) Magic Angle Spinning (MAS)NMR

The elegant 2D multiquantum (MQ) MAS NMR has been applied to investigate the coordination of Al atoms in SAPO-34.The results show that the effects of the template and /or water on the coordination of Al atoms are significant,which lead to the formation of various Al species.Up to four kinds of Al species are distinctly resolved.     

(29)Si NMR in LC-NMR analysis of silicones

It is demonstrated using a practical example that indirect detection of (29)Si NMR signals is sufficiently sensitive in LC-NMR stop-flow arrangement to analyze mixtures of siloxane polymers. New cryogenic probes with better signal-to-noise ratio will turn this version of LC-NMR into a routine method for analysis of siloxane polymers.     

NMR invisible" aluminum species in dealuminated mordenite zeolite:a ~1H/~(27)Al TRAPDOR NMR study

Ｈｉｇｈｃａｔａｌｙｔｉｃａｃｔｉｖｉｔｙｏｆｓｔｅａｍｅｄｆｏｒｍｓｏｆｍｏｒｄｅｎｉｔｅ,Ｙｚｅｏｌｉｔｅ,ａｎｄＺＳＭ5ｉｎｃａｔａｌｙｔｉｃｃｒａｃｋｉｎｇｉｓｍａｉｎｌｙａｔｔｒｉｂｕｔｅｄｔｏｔｈｅｉｒｐｏｓｓｅｓｓｉｎｇａｃｉｄｃａｔａｌｙｚｅｄａｃｔｉｖｉｔｙ[1].ＴｈｅｒｅａｒｅｍａｎｙＮＭＲｒｅｐｏｒｔｓｏｎｔｈｅｎａｔｕｒｅｏｆｄｅａｌｕｍｉｎａｔｅｄＹａｎｄＺＳＭ5ｚｅｏｌｉｔｅｓ.Ｈｏｗｅｖｅｒ,ｆｅｗａｒｅｋｎｏｗｎａｂｏｕｔａｌｕｍｉｎｕｍｓｐｅｃｉｅｓｉｎｄｅａｌｕｍｉｎ…     

Factor analysis of 27Al MAS NMR spectra for identifying nanocrystalline phases in amorphous geopolymers

Nanostructured materials offer enhanced physicochemical properties because of the large interfacial area. Typically, geopolymers with specifically synthesized nanosized zeolites are a promising material for the sorption of pollutants. The structural characterization of these aluminosilicates, however, continues to be a challenge. To circumvent complications resulting from the amorphous character of the aluminosilicate matrix and from the low concentrations of nanosized crystallites, we have proposed a procedure based on factor analysis of ²⁷Al MAS NMR spectra. The capability of the proposed method was tested on geopolymers that exhibited various tendencies to crystallize (i) completely amorphous systems, (ii) X‐ray amorphous systems with nanocrystalline phases, and (iii) highly crystalline systems. Although the recorded ²⁷Al MAS NMR spectra did not show visible differences between the amorphous systems (i) and the geopolymers with the nanocrystalline phase (ii), the applied factor analysis unambiguously distinguished these materials. The samples were separated into the well‐defined clusters, and the systems with the evolving crystalline phase were identified even before any crystalline fraction was detected by X‐ray powder diffraction. Reliability of the proposed procedure was verified by comparing it with ²⁹Si MAS NMR spectra. Factor analysis of ²⁷Al MAS NMR spectra thus has the ability to reveal spectroscopic features corresponding to the nanocrystalline phases. Because the measurement time of ²⁷Al MAS NMR spectra is significantly shorter than that of ²⁹Si MAS NMR data, the proposed procedure is particularly suitable for the analysis of large sets of specifically synthesized geopolymers in which the formation of the limited fractions of nanocrystalline phases is desired. Copyright © 2013 John Wiley & Sons, Ltd.