Substitution clustering in a non-stoichiometric celsian synthesized by the thermal transformation of barium exchanged zeolite X

The thermal transformation of Ba exchanged zeolite X to celsian has been studied by ²⁷Al and ²⁹Si MAS NMR spectroscopy. Evidence for the degradation of the zeolite framework is present in the ²⁹Si NMR spectra after thermal treatment at 850 °C. Confirmation is provided by the ²⁹Si NMR data that synthesis of celsian via the decomposition of Ba exchanged zeolite leads to a single defect phase. Clustering of the isomorphous replacement of aluminium by silicon must occur to explain the observed ²⁹Si chemical shifts. The ²⁷Al NMR data show distorted aluminium co-ordination sites upon the thermal transformation of Ba exchanged zeolite X. The distortions present in the amorphous matrix are greater than those present in the monoclinic and hexagonal crystalline phases of celsian.     

High magnetic field solid‐state NMR analyses by combining MAS,MQ‐MAS,homo‐nuclear and hetero‐nuclear correlation experiments

A general strategy of structural analysis of alumina silicate by combining various solid‐state NMR measurements such as single pulse, multi‐quantum magic angle spinning, double‐quantum homo‐nuclear correlation under magic angle spinning (DQ‐MAS), and cross‐polarization hetero‐nuclear correlation (CP‐HETCOR) was evaluated with the aid of high magnetic field NMR (800 MHz for ¹H Larmor frequency) by using anorthite as a model material. The high magnetic field greatly enhanced resolution of ²⁷Al in single pulse, DQ‐MAS, and even in triple‐quantum magic angle spinning NMR spectra. The spatial proximities through dipolar couplings were probed by the DQ‐MAS methods for homo‐nuclear correlations between both ²⁷Al–²⁷Al and ²⁹Si–²⁹Si and by CP‐HETCOR for hetero‐nuclear correlations between ²⁷Al–²⁹Si in the anorthite framework. By combining various NMR methodologies, we elucidated detailed spatial correlations among various aluminum and silicon species in anorthite that was hard to be determined using conventional analytical methods at low magnetic field. Moreover, the presented approach is applicable to analyze other alumina‐silicate minerals. Copyright © 2012 John Wiley & Sons, Ltd.     

Ammonolysis of 1,2‐Bis[dichloro(methyl)silyl]ethane. On the Structure of 1,3,6,8‐Tetramethyl‐2,7,11,12‐tetraaza‐1,3,6,8‐tetrasila‐tricyclo[6.2.1.13,6]‐dodecane

Ammonolysis of 1,2‐bis[dichloro(methyl)silyl]ethane afforded a crystalline tricyclic silazane along with polymeric material. The crystalline material could be isolated in pure state. It was analyzed by ¹H, ¹³C, ¹⁵N and ²⁹Si NMR spectroscopy in solution, by ¹³C, ¹⁵N and ²⁹Si MAS NMR spectroscopy in the solid state, as well as by single‐crystal and powder X‐ray diffraction. The title compound exists as a single isomer in solution, whereas in the solid state the presence of several modifications is indicated, in particular by the solid‐state MAS NMR spectra.     

Reactivity of Extra‐framework Species of USY Zeolites in Alkaline Medium

Zeolites of type USY (ultra‐stable Y) were obtained by steaming of NH₄NaY modification. Samples were modified by subsequent alkaline treatment in KOH solution. USY and USY‐KOH were characterised by chemical element analysis, XRD, IR, ²⁹Al and ²⁹Si MAS NMR spectroscopic measurements. Correct silicon to aluminium ratios (Si/Al) were determined by XRD and IR (double ring vibration w_DR) data whereas values calculated according to data of ²⁹Si MAS NMR and IR spectroscopy (asymmetrical TOT valence vibration w_TOT) appeared to be too high., In the latter case, the signals of the zeolite framework were strongly superimposed by that of extra‐framework silica gel (EFSi) formed during steaming. It was found that alkaline leaching induces desilication of silicon‐rich area of the zeolite framework and partial dissolution of EFSi. Silicate ions of both react with likewise dissolved extra‐framework aluminium (EFAl) to form X‐ray amorphous aluminosilicate. Consequently, the superposition of the ²⁹Si MAS NMR signals of the zeolite framework by silica gel was reduced for Q⁴(0Al) but increased for Q⁴ (2Al) and Q⁴(3Al) structure units. A reinsertion of EFAl into the zeolite framework has not been observed.     

Micro- to macroscopic observations of MnAlPO-5 nanocrystal growth in ionic-liquid media

Micro‐ and macroscopic studies of nucleation and growth processes of MnAlPO‐5 nanosized crystals under ionothermal synthesis conditions are reported herein. The samples treated at 150 °C were extracted from the reaction mixture at various stages of crystallization, and characterized by XRD; SEM; thermogravimetric analysis (TGA); ³¹P and ²⁷Al solid‐state magic angle spinning (MAS) NMR, Raman, UV/Vis, and X‐ray fluorescence spectroscopy (XRF). The starting raw materials (alumina, manganese, and phosphorous) were dissolved completely in the ionic liquid and transformed into an amorphous solid after 5 h of ionothermal treatment. This amorphous solid then undergoes structural changes over the following 5–25 h, which result in an intermediate phase that consists of octahedral Al species linked to the manganese and phosphate species. The first MnAlPO‐5 nuclei on the surface of the intermediate can be observed after 50 h ionoheating. These nuclei further grow, as the surface of the intermediate is in full contact with the ionic liquid, to give crystalline MnAlPO‐5 nanoparticles with a mean diameter of 80 nm. The crystals become fully detached from the intermediate and are then liberated as discrete particles after 90 h heating. The transformation process from amorphous to intermediate and then to the crystalline MnAlPO‐5 nanoparticles shows that nucleation starts at the solid–liquid interface and continues through surface‐to‐core reversed‐growth until the entire amorphous solid is transformed into discrete nanocrystals.     

Characterisation of Siliceous Extra‐Framework Species in DAY Zeolites by 29Si MAS NMR and IR Spectroscopic Measurements

Dealuminated Y zeolites (DAY) were obtained by steaming of NH₄NaY at temperatures between 450 °C and 700 °C. They were characterised by means of ²⁷Al and ²⁹Si MAS NMR, IR spectroscopic and XRD measurements. The Si/Al framework ratios of samples were calculated using the ²⁹Si MAS NMR signal intensities, the wave numbers of the double‐ring vibration band w_DR and the asymmetrical TOT valence vibration w_TOT of IR spectra as well as the XRD lattice constant a₀. In contrast to actual Si/Al ratio obtained from w_DR and a₀, the NMR spectroscopic and w_TOT values were determined to be too high because of the superposition of the signals coming from dealuminated zeolite framework and silica gel which forms in the zeolite as a result of steaming. The differently determined Si/Al ratios characterise the siliceous extra‐framework species.     

Silicon/aluminum and oxygen/nitrogen ordering in lanthanum U−phase (La3Si3Al3O12N2)

High-resolution ²⁹Si, ²⁷Al, ¹⁵N, and ¹⁷O MAS NMR spectra have been obtained for both glass and crystalline samples of lanthanum U-phase, La₃Si₃Al₃O₁₂N₂. Previous X-ray single-crystal studies have shown that this phase is iso-structural with rare-earth gallogermanates of the type Ln₃Ga₅GeO₁₄, the atomic arrangement consisting of layers of [(Si,Al)(O,N)₄] tetrahedra in the x, y plane of the hexagonal unit cell, linked together in the z-direction by [AlO₆] octahedra, with rare-earth cations occupying the large holes in this network. However, previous studies obtained only a limited amount of information about cation and anion ordering, mainly deduced from bond-length data. NMR spectra have not only enabled the change in structure from glass to crystalline ceramic to be monitored, but have also given detailed ordering information about the latter, indicating partial disorder of both (Si,Al) and (O,N) on their respective sites in the tetrahedra.     

Phase Transformations in Alkaline and Acid Leached Y Zeolites Dealuminated by Steaming

The steaming of zeolite Y (here at 873 K for 7 hours) leads to the formation of an amorphous aluminium aluminosilicate in addition to the dealuminated zeolite (DAY). An alkaline treatment of DAY causes the transformation of the non‐framework phase into an alkali aluminosilicate and the partial desilication of the DAY framework. The alkali aluminosilicate is decomposed by a moderate acid leaching under the formation of silica gel. The ²⁹Si MAS NMR and IR spectra of DAY and its chemically treated modifications are superimposed by the signals of the crystalline zeolite framework and the amorphous non‐framework materials whereas XRD measurements only characterize the current state of the framework.     

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.     

Spectroscopic characterization of crystalline AlF3 phases

A comprehensive spectroscopic characterization of all known crystalline AlF₃ phases (α-, β-, η-, κ-, θ-AlF₃) is presented for the first time in this study. Beside their X-ray diffraction powder patterns, which were already published in the literature, ²⁷Al and ¹⁹F MAS NMR, FT IR and XPS spectroscopic techniques were applied for all phases in a consistent manner. For all phases prepared the utilization of ²⁷Al satellite transition (SATRAS) NMR allowed to determine the quadrupolar parameters of the aluminium sites including their distributions.In addition, η-AlF₃ was isolated with high phase purity and characterized following a new preparation path different from those known so far in the literature.     

Charakterisierung der Protonen in polykristallinen Parawolframaten durch 1H‐MAS‐NMR‐Untersuchungen

Characterization of the Protons in Polycrystalline Paratungstates using ¹H MAS NMR Investigations ¹H MAS NMR experiments are used to characterize the non‐acid protons of the anions in polycrystalline paratungstates by means of the measured isotropic chemical shift values. The investigation of various hydrates of ammonium paratungstate allows a direct proof of protons in NH₄ ions and in water molecules while protons of the anions are not detectable. However, for both the potassium and the sodium paratungstates ¹H MAS NMR investigations detected the protons of water molecules and the non‐acid protons of the paratungstate anions. Additional ¹H broad‐line NMR experiments at 173 K support the interpretation of the results obtained by the ¹H MAS NMR investigations. For the NMR signal of the non‐acid protons of the paratungstate anion in the ¹H MAS NMR spectra of the potassium salt line‐splitting appears. This refers to the existence of two nonidentical positions of the protons in the crystal lattice and is in agreement with the results of the X‐ray structural analysis.     

11B-MAS-NMR-Untersuchungen zur Anionenstruktur von Boraten

¹¹B MAS NMR Studies on the Structure of Borate Anions The results of ¹¹B MAS NMR studies on selected crystalline borates and peroxoborates show that the boron coordination number can be determined not only from the quadrupole coupling constant but also from the chemical shift values. Correspondingly, the B[3]:B[4] ratio can be determined quantitatively. In contrast to ²⁷Al, ²⁹Si, and ³¹P NMR data, however, the observed small variation of the ¹¹B chemical shifts does not allow a more detailed information on the linkage of the coordination polyhedra and their environments. The method was applied to Ag borates with unknown structures. In the case of a borate with an Ag:B ratio of 1:3 the measured B[3]:B[4] ratio suggests a triborate structure of the anion.     

Further evidence of incorporation of chromium ions into the framework of silicoaluminophosphate molecular sieves

Three different molecular sieves were synthesised and characterized using³¹P and²⁷Al magic angle spinning nuclear magnetic resonance (³¹P and²⁷Al MAS NMR) spectroscopy and acidity measurement techniques. The synthesized solids were: a silicoaluminophosphate (SAPO-11) sample, a chromium-substituted silicoaluminophosphate (CrAPSO-11) sample and a chromium-supported SAPO-11 (Cr/SAPO-11) sample. Significant differences were observed between the CrAPSO-11 MAS NMR spectra and the spectra for the other two solids. The differences can be understood in terms of a different chemical environment for the Al(III) and P(V) ions in the molecular sieve framework, as a result of a different type of interaction, probably with substituted chromium ions in the framework. The acidity measurements were in agreement with the MAS NMR spectroscopy results, providing further evidence for the incorporation of chromium ions into the molecular sieve framework.     

HZSM-5分子筛焙烧脱铝的27Al MQMAS NMR研究

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”.     

Phosphatation of Zeolite H‐ZSM‐5: A Combined Microscopy and Spectroscopy Study

A variety of phosphated zeolite H‐ZSM‐5 samples are investigated by using a combination of Fourier transfer infrared (FTIR) spectroscopy, single pulse ²⁷Al, ²⁹Si, ³¹P, ¹H‐³¹P cross polarization (CP), ²⁷Al‐³¹P CP, and ²⁷Al 3Q magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, scanning transmission X‐ray microscopy (STXM) and N₂ physisorption. This approach leads to insights into the physicochemical processes that take place during phosphatation. Direct phosphatation of H‐ZSM‐5 promotes zeolite aggregation, as phosphorus does not penetrate deep into the zeolite material and is mostly found on and close to the outer surface of the zeolite, acting as a glue. Phosphatation of pre‐steamed H‐ZSM‐5 gives rise to the formation of a crystalline tridymite AlPO₄ phase, which is found in the mesopores of dealuminated H‐ZSM‐5. Framework aluminum species interacting with phosphorus are not affected by hydrothermal treatment. Dealuminated H‐ZSM‐5, containing AlPO₄, retains relatively more framework Al atoms and acid sites during hydrothermal treatment than directly phosphated H‐ZSM‐5.     

Solid‐state NMR characterization of oxygen sites in organically modified aluminosilicate xerogels

Solid‐state NMR characterization of hybrid aluminosilicate xerogels, by ¹⁷O magic angle spinning (MAS) and triple quantum magic angle spinning (MQMAS) techniques, evidences Si—O—Si and Si—O—Al oxygen sites, spectrally separated in MQMAS experiments. Inversion of the MQMAS spectra allows the measurement of quadrupolar parameters, isotropic chemical shifts, distribution of chemical shift and discussion of the mobility of the structural units. Copyright © 2003 John Wiley & Sons, Ltd.     

Fast Ion Conducting Nanocrystalline Alkaline Earth Fluorides Simply Prepared by Mixing or Manual Shaking

Simple mixing or shaking of alkaline earth hydroxides with ammonium fluoride results in nanocrystalline phase pure metal fluorides MF₂ (M: Ca, Sr, Ba). The formation of the alkaline earth fluorides was investigated by varying the reaction conditions. Evidence was found that just the contact between the starting materials is sufficient for the reaction to take place. X‐ray diffraction, elemental analysis, ¹⁹F MAS NMR spectroscopy, and measurements of DC conductivities were used to characterize the fluorides regarding properties like crystal structure, crystallite sizes, local fluorine coordination, and fluorine ion conductivity. The ¹⁹F MAS NMR spectra of the phase pure fluorides prepared showed several signals, which were assigned to defects, impurities, or geometric distortions. The fluorides prepared by mixing or shaking revealed fluorine ion conductivities several orders of magnitude higher than observed for the respective microcrystalline alkaline earth fluorides. Therefore, the synthesis routine presented in this study may open a path to a very quick and simple synthesis of nanocrystalline fast fluorine ion conductors.     

Chemical bonding in silicophosphate gels: Contribution of dipolar and J-derived solid state NMR techniques

A representative silicophosphate gel was synthesized, starting from orthophosphate groups and pyrophosphate species. At 136°C, a complex mixture of crystalline phases and amorphous components was obtained. A new panel of solid state NMR techniques was implemented, including dipolar based experiments (CP MAS), as well as J-derived techniques, in both homonuclear (³¹P INADEQUATE-MAS) and heteronuclear (³¹P/²⁹Si HMQC-MAS) versions. These experiments are suitable for the fine characterization of P–O–P, P–O–Si, P–OH…linkages in silicophosphate gels and materials.     

CXN天然沸石的研究 V. 结构超稳化

以离子交换结合控制焙烧的方法分别制得结构超稳化高硅H-STI-I和H-STI-II沸石. EDX, ²⁹Si MAS NMR, ²⁷Al MAS NMR, FT-IR等表征证明, 其骨架硅铝原子比分别为4.43和10.62. 分段程序升温焙烧后的沸石样品经粉末XRD表征表明, 其结构热稳定性达到1000 ℃以上. 结构稳定化沸石呈现反映微孔特性的I型吸附等温线, 吸附孔道完美、开放. 经历过酸处理的H-STI-II沸石, 结构缺陷增多, 其热稳定性、比表面积及孔容积略低于H-STI-I.     

Charged Si9 Clusters in Neat Solids and the Detection of [H2Si9]2− in Solution: A Combined NMR,Raman, Mass Spectrometric,and Quantum Chemical Investigation

Polyanionic silicon clusters are provided by the Zintl phases K₄Si₄, comprising [Si₄]⁴⁻ units, and K₁₂Si₁₇, consisting of [Si₄]⁴⁻ and [Si₉]⁴⁻ clusters. A combination of solid‐state MAS‐NMR, solution NMR, and Raman spectroscopy, electrospray ionization mass spectrometry, and quantum‐chemical investigations was used to investigate four‐ and nine‐atomic silicon Zintl clusters in neat solids and solution. The results were compared to ²⁹Si isotope‐enriched samples. ²⁹Si‐MAS NMR and Raman shifts of the phase‐pure solids K₄Si₄ and K₁₂Si₁₇ were interpreted by quantum‐chemical calculations. Extraction of [Si₉]⁴⁻ clusters from K₁₂Si₁₇ with liquid ammonia/222crypt and their transfer to pyridine yields in a red solid containing Si₉ clusters. This compound was characterized by elemental and EDX analyses and ²⁹Si‐MAS NMR and Raman spectroscopy. Charged Si₉ clusters were detected by ²⁹Si NMR in solution. ²⁹Si and ¹H NMR spectra reveal the presence of the [H₂Si₉]²⁻ cluster anion in solution.