129Xe,29Si and27Al NMR studies of dealuminated Y zeolite

The dealumination of a commercial Y zeolite by contact with SiCl₄ is monitored with NMR spectroscopy of²⁹Si,²⁷Al and¹²⁹Xe. The results are interpreted in terms of the changes in the material as silicon is incorporated in the framework and aluminum is deposited in the pores.     

Fast 29Si magic-angle-spinning NMR acquisitions by RAPT-CP 27Al --> 29Si polarization transfer

Using enhancement of the 27Al central-transition magnetization by applying RAPT prior to 27Al --> 29Si cross-polarization, we demonstrate fast acquisition of 29Si one-dimensional MAS and two-dimensional 27Al-29Si HETCOR spectra on a new sialon phase Ba2Al3Si9N13O5.     

Unambiguously distinguishing Si[3Si,1Al] and Si[3Si,1OH] stuctural units in zeolite by 1H/29Si/27Al triple resonance solid state NMR spectroscopy

We present an experimentally feasible triple-resonance NMR method that establishes the correlation among three different nuclei, avoiding the difficulty to directly explore the weak coupling between two NMR nuclei, such as (29)Si and (27)Al. Using this method, we are able to give an unambiguous assignment to the various peaks in (29)Si CP NMR spectrum of MCM-22 zeolite and discriminate (29)Si signals from SiOHAl and SiOH groups. In addition, in combination with (1)H/(27)Al double-resonance technique, the (1)H/(27)Al/(29)Si triple-resonance experiment suggests the presence of two different kinds of Br?nsted acid sites in H-MCM-22 zeolite.     

Determination of 27Al-29Si connectivities in zeolites with 2D 27Al-->29Si RAPT-CPMG-HETCOR NMR

The recently introduced concept of the combined use of rotor assisted population transfer (RAPT) and Carr-Purcell-Meiboom-Gill (CPMG) techniques to boost the sensitivity of cross polarization (CP) based NMR experiments is applied to a synthetic zeolite (ZSM-4). The sensitivity was increased by a factor of approximately 4, which enabled acquisition of a high quality two-dimensional 27Al-29Si HETCOR (heteronuclear correlation) spectrum. By separating the resonances in two dimensions, through-space connectivities between spins were revealed and the effective resolution was improved in both dimensions, which allowed determination of the existing ambiguities in spectral assignments in this material. The spectra provided clear indication of random distribution of aluminum and silicon within the ZSM-4 network. Additionally, unexpected correlations were observed between different components of inhomogeneously broadened 29Si and 27Al lines, which are most likely due to differences in the second coordination sphere environments.     

高岭土与针铁矿胶结样中27Al、29Si NMR谱与其原子电荷关系

由NMR谱实验得高岭土与针铁矿胶结样中²⁷Al、²⁹Si的化学位移较单一高岭土分别正移了2.7ppm和2.33ppm.由CNDO/2方法计算得到胶结样中Al、Si原子电行比高岭土分别减少了0.0787和0.0286.胶结样中Al、Si原子电荷的减少与²⁷Al、²⁹Si NMR谱化学位移相吻合,可以认为在高岭土与外铁矿的界面上形成了氢键而呈现胶结态.     

Three-dimensional through-bond homonuclear-heteronuclear correlation experiments for quadrupolar nuclei in solid-state NMR applied to (27)Al-O-(31)P-O-(27)Al networks

We present here the first 3D homonuclear/heteronuclear correlation experiment applied to quadrupolar nuclei and making use of the sole scalar J-coupling. This experiment, based on the 2D-Homonuclear-Heteronuclear Single Quantum Correlation (H-HSQC) experiment, uses a relayed transfer from the (27)Al central transition to neighbouring (31)P spins and to the central transition of a second (27)Al. It confirms the correlation map characterizing the two (27)Al and the (31)P NMR signatures of (27)Al-O-(31)P-O-(27)Al chemically bonded molecular motifs.     

Solid state (47,49)Ti, (87)Sr and (137)Ba NMR characterisation of mixed barium/strontium titanate perovskites

Solid state ^47,49Ti, ¹³⁷Ba, ⁸⁷Sr NMR spectra have been recorded on Ba_xSr_1−xTiO₃ (0 x 1) perovskite samples prepared by the powder sintering method. Multinuclear solid state NMR shows great potential for characterising such systems since the quadrupolar parameters are very sensitive to any geometric deformation around the studied nucleus. ^47,49Ti NMR powder lineshapes appear strongly influenced by the presence of even a small amount of barium (or strontium) in the coordination second sphere of the probed titanium site: substitution of strontium by barium induces the broadening of the peaks, due to quadrupolar effects, while the isotropic chemical shift increases. ¹³⁷Ba NMR spectra exhibit a distribution of the quadrupolar interaction, that could be tentatively quantified, C_Q increasing with the amount of strontium. Preliminary results were also obtained on ⁸⁷Sr NMR showing behaviour comparable to ¹³⁷Ba NMR, i.e. a broadening of the peaks due to an increasing quadrupolar interaction with the amount of barium distorting the environment of the strontium sites.     

Study of the excitation functions of27Al(n, α)24Na,27Al(n,p)27Mg and28Si(n,p)28Al reactions

Cross sections for the reactions²⁷Al(n, p)²⁷Mg and²⁸Si(n,p)²⁸Al were measured by activation method between 13.40 and 14.83 MeV neutron energy. An accuracy of about 4% was achieved using the²⁷Al(n, α)²⁴Na reaction as a reference at 14.1 MeV where the relative excitation function has also been measured. Results obtained were compared to a recent compilation and that calculated by the Hauser-Feshbach model. Using the back-shifted level density formula and taking into account the contribution of the separated levels, the calculations were extended to the energy range from the threshold to 18 MeV. A structure was observed in the²⁷Al(n, α)²⁴Na reaction cross section curve around 14 MeV neutron energy.     

Comparison of one and two-neutron transfer near the coulomb barrier for the27Al(18O,16O)29Al,27Al(180,17O)28Al and27Al(13C,12C)28Al reactions

Total reaction cross sections for the transfer reactions²⁷Al(¹⁸O,¹⁶O)²⁹Al,²⁷Al(¹⁸O,¹⁷O)²⁸Al and²⁷Al(¹³C,¹²C)²⁸Al are reported for center-of-mass energies between 13 and 20 MeV for¹⁸O projectiles and between 11 and 17.5 MeV for¹³C projectiles. The reaction products,²⁹Al and²⁸Al, beta decay to²⁹Si and²⁸Si, respectively, and the subsequentγ decays of²⁹Si and²⁸Si were measured. Due to the relatively long beta decay half lives, data were taken in a beam-off mode, resulting in very clean spectra. Total cross sections were calculated and compared with a theoretical model for barrier penetration proposed by C.Y. Wong. Differences between¹⁸O induced one and two-neutron total transfer reaction cross sections are discussed.     

The study of the width for intermediate resonances in the 27Al(d,p)28Al, 27Al(d, α)25Mg, 31P(d,p)32P and 31(d, α)29Si reactions

The protons and α-particles from the reactions ²⁷Al(d, p)²⁸Al(d, α)²⁵Mg, ³¹P(d, p)³²P and ³¹P(d, α)²⁹Si were measured and analyzed with the channel cross correlation function and auto-correlation function to determine the correlating numbers N_d and average width 〈Γ_μ〉. With these values, the theoretical intermediate widths were calculated to be 119 ± 30 keV in the ²⁹Si nucleus and 249 ± 46 keV in the ³³S nucleus, which were in good agreement, within the errors, with the present experimental results of 185 ± 37 keV in ²⁹Si and 204 ± 24 keV in ³³S.     

Giant multipole resonance effects in27Al(p n)27Si

A set of ten differential cross sections between 10 and 40 MeV for this charge exchange reaction have been analysed. In the analyses, amplitudes associated with the virtual excitation of the giant dipole and quadrupole reasonances in²⁸Si complement those associated with the direct reaction mechanism. Such resonance effects are essential to explain the rapid energy variation of the data.     

High-field 19.6T 27Al solid-state MAS NMR of in vitro aluminated brain tissue

The combination of (27)Al high-field solid-state NMR (19.6T) with rapid spinning speeds (17.8 kHz) is used to acquire (27)Al NMR spectra of total RNA human brain temporal lobe tissues exposed to 0.10 mM Al(3+) (as AlCl(3)) and of human retinal pigment epithelial cells (ARPE-19), grown in 0.10 mM AlCl(3). The spectra of these model systems show multiple Al(3+) binding sites, good signal/noise ratios and apparent chemical shift dispersions. A single broad peak (-3 to 11 ppm) is seen for the aluminated ARPE-19 cells, consistent with reported solution-state NMR chemical shifts of Al-transferrin. The aluminated brain tissue has a considerably different (27)Al MAS NMR spectrum. In addition to the transferrin-type resonance, additional peaks are seen. Tentative assignments include: -9 to -3 ppm, octahedral AlO(6) (phosphate and water); 9 ppm, condensed AlO(6) units (Al-O-Al bridges); 24 ppm, tetrahedral AlO(3)N and/or octahedral Al-carbonate; and 35 ppm, more N-substituted aluminum and /or tetrahedral AlO(4). Thus, brain tissue is susceptible to a broad range of coordination by aluminum. Furthermore, the moderate (27)Al C(Q) values (all less than 10 MHz) suggest future NMR studies may be performed at 9.4T and a spin rate of 20 kHz.     

29Si and 19F MAS NMR spectra of isolated 29Si(19F)2 and 29Si(19F)3 spin systems: experiments and simulations

We consider ²⁹Si and ¹⁹F MAS NMR spectra of isolated ²⁹Si(¹⁹F)₂ and ²⁹Si(¹⁹F)₃ spin systems in two organosilicon compounds of the type RR’SiF₂ and RSiF₃(R,R′=organic ligands). Experimental spectra are analysed by means of numerical simulations. It is found that the SiF₃ group in RSiF₃ is reorienting rapidly around the molecular Si–C bond direction in the solid state. The two ¹⁹F shielding tensors in RR’SiF₂ have strongly differing orientations relative to the two Si–F bond directions in the molecule. Possibilities and limitations of straightforward MAS NMR approaches for the full characterisation of ²⁹Si(¹⁹F)₂ and ²⁹Si(¹⁹F)₃ spin systems and other dipolar coupled two and three-spin systems are discussed.     

(Ti,Al,Si,C)N nanocomposite coatings synthesized by plasma-enhanced magnetron sputtering

Materials’ surface service property could be enhanced by transition metal nitride hard coatings due to their high hardness, wear and high temperature oxidation resistance, but the higher friction coefficient (0.4-0.9) of which aroused terrible abrasion. In this work, quinternary (Ti,Al,Si,C)N hard coating 3-4 μm was synthesized at 300 °C using plasma enhanced magnetron sputtering system. It was found that the coating's columnar crystals structure was restrained obviously with the increase of C content and a non-columnar crystals growth mode was indicated at the C content of 33.5 at.%. Both the XRD and TEM showed that the (Ti,Al,Si,C)N hard coatings had unique nanocomposite structures composed of nanocrystalline and amorphous nc-(Ti,Al)(C,N)/nc-AlN/a-Si₃N₄/a-Si/a-C. However, the coatings were still super hard with the highest hardness of 41 GPa in spite of the carbon incorporation. That a-C could facilitate the graphitization process during the friction process which could improve the coating's tribological performance. Therefore, that nanocomposite (Ti,Al,Si,C)N coatings with higher hardness (>36 GPa) and a lower friction coefficient (<0.2) could be synthesized and enhance the tribological performance and surface properties profoundly.     

Characterization of silicon sites in monoclinic zeolite ZSM-5 using 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) and molecular modelling

An attempt has been made to correlate the experimentally observed 29Si MAS NMR chemical shifts of monoclinic phase of highly siliceous ZSM-5 with their electronic properties. In order to incorporate the influence of next neighbor atoms on the 29Si chemical shielding of central SiO4, a pentameric cluster model (H12Si5O16) has been chosen. Each of the 24 crystallographically distinct Si sites, of ZSM-5 framework has been modelled by such cluster models. Based on semi-empirical quantum chemical calculations, a multiple linear regression analysis of the various electronic properties with the 29Si chemical shifts has been attempted. The relative difference in 29Si chemical shifts for the Si sites in ZSM-5 is reasonably accounted, although quantitative prediction may require non-empirical quantum chemical calculations.     

变生锆石的29Si MAS NMR与红外光谱研究

关于锆石变生过程中SiO₄四面体行为的信息对于了解变生态结构及变生过程机理有重要意义。虽然有人推测,在变生过程中,伴随着ZrO₈多面体上氧空位的产生可能同时发生SiO₄四面体的聚合^[7],但迄今并无直接的实验证据证明这一假设。本文的²⁹Si MASNMR研究表明,在锆石变生的最初阶段,Si的局部结构环境没有明显的变化,但在中等变生程度的样品中,探测到Q³和Q⁴Si环境,这是一个有力的证据,支持随着变生程度增加SiO₄四面体发生逐步聚合的假设。红外光谱的结果也显示,变生锆石中可能有无定形的氧化硅畴存在。     

Isobaric analogue states in28Si from (p, γ) reaction in27Al

Analogue states in²⁸Si are identified through (p, γ) reaction in²⁷Al in the energy rangeE _p =0.85–3.0 MeV. There appears hardly any indication of a mixing. Coulomb displacement energy ΔE _c for the isobaric pair²⁸Al-²⁸Si is obtained. A least squares analysis is also carried out on all the available experimental results of ΔE _c as a function of ¯Z/A ^1/3.     

High resolution gamma-ray spectroscopy of the27Al(p,γ)28Si resonance reaction

High resolution gamma-ray spectra have been measured from the²⁷Al (p,γ)²⁸Si reaction for the resonances atE _p=2·482, 2·511 and 2·735 MeV at ϑ _pγ=0°, 30°, 55° and 90° using a Ge (Li) gamma spectrometer. From the spectra and the angular distributions the properties of the resonance states have been obtained. These states are the isobaric analogues of the levels at 4·69, 4·75 and 4·93MeV levels respectively in the parent nucleus A²⁸l.