High-resolution heteronuclear correlation spectra between 31P and 27Al in microporous aluminophosphates

A solid-state nuclear magnetic resonance (NMR) experiment, which provides high-resolution two-dimensional heteronuclear correlation (HETCOR) spectra between 27Al and 31P, is described. The first part of the experiment uses triple-quantum or quintuple-quantum magic-angle spinning (MQMAS) NMR of spin-5/2 nuclei (27Al) to produce an isotropic echo that is unaffected by the second-order quadrupolar broadening. The magnetization is then transferred to the spin-1/2 (31P) nuclei via cross-polarization (CP), resulting in isotropic resolution in both spectral dimensions. To illustrate its usefulness, this method (referred to as MQHETCOR) is applied to two important microporous framework aluminophosphates, hydrated VPI-5 and AIPO4-40.     

Determination of J coupling constants between spin-1/2 and quadrupolar nuclei in inorganic solids from spin echo and refocused INEPT experiments: a case study on AlPO₄ berlinite

A systematic study utilizing rotor-synchronized homonuclear ((31)P, (27)Al) and heteronuclear ({(31)P}(27)Al and {(27)Al}(31)P) spin echo, and {(27)Al}(31)P refocused INEPT experiments (employing soft pulses for selective excitation of the central transition for the quadrupolar (27)Al (I=5/2)) have been performed on AlPO(4) berlinite at 30 kHz MAS to better understand the J modulation behavior involving half-integer quadrupolar nuclei in solid materials with framework structure. Analyses of the J modulation on either the (27)Al or (31)P coherence in both the {(31)P}(27)Al and {(27)Al}(31)P spin echo experiments, and both periods of the refocused INEPT experiment yield consistent results for the (2)J(AlP) (Al-O-P) coupling constant (ca. 25 Hz). It is noted that the coupling of each (27)Al to four (31)P spins during the first ((27)Al) evolution period of the refocused INEPT, and the populations of (31)P coupled to different numbers (0-4) of (27)Al in the ± 1/2 Zeeman states during (31)P coherence evolution, which have been neglected in previous studies, must be taken into account for proper treatment. Analysis of J modulation on the spin ((27)Al) coupled to spin-1/2 nuclei in general gives more accurate results. Weak long-range homonuclear (4)J(PP) (P-O-Al-O-P) coupling was also observed from the (31)P spin echo and INADEQUATE experiments.     

Spin-triplet superconductivity in UNi(2)Al(3) revealed by the (27)Al Knight shift measurement

We report (27)Al Knight shift ( (27)K) measurement on a single-crystal UNi(2)Al(3) that reveals a coexistence of superconductivity and a spin-density-wave (SDW) type of magnetic ordering ( T(SDW) = 4.5 K). The spin part of (27)K, (27)K(s), does not change down to 50 mK across the superconducting (SC) transition temperature T(c) approximately 0.9 K. In contrast with the isostructural compound UPd(2)Al(3) ( T(c) approximately 2 K), which was identified to be a spin-singlet d-wave superconductor, the behavior of (27)K strongly supports that UNi(2)Al(3) , like UPt(3) and Sr(2)RuO(4), belongs to a class of spin-triplet SC pairing state superconductors.     

13C-(27)Al TRAPDOR and REDOR experiments for the detection of (13)C-(27)Al dipolar interactions in solids.

We report (13)C-(27)Al double resonance experiments (REDOR and TRAPDOR) on several aluminum organic compounds with the aim of detecting (13)C-(27)Al dipolar couplings and distances in solids. The (13)C and (27)Al pulses are applied to the same probe channel because their resonance frequencies are in close proximity. The different possibilities of controlling the efficiency of the TRAPDOR approach (by varying the (27)Al RF amplitude and the MAS frequency) are investigated. The results indicate that TRAPDOR is superior to REDOR in resolving differences in (13)C-(27)Al distances when choosing the proper experimental conditions. Where known, the crystal structure data are in qualitative agreement with the distance information extracted from our experiments. The experiment should be very valuable in different fields of solid state chemistry, where the interaction of organic and inorganic sample fractions is of fundamental importance.     

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.     

Probing through bond connectivities with MQMAS NMR

Polarization transfer from quadrupolar (27Al) to spin-1/2 (31P) nuclei via J-coupling is employed to measure two-dimensional 27Al-31P heteronuclear correlation spectra with isotropic resolution. The proposed experiment, MQ-J-HETCOR, uses multiple quantum magic angle spinning (MQMAS) NMR for elimination of the second-order quadrupolar broadening and INEPT, INEPTR, INEPT+ and DEPT sequences for the polarization transfer. The experimental conditions leading to best sensitivity and resolution are detailed using AlPO4-14 as a test sample.     

Characterization of microporous aluminophosphate IST-1 using (1)H Lee-Goldburg techniques

The presence of two independent methylamine species in microporous aluminophosphate IST-1 (|(CH(3)NH(2))(4)(CH(3)NH(+)(3))(4)(OH(-))(4)|[Al(12)P(12)O(48)]) has been shown previously by synchrotron powder X-ray diffraction. One of these species, [N(1)-C(1)], links to a six-coordinated framework Al-atom [Al(1)], while the other methylamine [N(2)-C(2)] is protonated and hydrogen-bonded to three O-atoms [O(1), O(2) and O(12)]. We revisit the structure of IST-1 and report the complete assignment of the (1)H NMR spectra by combining X-ray data and high-resolution heteronuclear/homonuclear solid-state NMR techniques based on frequency-switched Lee-Goldburg homonuclear decoupling and (31)P-(31)P homonuclear recoupling. Careful analysis of the 2D (1)H-X homonuclear correlation (X=(1)H) and 2D heteronuclear correlation (X=(13)C, (31)P and (27)Al) spectra allowed the distinction of both methylamine species and the assignment of all (31)P and (13)C resonances. For the first time at a relatively high (9.4 T) magnetic field, symmetric doublet patterns have been observed in the (13)C spectra, caused by the influence of the (14)N second-order quadrupolar interaction.     

Double-resonance decoupling for resolution enhancement of 31P solid-state MAS and 27Al --> 31P MQHETCOR NMR

27Al decoupling has been used to remove residual J-coupling interactions between 31P and 27Al in microporous aluminophosphates AlPO4-14 and AlPO4-40. In combination with 1H high-power decoupling, 27Al adapted decoupling yields 31P spectra with optimal sensitivity and resolution. The importance of double-resonance decoupling is further demonstrated by incorporating this technique in the MQHETCOR sequence. Unambiguous assignment of all the AlPO4-14 nuclear magnetic resonances is achieved by combining multiple-quantum evolution in the 27Al dimension and double-resonance decoupling in the 31P acquisition domain.     

Messung von Wirkungsquerschnitten für die Reaktionen 27Al(N,P) 27Mg, 27Al(N, α)24Na und 27Al(N, α)24MNa im Energiebereich zwischen 6,3 MeV und 8,3 MeV

Measurements of Cross Sections for the Reactions ²⁷Al(N, P) ²⁷Mg, ²⁷Al(N, α)²⁴Na and ²⁷Al(N, α)^24mNa in the Energy Region between 6,3 MeV and 8,3 MeV Using the activation method cross-sections for the reactions ²⁷Al(n, α₀)²⁴Na, ²⁷Al(n, α₁)^24mNa and ²⁷Al(n, p)²⁷Mg have been measured in the energy range 6.3 MeV to 8.3 MeV. Fast neutrons were produced at the Stuttgart University 4 MV Dynamitron via the reaction ⁹Be(α, n)¹²C irradiating 0.52 μm beryllium layers on high pressure water-cooled copper backings. The energy of the He-ions was varied between 1.86 MeV and 2.76 MeV, while the average current was 200 μAmp. The neutron flux has been measured with a 2″ × 2″ NE 213 liquid scintillator cell.     

An advanced NMR protocol for the structural characterization of aluminophosphate glasses

In this work a combination of complementary advanced solid-state nuclear magnetic resonance (NMR) strategies is employed to analyse the network organization in aluminophosphate glasses to an unprecedented level of detailed insight. The combined results from MAS, MQMAS and (31)P-{(27)Al}-CP-heteronuclear correlation spectroscopy (HETCOR) NMR experiments allow for a detailed speciation of the different phosphate and aluminate species present in the glass. The interconnection of these local building units to an extended three-dimensional network is explored employing heteronuclear dipolar and scalar NMR approaches to quantify P-O-Al connectivity by (31)P{(27)Al}-heteronuclear multiple quantum coherence (HMQC), -rotational echo adiabatic passage double resonance (REAPDOR) and -HETCOR NMR as well as (27)Al{(31)P}-rotational echo double resonance (REDOR) NMR experiments, complemented by (31)P-2D-J-RESolved MAS NMR experiments to probe P-O-P connectivity utilizing the through bond scalar J-coupling. The combination of the results from the various NMR approaches enables us to not only quantify the phosphate units present in the glass but also to identify their respective structural environments within the three-dimensional network on a medium length scale employing a modified Q notation, Q(n)(m),(AlO)(x), where n denotes the number of connected tetrahedral phosphate, m gives the number of aluminate species connected to a central phosphate unit and x specifies the nature of the bonded aluminate species (i.e. 4, 5 or 6 coordinate aluminium).     

The determination of the average 27Al-31P distance in aluminophosphate molecular sieves with SEDOR NMR.

The average 27Al-31P distances in an aluminophosphate, AlPO4-5, and in a silicoaluminophosphate, SAPO-11, were determined by using Spin Echo DOuble Resonance (SEDOR). A calculated SEDOR curve was fitted to the data in order to obtain the dipolar coupling constant. The tetrahedral surrounding of 27Al by four 31P atoms in the second coordination sphere was taken into account in the calculation of the theoretical SEDOR curve. The average 27Al-31P distances obtained by using this technique proved to be in good agreement with X-ray diffraction data.     

Multinuclear (27Al, 29Si, 47,49Ti) solid-state NMR of titanium substituted zeolite USY

Multinuclear solid-state NMR spectroscopy, employing 29Si MAS,27Al MAS/3Q-MAS and (47,49)Ti wide-line experiments, has been used for the structural characterization of titanium substituted ultra-stable zeolite Y (Ti-USY). 27Al MAS experiments show the presence of aluminum in four (Al(IV)), five (Al(V)), and six (Al(VI)) coordination, whereas the multiplicity within Al(IV) and Al(VI) is revealed by 27Al 3Q-MAS experiments. Two different tetrahedral and octahedral Al environments are resolved and their isotropic chemical shifts (delta(CS)) and second-order quadrupole interaction parameters (P(Q)) have been determined by a graphical analysis of the 3Q-MAS spectra. The emergence of signal with higher intensity at -101 ppm in the 29Si MAS spectrum of Ti-USY samples indicates the possible occurrence of Q4(3Si,1Ti) type silicon environments due to titanium substitution in the faujasite framework. High-field (11.74T) operation, using a probehead specially designed to handle a large sample volume, has enabled the acquisition of 47,49Ti static spectra and identification of the titanium environment in the zeolite. The chemical shielding and electric field gradient tensors for the titanium environment in the zeolite have been determined by a computer simulation of the quadrupolar broadened static 47,49Ti NMR spectra.     

A solid-state NMR study of the formation of molecular sieve SAPO-34

This work examined the formation of a catalytically important microporous material, SAPO-34, in the presence of HF under hydrothermal synthesis conditions. The local environments of P, Al, F and Si atoms in several solid phases obtained at different stages of crystallization were characterized by several solid-state NMR techniques including ³¹P, ²⁷Al, ¹⁹F and ²⁹Si MAS, ²⁷Al triple-quantum MAS, ³¹P{²⁷Al} transfer of populations in double-resonance, ²⁷Al{³¹P} rotational-echo double-resonance (REDOR), ²⁷Al→³¹P heteronuclear correlation spectroscopy, ³¹P{¹⁹F} and ²⁷Al{¹⁹F} REDOR as well as ¹H→³¹P cross polarization. The NMR results provide the new insights into the formation of SAPO-34.     

27Al multiple-quantum MAS NMR of mechanically treated bayerite (alpha-Al(OH)3) and silica mixtures

Two-dimensional 27Al multiple-quantum magic angle spinning (MQMAS) NMR experiments are used to study mixtures of bayerite (alpha-Al(OH)3) with either silicic acid (SiO2.nH2O) or silica gel (SiO2) that have been ground together for varying lengths of time. This mechanical treatment produces changes in the 27Al MAS and MQMAS NMR spectra that correspond to the formation of new Al species. Mean values of the quadrupolar interaction (PQ) and isotropic chemical shift (deltacs) are extracted from the two-dimensional 27Al NMR spectra for each of these species. The presence of significant distributions of both 27Al quadrupolar and chemical shift parameters is demonstrated and the effect of grinding duration on the magnitudes of these distributions is discussed.     

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.     

27Al+27Al耗散反应中间双核系统的核温度

从²⁷Al+²⁷Al耗散反应产物的激发函数中提取能量相干宽度Г,再求出双核系统的核温度T,并用相干转动的概念进行以合与解释.     

27Al+27Al耗散反应中激发函数的测量与统计性质分析

通过测量能量从114—120MeV、能量步长为200keV的重离子耗散反应²⁷Al+²⁷Al从θ(cm)=50°—90°的角分布和激发函数,在对所有宏观出射道积分的基础上,分析了重离子耗散反应中激发函数涨落的物理性质.     

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.     

27Al and 23Na double-rotation NMR of sodalites.

The 27Al NMR spectra of calcium tungstate aluminate sodalite (CAW), Ca8[Al12O24](WO4)2, and the 23Na NMR spectra of sodium aluminosilicate sodalites of general composition Na9[Si6Al6O24]A2 with A = B(OH)4- (SBS), SCN- (SRS) and A2 = SO4(2-) (SSS), MoO4(2-) (SMS) have been measured using magic-angle spinning (MAS) and double-rotation (DOR) techniques. Rotor synchronized pulse excitation is applied in the DOR experiments. Dramatic line narrowing is observed in the DOR spectra of all samples. The 27Al DOR NMR spectra of CAW measured at 9.4 and 11.7 T and spinning rates of 800-1150 Hz of the outer and 5 kHz of the inner rotor show seven sharp central lines accompanied by a manifold of spinning sidebands. These lines correspond to the seven crystallographically inequivalent Al sites of the CAW framework derived from X-ray structure analysis. From the difference of the line positions in the 9.4 and 11.7 T spectra the quadrupole coupling constant, QCC, quadrupole induced shift, sigma qs, and isotropic chemical shift, delta cs, of each Al site have been calculated. QCC values in the range of 5 to 9 MHz are obtained which reflect the strong tetragonal distortion of the AlO4 tetrahedra in CAW. delta cs shows only small changes in the range between 74.4 and 77.2 ppm. A tentative assignment of all lines to the distinct Al sites is derived from the correlation between QCC and a "shear strain parameter" describing quantitatively the distortion of the AlO4 tetrahedra.(ABSTRACT TRUNCATED AT 250 WORDS)     

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.