Solid-state 1H and 27Al NMR studies of amorphous aluminum hydroxides

Two kinds of amorphous aluminum hydroxides, a sample precipitated from admixing AlCl3 and NaOH aqueous solutions and the commercial product, were measured by 27Al and 1H solid-state NMR spectroscopy. Pentahedral and tetrahedral coordinations, as well as octahedral coordination of oxygen atoms for aluminum, are observed in 27Al magic angle spinning (MAS) spectra of both amorphous samples. In contrast, octahedral coordination is only observed in gibbsite, bayerite, and boehmite. According to 1H MAS-NMR spectra under conditions of high spinning rate (35 kHz) and high field (14.09 T), free waters and OH groups coupled with aluminum for amorphous samples are observed at approximately 5 and approximately 4.5 ppm, respectively, the latter peak being broader. This is consistent with the differential spectra between spin echo and transfer of populations in double resonance. We conclude that the subunits of AlO4, AlO5, and AlO6 in amorphous aluminum hydroxides are bound through hydrogen bonds with a wide distribution of bonding strength.     

Triple-quantum magic angle spinning (27)Al NMR of aluminum hydroxides

We show that (27)Al triple-quantum magic angle spinning (3Q-MAS) experiments alleviate the second-order quadrupolar broadening to reveal the structure-building units of nonequivalent aluminum octahedra in the most extensively studied aluminum hydroxides, namely, gibbsite, bayerite, and boehmite. Further, aided by ab initio calculations of the electric field gradient tensors, the 3Q-MAS/MAS results are shown to lead to the assignment of (27)Al isotropic resonances to the aluminum positions in their X-ray-determined structures. The present work paves the way for future studies on various structurally transformed materials derived from these basic aluminum hydroxides.     

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

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Characterization of the malate-aluminum(III) complex using 1H and 27Al NMR spectroscopy

Structural elucidation of a malate-aluminum(III) complex has been carried out using 1H and 27Al NMR spectroscopy. The 1H chemical shift perturbation clearly indicated the interaction between malate and Al(III) ion. The measurements of 27Al NMR and 1H-13C HSQC spectra demonstrated that the major form of a complex comprised two equivalent malate ions and two unequivalent Al(III) ions. With this constraint, an equilibrium geometry of the complex was proposed by a semi-empirical molecular orbital calculation.     

New insights into the intercalation chemistry of Al(OH)3

This paper reports a number of recent developments in the intercalation chemistry of Al(OH)(3). From Rietveld refinement and solid-state NMR, it has been possible to develop a structural model for the recently reported [M(II)Al(4)(OH)(12)](NO(3))(2)·yH(2)O family of layered double hydroxides (LDHs). The M(2+) cations occupy half of the octahedral holes in the Al(OH)(3) layers, and it is thought that there is complete ordering of the metal ions while the interlayer nitrate anions are highly disordered. Filling the remainder of the octahedral holes in the layers proved impossible. While the intercalation of Li salts into Al(OH)(3) is facile, it was found that the intercalation of M(II) salts is much more capricious. Only with Co, Ni, Cu, and Zn nitrates and Zn sulfate were phase-pure LDHs produced. In other cases, there is either no reaction or a phase believed to be an LDH forms concomitantly with impurity phases. Reacting Al(OH)(3) with mixtures of M(II) salts can lead to the production of three-metal M(II)-M(II)'-Al LDHs, but it is necessary to control precisely the starting ratios of the two M(II) salts in the reaction gel because Al(OH)(3) displays selective intercalation of M nitrate (Li > Ni > Co ≈ Zn). The three-metal M(II)-M(II)'-Al LDHs exhibit facile ion exchange intercalation, which has been investigated in the first energy dispersive X-ray diffraction study of a chemical reaction system performed on Beamline I12 of the Diamond Light Source.     

Short- and medium-range order in sodium aluminophosphate glasses: new insights from high-resolution dipolar solid-state NMR spectroscopy

The structures of sodium aluminophosphate glasses prepared by both sol-gel as well as melt-cooling routes have been extensively characterized by high-resolution solid-state 23Na, 27Al, and 31P single and double-resonance NMR techniques, including quantitative connectivity studies by 27Al <--> 31P and 23Na <--> 31P rotational echo double-resonance (REDOR) methods. Studies along four compositional lines, I: (AlPO4)x -(NaPO3)1-x, II: (Na2O)x -(AlPO4)1-x, III: (NaAlO2)x -(NaPO3)1-x, and IV: (Al2O3)x (NaPO3)1-x, reveal that the network structures of those glasses that are accessible by either preparation method are essentially identical. However, the significantly extended glass-forming ranges available by the sol-gel route facilitate exploration of the structure/composition relationships in more detail, revealing a number of interesting universal features throughout the whole glass system. Both short- and medium-range order appear to be controlled strongly by the O/P ratio of the glasses studied: Up to an O/P ratio of 3.5 (pyrophosphate composition), aluminum is predominantly six-coordinated and fully connected to phosphorus (Al(OP)6 sites). In the region 3.5 < or = O/P < or = 4.0, a dramatic structural transformation takes place, leading to the appearance of additional four- and five-coordinated aluminum species whose second coordination spheres are also entirely dominated by phosphorus. The structure of glasses with an O/P ratio of precisely 4.0 (orthophosphate) is dominated by Al(OP)4 units. As the O/P ratio increases beyond 4.0, the average extent of Al-O-P connectivity is decreased significantly. Here, new types of five- and six-coordinated aluminum units, which are only weakly connected to phosphorus, are formed, while the network modifier is attracted mainly by the phosphate units.     

Fast and Efficient Reductive Amination of Aldehydes by NaBH4/B(OH)3 and NaBH4/Al(OH)3

Reductive amination a variety of aldehydes and anilines to their corresponding secondary amines were carried out with NaBH₄/B(OH)₃ and NaBH₄/Al(OH)₃ as new reducing systems in CH₃CN at room temperature in high to excellent yields of products (90‐96%).     

Five-coordinate iron(III) porphycenes: (1)H NMR, magnetic, and structural studies

Five-coordinate iron(III) 2,7,12,17-tetrapropylporphycene (TPrPc)Fe(III)X (X = C(6)H(5)O(-), Cl(-), Br(-), I(-), ClO(4)(-)) complexes have been investigated. The (1)H NMR spectra demonstrate downfield shifts for pyrrole resonances [(TPrPc)Fe(III)(C(6)H(5)O), 65.3 ppm; (TPrPc)Fe(III)Cl, 28.5 ppm] but large upfield ones for (TPrPc)Fe(III)Br (-7.8 ppm), (TPrPc)Fe(III)I (-49.4 ppm), and (TPrPc)Fe(III)ClO(4) (-77.1 ppm) (294 K, CD(2)Cl(2)). The pyrrole chemical shifts span the remarkable +70 to -80 ppm range. The variable-temperature (1)H NMR spectra of (TPrPc)Fe(III)X demonstrate anti-Curie behavior with a sign reversal for (TPrPc)Fe(III)Cl. These behaviors are consistent with the admixed S = 3/2, 5/2 ground electronic state with a dominating contribution of the S = 3/2 one. In terms of the chemical shift, (TPrPc)Fe(III)(ClO(4)) can be considered as an example of the purest S = 3/2 state in the investigated series. The extent of the S = 5/2 contribution in the admixed S = 3/2, 5/2 ground electronic state, as gradated solely the basis of the pyrrole proton paramagnetic shifts, is controlled by the strength of the axial ligand, following the magnetochemical series (Evans, D. R.; Reed, C. A. J. Am. Chem. Soc. 2000, 122, 4660). Significantly iron(III) 2,7,12,17-tetrapropylporphycene, soluble in typical organic solvents, can be considered as a universal framework to classify the ligand strength in a magnetochemical series, consistently using the beta-H pyrrole paramagnetic shifts as a fundamental criterion. The structure of (TPrPc)Fe(III)Cl has been determined by X-ray crystallography. The iron is five-coordinate with bonds of nearly equal length to the four pyrrole nitrogen atoms (Fe-N in the range 1.983(5)-2.006(6) A). The iron lies 0.583(1) A out of the mean plane of the macrocycle and 0.502(5) A out of the mean N(4) plane. In the solid, pairs of molecules are positioned about the center of symmetry so there is face-to-face pi-pi contact. The mean plane separation is 3.38 A, and the lateral shift of the porphycene center along the Fe-N bond is 4.490 A. The distance from one porphycene center to the other is 5.62 A, and the iron-iron separation is 6.304(2) A.     

17O and 29Si NMR parameters of MgSiO3 phases from high-resolution solid-state NMR spectroscopy and first-principles calculations

The 29Si and 17O NMR parameters of six polymorphs of MgSiO3 were determined through a combination of high-resolution solid-state NMR and first-principles gauge including projector augmented wave (GIPAW) formalism calculations using periodic boundary conditions. MgSiO3 is an important component of the Earth's mantle that undergoes structural changes as a function of pressure and temperature. For the lower pressure polymorphs (ortho-, clino-, and protoenstatite), all oxygen species in the 17O high-resolution triple-quantum magic angle spinning (MAS) NMR spectra were resolved and assigned. These assignments differ from those tentatively suggested in previous work on the basis of empirical experimental correlations. The higher pressure polymorphs of MgSiO3 (majorite, akimotoite, and perovskite) are stabilized at pressures corresponding to the Earth's transition zone and lower mantle, with perovskite being the major constituent at depths >660 km. We present the first 17O NMR data for these materials and confirm previous 29Si work in the literature. The use of high-resolution multiple-quantum MAS (MQMAS) and satellite-transition MAS (STMAS) experiments allows us to resolve distinct oxygen species, and full assignments are suggested. The six polymorphs exhibit a wide variety of structure types, providing an ideal opportunity to consider the variation of NMR parameters (both shielding and quadrupolar) with local structure, including changes in coordination number, local geometry (bond distances and angles), and bonding. For example, we find that, although there is a general correlation of increasing 17O chemical shift with increasing Si-O bond length, the shift observed also depends upon the exact coordination environment.     

Preparation of Al(OH)3/PMMA nanocomposites by emulsion polymerization

Al(OH)₃/PMMA nanocomposites were prepared by the emulsion polymerization of methyl methacrylate (MMA) in the presence of surface‐functionalized Al(OH)₃ particles. Nanosized Al(OH)₃ particles were previously functionalized with a silane coupling agent, 3‐(trimethoxysilyl) propyl methacrylate (γ‐MPS), which was confirmed by FT‐IR and XRF analysis. The average size of seed particles was around 70 nm, and the density of the coupling agent on the particles was calculated to be 8.9 µmol m^?2. The emulsion polymerization was attempted at relatively high solid content of 40–46 wt%. The ratio of the seed particles to MMA had a strong influence on the stability of latex as well as the morphology of composites. Nanocomposites where several PMMA nodules were attached on the surface of Al(OH)₃ core were produced with stable latex emulsion when the weight percents of Al(OH)₃ to MMA were below 20. In the case of higher ratio of 30%, however, the latexes became unstable with an aggregation, and the product morphology was in the shape of large composite. Thermogravimetric analysis showed an improved thermal stability of PMMA composites with the incorporation of Al(OH)₃ nanoparticles. Copyright © 2008 John Wiley & Sons, Ltd.     

Crystal structure of [Al4(OH)6(H2O)12][Al(H2O)6]2Br12: a new polyaluminum compound

A vertex-shared tetrahedral [Al(4)(OH)(6)(H(2)O)(12)](6+) (Al(4)) and a disordered [Al(H(2)O)(6)](3+) (Al(1)) that coexist in a 1:2 ratio within each unit cell were observed in the structure of [Al(4)(OH)(6)(H(2)O)(12)][Al(H(2)O)(6)](2)Br(12), which crystallized in a cubic Fd3m space group from a spontaneously hydrolyzed solution of AlBr(3). The former is composed of four AlO(6) octahedra that are connected to each other by sharing three vertexes of each octahedron and form a large regular tetrahedron with ideal T(d) symmetry. The central Al(3+) ion of the latter is coordinated by 6 disordered OH(2) molecules, that form a core-shell structure with ideal D(3d) symmetry.     

Al(HSO4)3 and Al2O3-SO3H as Efficient Catalysts for Modified Preparation of 3,4-Dihydropyrimidin-2 (1H)-ones/thiones

An environmentally friendly procedure for the preparation of dihydropyrimidinone derivatives or their sulfur analogues under thermal solvent-free conditions in the presence of aluminium hydrogen sulfate [Al(HSO₄)₃] and alumina sulfuric acid (Al₂O₃-SO₃H) as heterogeneous catalysts was developed.     

Thermodynamical and structural insights of orange II adsorption by MgRAlNO3 layered double hydroxides

[Mg_1−x Al_x(OH)₂][(NO₃)_x, nH₂O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar (R=(1−x)/x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg₂AlNO₃ displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg₂AlNO₃ at 40 °C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated. The experimental values for ΔG° in temperature range between 10 and 40 °C were found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange.     

Infrared and 1H NMR structural study of 3-tropane, 3-granatane and 3-bicyclo(3.2.1)octane epimeric amino acids

Five amino acids with known configuration: α- and β-3-amino-tropane- and 3-amino-bicyclo(3.2.1)octane-3-carboxylic acids and α -3-amino-granatane-3-carboxylic acid have been studied by i.r. and ¹H NMR spectroscopy. Both α- and γ-zwitterion structures have been found for tropane and granatane amino acids. Equatorial and axial ammonium groups in α-zwitterions can be distinguished by the number and frequencies of the ammonium deformation modes. A chair—boat conformation has been deduced for α-3-amino-granatane-3-carboxylic acid.     

Hydrothermal Synthesis of Porous Al2O3/Al Metal Ceramics: II. Mechanism of Formation of a Porous Al(OH)3/Al Composite

The formation of a porous layer of aluminum hydroxide on the surface of aluminum particles and the aggregation of Al(OH)₃/Al composite particles were analyzed theoretically. It was found that the diffusion mass transfer of the hydroxo complexes of aluminum through the porous structure of a growing layer of aluminum hydroxide to the outer surface is a rate-limiting step in the synthesis of the porous composite. A model mechanism of formation of the porous composite was developed, and rate equations were derived for describing the growth of an aluminum hydroxide layer on the surface of an aluminum particle and changes in the degree of aluminum conversion and the contact radius between composite particles. Based on the developed mathematical model and experimental data, the diffusion coefficient of the hydroxo complexes of aluminum in the porous structure of aluminum hydroxide was calculated.     

[H4tren]3/2·(Al6F24)·3H2O,the most condensed fluoride in the Al(OH)3-tren-HFaq.-ethanol system

The most condensed crystalline fluoride that appears in the Al(OH)₃-tren-HF_aq.-ethanol system at 190 °C is found to be [H₄tren]_3/2·(Al₆F₂₄)·3H₂O. The structure is monoclinic, P2₁/c, with a = 21.939(1) Å, b = 6.7180(2) Å, c = 23.329(1) Å, β = 111.324(2)°. _∞(Al₆F₂₄) chains result from the connection of (Al₇F₃₀)⁹⁻ polyanions by opposite AlF₆ octahedra. Hydrogen bonds are established between the _∞(Al₆F₂₄) chains and ordered or disordered [H₄tren]⁴⁺ cations and water molecules.