Über basische Aluminiumsalze und ihre Lösungen. XI. Vergleichende 27Al-NMR-Untersuchungen am Mineral Zunyit und basischen Aluminium-Salzen mit tridekameren Al-oxo-hydroxo-aquo-Kationen

Basic Aluminium Salts and their Solutions. XI. ²⁷Al-NMR Studies Comparing the Mineral Zunyite and Basic Aluminium Salts of Tridecameric Al-oxo-hydroxo-aquo-Cations Solid-state high resolution ²⁷Al NMR studies of basic aluminum sulphate and the mineral zunyite, both containing tridecameric Al-oxo-hydroxo groups, show different ²⁷Al spectra. While for zunyite both AlO₆ octahedra (0 ppm) and the central AlO₄ tetrahedron (69 ppm) are observed in the spectrum, in the case of the basic aluminum sulphate only the tetrahedrally coordinated Al (59 ppm) is detected by NMR. This behaviour is explained by structural data, which indicate stronger distortions of the AlO₆ octahedra in the case of the basic aluminum sulphate. The increased shielding of the fourcoordinated Al of the basic sulphate is attributed to an increased ionic character of the Al? O bond in this compound.     

27Al-MAS-NMR- und IR-spektroskopische Untersuchungen zur Aluminium-Koordination in röntgenamorphen SiO2 ?Al2O3-Festkörpern

²⁷Al MAS N.M.R. and I.R. Investigations on the Aluminium Coordination in Amorphous Silica-Alumina Gels Amorphous silica-alumina of different Si/Al ratios have been investigated by ²⁷Al magic-angle spinning n.m.r. (MAS n.m.r.) and i.r. spectroscopy. Aluminosilicate framework structures were found for the Na⁺- and NH₄⁺-exchanged forms of the investigated gels. The thermal deammoniation of the NH₄⁺-exchanged gels, producing the H⁺ forms, causes an irreversible damage of the aluminosilicate framework. This process is accompanied by a change of the coordination state of a part of the aluminium, converting AlO₄ into AlO₆ units. The progress of the solid-state reaction upon further thermal treatment of the H⁺ forms is reflected by a considerable broadening of the n.m.r. spectra and a decrease of the intensity. The possibility that well-known results, including those of nonframework aluminium, obtained for comparable zeolitic systems may also be valid for amorphous solids, is discussed.     

NMR Chemical Shift and Quadrupolar Interaction Parameters of Carbon‐Coordinated 27Al in Aluminium Carbide,Al4C3

Aluminium carbide, Al₄C₃, was characterised by ¹³C and ²⁷Al solid‐state NMR spectroscopy. The ¹³C NMR spectra display two resonances with an intensity ratio of 1:2, which is in agreement with the reported crystal structure. The ²⁷Al NMR spectra of Al₄C₃ under both static and MAS conditions were deconvoluted into two spectral components, belonging to the two aluminium species Al1 and Al2 in the crystal structure of Al₄C₃. The spectral fit allowed for determination of the relatively large quadrupolar coupling constants (χ ≈? 16 MHz) of both ²⁷Al species. One aluminium species displayed a tendency of having a χ of slightly smaller magnitude compared to the other. By carrying out DFT calculations of the EFG tensor at the ²⁷Al sites using the Wien2k software, we could tentatively assign the smaller χ site to be the crystallographic Al1 species. Also, the isotropic chemical shift for the carbon‐coordinated aluminium in Al₄C₃ could be determined, being in the range of 111 to 120 ppm. This is somewhat larger than those shift values observed for ²⁷Al in nitrogen coordination.     

Effect of phenyl group on the structure and formation of transitional alumina from Al (OPh)<Subscript>3</Subscript>

The structure of freshly prepared Al(OPh)₃, its decomposition product, the hydrolyzed products and their structural evolution were investigated employing ²⁷Al MAS NMR spectroscopy, PXRD, TGA/DTA/DSC/FTIR techniques. In the ²⁷Al MAS NMR spectrum of the aluminium phenoxide, three signals with the chemical shift at 3.78, 21 and 45 ppm were observed. The chemical shift at 3.78 and 45 ppm revealed the presence of four and sixfold coordinated aluminum. The signal at 21 ppm corresponded to fivefold coordinated aluminium. When the aluminium phenoxide was directly decomposed in air at 600 °C, it resulted in amorphous product as evidenced from the PXRD pattern. The observed signals with chemical shifts at 10.1, 42, 73.6 ppm in the ²⁷Al MAS NMR spectrum indicated the presence of 6, 5 and 4 coordination for the aluminium atoms suggesting disordered transitional γ-alumina to be the product. The hydrolysis studies of Al(OPh)₃ with excess of water at 70 °C yielded bohemite (γ-AlOOH). The alumina obtained after dehydration at 600 °C was X-ray amorphous. The dehydrated product at 600 °C showed the presence of four and six coordinated aluminium atoms in the ²⁷Al MAS NMR spectrum confirming it to be ordered γ-Al₂O₃. Crystalline γ-Al₂O₃ was obtained on further heating at 800 °C.     

27Al NMR diffusometry of Al13 Keggin nanoclusters

Although nanometer-sized aluminum hydroxide clusters (i.e., ϵ-Al₁₃, [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺) command a central role in aluminum ion speciation and transformations between minerals, measurement of their translational diffusion is often limited to indirect methods. Here, ²⁷Al pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has been applied to the AlO₄ core of the ϵ-Al₁₃ cluster with complementary theoretical simulations of the diffusion coefficient and corresponding hydrodynamic radii from a boundary element-based calculation. The tetrahedral AlO₄ center of the ϵ-Al₁₃ cluster is symmetric and exhibits only weak quadrupolar coupling, which results in favorable T₁ and T₂ ²⁷Al NMR relaxation coefficients for ²⁷Al PFGSTE NMR studies. Stokes–Einstein relationship was used to relate the ²⁷Al diffusion coefficient of the ϵ-Al₁₃ cluster to the hydrodynamic radius for comparison with theoretical simulations, dynamic light scattering from literature, and previously published ¹H PFGSTE NMR studies of chelated Keggin clusters. This first-of-its-kind observation proves that ²⁷Al PFGSTE NMR diffusometry can probe symmetric Al environments in polynuclear clusters of greater molecular weight than previously considered.     

Über basische Aluminiumsalze und ihre Lösungen. VII. Zum Einfluß der Herstellungsbedingungen,der Konzentration und der Alterungszeit auf die Zusammensetzung von Lösungen basischer Aluminiumsalze

Basic Aluminium Salts and their Solutions. VII. Influence of Preparation, Concentration, and Aging on the Constitution of Solutions of Basic Aluminium Salts 0.1 to 4 molar basic aluminium chloride solutions – prepared by dissolving aluminium metal in substoichiometric quantities of hydrochloric acid and 10^?4 to 0.2 molar basic solutions of aluminium chloride and perchlorate – prepared by adding alkali to the solutions of the neutral salts were investigated for the kinetics of their reactions with ferrone and by ²⁷Al NMR spectroscopy. In all solutions the contents of polymeric species decreases at equal basicity with increasing aluminium concentration. On the other hand the Al₁₃O₄₀ complex is only formed in solutions prepared by addition of alkali. The differences of composition are confirmed by the aging behaviour of the solutions.     

Donorstabilisiertes Aluminium(I)-iodid

Donorstabilized Aluminium(I) Iodide A metastable solution of Al^I-iodide is formed by quenching of gaseous Al^I-iodide, formed from Al_(I) and HI_(g) at about 1000°C with a mixture of toluene/diethylether. Using triethylamine as donor and solvent crystalline (AlI · NEt₃)₄ 1 can be isolated: a planar Al₄ ring with an Al? Al distance of 265 pm is the most important structural feature in this first roomtemperature stable Al^I-Iodide.     

Structural studies of sialon ceramics by high-resolution solid-state NMR

High-resolution solide-state ²⁷Al NMR with magic-angle spinning (MASNMR) readily monitors the quantity and coordination (four- and six-fold) of aluminium in two ceramic materials of the SiAlON system. Sialon X-phase, of approximate composition Si₃Al₆O₁₂N₂, contains aluminium-centred octahedra and tetrahedra in the ratio ca. 1.9:1.0, while another sample containing a mixture of sialon polytypoids shows AlO₆ octahedra and a large quantity of what is most probably nitrogen-coordinated tetrahedral aluminium. In addition, ²⁹Si MASNMR detects two different kinds of silicon in the latter sample in a 2:1 ratio. These observations are interpreted satisfactorily in terms of the crystal structures of the compounds and provide further examples of the potential of MASNMR in the investigation of complex ceramic systems.     

Synthesis of polyaluminocarbosilane with low branched molecular structure using liquid polysilacarbosilane and aluminum acetylacetonate by high‐pressure method

The synthesis of polyaluminocarbosilane (PACS) using liquid polysilacarbosilane (PSCS) and aluminum acetylacetonate [Al (acac)₃] by a high‐pressure method is reported for the first time. The effects of reaction time, temperature and feed ratio on the structure of PACS are investigated in detail by gel permeation chromatography, Fourier transform‐infrared, ¹H‐NMR, ²⁹Si‐NMR and ²⁷Al‐NMR methods. It was found that the molecular weight and its polydispersity, as well as the branching degree of the molecular structure of PACS, increase with reaction time and temperature. Increasing the weight percentage of Al (acac)₃ has a similar effect as temperature. Combined with the gas chromatography–mass spectroscopy results, the reaction mechanism is proposed, which contains three main reactions: (i) cleavage and rearrangement reaction of PSCS; (ii) silicon‐free radicals react with Al (acac)₃, leading to cleavage of O=C and/or O‐C bonds and formation of AlO_x ligands; and (iii) conversion reaction of Al ligands from AlO₆ into AlO₅ and AlO₄. It is also found that PACS prepared by high‐pressure method has a lower branched molecular structure in comparison to its analog prepared under ambient pressure conditions, and it is achieved to increase the molecular weight and ceramic yield of PACS, which is beneficial for the processing and overall quality of the final product.     

Crystalline oxyfluorinated open-framework compounds: Silicates, metal phosphates, metal fluorides and metal-organic frameworks (MOF)

This contribution is dedicated to a short overview on the utilization of fluorine for the preparation of crystalline microporous frameworks including different families of solids: zeolites, metal phosphates and metal-organic frameworks (MOF-type). Beside the silicates compounds, this presentation is focused on the different types of fluorinated aluminum or gallium phosphates hydrothermally obtained in the presence of organic structure-directing agent or templates. The structural features of aluminum fluorides synthesized with amines are also detailed as well as the influence of fluorine in the synthesis of the metal-organic frameworks involving trivalent metals. The role of fluorine is described for the hydrothermal synthesis of the different classes of materials. Fluorine is known for playing the role of mineralizing agent and favors the formation of well crystalline phases. The use of HF modifies the pH of the reaction, which allows for the insertion of additional metallic cations on the mineral network. From the structural point of view, fluoride anions can be located within small cavities of the 3D framework and interactions with metals T (T = Si, Al, Ga, …) are often observed, resulting in the coordination change (from tetrahedral unit TO₄ to trigonal bipyramid TO₄F or octahedron TO₄F₂). Several configurations are found for fluorine and it seems to favor the stabilization of the specific cubane-like building unit (D4R), in which it is trapped, or participates to the coordination sphere of the metal atoms with bridging or terminal bondings. In general, new three-dimensional topologies with extra-large pores are obtained. The synthesis of purely aluminum fluorides with structure-directing agent is considered but only molecular or low-dimensional structures (chain-like or layered) compounds have been described. Fluorine is also used as a mineralizing agent for the preparation of well crystalline porous aluminum or chromium carboxylates and it was observed to partly substitute the aquo ligands in the giant pore of the compound MIL-100.     

Speciation of Aluminium in Mixtures of the Ionic Liquids [C3mpip][NTf2] and [C4mpyr][NTf2] with AlCl3: An Electrochemical and NMR Spectroscopy Study

This paper reports on the electrodeposition of aluminium on several substrates from the air‐ and water‐stable ionic liquids 1‐propyl‐1‐methylpiperidinium bis(trifluoromethylsulfonyl)amide ([C₃mpip][NTf₂]) and 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([C₄mpyr][NTf₂]), which contain anhydrous AlCl₃. At an AlCl₃ concentration of 0.75 molal, no evidence for aluminium electrodeposition was observed in either system at room temperature. However, aluminium electrodeposition becomes feasible upon heating the samples to 80 °C. Aluminium electrodeposition from bis(trifluoromethylsulfonyl)amide‐based ionic liquids that contain AlCl₃ has previously been shown to be very dependent upon the AlCl₃ concentration and has not been demonstrated at AlCl₃ concentrations below 1.13 molal. The dissolution of AlCl₃ in [C₃mpip][NTf₂] and [C₄mpyr][NTf₂] was studied by variable‐temperature ²⁷Al NMR spectroscopy to gain insights on the electroactive species responsible for aluminium electrodeposition. A similar change in the aluminium speciation with temperature was observed in both ionic liquids, thereby indicating that the chemistry was similar in both. The electrodeposition of aluminium was shown to coincide with the formation of an asymmetric four‐coordinate aluminium‐containing species with an ²⁷Al chemical shift of δ=94 and 92 ppm in the [C₃mpip][NTf₂]–AlCl₃ and [C₄mpyr][NTf₂]–AlCl₃ systems, respectively. It was concluded that the aluminium‐containing species that give rise to these resonances corresponds to the electroactive species and was assigned to [AlCl₃(NTf₂)]^?.     

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al bridges, the synthesis of well‐defined, soluble, molecular models for these materials is challenging. Here we show that reactions of the potassium aluminyl complex K₂[( NON )Al]₂ ( NON =4,5‐bis(2,6‐diiso‐propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) with CO₂, PhNCO and N₂O all proceed via a common aluminium oxide intermediate. This highly reactive species can be trapped by coordination of a THF molecule as the anionic oxide complex [( NON )AlO(THF)]^?, which features discrete Al?O bonds and dimerizes in the solid state via weak O???K interactions. This species reacts with a range of small molecules including N₂O (to give a hyponitrite ([N₂O₂]^2?) complex) and H₂, the latter offering an unequivocal example of heterolytic E?H bond cleavage across a main group M?O bond.     

PbCa2[Al8O15] with a novel three‐dimensional aluminate anion

The asymmetric unit of the title compound, lead(II) dicalcium octaaluminate, contains one Pb, one Ca, four Al and eight O atoms, with the Pb atom and one O atom situated on mirror planes. Three Al atoms exhibit slightly distorted tetrahedral coordinations with a mean Al—O bond length of 1.76 Å. The fourth Al atom is in a considerably distorted trigonal–bipyramidal coordination with a mean Al—O bond length of 1.89 Å. One AlO₄ tetrahedron forms infinite chains parallel to [100] via corner‐sharing. These chains are linked by parallel chains of edge‐sharing AlO₅ trigonal bipyramids into layers A of six‐membered double rings extending parallel to (010). The second layer B is made up of the remaining two AlO₄ tetrahedra. These tetrahedra share corners, resulting in likewise six‐membered double rings. Finally, the parallel layers A and B are linked into a three‐dimensional framework by common corners. Charge compensation is achieved by the Pb²⁺ and Ca²⁺ cations, which are situated in the cavities of the anionic framework, and which are surrounded by seven and six O atoms, respectively, both within highly irregular coordination polyhedra.     

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.     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Aluminum Complexes with a Donor Polymer: New Route to Organic/Inorganic Polymer Hybrids

The formation of alumina particles from aluminum salts in the presence of poly(1-vinylimidazole) was investigated by quantitative ²⁷Al NMR, potentiometry and FTIR spectra. The interaction of poly(1-vinylimidazole) with aluminum chloride and nitrate in an aqueous medium stabilizes [AlO₄Al₁₂(OH)₂₄]⁷⁺ and less ordered polymeric particles. The addition of NaOH (NaOH: Al 2) results in water-insoluble organic/inorganic hydrogen-bonded composites. Stabilization of the complexes is realized by cooperative hydrogen N···H—O—Al bonds, without N Al donor-acceptor interactions.     

Characteristics and formation of [AlO4Al12(OH)24(H2O)12]7+ in electrolysis process

[AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺ (Al₁₃) formation in electrolysis process is studied. The results detected by²⁷Al NMR spectroscopy show that high content of Al₁₃ polymer is formed in the partially hydrolyzed aluminum solution prepared by controlled electrolysis process. In the produced electrolyte of total Al concentration ([Al_T]) 2.0 mol · L⁻¹ with a basicity (B = OH/Al molar ratios) of 2.0, the content of Al₁₃ polymer is over 60% of total Al. Dynamic light scattering shows that the size distribution of the final electrolyte solutions ([Al_T] = 2.0 mol · L⁻¹) is trimodal with B = 2.0 and bimodal with B = 2.5. The aggregates of Al₁₃ complexes increase the particle size of partially hydrolyzed aluminum solution.     

27Al NMR MAS Spectral Studies Inferring the Initiation of Geopolymerization Reaction on Together Mechanochemical Grinding of Raw Materials

Chemical shifts and intensities of the ²⁷Al NMR signals provide structural information about the environment of Al nuclei in presence of an external magnetic field. This paper analyzes the structural information of the aluminum nuclei present in the precursor material after mechanochemical co‐grinding of the raw materials, namely fly ash, NaOH, and amorphous tricalcium phosphate [Ca₃(PO₄)₂], with the help of ²⁷Al MAS NMR spectral studies. The results indicate transformation of the sixfold coordination Al ions with oxygen AlQ6 present in aluminosilicate material fly ash to fourfold AlQ4 and fivefold AlQ5 in the precursor material. The variation in chemical shift is between δ 64 and 65 ppm. This indicates that, in addition to direct bonding to the oxygen atom, the Al tetrahedron is also bonded to Si as [AlQ4(4Si)]. Thus, the mechanochemical co‐grinding of the raw materials initiates a solid‐state chemical reaction among them. The addition of water alone to this precursor material results in the formation of the geopolymeric material unlike the conventional geopolymeric system which requires the addition of a highly alkaline aqueous solution to fly ash. This study helps in the determination of the reaction mechanism during the mechanochemical transformation of raw materials into the geopolymeric product by a novel process.     

Über basische Aluminiumsalze und ihre Lösungen. X. NMR-Untersuchungen am tridekameren Al-oxo-hydroxo-Kation

Basic Aluminum Salts and their Solutions. X. NMR-Investigations on the Tridecameric Al-Oxo-Hydroxo Cation Using solid-state high resolution ²⁷Al-NMR it is shown that in the basic aluminum chloride with a degree of alkalinity r = OH/Al = 2.5 cations of the [Al₁₃O₄(OH)₂₅(H₂O)₁₁]⁶⁺ type exist. The ¹H-NMR detects besides the constitutional water still an amount of mobile, enclosed H₂O molecules which can be removed by thermal treatment at 104°C. The ²⁷Al spectrum of the aqueous solutions of the chloride shows only one peak at 62.5 ppm which is characteristic for the tridecameric cation. Adding HCl to the solution causes a decomposition to low-molecular species (peak at 0 ppm). Adding NaOH to the aqueous solution of the chloride effects a rearrangement of the tridecameric cations to higher molecular particles which are no more accessible by ²⁷Al-NMR.