Synthesis of aluminum phosphate molecular sieves using cobalticinium hydroxide

The metal complex bis(cyclopentadienyl)cobalt(III) hydroxide, Cp₂CoOH, was found to be a template for the synthesis of AlPO₄-5 and AlPO₄-16 molecular sieves. The metal complexes are included in the molecular sieves and are not removed by solvent extraction or ion-exchange methods. The molecular sieves were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-VIS) detection and scanning electron microscopy (SEM) as well as elemental analysis.     

氢氧化铝表面的硬脂酸改性及溶解动力学研究

抗酸类药物大都为复方制剂,目前正朝着复合消炎、成膜缓释方向发展[1].氢氧化铝作为大多数抗酸剂的基本成分,其临床药理学的研究早已完成[2,3],但有关氢氧化铝在体内和离体环境下的溶解动力学研究未见报道.研究氢氧化铝及改性氢氧化铝在类胃酸环境中的溶解动力学特征,对研发以氢氧化铝为基体或载体的复合型胃药剂型有一定理论意义.     

Molecular models of aluminum hydroxide

A method is presented for taking into account the boundary conditions in cluster models of crystal structures containing aluminum atoms in the octahedral oxygen environment. The method of modified neglect of diatomic overlap (MNDO) was used to calculate energy and geometric characteristics of molecular models of the elementary layer of the aluminum hydroxide crystal.Institute of Surface Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 4, pp. 471–473, July–August, 1991. Original article submitted October 12, 1990.     

Intercalation compounds of aluminum hydroxide

Crystalline aluminum trihydroxides Al(OH)₃ (gibbsite, baverite, and nordstrandite) can serve as layered intercalation matrices in which metal salts are arranged in a specific way. Small cations (lithium, magnesium, and transition metals) lie in the octahedral voids of aluminum hydroxide layers, and water molecules are located between the layers. This localization of small cations gives rise to the molecular sieve effect, where alkaline and alkaline earth cations (Na⁺, K⁺, Ca²⁺, etc.), which are large relative to the octahedral voids, are not intercalated into aluminum trihydroxides. In the first step of lithium salt intercalation, the cations, the anions, and the water molecules are incorporated into the interlayer space of aluminum hydroxide with subsequent transition of lithium into the voids of the layer. Translated fromZhurnal Strukturnoi Khimii, Vol. 40, No. 5, pp. 832–848, September-October, 1999.     

Coprecipitation of silica with aluminum hydroxide

Summary The reaction between aqueous solutions of aluminum nitrate and sodium silicate was studied over a wide range of concentrations and pH values. Turbidity and precipitate volume measurements allowed solubility boundaries to be determined and the conditions to be defined for the formation of stable and unstable sols. The classification of the precipitates was made in terms of their colloidal stability correlated with particle charge measurements determined by electro-osmosis. The stability domains have been compared with previous work involving the interaction of aluminum salt solutions with preformed silica sols. The results were interpreted in terms of the solubilities of silica and alumina, respectively, of their interaction as oppositely charged sols, and of the possible formation of alumino-silicates.

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Zusammenfassung Die Reaktionen zwischen den wässerigen Lösungen von Aluminiumnitrat und Natriumsilikat wurden als Funktion von Lösungskonzentrationen und pH untersucht. Die Fällungsgrenzen sowohl wie die Stabilität der gefällten Systeme wurden durch Trübungsmessungen und Niederschlagvolumen bestimmt. Die Teilchenladungen wurden endo-osrnotisch ermittelt. Die Stabilitätsgebiete wurden mit den schon früher erhaltenen Resultaten bezüglich der Effekte von Aluminiumsalzen an Silica-Solen verglichen und in guter Übereinstimmung gefunden. Die neuen Daten wurden durch die Löslichkeit von Silica und Alumina, sowie durch die Wechselwirkungen der Sole entgegengesetzter Ladungen erklärt.

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Supported by Unilever Research Laboratory, Port Sunlight, England, and by the NSF Grant Eng. 75 08403.     

Synthesis and structural characterization of a terminal hydroxide containing alumoxane via hydrolysis of aluminum hydrides

A novel terminal hydroxide containing dinuclear alumoxane LAl(OH)OAlL(OCH=N-tBu) (3; L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3) was prepared by treatment of aluminum dihydride LAlH2 (1) and tert-butyl isocyanate in the presence of trace amounts of water and alternatively from 1 and LAlH(OCH=N-tBu) (2) with water. Compound 2 was obtained from the reaction of 1 and tert-butyl isocyanate.     

Oxidative bromination reaction using vanadium catalyst and aluminum halide under molecular oxygen

The vanadium-catalyzed oxidative bromination reaction of arenes, alkenes, and alkynes was performed in the presence of AlBr₃ to provide an alternative method for conventional bromination using hazardous bromine. The catalytic cycle is formed under molecular oxygen, which is more advantageous to vanadium bromoperoxidase (VBrPO) requiring hydrogen peroxide as a terminal oxidant.     

Removal of phosphate by aluminum oxide hydroxide

The development and manufacture of an adsorbent to remove phosphate ion for the prevention of eutrophication in lakes are very important. The characteristics of phosphate adsorption onto aluminum oxide hydroxide were investigated to estimate the adsorption isotherms, the rate of adsorption, and the selectivity of adsorption. Phosphate was easily adsorbed onto aluminum oxide hydroxide, because of the hydroxyl groups. The adsorption of phosphate onto aluminum oxide hydroxide was influenced by pH in solution: the amount adsorbed was greatest at pH 4, ranging with pH from 2 to 9. The optimum pH for phosphate removal by aluminum oxide hydroxide is 4. The selectivity of phosphate adsorption onto aluminum oxide hydroxide was evaluated based on the amount of phosphate ion adsorbed onto aluminum oxide hydroxide from several anion complex solutions. It is phosphate that aluminum oxide hydroxide can selectively adsorb. The selectivity of phosphate onto aluminum oxide hydroxide was about 7000 times that of chloride. This result indicated that the hydroxyl groups on aluminum oxide hydroxide have selective adsorptivity for phosphate and could be used for the removal of phosphate from seawater.     

Interactions of bovine serum albumin with aluminum polyoxocations and aluminum hydroxide

Interactions of aqueous solutions of aluminum polyoxocations (Al13-mers and Al30-mers) and aluminum hydroxide suspensions of varying particle sizes (26, 55, and 82 nm) with a model protein, bovine serum albumin (BSA), have been investigated using potentiometry, conductometry, viscometry, 27Al solution NMR, UV-vis spectroscopy, dynamic light scattering, zeta-potential measurements, thermogravimetry, X-ray diffraction, and scanning electron microscopy. Increasing amounts of BSA partially convert Al13-mers and, to a larger extent, Al30-mers into amorphous Al hydroxide without gel formation. At the same time, BSA molecules can form unstable aggregates in the Al polyoxocation solutions which redisperse easily upon standing. In the case of Al hydroxide sols, BSA addition causes substantial gelation, the extent of which is proportional to the amount of BSA added and inversely related to the Al hydroxide particle size. Upon freeze-drying or centrifugation of Al species-BSA solutions, an interesting sheetlike morphology with 150-200 nm wide nanoribbons is observed for pure Al hydroxide nanoparticles and for solutions of Al polyoxocations with the highest amount of BSA studied. On the basis of the combined solution, colloidal and solid-state characterization of model Al species-BSA systems, a qualitative model of possible interactions in the Al polyoxocation-BSA and Al hydroxide-BSA systems is proposed wherein core-shell hybrid nanoparticles are formed from protein "core" and Al polyoxocation "shell" or Al hydroxide "core" and protein "shell".     

Colloidal magnesium aluminum hydroxide and heterocoagulation with a clay mineral. I. Properties of colloidal magnesium aluminum hydroxide

Magnesium aluminum hydroxide, the most important member of layered double hydroxides, was peptized by intense washing. The particle diameter, 70–130 nm, depended on the temperature of aging the parent material. The electrophoretic mobility of the particles decreased with increasing pH, from 3.7 × 10⁻⁸ m²/Vs at pH 5 to 0.5 × 10⁻⁸ m²/Vs at pH 12.3. An isoelectric point at pH∼7 was reached with the addition of 87 mmol/l NaSCN, 3 mmol/l Na₂SO₄ and Na₂CO₃, and 0.7 mmol/l Na₂HPO₄. The critical coagulation concentration for the 2% (w/w) dispersion was 88 mmol/l NaCl, 1.8 mmol/l Na₂CO₃, 1.4 mmol/l Na₂SO₄, and 1.2 mmol/l Na₂HPO₄ at pH∼7. The 2% dispersion at pH∼7 showed an almost Newtonian flow behavior. Yield values were developed after salt addition. The 2% dispersion reached a yield value of 2 Pa at 100 mmol/l NaCl, 3 Pa at 100 mmol/l Na₂SO₄, and 5 Pa at 100 mmol/l Na₂CO₃. Sodium phosphate in comparison with the other salts showed a liquefying effect. The yield value increased to 3 Pa at 1–10 mmol/l Na₂HPO₄ and decreased to 0.5 Pa at 100 mmol/l Na₂HPO₄. Received: 28 February 2001 Accepted: 8 March 2001     

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Dissociative adsorption of molecular oxygen (O₂) on aluminum (Al) clusters has attracted much interest in the field of surface science and catalysis, but theoretical predictions of the reactivity of this reaction in terms of barrier height is still challenging. In this regard, we systematically investigate the reactivity of O₂ with Al clusters using density functional theory (DFT) and atom‐centered density matrix propagation (ADMP) simulations. We also calculate potential energy surfaces (PESs) of the reaction between O₂ and Al clusters to estimate the barrier energy of this reaction. The M06‐2X functional gives the barrier energy in agreement with the one calculated by coupled cluster singles and doubles with perturbed triples (CCSD(T)) while the TPSSh functional significantly underestimates the barrier height. The ADMP simulation using the M06‐2X functional predicts the reactivity of O₂ with the Al cluster in agreement with the experimental findings, that is, singlet O₂ readily reacts with Al clusters but triplet O₂ is less reactive. We found that the ability of a DFT functional to describe the charge transfer appropriately is critical for calculating the barrier energy and the reactivity of the reaction of O₂ with Al clusters. The M06‐2X functional is relevant for investigating chemical reactions involving Al and O₂. © 2016 Wiley Periodicals, Inc.     

On the early stage of aluminum oxidation: An extraction mechanism via oxygen cooperation

We propose a barrierless mechanism for describing the oxidation of Al(111) in which oxygen atoms located on the outer surface extract aluminum atoms of the surface layers through local cooperation of other pre-adsorbed oxygen atoms. We show the details of this complex chemical process that kinetically competes with the non-destructive formation of an oxygen monolayer onto the Al surface, thus elucidating the initial aluminum oxidation regime. We demonstrate that further stripping of the complete surface Al layer is consistent with both (i) the formation of a defective alumina structure and (ii) an oxide capping layer preventing further oxidation at low temperature.     

Textural properties of sulfated iron hydroxide promoted with aluminum

Abstract  Aluminum-promoted sulfated iron hydroxide samples were prepared by a coprecipitation method with different loading levels of Al^III followed by sulfation and calcination at 870 K. These samples were characterized by means of thermal gravimetric analysis, X-ray powder diffraction, nitrogen adsorption at 77 K, diffuse reflectance spectroscopy, and FT-IR spectroscopy using KBr pellets. TGA profiles showed sulfated species with different thermal stabilities in the samples, and incorporation of Al^III causes an increase in the thermal stability of the surface sulfate species. The presence of sulfate ions and Al^III promotion did not modify the crystal phase of α-Fe₂O₃, but it did increase the crystallite size. A textural study showed that the incorporation of Al^III into the sulfated samples led to diminished surface area and pore volume. The pore size distribution exhibited a wide spectrum of mesoporosity in all samples. Graphical Abstract        

Generation of singlet oxygen via the composites of water-soluble thiol-capped CdTe quantum dots-sulfonated aluminum phthalocyanines

Singlet oxygen (1O2), one of the reactive oxygen species, plays an important role in many biomedical applications. The various compounds including the phthalocyanines, quantum dots (QDs) and QD complex, which may have potential to produce 1O2, thus received more and more attentions in recent years. By means of the direct detection of near-infrared 1270 nm, we found that the water-soluble thiol-capped CdTe QDs can photoproduce 1O2 in deuterated water with a low quantum yield (QY) of 1%. When sulfonated aluminum phthalocyanines (AlSPc's) were connected to these QDs, forming water-soluble QD-Pc composites, the 1O2 QY of the composites increased to 15% under the excitation of 532 nm, while little 1O2 production can be found for AlSPc alone at the same excitation because of the poor absorption of AlSPc in this region. The results of indirect measurements of 1O2, obtained from the photodegradation of the 1O2 chemical trap anthracene-9,10-diyl-bis-methylmalonate (ADMA), confirmed 1O2 yields in both QD and QD-Pc composite solutions. The QD-Pc composites have the advantage of extending the excitation region to 400-600 nm with remarkably enhanced extinction coefficients as compared with that of AlSPc. Therefore QD-Pc composites can fully utilize visible region light excitation to effectively produce 1O2, which may facilitate the applications of QD-Pc composites in broad areas.     

Heterostructured FeNi hydroxide for effective electrocatalytic oxygen evolution

Hydrogen production technology by water splitting has been heralded as an effective means to alleviate the envisioned energy crisis. However, the overall efficiency of water splitting is limited by the effectiveness of the anodic oxygen evolution reaction (OER) due to the high energy barrier of the 4e⁻ process. The key to addressing this challenge is the development of high-performing catalysts. Transition-metal hydroxides with high intrinsic activity and stability have been widely studied for this purpose. Herein, we report a gelatin-induced structure-directing strategy for the preparation of a butterfly-like FeNi/Ni heterostructure (FeNi/Ni HS) with excellent catalytic performance. The electronic interactions between Ni²⁺ and Fe³⁺ are evident both in the mixed-metal “torso” region and at the “torso/wing” interface with increasing Ni³⁺ as a result of electron transfer from Ni²⁺ to Fe³⁺ mediated by the oxo bridge. The amount of Ni³⁺ also increases in the “wings”, which is believed to be a consequence of charge balancing between Ni and O ions due to the presence of Ni vacancies upon formation of the heterostructure. The high-valence Ni³⁺ with enhanced Lewis acidity helps strengthen the binding with OH⁻ to afford oxygen-containing intermediates, thus accelerating the OER process. Direct evidence of FeNi/Ni HS facilitating the formation of the Ni–OOH intermediate was provided by in situ Raman studies; the intermediate was produced at lower oxidation potentials than when Ni₂(CO₃)(OH)₂ was used as the reference. The Co congener (FeCo/Co HS), prepared in a similar fashion, also showed excellent catalytic performance.

A butterfly-like FeNi/Ni HS featuring a “torso” of Ni-doped FeOOH and two “wings” of Ni₂(CO₃)(OH)₂ showed excellent activity in electrocatalytic oxygen evolution reaction attributable to the increase of higher-valance Ni³⁺ in the heterostructure.     

Transparent and flame retardant cellulose/aluminum hydroxide nanocomposite aerogels

Cellulose-based nanocomposite aerogels were prepared by incorporation of aluminum hydroxide (AH) nanoparticles into cellulose gels via in-situ sol-gel synthesis and following supercritical CO₂ drying. The structure and properties of cellulose/AH nanocomposite aerogels were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, ultraviolet-visible spectrometry, N₂ adsorption, thermogravimetric analysis, and micro-scale combustion calorimetry. The results indicated that the AH nanoparticles were homogeneously distributed within matrix, and the presence of AH nanoparticles did not affect the homogeneous nanoporous structure and morphology of regenerated cellulose aerogels prepared from 1-allyl-3-methylimidazolium chloride solution. The resultant nanocomposite aerogels exhibited good transparency and excellent mechanical properties. Moreover, the incorporation of AH was found to significantly decrease the flammability of cellulose aerogels. Therefore, this work provides a facile method to prepare transparent and flame retardant cellulose-based nanocomposite aerogels, which may have great potential in the application of building materials.     

Competitive adsorption of organic matter with phosphate on aluminum hydroxide

The effects of orthophosphate on the adsorption of natural organic matter (NOM) on aluminum hydroxide were investigated using three organic compounds as surrogates, including humic acid (HA), phthalic acid, and 2,3-dihydroxybenzoic acid (2,3-DHBA). The adsorption of phthalic acid and 2,3-DHBA was very limited compared to that of HA, whereas their adsorption was reduced much more significantly than that of HA by phosphate. The efficiency of phosphate in reducing HA adsorption increased with increasing phosphate concentration. Phosphate adsorption was slightly reduced by phthalic acid and 2,3-DHBA but moderately suppressed by HA. The adjacent carboxylic groups mainly contributed to the adsorption of humic acid at low pH, while the adjacent phenol groups were responsible for the adsorption of humic acid at high pH. HPLC-SEC and SUVA analysis revealed that HA molecules with high molecular weight were adsorbed preferentially but were easily displaced by the specifically adsorbed phosphate. TM-AFM images revealed that the aggregation of HA molecules and the protonation of carboxylic groups at low pH facilitated the adsorption under acidic conditions. The presence of phosphate increases the coagulant dosage for NOM removal as some sites on the coagulant precipitates become utilized by phosphate.     

Mononuclear aluminum hydroxide for the design of well-defined homogeneous catalysts

An unprecedented aluminum hydroxide LAlMe(OH) (5; L = HC[(CMe)(2,6-iPr2C6H3N)]2) has been prepared by the hydrolysis of LAlMeCl (4). For the preparation of 5, the reagents of KOH, water, and KH, as well as the two-phase ammonia/toluene system, were used. Further reactions of 5 with Cp2ZrMe2 (8) and Cp2ZrHCl in toluene lead to the intermolecular elimination of CH4 and H2 and the formation of mu-O-bridged dinuclear aluminum and zirconium complexes [LAlMe(mu-O)ZrMeCp2] (6) and [LAlMe(mu-O)ZrClCp2] (7), respectively, in high yields. The crystal structure reveals that 5 is a monomer with terminal OH and Me groups. The X-ray structure analysis shows that 6 and 7 contain a bent Al-(mu-O)-Zr core with terminal Al-Me and Zr-Me or Zr-Cl arrangements. The methylalumoxane (MAO)-activated compounds 6 and 7 exhibit high catalytic activity for the polymerization of ethylene. Under comparable polymerization conditions, the MAO/6 and MAO/7 catalyst systems show considerably higher activity and much lower MAO:catalyst ratios than that of MAO/8.