Stability and thermal behaviour of BH4-anions inside pores of sodium-potassium-tetrahydroborate aluminosilicate sodalite (Na1?x Kx)8[AlSiO4]6(BH4)2; x?~?0.5

Tetrahydroborate enclathrated sodalites are interesting compounds which offer new concepts for hydrogen storage as well as possibilities of special chemical reactions inside pores by the strong reduction force of tetrahydroborate. In the present paper, we show that these new materials can be further modified by hydrothermal cation exchange without decomposition of the predominant amounts of the hydrolysis sensitive BH₄ ⁻ anions inside the sodalite cages. We succeeded in preparing sodalite (Na_1−x K_x)₈[AlSiO₄]₆(BH₄)₂; (x ~ 0.5) by hydrothermal treatment of the pure sodium tetrahydroborate sodalite in KNO₃-solution at 473 K for 48 h. This product was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and temperature dependent FT-IR-spectroscopy. Investigations of thermal reaction behaviour of the enclathrated BH₄ ⁻ anions revealed a decrease in metaborate formation temperature close to 100 K compared with the pure sodium tetrahydroborate sodalite. This is discussed by structural changes according to potassium incorporation and the influence of degradation of crystallinity during cation exchange.     

Synthesis and Properties of Zeolites from Autoclaved Aerated Concrete (AAC) Waste

Syntheses routes for the conversion of autoclaved aerated concrete (AAC) waste into aluminosilicate zeolites like LTA and related phases were developed. The procedures always started with leaching steps of the pure AAC waste by combinations of strong alkaline (NaOH) and mild acid (citric acid) treatments, before the real crystallization process was performed separately under addition of sodium aluminate. All products were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM) combined with energy dispersive X‐ray analysis (EDX‐analysis) and Fourier‐transform infrared spectroscopy (FTIR). Zeolites LTA and related phases basic sodalite (SOD), hydrosodalite (SOD), cancrinite (CAN) and an intermediate phase between SOD and CAN were observed. Depending on the preparation route tailor made synthesis of pure phase zeolite LTA with crystal sizes up to 5 μm was worked out. In addition to syntheses procedures important properties of the zeolites were discussed with respect to the treatment procedure of AAC. It is shown, that the special synthesis pathway is not only responsible for the product composition and formation of a certain structure type but also exhibits a strong influence on the crystallinity, crystal size, and morphology. The water sorption capacity and the hydrothermal stability of the products were selected for those further investigations. Whereas adequate water sorption capacity up to 272 mg · g^–1 were measured for zeolites LTA obtained from two different reaction routes, limited hydrothermal stabilities were revealed for other products. Under the conditions of strong hydrothermal treatment at a temperature of 473 K for 72 h, a more or less extended phase transformation into ANA‐Type zeolites occurred. This process was least extensive for pure phase zeolite LTA obtained from the alkaline solution of AAC leaching.     

Amorphous alloy catalysis: Part 1. Dehydrogenation of 2-propanol on amorphous Cu61Zr39 alloy precursors

The dehydrogenation of 2-propanol to acetone on Cu₆₁Zr₃₉ alloy has been studied for the first time. The dehydrogenation reaction (flow reactor, 573 K) on as-received or pre- activated (hydrogen, 573 K, 3 h or 473 K, 16 h) alloy brings about a continuous activation of the catalyst. Other types of pretreatment (heat treatment at 800 K for 0.5 h, or treatment with water vapour at 500 K for 24 h) induce an initially high, but unstable, activity. The activity changes parallel changes in the copper surface area (determined via N₂O decomposition), except for samples prepared by HF dissolution, which results in a highly active and stable catalyst with a low surface area. XRD and DSC indicate crystallisation of the amorphous alloy samples under the given reaction conditions and as a result of pretreatment.     

Phase Transformations in Alkaline and Acid Leached Y Zeolites Dealuminated by Steaming

The steaming of zeolite Y (here at 873 K for 7 hours) leads to the formation of an amorphous aluminium aluminosilicate in addition to the dealuminated zeolite (DAY). An alkaline treatment of DAY causes the transformation of the non‐framework phase into an alkali aluminosilicate and the partial desilication of the DAY framework. The alkali aluminosilicate is decomposed by a moderate acid leaching under the formation of silica gel. The ²⁹Si MAS NMR and IR spectra of DAY and its chemically treated modifications are superimposed by the signals of the crystalline zeolite framework and the amorphous non‐framework materials whereas XRD measurements only characterize the current state of the framework.     

Crystallization kinetics of Na7.4(AlSiO4)6(CO3)0.7·4H2O, an intermediate phase between cancrinite and sodalite, grown under low temperature hydrothermal conditions

During low temperature hydrothermal alkaline conversion of kaolinite in the presence of sodium carbonate a disordered phase crystallizes showing structural features between the sodalite and cancrinite minerals. A detailed study of its formation field and the kinetics of crystallization is the first step for further investigations of this zeolite-like material. The crystallization kinetics was investigated in the early stage of the reaction for times up to 192 h at a temperature of 353 K. Besides X-ray powder diffraction²⁷Al MAS NMR has been found to be the preferred method to follow the reaction kinetics because a signal assigned to six-coordinated aluminium of the starting kaolinite can be clearly distinguished from a second resonance, being typical for aluminium in four-coordinate position of an aluminosilicate framework structure. Important conclusions can also be drawn from the experiments for the synthesis of ideal ordered cancrinites.     

Stability of hydrogen peroxide during perhydrolysis of carboxylic acids on acidic heterogeneous catalysts

This paper describes a study of the stability of hydrogen peroxide in the presence of different aluminosilicate materials, in connection with an investigation of carboxylic acid perhydrolysis. During the reaction, aluminosilicate materials such as H-β zeolites, mesoporous material H-MCM-41 and alumina initiate the decomposition of hydrogen peroxide. The reason of the spontaneous decomposition of H₂O₂ is related to the partial dealumination of these zeolites. However, in the case of experiments carried out with H-ZSM-5 zeolite catalysts, a slight catalytic effect on the perhydrolysis and no spontaneous decomposition of hydrogen peroxide were noticed. The use of cation exchange resins as catalysts is more kinetically beneficial than H-ZSM-5 zeolite catalysts.     

State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

The state of Ni supported on HZSM‐5 zeolite, silica, and sulfonated carbon was studied during aqueous‐phase catalysis of phenol hydrodeoxygenation using in situ extended X‐ray absorption fine structure spectroscopy. On sulfonated carbon and HZSM‐5 supports, NiO and Ni(OH)₂ were readily reduced to Ni⁰ under reaction conditions (≈35 bar H₂ in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). In contrast, Ni supported on SiO₂ was not stable in a fully reduced Ni⁰ state. Water enables the formation of Ni^II phyllosilicate, which is more stable, that is, difficult to reduce, than either α‐Ni(OH)₂ or NiO. Leaching of Ni from the supports was not observed over a broad range of reaction conditions. Ni⁰ particles on HZSM‐5 were stable even in presence of 15 wt. % acetic acid at 473 K and 35 bar H₂.     

Formation and Properties of Losod,a New Sodium Zeolite

Losod, a new type of crystalline hydrated sodium aluminosilicate, Na₁₂Al₁₂Si₁₂O₄₈ · q H₂O, has been prepared from reaction mixtures containing bulky quaternary alkylammonium ions, particularly azonia-spiro[4.4]nonane, besides sodium ions. Losod crystallizes from batches with a low sodium content (Na/Al ≤ 1 and Si/Al ≈? 1). The quaternary ammonium hydroxide primarily serves as a source of hydroxide ions and is not incorporated into the zeolite crystals. These bulky bases provide a useful means for controlling the alkalinity of the system independently of the concentration of the necessary cations built into the zeolite. The crystals of Losod are hexagonal (a = 12.91 and c = 10.54 Å) and the proposed framework structure shows a polytypic relationship to sodalite and cancrinite. Losod has reversible sorption and ion exchange properties typical of a small-pore zeolite and in essential agreement with the proposed structure.     

Synthesis of Oligomers with Unsaturated End-Groups Based on Dianic Epoxy Resin and Crotonic Acid

Abstract

The synthesis of oligomers with unsaturated double end-bonds based on the reaction of dianic epoxy resin and crotonic acid was investigated. Experimental conditions included temperatures from 353–383 K and reaction times from 3.5–4.0h in the presence of quaternary ammonium salts dissolved in various organic solvents. The main kinetic parameters of the reaction were determined.     

Investigation of the Reaction of Roasted Serpentine Ore with Some Ammonium Salts

The reaction between roasted serpentine ore and ammonium sulfate was studied at the range of temperature 250–1000°C using different molar ratios to determine the maximum extraction of magnesia and also to characterize the different reaction products. The maximum extraction of MgO from the roasted ore reached 92.4% at 400°C. It was found from XRD that ammonium magnesium sulfate [(NH₄)₂Mg₂(SO₄)₃] was produced as the main product at 400°C, which decomposes to magnesium sulfate at 500–600°C. The last compound decomposes to magnesium oxide at 900–1000°C. Thermal analysis of the reaction mixture confirmed the results obtained by XRD. Extraction of magnesia by ammonium chloride at 300–400°C showed low percentage of extraction (7.8%). Comparison was made between using ammonium chloride instead of sulfate taking into consideration the thermal decomposition products of both ammonium salts. Extraction of magnesia from the roasted ore by aqueous ammonium sulfate or ammonium chloride showed good results.     

Mechanism of reaction between cobalt(II) oxide and ammonium chloride

A reaction between cobalt oxide and ammonium chloride was studied. A possible mechanism of this reaction was determined by TGA and DSC. The reaction products were identified by IR spectroscopy, chemical and XRD analyses. A multistage mechanism was established for reaction between cobalt oxide and ammonium chloride. Cobalt chloride was determined to be the final product; the reaction occurs via the formation and decomposition of (NH₄)₃CoCl₅, (NH₄)₂CoCl₄, and NH₄CoCl₃.     

Hydrothermal synthesis,characterization, and thermal properties of alumino silicate azide sodalite,Na<Subscript>8</Subscript>[AlSiO<Subscript>4</Subscript>]<Subscript>6</Subscript>(N<Subscript>3</Subscript>)<Subscript>2</Subscript>

First time we report the synthesis, structural characterization and thermal behavior of an unusual N₃ ^? containing alumino-silicate sodalite mineral. Azide sodalite, Na₈[AlSiO₄]₆(N₃)₂ has been synthesized under hydrothermal conditions at 433 K in steel lined Teflon autoclave. The structural and microstructural properties of azide sodalite mineral was characterized by various methods including FT-IR, XRD, SEM, TGA, and MAS NMR. Crystal structure have been refined by Rietveld method in \(P\bar 43n\) space group, indicating that the N₃ ^? sodalite has cubic in lattice. High temperature study was carried out to see the effect of thermal expansion on cell dimension (a ^o) of azide sodalite. Thermal behavior of sodalite was also assessed by thermogravimetric method.     

The state of palladium in the system potassium palladium-11-tungstosilicate on aluminosilicate as studied by DRIFT spectroscopy

The influence of redox treatments on the state of palladium in the heteropoly acid K₆[SiW₁₁PdO₃₉] supported on amorphous aluminosilicate was studied by diffuse-reflectance IR spectroscopy using CO as a probe molecule. A bulk sample of the K₆[SiW₁₁PdO₃₉]·11H₂O heteropoly compound (HPC) was studied for comparison. The deposition of the bulk sample on aluminosilicate leads to the partial decomposition of Keggin structure and to the removal of palladium cations from the HPC framework. The metal introduced into the K₆[SiW₁₁PdO₃₉]/SiO₂-Al₂O₃ system within HPC displays higher thermal stability in redox cycles compared to that of the bulk HPC. A highly dispersed state of palladium persists up to 573 K.     

Immobilization of a Pd(II) complex on hydrophilic graphite oxide and its catalytic investigation in the Heck coupling reaction

Tetraamminepalladium(II) chloride monohydrate was heterogenized on hydrophilic graphite oxide (GO), synthesized by Brodie's method. Two samples, with Pd contents of 2% and 5%, referred to as Pd2 and Pd5, respectively, were prepared by a simple and scalable impregnation method and tested as catalysts in the Heck coupling reaction of styrene and bromobenzene. The reactions were carried out at 423 K for 3 hr by applying Na₂CO₃ as a base and N-methylpirrolidone or dimethylformamide (DMF) as a solvent. The Pd complexes heterogenized on graphene oxide platelets proved to be highly active and selective catalysts, and Pd2 was more efficient than Pd5. The effect of quaternary ammonium salts (tetrabutylammonium bromide and tetrabutylammonium chloride, TBAC) as modifiers and that of an ionic liquid (1-butyl-3-methylimidazolium bromide, bmim) was studied and the highest conversions were obtained when TBAC was employed. The selectivity for the formation of the main product, E-stilbene, was in the range 91–96%. Catalyst recycling was investigated and the extent of leaching was found to depend on the solvent. DMF proved to be a highly feasible reaction medium because both catalysts could be recycled five times in this solvent without any significant loss of activity. A hot filtration test was performed and gave evidence that leaching of the active Pd species did not take place under the above reaction conditions. These results substantiate the fact that simple cationic Pd species can be efficiently immobilized on pristine GO surfaces without the requirement of the functionalization of GO with nitrogen-containing mono or multidentate ligands as binding sites.     

Aluminium(III) fluoride originating from decomposition of hydrazinium fluoroaluminate(III) under oxidative conditions: Syntheses, X-ray photoelectron spectroscopy and some catalytic reactions

Decomposition of hydrazinium pentafluoroaluminate under oxidative (F₂) conditions leads to aluminium(III) fluoride whose properties are highly dependent on the conditions used for synthesis. In the presence of anhydrous HF, which probably acts as a heat exchange agent, samples have high BET areas, whereas BET areas of samples prepared under gas-solid conditions are small. XPS data are consistent with the presence of Lewis acid centres but, more importantly, emphasise the importance of surface hydroxyl groups, particularly in high surface area compounds. Catalytic behaviour towards isomerisation of 1,1,2-trichlorotrifluoroethane and subsequent dismutations at moderate temperatures and towards room temperature dehydrochlorination of tert-butyl chloride has been demonstrated for some high BET samples; both reactions indicate that surface Lewis sites exist. Catalytic ability is inhibited by surface hydroxyl groups but is improved by prior fluorination of the surface with CCl₂F₂. Catalysis is inhibited also by the presence of ammonium fluoroaluminate, a by-product of the decomposition process. The [NH₄]⁺ salt level can be reduced by washing with anhydrous HF.     

CO2-Enhanced Production and Synthesis of 2,5- Furandicarboxylic Acid under CO2 Flow through Henkel Reaction

The present study investigated the preparation of 2,5-furandicarboxylic acid (FDCA) via the Henkel reaction between furoic acid alkali metal salts and zinc chloride under a continuous CO₂ flow at atmospheric pressure. The results obtained were compared with those of previous studies that used high-pressure conditions or toxic cadmium catalysts. The pathways and rate-determining steps of the reaction are revealed for the first time. Furthermore, the enhanced formation of FDCA through the promotion of carboxyl exchange and rearrangement during the reaction under a CO₂ flow was examined. The CO₂-rich environment afforded a high FDCA yield of 86.30 %, which is the highest yield obtained to date using the Henkel reaction. The findings of this study offer economically improved conditions for large-scale FDCA production.     

Anion exchange studies of zirconium(iv) in citrate solution separation from mixtures

The anion exchange behaviour of zirconium(IV) in a citrate system is described. Nitric acid, hydrochloric acid, perchloric acid and ammonium chloride were tested as eluants on Dowex ₂₁K column. Zirconium is separated from fission product elements e.g., barium, strontium, cadmium, caesium, molybdate and also from lead.     

Dealumination and characterization of chabazite for catalytic application

Dealumination of the small-pore zeolite chabazite (CHA) was performed with ammonium hexafluorosilicate under solid and liquid-state conditions to increase the Si-to-Al ratio from 2.0 to 6.0. In the solid state, the mesopore fraction increased with repeating hydrothermal synthesis at 423 K, which was confirmed by nitrogen adsorption?Cdesorption. In the liquid state, the formation of mesopores decreased substantially and the resulting CHA had an Si-to-Al ratio of ca. 5. The result of desorption of NO?CNO₂ from the Cu ion-exchanged dealuminated CHA in the solid state indicated that the presence of mesopores reduced NO?CNO₂ adsorption and desorption of NO₂ occurred at 383 and 683 K whereas for the high-silica analog SSZ-13 desorption of NO₂ occurred mostly at 473 and at 673 K.     

Nitrous Oxide Adsorption and Decomposition on Zeolites and Zeolite-like Materials

Decomposition of N₂O on modified zeolites, crystalline titanosilicalites, and related amorphous systems is studied by the catalytic and spectroscopic methods. Zinc-containing HZSM-5 zeolites and titanosilicalites with moderate Ti/Si ratios are shown to exhibit a better catalytic performance in N₂O decomposition as compared with conventionally used Cu/HZSM-5 zeolites and amorphous Cu-containing catalysts. Dehydroxylation of the HZSM-5 zeolite by calcination at 1120 K results in an enhancement of the N₂O conversion. The mechanism of the reaction and the role of coordinatively unsaturated cations and Lewis acid sites in N₂O decomposition are discussed on the basis of the spectroscopic data.     

粗硼砂的氯化铵溶液浸提动力学

研究了反应温度、溶液浓度、固液比、固体粒径大小和搅拌速度对氯化铵溶液浸提粗硼砂(十水四硼酸钠,Na₂B₄O₇·10H₂O)动力学的影响。结果表明反应速率随反应温度、溶液浓度的增加和固体粒径、固液比的减小而增加,但搅拌速度对溶解速率无显著影响。根据均相和多相动反应力学模型研究了粗硼砂的溶解过程。结果表明溶解速率遵从假一级均相反应模型。粗硼砂在氯化铵溶液中溶解的活化能为82.73 kJ·mol^-1。