Photocatalytic degradation of aqueous organocholorine pesticide on the layered double hydroxide pillared by Paratungstate A ion, Mg12Al6(OH)36(W7O24)·4H2O

Layered double hydroxide pillared by Paratungstate A ion, Mg₁₂Al₆(OH)₃₆(W₇O₂₄)·4H₂O, was prepared via anion exchange reaction of the synthetic precursor, Mg₄Al₂(OH)₁₂TA·xH₂O (TA²⁻=terephthalate), and [W₇O₂₄]⁶⁻ ion. Some physico-chemical properties were measured and the preparation conditions were studied. Trace aqueous organocholorine pesticide, hexachlorocyclohexane (HCH), was totally degraded and mineralized into CO₂ and HCl by irradiating a Mg₁₂Al₆(OH)₃₆(W₇O₂₄)·4H₂O suspension in the near UV area. Disappearance of trace HCH follows Langmuir–Hinshelwood first-order kinetics. The model and mechanism for the photocatalytic degradation of HCH on the Mg₁₂Al₆(OH)₃₆(W₇O₂₄)·4H₂O were proposed, indicating that the interlayer space is the reaction field, and that photogeneration of OH√ radicals are responsible for the degradation pathway.     

Preparation of catalyst precursors for selective oxidation of n-butane by exfoliation–reduction of VOPO4·2H2O in primary alcohol

A new method through intercalation and exfoliation of VOPO₄·2H₂O crystallites in primary alcohol (1-propanol or 1-butanol), followed by reduction with the alcohol, have been investigated for the preparation of catalyst precursor. Lamellar compounds, consisting of V⁴⁺, P⁵⁺ and alkyl group with thin film-like morphology, were formed and was characterized by means of XRD, IR, TG/DTA, and elemental analysis. The chemical formula of the precursor obtained by exfoliation–reduction in 1-butanol was shown to be VO{(n-C₄H₉)_0.16H_0.84}PO₄·0.8H₂O. On the other hand, a direct reduction of VOPO₄·2H₂O in the alcohol gave a mixed phase shown by (VOHPO₄·0.5H₂O)_0.3(VO{(n-C₄H₉)_0.3H_0.7}PO₄·3H₂O)_0.7 comprising plate-like microcrystallites. These precursors transformed to (VO)₂P₂O₇ phase during an activation process at 703 K in the presence of a mixture of n-butane 1.5% and O₂ 17% in He balance. The obtained (VO)₂P₂O₇ through the exfoliation–reduction was well crystallized and consisted of thin flaky crystallites. It was found that (VO)₂P₂O₇ thus prepared through the exfoliation–reduction was highly active and selective for oxidation of n-butane.     

Structural phase transition and high temperature phase structure of Friedels salt, 3CaO · Al2O3 · CaCl2 · 10H2O

Friedels salt, the chlorinated compound 3CaO · Al₂O₃ · CaCl₂ · 10H₂O (AFm phase), presents a structural phase transition at about 30°C from a monoclinic to a rhombohedral phase. It has been studied by X-ray powder diffraction and optical microscopy in transmitted light with crossed polarisers on single crystals prepared by hydrothermal synthesis. The high temperature phase was determined at 37°C from X-ray single crystal diffraction data. The compound crystallises in the space group R c with lattice parameters of a = 5.7358(6)Å and c = 46.849(9)Å (Z = 3 and D_x = 2.111 g/cm³). The refinement of 498 independent reflections with I > 2σ(I) led to a residual factor of 7.1%. The Friedels salt can be described as a layered structure with positively charged main layers of composition [Ca₂Al(OH)₆]⁺ and negatively charged layers of composition [Cl⁻,2H₂O]. The chloride anions are surrounded by 10 hydrogen atoms, of which six belong to hydroxyl groups and four to water molecules. The structural phase transition may be related to the size of the chloride anions, which are not adapted to the octahedral cavity formed by bonded water molecules.     

Study of interactions at water-soluble polymer/Ca(OH)2 or gibbsite interfaces by XPS

In an attempt to better understand interactions occuring at hydrated cement/organic polymer interfaces, the reaction mechanism and products formed at the interfaces between poly(acrylic acid), p(AA) or poly(acrylamide), p(AM), and Ca(OH)₂ or gibbsite, Al₂O₃·3H₂O, were explored using x-ray photoelectron spectroscopy (XPS). It was estimated that at p(AA)/Ca(OH)₂ interfaces, a Ca-complexed carboxylate interfacial reaction product was formed by an ionic reaction between the COOH in p(AA) and Ca²⁺ ions from Ca(OH)₂. A similar reaction product was formed at p(AM)/Ca(OH)₂ interfaces as a result of an inter-facial transformation of amide in p(AM) into carboxylic acid, caused by the alkali-catalyzed hydrolysis of the amide. The proton-accepting hydroxyl groups existing at the outermost surface sites of Al₂O₂·3H₂O react favorably with proton-donating COOH groups in p(AA). This acidbase interaction at the p(AA)/Al₂O₃·3H₂O joint formed hydrogen bonds. Whereas, when the p(AM) was applied on Al₂O₃·3H₂O surfaces, interfacial electrostatic bonds were formed through charge-transferring reaction mechanisms in which the charge density was transferred from the Al in Al₂O₃·3H₂O to the C=0 oxygen in p(AM).     

Crystal chemistry of calcium silicates: Germinate and chromate analogues of KF·2[Ca6(SO4)(SiO4)2O]

The germanate KF·2[Ca₆(SO₄) (GeO₄)₂O] was synthesized by solid state reactions; comparison of the observed and calculated powder pattern, assuming an isostructural relationship with the silicate phase, gives good agreement. Sulphate groups may also be substituted by CrO₄²⁻ to give the isostructural KF·2[Ca₆(CrO₄)(SiO₄)₂O].     

Porous structures constructed from [SiMo12O40] and [SiW12O40] Keggin units

Three compounds, K₂(H₂O)₄H₂SiMo₁₂O₄₀ · 7H₂O (1), K₂Na₂(H₂O)₄SiW₁₂O₄₀ · 4H₂O (2), and Na₄(H₂O)₈SiMo₁₂O₄₀ · 6H₂O (3) have been synthesized and structurally characterized by single-crystal X-ray analysis, IR, and thermogravimetry. Compounds 1 and 2 both show the high symmetry trigonal space group P3₂21 and a novel 3D network structure. The Keggin anions [SiM₁₂O₄₀]⁴⁻(M = Mo, W) are linked by potassium or sodium cations to generate hexagon-shaped channels along the c-axis, in which water molecules are accommodated. Compound 3 is tetragonal, space group P4/mnc constructed from [SiMo₁₂O₄₀]⁴⁻ anions and Na ions.     

AgBr/Zn3(OH)2V2O7·2H2O可见光催化降解亚甲基蓝溶液

采用水热和沉淀两步合成法制备AgBr/Zn₃(OH)₂V₂O₇·2H₂O催化剂,研究其在可见光下降解亚甲基蓝溶液的性能,并考察催化剂用量、亚甲基蓝溶液初始浓度、pH值以及盐浓度对光催化性能的影响,评价AgBr/Zn₃(OH)₂V₂O₇·2H₂O催化剂的重复使用性能。结果表明,在前驱液pH为10、120 ℃水热10 h、Ag与Br物质的量比为0.20条件下制备的复合催化剂在可见光下反应120 min后,1.0 g·L^-1的催化剂对10 mg·L^-1的亚甲基蓝溶液脱色率达到85.2%。NaCl对亚甲基蓝的降解起抑制作用,Na₂SO₄对亚甲基蓝的降解起促进作用。催化剂重复使用4次后,光照120 min后的亚甲基蓝溶液脱色率可达66.4%。催化剂对不同初始浓度亚甲基蓝溶液的光催化降解符合一级动力学模型。     

The removal of NOx from a lean exhaust gas using storage and reduction on H3PW12O40·6H2O

NO_x sorption and reduction capacities of 12-tungstophosphoric acid hexahydrate (H₃PW₁₂O₄₀·6H₂O, HPW) were measured under representative alternating conditions of lean and rich exhaust-type gas mixture. Under lean conditions, the sorption of NO_x is large and is equivalent to 37 mg of NO_x/g_HPW. Although a part of these NO_x remains unreduced, HPW is able to reduce some of the NO_x to produce N₂ by a reaction between the sorbed NO₂ and hydrocarbon (HC), but this process is slow. The addition of 1% Pt affects strongly the chemical behaviour occurring during the course of a rich operation. The NO desorption observed at the beginning of the rich phase is strongly accelerated. The direct correlation between NO₂ consumption and CO₂ production shows that the principal pathway is the reaction CO+NO₂→CO₂+NO. In a mixture of reducing gas (CO, HC, H₂), the competition is strongly in favour of CO though in its absence the reaction observed was the hydrogenation of propene to propane.     

Influence of CO2 and H2O on NOx storage and reduction on a Pt–Ba/γ-Al2O3 catalyst

In this paper, the effect of CO₂ and H₂O on NO_x storage and reduction over a Pt–Ba/γ-Al₂O₃ (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO₂ and H₂O, NO_x is stored on BaCO₃ sites only. Moreover, H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N₂ as well as complete regeneration of stored NO. In the presence of CO₂, NO is oxidized into NO₂ and more NO_x is stored as in the presence of H₂O, resulting in 30% barium utilization. Bulk barium sites are inactive in NO_x trapping in the presence of CO₂·NH₃ formation is seen in the rich phase and the selectivity towards N₂ is 83%. Ba(NO₃)₂ is always completely regenerated during the subsequent rich phase. In the absence of CO₂ and H₂O, both surface and bulk barium sites are active in NO_x storage. As lean/rich cycling proceeds, the selectivity towards N₂ in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NO_x storage.     

An anionic framework aluminophosphate |(CH2)6N4H3·H2O|[Al11P12O48] and computer simulation of the template positions

A new aluminophosphate compound |(CH₂)₆N₄H₃·H₂O|[Al₁₁P₁₂O₄₈] (denoted AlPO-CJB2) with a three-dimensional open framework and an Al/P ratio of 11/12 has been synthesized solvothermally by using hexamethylenetetramine as a template. It was characterized by X-ray powder diffraction, inductively coupled plasma, elemental (CHN), and thermogravimetric analyses, and the structure was determined by single-crystal X-ray diffraction analysis. AlPO-CJB2 crystallizes in the trigonal space group R-3c with a=14.088(2) Å, c=42.199(9) Å, and Z=6. Its structure features two new kinds of cages, i.e., cage 1, 4¹²4³6⁶8⁶ and cage 2, 4¹²6¹². The two cages alternate along the [0 0 1] direction forming an infinite column by sharing a common snowflake-like chiral motif, which is constructed from an AlO₆-centered six four-membered rings. The title compound is constructed from strictly alternating Al polyhedra (AlO₄ and AlO₆) and P tetrahedra (PO₄) via bridging oxygen atoms, and presents a new type of stoichiometry with an Al/P ratio of 11/12 in the aluminophosphate family. Computer simulation was used to determine the possible positions of the organic template within the cages.     

Synthesis of NiO–ZrO2 powders for solid oxide fuel cells

With NH₃·H₂O, NH₃·H₂O-NH₄HCO₃ buffer solution and NaOH solution as coprecipitation agents, NiO–ZrO₂, anode powder of solid oxide fuel cell, was synthesized by coprecipitation methods. Composition accuracy was analyzed by comparing the original composition with the mass of the eventually obtained powder. It was shown that cubic NiO and cubic YSZ with a cascade powder distribution were obtained after the powder was calcined for 1h at different temperatures. Composition analysis of the powder synthesized with NH₃·H₂O as coprecipitation agent showed that NiO–YSZ powder greatly deviated from the original composition due to the loss of Ni²⁺ in the form of [Ni(NH₃)₄]²⁺. When NH₃·H₂O–NH₄HCO₃ buffer solution was used, productive output of nickel was increased. The loss of nickel can be totally avoided and better control of the powder composition could be realized when NaOH was used as coprecipitation agent.     

Fabrication of Fe-, Ni- and FeNi-coated Al2O3 core-shell microspheres by heterogeneous precipitation

The precursors with NiCO₃·2Ni(OH)₂·2H₂O-, Fe₂O₃·nH₂O-, or both of NiCO₃·2Ni(OH)₂·2H₂O- and Fe₂O₃·nH₂O-coated alumina microspheres were prepared, respectively, by the aqueous heterogeneous precipitation using metal salts, ammonium hydro-carbonate and -Al₂O₃ micropowders as the starting materials. Subsequently, magnetic metallic Ni-, -Fe- and γ-FeNi-coated alumina core-shell structural microspheres were successfully obtained by thermal reduction of the as-prepared precursors at 700 °C for 2 h, respectively. Optimized precipitation processing parameters of the concentration of alumina micropowders (15 g/L), the rate of adding reactants (5 mL/min) and pH value were determined by a trial and error method. Powders of the precursors and the resultant metal (Ni, -Fe, γ-FeNi alloy)-coated alumina micropowders were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The experimental results show that it is possible to adjust metal coating thicknesses and fabricate multilayer structured metal/ceramics core-shell microspherical powder materials and these materials may be applied for high performance of functional materials and devices.     

Synthesis and crystal structure of carbonate cancrinite Na8[AlSiO4]6CO3(H2O)3.4, grown under low-temperature hydrothermal conditions

The synthesis of cancrinite in the system Na₂O–SiO₂–Al₂O₃–Na₂CO₃–H₂O was studied under low-temperature hydrothermal conditions in the 353 K<T<473 K interval. The aim was to reveal the suitable range for the crystallization of pure-phase carbonate cancrinite with the ideal composition Na₈[AlSiO₄]₆CO₃(H₂O)₂ without cocrystallization of sodalite or intermediate disordered phases between cancrinite and sodalite. It was found that cancrinite formation reacts very sensitive on the temperature within the autoclaves whereas the concentration of reactants and the alkalinity of the hydrothermal solution have a much lower influence on the phase formation. Thus the temperature of crystallization of carbonate cancrinite without any by-products should not remain below 473 K. At the lower reaction temperature of 353 K the formation of a disordered intermediate phase between the cancrinite and the sodalite structure has been obtained in every case, independent of the template concentrations and the base. Some problems to detect this in a typical powder product mixture are discussed. Besides the ²⁹Si and ²⁷Al MAS NMR characterization of the products, the crystal structure refinement of pure carbonate cancrinite of ideal composition Na₈[AlSiO₄]₆CO₃(H₂O)_3.4, has been carried out from X-ray powder data using the Rietveld method: P6₃, a=1271.3(1) pm, c=518.6(1) pm, R_WP=0.073, R_F=0.016 for 347 structure factors and 45 variable positional parameters.     

Formation of Y3Al5O12–Al2O3 eutectic microstructure with off-eutectic composition

Homogeneous-eutectic microstructure of Y₃Al₅O₁₂–Al₂O₃ system without coarse primary crystals was formed at an off-eutectic composition. This method utilizes a low migration rate in an amorphous phase. A mixture of Y₂O₃ and Al₂O₃ having the off-eutectic composition was melted and quenched rapidly to form an amorphous phase. A heat-treatment of the amorphous phase at 1000 °C and 1300 °C for 30 min formed Y₃Al₅O₁₂ and Al₂O₃ phases. SEM observation of this material, which was formed from the amorphous phase at 1300 °C for 30 min, showed homogeneous eutectic-like microstructure. The formation of the primary crystals (coarse Al₂O₃), which are always observed in the off-eutectic compositions by ordinary method, was completely suppressed.     

Microwave-assisted rapid fabrication of Co3O4 nanorods and application to the degradation of phenol

A novel microwave-assisted hydrothermal route for preparation of Co₃O₄ nanorods had been developed. The process contained two steps: first, nanorods of cobalt hydroxide carbonate were obtained from a mixed solution of 50 ml of 0.6 M Co(NO₃)₂·6H₂O and 2.4 g of urea under 500 W microwave irradiated for 3 min. Then, the cobalt hydroxide carbonate nanorods were calcined at 400 °C to fabricate pure cobaltic oxide (Co₃O₄) nanorods. Both nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG), infrared (IR) and temperature-programmed reduction (TPR). The catalytic activity towards the degradation of phenol over Co₃O₄ nanorods was further studied under continuous bubbling of air through the liquid phase. The results showed that phenol was degraded into harmless products (CO₂ and malonic acid). The mechanism of phenol degradation was also discussed.     

Crystal structure of zeolite X nickel(II) exchanged at pH 4.3 and partially dehydrated, Ni2(NiOH)35(Ni4AlO4)2(H3O)46Si101Al91O384

Complete Ni²⁺ exchange of a single crystal of zeolite X of composition Na₉₂Si₁₀₀Al₉₂O₃₈₄ per unit cell was attempted at 73°C with flowing aqueous 0.05 M NiCl₂ (pH=4.3 at 23°C). After partial dehydration at 23°C and ≈10⁻³ Torr for two days, its structure, now of composition Ni₂(NiOH)₃₅(Ni₄AlO₄)₂(H₃O)₄₆Si₁₀₁Al₉₁O₃₈₄ per unit cell, was determined by X-ray diffraction techniques at 23°C (space group Fd , a₀=24.788(5) Å). It was refined using all intensities; R₁=0.080 for the 236 reflections for which F_o>4σ(F_o), and wR₂=0.187 using all 1138 unique reflections measured. At four crystallographic sites, 45 Ni²⁺ ions were found per unit cell. Thirty of these are at two different site III′ positions. Twenty of those are close to the sides of 12-rings near O–Si–O sequences, where each coordinates octahedrally to two framework oxygens, to three water molecules which hydrogen bond to the zeolite framework, and to an OH⁻ ion. The remaining 10 are near O–Al–O sequences; only three members of a likely octahedral coordination sphere could be found. In addition, two Ni²⁺ ions are at site I, eight are at site I′, and five are at site II. Forty six H₃O⁺ ions per unit cell, 24 at site II′ and 22 at site II, each hydrogen bond triply to six rings of the zeolite framework. Each of the 22 H₃O⁺ ions also hydrogen bonds to a H₂O molecule that coordinates to a site III′ Ni²⁺ ion. Six of the eight sodalite cages each contain four H₃O⁺ ions at site II′; the remaining two each contains a tetrahedral orthoaluminate anion at its center. Each tetrahedral face of each orthoaluminate ion is centered by a site I′ Ni²⁺ ion to give two Ni₄AlO₄ clusters. The five site II Ni²⁺ ions each coordinate to a OH⁻ ion. With 46 H₃O⁺ ions per unit cell, the great tendency of hydrated Ni²⁺ to hydrolyze within zeolite X is demonstrated. With a relatively weak single-crystal diffraction pattern, with dealumination of the zeolite framework, and with an apparent decrease in long-range Si/Al ordering likely due to the formation of antidomains, this crystal like others treated with hydrolyzing cations appears to have been damaged by Ni²⁺ exchange and partial dehydration.     

A porous mixed-valent iron MOF exhibiting the acs net: Synthesis, characterization and sorption behavior of Fe3O(F4BDC)3(H2O)3·(DMF)3.5

A new mixed-valent iron MOF, formulated as Fe₃O(F₄BDC)₃(H₂O)₃·(DMF)_3.5 (1), has been synthesized by using a perfluorinated linear dicarboxylate to link trigonal prismatic Fe₃(μ³-O)(O₂C–)₆ clusters. The structure refinement based on single crystal X-ray diffraction data collected from 1 reveals the material exhibits the acs topology with large channels along the crystallographic c-axis. Due to the presence of fluorine atoms the organic link, 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate (F₄BDC), has a 63° torsion angle between the carboxylate and aromatic planes, resulting in larger channels compared to those in the isoreticular material MOF-235. While few iron-based MOFs have demonstrated porosity, nitrogen and hydrogen sorption experiments carried out at 77 K proved the porosity of outgassed 1, which has a Langmuir surface are of 635 m²/g and a gravimetric capacity of 0.9 wt% of hydrogen at 1 bar.     

Time resolved powder neutron diffraction investigations of reactions of solids with water

The reactions of brownmillerite (C₄AF) with D₂O as well as those of a mixture of C₁₂A₇ and CaSO₄. 2D₂O with D₂O were investigated by on-line powder neutron diffraction. The crystalline reaction products in the hydrolysis of C₄AF are Ca₃Al₂(OD)₁₂ with Ca(OD)₂. For the sulphate containing system a precursor phase was observed before the formation of deuterated ettringite, Ca₆Al₂(OD)₁₂(SO₄)₃. 26D₂O.     

Hydration reactions in pastes C3S+C3A+CaSO4.2aq+H2O at 25°C.I

A characteristic retardation of the hydration of C₃A is found in pastes C₃S+C₃A+CaSO₄.2aq+H₂O of weight ratios 1:3:z:4 at certain values of z, when sulphate concentration becomes insufficient for monosulphate formation. This retardation is ascribed to precipitation of amorphous Al(OH)₃, when C₃A dissolves in a limited amount of the aqueous phase shielded from the rest by C₄AH₁₃ or C₄AH₁₉. Evidence for the conversion of C₃AH₆ into C₄AH_n in supersaturated Ca(OH)₂ solution is found.     

Activity enhancement of SnO2-doped Ga2O3–Al2O3 catalysts by coexisting H2O for the selective reduction of NO with propene

Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO₂-doped Ga₂O₃–Al₂O₃ prepared by sol–gel method. Although SnO₂-doped Ga₂O₃–Al₂O₃ gave lower NO conversion than Ga₂O₃–Al₂O₃ in the absence of H₂O, the activity was enhanced considerably by the presence of H₂O and much higher than that of Ga₂O₃–Al₂O₃. The presence of SnO₂ and Ga₂O₃–Al₂O₃ species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H₂O. The promotional effect of H₂O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H₂O. The other is the selective inhibition by H₂O of the reaction steps resulting in propene oxidation to CO_x without reducing NO.