Ni-Fe层状双金属氢氧化物的制备及性能研究

采用水热法制备了Ni-Fe层状双金属氢氧化物(Ni-Fe LDHs),研究了反应温度、反应时间、镍铁比和柠檬酸三钠用量对Ni-FeLDHs生长的影响,并研究其对甲基橙和亚甲基蓝的吸附性能.利用X-射线衍射、扫描电镜和交变梯度磁强计等测试方法研究了工艺条件对Ni-Fe-LDHs形貌、粒径、结晶性和磁性能的影响.实验结果表明:延长反应时间或升高反应温度都不利于得到结晶性好的Ni-Fe-LDHs.镍铁比对样品的结晶性和形貌有重要影响;镍铁比为2∶1,样品的结晶性和磁性能最好,增加镍铁比,得到片层组装形成得花状结构;镍铁比为3∶ 1时,Ni-Fe-LDHs对甲基橙和亚甲基蓝表现出良好的吸附性.     

Comparative Study of the Synthesis and Properties of Polyoxometalate Pillared Layered Double Hydroxides (POM-LDHs)

The pillaring of (NO₃)-ZnAl-LDHs with the polyoxometalates (POMs) [PV₂W₁₀O₄₀]^5–, [Mo₇O₂₄]^6–, [V₁₀O₂₈]^6– and [H₂W₁₂O₄₀]^6–, using large organic anions like terephthalate for pre-swelling the LDH structure forms a promising method for the controlled creation of small micropores. The use of the terephthalate precursor ((T)-ZnAl-LDH) avoided almost completely the formation of undesired side phases during pillaring, although anion exchange with the large POM complexes proceeded with more difficulty than in the case where (NO₃)-LDHs were used as a starting material. Direct pillaring via the (NO₃)-LDHs resulted in multiphased materials, and no correlation was found between the M(II)/M(III) ratios in the starting LDHs and the created porosity. For the [POM]-ZnAl-LDHs pillared via the terephthalate precursor, the layer charge density arising from the amount of isomorphically substituted Al³⁺ in the LDH layers forms the crucial parameter with regard to the created microporosity. Improving the surface area (SA) and micropore volume (PV) values was accomplished by lowering the charge density on the LDH layers (increasing the Zn²⁺/Al³⁺ ratio). In this way, a [PV₂W₁₀O₄₀]-ZnAl-LDH (Zn²⁺/Al³⁺ = 4.26) with a SA (BET) of 166 m²/g and a PV of 0.047 cm³/g was formed.For the different types of pillars, small micropores were formed due to the pillaring process. In the case of the smaller POM complexes [Mo₇O₂₄]⁶⁺ and [V₁₀O₂₈]⁶⁺, an increase in PV and SA was not accompanied by a detectable shift in average pore size, which was the case for the second group of complexes, [PV₂W₁₀O₄₀]^5– and [H₂W₁₂O₄₀]^6–. Due to their larger dimensions, mainly micropores between 0.71 and 1.06 nm were created at high Zn²⁺/Al³⁺ ratios, together with a substantial amount of pores smaller than 0.71 nm.     

焙烧水滑石去除氯离子性能研究

利用水滑石 (LDH)焙烧后在一定条件下可重新吸收水和阴离子从而部分恢复层状结构的结构记忆效应 ,研究了 3种工业级LDH不同温度下的焙烧产物即焙烧水滑石 (CLDH)去除Cl-的行为。射线粉末衍射仪表征了它们的结构特征。CLDH对氯离子的去除实验表明 ,n(Mg)∶n(Al)比值为 3和 4的LDH在 5 0 0～ 6 0 0℃下焙烧的CLDH对氯离子的去除率达到 95 %以上 ,1gCLDH去除氯离子的最大量约 5 9 6mg。     

Structure and Basicity of Mesoporous Materials from Mg/Al/In Layered Double Hydroxides Prepared by Separate Nucleation and Aging Steps Method

This paper presents the synthesis of mesoporous materials from hydrotalcite-like layered double hydroxides (LDHs) with the Mg^{2 +}/(Al^{3 +} + In^{3 +}) molar ratio of 3.0 on the brucite-like lattice and the interlayer carbonate anions, using a novel separate nucleation and aging steps method developed in our laboratory. The physicochemical properties of as-synthesized LDHs and resulting calcined products at 500C were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), simultaneous thermogravimetric and differential thermal analysis (TG-DTA), ²⁷Al nuclear magnetic resonance (NMR) and low-temperature nitrogen adsorption-desorption experiments. The results indicate calcination of LDHs with a well-crystallized single phase and nanoscale crystallites leads to the formation of the type MgO-like phase, and the pore size distributions of uncalcined and calcined LDHs are mostly in the range of mesopores. Furthermore, calcined materials have higher surface areas, pore volumes, pore diameters and surface basicities than corresponding precursors. When used as solid base catalysts for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde, the material with higher density of base sites on the surface also exhibited a higher catalytic activity. Particularly, calcined MgAlIn-LDH has highest density of base sites resulting in a highest catalytic activity, as points to an important role of indium as a modifier of the surface properties of solid base catalysts.     

Layered Double Hydroxides Derived from MIL-88A(Fe) as an Efficient Adsorbent for Enhanced Removal of Lead (II) from Water

The efficient removal of lead (II) from aqueous solution remains a big problem and the development of novel nanomaterials as adsorbents by various technologies to solve this problem is promising. This study contributed a novel nanostructure of MIL-88A-layered double hydroxides (LDHs) as the adsorbent for Pb²⁺, which was synthesized by a two-step solvothermal method with MIL-88A(Fe) as the precursor. The as-prepared material featured a chestnut-like core-shell structure, and exhibited excellent removal performance towards Pb²⁺ from water in comparison to MIL-88A(Fe) and LDHs (directly synthesized). The adsorption of Pb²⁺ by the MIL-88A-LDHs conformed to the pseudo-second-order kinetic model and the Langmuir and Freundlich isotherm models. The maximal adsorption capacity was 526.32, 625.00, and 909.09 mg g⁻¹ at 278, 298, and 318 K, respectively. The thermodynamic parameters suggested that the adsorption was an endothermic, entropy-increasing, and spontaneous reaction. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface complexation was mostly responsible for Pb²⁺ elimination. The MIL-88A-LDHs can be readily regenerated and showed good cyclic performance towards Pb²⁺. Thus, the as-prepared MIL-88A-LDHs may hold promise for the elimination of aqueous heavy metals.     

水滑石基电极材料的结构调控及电化学储能应用研究进展

水滑石是一种具有层板金属阳离子可搭配、层间客体可替代和高分散性的二维层板状纳米材料,在能量存储与转换应用领域获得广泛的关注和研究.但由于水滑石自身存在容易聚集和电导率差并且在电化学循环过程中易粉化的问题,因此需对水滑石基电极材料进行针对性结构设计,从而提高其电化学性能.系统介绍了水滑石材料的结构与性质特点和当下对其结构...     

纳米双羟基复合金属氧化物(LDHs)对聚氯乙烯(PVC)阻燃抑烟研究

总结了聚氯乙烯(PVC)塑料燃烧时产生烟雾的机理及其阻燃抑烟原理,并且在已开发出的常用无机阻燃抑烟剂的基础上研究了一种新型的无毒环保型无机纳米级阻燃抑烟剂———纳米双羟基复合金属氧化物(LDHs)。分析了其对PVC的阻燃抑烟机理,并且试验证实了它的阻燃抑烟效果。试验结果表明,该阻燃剂只需少量添加就有明显的阻燃抑烟效果,并且克服了以往由于大量添加无机阻燃剂而造成的力学性能下降的缺点,是一种很有发展前景的新型阻燃抑烟剂。     

Evaluation of the microporosity of pillared [Fe(CN)6]–MgAl–LDHs

Layered double hydroxides (LDHs) containing Mg²⁺ and Al³⁺ in the basic layers and NO⁻₃ as an interlayer anion were synthesized by the method of coprecipitation (pH 10). By changing the Mg²⁺/Al³⁺ ratio (1.5–4.5), the charge density on the (NO₃)–MgAl–LDH sheets was varied. After pillaring with Fe(CN)³⁻₆, which was based on an anion exchange process, the interlayer space became accessible. This was reflected in the large created surface areas and micropore volumes. The applied models for the calculation of the micropore size distributions (Maes–Zhu–Vansant and Horvath–Kawazoe) gave matching results, revealing narrow distributions for all the samples, with the majority of the pores smaller than 0.71 nm. A correlation was found between the Mg²⁺/Al³⁺ ratio and the resulting microporosity after pillaring. The optimal ratio was situated around 3.3, resulting in a pillared [Fe(CN)₆]–MgAl–LDH with a Langmuir surface area of 499 m²/g and a micropore volume between 0.158 ml/g (μPV_min) and 0.177 ml/g (μPV_max). As an alternative, direct coprecipitation of the pillared LDHs was evaluated. This one-step mechanism proved to be a method producing similar results. Taking all this into consideration, one can conclude that hexacyanoferrate(III) complexes form ideal anionic pillars for the creation of microporous layered double hydroxides.     

Effect of viscosity and applied potential on oscillations at a Pt-Pt dual-electrode in a ferricyanide system

This paper outlines the effect of viscosity and applied potential on oscillations occurring at two platinum electrodes placed proximal to each other. Potential oscillations taking place on the primary electrode (WE1) under galvanostatic control in the ferricyanide system are affected by the solution viscosity as it modifies the convective feedback mechanism necessary for oscillations. Measured transition times correlate with those calculated using Sand equation thus allowing the estimation of current density windows for periodic oscillation for different solution viscosities for pre-determined transition times. Current oscillations on the secondary working electrode (WE2) - under potentiostatic control and induced by the potential oscillations on WE1 - can be tuned through the applied potential. At higher potentials the reaction is oxidation of [Fe(CN)₆]⁴⁻ and the coupling is primarily through the transfer of [Fe(CN)₆]⁴⁻ from WE1 to WE2 via H₂ evolution whilst at more cathodic potentials the reduction of [Fe(CN)₆]³⁻ takes place at both WE1 and WE2 and the convective feedback from WE1 refreshes the surface of both electrodes simultaneously.     

Complexes in the Photocatalytic Reaction of CO(2) and H(2)O: Theoretical Studies

Complexes (H(2)O/CO(2), e-(H(2)O/CO(2)) and h(+)-(H(2)O/CO(2))) in the reaction system of CO(2) photoreduction with H(2)O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H(2)O/CO(2) captured photo-induced electron and hole produced e-(H(2)O/CO(2)) and h(+)-(H(2)O/CO(2)), respectively. The results revealed that CO(2) and H(2)O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO(2) and H(2)O, which might be attributed to the synergistic effect and which could not be captured experimentally.     

Oxidation of Acid Red-151 Aqueous Solutions by the Peroxone Process and its Kinetic Evaluation

Oxidation of an azo dye solution, namely, Acid Red 151 by the peroxone process was investigated experimentally at different pH values, initial dye and ozone concentrations, and the initial molar ratios (r) of hydrogen peroxide to ozone. At pH 2.5 in this process, the obtained color and chemical oxygen demand (COD) removals were higher than those at pH of 7 and 10. The best value of r yielding the highest treatment efficiency at each pH was determined as 0.5. The application of the “initial rates method” to the kinetic data for peroxone oxidation of aqueous Acid Red 151 solutions showed that the individual orders with respect to O₃ and dye were one, the total order of the reaction being two. The rate constants based on the initial rates of dye degradation were determined as 98.9, 77.3 and 65.7 mM^?1min^?1 at the pH values of 2.5, 7 and 10, respectively.     

Early C3A hydration in the presence of different kinds of calcium sulfate

Hydration reactions of C₃A with various amounts of calcium sulfate hemihydrate, gypsum or a mixture of the two, were investigated by isothermal microcalorimetry, and a monitoring of the ionic concentrations of diluted suspensions. This study shows that sulfate type used modifies the early C₃A–CaSO₄ hydration products and the rate of this hydration. The fast initial AFm formation observed before ettringite precipitation in the C₃A–gypsum system is avoided as soon as hemihydrate is present in the suspension. This was attributed to higher super saturation degrees and then higher nucleation frequency with regard to the ettringite obtained in the presence of hemihydrate. Moreover, replacement of gypsum by hemihydrate also leads to an increase of the ettringite formation rate during at least the five first hours under experimental conditions.     

Effects of Nickel-Loading Method on the Water-Splitting Activity of a Layered NiO x /Sr4Ti3O10 Photocatalyst

Sr₄Ti₃O₁₀, which is known to have a Ruddlesden-Popper phase as a layered perovskite-type oxide, showed activity leading to the decomposition of pure water into H₂ and O₂ without any co-catalyst, when irradiated with light under 395 nm. When NiO _x was loaded onto Sr₄Ti₃O₁₀ both by the impregnation (I) method and the vapor deposition (VD) method, this photocatalytic activity drastically increased. Nickel acetylacetonate, when used with the VD method, was found to give rise to more efficient photocatalytic activity than that obtained using nickel nitrate with the impregnation method.     

Adsorption of Cu(II) from Aqueous Solution by Porous Mn3[Co(CN)6]2 · nH2O Nanospheres

Prussian blue analogue of porous Mn₃[Co(CN)₆]₂ · nH₂O nanospheres with a large surface area were prepared by simple mixing K₃[Co(CN)₆]₂ and manganous nitrate solution at room temperature. The morphology and structure of the prepared products were characterized by XRD, FE-SEM, TEM, and BET. The results indicated that the product was composed of nanospheres with the diameter of ～250 nm, which was of porous structure with the pore diameter in the 2.5–4 nm range. The adsorption behavior of Cu(II) ions from aqueous solution onto porous nanospheres was investigated as a function of parameters, such as the equilibrium time, the pH, the initial concentration, and the temperature. A maximum adsorption capacity of 140.85 mg g^?1 of Cu(II) was achieved. Due to the simple synthetic method and its high adsorption capacity, the porous nanospheres had the potential to be utilized as an effective adsorbent for Cu(II) removal.     

Influence of Portland cement composition on early age reactions with metakaolin

The reactivity of two metakaolins, which vary principally in their surface area, and Portland cements of varying composition were examined via isothermal calorimetry for pastes at water-to-cementitious materials ratio of 0.50 containing 8% cement replacement by weight of metakaolin. Both metakaolins examined appear to have a catalysing effect on cement hydration. Calorimetry showed accelerated hydration, a slight increase in cumulative heat evolved during early hydration, and - for some cements examined - apparently an increased intensity of the heat evolved, particularly during the period typically associated with hydration of calcium aluminates. The higher surface area metakaolin had a greater effect. It is proposed that the presence of metakaolin may enhance dissolution of cementitious phases and/or provide additional, well-dispersed sites for nucleation of hydration products, in addition to increasing the early age concentration of solubilized aluminium (due to metakaolin dissolution). The increased intensity of some of the calorimetry data also suggests that some additional exothermic reactions are occurring, which may be related to an increased reactivity of calcium aluminate phases in the cement as well as the reaction of the metakaolin. This effect is apparently increased as the cement equivalent alkali content increases.     

Evaluation of Pulps,Rayon Fibers,and Cellulose Acetate by GPC and Other Fractionation Methods

Abstract

Chain length distribution of a broad spectrum of wood celluloses and cellulose derivatives was determined by gel permeation chromatography. Relative amounts of short and long chain-length species were characterized, and uniformity indices were calculated. Prefractionation was found to be a desirable approach to amplify low- and high-DP regions. This was accomplished using a 55/45 ethyl acetate/ethyl alcohol mixture to yield the low-DP fraction and with a van-ing composition acetone/water system to obtain high-DP material. Fractions of regenerated cellulose from rayon obtained by treatment with 6.5 and 10% sodium hydroxide and by acid hydrolysis were characterized. Wood celluloses and rayons were analyzed in their nitrate form, whereas cellulose acetates were studied directly. This work was aimed primarily at elucidating the gel fraction that appears in the form of a peak of apparently high-DP material, resulting in a bimodal distribution.     

Electrochemical behavior and its electrocatalytic properties of chemically modified electrode with Keggin-type [SiNi(H2O)W11O39]

A monolayer of Keggin-type heteropolyanion [SiNi(H₂O)W₁₁O₃₉]⁶⁻ was fabricated by electrodepositing [SiNi(H₂O)W₁₁O₃₉]⁶⁻ on cysteamine modified gold electrode. The monolayer of [SiNi(H₂O)W₁₁O₃₉]⁶⁻ modified gold electrode was characterized by atomic force microscopy (AFM) and electrochemical method. AFM results showed the [SiNi(H₂O)W₁₁O₃₉]⁶⁻ uniformly deposited on the electrode surface and formed a porous monolayer. Cyclic voltammetry exhibited one oxidation peak and two reduction peaks in 1.0 M H₂SO₄ in the potential range of −0.2 to 0.7 V. The constructed electrode could exist in a large pH (0-7.6) range and showed good catalytic activity towards the reduction of bromate anion (BrO₃⁻) and nitrite (NO₂⁻), and oxidation of ascorbic acid (AA) in acidic solution. The well catalytic active of the electrode was ascribed to the porous structure of the [SiNi(H₂O)W₁₁O₃₉]6⁻ monolayer.     

Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers

For adsorption of three different allylether-based PCE superplasticizers on CaCO₃ surface, the thermodynamic parameters ΔH, ΔS and ΔG were determined experimentally. The GIBBS standard free energy of adsorption ΔG_0ads, the standard enthalpy of adsorption ΔH_0ads and the standard entropy of adsorption ΔS_0ads applying to an unoccupied CaCO₃ surface were obtained via a linear regression of ln K (equilibrium constant) versus 1 / T (VAN'T HOFF plot). Additionally, the thermodynamic parameters characteristic for a CaCO₃ surface loaded already with polymer (isosteric conditions) were determined using a modified CLAUSIUS-CLAPEYRON equation.For all PCE molecules, negative ΔG values were found, indicating that adsorption of these polymers is energetically favourable and a spontaneous process. Adsorption of PCEs possessing short side chains is mainly instigated by electrostatic attraction and a release of enthalpy. Contrary to this, adsorption of PCEs with long side chains occurs because of a huge gain in entropy. The gain in entropy results from the release of counter ions attached to the carboxylate groups of the polymer backbone and of water molecules and ions adsorbed on the CaCO₃ surface. With increased surface loading, however, ΔG_isosteric decreases and adsorption ceases when ΔG becomes 0. The presence of Ca²⁺ ions in the pore solution strongly impacts PCE adsorption, due to complexation of carboxylate groups and a reduced anionic charge amount of the molecule. In the presence of Ca²⁺, adsorption of allylether-based PCEs is almost exclusively driven by a gain in entropy. Consequently, PCEs should produce a strong entropic effect upon adsorption to be effective cement dispersants. Molecular architecture, anionic charge density and molecular weight as well as the type of anchor groups present in a superplasticizer determine whether enthalpy or entropy is the dominant force for superplasticizer adsorption.