Nitrate and chloride transport through a smart membrane

To develop membranes having ionic selective properties under control of external stimuli is a challenge of the membrane and material scientific community. Conducting polymers swell and shrink under electrochemical control, so they are good candidates to prepare such smart membranes. The ionic transport through a new free-standing polypyrrole film working as a membrane in a diffusion cell was studied. The driving forces were transversal electric fields or concentration gradients across the film. The obtained ionic conductivity was dependent on both the electrolyte nature and concentration, as well as on the oxidation degree of the film, which was controlled by the applied external electric potential. Reverse and continuous changes of up to one order of magnitude on the transversal ionic conductivity are obtained when the membrane is in stationary oxidation states attained by polarisations at a constant potential in the range between −0.6 V and +0.4 V, respectively. A prevalent conductivity of anions (t₋ = 0.94) was obtained from Donnan potential measurements. The experimental results indicate that the oxidised film behaves as a nanoporous membrane highly permeable to nitrate ions, while the rejection of these ions is very high in the reduced film. The free-standing polypyrrole film works then as a smart membrane selective to nitrate ions under concentration gradient.     

Thermal decomposition of the hydrotalcite

Summary A combination of thermogravimetry and hot stage Raman spectroscopy has been used to study the thermal decomposition of the synthesised zinc substituted takovite Zn₆Al₂CO₃(OH)₁₆·4H₂O. Thermogravimetry reveals seven mass loss steps at 52, 135, 174, 237, 265, 590 and ~780°C. MS shows that the first two mass loss steps are due to dehydration, the next two to dehydroxylation and the mass loss step at 265°C to combined dehydroxylation and decarbonation. The two higher mass loss steps are attributed to decarbonation. Raman spectra of the hydroxyl stretching region over the 25 to 200°C temperature range, enable identification of bands attributed to water stretching vibrations, MOH stretching modes and strongly hydrogen bonded CO₃^2--water bands. CO₃^2- symmetric stretching modes are observed at 1077 and 1060 cm^-1. One possible model is that the band at 1077 cm^-1is ascribed to the CO₃^2- units bonded to one OH unit and the band at 1092 cm^-1is due to the CO₃^2- units bonded to two OH units from the Zn-takovite surface. Thermogravimetric analysis when combined with hot stage Raman spectroscopy forms a very powerful technique for the study of the thermal decomposition of minerals such as hydrotalcites.</o:p>     

Protein template effect on hydrotalcite morphology

Layered double hydroxides (LDHs), hydrotalcite‐like compounds, or hydrotalcites are porous materials, which may be used in catalysis, biomedicine, or adsorption as they may work as anion exchangers or drug deliverers. The morphology of hydrotalcites determines their use: in catalysis or in adsorption, reagents and gases have to reach as much surface as possible; in biomedicine, drugs have to be encapsulated and delivered later on. In this work, we synthesize hydrotalcites in presence of protein templates (egg white and yolk) and under two crystallization conditions (conventional and microwave). The obtained materials are hydrotalcites whose morphologies correspond to platelets organized as sand roses. Depending on the template and the preparation procedure, the amount of platelets can be increased. This feature is explained through the template effect of egg components. The resulting materials are promising adsorbers. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of nanodispersed hydrotalcite on polypropylene photooxidation

Nanocomposites containing hydrotalcite and prepared by melt compounding with polypropylene were UV-light irradiated in artificial accelerated conditions representative of solar irradiation (λ > 300 nm) at 60 °C in air. The chemical modifications resulting from photooxidation were followed by IR and UV-visible spectroscopies.The presence of hydrotalcite was shown to change the global rate of photooxidation of polypropylene by reducing the oxidation induction time and increasing the oxidation rate. The differences of the oxidation induction time disappeared after solvent extraction of the antioxidant. They were attributed to a quenching of the antioxidant activity resulting from a migration onto the filler surface induced by the preferential interaction with the polar hydrotalcite. Extracting the antioxidant did not change the oxidation rate at the permanent regime. The increase of the oxidation rate was attributed to transition metal ions, present as impurities in hydrotalcite, which can accelerate the oxidation of the polymer by various mechanisms including a catalysed decomposition of hydroperoxides.     

Thermal decomposition of the synthetic hydrotalcite woodallite

The thermal stability and thermal decomposition pathways for synthetic woodallite have been determined using thermogravimetry in conjunction with evolved gas mass spectrometry. Chemical analysis showed the formula of the synthesised woodallite to be Mg_6.28Cr_1.72Cl(OH)₁₆(CO₃)_0.36⋅8.3H₂O and X-ray diffraction confirms the layered LDH structure. Dehydration of the woodallite occurred at 65°C. Dehydroxylation occurred at 302 and 338°C. Both steps were associated with the loss of carbonate. Hydrogen chloride gas was evolved over a wide temperature range centred on 507°C. The products of the thermal decomposition were MgO and a spinel MgCr₂O₄. Experimentally it was found to be difficult to eliminate CO₂ from inclusion in the interlayer during the synthesis of the woodallite compound and in this way the synthesised woodallite resembled the natural mineral.     

Thermal decomposition of the synthetic hydrotalcite iowaite

The thermal stability and thermal decomposition pathways for synthetic iowaite have been determined using thermogravimetry in conjunction with evolved gas mass spectrometry. Chemical analysis showed the formula of the synthesised iowaite to be Mg_6.27Fe_1.73(Cl)_1.07(OH)₁₆(CO₃)_0.336.1H₂O and X-ray diffraction confirms the layered structure. Dehydration of the iowaite occurred at 35 and 79°C. Dehydroxylation occurred at 254 and 291°C. Both steps were associated with the loss of CO₂. Hydrogen chloride gas was evolved in two steps at 368 and 434°C. The products of the thermal decomposition were MgO and a spinel MgFe₂O₄. Experimentally it was found to be difficult to eliminate CO₂ from inclusion in the interlayer during the synthesis of the iowaite compound and in this way the synthesised iowaite resembled the natural mineral.     

Chemisorption of carbon dioxide on potassium-carbonate-promoted hydrotalcite

New equilibrium and column dynamic data for chemisorption of carbon dioxide from inert nitrogen at 400 and 520 degrees C were measured on a sample of potassium-carbonate-promoted hydrotalcite, which was a reversible chemisorbent for CO(2). The equilibrium chemisorption isotherms were Langmuirian in the low-pressure region (p(CO(2)) < 0.2 atm) with a large gas-solid interaction parameter. The isotherms deviated from Langmuirian behavior in the higher pressure region. A new analytical model that simultaneously accounted for Langmuirian chemisorption of CO(2) on the adsorbent surface and additional reaction between the gaseous and sorbed CO(2) molecules was proposed to describe the measured equilibrium data. The model was also capable of describing the unique loading dependence of the isosteric heat of chemisorption of CO(2) reported in the literature. The column breakthrough curves for CO(2) sorption from inert N(2) on the chemisorbent could be described by the linear driving force (LDF) model in conjunction with the new sorption isotherm. The CO(2) mass-transfer coefficients were (i) independent of feed gas CO(2) concentration in the range of the data at a given temperature and (ii) a weak function of temperature. The ratio of the mass-transfer zone length to the column length was very low due to highly favorable CO(2) sorption equilibrium.     

MgAl-PdCl4水滑石的合成与表征

以MgAl-NO3水滑石为前驱体,用离子交换法将PdCl42-作为客体插入水滑石的层间,通过XRD、IR、DTA、比表面积等表征制备的水滑石,探讨了Pd含量、插层时间、Mg/Al摩尔比以及焙烧温度对制备水滑石结构的影响.结果表明,插层产物中PdCl42-与NO3-共存于层间,PdCl42-的引入,减小了水滑石的层间距,PdCl42-引入量越多,层间距减少的越多.Mg/Al摩尔比在2～4均可以形成MgAl- PdCl4-HLTcs,但是其值增大时,水滑石的层间距逐渐降低.插层交换时间延长有利于PdCl42-插入层间,但从制备水滑石的角度看,晶化时间8 h,即可得到结晶良好的水滑石化合物.DTA分析结果显示,在较高的PdCl42-引入量,或较高的Mg/Al摩尔比时层间PdCl42-失去Cl-转化成PdO的温度在370 ℃左右,层间NO3-的脱除温度在410 ℃附近;在低的PdCl42-引入量,或低的Mg/Al摩尔比两个脱除过程一起进行,在500 ℃左右完成.随着层间PdCl42-的分解及NO3-的脱除,400 ℃时MgO-Al2O3-PdO物相开始形成,600 ℃时基本形成完全,比表面积也达到最大,进一步提高焙烧温度至800 ℃,由于金属氧化物的晶粒变大及出现少量的MgAl2O4尖晶石物相,其比表面积有所下降.     

Nitrate

Ohne Zusammenfassung     

Thermal analysis of hydrotalcite synthesised from aluminate solutions

The aluminate hydrotalcites are proposed to have either of the following formulas: Mg₄Al₂(OH)₁₂(CO₃ ²⁻)·xH₂O or Mg₄Al₂(OH)₁₂(CO₃ ²⁻, SO₄ ²⁻)·xH₂O. A pure hydrotalcite phase forms when magnesium chloride and aluminate solutions are mixed at a 1:1 volumetric ratio at pH 14. The synthesis of the aluminate hydrotalcites using seawater results in the formation of an impurity phase bayerite. Two decomposition steps have been identified for the aluminate hydrotalcites: (1) removal of interlayer water (230 °C) and (2) simultaneous dehydroxylation and decarbonation (330 °C). The dehydration of bayerite was observed at 250 °C. X-ray diffraction techniques determined that the synthesis of aluminate hydrotalcite with seawater and a volumetric ratio of 4.5 results in very disordered structures. This was shown by a reduction in the mass loss associated with the removal of interlayer water due to the reduction of interlayer sites caused by the misalignment of the metal-hydroxyl layers.     

Effects of intercalated hydrotalcite on drug release behavior for poly(acrylic acid-co-N-isopropyl acrylamide)/intercalated hydrotalcite hydrogels

The influence of positively charged intercalated hydrotalcite (IHT) in the anionic poly(acrylic acid-co-N-isopropyl acrylamide), poly(AA-co-NIPAAm)/hydrotalcite nanocomposite hydrogels on the drug release behavior for the drugs with different charges was investigated in this study. Results show that the loading amount and release ratio of indomethacin are affected by the swelling ratio in saline solution and related to the affinity in the alcohol solution, respectively. The loading amount and release ratio of caffeine are affected by the swelling ratio. The loading amount of crystal violet (CV) increased with an increase of the content of intercalating agent in IHT of the gel but the fractional release of CV in the gels decreases with increase in intercalating agent content. The result of release and loading for phenol red in the hydrogels is contrary to CV.     

Catalyst design of hydrotalcite compounds for efficient oxidations

Various Mg-Al type hydrotalcites were examined as catalysts for the epoxidation of olefins and N-oxidation of pyridines using hydrogen peroxide. The catalytic activity of hydrotalcites increased with increasing the basicity of their surface. Adding cationic surfactants, e.g., n-dodecyltrimethylammonium bromide, to the above system remarkably accelerated the reaction rate. The hydrotalcites, into which were introduced both Ru and Co cations in the Brucite layers, were found to be good catalysts for the oxidation of various alcohols in the presence of molecular oxygen. Moreover, these hydrotalcites could smoothly catalyze also the oxygenation of diphenylmethane, fluorene, and xanthene at benzylic position with excellent yields. The hydrotalcite catalysts could be easily separated from the reaction mixture and reused with retention of their high catalytic performance for the above oxidations.     

Structure property correlations in alcohols through two-photon absorption cross-section measurements

Two-photon absorption (TPA) cross-sections of neat alcohols are shown to be a femtosecond laser measurable property with useful structure property correlations that are directly correlated to the self-phase modulation of the alcohol in question. The amount of self-phase modulation is shown to be a molecular structure dependent property. The real and the imaginary components of the second-order hyperpolarizability are thus shown to be interrelated. Such TPA measurements prove that it is not possible to predict two-photon absorption properties by simple doubling the wavelengths of one-photon absorption spectra.     

Adsorption of phosphate from wastewater by a ZnO-ZnAl hydrotalcite

ABSTRACT

A ZnO-ZnAl hydrotalcite (ZZA) was prepared by a new centrifugal method, and its micromorphology was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) analyses. The adsorption by ZZA of phosphate in a simulated wastewater was studied in detail. The effects of a variety of factors, including pH, coexisting ions, adsorption time, ZZA dosage, and adsorption temperature, on the phosphate adsorption were evaluated. The reaction of ZZA adsorbing phosphate in the simulated wastewater may be an endothermic reaction. The adsorption process is more in line with the Langmuir model equation, indicating that it may be homogeneous surface monolayer chemisorption. By studying the thermodynamic index of ZZA adsorbing phosphate in simulated wastewater, it was suggested that the adsorption is a spontaneous, endothermic, and entropy-increasing process. For moderate and low level of phosphate amount wastewater, the emission requirements can be met.     

Heterogeneous Suzuki cross-coupling reactions over palladium/hydrotalcite catalysts

The efficiency of various heterogeneous solids consisting of palladium supported on hydrotalcite as catalysts in the Suzuki cross-coupling reaction between bromobenzene and phenylboronic acid was studied. Based on the catalytic activity results, the reaction develops to an acceptable extent with 100% selectivity at moderate temperatures in the presence of some of the catalysts. The best results were provided by a catalyst consisting of an acetate-pyridine complex of Pd supported on hydrotalcite that gave high conversion values even after three reuses. The reactions conditions were very mild (a temperature of 55 degrees C and atmospheric pressure). In fact, the catalyst provided conversion and selectivity results surpassing those of existing heterogeneous phase catalysts and most homogeneous phase catalysts for the same purpose.     

Adsorption and separation of proteins by a synthetic hydrotalcite

In this study, the potential use of a synthetic Mg/Al hydrotalcite (layered double hydroxide) as a novel chromatography material for protein purification was investigated. The hydrotalcite is present in its carbonate form and is characterized by an Al/Mg-ratio of 1.85. Zetapotential measurements confirm a positive surface potential up to pH 10 suggesting applicability as anion exchanger. The binding of model proteins covering a broad range of isoelectric points and molecular weights was performed at different pH-values under batch conditions to evaluate the binding behaviour of the hydrotalcite. Furthermore, static binding capacities were exemplarily determined for hemoglobin and human serum albumin. Additionally, the adsorption and elution of hemoglobin was studied under dynamic conditions. The binding behaviour of the hydrotalcite was compared to commercially available anion exchangers and was found to be a function of pH, depending on the model protein. Variant adsorption behaviour is explained by further interactions like hydrogen bonds and by an unequal charge distribution over the protein surfaces. The hydrotalcite reveals high adsorption capacities under static (260 mg/g) as well as under dynamic conditions (88 mg/g at 34 cm/h; 61 mg/g at 340 cm/h). With appropriate buffers like 500 mM carbonate (pH 10) the adsorbed proteins can be nearly completely desorbed making regeneration possible. Due to the binding and elution properties it is concluded, that the hydrotalcite can serve anion exchange material for chromatographic protein separations.