Efficient Removal of Phosphate from Aqueous Solutions Using Corundum-hollow-spheres Supported Caclined Hydrotalcite Porous Thin Films

Phosphate was removed from aqueous environment by corundum-hollow-spheres supported caclined hydrotalcite (cHT) thin films. Mg-Al-CO3 hydrotalcite (HT) thin films were deposited on corundumhollow-sphere substrates by hydrothermal homogeneous precipitation at 120℃for 30-240 min and cHT thin films were obtained by annealing of the HT thin films at 500℃for 180 min. Their crystal phase, morphology and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results show that homogeneous, well-crystallized and hierarchical flower-like thin films were deposited firmly on the surface of the corundum. The mechanism of nucleation and growth of the HT thin films was fitted well with the anion coordination polyhedron growth unit model. To determine the absorption of phosphate by this adsorbent, different bed depth (10-30 cm) and flow rate (1.0-3.0 m L/min) were examined by column experiments. The highest removal efficiency of phosphate amounted to 98.5%under optimum condition (pH=7.2). The adsorption capacity increased as the bed depth increased and decreased as the flow rate increased.

Effect and Mechanism of Rare Earth Hydrotalcite Inhibiting Coal Spontaneous Combustion

A hydrotalcite(layered double hydroxide, LDH) inhibitor which is suitable for the whole process of coal spontaneous combustion and a LDH inhibitor containing rare earth lanthanum elements were prepared. The inhibition effect and mechanism were analyzed by scanning electron microscopy(SEM),X-ray diffraction(XRD), thermal performance analysis, in-situ diffuse reflectance infrared spectroscopy and temperature-programmed experiment. The results have shown that the inhibitor containing lanthanum can play a good inhibitory role in every stage of coal oxidation. During the slow oxidation of coal samples, the inhibitor containing lanthanum ions can slow down the oxidation process of coal and increase the initial temperature of coal spontaneous combustion. At the same time, because the hydroxyl groups in LDHs are connected with-COO-groups on the coal surface through hydrogen bonds, the stability of coal is improved. With the increase of temperature, LDHs can remove interlayer water molecules and reduce the surface temperature of coal. CO release rate of coal samples decreases significantly after adding inhibitor containing lanthanum element, and the maximum inhibition rate of the inhibitor is 58.1%.

Graphene oxide/hydrotalcite modified polyethersulfone nanohybrid membrane for the treatment of lead ion from battery industrial effluent

In the present study, polyethersulfone based nanohybrid membranes were effectively fabricated by incorporating graphene oxide(GO) and hydrotalcite(HT) nanosheets into the membrane structure. HT was prepared to overcome the irreversible agglomeration behavior of GO at a high concentration which affects the performance of the membranes. In particular, the shedding of HT in formamide provides a two-dimensional nanosheet with a higher positive charge density to prevent the restacking of GO nanosheets. Here, exfoliated GO and HT with different combinations(1:1, 1:2 and 1:3) were infused in the membrane matrix to treat lead-acid battery effluent effectively. Finally, the hybrid membranes were characterized for hydrophilicity, mechanical strength and pure water flux. In combination with the superior properties of GO and HT, the prepared hybrid membranes can be used as effectively to improve the separation and permeation performance. The phase inversion process eliminated the leaching of nanoparticles from the membrane matrix. The reusability of the hybrid membrane was achieved using0.1 mol·L^(-1)NaOH solution and reused without significant reduction in lead removal efficiency. The cost analysis of the membrane was also estimated from the lab study. Therefore, the present study suggested the selective and sustainable treatment of lead from a real-life effluent.

Corrosion resistance of in-situ Mg-Al hydrotalcite conversion film on AZ31 magnesium alloy by one-step formation

In situ growth of nano-sized layered double hydroxides （LDH） conversion film on AZ31 alloy was synthesized by a urea hydrolysis method. The formation mechanism of the film was proposed. Firstly, the dissolved Mg2＋ ions deposited into a precursor film consisted of MgCO3 and Mgs（CO3）4（OH）2·4H2O; secondly, the precursor translated into the crystalline Mg（OH）2 in alkaline conditions; finally, the Mg2＋ ions in Mg（OH）z were replaced by A13＋ ions, Mg（OH）2 translated into the more stable LDH structure, simultaneously, the OH- ions in the interlayer were exchanged by CO32-, thus led to the formation of the LDH （Mg6Alz（OHh6CO3·4H2O） film. The results indicated that the LDH film characterized by interlocking plate-like nanostructures and ion-exchange ability significantly improved the corrosion resistance of the AZ31 Mg alloy.

Hydrotalcite的合成与应用

介绍了以碱式碳酸镁、铝酸碱金属盐为原料合成Hydrotalcite的方法,并论述了其作为制酸剂和抗胃脘剂、聚烯烃树脂的中和剂、PVC热稳定剂的应用。

Effects of hydrotalcite combined with esomeprazole on gastric ulcer healing quality: A clinical observation study

AIM To evaluate the effects of hydrotalcite combined with esomeprazole on gastric ulcer healing quality. METHODS Forty-eight patients diagnosed with gastric ulcer between June 2014 and February 2016 were randomly allocated to the combination therapy group or monotherapy group. The former received hydrotalcite combined with esomeprazole, and the latter received esomeprazole alone, for 8 wk. Twenty-four healthy volunteers were recruited and acted as the healthy control group. Endoscopic ulcer healing was observed using white light endoscopy and narrow band imaging magnifying endoscopy. The composition of collagen fibers, amount of collagen deposition, expression of factor. and TGF-beta 1, and hydroxyproline content were analyzed by Masson staining, immunohistochemistry, immunofluorescent imaging and ELISA. RESULTS Following treatment, changes in the gastric microvascular network were statistically different between the combination therapy group and the monotherapy group (P < 0.05). There were significant differences (P < 0.05) in collagen deposition, expression level of Factor. and TGF-beta 1, and hydroxyproline content in the two treatment groups compared with the healthy control group. These parameters in the combination therapy group were significantly higher than in the monotherapy group (P < 0.05). The ratio of collagen. to collagen. was statistically different among the three groups, and was significantly higher in the combination therapy group than in the monotherapy group (P < 0.05). CONCLUSION Hydrotalcite combined with esomeprazole is superior to esomeprazole alone in improving gastric ulcer healing quality in terms of improving microvascular morphology, degree of structure maturity and function of regenerated mucosa.

Adsorption removal of thiocyanate from aqueous solution by calcined hydrotalcite

A hydrotalcite with Mg/AI molar ratio 2 was prepared by co-precipitation method and was characterized by XRD, TG/DTA, Zeta potential and BET surface area. The hydrotalcite was calcined at 500℃, with the dehydration from interlayer, the dehydroxilation from the brucite-like layer and the decomposition of carbonate successively, transformed into the mixed oxide type. The removal of thiocyanate from aqueous solution by using the original hydrotalcite and calcined hydrotalcite （HTC-500） was investigated. The results showed that the thiocyanate adsorption capacity of calcined hydrotalcite was much higher than that of the original form. Calcined hydrotalcite was particularly effective at removing thiocyanate, and that the effective range of pH for the thiocyanate removal are between 5.5-10.0. The experimental data of thiocyanate removal fit nicely with Langmuir isotherm, and the saturated adsorption uptake was 96.2 mg SCN-/g HTC-500. The adsorption of thiocyanate by calcined hydrotalcite follows first-order kinetics. And the intercalation to the structure recovery for calcined hydrotalcite. But the presence of additional anions could affect the adsorption behavior of thiocyanate.

Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:Model reaction for upgrading of bio-oil

A series of Cu-Mg-Al hydrotalcites derived oxides with a(Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio(from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 ?C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.

Hierarchical Ni-Al hydrotalcite supported Pt catalyst for efficient catalytic oxidation of formaldehyde at room temperature

Catalytic oxidation at room temperature is recognized as the most promising method for formaldehyde(HCHO)removal.Pt‐based catalysts are the optimal catalyst for HCHO decomposition at room temperature.Herein,flower‐like hierarchical Pt/NiAl‐LDHs catalysts with different[Ni2+]/[Al3+]molar ratios were synthesized via hydrothermal method followed by NaBH4 reduction of Pt precursor at room temperature.The flower‐like hierarchical Pt/NiAl‐LDHs were composed of interlaced nanoplates and metallic Pt nanoparticles(NPs)approximately 3–4 nm in diameter were loaded on the surface of the Pt/NiAl‐LDHs with high dispersion.The as‐prepared Pt/NiAl21 nanocomposite was highly efficient in catalyzing oxidation of HCHO into CO2 at room temperature.The high activity of the hierarchical Pt/NiAl21 nanocomposite was maintained after seven recycle tests,suggesting the high stability of the catalyst.Based on in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies,a reaction mechanism was put forward about HCHO decomposition at room temperature.This work provides new insights into designing and fabricating high‐performance catalysts for efficient indoor air purification.

Tuning the base properties of Mg–Al hydrotalcite catalysts using their memory effect

Herein,the relationship between the structure and base properties of Mg–Al hydrotalcite catalysts was comprehensively investigated in relation to heat treatment and rehydration processes,which are well known as memory effects of hydrotalcite.The structure of Mg–Al hydrotalcites changed from layered double hydroxide(LDH)to mixed metal oxide and subsequently to a spinel structure during heat treatment,and it was returned from mixed metal oxide to a LDH structure by rehydration.Based on various characterizations,we successfully proposed a detailed mechanism of memory effect.We also confirmed that the Mg–Al hydrotalcites had weak or strong base sites and that their base properties could be systematically tuned by heat treatment and rehydration.The prepared Mg–Al hydrotalcites were applied to a model reaction,isomerization of glucose to fructose,as base catalysts.Among the catalysts tested,the rehydrated Mg–Al hydrotalcite efficiently produced fructose due to its appropriate base and structure properties.We finally concluded that the base sites of Mg–Al hydrotalcites can be designed as desired by heat treatment and rehydration.Moreover,through systematic design of the base sites of Mg–Al hydrotalcites,these can be promising catalysts for various heterogeneous reactions over base catalysts,giving excellent catalytic performances.

Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO_2 methanation: cooperative effect between Ni nanoparticles and a basic support

Ni-Al hydrotalcite derived catalyst （Ni-Al2O3-HT） exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO2 over this catalyst initiated at 225℃ and reached 82.5% CO2 conversion with 99.5% CH4 selectivity at 350℃, which was much better than its impregnated counterpart. Characterizations by means of CO2 microcalorimetry and 27 Al NMR indicated that large amount of strong basic sites existed on Ni-Al2O3-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO2 and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction. Keywords

Zn-Zr-Al oxides derived from hydrotalcite precursors for ethanol conversion to diethyl carbonate

Ethanol conversion to high-value-added products has attracted considerable attention in both academic research and industrial fields.In this study,we synthesized a series of tunable acid–base bifunctional Zn-Zr-Al metal oxides(represented as Zn2ZrxAl-MMO)in light of the structural topotactic transformation of Zn2ZrxAl-hydrotalcite precursors(Zn2ZrxAl-LDH).The resulting Zn2ZrxAl-MMO catalysts were employed in the conversion of ethanol to diethyl carbonate.The Zr^4+ ion content of the LDH precursor plays a key role in modulating the acid-base properties and determining catalytic performance:the Zn2Zr0.1Al-MMO sample exhibits the optimal catalytic behavior with a diethyl carbonate(DEC)yield of 42.1%,which is the highest reported for metal oxide catalysts.Structure-property correlation investigations revealed that the synergic catalysis between medium-strong basic sites and weak acid sites plays a predominant role in the catalytic behavior.Furthermore,in situ Fourier transform infrared measurements showed that the weak acidic site promotes activation adsorption of the reactant(urea)and the intermediate product(ethyl carbamate),while the medium-strong basic site accelerates ethanol activation.Moreover,the Zn2Zr0.1Al-MMO catalyst has the advantages of cost effectiveness,good stability,and reusability.Therefore,the acid-base bifunctional catalysts developed in this work can be employed as promising candidates in acid-base catalytic reactions such as ethanol conversion.

Influence of the preparation method on the catalytic activity of Mg-Al hydrotalcites as solid base catalysts

Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.

Geometric effect promoted hydrotalcites catalysts towards aldol condensation reaction

In solid basic catalysis field,how to achieve optimized activity and desired stability through elaborate control over basic site properties remains a challenge.In this work,taking advantage of the structure memory effect of layered double hydroxides(LDHs),rehydrated Ca4 Al1-x Gax-LDHs and Ca4 Al1-x Inx-LDHs catalysts were prepared and applied in aldol condensation reaction that isobutyraldehyde(IBD)reacts with formaldehyde(FA)to obtain hydroxypivalaldehyde(HPA).Notably,the resulting re-Ca4 Al0.90Ga0.10-LDHs exhibits an extraordinarily-high catalytic activity(HPA yield:72%),which is to our best knowledge the highest level in this reaction.The weak Br?nsted basic site,7-coordinated Ca-OH group,which serves as an active site,catalyzes the condensation process and promotes the product desorption.Studies on structure-property correlations demonstrate that Ga as a structural promoter induces a moderate expansion of the laminate lattice,which results in a significant increase in the concentration of weak basic sites in re-Ca4Al0.90Ga0.10-LDHs,accounting for its high catalytic activity.This work illuminates that geometric structure of basic active sites can be tuned via introducing catalyst additive,which leads to a largely improved performance of hydrotalcite solid basic catalysts towards aldol condensation reaction.

Catalytic depolymerization of calcium lignosulfonate by NiMgFeO_x derived from sub-micron sized NiMgFe hydrotalcite prepared by introducing hydroxyl compounds

A new method for regulating the synthesis of Ni Mg Fe hydrotalcites(NMF LDHs) with the addition of hydroxyl compounds was proposed. A series of NMF LDHs were prepared by the above method, and then were calcined to obtain the Ni Mg FeOx(NMFOx) samples. The NMFOxsamples were characterized by XRD,SEM, TG-DTG, XPS and CO2-TPD, respectively. The catalytic performance of NMFOxfor depolymerizing calcium lignosulfonate(CLS) was evaluated by hydrothermal reaction. The results showed that the addition of hydroxyl compounds favored reducing the particle sizes of NMF LDHs. For the depolymerization of CSL, the yield of liquid product increased from 45% to 75.8% with the addition of NMFOx-ethanol(NMFOxET). The liquid products were mainly phenolics, aromatics, ketones and esters. The total selectivity of oxy-containing compounds was over 90.6%, among them, the phenolics were approximately 35.2%. The valence of Ni and Fe, crystalline phase and basicity almost remained unchanged. The NMFOx-ET samples were recycled for the depolymerization of CLS, moreover, the NMFOx-ET samples had high activity and stability after 4 cycles.

Structure and Properties of Hydrotalcite Using Electrostatic Potential Energy Model

The electrostatic potential energy model of hydrotalcites was based on the theory of crystallography. The anionic potential energy of MgAl-hydrotalcites, with 20 layers and 2107 anions per layer, was calculated, and the anionic stability of the hydrotalcites was investigated. The charge density of the layer and the distance between the adjacent anions varied with the molar ratio of Al^3＋/（Mg^2＋ ＋ Al^3＋）. Anionic potential energy depended on the charge and size of the anions. Calculation results remained consistent with thermal stability and the ion exchange ability reported. This model is able to predict anionic stability of the hydrotalcites.

Preparation,Characterization and Application of ZnAlLa-Hydrotalcite-Like Compounds

The preparation of ZnAlLa-hydrotalcite-like compounds [ZnAlLa-HTLcs] wasstudied. ZnAlLa-HTLcs were synthesized by a method of variable pH with the raw materials ofZn(NO_3)_2, Al(NO_3)_3, La(NO_3)_3, and NaOH. The eS'ccts of some factors (i.e. pH values, the moleratio of Al^(3+) to La^(3+), temperature and the period of hydrothermal treatment) on thepreparation of HTLcs were discussed systematically. XRD, TG-DTA, FT-IR spectroscopy, and ICP wereperformed to characterize ZnAlLa-HTLcs samples, and the thermal stability of HTLcs was alsodiscussed. It was shown that unique ZnAlLa-HTLcs with high crystallinity can be prepared, under theconditions of pH = 5.5-6.5, n(Zn^(2+))/n(Al^(3+) + La^(3+))=2 and the atomic ratio of La^(3+) toAl^(3+) ranging from 0.07 to 2, hydrothermal treatment at 120 ℃ for 5 h. When the calcination ofthe HTLcs is performed at temperatures above 200 ℃, ZnO phase is detected with Al_2O_3 and La_2O_3spreading on its top. The complex metal oxides derived from ZnAlLa-HTLcs at 500 ℃ have highercatalytic activity and selectivity than those from ZnAl-HTLcs for the esterification of acetic acidwith n-butanol under the same reaction conditions.

Preparation, Characterization of Hydrotalcites and the Catalytic Properties in Synthesis of o-Phenylphenol over Pt/CHT

Mg/Al mixed oxides with molar ratios of 2_6 of Mg to Al used as supports for platinum catalysts were obtained by the thermal decomposition method. The effect of the composition of the mixed oxides on the physicochemical properties was studied by TPD, nitrogen sorption, XRD and TG-DTA characterization methods. The synthesis of o-phenylphenol(OPP) from a dimer(obtained from cyclohexanone condensation) was investigated over Pt/CHT catalysts and compared with those over Pt/MgO and Pt/Al 2O 3 catalysts. These catalysts show a high activity and selectivity for OPP, with a conversion reaching 93.8% and a selectivity reaching 87.9% in some experiments. For Pt/CHTx catalysts, the calcined hydrotalcites exhibited strong base sites, which were necessary to catalyze the synthesis of OPP.

Preparation and Characterization of Mg/Al/Fe Hydrotalcite with Superb Absorption Capacity toward Congo Red

Mg/Al/Fe layered double hydroxide(MAF-LDH1) was prepared by solvothermal method with the sodium dodecyl sulfate as the template, and the ethanol system was benefit to growth of sample. The nature in the resulting MAF-LDH was investigated by X-ray diffraction, field emission scanning electron microscopy, Fourier transformed infrared spectra, thermogravimetric analysis, and N2 adsorption-desorption.The morphology of MAF-LDH1 is petal-like with the size of 400-500 nm and the thickness about 10-20 nm. The adsorption performance of the samples was evaluated by absorption of the Congo red(CR) solutions. Compared with Mg/Al layered double hydroxide(MA-LDH), the maximum adsorption capacities of the MAF-LDH1 samples were 943.4 mg/g which was greatly enhanced. Furthermore, after seven cycling tests, the adsorption performance was still up to 90%. Theoretical calculation results revealed that the adsorption process was spontaneous and followed the pseudo-second-order kinetic model and Freundlich model. This work provides a promising alternative strategy to enhance the adsorptive properties of hydrotalcite-like materials.

“Intelligent” reforming catalysts:Trace noble metal-doped Ni/Mg(Al)O derived from hydrotalcites

Trace amounts of noble metal-doped Ni/Mg（AI）O catalysts were pre- pared starting from Mg-Al hydrotalcites （HTs） and tested in daily start-up and shut-down （DSS） operation of steam reforming （SR） of methane or partial oxidation （PO） of propane. Although Ni/Mg（Al）O catalysts prepared from Mg（Ni）-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg（Al）O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a ＂memory effect＂ of HTs. Moreover, the noble metal-doped Ni/Mg（Al）O catalysts exhibited ＂intelligent＂ catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2＋ in Mg（Ni,Al）O periclase to Ni^0 assisted by hydrogen spillover from Pt （or Pt-Ni alloy）. The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg（Al）O periclase crystal; surface Ni^0 was oxidized to Ni2＋ by steam and incorporated into Mg（Ni2＋,Al）O periclase, whereas the Ni2＋ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a ＂green＂ preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.