Phase behavior of aqueous suspensions of Mg(2)Al layered double hydroxide: the competition among nematic ordering, sedimentation, and gelation

Birefringence observations and rheological measurements were used to monitor the phase behavior of Mg/Al (the molar ratio of Mg(2+) to Al(3+) being 2:1) layered double hydroxide (LDH) suspensions. The suspensions of concentration lower than 16% (w/w) appear isotropic (I) between crossed polarizers. In contrast, the suspensions of concentration between 16% and 30% (w/w) showed an isotropic (I)-nematic (N) biphasic coexistence. Detailed observations led us to divide the suspensions in the gap into three groups according to their behaviors: the suspensions with concentration between 16% and 25% (w/w) experienced an I-N phase transition and particle sedimentation simultaneously, while the suspensions of 25% to 27% (w/w) showed I-N transition after particle sedimentation, and in the suspension of 30% (w/w), a critical sol-gel transition appeared with an I-N transition. Above 33% (w/w), the gel network hindered a complete I-N separation in the suspensions. Upon raising the NaCl concentration, the liquid crystalline phase transition and the sol-gel transition shifted to higher particle concentrations. The facts demonstrate that the phase behavior of aqueous LDH suspensions is controlled by the competition among liquid crystal phase transition, sedimentation, and gelation.     

Dispersion and size control of layered double hydroxide nanoparticles in aqueous solutions

We report a simple but efficient method to prepare stable homogeneous suspensions containing monodispersed MgAl layered double hydroxide (LDH) nanoparticles that have wide promising applications in cellular drug (gene) delivery, polymer/LDH nanocomposites, and LDH thin films for catalysis, gas separation, sensing, and electrochemical materials. This new method involves a fast coprecipitation followed by controlled hydrothermal treatment under different conditions and produces stable homogeneous LDH suspensions under variable hydrothermal treatment conditions. Moreover, the relationship between the LDH particle size and the hydrothermal treatment conditions (time, temperature, and concentration) has been systematically investigated, which indicates that the LDH particle size can be precisely controlled between 40 and 300 nm by adjusting these conditions. The reproducibility of making the identical suspensions under identical conditions has been confirmed with a number of experiments. The dispersion of agglomerated LDH aggregates into individual LDH crystallites during the hydrothermal treatment has been further discussed. This method has also been successfully applied to preparing stable homogeneous LDH suspensions containing various other metal ions such as Ni(2+), Fe(2+), Fe(3+), Co(2+), Cd(2+), and Gd(3+) in the hydroxide layers and many inorganic anions such as Cl(-), CO(3)(2-), NO(3)(-), and SO(4)(2-).     

Synthesis and coating of silica supported Nickel Oxide particles over ceramic pre-forms through sol–gel derived layered double hydroxides

Silica supported Nickel Oxide fine particles have been synthesized through sol–gel derived Ni–Al Layered Double Hydroxide (LDH) and coated over honeycomb ceramic pre-forms through dip-coating technique. The powder products of supported materials have low crystallinity, negative zeta potential, exhibit high dispersibility and suitable for further processing by coating techniques. The powder X-ray diffraction (XRD) patterns have shown that there is an increase of basal spacing by 3.02 Å in acetylacetonate intercalated LDH. The particles of <2 μm size increase with the rise of LDH component in the composite. The particles of NiO structure formed on decomposition of composites have crystallite size <20 nm. Due to the interlayer reduction of NiO crystallites, the unsupported LDH on calcination gives Ni⁰ particles of size around 4.18 nm. The Scanning Electron Microscopy (SEM) patterns of coated supported suspensions over ceramic substrates show formation of thin, crack free coats with uniform distribution of particles.     

Formation of Layered Single- and Double-Metal Hydroxide Precipitates at the Mineral/Water Interface: A Multiple-Scattering XAFS Analysis

Spectroscopic and microscopic studies have shown that Ni and Co sorption by clay minerals may proceed via formation of surface precipitates. Several studies employing X-ray absorption fine structure (XAFS) spectroscopy suggested the formation of turbostratic, alpha-type metal hydroxides, of layered double hydroxides (LDH) with Al-for-metal substitution, and of 1:1 or 2:1 phyllosilicates. Distinction of these phases is difficult because they have low crystallinity and/or a small mass compared to the sorbents, and because they have similar metal-metal distances in their hydroxide layers/sheets. Distinction of these phases is crucial, however, because they have substantially differing solubilities. In this paper we show that an XAFS beat pattern at about 8 ?(-1) can be used as a fingerprint to unequivocally distinguish LDH from the alpha-type hydroxides and phyllosilicates. Full multiple-scattering simulations and experimental spectra of model compounds indicate that the beat pattern is due to focused multiple scattering at Me/Al ratios between 1 and 4 (Me=Ni, Co). By applying the fingerprint method to new and to already published XAFS data on Ni and Co surface precipitates, we found that LDH preferentially forms in the presence of the Al-containing sorbents pyrophyllite, illite, kaolinite, gibbsite, and alumina above pH 7.0. However, alpha-type metal hydroxides form in the presence of the Al-free sorbents talc, silica, and rutile, and in the presence of the Al-containing clay minerals montmorillonite and vermiculite. We believe that the high permanent charge of these latter minerals prevents or retards the release of Al. When Al is available, the formation of LDH seems to be thermodynamically and/or kinetically favored over the formation of alpha-type hydroxides. Copyright 2000 Academic Press.     

Effect of hydrothermal treatment on properties of Ni-Al layered double hydroxides and related mixed oxides

The Ni-Al layered double hydroxides (LDHs) with Ni/Al molar ratio of 2, 3, and 4 were prepared by coprecipitation and treated under hydrothermal conditions at 180 °C for times up to 20 h. Thermal decomposition of the prepared samples was studied using thermal analysis and high-temperature X-ray diffraction. Hydrothermal treatment increased significantly the crystallite size of coprecipitated samples. The characteristic LDH diffraction lines disappeared completely at ca. 350 °C and a gradual crystallization of NiO-like mixed oxide was observed at higher temperatures. Hydrothermal treatment improved thermal stability of the Ni2Al and Ni3Al LDHs but only a slight effect of hydrothermal treatment was observed with the Ni4Al sample. The Rietveld refinement of powder XRD patterns of calcination products obtained at 450 °C showed a formation of Al-containing NiO-like oxide and a presence of a considerable amount of Al-rich amorphous component. Hydrothermal aging of the LDHs resulted in decreasing content of the amorphous component and enhanced substitution of Al cations into NiO-like structure. The hydrothermally treated samples also exhibited a worse reducibility of Ni²⁺ components. The NiAl₂O₄ spinel and NiO still containing a marked part of Al in the cationic sublattice were detected in the samples calcined at 900 °C. The Ni2Al LDHs hydrothermally treated for various times and related mixed oxides obtained at 450 °C showed an increase in pore size with increasing time of hydrothermal aging. The hydrothermal treatment of LDH precursor considerably improved the catalytic activity of Ni2Al mixed oxides in N₂O decomposition, which can be explained by suppressing internal diffusion effect in catalysts grains.     

Synthesis of NiGa layered double hydroxides. A combined EXAFS, SAXS, and TEM study. 2. Hydrolysis of a Ni2+/Ga3+ solution

Takovites are nickel-based layered double hydroxides (LDH) with a general formula that can be written as Ni(1-x)Al(x)(OH)2, A(z-)(x/z), yH(2)O, where A is a compensating interlayer anion. As in some other LDH samples, the positive charge of the layer can be adjusted upon synthesis and various anions can be exchanged in the interlayer region. It is then important to understand the synthesis pathway of these materials. We then undertook a study on the hydrolytic behavior of pure Ni salts and mixtures of Ni and Ga salts. This paper focuses on the hydrolysis of Ni(2+) and Ga(3+) ions, together in solution, carried out by base addition. The samples will be defined by their hydrolysis ratio R = [OH(-)]/([Ni(2+)] + [Ga(3+)]). Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) were used to obtain information on the colloidal species size and shape on a large scale. Each hydrolyzed sample was also studied by Ni K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS) to obtain information on the local structure of the species in suspension. SAXS curves reveal the presence of bidimensional objects whatever the R values. The platelets formed for R values >/=1.1 are slightly thicker and smaller in size, which may be linked to their different natures. Complementary information is provided by TEM analysis: the first colloids formed have a structure very close to that of alpha-GaOOH, as shown by electronic diffraction. Those structures are progressively replaced by Ni-Ga LDH platelets with increasing hydrolysis ratio, which are the only species in suspension for R = 2.0, as shown by XRD. EXAFS results confirm the complete hydrolysis of gallium before the formation of Ni-Ga LDH phases.     

Temperature Driven Transformation of the Flexible Metal–Organic Framework DUT-8(Ni)

DUT-8(Ni) metal–organic framework (MOF) belongs to the family of flexible pillared layer materials. The desolvated framework can be obtained in the open pore form (op) or in the closed pore form (cp), depending on the crystal size regime. In the present work, we report on the behaviour of desolvated DUT-8(Ni) at elevated temperatures. For both, op and cp variants, heating causes a structural transition, leading to a new, crystalline compound, containing two interpenetrated networks. The state of the framework before transition (op vs. cp) influences the transition temperature: the small particles of the op phase transform at significantly lower temperature in comparison to the macroparticles of the cp phase, transforming close to the decomposition temperature. The new compound, confined closed pore phase (ccp), was characterized by powder X-ray diffraction and spectroscopic techniques, such as IR, EXAFS, and positron annihilation lifetime spectroscopy (PALS). Thermal effects of structural transitions were studied using differential scanning calorimetry (DSC), showing an overall exothermic effect of the process, involving bond breaking and reformation. Theoretical calculations reveal the energetics, driving the observed temperature induced phase transition.     

Thermo-XRD-analysis and peptization study of the adsorption of alizarinate by Co-, Ni-, and Cu-montmorillonite

The adsorption of the monovalent anionic dye alizarinate onto Co-, Ni- and Cu-montmorillonite was carried out by adding the dye into aqueous clay suspensions. During the loading of the clay suspension by alizarinate, only some of the added organic anion is adsorbed by the clay forming d-coordination chelate complexes on the clay surface. Maximum adsorption of Co-, Ni- and Cu-clay were 13, 13 and 25 mmol dye per 100 g clay. Since the capacity of the clay for these transition metal cations is 38 mmol per 100 g clay, these saturations indicate that only part of the transition metal cations form positively charged d-coordination chelate complexes with metal:ligand ratio of 1. The complex cations can be located inside the interlayer spaces or on the broken bonds surfaces. Thermo-XRD-analysis and peptization studies of the solids and the clay water systems respectively were used here to identify the sorption sites. The Co and Ni complexes were obtained on the broken bonds surfaces whereas the Cu complexes were obtained in the interlayer space. Co²⁺, Ni²⁺ and Cu²⁺ were extracted from the clay into suspensions containing excess alizarinate.     

Studies on Mechanochemical Method to Synthesize LDH Nanoparticles

Magnesium‐ferrum layered double hydroxide (Mg‐Fe‐LDH) and zinic‐aluminum layered double hydroxide (Zn‐Al‐LDH) compounds were prepared through a mechanochemical method. The influence of molar ratio of M²⁺ to M³⁺ (R value) on the property of LDH nanoparticles has been studied and the results showed that R=3:1 is the optimum value for the both samples. Besides pure water, the mixture of water and ethanol with the volume ratio of 3:1 is also used to wash the precipitates and used as suspending agent during the peptization process and our results showed that the addition of ethanol can improve the monodispersity of LDH nanoparticles greatly.     

An Effective Asphalt UV Blocking Material Based on Host‐Guest Schiff Base/Layered Double Hydroxides

The development of asphalt‐based UV blocking materials is important to extend the alphalt lifespan in road construction. In this work, we put forward that the fabrication of host‐guest system can be an effective way to obtain UV blocking materials. Firstly, a new anionic Schiff base, N ,N' ‐bis(salicylidine)‐4,4'‐diaminostilbene‐2,2'‐disulfonic acid (SDSD ), has been synthesized, which was intercalated into Zn‐Al‐LDH by anion‐exchange method. FT‐IR and XRD illustrate the layered organic–inorganic composite, Zn‐Al‐SDSD‐LDH , has been successfully synthesized with high crystallinity. Laser particle size analyzer, SEM and TEM show that particle size distributions of Zn‐Al‐SDSD‐LDH is in the range 100–500 nm. UV –vis absorption spectra show that Zn‐Al‐SDSD‐LDH has better UV absorption than the pristine Zn‐Al‐LDH and SDSD . Furthermore, the mixture of asphalt and 3 wt% Zn‐Al‐SDSD‐LDH presents enhanced UV blocking property relative to the pristine asphalt after irradiating by UV spray accelerated weathering test. Therefore, this work not only develops a new type of host‐guest Zn‐Al‐SDSD‐ LDH , but also confirms it can be an effective asphalt UV blocking material for practical application.     

Effect of environmental parameters on the sequestration of radionickel by Mg2Al layered double hydroxide

In this work, sequestration of Ni(II) from aqueous solution to Mg₂Al layered double hydroxide (Mg₂Al LDH) by adsorption process as a function of various water quality parameters and temperature was investigated. The results showed that the kinetic adsorption could be described by a pseudo-second order model very well. The adsorption of Ni(II) on Mg₂Al LDH was strongly dependent on pH and ionic strength. The presence of humic acid (HA)/fulvic acid (FA) enhanced the adsorption of Ni(II) on Mg₂Al LDH at low pH, whereas reduced Ni(II) adsorption at high pH. The Langmuir model fitted the adsorption isotherms of Ni(II) better than the Freundlich model at three different temperatures of 298, 318 and 338 K. The thermodynamic parameters (ΔH^o, ΔS^o and ΔG^o) calculated from the temperature dependent adsorption isotherms indicated that the adsorption process of Ni(II) on Mg₂Al LDH was endothermic and spontaneous. The results show that Mg₂Al LDH is a promising material for the preconcentration and separation of pollutants from large volumes of aqueous solutions.     

Catalytic reduction of NO_x by CO on hydro-talcites-derived mixed oxides Co AIM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M= Cr, Mn, Fe, Co, Ni, Cu) , were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc) . The ratio of Mg: Al: M (or Co: Al: M) was 3:1:1. The catalytic activity of all samples for the reaction of NO CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced . The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al:Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO     

Re-entrant volume phase transition of hydrogel membrane of microcapsule

Re-entrant volume phase transition of hydrogel wall membrane of microcapsules (MC) was first observed using MC suspensions consisting of poly (L-lysine-alt-terephthalic acid) wall and aqueous inner and outer solutions with different pHs. To analyze the dynamics of the re-entrant phase transition, we extended the theory for the swelling and the shrinking dynamics of the microcapsule gel [T. Narita, T. Yamamoto, D. Suzuki, T. Dobashi, Langmuir 19 (2004) 4051]. In the theory, the microcapsule size and the force constant for the driving force which gives rise to the size relaxation were chosen as the thermodynamic variables. The time course of the cross-sectional area of the microcapsules fitted well to the theoretical equations, and the time constants determined as the fitting parameters were discussed in terms of the force constant relaxation and the size relaxation.     

基于层状氢氧化物衍生复合氧载体的生物质化学链气化实验研究

通过低饱和共沉淀法合成了类水滑石结构的层状氢氧化物(Layered Double Hydroxide,LDH)前驱体,经煅烧获得衍生Cu/Al/Zn、Cu/Al/Ni、Cu/Al/Ni/Zn高分散复合氧载体。采用XRD、XRF、H2-TPR、SEM及BET等分析手段对氧载体的结构及反应性能进行了表征,并通过固定床反应器开展了氧载体与生物质化学链气化实验。结果表明,合成的三种前驱体都具有典型的水滑石特征衍射峰,且层板稳定。Cu/Al/Zn前驱体层间厚度为0.264 2 nm,Ni2+引入后,层间距减小。前驱体煅烧后形成的复合氧载体中元素含量与制备试剂基本一致。氧载体中Zn、Ni元素的引入可提升Cu O的反应活性,降低H2还原的反应温度,Zn元素与Cu具有更好的协同作用。Cu/Al/Ni/Zn氧载体在固定床化学链气化中具有较好的碳转化率和气体产率,其碳转化率为82.03%。反应后氧载体比表面积为5.995 m2/g,具有较好的可再生性与抗烧结性,是生物质化学链气化反应较为理想的氧载体。     

Facile and large-scale production of ZnO/Zn-Al layered double hydroxide hierarchical heterostructures

ZnO/Zn-Al layered double hydroxide (ZnO/Zn-Al LDH) hierarchical architecture, a new type of ZnO-based heterostructure, has been synthesized directly on an Al substrate via a facile solution phase process. The firecracker-like heterostructures consist of uniform ZnO nanorods orderly standing at the edges of two-dimensional (2D) surfaces of Zn-Al LDH nanoplatelets. Experimental result obtained from the early growth stage indicates that the underlying Zn-Al LDH nanoplatelet arrays are well constructed with their (00l) planes perpendicular to the surface of Al substrate. We propose that the "edge effect" of Zn-Al LDH and the "lattice match" between ZnO and Zn-Al LDH are vital to the growth of such heterostructures. The effects of total solution volume and NH3.H2O concentration on the formation of heterostructures are investigated. It is found that other LDH-based complex structures can also be achieved controllably by varying the mentioned experimental factors. Our work is the first demonstration of fabricating intricate ZnO/Zn-Al LDH heterostructures as well as well-defined Zn-Al LDH arrays on an Al substrate, for which several promising applications such as optoelectronics, biosensors, and catalysis can be envisioned.     

Concomitant synthesis of highly crystalline Zn-Al layered double hydroxide and ZnO: phase interconversion and enhanced photocatalytic activity

Metal oxide/hydroxide with hierarchical nanostructures has emerged as one of the most promising materials for their unique, attractive properties and feasibility of applications in various fields. In this report, a concomitant synthesis of crystalline zinc aluminum layered double hydroxide (ZnAl-LDH) nanostructure and ZnO is presented using Al substrate as template. Studies on interconversion of ZnO to LDH phase in bulk solution under hydrothermal conditions produced Al-doped ZnO (AZO) in one case, and in other, it improves the crystallinity of LDH film templated on Al substrate. In presence of Al salt, the self-limiting growth nature of plate LDH turned to non-self-limiting. Materials obtained during phase transition, AZO in bulk solution and crystalline porous ZnAl-LDH on substrate, have been demonstrated as effective photocatalysts for decomposition of congo red in aqueous medium.     

Catalytic reduction of NOx by CO on hydrotalcites-derived mixed oxides CoAlM and MgAlM (M=Cr,Mn, Fe,Co, Ni,Cu)

Two series of mixed oxides, GIAlM and MgAlM (M= G, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: M) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H₂-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, Different ratio of Co: Al: Cu and at different calcination temperatures. were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.     

Incorporation of transition metals into Mg-Al layered double hydroxides: Coprecipitation of cations vs. their pre-complexation with an anionic chelator

A comparative study on two different methods for preparing Mg-Al layered double hydroxides (LDH) containing various divalent transition metals M (M=Co, Ni, Cu) has been carried out. The first (conventional) method involved coprecipitation of divalent metals M(II) with Mg(II) and Al(III) cations using carbonate under basic conditions. The second approach was based on the ability of transition metals to form stable anionic chelates with edta⁴⁻ (edta⁴⁻=ethylenediaminetetraacetate) that were synthesized and further introduced into LDH by coprecipitation with Mg and Al. The synthesized LDHs were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods, thermogravimetry with mass-selective detection of decomposition products (TG-MSD), Fourier transform infrared (FTIR) and Raman spectroscopy techniques. The results obtained were discussed in terms of efficiency of transition metal incorporation into the LDH structure, thermal stability of materials and the ability of metal chelates to intercalate the interlayer space of Mg-Al LDH. Vibrational spectroscopy studies confirmed that the integrity of the metal chelates was preserved upon incorporation into the LDH.     

Statistical theory for hydrogen bonding fluid system of A_aD_d type (I): The geometrical phase transition

The influence of hydrogen bonds on the physical and chemical properties of hydrogen bonding fluid system of AaDd type is investigated from two viewpoints by the principle of statistical mechanics. In detail, we proposed two new ways that can be used to obtain the equilibrium size distribution of the hydrogen bonding clusters, and derived the analytical expression of a relationship between the hydrogen bonding free energy and hydrogen bonding degree. For the nonlinear hydrogen bonding systems, it is shown that the sol-gel phase transition can take place under proper conditions, which is further proven to be a kind of geometrical phase transition rather than a thermodynamic one. Moreover, several problems associated with the geometrical phase transition and liquid-solid phase transition in nonlinear hydrogen bonding systems are discussed.     

Statistical theory for hydrogen bonding fluid system of AaDd type (I): The geometrical phase transition

The influence of hydrogen bonds on the physical and chemical properties of hydrogen bonding fluid system of A _a D _d type is investigated from two viewpoints by the principle of statistical mechanics. In detail, we proposed two new ways that can be used to obtain the equilibrium size distribution of the hydrogen bonding clusters, and derived the analytical expression of a relationship between the hydrogen bonding free energy and hydrogen bonding degree. For the nonlinear hydrogen bonding systems, it is shown that the sol-gel phase transition can take place under proper conditions, which is further proven to be a kind of geometrical phase transition rather than a thermodynamic one. Moreover, several problems associated with the geometrical phase transition and liquid-solid phase transition in nonlinear hydrogen bonding systems are discussed.