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Sample records for double hydroxide ldh

  1. [Role of layered double hydroxide (LDH) in the protection of herring testis DNA from heavy metals].

    PubMed

    Tang, Yi-Ni; Wu, Ping-Xiao; Zhu, Neng-Wu

    2012-10-01

    The role of layered double hydroxide (LDH) in the protection of herring testis DNA from heavy metals Cd2+ and Pb2+ was studied by X-ray diffraction ( XRD) spectra, Fourier transform infrared (FTIR) spectra, Scanning Electron Microscopy (SEM), Cyclic Voltammetry and Ultraviolet Spectrometry. Size expansion of the basal spacing (003) from 0. 76 nm in LDH to 2. 30 nm was observed in the resulting DNA-LDH nanohybrids and it gave peaks corresponding to C=O (1 534 cm(-1) and 1488 cm(-1)) in skeleton and bases, C-O stretching vibration (1228 cm(-1)), and P-O symmetrical stretching vibration (1096 cm(-1)) in functional groups of DNA, indicating that DNA were intercalated into the LDH by the ion exchange. However, the displacement of NO3(-) was not fully complete (partial intercalation of DNA). The DNA outside LDH interlayers was absorbed on the surface of LDH. The cyclic voltammetric curves showed that DNA in the composites exhibited a very similar peaks, which corresponded to the two reduction current peaks (E(P) = - 1.2 mV and E(P) = -2.4 mV) of free DNA. Also there was no cathode sag emerging in cyclic voltammetric curves, suggesting that both Cd2+ and Pb2+ cannot insert into the groove of DNA to associate with base pairs or other groups when DNA was bound on LDH. The results showed that, on the one hand, both Cd2+ and Pb2+ were absorbed on the external surface of LDH for immobilization, on the other hand, the layer of LDH provided ideal space for DNA by the action of protecting DNA molecules from Cd2+ and Pb2+.

  2. Layered double hydroxide/polyethylene terephthalate nanocomposites. Influence of the intercalated LDH anion and the type of polymerization heating method

    SciTech Connect

    Herrero, M.; Martinez-Gallegos, S.; Labajos, F.M.; Rives, V.

    2011-11-15

    Conventional and microwave heating routes have been used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate had been previously intercalated in the LDH. PXRD and TEM were used to detect the degree of dispersion of the filler and the type of the polymeric composites obtained, and FTIR spectroscopy confirmed that the polymerization process had taken place. The thermal stability of these composites, as studied by thermogravimetric analysis, was enhanced when the microwave heating method was applied. Dodecyl sulphate was more effective than terephthalate to exfoliate the samples, which only occurred for the terephthalate ones under microwave irradiation. - Graphical abstract: Conventional and microwave heating routes were used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate was previously intercalated into the LDH. The microwave process improves the dispersion and the thermal stability of nanocomposites due to the interaction of the microwave radiation and the dipolar properties of EG and the homogeneous heating. Highlights: > LDH-PET compatibility is enhanced by preintercalation of organic anions. > Dodecylsulphate performance is much better than that of terephthalate. > Microwave heating improves the thermal stability of the composites. > Microwave heating improves as well the dispersion of the inorganic phase.

  3. Adsorption study of anionic reactive dye from aqueous solution to Mg-Fe-CO3 layered double hydroxide (LDH)

    NASA Astrophysics Data System (ADS)

    Ahmed, I. M.; Gasser, M. S.

    2012-10-01

    Mg-Fe-Cl Layered double hydroxides (LDHs) have been prepared using a method involving separate nucleation and aging steps with Mg/Fe = 3. The interlayer anions readily replaced by carbonate are characterized by X-ray diffraction (XRD) and FTIR. The effects of different parameters, such as pH, contact time, concentration of dye and temperature on the capacity and adsorption mechanism of Mg-Fe-CO3-LDH in removing an anionic dye (congo red, CR) from aqueous solution were separately investigated. The results show that Mg-Fe-CO3-LDH is particularly efficient in removing CR and the dye removal increases with decreasing pH. The adsorption of CR on Mg-Fe-CO3-LDH reached equilibrium after 15 min where 100 mg/L CR was removed. The equilibrium isotherm indicates that the adsorption of CR onto Mg-Fe-CO3-LDH fits to Langmuir and Freundlich equation as well. The adsorption data obtained from the Langmuir model gave good values of the determination coefficient and the saturated adsorption capacity of Mg-Fe-CO3-LDH for CR was found to be 104.6 mg/g. The regeneration study indicates that the prepared LDH could be used for several cycles. The thermodynamic parameters have been calculated, and the adsorption process was found to be spontaneous, endothermic in nature and follows a pseudo-second-order kinetic model.

  4. ZnCr layered double hydroxide (LDH) nanosheets assisted formation of hierarchical flower-like CdZnS@LDH microstructures with improved visible-light-driven H2 production.

    PubMed

    Yao, Lihua; Wei, Ding; Yan, Dongpeng; Hu, Changwen

    2015-03-01

    The development of new semiconductor photocatalysts toward splitting water has supplied a promising way to obtain sustainable and clean hydrogen energy. Herein, CdZnS@layered double hydroxide (LDH) composites with a hierarchical flower-like microstructure have been fabricated with the aid of ZnCr-LDH nanosheets as templates. XRD, SEM and HRTEM show that the ZnCr-LDH nanosheets are uniformly dispersed within the composites. The surface of the hierarchical structures is rough and composed of numerous nanocrystals of CdZnS. The HRTEM images indicate that the surface of CdZnS nanocrystals is mainly composed of the (111) plane. Moreover, the visible-light-driven H2 production performance of the CdZnS in the presence and absence of ZnCr-LDH nanosheets has been measured. The results show that ZnCr-LDH nanosheets play an important role in the hierarchical morphology and photocatalytic activity of the as-prepared samples. In the water-splitting process, the visible-light-driven H2 -production rate of hierarchical flower-like CdZnS@LDH is 4.03 times and nearly 10 times higher than that of pristine CdZnS microsphere and pure commercial CdS, respectively. Therefore, this work not only achieves enhanced catalytic performance of the CdZnS by the introduction of ZnCr-LDH nanosheets, but also supplies an insight into the relationship between the hierarchical morphology and the semiconductor photocatalytic activity.

  5. Highly efficient and selective adsorption of In3+ on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh; Park, Sung Soo; Vinu, Ajayan; Ha, Chang-Sik

    2016-01-01

    A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In3+ ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In3+ intake. The structure and properties of Zn/Al-LDH and In3+ adsorbed Zn/Al-LDH (In-Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N2-sorption/desorption, UV-vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In3+ adsorption and quite stable even after the adsorption process. The selective adsorption of In3+ on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn2+, Co2+, Ni2+, Cd2+, Pb2+, and Cu2+. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In3+ from large volumes of aqueous solutions.

  6. Highly efficient and selective adsorption of In{sup 3+} on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

    SciTech Connect

    Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh; Park, Sung Soo; Vinu, Ajayan; Ha, Chang-Sik

    2016-01-15

    A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+} adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.

  7. Anomalous self-reduction of layered double hydroxide (LDH): from α-Ni(OH)2 to hexagonal close packing (HCP) Ni/NiO by annealing without a reductant.

    PubMed

    Ge, X; Gu, C D; Wang, X L; Tu, J P

    2015-01-21

    The traditional concept that nickel layered double hydroxide (Ni LDH, also known as α-Ni(OH)2) converts to NiO after annealing has been taken without doubt and utilized to fabricate NiO for years. This work reports that an anomalous self-reduction phenomenon can occur for Ni LDH synthesized from an ionic liquid system.

  8. A new approach to reducing the flammability of layered double hydroxide (LDH)-based polymer composites: preparation and characterization of dye structure-intercalated LDH and its effect on the flammability of polypropylene-grafted maleic anhydride/d-LDH composites.

    PubMed

    Kang, Nian-Jun; Wang, De-Yi; Kutlu, Burak; Zhao, Peng-Cheng; Leuteritz, Andreas; Wagenknecht, Udo; Heinrich, Gert

    2013-09-25

    Dye structure-intercalated layered double hydroxide (d-LDH) was synthesized using a one-step method, and its intercalated behaviors have been characterized by Fourier transform infrared spectroscopy (FTIR), wide angle X-ray scattering (WAXS), scanning electron microscopy, thermogravimetric analysis (TGA), etc. As a novel functional potential fire-retarding nanofiller, it was used to prepare a polypropylene-grafted maleic anhydride (PP-g-MA)/d-LDH composite by refluxing the mixture of d-LDH and PP-g-MA in xylene, aiming to investigate its effect on the flammability of the PP-g-MA composite. The morphological properties, thermal stability, and flame retardant properties of the PP-g-MA/d-LDH composite were determined by FTIR, WAXS, transmission electron microscopy, TGA, and microscale combustion calorimetry. Compared with NO3-LDH (unmodified LDH) and LDH intercalated by sodium dodecylbenzenesulfonate (conventional organo-modified LDH), d-LDH can significantly decrease the heat release rate and the total heat release of the PP-g-MA composite, offering a new approach to imparting low flammability to LDH-based polymer composites.

  9. Solubility and release of fenbufen intercalated in Mg, Al and Mg, Al, Fe layered double hydroxides (LDH): The effect of Eudragit S 100 covering

    SciTech Connect

    Arco, M. del; Fernandez, A.; Martin, C.; Rives, V.

    2010-12-15

    Following different preparation routes, fenbufen has been intercalated in the interlayer space of layered double hydroxides with Mg{sup 2+} and Al{sup 3+} or Mg{sup 2+}, Al{sup 3+} and Fe{sup 3+} in the layers. Well crystallized samples were obtained in most of the cases (intercalation was not observed by reconstruction of the MgAlFe matrix), with layer heights ranging between 16.1 and 18.8 A. The presence of the LDH increases the solubility of fenbufen, especially when used as a matrix. The dissolution rate of the drug decreases when the drug is intercalated, and is even lower in those systems containing iron; release takes place through ionic exchange with phosphate anions from the solution. Preparation of microspheres with Eudragit S 100 leads to solids with an homogeneous, smooth surface with efficient covering of the LDH surface, as drug release was not observed at pH lower than 7. - Graphical abstract: LDHs containing Mg, Al, Fe increase fenbufen solubility, release takes place through ionic exchange with phosphate anions from the medium. Spherical solids with homogeneous, smooth surface are formed when using Eudragit S 100, efficiently covering the LDH surface. Display Omitted

  10. Fe(II) sorption on pyrophyllite: Effect of structural Fe(III) (impurity) in pyrophyllite on nature of layered double hydroxide (LDH) secondary mineral formation

    SciTech Connect

    Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.; Elzinga, Evert J.; Sparks, Donald L.

    2016-11-01

    Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96% N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.

  11. Novel synthesis of layered double hydroxides (LDHs) from zinc hydroxide

    NASA Astrophysics Data System (ADS)

    Meng, Zilin; Zhang, Yihe; Zhang, Qian; Chen, Xue; Liu, Leipeng; Komarneni, Sridhar; Lv, Fengzhu

    2017-02-01

    The most common synthesis methods for layered double hydroxides (LDHs) are co-precipitation and reconstruction, which can have some limitations for application. Here, we report a novel synthesis method for LDHs. We use zinc hydroxide as the precursor to synthesize LDHs phase through a simple transformation process of zinc hydroxide phase. For this transformation process, aluminum can enter into zinc hydroxide and replace zinc quickly to transform it into LDH by creating positive charges in the zinc hydroxide solid phase. The mechanism of LDH formation was through Al3+ reaction first with zinc hydroxide followed by recrystallization of the original structure of zinc hydroxide. Thus, the new process of LDH formation involves a reaction of Al to substitute for Zn and recrystallization leading to LDH and the final pH influences the crystallization of LDHs by this process. In addition, Cr3+ was employed as a trivalent cation for LDH formation to react with zinc hydroxide, which also led to LDH structure.

  12. Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

    NASA Technical Reports Server (NTRS)

    Boclair, J. W.; Braterman, P. S.

    1999-01-01

    Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

  13. Biological evaluation of layered double hydroxides as efficient drug vehicles.

    PubMed

    Li, Yan; Liu, Dan; Ai, Hanhua; Chang, Qing; Liu, Dandan; Xia, Ying; Liu, Shuwen; Peng, Nanfang; Xi, Zhuge; Yang, Xu

    2010-03-12

    Recently there has been a rapid expansion of the development of bioinorganic hybrid systems for safe drug delivery. Layered double hydroxides (LDH), a variety of available inorganic matrix, possess great promise for this purpose. In this study, an oxidative stress biomarker system, including measurement of reactive oxygen species, glutathione content, endogenous nitric oxide, carbonyl content in proteins, DNA strand breaks and DNA-protein crosslinks, was designed to evaluate the biocompatibility of different concentrations of nano-Zn/Al-LDH with a Hela cell line. The drug delivery activity of the LDH-folic-acid complex was also assessed. The resulting data clearly demonstrated that nano-LDH could be applied as a relatively safe drug vehicle with good delivery activity, but with the caveat that the effects of high dosages observed here should not be ignored when attempting to maximize therapeutic activity by increasing LDH concentration.

  14. Synthesis of layered double hydroxide nanosheets by coprecipitation using a T-type microchannel reactor

    SciTech Connect

    Pang, Xiujiang; Sun, Meiyu; Ma, Xiuming; Hou, Wanguo

    2014-02-15

    The synthesis of Mg{sub 2}Al–NO{sub 3} layered double hydroxide (LDH) nanosheets by coprecipitation using a T-type microchannel reactor is reported. Aqueous LDH nanosheet dispersions were obtained. The LDH nanosheets were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy and particle size analysis, and the transmittance and viscosity of LDH nanosheet dispersions were examined. The two-dimensional LDH nanosheets consisted of 1–2 brucite-like layers and were stable for ca. 16 h at room temperature. In addition, the co-assembly between LDH nanosheets and dodecyl sulfate (DS) anions was carried out, and a DS intercalated LDH nanohybrid was obtained. To the best of our knowledge, this is the first report of LDH nanosheets being directly prepared in bulk aqueous solution. This simple, cheap method can provide naked LDH nanosheets in high quantities, which can be used as building blocks for functional materials. - Graphical abstract: Layered double hydroxide (LDH) nanosheets were synthesized by coprecipitation using a T-type microchannel reactor, and could be used as basic building blocks for LDH-based functional materials. Display Omitted - Highlights: • LDH nanosheets were synthesized by coprecipitation using a T-type microchannel reactor. • Naked LDH nanosheets were dispersed in aqueous media. • LDH nanosheets can be used as building blocks for functional materials.

  15. Methotrexate intercalated ZnAl-layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Chakraborty, Manjusha; Dasgupta, Sudip; Soundrapandian, Chidambaram; Chakraborty, Jui; Ghosh, Swapankumar; Mitra, Manoj K.; Basu, Debabrata

    2011-09-01

    The anticancerous drug methotrexate (MTX) has been intercalated into an ZnAl-layered double hydroxide (LDH) using an anion exchange technique to produce LDH-MTX hybrids having particle sizes in the range of 100-300 nm. X-ray diffraction studies revealed increases in the basal spacings of ZnAl-LDH-MTX hybrid on MTX intercalation. This was corroborated by the transmission electron micrographs, which showed an increase in average interlayer spacing from 8.9 Å in pristine LDH to 21.3 Å in LDH-MTX hybrid. Thermogravimetric analyses showed an increase in the decomposition temperature for the MTX molecule in the LDH-MTX hybrid indicating enhanced thermal stability of the drug molecule in the LDH nanovehicle. The cumulative release profile of MTX from ZnAl-LDH-MTX hybrids in phosphate buffer saline (PBS) at pH 7.4 was successfully sustained for 48 h following Rigter-Peppas model release kinetics via diffusion.

  16. Layered double hydroxides: an attractive material for electrochemical biosensor design.

    PubMed

    Shan, Dan; Cosnier, Serge; Mousty, Christine

    2003-08-01

    Electrochemical biosensors for phenol determination were developed based on the immobilization of polyphenol oxidase (PPO) within two different clay matrixes, one anionic (layered double hydroxide, LDH) and the other cationic (Laponite). The biosensor based on the enzyme immobilized in [Zn-Al-Cl] LDH shows greater sensitivity (7807 mA M(-1) cm(-2)) and maximum current (492 microA cm(-2)). Biosensor characteristics, such as Michaelis-Menten constant, recycling constant, activation energy, and permeability highlight the advantages of LDH matrixes to immobilize PPO. It appears that LDH provides a favorable environment to PPO activity. The best PPO/[Zn-Al-Cl] configuration was used to determine five different phenol derivatives reaching extremely sensitive detection limits (< or = 1 nM).

  17. Hierarchical CoNi-Sulfide Nanosheet Arrays Derived from Layered Double Hydroxides toward Efficient Hydrazine Electrooxidation.

    PubMed

    Zhou, Lei; Shao, Mingfei; Zhang, Cong; Zhao, Jingwen; He, Shan; Rao, Deming; Wei, Min; Evans, David G; Duan, Xue

    2017-02-01

    A hierarchical CoNi-sulfide nanosheet array is fabricated via an in situ reduction of CoNi-layered double hydroxide (LDH) nanosheets, then a vulcanization process. The material inherits the morphology of the LDH precursor, consisting of well-distributed CoNi-alloy@CoNi-sulfide nanoparticles with a core-shell structure, and demonstrates promising performance toward hydrazine electrooxidation.

  18. Fluorescein dye intercalated layered double hydroxides for chemically stabilized photoluminescent indicators on inorganic surfaces.

    PubMed

    Lee, Jong Hyeon; Jung, Duk-Young; Kim, Eunchul; Ahn, Tae Kyu

    2014-06-14

    A new photoactive thin film of layered double hydroxide (LDH) nanocrystals containing fluorescein dyes (LDH-F) has been developed by self-assembly of the LDH nanocrystals and well-controlled intercalation of the dyes in organic media. XRD results and absorption spectra confirmed the highly oriented interlayer arrangement of the dianionic form of the fluorescein dyes in the LDH interlayers, in which the dye molecules were electrostatically immobilized between the positively charged LDH layers with a monolayer packing structure. An intensity weighted average PL lifetime was estimated to be 1.45 ns and fluorescence lifetime imaging microscopy revealed that the individual LDH nanocrystals on the LDH-F film had largely similar lifetimes, which were ascribed to the uniform loading of fluorescein dyes onto the LDH matrix without photoluminescence quenching.

  19. Hybrid and biohybrid layered double hydroxides for electrochemical analysis.

    PubMed

    Mousty, Christine; Prévot, Vanessa

    2013-04-01

    Layered double hydroxides (LDH) are lamellar materials that have been extensively used as electrode modifiers. Nanostructured organic-inorganic materials can be designed by intercalation of organic or metallic complexes within the interlayer space of these materials or by the formation of composite materials based on biopolymers (alginate or chitosan) or biomolecules, such as enzymes. These hybrid or biohybrid materials have interesting properties applicable in electroanalytical devices. From an exhaustive review of the literature, the relevance of these hybrid and biohybrid LDH materials as electrode materials for electrochemical detection of species with an environmental or health impact is evaluated. The analytical characteristics (sensitivity and detection limit) of LDH-based amperometric sensors or biosensors are scrutinized.

  20. A hybrid Mg-Al layered double hydroxide/graphene nanostructure obtained via hydrothermal synthesis

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaodong; Cao, Jian-Ping; Zhao, Jun; Hu, Guo-Hua; Dang, Zhi-Min

    2014-06-01

    A hybrid Mg-Al layered double hydroxide/graphene (LDH-GR) material nanostructure has been fabricated by employing the hydrothermal treatment at 140 °C for 10 h. Graphene oxide is simultaneously reduced to graphene during the hydrothermal treatment. The LDH and LDH-GR have high degree of crystallinity and assembled layer structure, which is attributed to electrostatic interaction mechanism. The obtained hybrid nanostructure materials can be used as flame retardant or conductor of electricity and heat due to the combination of different properties arising from graphene and LDH.

  1. Sugar-anionic clay composite materials: intercalation of pentoses in layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Aisawa, Sumio; Hirahara, Hidetoshi; Ishiyama, Kayoko; Ogasawara, Wataru; Umetsu, Yoshio; Narita, Eiichi

    2003-09-01

    The intercalation of non-ionized guest pentoses (ribose and 2-deoxyribose) into the Mg-Al and Zn-Al layered double hydroxides (LDHs) was carried out at 298 K by the calcination-rehydration reaction using the Mg-Al and Zn-Al oxide precursors calcined at 773 K. The resulting solid products reconstructed the LDH structure with incorporating pentoses, and the maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 20 times that by the Zn-Al oxide precursor. The ribose/Mg-Al LDH was observed to have the expanded LDH structure with a broad (003) spacing of 0.85 nm. As the thickness of the LDH hydroxide basal layer is 0.48 nm, the interlayer distance of the ribose/Mg-Al LDH is 0.37 nm. This value corresponds to molecular size of ribose in thickness (0.36 nm), supporting that ribose is horizontally oriented in the interlayer space of LDH. The maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 5 times that of 2-deoxyribose. Ribose is substituted only by the hydroxyl group at C-2 position for 2-deoxyribose. Therefore, the number of hydroxyl group of sugar is essentially important for the intercalation of sugar molecule into the LDH, suggesting that the intercalation behavior of sugar for the LDH was greatly influenced by hydrogen bond between hydroxyl group of the intercalated pentose and the LDH hydroxide basal layers.

  2. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

    PubMed

    Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

    2013-06-12

    Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

  3. [Sorption of nitrobenzene to anionic surfactant modified layered double hydroxides].

    PubMed

    Xia, Yan; Zhu, Run-Liang; Tao, Qi; Liu, Han-Yang

    2013-01-01

    Sodium dodecyl sulfate (SDS) modified MgAl layered double hydroxides (LDHs) were synthesized at different surfactant concentrations (0.5-2.0 TAEC) by the co-precipitation method. The LDH-DS samples obtained were characterized by powder X-ray diffraction and FT-IR spectroscopy. The results showed that SDS was successfully intercalated into the interlayer of the LDH, and the basal spacing was expanded from 0.80 nm to 3.98 nm. The intercalated SDS was considered consistent with a paraffin bilayers arrangement. The sorption of nitrobenzene on LDH-DS was examined, and the results showed that linear model could fit the sorption isotherms well (R2 > 0.99), which implied a partitioning sorption process. The sorption coefficient of nitrobenzene (K(d)) on LDH-DS was positively related to the DS - loading amount, but the organic carbon content normalized sorption coefficient of nitrobenzene (K(oc)) was shown to remain relatively constant. The sorption thermodynamics results showed that the sorption of nitrobenzene on LDH-DS was an endothermic process, and the increase of entropy was the driving force for the sorption process.

  4. Polymer Coated CaAl-Layered Double Hydroxide Nanomaterials for Potential Calcium Supplement

    PubMed Central

    Kim, Tae-Hyun; Lee, Jeong-A; Choi, Soo-Jin; Oh, Jae-Min

    2014-01-01

    We have successfully prepared layered double hydroxide (LDH) nanomaterials containing calcium and aluminum ions in the framework (CaAl-LDH). The surface of CaAl-LDH was coated with enteric polymer, Eudragit®L 100 in order to protect nanomaterials from fast dissolution under gastric condition of pH 1.2. The X-ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron and transmission electron microscopy revealed that the pristine LDH was well prepared having hydrocalumite structure, and that the polymer effectively coated the surface of LDH without disturbing structure. From thermal analysis, it was determined that only a small amount (less than 1%) of polymer was coated on the LDH surface. Metal dissolution from LDH nanomaterials was significantly reduced upon Eudragit®L 100 coating at pH 1.2, 6.8 and 7.4, which simulates gastric, enteric and plasma conditions, respectively, and the dissolution effect was the most suppressed at pH 1.2. The LDH nanomaterials did not exhibit any significant cytotoxicity up to 1000 μg/mL and intracellular calcium concentration significantly increased in LDH-treated human intestinal cells. Pharmacokinetic study demonstrated absorption efficiency of Eudragit®L 100 coated LDH following oral administration to rats. Moreover, the LDH nanomaterials did not cause acute toxic effect in vivo. All the results suggest the great potential of CaAl-LDH nanomaterials as a calcium supplement. PMID:25490138

  5. Polymer coated CaAl-layered double hydroxide nanomaterials for potential calcium supplement.

    PubMed

    Kim, Tae-Hyun; Lee, Jeong-A; Choi, Soo-Jin; Oh, Jae-Min

    2014-12-05

    We have successfully prepared layered double hydroxide (LDH) nanomaterials containing calcium and aluminum ions in the framework (CaAl-LDH). The surface of CaAl-LDH was coated with enteric polymer, Eudragit®L 100 in order to protect nanomaterials from fast dissolution under gastric condition of pH 1.2. The X-ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron and transmission electron microscopy revealed that the pristine LDH was well prepared having hydrocalumite structure, and that the polymer effectively coated the surface of LDH without disturbing structure. From thermal analysis, it was determined that only a small amount (less than 1%) of polymer was coated on the LDH surface. Metal dissolution from LDH nanomaterials was significantly reduced upon Eudragit®L 100 coating at pH 1.2, 6.8 and 7.4, which simulates gastric, enteric and plasma conditions, respectively, and the dissolution effect was the most suppressed at pH 1.2. The LDH nanomaterials did not exhibit any significant cytotoxicity up to 1000 μg/mL and intracellular calcium concentration significantly increased in LDH-treated human intestinal cells. Pharmacokinetic study demonstrated absorption efficiency of Eudragit®L 100 coated LDH following oral administration to rats. Moreover, the LDH nanomaterials did not cause acute toxic effect in vivo. All the results suggest the great potential of CaAl-LDH nanomaterials as a calcium supplement.

  6. Double-Shelled Nanocages with Cobalt Hydroxide Inner Shell and Layered Double Hydroxides Outer Shell as High-Efficiency Polysulfide Mediator for Lithium-Sulfur Batteries.

    PubMed

    Zhang, Jintao; Hu, Han; Li, Zhen; Lou, Xiong Wen David

    2016-03-14

    Lithium-sulfur (Li-S) batteries have been considered as a promising candidate for next-generation electrochemical energy-storage technologies because of their overwhelming advantages in energy density. Suppression of the polysulfide dissolution while maintaining a high sulfur utilization is the main challenge for Li-S batteries. Here, we have designed and synthesized double-shelled nanocages with two shells of cobalt hydroxide and layered double hydroxides (CH@LDH) as a conceptually new sulfur host for Li-S batteries. Specifically, the hollow CH@LDH polyhedra with complex shell structures not only maximize the advantages of hollow nanostructures for encapsulating a high content of sulfur (75 wt %), but also provide sufficient self-functionalized surfaces for chemically bonding with polysulfides to suppress their outward dissolution. When evaluated as cathode material for Li-S batteries, the CH@LDH/S composite shows a significantly improved electrochemical performance.

  7. Chemical modification of zinc hydroxide nitrate and Zn-Al-layered double hydroxide with dicarboxylic acids.

    PubMed

    Arizaga, Gregorio Guadalupe Carbajal; Mangrich, Antonio Salvio; da Costa Gardolinski, José Eduardo Ferreira; Wypych, Fernando

    2008-04-01

    A zinc hydroxide nitrate (ZHN), Zn5(OH)8(NO3)2.2H2O, and a layered double hydroxide (LDH), Zn/Al-NO3 were doped with 0.2 mol% of Cu2+ during alkaline chemical precipitation. Both compounds were intercalated with adipate ((-)OOC(CH2)4COO(-)), azelate ((-)OOC(CH2)7COO(-)), and benzoate (C6H5COO(-)) ions through ion exchange reactions. Solid state 13C nuclear magnetic resonance spectroscopy showed only one signal of carboxylic carbon for adipate and azelate intercalated into LDH, indicating that the carboxylic ends of both acids were equivalent, whereas the signal split when the intercalation was into the ZHN matrix. The electron paramagnetic resonance (EPR) spectrum of copper in octahedral cation sites of LDH layers showed a Hamiltonian parameter ratio g ||/A ||=170 cm and, after intercalation of adipate, the change was not significant: g ||/A ||=174 cm. This result indicates that the carboxylate ions did not coordinate with copper centers. Nonetheless, the intercalation of azelate increased the ratio to g ||/A ||=194 cm, similar to the spectra of ZHN modified with adipate, g ||/A ||=199 cm, and azelate, g ||/A ||=183 and 190 cm, which are associated with the coordination of copper by weak carboxylate anion ligands. Copper occupies octahedral or tetrahedral sites in ZHN layers, and the EPR spectra indicate that the dicarboxylate anions reacted preferentially with octahedral sites, whereas benzoate reacted with both sites.

  8. Cellulose supported layered double hydroxides for the adsorption of fluoride from aqueous solution.

    PubMed

    Mandal, S; Mayadevi, S

    2008-06-01

    Cellulose supported layered double hydroxides (CSLDHs) were synthesized and tested for adsorption of fluoride in aqueous medium. Three samples of cellulose supported LDHs were synthesized by varying the LDH loading on cellulose. The raw cellulose, unsupported LDH and cellulose supported LDHs were characterized by XRD, SEM and BET surface area. Batch adsorption as well as fixed-bed column experiments were performed for determining the fluoride adsorption characteristics of CSLDHs. The fluoride adsorption properties of CSLDHs were found to be superior to that of reported adsorbents, including activated alumina and carbon nanotubes. Defluoridation capacity of the CSLDHs was 2-4 times higher than that of unsupported LDH. The cellulose supported LDH, CSLDH-50, having an LDH loading of 27% showed maximum fluoride uptake capacity (5.29 mg g(-1) of CSLDH, 25.18 mg g(-1) of LDH) in fixed-bed column study.

  9. Layered Double Hydroxide-Based Nanocarriers for Drug Delivery

    PubMed Central

    Bi, Xue; Zhang, Hui; Dou, Liguang

    2014-01-01

    Biocompatible clay materials have attracted particular attention as the efficient drug delivery systems (DDS). In this article, we review developments in the use of layered double hydroxides (LDHs) for controlled drug release and delivery. We show how advances in the ability to synthesize intercalated structures have a significant influence on the development of new applications of these materials. We also show how modification and/or functionalization can lead to new biotechnological and biomedical applications. This review highlights the most recent progresses in research on LDH-based controlled drug delivery systems, focusing mainly on: (i) DDS with cardiovascular drugs as guests; (ii) DDS with anti-inflammatory drugs as guests; and (iii) DDS with anti-cancer drugs as guests. Finally, future prospects for LDH-based drug carriers are also discussed. PMID:24940733

  10. Structural characterisation of a layered double hydroxide nanosheet

    NASA Astrophysics Data System (ADS)

    Funnell, Nicholas P.; Wang, Qiang; Connor, Leigh; Tucker, Matthew G.; O'Hare, Dermot; Goodwin, Andrew L.

    2014-06-01

    We report the atomic-scale structure of a Zn2Al-borate layered double hydroxide (LDH) nanosheet, as determined by reverse Monte Carlo (RMC) modelling of X-ray total scattering data. This study involves the extension of the RMC method to enable structural refinement of two-dimensional nanomaterials. The refined LDH models show the intra-layer geometry in this highly-exfoliated phase to be consistent with that observed in crystalline analogues, with the reciprocal-space scattering data suggesting a disordered arrangement of the Zn2+ and Al3+ cations within the nanosheet. The approach we develop is generalisable and so offers a method of characterising the structures of arbitrary nanosheet phases, including systems that support complex forms of disorder within the nanosheets themselves.We report the atomic-scale structure of a Zn2Al-borate layered double hydroxide (LDH) nanosheet, as determined by reverse Monte Carlo (RMC) modelling of X-ray total scattering data. This study involves the extension of the RMC method to enable structural refinement of two-dimensional nanomaterials. The refined LDH models show the intra-layer geometry in this highly-exfoliated phase to be consistent with that observed in crystalline analogues, with the reciprocal-space scattering data suggesting a disordered arrangement of the Zn2+ and Al3+ cations within the nanosheet. The approach we develop is generalisable and so offers a method of characterising the structures of arbitrary nanosheet phases, including systems that support complex forms of disorder within the nanosheets themselves. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01265h

  11. Anion-exchange membranes derived from quaternized polysulfone and exfoliated layered double hydroxide for fuel cells

    NASA Astrophysics Data System (ADS)

    Liu, Wan; Liang, Na; Peng, Pai; Qu, Rong; Chen, Dongzhi; Zhang, Hongwei

    2017-02-01

    Layered double hydroxides (LDH) are prepared by controlling urea assisted homogeneous precipitation conditions. Morphology and crystallinity of LDHs are confirmed by X-ray diffraction and scanning electron microscope. After LDHs are incorporated into quaternized polysulfone membranes, transmission electron microscope is used to observe the exfoliated morphology of LDH sheets in the membranes. The properties of the nanocomposite membranes, including water uptake, swelling ratio, mechanical property and ionic conductivity are investigated. The nanocomposite membrane containing 5% LDH sheets shows more balanced performances, exhibiting an ionic conductivity of 2.36×10-2 S cm-1 at 60 °C.

  12. Complex formation with layered double hydroxides for the remediation of hygroscopicity.

    PubMed

    Hayashi, Aki; Kubota, Mai; Okamura, Miki; Nakayama, Hirokazu

    2015-01-01

    Layered double hydroxides (LDHs) have been used commercially as antacids, to stabilize drugs, to allow the controlled release of incorporated drugs, and to act as drug carriers to reduce drug accumulation within the body. Several types of LDH were investigated: nitrate type (LDH-NO3); chloride type (LDH-Cl); and carbonate type (LDH-CO3). Each type was added to an aqueous or methanol (MeOH) solution containing a drug (pravastatin or nateglinide). With pravastatin sodium, the interlayer distance expanded after reaction with LDH-NO3 and LDH-Cl in aqueous solution. In contrast, the interlayer distance of LDH-CO3 increased in methanol with nateglinide. Each drug was intercalated into the interlayer space of LDH by ion exchange. The hygroscopicity of the drug substances, complexes, and physical mixtures were determined at 70% relative humidity. Increases in weight (%) of the complexes were less than those of the physical mixtures, which demonstrates that hygroscopicity was reduced upon complexation with LDH due to the layer of LDH over the drugs.

  13. Tris(hydroxymethyl)aminomethane modified layered double hydroxides greatly facilitate polyoxometalate intercalation.

    PubMed

    Chen, Yang; Yan, Dongpeng; Song, Yu-Fei

    2014-10-21

    Polyoxometalate (POM) intercalation to layered double hydroxides (LDHs) has been greatly restricted by the geometry, charge and size of POMs. We report herein, for the first time, the intercalation of Na3[PW12O40]·15H2O into tris(hydroxymethyl)-aminomethane (Tris) modified layered double hydroxides (Tris-LDH-CO3) using an ion exchange method, resulting in the formation of novel intercalated Tris-LDH-PW12 under ambient conditions without the necessity of degassing CO2. Theoretical calculations show the decreased energy and the slightly distorted LDH layer after Tris modification, indicating that the Tris-modified LDH layers greatly facilitate the intercalation of PW12. Further application of Tris-LDH-PW12 for oxygenation of sulfides shows highly efficient and selective catalytic activities under mild conditions. The Tris-LDH-PW12 can be easily recovered and reused for more than 10 times without any obvious decrease of reactivity. This opens a completely new pathway for engineering POM-LDH advanced functional materials.

  14. APPLICATIONS OF LAYERED DOUBLE HYDROXIDES IN REMOVING OXYANIONS FROM OIL REFINING AND COAL MINING WASTEWATER

    SciTech Connect

    Song Jin; Paul Fallgren

    2006-03-01

    Western Research Institute (WRI), in conjunction with the U.S. Department of Energy (DOE), conducted a study of using the layered double hydroxides (LDH) as filter material to remove microorganisms, large biological molecules, certain anions and toxic oxyanions from various waste streams, including wastewater from refineries. Results demonstrate that LDH has a high adsorbing capability to those compounds with negative surface charge. Constituents studied include model bacteria, viruses, arsenic, selenium, vanadium, diesel range hydrocarbons, methyl tert-butyl ether (MTBE), mixed petroleum constituents, humic materials and anions. This project also attempted to modify the physical structure of LDH for the application as a filtration material. Flow characterizations of the modified LDH materials were also investigated. Results to date indicate that LDH is a cost-effective new material to be used for wastewater treatment, especially for the treatment of anions and oxyanions.

  15. Antibacterial carboxymethyl cellulose/Ag nanocomposite hydrogels cross-linked with layered double hydroxides.

    PubMed

    Yadollahi, Mehdi; Namazi, Hassan; Aghazadeh, Mohammad

    2015-08-01

    This paper deals with the preparation of antibacterial nanocomposite hydrogels through the combination of carboxy methyl cellulose (CMC), layered double hydroxides (LDH), and silver nanoparticles (AgNPs). CMC-LDH hydrogels were prepared by intercalating CMC into different LDHs. Then, Ag/CMC-LDH nanocomposite hydrogels were prepared through in situ formation of AgNPs within the CMC-LDHs. XRD analysis confirmed the intercalating CMC into the LDH sheets and formation of intercalated structures, as well as formation of AgNPs within the CMC-LDHs. SEM and TEM micrographs indicated well distribution of AgNPs within the Ag/CMC-LDHs. The prepared hydrogels showed a pH sensitive swelling behavior. The Ag/CMC-LDH nanocomposite hydrogels have rather higher swelling in different aqueous solutions in comparison with CMC-LDHs. The antibacterial activity of CMC-LDHs increased considerably after formation of AgNPs and was stable for more than one month.

  16. Bionanocomposites based on layered double hydroxides as drug delivery systems

    NASA Astrophysics Data System (ADS)

    Aranda, Pilar; Alcântara, Ana C. S.; Ribeiro, Ligia N. M.; Darder, Margarita; Ruiz-Hitzky, Eduardo

    2012-10-01

    The present work introduces new biohybrid materials involving layered double hydroxides (LDH) and biopolymers to produce bionanocomposites, able to act as effective drug delivery systems (DDS). Ibuprofen (IBU) and 5-aminosalicylic acid (5-ASA) have been chosen as model drugs, being intercalated in a Mg-Al LDH matrix. On the one side, the LDHIBU intercalation compound prepared by ion-exchange reaction was blended with the biopolymers zein, a highly hydrophobic protein, and alginate, a polysaccharide widely applied for encapsulating drugs. On the other side, the LDH- 5-ASA intercalation compound prepared by co-precipitation was assembled to the polysaccharides chitosan and pectin, which show mucoadhesive properties and resistance to acid pH values, respectively. Characterization of the intercalation compounds and the resulting bionanocomposites was carried out by means of different experimental techniques: X-ray diffraction, infrared spectroscopy, chemical and thermal analysis, as well as optical and scanning electron microscopies. Data on the swelling behavior and drug release under different pH conditions are also reported.

  17. Layered double hydroxide-oxidized carbon nanotube hybrids as highly efficient flame retardant nanofillers for polypropylene.

    PubMed

    Gao, Yanshan; Zhang, Yu; Williams, Gareth R; O'Hare, Dermot; Wang, Qiang

    2016-10-18

    Aqueous miscible organic layered double hydroxides (AMO-LDHs) can act as organophilic inorganic flame retardant nanofillers for unmodified non-polar polymers. In this contribution, AMO [Mg3Al(OH)8](CO3)0.5·yH2O LDH-oxidized carbon nanotube (AMO-LDH-OCNT) hybrids are shown to perform better than the equivalent pure AMO-LDH. A synergistic effect between the AMO-LDH and OCNT was observed; this endows the hybrid material with enhanced flame retardancy, thermal stability, and mechanical properties. The thermal stability of polypropylene (PP) was significantly enhanced by adding AMO-LDH-OCNT hybrids. For PP mixed with AMO-LDH-OCNT hybrids to produce a composite with 10 wt% LDH and 2 wt% OCNT, the 50% weight loss temperature was increased by 43 °C. Further, a system with 10 wt% of AMO-LDH and 1 wt% OCNT showed a peak heat release rate (PHRR) reduction of 40%, greater than the PHRR reduction with PP/20 wt% AMO-LDH (31%). The degree of dispersion (mixability) between AMO-LDH and OCNT has a significant effect on the flame retardant performance of the hybrids. In addition, the incorporation of AMO-LDH-OCNT hybrids led to better mechanical properties, such as higher tensile strength (27.5 MPa) and elongation at break (17.9%), than those composites containing only AMO-LDH (25.6 MPa and 7.5%, respectively).

  18. Cadmium-Aluminum Layered Double Hydroxide Microspheres for Photocatalytic CO2 Reduction.

    PubMed

    Saliba, Daniel; Ezzeddine, Alaa; Sougrat, Rachid; Khashab, Niveen M; Hmadeh, Mohamad; Al-Ghoul, Mazen

    2016-04-21

    We report the synthesis of cadmium-aluminum layered double hydroxide (CdAl LDH) using the reaction-diffusion framework. As the hydroxide anions diffuse into an agar gel matrix containing the mixture of aluminum and cadmium salts at a given ratio, they react to give the LDH. The LDH self-assembles inside the pores of the gel matrix into a unique spherical-porous shaped microstructure. The internal and external morphologies of the particles are studied by electron microscopy and tomography revealing interconnected channels and a high surface area. This material is shown to exhibit a promising performance in the photoreduction of carbon dioxide using solar light. Moreover, the palladium-decorated version shows a significant improvement in its reduction potential at room temperature.

  19. Nitrogen-enriched, double-shelled carbon/layered double hydroxide hollow microspheres for excellent electrochemical performance

    NASA Astrophysics Data System (ADS)

    Xu, Jie; He, Fei; Gai, Shili; Zhang, Shenghuan; Li, Lei; Yang, Piaoping

    2014-08-01

    A unique, double-shelled, hollow, carbon-based composite with enriched nitrogen has been prepared through a facile and versatile synthetic strategy. The hierarchical composite employs the nitrogen-enriched carbon hollow sphere as an interior shell and intercrossed Ni/Al layered double hydroxide (LDH) nanosheets as an exterior shell. The obtained N-C@LDH hollow microspheres (HMS) have high nitrogen enrichment, large specific surface area (337 m2 g-1), and uniform and open mesoporous structure. Taking advantage of these characteristics, the composite exhibits obviously superior capacitive behavior, including high specific capacitance, excellent rate capability and good cycling stability, compared with nitrogen-free carbon@LDH composite and hollow LDH without carbon shell. The composite displays high specific capacitance of 1711.51 F g-1 at a current density of 1 A g-1. In particular, the high specific capacitance can be kept to 997.3 F g-1 at a high current density of 10 A g-1, which still retains 94.97% of the initial specific capacitance after 500 cycles at this high current density. This N-enriched, hollow carbon/LDH composite can be expected to be a promising electrode material for electrochemical capacitors due to its high electrochemical performance.A unique, double-shelled, hollow, carbon-based composite with enriched nitrogen has been prepared through a facile and versatile synthetic strategy. The hierarchical composite employs the nitrogen-enriched carbon hollow sphere as an interior shell and intercrossed Ni/Al layered double hydroxide (LDH) nanosheets as an exterior shell. The obtained N-C@LDH hollow microspheres (HMS) have high nitrogen enrichment, large specific surface area (337 m2 g-1), and uniform and open mesoporous structure. Taking advantage of these characteristics, the composite exhibits obviously superior capacitive behavior, including high specific capacitance, excellent rate capability and good cycling stability, compared with nitrogen

  20. Micrometer-Thick Graphene Oxide-Layered Double Hydroxide Nacre-Inspired Coatings and Their Properties.

    PubMed

    Yan, You-Xian; Yao, Hong-Bin; Mao, Li-Bo; Asiri, Abdullah M; Alamry, Khalid A; Marwani, Hadi M; Yu, Shu-Hong

    2016-02-10

    Robust, functional, and flame retardant coatings are attractive in various fields such as building construction, food packaging, electronics encapsulation, and so on. Here, strong, colorful, and fire-retardant micrometer-thick hybrid coatings are reported, which can be constructed via an enhanced layer-by-layer assembly of graphene oxide (GO) nanosheets and layered double hydroxide (LDH) nanoplatelets. The fabricated GO-LDH hybrid coatings show uniform nacre-like layered structures that endow them good mechanic properties with Young's modulus of ≈ 18 GPa and hardness of ≈ 0.68 GPa. In addition, the GO-LDH hybrid coatings exhibit nacre-like iridescence and attractive flame retardancy as well due to their well-defined 2D microstructures. This kind of nacre-inspired GO-LDH hybrid thick coatings will be applied in various fields in future due to their high strength and multifunctionalities.

  1. Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

    PubMed

    Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

    2016-05-24

    Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

  2. Nanohybrids of Mg/Al layered double hydroxide and long-chain (C18) unsaturated fatty acid anions: Structure and sorptive properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Long-chain (C18) unsaturated fatty acid anions, elaidate (ELA), oleate (OLE), linoleate (LINO), and linolenate (LINOLEN), were intercalated into Mg/Al (3:1) layered double hydroxide (LDH) and the resultant organo-LDH nanohybrid materials were characterized and subsequently evaluated as sorbents of s...

  3. Cation ordering and superstructures in natural layered double hydroxides.

    PubMed

    Krivovichev, Sergey V; Yakovenchuk, Victor N; Zolotarev, Andrey A; Ivanyuk, Gregory N; Pakhomovsky, Yakov A

    2010-01-01

    Layered double hydroxides (LDHs) constitute an important group of materials with many applications ranging from catalysis and absorption to carriers for drug delivery, DNA intercalation and carbon dioxide sequestration. The structures of LDHs are based upon double brucite-like hydroxide layers [M(2+)(n)M(3+)(m)(OH)(2(m+n)](m+), where M(2+) = Mg(2+), Fe(2+), Mn(2+), Zn(2+), etc.; M(3+) = Al(3+), Fe(3+), Cr(3+), Mn(3+), etc. Structural features of LDHs such as cation ordering, charge distribution and polytypism have an immediate influence upon their properties. However, all the structural studies on synthetic LDHs deal with powder samples that prevent elucidation of such fine details of structure architecture as formation of superstructures due to cation ordering. In contrast to synthetic materials, natural LDHs are known to form single crystals accessible to single-crystal X-ray diffraction analysis, which provides a unique possibility to investigate 3D cation ordering in LDHs that results in formation of complex superstructures, where 2D cation order is combined with a specific order of layer stacking (polytypism). Therefore LDH minerals provide an indispensable source of structural information for modeling of structures and processes happening in LDHs at the molecular and nanoscale levels.

  4. Enhanced thermal- and photo-stability of acid yellow 17 by incorporation into layered double hydroxides

    SciTech Connect

    Wang Qian; Feng Yongjun; Feng Junting; Li Dianqing

    2011-06-15

    2,5-dichloro-4-(5-hydroxy-3-methyl-4-(sulphophenylazo) pyrazol-1-yl) benzenesulphonate (DHSB) anions, namely acid yellow 17 anions, have been successfully intercalated into Zn-Al layered double hydroxides (LDH) to produce a novel organic-inorganic pigment by a simple method involving separate nucleation and aging steps (SNAS), and the dye-intercalated LDH was analyzed by various techniques, e.g., XRD, SEM, FT-IR, TG-DTA and ICP. The d-spacing of the prepared LDH is 2.09 nm. Furthermore, the incorporation of the DHSB aims to enhance the thermal- and photo-stability of the guest dye molecule, for example, the less color change after accelerated thermal- and photo-aging test. - Graphical abstract: Acid yellow anions were successfully assembled into ZnAl layered double hydroxides (LDH) to produce a novel organic-inorganic composite pigment by a simple method involving separate nucleation and aging steps (SNAS). Highlights: > Acid yellow 17 was directly intercalated into ZnAl-LDH to form a novel pigment. > The pigment was prepared by a method involving separate nucleation and aging steps. > The intercalation of dye anions enhances its thermal- and photo-stability.

  5. Synthesis of ACECLOFENAC/HYDROXYPROPYL-β-CYCLODEXTRIN Intercalated Layered Double Hydroxides and Controlled Release Properties

    NASA Astrophysics Data System (ADS)

    Li, Shifeng; Shen, Yanming; Liu, Dongbin; Fan, Lihui; Wu, Keke; Xiao, Min

    2013-04-01

    Aceclofenac (AC)/hydroxypropyl-β-cyclodextrin (HP-β-CD) complex intercalated layered double hydroxides (LDHs) have been synthesized by reconstruction method. X-ray diffraction, Fourier transform infrared and thermal gravimetric analyses indicated a successful intercalation of AC/HP-β-CD complex into the LDHs gallery. The AC release properties were also studied in different pH values buffer solution. The results indicate that the AC/HP-β-CD intercalated LDH has a potential application in drug delivery agent.

  6. Calcined Mg-Fe layered double hydroxide as an absorber for the removal of methyl orange

    NASA Astrophysics Data System (ADS)

    Peng, Chao; Dai, Jing; Yu, Jianying; Yin, Jian

    2015-05-01

    In this work, methyl orange (MO) was effectively removed from aqueous solution with the calcined product of hydrothermal synthesized Mg/Fe layered double hydroxide (Mg/Fe-LDH). The structure, composition, morphology and textural properties of the Mg/Fe-LDH before and after adsorption were characterized by X-ray diffraction, Fourier transformation infrared spectroscopy, transmission electron microscopy, nitrogen adsorption apparatus and X-ray photoelectron spectroscopy. It was confirmed that MO had been absorbed by calcined Mg/Fe-LDH which had strong interactions with MO. The adsorption of MO onto the Mg/Fe-LDH was systematically investigated by batch tests. The adsorption capacity of the Mg/Fe-LDH toward MO was found to be 194.9 mg • g-1. Adsorption kinetics and isotherm studies revealed that the adsorption of MO onto Mg/Fe-LDH was a spontaneous and endothermic process. These results indicate that Mg/Fe-LDH is a promising material for the removal of MO.

  7. Calcined Mg-Fe layered double hydroxide as an absorber for the removal of methyl orange

    SciTech Connect

    Peng, Chao; Dai, Jing; Yu, Jianying; Yin, Jian

    2015-05-15

    In this work, methyl orange (MO) was effectively removed from aqueous solution with the calcined product of hydrothermal synthesized Mg/Fe layered double hydroxide (Mg/Fe-LDH). The structure, composition, morphology and textural properties of the Mg/Fe-LDH before and after adsorption were characterized by X-ray diffraction, Fourier transformation infrared spectroscopy, transmission electron microscopy, nitrogen adsorption apparatus and X-ray photoelectron spectroscopy. It was confirmed that MO had been absorbed by calcined Mg/Fe-LDH which had strong interactions with MO. The adsorption of MO onto the Mg/Fe-LDH was systematically investigated by batch tests. The adsorption capacity of the Mg/Fe-LDH toward MO was found to be 194.9 mg • g{sup −1}. Adsorption kinetics and isotherm studies revealed that the adsorption of MO onto Mg/Fe-LDH was a spontaneous and endothermic process. These results indicate that Mg/Fe-LDH is a promising material for the removal of MO.

  8. Recyclable Mg-Al layered double hydroxides for fluoride removal: Kinetic and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-12-30

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg-Al LDH) and Cl(-) (Cl · Mg-Al LDH) were found to adsorb fluoride from aqueous solutions. Fluoride is removed by anion exchange in solution with NO3(-) and Cl(-) intercalated in the LDH interlayer. In both cases, the residual F concentration is lower than the effluent standards for F in Japan (8 mg/L). The rate-determining step in the removal of F using NO3 · Mg-Al and Cl · Mg-Al LDH is chemical adsorption involving F(-) anion exchange with intercalated NO3(-) and Cl(-) ions. The removal of F is described by pseudo-second-order reaction kinetics, with Langmuir-type adsorption. The values obtained for the maximum adsorption and the equilibrium adsorption constant are respectively 3.3 mmol g(-1) and 2.8 with NO3 · Mg-Al LDH, and 3.2 mmol g(-1) and 1.5 with Cl · Mg-Al LDH. The F in the F · Mg-Al LDH produced in these reactions was found to exchange with NO3(-) and Cl(-) ions in solution. The regenerated NO3 · Mg-Al and Cl · Mg-Al LDHs thus obtained can be used once more to capture aqueous F. This suggests that NO3 · Mg-Al and Cl · Mg-Al LDHs can be recycled and used repeatedly for F removal.

  9. Zn-Al-NO(3)-layered double hydroxides with intercalated diclofenac for ocular delivery.

    PubMed

    Cao, Feng; Wang, Yanjun; Ping, Qineng; Liao, Zhenggen

    2011-02-14

    This study was aimed to evaluate the potential use of a drug delivery system, drug-layered double hydroxide (LDH) nanocomposites for ocular delivery. Diclofenac was successfully intercalated into Zn-Al-NO(3)-LDH by coprecipitation method. The nanocomposites were characterized by particle size, elemental chemical analysis, thermogravimetric analysis, etc. A tilt bilayer of diclofenac molecules formed in the interlayer with the gallery height of 1.868 nm. In vivo precorneal retention studies were conducted with diclofenac sodium (DS) saline, diclofenac-LDH nanocomposite dispersion, 2% polyvinylpyrrolidone (PVP) K30-diclofenac-LDH nanohybrid dispersion and 10% PVP K30-diclofenac-LDH nanohybrid dispersion, separately. Compared with DS saline, all the dispersions have extended the detectable time of DS from 3h to 6h; C(max) and AUC(0-t) of diclofenac-LDH nanocomposite dispersion showed 3.1-fold and 4.0-fold increase, respectively; C(max) and AUC(0-t) of 2% PVP K30-LDH nanohybrid dispersion were about 5.3-fold and 6.0-fold enhancement, respectively. Results of the Draize test showed that no eye irritation was demonstrated in rabbits after single and repeated administration. These results suggest that this novel ocular drug delivery system appears to offer promise as a means to improving the bioavailability of drugs after ophthalmic applications.

  10. Crosslinking to enhance colloidal stability and redispersity of layered double hydroxide nanoparticles.

    PubMed

    Zuo, Huali; Gu, Zi; Cooper, Helen; Xu, Zhi Ping

    2015-12-01

    This article introduces a strategy for stabilizing and redispersing layered double hydroxide (LDH) nanoparticles by crosslinking bovine serum albumin (BSA) coated onto the surface. The strategy involves optimization of the amount of the crosslinking agent glutaraldehyde (GTA) to achieve minimal aggregation and ready redispersion. LDH nanoparticles were prepared by co-precipitation and hydrothermal treatment, with subsequent BSA coating at the BSA/LDH mass ratio of 5:2. BSA coated onto LDH nanoparticles was crosslinked with different amounts of GTA. Aggregation studies using dilution assays, dynamic light scattering, and zeta potential analysis indicated that severe aggregation at lower LDH nanoparticle concentrations can be prevented by proper crosslinking of BSA with GTA. The GTA-crosslinked BSA-coated nanoparticles showed excellent redispersity compared to the non-crosslinked nanoparticles. In vitro cytotoxicity and cell uptake were found to be minimally affected by GTA-crosslinking. The new strategy therefore provides a much more effective method for the prevention of LDH nanoparticle aggregation and improved LDH nanoparticle redispersion for use in a wide variety of bio-applications in vitro and in vivo.

  11. Novel HCN sorbents based on layered double hydroxides: sorption mechanism and performance.

    PubMed

    Zhao, Qian; Tian, Senlin; Yan, Linxia; Zhang, Qiulin; Ning, Ping

    2015-03-21

    Layered double hydroxides (LDHs) and layered double oxides (LDOs) have been prepared and used as sorbents for hydrogen cyanide (HCN). Based on results from sorbent optimization experiments, the optimal performance for HCN removal was found in Ni-Al LDH. As evidenced by fixed-bed sorption studies, the Ni-Al LDO with the greatest surface area showed better performance and outperformed products calcined at 200, 400, or 500 °C, whereas, the Ni-Al LDH showed a more twofold higher sorption capacity than the Ni-Al LDO. Investigation of the mechanisms between HCN and sorbents reveals that the HCN removal by the Ni-Al LDH and Ni-Al LDO leads to the formation of the complex anion, [Ni(CN)4](2-). Nevertheless, the [Ni(CN)4](2-) can enter interlayer region of the Ni-Al LDH due to its anion exchangeability, which endows this LDH with more binding sites, not only on its external surfaces, but also on its internal surfaces located in the interlayer region. In contrast, [Ni(CN)4](2-) were only adsorbed on the external surface of the Ni-Al LDO. As a result, the sorption capacity of the Ni-Al LDH for HCN is twice as high as that of the Ni-Al LDO, which is at 21.55 mg/g.

  12. Superior coagulation of graphene oxides on nanoscale layered double hydroxides and layered double oxides.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Chen, Zhongshan; Yao, Wen; Ai, Yuejie; Liu, Yunhai; Hayat, Tasawar; Alsaedi, Ahmed; Alharbi, Njud S; Wang, Xiangke

    2016-12-01

    With the development and application of graphene oxides (GO), the potential toxicity and environmental behavior of GO has become one of the most forefront environmental problems. Herein, a novel nanoscale layered double hydroxides (glycerinum-modified nanocrystallined Mg/Al layered double hydroxides, LDH-Gl), layered double oxides (calcined LDH-Gl, LDO-Gl) and metallic oxide (TiO2) were synthesized and applied as superior coagulants for the efficient removal of GO from aqueous solutions. Coagulation of GO as a function of coagulant contents, pH, ionic strength, GO contents, temperature and co-existing ions were studied and compared, and the results showed that the maximum coagulation capacities of GO were LDO-Gl (448.3 mg g(-1)) > TiO2 (365.7 mg g(-1)) > LDH-Gl (339.1 mg g(-1)) at pH 5.5, which were significantly higher than those of bentonite, Al2O3, CaCl2 or other natural materials due to their stronger reaction active and interfacial effect. The presence of SO3(2-) and HCO3(-) inhibited the coagulation of GO on LDH-Gl and LDO-Gl significantly, while other cations (K(+), Mg(2+), Ca(2+), Ni(2+), Al(3+)) or anion (Cl(-)) had slightly effect on GO coagulation. The interaction mechanism of GO coagulation on LDO-Gl and TiO2 might due to the electrostatic interactions and strong surface complexation, while the main driving force of GO coagulation on LDH-Gl might be attributed to electrostatic interaction and hydrogen bond, which were further evidenced by TEM, SEM, FT-IR and XRD analysis. The results of natural environmental simulation showed that LDO-Gl, TiO2 or other kinds of natural metallic oxides could be superior coagulants for the efficient elimination of GO or other toxic nanomaterials from aqueous solutions in real environmental pollution cleanup.

  13. Highly stable layered double hydroxide colloids: a direct aqueous synthesis route from hybrid polyion complex micelles.

    PubMed

    Layrac, Géraldine; Destarac, Mathias; Gérardin, Corine; Tichit, Didier

    2014-08-19

    Aqueous suspensions of highly stable Mg/Al layered double hydroxide (LDH) nanoparticles were obtained via a direct and fully colloidal route using asymmetric poly(acrylic acid)-b-poly(acrylamide) (PAA-b-PAM) double hydrophilic block copolymers (DHBCs) as growth and stabilizing agents. We showed that hybrid polyion complex (HPIC) micelles constituted of almost only Al(3+) were first formed when mixing solutions of Mg(2+) and Al(3+) cations and PAA3000-b-PAM10000 due to the preferential complexation of the trivalent cations. Then mineralization performed by progressive hydroxylation with NaOH transformed the simple DHBC/Al(3+) HPIC micelles into DHBC/aluminum hydroxide colloids, in which Mg(2+) ions were progressively introduced upon further hydroxylation leading to the Mg-Al LDH phase. The whole process of LDH formation occurred then within the confined environment of the aqueous complex colloids. The hydrodynamic diameter of the DHBC/LDH colloids could be controlled: it decreased from 530 nm down to 60 nm when the metal complexing ratio R (R = AA/(Mg + Al)) increased from 0.27 to 1. This was accompanied by a decrease of the average size of individual LDH particles as R increased (for example from 35 nm at R = 0.27 down to 17 nm at R = 0.33), together with a progressive favored intercalation of polyacrylate rather than chloride ions in the interlayer space of the LDH phase. The DHBC/LDH colloids have interesting properties for biomedical applications, that is, high colloidal stability as a function of time, stability in phosphate buffered saline solution, as well as the required size distribution for sterilization by filtration. Therefore, they could be used as colloidal drug delivery systems, especially for hydrosoluble negatively charged drugs.

  14. Structural characterization and electrocatalytic application of hemoglobin immobilized in layered double hydroxides modified with hydroxyl functionalized ionic liquid.

    PubMed

    Zhan, Tianrong; Yang, Qi; Zhang, Yumei; Wang, Xinjun; Xu, Jie; Hou, Wanguo

    2014-11-01

    Hemoglobin (Hb) was immobilized in Zn2Al-Layered Double Hydroxides (LDH) modified with Hydroxyl Functionalized Ionic Liquid (HFIL) through adsorption and coprecipitation method, respectively. Adsorption experiments showed that the presence of HFIL could enhance the maximum protein loading. However, the Hb loading through coprecipitation technique was far higher than that for adsorption. The role of HFIL on the interaction between Hb and LDH was investigated by XRD, FTIR, UV-vis and fluorescence spectroscopies. Although the quaternary structure of Hb entrapped in HFIL-LDH through coprecipitation technique (denoted as HFIL-LDH-Hbcop) might be altered slightly more than that in LDH (LDH-Hbcop), its secondary structure and redox-active heme groups kept intact. Morphologies of LDH-Hbcop and HFIL-LDH-Hbcop biohybrids were analyzed through SEM and TEM images. The direct electrochemistry of the immobilized Hb indicated that the coprecipitation bioelectrode performed better than that of the corresponding adsorption one. Regardless of adsorption and coprecipitation, the introduction of HFIL could distinctly promote the electron transport. Among all bioelectrodes, HFIL-LDH-Hbcop/GCE displayed the best electrocatalytic activity for H2O2 determination with a larger electroactive Hb percentage (6.76%), higher sensitivity (40.63A/Mcm(2)) and lower detection limit (0.0054μmol/L). So HFIL-LDH could effectively immobilize enzymes via coprecipitation technique, which had potential applications in the fabrication of electrochemical biosensors.

  15. Layered double hydroxide stability. 2. Formation of Cr(III)-containing layered double hydroxides directly from solution

    NASA Technical Reports Server (NTRS)

    Boclair, J. W.; Braterman, P. S.; Jiang, J.; Lou, S.; Yarberry, F.

    1999-01-01

    Solutions containing divalent metal [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+] chlorides and CrCl3 6H2O were titrated with NaOH to yield, for M(II) = Zn, Co, and Ni, hydrotalcite-like layered double hydroxides (LDHs), [[M(II)]1-z[Cr(III)]z(OH)2][Cl]z yH2O, in a single step, without intermediate formation of chromium hydroxide. Analysis of the resultant titration curves yields solubility constants for these compounds. These are in the order Zn < Ni approximately Co, with a clear preference for formation of the phase with z = 1/3. With Mg2+ as chloride, titration gives a mixture of Cr(OH)3 and Mg(OH)2, but the metal sulfates give Mg2Cr(OH)6 1/2(SO4) by a two-step process. Titrimetric and spectroscopic evidence suggests short-range cation order in the one-step LDH systems.

  16. Tungstocobaltate-pillared layered double hydroxides: Preparation, characterization, magnetic and catalytic properties

    SciTech Connect

    Wei Xiaocui; Fu Youzhi; Xu Lin Li Fengyan; Bi Bo; Liu Xizheng

    2008-06-15

    A new polyoxometalate anion-pillared layered double hydroxide (LDH) was prepared by aqueous ion exchange of a Mg-Al LDH precursor in nitrate form with the tungstocobaltate anions [CoW{sub 12}O{sub 40}]{sup 5-}. The physicochemical properties of the product were characterized by the methods of powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. It was confirmed that [CoW{sub 12}O{sub 40}]{sup 5-} was intercalated between the brucite-type layers of the LDHs without a change in the structure. Magnetic measurement shows the occurrence of antiferromagnetic interactions between the magnetic centers. The investigation of catalytic performance for this sample exhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide. - Graphical abstract: A tungstocobaltate anion [CoW{sub 12}O{sub 40}]{sup 5-} pillared layered double hydroxide (LDH) was prepared by aqueous ion exchange with a Mg-Al LDH precursor in nitrate form, demonstrating that [CoW{sub 12}O{sub 40}]{sup 5-} was intercalated between the brucite-type layers of the LDHs without change in structure. Magnetic measurement shows the occurrence of antiferromagnetic interactions between the magnetic centers. The investigation of catalytic performance for this sample exhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide.

  17. X-ray Diffraction Analysis on Post Treatment of Ca-Mg-Al-Layered Double Hydroxide Slurry

    NASA Astrophysics Data System (ADS)

    Heraldy, E.; Nugrahaningtyas, K. D.; Heriyanto

    2017-02-01

    This research objectives to study post treatment on Ca-Mg-Al-Layered Double Hydroxide (Ca-Mg-Al-LDH) slurry which was prepared from brine water by cooling treatment. The cooling rate was varied from 1 to 3 °C/min by using stirring and without stirring, and the cooling time was done at 0, 30 minutes and 24 hours. The quantitative X-ray diffraction (QXRD) was employed on Ca-Mg-Al-LDH using Le Bail refinement method. The refinement results found another Mg-Al-LDH and Ca-Al-LDH phases, such as Mg(OH)2, Al(OH)3 and CaCO3. The highest phase composition on material Ca-Mg-Al-LDH using Le Bail refinement was showed by Al(OH)3.

  18. Synthesis and characterization of Cd-Cr and Zn-Cd-Cr layered double hydroxides intercalated with dodecyl sulfate

    SciTech Connect

    Guo Ying; Zhang He; Zhao Lan; Li Guodong; Chen Jiesheng . E-mail: chemcj@mail.jlu.edu.cn; Xu Lin

    2005-06-15

    Cd-Cr and Zn-Cd-Cr layered double hydroxides (CdCr-LDH and ZnCdCr-LDH) containing alkyl sulfate as the interlamellar anion have been prepared through a coprecipitation technique. The resulting compounds were characterized using X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Magnetic property measurements indicate that antiferromagnetic interactions occur between the chromium ions in the two compounds at low temperatures. The introduction of zinc influences the ligand field of Cr{sup III} and the Cr{sup III}-Cr{sup III} interactions in the LDH compound. It is found that both CdCr-LDH and ZnCdCr-LDH can be delaminated by dispersion in formamide, leading to translucent and stable colloidal solutions.

  19. Aerosol-assisted self-assembly of hybrid Layered Double Hydroxide particles into spherical architectures.

    PubMed

    Prevot, Vanessa; Szczepaniak, Claire; Jaber, Maguy

    2011-04-15

    Acetate intercalated NiAl-Layered Double Hydroxide nanoparticles were prepared by polyol process and further used as building blocks to form hybrid LDH spheres by a spray drying technique. The spherical aggregated LDH particles display a polydispersed size with a diameter ranging from 47 nm to 2 μm. The analysis of the thermal behavior evidenced that the spherical form was maintained upon calcination up to 1100°C, giving rise to derived mixed oxide (NiO+NiAl(2)O(4)) nanospheres. Interestingly, the spherical morphology of the LDH materials was also retained during anion exchange process. The replacement of the intercalated acetate anion by of a voluminous anion such as dodecylsulfate induces an increase of the nanosphere mean diameter of 65%. The different materials were deeply characterized using X-ray diffraction, FTIR spectroscopy, scanning and transmission electron microscopies, dynamic light scattering, thermal analysis and nitrogen sorption.

  20. Large Scale Synthesis of NiCo Layered Double Hydroxides for Superior Asymmetric Electrochemical Capacitor

    PubMed Central

    Li, Ruchun; Hu, Zhaoxia; Shao, Xiaofeng; Cheng, Pengpeng; Li, Shoushou; Yu, Wendan; Lin, Worong; Yuan, Dingsheng

    2016-01-01

    We report a new environmentally-friendly synthetic strategy for large-scale preparation of 16 nm-ultrathin NiCo based layered double hydroxides (LDH). The Ni50Co50-LDH electrode exhibited excellent specific capacitance of 1537 F g−1 at 0.5 A g−1 and 1181 F g−1 even at current density as high as 10 A g−1, which 50% cobalt doped enhances the electrical conductivity and porous and ultrathin structure is helpful with electrolyte diffusion to improve the material utilization. An asymmetric ultracapacitor was assembled with the N-doped graphitic ordered mesoporous carbon as negative electrode and the NiCo LDH as positive electrode. The device achieves a high energy density of 33.7 Wh kg−1 (at power density of 551 W kg−1) with a 1.5 V operating voltage. PMID:26754281

  1. Enhanced thermal- and photo-stability of acid yellow 17 by incorporation into layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Wang, Qian; Feng, Yongjun; Feng, Junting; Li, Dianqing

    2011-06-01

    2,5-dichloro-4-(5-hydroxy-3-methyl-4-(sulphophenylazo) pyrazol-1-yl) benzenesulphonate (DHSB) anions, namely acid yellow 17 anions, have been successfully intercalated into Zn-Al layered double hydroxides (LDH) to produce a novel organic-inorganic pigment by a simple method involving separate nucleation and aging steps (SNAS), and the dye-intercalated LDH was analyzed by various techniques, e.g., XRD, SEM, FT-IR, TG-DTA and ICP. The d-spacing of the prepared LDH is 2.09 nm. Furthermore, the incorporation of the DHSB aims to enhance the thermal- and photo-stability of the guest dye molecule, for example, the less color change after accelerated thermal- and photo-aging test.

  2. Synthesis and photoluminescence of red emitting phosphors of europium complex intercalated layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Gao, Xiaorui; Gao, Zhen; Yin, Xiaoru; Xie, Juan

    2015-12-01

    An inorganic-organic red emitting phosphor, europium ethylenediaminetetraacetate complex ([Eu(EDTA)]-) anions intercalated Mg/Al and Zn/Al layered double hydroxides (LDHs) were synthesized through an ion exchange method. X-ray powder diffraction (XRD) results exhibit that a nearly vertical arrangement of [Eu(EDTA)]- anions with the maximal dimension in the gallery is adopted. Measurement of the excitation and emission spectra show that the two materials display high red luminescence from Eu3+ ions. Furthermore, Mg/Al LDH containing europium complex has higher luminescence intensity than Zn/Al LDH, which probably was related with more inversion asymmetry sites of Eu3+ occurring in the Mg/Al LDH.

  3. Large Scale Synthesis of NiCo Layered Double Hydroxides for Superior Asymmetric Electrochemical Capacitor

    NASA Astrophysics Data System (ADS)

    Li, Ruchun; Hu, Zhaoxia; Shao, Xiaofeng; Cheng, Pengpeng; Li, Shoushou; Yu, Wendan; Lin, Worong; Yuan, Dingsheng

    2016-01-01

    We report a new environmentally-friendly synthetic strategy for large-scale preparation of 16 nm-ultrathin NiCo based layered double hydroxides (LDH). The Ni50Co50-LDH electrode exhibited excellent specific capacitance of 1537 F g‑1 at 0.5 A g‑1 and 1181 F g‑1 even at current density as high as 10 A g‑1, which 50% cobalt doped enhances the electrical conductivity and porous and ultrathin structure is helpful with electrolyte diffusion to improve the material utilization. An asymmetric ultracapacitor was assembled with the N-doped graphitic ordered mesoporous carbon as negative electrode and the NiCo LDH as positive electrode. The device achieves a high energy density of 33.7 Wh kg‑1 (at power density of 551 W kg‑1) with a 1.5 V operating voltage.

  4. Intercalation and controlled release properties of vitamin C intercalated layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Gao, Xiaorui; Lei, Lixu; O'Hare, Dermot; Xie, Juan; Gao, Pengran; Chang, Tao

    2013-07-01

    Two drug-inorganic composites involving vitamin C (VC) intercalated in Mg-Al and Mg-Fe layered double hydroxides (LDHs) have been synthesized by the calcination-rehydration (reconstruction) method. Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), and UV-vis absorption spectroscopy indicate a successful intercalation of VC into the interlayer galleries of the LDH host. Studies of VC release from the LDHs in deionised water and in aqueous CO32- solutions imply that Mg3Al-VC LDH is a better controlled release system than Mg3Fe-VC LDH. Analysis of the release profiles using a number of kinetic models suggests a solution-dependent release mechanism, and a diffusion-controlled deintercalation mechanism in deionised water, but an ion exchange process in CO32- solution.

  5. The in vitro sustained release profile and antitumor effect of etoposide-layered double hydroxide nanohybrids

    PubMed Central

    Qin, Lili; Wang, Mei; Zhu, Rongrong; You, Songhui; Zhou, Ping; Wang, Shilong

    2013-01-01

    Magnesium-aluminum layered double hydroxides intercalated with antitumor drug etoposide (VP16) were prepared for the first time using a two-step procedure. The X-ray powder diffraction data suggested the intercalation of VP16 into layers with the increased basal spacing from 0.84–1.18 nm was successful. Then, it was characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential thermal analysis, and transmission electron microscopy. The prepared nanoparticles, VP16-LDH, showed an average diameter of 62.5 nm with a zeta potential of 20.5 mV. Evaluation of the buffering effect of VP16-LDH indicated that the nanohybrids were ideal for administration of the drugs that treat human stomach irritation. The loading amount of intercalated VP16 was 21.94% and possessed a profile of sustained release. The mechanism of VP16-LDH release in the phosphate buffered saline solution at pH 7.4 is likely controlled by the diffusion of VP16 anions from inside to the surface of LDH particles. The in vitro cytotoxicity and antitumor assays indicated that VP16-LDH hybrids were less toxic to GES-1 cells while exhibiting better antitumor efficacy on MKN45 and SGC-7901 cells. These results imply that VP16-LDH is a potential antitumor drug for a broad range of gastric cancer therapeutic applications. PMID:23737669

  6. Three-dimensional porous MXene/layered double hydroxide composite for high performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Wang, Ya; Dou, Hui; Wang, Jie; Ding, Bing; Xu, Yunling; Chang, Zhi; Hao, Xiaodong

    2016-09-01

    In this work, an exfoliated MXene (e-MXene) nanosheets/nickel-aluminum layered double hydroxide (MXene/LDH) composite as supercapacitor electrode material is fabricated by in situ growth of LDH on e-MXene substrate. The LDH platelets homogeneously grown on the surface of the e-MXene sheets construct a three-dimensional (3D) porous structure, which not only leads to high active sites exposure of LDH and facile liquid electrolyte penetration, but also alleviates the volume change of LDH during the charge/discharge process. Meanwhile, the e -MXene substrate forms a conductive network to facilitate the electron transport of active material. The optimized MXene/LDH composite exhibits a high specific capacitance of 1061 F g-1 at a current density of 1 A g-1, excellent capacitance retention of 70% after 4000 cycle tests at a current density of 4 A g-1 and a good rate capability with 556 F g-1 retention at 10 A g-1.

  7. Composites of Quasi-Colloidal Layered Double Hydroxide Nanoparticles and Agarose Hydrogels for Chromate Removal

    PubMed Central

    Gwak, Gyeong-Hyeon; Kim, Min-Kyu; Oh, Jae-Min

    2016-01-01

    Composite hydrogels were prepared that consisted of quasi-colloidal layered double hydroxide (LDH) nanoparticles and agarose via the electrophoretic method, starting from three different agarose concentrations of 0.5, 1, and 2 wt/v%. The composite hydrogel was identified to have a uniform distribution of LDH nanoparticles in agarose matrix. Microscopic studies revealed that the composite hydrogel had a homogeneous quasi-colloidal state of LDHs, while the simple mixture of LDH powder and agarose hydrogels did not. It was determined that agarose concentration of the starting hydrogel did not significantly influence the amount of LDH that developed in the composite. The chromate scavenging efficiency of the composite hydrogel and corresponding agarose or mixture hydrogel was evaluated with respect to time, and chromate concentration. In general, the composite hydrogels exhibited much higher chromate removal efficacy compared with agarose or mixture hydrogels. Through estimating chromate adsorption by LDH moiety in the composite or mixture hydrogel, it was suggested that the agarose component facilitated the stability and dispersibility of the quasi-colloidal state of LDH nanoparticles in the composite resulting in high adsorption efficacy. From Freundlich isotherm adsorption fitting, composites were determined to possess beneficial cooperative adsorption behavior with a high adsorption coefficient. PMID:28344282

  8. Intercalation and structural aspects of macroRAFT agents into MgAl layered double hydroxides

    PubMed Central

    Kostadinova, Dessislava; Cenacchi Pereira, Ana; Lansalot, Muriel; D’Agosto, Franck; Bourgeat-Lami, Elodie; Leroux, Fabrice; Taviot-Guého, Christine; Cadars, Sylvian

    2016-01-01

    Increasing attention has been devoted to the design of layered double hydroxide (LDH)-based hybrid materials. In this work, we demonstrate the intercalation by anion exchange process of poly(acrylic acid) (PAA) and three different hydrophilic random copolymers of acrylic acid (AA) and n-butyl acrylate (BA) with molar masses ranging from 2000 to 4200 g mol−1 synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, into LDH containing magnesium(II) and aluminium(III) intralayer cations and nitrates as counterions (MgAl-NO3 LDH). At basic pH, the copolymer chains (macroRAFT agents) carry negative charges which allowed the establishment of electrostatic interactions with the LDH interlayer and their intercalation. The resulting hybrid macroRAFT/LDH materials displayed an expanded interlamellar domain compared to pristine MgAl-NO3 LDH from 1.36 nm to 2.33 nm. Depending on the nature of the units involved into the macroRAFT copolymer (only AA or AA and BA), the intercalation led to monolayer or bilayer arrangements within the interlayer space. The macroRAFT intercalation and the molecular structure of the hybrid phases were further characterized by Fourier transform infrared (FTIR) and solid-state 13C, 1H and 27Al nuclear magnetic resonance (NMR) spectroscopies to get a better description of the local structure. PMID:28144548

  9. Layered double hydroxide materials coated carbon electrode: New challenge to future electrochemical power devices

    NASA Astrophysics Data System (ADS)

    Djebbi, Mohamed Amine; Braiek, Mohamed; Namour, Philippe; Ben Haj Amara, Abdesslem; Jaffrezic-Renault, Nicole

    2016-11-01

    Layered double hydroxides (LDHs) have been widely used in the past years due to their unique physicochemical properties and promising applications in electroanalytical chemistry. The present paper is going to focus exclusively on magnesium-aluminum and zinc-aluminum layered double hydroxides (MgAl & ZnAl LDHs) in order to investigate the property and structure of active cation sites located within the layer structure. The MgAl and ZnAl LDH nanosheets were prepared by the constant pH co-precipitation method and uniformly supported on carbon-based electrode materials to fabricate an LDH electrode. Characterization by powder x-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy revealed the LDH form and well-crystallized materials. Wetting surface properties (hydrophilicity and hydrophobicity) of both prepared LDHs were recorded by contact angle measurement show hydrophilic character and basic property. The electrochemical performance of these hybrid materials was investigated by mainly cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques to identify the oxidation/reduction processes at the electrode/electrolyte interface and the effect of the divalent metal cations in total reactivity. The hierarchy of the modified electrode proves that the electronic conductivity of the bulk material is considerably dependent on the divalent cation and affects the limiting parameter of the overall redox process. However, MgAl LDH shows better performance than ZnAl LDH, due to the presence of magnesium cations in the layers. Following the structural, morphological and electrochemical behavior studies of both synthesized LDHs, the prepared LDH modified electrodes were tested through microbial fuel cell configuration, revealing a remarkable, potential new pathway for high-performance and cost-effective electrode use in electrochemical power devices.

  10. Interlayer interaction in Ca-Fe layered double hydroxides intercalated with nitrate and chloride species

    NASA Astrophysics Data System (ADS)

    Al-Jaberi, Muayad; Naille, Sébastien; Dossot, Manuel; Ruby, Christian

    2015-12-01

    Ca-Fe layered double hydroxide (LDH) intercalated with chloride and nitrate ions has been synthesized with varying CaII:FeIII molar ratios of the initial solution. Phase pure LDH is observed with CaII:FeIII molar ratio of 2:1 and a mixture of LDH and Ca(OH)2 is formed for CaII:FeIII molar ratios higher than 2:1. Vibrational spectroscopies (Raman and IR) were used successfully to understand the interaction between the cationic and anionic sheets. The Raman bands positions at lower frequencies (150-600 cm-1) are intimately correlated to the nature of the divalent and trivalent ions but also to the nature of the anions. Indeed, a shift of ˜9 cm-1 is observed for the Raman double bands situated in the 300-400 cm-1 region when comparing Raman spectra of CaFe-LDH containing either nitrate or chloride ions. Two types of nitrate environments are observed namely free (non-hydrogen bonded) nitrate and nitrate hydrogen bonded to the interlayer water or to the 'brucite-like' hydroxyl surface. Multiple types of water structure are observed and would result from different hydrogen bond structures. Water bending modes are identified at 1645 cm-1 greater than the one observed for LDH intercalated with chloride anions (1618 cm-1), indicating that the water is strongly hydrogen bonded to the nitrate anions.

  11. Controlled supramolecular structure of guanosine monophosphate in the interlayer space of layered double hydroxide

    PubMed Central

    2016-01-01

    Guanosine monophosphates (GMPs) were intercalated into the interlayer space of layered double hydroxides (LDHs) and the molecular arrangement of GMP was controlled in LDHs. The intercalation conditions such as GMP/LDH molar ratio and reaction temperature were systematically adjusted. When the GMP/LDH molar ratio was 1:2, which corresponds to the charge balance between positive LDH sheets and GMP anions, GMP molecules were well-intercalated to LDH. At high temperature (100 and 80 °C), a single GMP molecule existed separately in the LDH interlayer. On the other hand, at lower temperature (20, 40 and 60 °C), GMPs tended to form ribbon-type supramolecular assemblies. Differential scanning calorimetry showed that the ribbon-type GMP assembly had an intermolecular interaction energy of ≈101 kJ/mol, which corresponds to a double hydrogen bond between guanosine molecules. Once stabilized, the interlayer GMP orientations, single molecular and ribbon phase, were successfully converted to the other phase by adjusting the external environment by stoichiometry or temperature control. PMID:28144541

  12. Synthesis and adsorption properties of p-sulfonated calix[4 and 6]arene-intercalated layered double hydroxides

    SciTech Connect

    Sasaki, Satoru; Aisawa, Sumio; Hirahara, Hidetoshi; Sasaki, Akira; Nakayama, Hirokazu; Narita, Eiichi . E-mail: enarita@iwate-u.ac.jp

    2006-04-15

    The intercalation of water-soluble p-sulfonated calix[4 and 6]arene (CS4 and CS6) in the interlayer of the Mg-Al and Zn-Al layered double hydroxide (LDH) by the coprecipitation method has been investigated, as well as the adsorption properties of the resulting CS/LDHs for benzyl alcohol (BA) and p-nitrophenol (NP) to prepare new microporous organic-inorganic hybrid adsorbents. The amount and arrangement of CS intercalated was different by the kind of the host metal ions. CS4 cavity axis was perpendicular for the Mg-Al LDH basal layer and parallel for the Zn-Al LDH basal layer, while CS6 cavity axis was perpendicular for both the LDH basal layers. In the BET surface area measurement, the surface area of the Zn-Al/CS4/LDH was four times than that of the Mg-Al/CS4/LDH, expecting that the former has higher adsorption capacity than the latter. In fact, the adsorption ability of the CS/LDHs for BA and NP in aqueous solution was found to be larger in the Zn-Al/CS4/LDH than in the Mg-Al/CS4/LDH. In addition, the adsorption ability of both the LDHs was larger in the CS6/LDHs than in the CS4/LDHs. These results were explained by the difference in the amount and arrangement of CS intercalated in the LDH interlayer space.

  13. Physical properties of fixed-charge layer double hydroxides

    NASA Astrophysics Data System (ADS)

    Hines, D. R.; Solin, S. A.; Costantino, Umberto; Nocchetti, Morena

    2000-05-01

    The physical properties of a series of layer double hydroxides (LDH) of the form [(CO3)0.195(1-x)Cl0.39x(H2O)y]:[Zn0.61Al0.39(OH)2], 0<=x<=1, 0<=y<=(0.4+0.2x) have been studied. The hydration dynamics of these materials indicate that the guest layer water molecules form a hydration ring which defines the height of the solvated, nested Cl anion. The water molecules can tilt around their C2v axis such that the height of the solvated Cl ion is a function of the number of molecules forming the hydration ring. The composition dependence of the basal spacing, determined from x-ray-diffraction powder patterns measured as a function of humidity and temperature for these materials, is a function of both the Cl concentration (x) and the number of guest layer water molecules (y). Distinct basal spacing curves are observed for fully hydrated, partially hydrated, and dehydrated materials. At x=1 the Cl end-member material exhibits a change in stacking sequence from a 3R polytype to a 2H polytype upon dehydration. The dehydrated form of this material also exhibits a (3×3)R30° superlattice ordering of the Cl ions. Due to the nesting of the Cl ion and the active nature of the water molecules, the basal spacing vs x curve for the dehydrated materials is the only curve that can be fit by the discrete finite layer rigidity model. The interlayer rigidity parameter for LDH materials has been determined to be p=4.84+/-0.06 indicating that these materials are stiffer than class-II layered solids but not as stiff as class-III layered solids.

  14. Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

    PubMed Central

    Tsukanov, A.A.; Psakhie, S.G.

    2016-01-01

    The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered. PMID:26817816

  15. Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Tsukanov, A. A.; Psakhie, S. G.

    2016-01-01

    The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered.

  16. Magnetic cellulose ionomer/layered double hydroxide: An efficient anion exchange platform with enhanced diclofenac adsorption property.

    PubMed

    Hossein Beyki, Mostafa; Mohammadirad, Mosleh; Shemirani, Farzaneh; Saboury, Ali Akbar

    2017-02-10

    Polymeric ionomers with anion exchange capability are considered to be classes of environmentally friendly compounds as combination of them with anionic layered hydroxides constitute emerging advance materials. Biosorption by polymeric ionomer - layered double hydroxide (LDH) hybrid material exhibits an attractive green, low cost and low toxic - clean way. As a result, a novel anion exchange platform has been developed by the reaction of CaAl - LDH with Fe(2+), cellulose solution, epichlorohydrin and pyridine. Magnetite cellulose - LDH (MCL) and the ionomer were used for efficient biosorption of diclofenac sodium (DF). Results showed that ionomer has more efficiency for DF adsorption relative to MCL. Magnetite ionomer showed fast equilibrium time (2min) with maximum uptake of 268mgg(-1). Isotherm and Kinetic models were also studied. Regeneration of the sorbent was performed with a mixture of methanol -NaOH (2.0molL(-1)) solution.

  17. Direct observation of grafting interlayer phosphate in Mg/Al layered double hydroxides

    SciTech Connect

    Shimamura, Akihiro; Kanezaki, Eiji; Jones, Mark I.; Metson, James B.

    2012-02-15

    The grafting of interlayer phosphate in synthetic Mg/Al layered double hydroxides with interlayer hydrogen phosphate (LDH-HPO{sub 4}) has been studied by XRD, TG/DTA, FT-IR, XPS and XANES. The basal spacing of crystalline LDH-HPO{sub 4} decreases in two stages with increasing temperature, from 1.06 nm to 0.82 nm at 333 K in the first transition, and to 0.722 nm at 453 K in the second. The first stage occurs due to the loss of interlayer water and rearrangement of the interlayer HPO{sub 4}{sup 2-}. In the second transition, the interlayer phosphate is grafted to the layer by the formation of direct bonding to metal cations in the layer, accompanied by a change in polytype of the crystalline structure. The grafted phosphate becomes immobilized and cannot be removed by anion-exchange with 1-octanesulfonate. The LDH is amorphous at 743 K but decomposes to Mg{sub 3}(PO{sub 4}){sub 2}, AlPO{sub 4}, MgO and MgAl{sub 2}O{sub 4} after heated to 1273 K. - Graphical abstract: The cross section of the synthetic Mg, Al layered double hydroxides in Phase 1, with interlayer hydrogen phosphate Phase 2, and with grafted phosphate, Phase 3. Highlights: Black-Right-Pointing-Pointer The grafting of hydrogen phosphate intercalated Mg/Al-LDH has been studied. Black-Right-Pointing-Pointer The basal spacing of crystalline LDH-HPO{sub 4} decreases in two stages with increasing temperature. Black-Right-Pointing-Pointer The first decrease is due to loss of interlayer water, the second is attributed to phosphate grafting. Black-Right-Pointing-Pointer The grafted interlayer phosphate becomes immobilized and cannot be removed by anion-exchange.

  18. Polarized immune responses modulated by layered double hydroxides nanoparticle conjugated with CpG.

    PubMed

    Yan, Shiyu; Rolfe, Barbara E; Zhang, Bing; Mohammed, Yousuf H; Gu, Wenyi; Xu, Zhi P

    2014-11-01

    Modulation of the immune response is an important step in the induction of protective humoral and cellular immunity against pathogens. In this study, we investigated the possibility of using a nanomaterial conjugated with the toll-like receptor (TLR) ligand CpG to modulate the immune response towards the preferred polarity. MgAl-layered double hydroxide (LDH) nanomaterial has a very similar chemical composition to Alum, an FDA approved adjuvant for human vaccination. We used a model antigen, ovalbumin (OVA) to demonstrate that MgAl-LDH had comparable adjuvant activity to Alum, but much weaker inflammation. Conjugation of TLR9 ligand CpG to LDH nanoparticles significantly enhanced the antibody response and promoted a switch from Th2 toward Th1 response, demonstrated by a change in the IgG2a:IgG1 ratio. Moreover, immunization of mice with CpG-OVA-conjugated LDH before challenge with OVA-expressing B16/F10 tumor cells retarded tumor growth. Together, these data indicate that LDH nanomaterial can be used as an immune adjuvant to promote Th1 or Th2 dominant immune responses suitable for vaccination purposes.

  19. Intercalation of IR absorber into layered double hydroxides: Preparation, thermal stability and selective IR absorption

    SciTech Connect

    Zhu, Haifeng; Tang, Pinggui; Feng, Yongjun; Wang, Lijing; Li, Dianqing

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer PMIDA anions were intercalated into Mg{sub 2}Al-NO{sub 3} LDH by anion-exchange method. Black-Right-Pointing-Pointer The prepared material has highly selective IR absorption property in 9-11 {mu}m. Black-Right-Pointing-Pointer The obtained material has practical applications as heat-retaining additive. -- Abstract: N-phosphonomethyl aminodiacetic acid (PMIDA) was intercalated into the interlayer spacing of layered double hydroxides (LDH) by an anion-exchange method. The intercalated LDHs were characterized by various techniques such as powder X-ray diffraction (XRD), FT-IR spectroscopy, elemental analysis and simultaneous thermogravimetric and mass spectrometry (TG-MS) in details. The results show the formation of Mg{sub 2}Al-PMIDA LDH based on the expansion of d-spacing from 0.89 nm to 1.22 nm and the disappearance of the characteristic IR absorption band at 1384 cm{sup -1} for NO{sub 3}{sup -} anions. The incorporation of Mg{sub 2}Al-PMIDA LDH into the low density polyethylene (LDPE) as an additive enhances the selectivity of IR absorption in the main wavelength region 9-11 {mu}m for radiant heat loss at night. Mg{sub 2}Al-PMIDA LDH as a heat-retaining additive has practical application in agricultural plastic films.

  20. Starch Biocatalyst Based on α-Amylase-Mg/Al-Layered Double Hydroxide Nanohybrids.

    PubMed

    Bruna, Felipe; Pereira, Marita G; Polizeli, Maria de Lourdes T M; Valim, João B

    2015-08-26

    The design of new biocatalysts through the immobilization of enzymes, improving their stability and reuse, plays a major role in the development of sustainable methodologies toward the so-called green chemistry. In this work, α-amylase (AAM) biocatalyst based on Mg3Al-layered double-hydroxide (LDH) matrix was successfully developed with the adsorption method. The adsorption process was studied and optimized as a function of time and enzyme concentration. The biocatalyst was characterized, and the mechanism of interaction between AAM and LDH, as well as the immobilization effects on the catalytic activity, was elucidated. The adsorption process was fast and irreversible, thus yielding a stable biohybrid material. The immobilized AAM partially retained its enzymatic activity, and the biocatalyst rapidly hydrolyzed starch in an aqueous solution with enhanced efficiency at intermediate loading values of ca. 50 mg/g of AAM/LDH. Multiple attachments through electrostatic interactions affected the conformation of the immobilized enzyme on the LDH surface. The biocatalyst was successfully stored in its dry form, retaining 100% of its catalytic activity. The results reveal the potential usefulness of a LDH compound as a support of α-amylase for the hydrolysis of starch that may be applied in industrial and pharmaceutical processes as a simple, environmentally friendly, and low-cost biocatalyst.

  1. Synthesis and characterization of 10-hydroxycamptothecin - sebacate - layered double hydroxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Pang, Xiujiang; Ma, Xiuming; Li, Dongxiang; Hou, Wanguo

    2013-02-01

    10-Hydroxycamptothecin (HCPT) as a hydrophobic anticancer drug brings many challenges in the clinical applications due to its poor water solubility and the presence of a chemically unstable lactone ring. In this work, the nanocomposites of HCPT intercalated layered double hydroxide (LDH) were prepared by a secondary intercalation method, and the encapsulated HCPT could keep the biologically active lactone form. A Zn-Al-NO3 LDH was pillared with sebacate anions by a co-precipitation method in an aqueous medium, and then HCPT was intercalated into the LDH's gallery via hydrophobic interaction in an ethanol medium. The parallel alkyl chains of perpendicularly arranged sebacate anions in the LDH gallery provide a hydrophobic space for the drug intercalation. The in vitro release kinetics of HCPT from the nanocomposites could be fitted with the pseudo-second-order kinetic model, and the diffusion of HCPT through the LDH particles played an important role in controlling the drug release. The nanocomposites can be considered as a potential drug delivery system.

  2. Double layered hydroxides as potential anti-cancer drug delivery agents.

    PubMed

    Riaz, Ufana; Ashraf, S M

    2013-04-01

    The emergence of nanotechnology has changed the scenario of the medical world by revolutionizing the diagnosis, monitoring and treatment of cancer. This nanotechnology has been proved miraculous in detecting cancer cells, delivering chemotherapeutic agents and monitoring treatment from non-specific to highly targeted killing of tumor cells. In the past few decades, a number of inorganic materials have been investigated such as calcium phosphate, gold, carbon materials, silicon oxide, iron oxide, and layered double hydroxide (LDH) for examining their efficacy in targeting drug delivery. The reason behind the selection of these inorganic materials was their versatile and unique features efficient in drug delivery, such as wide availability, rich surface functionality, good biocompatibility, potential for target delivery, and controlled release of the drug from these inorganic nanomaterials. Although, the drug-LDH hybrids are found to be quite instrumental because of their application as advanced anti-cancer drug delivery systems, there has not been much research on them. This mini review is set to highlight the advancement made in the use of layered double hydroxides (LDHs) as anti-cancer drug delivery agents. Along with the advantages of LDHs as anti-cancer drug delivery agents, the process of interaction of some of the common anti-cancer drugs with LDH has also been discussed.

  3. Antimycobacterial, antimicrobial, and biocompatibility properties of para-aminosalicylic acid with zinc layered hydroxide and Zn/Al layered double hydroxide nanocomposites

    PubMed Central

    Saifullah, Bullo; El Zowalaty, Mohamed E; Arulselvan, Palanisamy; Fakurazi, Sharida; Webster, Thomas J; Geilich, Benjamin M; Hussein, Mohd Zobir

    2014-01-01

    The treatment of tuberculosis by chemotherapy is complicated due to multiple drug prescriptions, long treatment duration, and adverse side effects. We report here for the first time an in vitro therapeutic effect of nanocomposites based on para-aminosalicylic acid with zinc layered hydroxide (PAS-ZLH) and zinc-aluminum layered double hydroxides (PAS-Zn/Al LDH), against mycobacteria, Gram-positive bacteria, and Gram-negative bacteria. The nanocomposites demonstrated good antimycobacterial activity and were found to be effective in killing Gram-positive and Gram-negative bacteria. A biocompatibility study revealed good biocompatibility of the PAS-ZLH nanocomposites against normal human MRC-5 lung cells. The para-aminosalicylic acid loading was quantified with high-performance liquid chromatography analysis. In summary, the present preliminary in vitro studies are highly encouraging for further in vivo studies of PAS-ZLH and PAS-Zn/Al LDH nanocomposites to treat tuberculosis. PMID:25114509

  4. Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites.

    PubMed

    Nedim Ay, Ahmet; Konuk, Deniz; Zümreoglu-Karan, Birgul

    2011-02-03

    A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

  5. Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

    PubMed Central

    2011-01-01

    A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules. PMID:21711652

  6. Silica coating and photochemical properties of layered double hydroxide/4,4'-diaminostilbene-2,2'-disulfonic acid nanocomposite.

    PubMed

    El-Toni, Ahmed Mohamed; Yin, Shu; Sato, Tsugio

    2006-01-15

    Organic ultraviolet (UV) rays absorbents have been used as sunscreen materials, but they may pose a safety problem when used at high concentration. In order to prevent direct contact of organic UV rays absorbent to the human skin, a typical organic UV-absorbent, 4,4(')-diaminostilbene-2,2(')-disulfonic acid (DASDSA), was intercalated into Zn(2)Al layered double hydroxide (Zn(2)Al-LDH) by coprecipitation reaction. However, deintercalation of DASDSA from Zn(2)Al-LDH, by the anion exchange reaction with carbonate ion, was observed. Therefore, Zn(2)Al-LDH/DASDSA was directly coated with silica by means of polymerization technique based on the Stöber method. Silica coating effectively depressed the deintercalation of DASDSA from Zn(2)Al-LDH. The amorphous silica was confirmed by XRD, SEM, TEM and FT-IR. The deintercalation behaviors as well as UV-shielding properties were investigated for coated particles.

  7. Detection of copper ions from aqueous solutions using layered double hydroxides thin films deposited by PLD

    NASA Astrophysics Data System (ADS)

    Vlad, A.; Birjega, R.; Matei, A.; Luculescu, C.; Nedelcea, A.; Dinescu, M.; Zavoianu, R.; Pavel, O. D.

    2015-10-01

    Layered double hydroxides (LDHs) thin films with Mg-Al were deposited using pulsed laser deposition (PLD) technique. We studied the ability of our films to detect copper ions in aqueous solutions. Copper is known to be a common pollutant in water, originating from urban and industrial waste. Clay minerals, including layered double hydroxides (LDHs), can reduce the toxicity of such wastes by adsorbing copper. We report on the uptake of copper ions from aqueous solution on LDH thin films obtained via PLD. The obtained thin films were characterized using X-ray Diffraction, Atomic Force Microscopy, and Scanning Electron Microscopy with Energy Dispersive X-ray analysis. The results in this study indicate that LDHs thin films obtained by PLD have potential as an efficient adsorbent for removing copper from aqueous solution.

  8. Layered double hydroxide-oxidized carbon nanotube hybrids as highly efficient flame retardant nanofillers for polypropylene

    NASA Astrophysics Data System (ADS)

    Gao, Yanshan; Zhang, Yu; Williams, Gareth R.; O’Hare, Dermot; Wang, Qiang

    2016-10-01

    Aqueous miscible organic layered double hydroxides (AMO-LDHs) can act as organophilic inorganic flame retardant nanofillers for unmodified non-polar polymers. In this contribution, AMO [Mg3Al(OH)8](CO3)0.5·yH2O LDH–oxidized carbon nanotube (AMO-LDH–OCNT) hybrids are shown to perform better than the equivalent pure AMO-LDH. A synergistic effect between the AMO-LDH and OCNT was observed; this endows the hybrid material with enhanced flame retardancy, thermal stability, and mechanical properties. The thermal stability of polypropylene (PP) was significantly enhanced by adding AMO-LDH–OCNT hybrids. For PP mixed with AMO-LDH–OCNT hybrids to produce a composite with 10 wt% LDH and 2 wt% OCNT, the 50% weight loss temperature was increased by 43 °C. Further, a system with 10 wt% of AMO-LDH and 1 wt% OCNT showed a peak heat release rate (PHRR) reduction of 40%, greater than the PHRR reduction with PP/20 wt% AMO-LDH (31%). The degree of dispersion (mixability) between AMO-LDH and OCNT has a significant effect on the flame retardant performance of the hybrids. In addition, the incorporation of AMO-LDH–OCNT hybrids led to better mechanical properties, such as higher tensile strength (27.5 MPa) and elongation at break (17.9%), than those composites containing only AMO-LDH (25.6 MPa and 7.5%, respectively).

  9. Layered double hydroxide-oxidized carbon nanotube hybrids as highly efficient flame retardant nanofillers for polypropylene

    PubMed Central

    Gao, Yanshan; Zhang, Yu; Williams, Gareth R.; O’Hare, Dermot; Wang, Qiang

    2016-01-01

    Aqueous miscible organic layered double hydroxides (AMO-LDHs) can act as organophilic inorganic flame retardant nanofillers for unmodified non-polar polymers. In this contribution, AMO [Mg3Al(OH)8](CO3)0.5·yH2O LDH–oxidized carbon nanotube (AMO-LDH–OCNT) hybrids are shown to perform better than the equivalent pure AMO-LDH. A synergistic effect between the AMO-LDH and OCNT was observed; this endows the hybrid material with enhanced flame retardancy, thermal stability, and mechanical properties. The thermal stability of polypropylene (PP) was significantly enhanced by adding AMO-LDH–OCNT hybrids. For PP mixed with AMO-LDH–OCNT hybrids to produce a composite with 10 wt% LDH and 2 wt% OCNT, the 50% weight loss temperature was increased by 43 °C. Further, a system with 10 wt% of AMO-LDH and 1 wt% OCNT showed a peak heat release rate (PHRR) reduction of 40%, greater than the PHRR reduction with PP/20 wt% AMO-LDH (31%). The degree of dispersion (mixability) between AMO-LDH and OCNT has a significant effect on the flame retardant performance of the hybrids. In addition, the incorporation of AMO-LDH–OCNT hybrids led to better mechanical properties, such as higher tensile strength (27.5 MPa) and elongation at break (17.9%), than those composites containing only AMO-LDH (25.6 MPa and 7.5%, respectively). PMID:27752096

  10. Rapid exchange between atmospheric CO2 and carbonate anion intercalated within magnesium rich layered double hydroxide.

    PubMed

    Sahoo, Pathik; Ishihara, Shinsuke; Yamada, Kazuhiko; Deguchi, Kenzo; Ohki, Shinobu; Tansho, Masataka; Shimizu, Tadashi; Eisaku, Nii; Sasai, Ryo; Labuta, Jan; Ishikawa, Daisuke; Hill, Jonathan P; Ariga, Katsuhiko; Bastakoti, Bishnu Prasad; Yamauchi, Yusuke; Iyi, Nobuo

    2014-10-22

    The carbon cycle, by which carbon atoms circulate between atmosphere, oceans, lithosphere, and the biosphere of Earth, is a current hot research topic. The carbon cycle occurring in the lithosphere (e.g., sedimentary carbonates) is based on weathering and metamorphic events so that its processes are considered to occur on the geological time scale (i.e., over millions of years). In contrast, we have recently reported that carbonate anions intercalated within a hydrotalcite (Mg0.75Al0.25(OH)2(CO3)0.125·yH2O), a class of a layered double hydroxide (LDH), are dynamically exchanging on time scale of hours with atmospheric CO2 under ambient conditions. (Ishihara et al., J. Am. Chem. Soc. 2013, 135, 18040-18043). The use of (13)C-labeling enabled monitoring by infrared spectroscopy of the dynamic exchange between the initially intercalated (13)C-labeled carbonate anions and carbonate anions derived from atmospheric CO2. In this article, we report the significant influence of Mg/Al ratio of LDH on the carbonate anion exchange dynamics. Of three LDHs of various Mg/Al ratios of 2, 3, or 4, magnesium-rich LDH (i.e., Mg/Al ratio = 4) underwent extremely rapid exchange of carbonate anions, and most of the initially intercalated carbonate anions were replaced with carbonate anions derived from atmospheric CO2 within 30 min. Detailed investigations by using infrared spectroscopy, scanning electron microscopy, powder X-ray diffraction, elemental analysis, adsorption, thermogravimetric analysis, and solid-state NMR revealed that magnesium rich LDH has chemical and structural features that promote the exchange of carbonate anions. Our results indicate that the unique interactions between LDH and CO2 can be optimized simply by varying the chemical composition of LDH, implying that LDH is a promising material for CO2 storage and/or separation.

  11. Large-scale simulations of layered double hydroxide nanocomposite materials

    NASA Astrophysics Data System (ADS)

    Thyveetil, Mary-Ann

    Layered double hydroxides (LDHs) have the ability to intercalate a multitude of anionic species. Atomistic simulation techniques such as molecular dynamics have provided considerable insight into the behaviour of these materials. We review these techniques and recent algorithmic advances which considerably improve the performance of MD applications. In particular, we discuss how the advent of high performance computing and computational grids has allowed us to explore large scale models with considerable ease. Our simulations have been heavily reliant on computational resources on the UK's NGS (National Grid Service), the US TeraGrid and the Distributed European Infrastructure for Supercomputing Applications (DEISA). In order to utilise computational grids we rely on grid middleware to launch, computationally steer and visualise our simulations. We have integrated the RealityGrid steering library into the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) 1 . which has enabled us to perform re mote computational steering and visualisation of molecular dynamics simulations on grid infrastruc tures. We also use the Application Hosting Environment (AHE) 2 in order to launch simulations on remote supercomputing resources and we show that data transfer rates between local clusters and super- computing resources can be considerably enhanced by using optically switched networks. We perform large scale molecular dynamics simulations of MgiAl-LDHs intercalated with either chloride ions or a mixture of DNA and chloride ions. The systems exhibit undulatory modes, which are suppressed in smaller scale simulations, caused by the collective thermal motion of atoms in the LDH layers. Thermal undulations provide elastic properties of the system including the bending modulus, Young's moduli and Poisson's ratios. To explore the interaction between LDHs and DNA. we use molecular dynamics techniques to per form simulations of double stranded, linear and plasmid DNA up

  12. Phosphate-intercalated Ca-Fe-layered double hydroxides: Crystal structure, bonding character, and release kinetics of phosphate

    NASA Astrophysics Data System (ADS)

    Woo, Myong A.; Woo Kim, Tae; Paek, Mi-Jeong; Ha, Hyung-Wook; Choy, Jin-Ho; Hwang, Seong-Ju

    2011-01-01

    The nitrate-form of Ca-Fe-layered double hydroxide (Ca-Fe-LDH) was synthesized via co-precipitation method, and its phosphate-intercalates were prepared by ion-exchange reaction. According to X-ray diffraction analysis, the Ca-Fe-LDH-NO 3- compound and its H 2PO 4--intercalate showed hexagonal layered structures, whereas the ion-exchange reaction with HPO 42- caused a frustration of the layer ordering of LDH. Fe K-edge X-ray absorption spectroscopy clearly demonstrated that the Ca-Fe-LDH lattice with trivalent iron ions was well-maintained after the ion-exchange with HPO 42- and H 2PO 4-. Under acidic conditions, phosphate ions were slowly released from the Ca-Fe-LDH lattice and the simultaneous release of hydroxide caused the neutralization of acidic media. Fitting analysis based on kinetic models indicated a heterogeneous diffusion process of phosphates and a distinct dependence of release rate on the charge of phosphates. This study strongly suggested that Ca-Fe-LDH is applicable as bifunctional vector for slow release of phosphate fertilizer and for the neutralization of acid soil.

  13. Intercalation and controlled release properties of vitamin C intercalated layered double hydroxide

    SciTech Connect

    Gao, Xiaorui; Lei, Lixu; O'Hare, Dermot; Xie, Juan; Gao, Pengran; Chang, Tao

    2013-07-15

    Two drug-inorganic composites involving vitamin C (VC) intercalated in Mg–Al and Mg–Fe layered double hydroxides (LDHs) have been synthesized by the calcination–rehydration (reconstruction) method. Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), and UV–vis absorption spectroscopy indicate a successful intercalation of VC into the interlayer galleries of the LDH host. Studies of VC release from the LDHs in deionised water and in aqueous CO{sub 3}{sup 2−} solutions imply that Mg{sub 3}Al–VC LDH is a better controlled release system than Mg{sub 3}Fe–VC LDH. Analysis of the release profiles using a number of kinetic models suggests a solution-dependent release mechanism, and a diffusion-controlled deintercalation mechanism in deionised water, but an ion exchange process in CO{sub 3}{sup 2−} solution. - Graphical abstract: Vitamin C anions have been intercalated in the interlayer space of layered double hydroxide and released in CO{sub 3}{sup 2−} solution and deionised water. - Highlights: • Vitamin C intercalated Mg–Al and Mg–Fe layered double hydroxides were prepared. • Release property of vitamin C in aqueous CO{sub 3}{sup 2−} solution is better. • Avrami-Erofe’ev and first-order models provide better fit for release results. • Diffusion-controlled and ion exchange processes occur in deionised water. • An ion exchange process occurs in CO{sub 3}{sup 2−} solution.

  14. Lubrication performance and mechanisms of Mg/Al-, Zn/Al-, and Zn/Mg/Al-layered double hydroxide nanoparticles as lubricant additives

    NASA Astrophysics Data System (ADS)

    Li, Shuo; Bhushan, Bharat

    2016-08-01

    Solid lubricant particles are commonly used as oil additives for low friction and wear. Mg/Al-, Zn/Al-, and Zn/Mg/Al-layered double hydroxides (LDH) were synthesized by coprecipitation method. The benefits of LDH nanoparticles are that they can be synthesized using chemical methods where size and shape can be controlled, and can be modified organically to allow dispersal in fluids. The LDH nanoparticles were characterized by X-ray diffraction, scanning electron microscope, thermogravimetry, and differential scanning calorimetry. A pin-on-disk friction and wear tester was used for evaluating the friction and wear properties of LDH nanoparticles as lubricant additives. LDH nanoparticles have friction-reducing and anti-wear properties compared to oil without LDHs. Mg/Al-LDH has the best lubrication, possibly due to better thermal stability in severe conditions.

  15. Binder-free Co3O4@NiCoAl-layered double hydroxide core-shell hybrid architectural nanowire arrays with enhanced electrochemical performance

    NASA Astrophysics Data System (ADS)

    Li, Xuan; Yang, Zhengchun; Qi, Wen; Li, Yutao; Wu, Ying; Zhou, Shaoxiong; Huang, Shengming; Wei, Jun; Li, Huijun; Yao, Pei

    2016-02-01

    Herein, binder-free Co3O4@NiCoAl-layered double hydroxide (Co3O4@LDH) core-shell hybrid architectural nanowire arrays were prepared via a two-step hydrothermal synthesis route. LDH nanosheets possessing a large electroactive surface area uniformly dispersed on the surface of Co3O4 nanowires were successfully fabricated allowing for fast electron transport that enhances the electrochemical performance of LDH nanosheets. Co3O4@LDH nanowire arrays of 2 to 1.5 molar ratio (Co3O4:LDH) exhibit high specific capacitance (1104 F g-1 at 1 A g-1), adequate rate capability and cycling stability (87.3% after 5000 cycles), attributed to the synergistic effect between the robust Co3O4 nanowire arrays and LDH nanosheets.

  16. Cobalt-based layered double hydroxides as oxygen evolving electrocatalysts in neutral electrolyte

    NASA Astrophysics Data System (ADS)

    Lin, Hong; Zhang, Ye; Wang, Gang; Li, Jian-Bao

    2012-06-01

    Co-M (M= Co, Ni, Fe, Mn) layered double hydroxides (LDHs) were successfully fabricated by a hexamethylenetetramine (HMT) pyrolysis method. Composite electrodes were made using a self-assembly fashion at inorganic/organic surface binder-free and were used to catalyze oxygen evolution reaction. Water oxidation can take place in neutral electrolyte operating with modest overpotential. The doping of other transitional metal cations affords mix valences and thus more intimate electronic interactions for reversible chemisorption of dioxygen molecules. The application of employing LDH materials in water oxidation process bodes well to facilitate future hydrogen utilization.

  17. Wetting behavior and drag reduction of superhydrophobic layered double hydroxides films on aluminum

    NASA Astrophysics Data System (ADS)

    Zhang, Haifeng; Yin, Liang; Liu, Xiaowei; Weng, Rui; Wang, Yang; Wu, Zhiwen

    2016-09-01

    We present a novel method to fabricate Zn-Al LDH (layered double hydroxides) film with 3D flower-like micro-and nanostructure on the aluminum foil. The wettability of the Zn-Al LDH film can be easily changed from superhydrophilic to superhydrophobic with a simple chemical modification. The as-prepared superhydrophobic surfaces have water CAs (contact angles) of 165 ± 2°. In order to estimate the drag reduction property of the surface with different adhesion properties, the experimental setup of the liquid/solid friction drag is proposed. The drag reduction ratio for the as-prepared superhydrophobic sample is 20-30% at low velocity. Bearing this in mind, we construct superhydrophobic surfaces that have numerous technical applications in drag reduction field.

  18. Texture effect of layered double hydroxides on chemisorption of Orange II

    NASA Astrophysics Data System (ADS)

    Géraud, Erwan; Bouhent, Mustapha; Derriche, Zoubir; Leroux, Fabrice; Prévot, Vanessa; Forano, Claude

    2007-05-01

    The chemisorption properties of hydrotalcite (HT) with novel macroporous properties have been investigated for azo dye, Orange II (O-II), and compared to coprecipitated HT and their calcined derivatives. Adsorption isotherms satisfactorily fit the Langmuir model. Adsorption capacities of the layered double hydroxides (LDH) macroporous structures are very high, particularly for the calcined materials (4.34 mmol/g) compared to standard HT (0.504 mmol/g), showing that accessibility to the LDH layer surface insures better sorptive properties. For both synthetic materials, the calcination/reconstruction process gives rise to highest concentrations of adsorbed O-II and a partial intercalation of O-II molecules in the structure as shown by the expansion of the basal spacing (d=2.4nm). Conversely, the uncalcined HT phases mainly display a surface exchange chemisorption process.

  19. Mg-Al layered double hydroxide intercalated with porphyrin anions: molecular simulations and experiments.

    PubMed

    Kovár, Petr; Pospísil, Miroslav; Káfunková, Eva; Lang, Kamil; Kovanda, Frantisek

    2010-02-01

    Molecular modeling in combination with powder X-ray diffraction (XRD) provided new information on the organization of the interlayer space of Mg-Al layered double hydroxide (LDH) containing intercalated porphyrin anions [5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS)]. Anion-exchange and rehydration procedures were used for the preparation of TPPS-containing LDH with an Mg/Al molar ratio of 2. Molecular modeling was carried out in the Cerius(2) and Materials Studio modeling environment. Three types of models were created in order to simulate the experimental XRD patterns of LDH intercalates with a TPPS loading of 70-80% with respect to the theoretical anion exchange capacity (AEC). The models represent single-phase systems with a 100% TPPS loading in the interlayer space (Type 1) and models represent the coexistence of two phases corresponding to the total exchange from 75 to 92% (Type 2). To cover other possible arrangements, models with the coexistence of both TPPS and NO(3)(-) anions in the same interlayer space were calculated (Type 3). The models are described and compared with experimental data. In all cases, guest TPPS anions are tilted with respect to the hydroxide layers, and are horizontally shifted to each other by up to one-half of the TPPS diameter. According to the energy characteristics and simulated XRD, the most probable arrangement is of Type 2, where some layers are saturated with TPPS anions and others are filled with original NO(3)(-) anions.

  20. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis.

    PubMed

    Song, Fang; Hu, Xile

    2014-07-17

    The oxygen evolution reaction is a key reaction in water splitting. The common approach in the development of oxygen evolution catalysts is to search for catalytic materials with new and optimized chemical compositions and structures. Here we report an orthogonal approach to improve the activity of catalysts without alternating their compositions or structures. Specifically, liquid phase exfoliation is applied to enhance the oxygen evolution activity of layered double hydroxides. The exfoliated single-layer nanosheets exhibit significantly higher oxygen evolution activity than the corresponding bulk layered double hydroxides in alkaline conditions. The nanosheets from nickel iron and nickel cobalt layered double hydroxides outperform a commercial iridium dioxide catalyst in both activity and stability. The exfoliation creates more active sites and improves the electronic conductivity. This work demonstrates the promising catalytic activity of single-layered double hydroxides for the oxygen evolution reaction.

  1. Layered double hydroxide nanoparticles promote self-renewal of mouse embryonic stem cells through the PI3K signaling pathway

    NASA Astrophysics Data System (ADS)

    Wu, Youjun; Zhu, Rongrong; Zhou, Yang; Zhang, Jun; Wang, Wenrui; Sun, Xiaoyu; Wu, Xianzheng; Cheng, Liming; Zhang, Jing; Wang, Shilong

    2015-06-01

    Embryonic stem cells (ESCs) hold great potential for regenerative medicine due to their two unique characteristics: self-renewal and pluripotency. Several groups of nanoparticles have shown promising applications in directing the stem cell fate. Herein, we investigated the cellular effects of layered double hydroxide nanoparticles (LDH NPs) on mouse ESCs (mESCs) and the associated molecular mechanisms. Mg-Al-LDH NPs with an average diameter of ~100 nm were prepared by hydrothermal methods. To determine the influences of LDH NPs on mESCs, cellular cytotoxicity, self-renewal, differentiation potential, and the possible signaling pathways were explored. Evaluation of cell viability, lactate dehydrogenase release, ROS generation and apoptosis demonstrated the low cytotoxicity of LDH NPs. The alkaline phosphatase activity and the expression of pluripotency genes in mESCs were examined, which indicated that exposure to LDH NPs could support self-renewal and inhibit spontaneous differentiation of mESCs under feeder-free culture conditions. The self-renewal promotion was further proved to be independent of the leukemia inhibitory factor (LIF). Furthermore, cells treated with LDH NPs maintained the potential to differentiate into all three germ layers both in vitro and in vivo through formation of embryoid bodies and teratomas. In addition, we observed that LDH NPs initiated the activation of the PI3K/Akt pathway, while treatment with the PI3K inhibitor LY294002 could block the effects of LDH NPs on mESCs. The results confirmed that the promotion of self-renewal by LDH NPs was associated with activation of the PI3K/Akt signaling pathway. Altogether, our studies identified a new role of LDH NPs in maintaining self-renewal of mouse ES cells which could potentially be applied in stem cell research.Embryonic stem cells (ESCs) hold great potential for regenerative medicine due to their two unique characteristics: self-renewal and pluripotency. Several groups of nanoparticles

  2. Preparation of Nickel-Aluminum-Containing Layered Double Hydroxide Films by Secondary (Seeded) Growth Method and Their Electrochemical Properties.

    PubMed

    Zhang, Fazhi; Guo, Li; Xu, Sailong; Zhang, Rong

    2015-06-23

    Thin films of nickel-aluminum-containing layered double hydroxide (NiAl-LDH) have been prepared on nickel foil and nickel foam substrates by secondary (seeded) growth of NiAl-LDH seed layer. The preparation procedure consists of deposition of LDH seeds from a colloidal suspension on the substrate by dip coating, followed by hydrothermal treatment of the nanocrystals to form the LDH film. The secondary grown film is found to provide a higher crystallinity and more uniform composition of metal cations in the film layer than the in situ grown film on seed-free substrate under identical hydrothermal conditions. A systematic investigation of the film evolution process reveals that the crystallite growth rate is relatively fast for the secondary grown film because of the presence of LDH nanocrystal seeds. Electrochemical performance of the resulting NiAl-LDH films as positive electrode material was further assessed as an example of their practical applications. The secondary grown film electrode delivers improved recharge-discharge capacity and cycling stability compared with that of the in situ grown film, which can be explained by the existence of a unique microstructure of the former. Our findings show an example for the effective fabrication of LDH film with controllable microstructure and enhanced application performance through a secondary (seeded) growth procedure.

  3. Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine.

    PubMed

    Li, Meixia; Zhu, Jun E; Zhang, Lili; Chen, Xu; Zhang, Huimin; Zhang, Fazhi; Xu, Sailong; Evans, David G

    2011-10-05

    Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach.

  4. Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives

    NASA Astrophysics Data System (ADS)

    Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

    2016-03-01

    High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application.

  5. Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives

    PubMed Central

    Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

    2016-01-01

    High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application. PMID:26951794

  6. Novel morphology-controlled hierarchical core@shell structural organo-layered double hydroxides magnetic nanovehicles for drug release.

    PubMed

    Bi, Xue; Fan, Ting; Zhang, Hui

    2014-11-26

    Novel hierarchical core@shell structured salicylate (SA) intercalated ZnAl-LDH (layered double hydroxides) magnetic nanovehicles were obtained via a special double-drop coprecipitation strategy assembling organo-ZnAl-LDH nanocrystals onto the surface of Fe3O4 submicrospheres (∼480 nm) from cheap aspirin and Zn- and Al-nitrates in alkaline solutions. The obtained Fe3O4@SA-LDH-r nanovehicles exhibit varied morphologies with hexagonal LDH ab-face horizontal, vertical, and vertical/slant/horizontal to the surfaces of Fe3O4 upon proper mass ratio (r) of Zn-salt to Fe3O4 from 1.93 to 7.71 in a low supersaturation system and possess moderate drug loadings and strong superparamagnetism. An in vitro release study reveals that under "no MF" mode (without external magnetic field) the SA release exhibits the higher accumulated release amount and smaller half-life (t0.5) for Fe3O4@SA-LDH-3.85 (41.2%, 1.63 min) and Fe3O4@SA-LDH-7.71 (51.1%, 1.66 min) probably owing to their mainly vertical LDH orientations, while the dramatically reduced SA release (10.0%) and greatly elongated t0.5 (25.6 min) for Fe3O4@SA-LDH-1.93 may be due to its relatively stronger host-guest interaction and compact horizontally oriented LDH shell stack. Under "MF on" mode, all the magnetic samples show a detectable reduced SA release owing to the particle-particle interactions among the magnetic nanovehicles. The kinetic fittings show that the release processes of all the samples involve the bulk and surface diffusion. The SA release from Fe3O4@SA-LDH-1.93 is mainly determined by the interparticle diffusion among the horizontally oriented LDH shell nanocrystals while those of Fe3O4@SA-LDH-3.85 and Fe3O4@SA-LDH-7.71 mainly involve the interlayer intraparticle diffusion between LDHs layers due to their largely vertical LDH shell nanocrystals.

  7. Fire and thermal properties of layered double hydroxides and polyurea nanocomposites

    NASA Astrophysics Data System (ADS)

    Nyambo, Calistor

    Layered double hydroxide (LDH) intercalated with linear alkyl carboxylates (CH3(CH2)n COO-, n = 8, 10, 12, 14, 16, 20), borate and benzyl anions were prepared. The effect on fire and thermal properties of the mode of preparation for LDHs (i.e. ion exchange, coprecipitation and rehydration of the calcined LDH methods) has been studied. After characterization, the LDHs were used to prepare nanocomposites with a range of polar and non-polar polymers. Characterization of the LDHs and the nanocomposites was performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetry analysis (TGA), transmission electron microscopy (TEM) and cone calorimetry. FTIR and XRD analyses confirmed the presence of the charge balancing anions in the galleries of the LDHs. Improvements in fire and thermal properties of the nanocomposites were observed. The cone calorimeter revealed that the addition of LDHs reduces the peak heat release rate significantly. LDHs were combined with commercial fire retardants. Synergistic effects were observed in both TGA and cone calorimetry for formulations containing both LDH and ammonium polyphosphate (APP). Physical and chemical interactions between LDH and APP are responsible for the observed synergy in thermal stability and fire performance.

  8. Layered Double Hydroxide Nanotransporter for Molecule Delivery to Intact Plant Cells

    PubMed Central

    Bao, Wenlong; Wang, Junya; Wang, Qiang; O’Hare, Dermot; Wan, Yinglang

    2016-01-01

    Here we report a powerful method that facilitates the transport of biologically active materials across the cell wall barrier in plant cells. Positively charged delaminated layered double hydroxide lactate nanosheets (LDH-lactate-NS) with a 0.5‒2 nm thickness and 30‒60 nm diameter exhibit a high adsorptive capacity for negatively charged biomolecules, including fluorescent dyes such as tetramethyl rhodamine isothiocyanate (TRITC), fluorescein isothiocyanate isomer I(FITC) and DNA molecules, forming neutral LDH-nanosheet conjugates. These neutral conjugates can shuttle the bound fluorescent dye into the cytosol of intact plant cell very efficiently. Furthermore, typical inhibitors of endocytosis and low temperature incubation did not prevent LDH-lactate-NS internalization, suggesting that LDH-lactate-NS penetrated the plasma membrane via non-endocytic pathways, which will widen the applicability to a variety of plant cells. Moreover, the absence of unwanted side effects in our cytological studies, and the nuclear localization of ssDNA-FITC suggest that nano-LDHs have potential application as a novel gene carrier to plants. PMID:27221055

  9. Thermal, solution and reductive decomposition of Cu-Al layered double hydroxides into oxide products

    SciTech Connect

    Britto, Sylvia; Vishnu Kamath, P.

    2009-05-15

    Cu-Al layered double hydroxides (LDHs) with [Cu]/[Al] ratio 2 adopt a structure with monoclinic symmetry while that with the ratio 0.25 adopt a structure with orthorhombic symmetry. The poor thermodynamic stability of the Cu-Al LDHs is due in part to the low enthalpies of formation of Cu(OH){sub 2} and CuCO{sub 3} and in part to the higher solubility of the LDH. Consequently, the Cu-Al LDH can be decomposed thermally (150 deg. C), hydrothermally (150 deg. C) and reductively (ascorbic acid, ambient temperature) to yield a variety of oxide products. Thermal decomposition at low (400 deg. C) temperature yields an X-ray amorphous residue, which reconstructs back to the LDH on soaking in water or standing in the ambient. Solution decomposition under hydrothermal conditions yields tenorite at 150 deg. C itself. Reductive decomposition yields a composite of Cu{sub 2}O and Al(OH){sub 3}, which on alkali-leaching of the latter, leads to the formation of fine particles of Cu{sub 2}O (<1 {mu}m). - Graphical abstract: SEM image of (a) the Cu{sub 2}O-Al(OH){sub 3} composite obtained on reductive decomposition of CuAl{sub 4}-LDH and (b) Cu{sub 2}O obtained on leaching of Al(OH){sub 3} from (a).

  10. Dual nutraceutical nanohybrids of folic acid and calcium containing layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Kim, Tae-Hyun; Oh, Jae-Min

    2016-01-01

    Dual nutraceutical nanohybrids consisting of organic nutrient, folic acid (FA), and mineral nutrient, calcium, were prepared based on layered double hydroxide (LDH) structure. Among various hybridization methods such as coprecipitation, ion exchange, solid phase reaction and exfoliation-reassembly, it was found that exfoliation-reassembly was the most effective in terms of intercalation of FA moiety between Ca-containing LDH layers. X-ray diffraction patterns and infrared spectra indicated that FA molecules were well stabilized in the interlayer space of LDHs through electrostatic interaction. From the atomic force and scanning electron microscopic studies, particle thickness of LDH was determined to be varied with tens, a few and again tens of nanometers in pristine, exfoliated and reassembled state, respectively, while preserving particle diameter. The result confirmed layer-by-layer hybrid structure of FA and LDHs was obtained by exfoliation-reassembly. Solid UV-vis spectra showed 2-dimensional molecular arrangement of FA moiety in hybrid, exhibiting slight red shift in n→π* and π→π* transition. The chemical formulae of FA intercalated Ca-containing LDH were determined to Ca1.30Al(OH)4.6FA0.74·3.33H2O and Ca1.53Fe(OH)5.06FA2.24·9.94H2O by inductively coupled plasma-atomic emission spectroscopy, high performance liquid chromatography and thermogravimetry, showing high nutraceutical content of FA and Ca.

  11. Facile assembly for fast construction of intercalation hybrids of layered double hydroxides with anionic metalloporphyrin.

    PubMed

    Ma, Juanjuan; Liu, Lin; Li, Shanzhong; Chen, Yonghao; Zhuo, Meng; Shao, Feng; Gong, Junyan; Tong, Zhiwei

    2014-07-14

    Anionic manganese tetrasulfonatophenyl porphyrin (MnTSPP) has been intercalated into the interlamellar space of Mg-Al and Ni-Al layered double hydroxides (LDHs) through the exfoliation/restacking approach by using exfoliated LDH nanosheets and guest molecules as building blocks. The obtained hybrids were characterized by a variety of analytical techniques such as CHN analysis, XRD, FTIR, SEM, HRTEM, UV-vis spectroscopy and thermal analysis. Interlayer spacings determined from XRD patterns reveal a perpendicular orientation of the MnTSPP anions between the hyroxylated layers of both LDHs. The results of zeta potential measurements give information about the surface charge change of LDH nanoparticles associated with the spontaneous coassembly process. The catalytic performance of the heterogeneous catalysts MnTSPP/Mg-Al LDH2.0 and MnTSPP/Ni-Al LDH1.0 for the epoxidation of cyclohexene was investigated using molecular oxygen as an oxidant and isobutylaldehyde as a co-reductant. The intercalated hybrids appear to be promising catalysts owing to their good catalytic activity and selectivity.

  12. Novel biohybrids of layered double hydroxide and lactate dehydrogenase enzyme: Synthesis, characterization and catalytic activity studies

    NASA Astrophysics Data System (ADS)

    Djebbi, Mohamed Amine; Braiek, Mohamed; Hidouri, Slah; Namour, Philippe; Jaffrezic-Renault, Nicole; Ben Haj Amara, Abdesslem

    2016-02-01

    The present work introduces new biohybrid materials involving layered double hydroxides (LDH) and biomolecule such as enzyme to produce bioinorganic system. Lactate dehydrogenase (Lac Deh) has been chosen as a model enzyme, being immobilized onto MgAl and ZnAl LDH materials via direct ion-exchange (adsorption) and co-precipitation methods. The immobilization efficiency was largely dependent upon the immobilization methods. A comparative study shows that the co-precipitation method favors the immobilization of great and tunable amount of enzyme. The structural behavior, chemical bonding composition and morphology of the resulting biohybrids were determined by X-ray diffraction (XRD) study, Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM), respectively. The free and immobilized enzyme activity and kinetic parameters were also reported using UV-Visible spectroscopy. However, the modified LDH materials showed a decrease in crystallinity as compared to the unmodified LDH. The change in activity of the immobilized lactate dehydrogenase was considered to be due, to the reduced accessibility of substrate molecules to the active sites of the enzyme and the partial conformational change of the Lac Deh molecules as a result of the immobilization way. Finally, it was proven that there is a correlation between structure/microstructure and enzyme activity dependent on the immobilization process.

  13. CdS-pillared CoAl-layered double hydroxide nanosheets with superior photocatalytic activity

    SciTech Connect

    Qiu, Yanqiang; Lin, Bizhou Jia, Fangcao; Chen, Yilin; Gao, Bifen; Liu, Peide

    2015-12-15

    Graphical abstract: - Highlights: • CdS nanocrystals were intercalated into CoAl-LDH interlayer. • The nanohybrid display superior visible-light photocatalytic activity. • A photoexcitation model for the pillared heterostructured system was proposed. - Abstract: A new nanohybrid was synthesized by mixing the positively charged 2D nanosheets of CoAl-layered double hydroxide (CoAl-LDH) and the negatively charged CdS nanosol suspensions. It was revealed that the CdS nanoparticles were intercalated into the interlayer region of CoAl-LDH with a spacing of 2.62 nm. The obtained nanohybrid exhibited a mesoporous texture with an expanded specific surface area of 62 m{sup 2} g{sup −1} and a superior photocatalytic activity in the degradation of acid red with a reaction constant of 1.26 × 10{sup −2} min{sup −1} under visible-light radiation, which is more than 2 times those of his parents CoAl-LDH and CdS.

  14. A thermochromic thin film based on host-guest interactions in a layered double hydroxide.

    PubMed

    Wang, Xinrui; Lu, Jun; Shi, Wenying; Li, Feng; Wei, Min; Evans, David G; Duan, Xue

    2010-01-19

    Optically transparent thin films with thermochromic properties have been fabricated by means of cointercalation of different molar ratios of 4-(4-anilinophenylazo)benzenesulfonate (AO5) and sodium dodecylbenzene sulfonate (SDS) into the galleries of a ZnAl layered double hydroxide (LDH). The X-ray diffraction (XRD) patterns of these thin films show that they are assembled in a highly c-oriented manner, and the basal spacing ranges from 2.95 to 2.63 nm with varying AO5/SDS molar ratio. The preferential orientation of AO5 in the galleries of 10% AO5-LDH (AO5/SDS = 10:90, molar percentage) was evaluated by the fluorescence polarization technique; the results show that AO5 anions are accommodated between sheets of ZnAl-LDH as monomeric units with a tilt angle Psi (defined as the angle between the transition dipole moment of the AO5 anion with respect to the normal to the LDH layer) of 74 degrees. It was found that the composite film exhibits marked thermochromic behavior (light yellow <==> reddish-orange) in the temperature range of 35-65 degrees C, which is reversible over a number of heating-cooling cycles. It has been demonstrated that the thermochromic behavior results from tautomerism of interlayer AO5 and furthermore that both the host-guest and guest-guest interactions are key factors, since pristine AO5 shows no thermochromic performance. The 10% AO5-LDH film shows the highest thermochromic efficiency of all the films examined. Furthermore, a reversible contraction and expansion of the LDH basal spacing was also observed for this thin film over the same temperature range.

  15. Dual nutraceutical nanohybrids of folic acid and calcium containing layered double hydroxides

    SciTech Connect

    Kim, Tae-Hyun; Oh, Jae-Min

    2016-01-15

    Dual nutraceutical nanohybrids consisting of organic nutrient, folic acid (FA), and mineral nutrient, calcium, were prepared based on layered double hydroxide (LDH) structure. Among various hybridization methods such as coprecipitation, ion exchange, solid phase reaction and exfoliation-reassembly, it was found that exfoliation-reassembly was the most effective in terms of intercalation of FA moiety between Ca-containing LDH layers. X-ray diffraction patterns and infrared spectra indicated that FA molecules were well stabilized in the interlayer space of LDHs through electrostatic interaction. From the atomic force and scanning electron microscopic studies, particle thickness of LDH was determined to be varied with tens, a few and again tens of nanometers in pristine, exfoliated and reassembled state, respectively, while preserving particle diameter. The result confirmed layer-by-layer hybrid structure of FA and LDHs was obtained by exfoliation-reassembly. Solid UV–vis spectra showed 2-dimensional molecular arrangement of FA moiety in hybrid, exhibiting slight red shift in n→π* and π→π* transition. The chemical formulae of FA intercalated Ca-containing LDH were determined to Ca{sub 1.30}Al(OH){sub 4.6}FA{sub 0.74}·3.33H{sub 2}O and Ca{sub 1.53}Fe(OH){sub 5.06}FA{sub 2.24}·9.94H{sub 2}O by inductively coupled plasma-atomic emission spectroscopy, high performance liquid chromatography and thermogravimetry, showing high nutraceutical content of FA and Ca. - Highlights: • We successfully intercalated FA molecules into Ca-containing LDHs. • Exfoliation-reassembly was proven to be the most effective. • The interaction between LDH and FA were studied by FT-IR and UV–vis spectra. • Thermal stability of FA were enhanced by electrostatic interaction with LDH layers.

  16. Intercalation of p-methycinnamic acid anion into Zn-Al layered double hydroxide to improve UV aging resistance of asphalt

    SciTech Connect

    Peng, Chao; Dai, Jing; Yu, Jianying; Yin, Jian

    2015-02-15

    A UV absorber, p-methycinnamic acid (PMCA), was intercalated into Zn-Al layered double hydroxide (LDH) by calcination recovery. Fourier transform infrared spectroscopy showed that the PMCA anions completely replaced the CO{sub 3}{sup 2−} anions in the interlayer galleries of Zn-Al-LDH containing PMCA anions (Zn-Al-PMCA-LDH). X-ray diffraction and transmission electron microscopy showed that the interlayer distance increased from 0.78 nm to 1.82 nm after the substitution of PMCA anions for CO{sub 3}{sup 2−} anions. The similar diffraction angles of the CO{sub 3}{sup 2−} anion-containing Zn-Al-LDH (Zn-Al-CO{sub 3}{sup 2−}-LDH) and the Zn-Al-CO{sub 3}{sup 2−}-LDH/styrene–butadiene–styrene (SBS) modified asphalt implied that the asphalt molecules do not enter into the LDH interlayer galleries to form separated-phase structures. The different diffraction angles of Zn-Al-PMCA-LDH and Zn-Al-PMCA-LDH/SBS modified asphalt indicated that the asphalt molecules penetrated into the LDH interlayer galleries to form an expanded-phase structure. UV-Vis absorbance analyses showed that Zn-Al-PMCA-LDH was better able to block UV light due to the synergistic effects of PMCA and Zn-Al-LDH. Conventional physical tests and atomic force microscopy images of the SBS modified asphalt, Zn-Al-CO{sub 3}{sup 2−}-LDH/SBS modified asphalt and Zn-Al-PMCA-LDH/SBS modified asphalt before and after UV aging indicated that Zn-Al-PMCA-LDH improved the UV aging resistance of SBS modified asphalts.

  17. Hierarchical Ni-Co layered double hydroxide nanosheets entrapped on conductive textile fibers: a cost-effective and flexible electrode for high-performance pseudocapacitors

    NASA Astrophysics Data System (ADS)

    Nagaraju, Goli; Raju, G. Seeta Rama; Ko, Yeong Hwan; Yu, Jae Su

    2015-12-01

    Hierarchical three-dimensional (3D) porous nanonetworks of nickel-cobalt layered double hydroxide (Ni-Co LDH) nanosheets (NSs) are grown and decorated on flexible conductive textile substrate (CTs) via a simple two-electrode system based electrochemical deposition (ED) method. By applying a proper external cathodic voltage of -1.2 V for 15 min, the Ni-Co LDH NSs are densely deposited over the entire surface of the CTs with good adhesion. The flexible Ni-Co LDH NSs on CTs (Ni-Co LDH NSs/CTs) architecture with high porosity facilitates enhanced electrochemical performance in 1 M KOH electrolyte solution. The effect of growth concentration and external cathodic voltage on the electrochemical properties of Ni-Co LDH NSs/CTs is also investigated. The Ni10Co5 LDH NSs/CTs electrode exhibits a high specific capacitance of 2105 F g-1 at a current density of 2 A g-1 as well as an excellent cyclic stability as a pseudocapacitive electrode due to the advantageous properties of 3D interconnected porous frameworks of Ni10Co5 LDH NSs/CTs. This facile fabrication of bimetallic hydroxide nanostructures on CTs can provide a promising electrode for low-cost energy storage device applications.Hierarchical three-dimensional (3D) porous nanonetworks of nickel-cobalt layered double hydroxide (Ni-Co LDH) nanosheets (NSs) are grown and decorated on flexible conductive textile substrate (CTs) via a simple two-electrode system based electrochemical deposition (ED) method. By applying a proper external cathodic voltage of -1.2 V for 15 min, the Ni-Co LDH NSs are densely deposited over the entire surface of the CTs with good adhesion. The flexible Ni-Co LDH NSs on CTs (Ni-Co LDH NSs/CTs) architecture with high porosity facilitates enhanced electrochemical performance in 1 M KOH electrolyte solution. The effect of growth concentration and external cathodic voltage on the electrochemical properties of Ni-Co LDH NSs/CTs is also investigated. The Ni10Co5 LDH NSs/CTs electrode exhibits a high

  18. Accessing the biocompatibility of layered double hydroxide by intramuscular implantation: histological and microcirculation evaluation

    PubMed Central

    Cunha, Vanessa Roberta Rodrigues; de Souza, Rodrigo Barbosa; da Fonseca Martins, Ana Maria Cristina Rebello Pinto; Koh, Ivan Hong Jun; Constantino, Vera Regina Leopoldo

    2016-01-01

    Biocompatibility of layered double hydroxides (LDHs), also known as hydrotalcite-like materials or double metal hydroxides, was investigated by in vivo assays via intramuscular tablets implantation in rat abdominal wall. The tablets were composed by chloride ions intercalated into LDH of magnesium/aluminum (Mg2Al-Cl) and zinc/aluminum (Zn2Al-Cl). The antigenicity and tissue integration capacity of LDHs were assessed histologically after 7 and 28 days post-implantation. No fibrous capsule nearby the LDH was noticed for both materials as well any sign of inflammatory reactions. Sidestream Dark Field imaging, used to monitor in real time the microcirculation in tissues, revealed overall integrity of the microcirculatory network neighboring the tablets, with no blood flow obstruction, bleeding and/or increasing of leukocyte endothelial adhesion. After 28 days Mg2Al-Cl promoted multiple collagen invaginations (mostly collagen type-I) among its fragments while Zn2Al-Cl induced predominantly collagen type–III. This work supports previous results in the literature about LDHs compatibility with living matter, endorsing them as functional materials for biomedical applications. PMID:27480483

  19. Phosphate-intercalated Ca-Fe-layered double hydroxides: Crystal structure, bonding character, and release kinetics of phosphate

    SciTech Connect

    Woo, Myong A.; Woo Kim, Tae; Paek, Mi-Jeong; Ha, Hyung-Wook; Choy, Jin-Ho; Hwang, Seong-Ju

    2011-01-15

    The nitrate-form of Ca-Fe-layered double hydroxide (Ca-Fe-LDH) was synthesized via co-precipitation method, and its phosphate-intercalates were prepared by ion-exchange reaction. According to X-ray diffraction analysis, the Ca-Fe-LDH-NO{sub 3}{sup -} compound and its H{sub 2}PO{sub 4}{sup -}-intercalate showed hexagonal layered structures, whereas the ion-exchange reaction with HPO{sub 4}{sup 2-} caused a frustration of the layer ordering of LDH. Fe K-edge X-ray absorption spectroscopy clearly demonstrated that the Ca-Fe-LDH lattice with trivalent iron ions was well-maintained after the ion-exchange with HPO{sub 4}{sup 2-} and H{sub 2}PO{sub 4}{sup -}. Under acidic conditions, phosphate ions were slowly released from the Ca-Fe-LDH lattice and the simultaneous release of hydroxide caused the neutralization of acidic media. Fitting analysis based on kinetic models indicated a heterogeneous diffusion process of phosphates and a distinct dependence of release rate on the charge of phosphates. This study strongly suggested that Ca-Fe-LDH is applicable as bifunctional vector for slow release of phosphate fertilizer and for the neutralization of acid soil. -- Graphical abstract: We synthesized phosphate-intercalated Ca-Fe-LDH materials that can act as bifunctional inorganic vectors for the slow release of phosphate fertilizer and also the neutralization of acid soil. Fitting analysis based on kinetic models indicated a heterogeneous diffusion process of phosphates and a distinct dependence of release rate on the charge of phosphates. Display Omitted Research Highlights: {yields} The phosphate forms of Ca-Fe-layered double hydroxide (Ca-Fe-LDH) were synthesized via co-precipitation method. The crystal structure, bonding character, and release kinetics of phosphate of the phosphate-intercalates were investigated. These Ca-Fe-LDH materials are applicable as bifunctional vector for slow release of phosphate fertilizer and for the neutralization of acid soil.

  20. Study of the structure and luminescent properties of terbium complex intercalated Zn/Al layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Gao, Xiaorui; Xie, Juan; Yin, Yaobing; Hao, Yongjing; Lian, Yiwei

    2016-01-01

    Terbium complex of ethylenediaminetetraacetate ([Tb(EDTA)]-) intercalated Zn/Al layered double hydroxide (LDH), as an inorganic-organic green-emitting phosphor, was synthesized through an ion exchange method. X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) spectra exhibit a successful intercalation of [Tb(EDTA)]- anions between the hydroxide sheets of the LDH. The basal spacing of 14.5 Å indicate a vertical arrangement of [Tb(EDTA)]- anions with the maximal dimension in the gallery is adopted. The luminescent properties of this material were studied by excitation and emission spectra. The results show that the strongest emission peak of Tb3+ ion occurs at 544 nm. This material may supply a candidate of green light emitting phosphor.

  1. Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions.

    PubMed

    You, Youwen; Vance, George F; Sparks, Donald L; Zhuang, Jie; Jin, Yan

    2003-01-01

    Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.

  2. Facile synthesis of novel two-dimensional silver-coated layered double hydroxide nanosheets as advanced anode material for Ni-Zn secondary batteries

    NASA Astrophysics Data System (ADS)

    Yang, Bin; Yang, Zhanhong; Wang, Ruijuan

    2014-04-01

    Silver-coated layered double hydroxide (Ag-coated LDH) nanosheets are successfully prepared by a facile silver mirror reaction and their electrochemical performance has been evaluated as anode materials for Ni-Zn secondary batteries. The microstructure and morphology of as-prepared Ag-coated Zn/Al-LDH are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). As anode material for Ni-Zn secondary batteries, Ag-coated Zn/Al-LDH exhibits high specific capacity (400 mAh g-1), good charge-discharge properties and excellent cycling performance, which is attributed to the effect of the electron conductivity improvement by the Ag coating on the surface of Zn/Al-LDH nanosheet. This newly designed Ag-coated Zn/Al-LDH may offer a promising anode candidate for high-performance Ni-Zn secondary batteries.

  3. Drug intercalation in layered double hydroxide clay: application in the development of a nanocomposite film for guided tissue regeneration.

    PubMed

    Chakraborti, Michelle; Jackson, John K; Plackett, David; Brunette, Donald M; Burt, Helen M

    2011-09-15

    It has been proposed that localized and controlled delivery of alendronate and tetracycline to periodontal pocket fluids via guided tissue regeneration (GTR) membranes may be a valuable adjunctive treatment for advanced periodontitis. The objectives of this work were to develop a co-loaded, controlled release tetracycline and alendronate nanocomposite plasticized poly(lactic-co-glycolic acid) (PLGA) film that would form a suitable matrix supporting osteoblast proliferation and differentiation. Alendronate release was successfully controlled, with complete suppression of the burst phase of release by intercalation of alendronate anions in magnesium/aluminum layered double hydroxide (LDH) clay nanoparticles and dispersed in the PLGA film matrix. Tetracycline, loaded as free drug into the film together with alendronate-LDH clay complex released more rapidly than alendronate, but showed evidence of intercalation in the LDH clay particles. The dual drug loaded nanocomposite films were biocompatible with osteoblasts and after 5 week incubations, significant increase in alkaline phosphatase activity and bone nodule formation were observed.

  4. Improvement of pharmacokinetic and antitumor activity of layered double hydroxide nanoparticles by coating with PEGylated phospholipid membrane

    PubMed Central

    Yan, Mina; Zhang, Zhaoguo; Cui, Shengmiao; Lei, Ming; Zeng, Ke; Liao, Yunhui; Chu, Weijing; Deng, Yihui; Zhao, Chunshun

    2014-01-01

    Layered double hydroxide (LDH) has attracted considerable attention as a drug carrier. However, because of its poor in vivo behavior, polyethylene glycolylated (PEGylated) phospholipid must be used as a coformer to produce self-assembled core–shell nanoparticles. In the present study, we prepared a PEGylated phospholipid-coated LDH (PLDH) (PEG-PLDH) delivery system. The PEG-PLDH nanoparticles had an average size of 133.2 nm. Their core–shell structure was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. In vitro liposome-cell-association and cytotoxicity experiments demonstrated its ability to be internalized by cells. In vivo studies showed that PEGylated phospholipid membranes greatly reduced the blood clearance rate of LDH nanoparticles. PEG-PLDH nanoparticles demonstrated a good control of tumor growth and increased the survival rate of mice. These results suggest that PEG-PLDH nanoparticles can be a useful drug delivery system for cancer therapy. PMID:25364245

  5. Gold Nanoparticles Supported on a Layered Double Hydroxide as Efficient Catalysts for the One-Pot Synthesis of Flavones.

    PubMed

    Yatabe, Takafumi; Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-11-02

    Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step-by-step procedures using stoichiometric amounts of reagents. Herein, a catalytic one-pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg-Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2'-hydroxyacetophenones and benzaldehydes (or benzyl alcohols). The present one-pot procedure consists of a sequence of several reactions, and Au/LDH can catalyze all these different types of reactions. The catalysis is shown to be truly heterogeneous, and Au/LDH can be readily recovered and reused.

  6. Effect of reaction time and (Ca+Mg)/Al molar ratios on crystallinity of Ca-Mg-Al layered double Hydroxide

    NASA Astrophysics Data System (ADS)

    Heraldy, E.; Nugrahaningtyas, K. D.; Sanjaya, F. B.; Darojat, A. A.; Handayani, D. S.; Hidayat, Y.

    2016-02-01

    Ca-Mg-Al Layered Double Hydroxides (Ca-Mg-Al-LDH) compounds were successfully synthesized from brine water and AlCl3.6H2O as the starting materials by coprecipitation method. The product result was characterized by X-ray powder diffraction (XRD) and Fourier transform infrared (FT-IR). The effects of the reaction time and the molar ratios of the raw material on the crystallinity of Ca-Mg-Al-LDH were examining. Results show that increasing reaction time (30; 60 and 90 min.) could improve the crystallinity and monodispersity of layered double hydroxide compounds particles. The well-defined Ca-Mg- Al-LDH could be prepared with (Ca+Mg)/Al molar ratios 0.5.

  7. Controlled drug release from antibiotic-loaded layered double hydroxide coatings on porous titanium implants in a mouse model.

    PubMed

    Badar, Muhammad; Rahim, Muhammad Imran; Kieke, Marc; Ebel, Thomas; Rohde, Manfred; Hauser, Hansjörg; Behrens, Peter; Mueller, Peter P

    2015-06-01

    As an alternative to degradable organic coatings the possibility of using layered double hydroxides (LDHs) to generate implant coatings for controlled drug delivery was evaluated in vivo and in vitro. Coatings prepared from LDH suspensions dissolved slowly and appeared compatible with cultured cells. LDH coatings loaded with an antibiotic resulted in antibacterial effects in vitro. The LDH coating prolonged the drug release period and improved the proliferation of adherent cells in comparison to pure drug coatings. However, during incubation in physiological solutions the LDH coatings became brittle and pieces occasionally detached from the surface. For stress protection porous titanium implants were investigated as a substrate for the coatings. The pores prevented premature detachment of the coatings. To evaluate the coated porous implants in vivo a mouse model was established. To monitor bacterial infection of implants noninvasive in vivo imaging was used to monitor luminescently labeled Pseudomonas aeruginosa. In this model porous implants with antibiotic-loaded LDH coatings could antagonize bacterial infections for over 1 week. The findings provide evidence that delayed drug delivery from LDH coatings could be feasible in combination with structured implant surfaces.

  8. DFT-Based Simulation and Experimental Validation of the Topotactic Transformation of MgAl Layered Double Hydroxides.

    PubMed

    Zhang, Shi-Tong; Dou, Yibo; Zhou, Junyao; Pu, Min; Yan, Hong; Wei, Min; Evans, David G; Duan, Xue

    2016-09-05

    The thermal topotactic transformation mechanism of MgAl layered double hydroxides (LDHs) is investigated by a combined theoretical and experimental study. Thermogravimetric differential thermal analysis (TG-DTA) results reveal that the LDH phase undergoes four key endothermic events at 230, 330, 450, and 800 °C. DFT calculations show that the LDH decomposes into CO2 and residual O atoms via a monodentate intermediate at 330 °C. At 450 °C, the metal cations almost maintain their original distribution within the LDH(001) facet during the thermal dehydration process, but migrate substantially along the c-axis direction perpendicular to the (001) facet; this indicates that the metal arrangement/dispersion in the LDH matrix is maintained two-dimensionally. A complete collapse of the layered structure occurs at 800 °C, which results in a totally disordered cation distribution and many holes in the final product. The structures of the simulated intermediates are highly consistent with the observed in situ powder XRD data for the MgAl LDH sample calcined at the corresponding temperatures. Understanding the structural topotactic transformation process of LDHs would provide helpful information for the design and preparation of metal/metal oxides functional materials derived from LDH precursors.

  9. Layered double hydroxide intercalated with p-methylbenzoate and p-bromobenzoate: molecular simulations and XRD analysis.

    PubMed

    Kovár, Petr; Melánová, Klára; Zima, Vítezslav; Benes, Ludvík; Capková, Pavla

    2008-03-01

    Samples of Mg4Al2 layered double hydroxide (LDH) intercalated with p-methylbenzoate and p-bromobenzoate anions were prepared by reconstruction of calcined LDH. The interlayer arrangement of guests was investigated by molecular modeling combined with X-ray powder diffraction and thermogravimetry. Molecular modeling was carried out in a Cerius2 modeling environment. In both structures the guest anions adopt a nearly perpendicular arrangement of their long axis with respect to the host layers and they are anchored to the OH groups of the layers through COO* groups via electrostatic interactions. Molecular modeling revealed that both structures of the intercalates exhibit a certain disorder of guest anions in the interlayer space. In the case of LDH-p-methylbenzoate intercalate the anions tend to be situated in disordered rows, and the LDH-p-bromobenzoate intercalate exhibits a total disorientation of guest anions. A good agreement between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings was obtained. In the LDH-p-methylbenzoate intercalate d exp=16.96 A and d calc=16.97 A, and in the case of LDH-p-bromobenzoate intercalate d exp=17.19 A and d calc=17.40 A.

  10. Facile synthesis of methotrexate intercalated layered double hydroxides: particle control, structure and bioassay explore.

    PubMed

    Tian, De-Ying; Liu, Zhen-Lei; Li, Shu-Ping; Li, Xiao-Dong

    2014-12-01

    To study the influence of particle size on drug efficacy and other properties, a series of methotrexate intercalated layered double hydroxides (MTX/LDHs) were synthesized through the traditional coprecipitation method, using a mixture of water and polyethylene glycol (PEG-400) as the solvent. To adjust the particle size of MTX/LDHs, the dropping way, the volume ratio of water to PEG-400 and different hydrothermal treatment time changed accordingly, and the results indicate that the particle size can be controlled between 90 and 140 nm. Elemental C/H/N and inductive coupled plasma (ICP) analysis indicated that different synthesis conditions almost have no effect on the compositions of the nanohybrids. X-ray diffraction (XRD) patterns manifested the successful intercalation of MTX anions into the LDH interlayers, and it's also found out that different volume ratios of water to PEG-400 and variable dropping way can affect the crystallinity of the final samples, i.e., the volume ratio of 3:1 and pH decreasing are proved to be optimum conditions. Furthermore, both antiparallel monolayer and bilayers adopting different orientations are suggested for four samples from XRD results. Fourier transform infrared spectroscopy (FTIR) investigations proved the coexistence of CO3(2-) and MTX anions in the interlayer of the nanohybrids. MTX/LDH particles exhibited hexagonal platelet morphology with round corner and different dropping ways can affect the morphology greatly. Moreover, a DSC study indicated that longer time treatment can weaken the bond between the MTX anions and LDH layers. The kinetic release profiles told us that larger MTX/LDH particles have enhanced the ability of LDH layers to protect interlayer molecules. At last, the bioassay study indicated that the nanohybrids with larger diameters have higher tumor suppression efficiency.

  11. Compositional and Structural Control on Anion Sorption Capability of Layered Double Hydroxides (LDHS)

    SciTech Connect

    Y. Wang; H. Gao

    2006-03-16

    Layered double hydroxides (LDHs) have shown great promise as anion getters. In this paper, we demonstrate that the sorption capability of a LDH for a specific oxyanion can be greatly increased by appropriately manipulating material composition and structure. A large set of LDH materials have been synthesized with various combinations of metal cations, interlayer anions, and the molar ratios of divalent cation M(II) to trivalent cation M(III). The synthesized materials have then been tested systematically for their sorption capabilities for pertechnetate (TcO{sub 4}{sup -}). It is discovered that for a given interlayer anion (either CO{sub 3}{sup 2-} or NO{sub 3}{sup -}) the Ni-Al LDH with a Ni/Al ratio of 3:1 exhibits the highest sorption capability among all the materials tested. The distribution coefficient (K{sub d}) is determined to be as high as 307 mL/g for Ni{sub 6}Al{sub 2}(0H){sub 16}CO{sub 3}nH{sub 2}O and 1390 mL/g for Ni{sub 6}Al{sub 2}(OH){sub 16}NO{sub 3}nH{sub 2}O at a pH of 8. The sorption of TcO{sub 4}{sup -} on M(II)-M(III)-CO{sub 3} LDHs is dominated by the edge sites of LDH layers and strongly correlated with the basal spacing d{sub 003} of the materials, which increases with the decreasing radii of both divalent and trivalent cations. The sorption reaches its maximum when the layer spacing is just large enough for a pertechnetate anion to fit into a cage space between two neighboring octahedra of metal hydroxides at the edge. Furthermore, the sorption is found to increase with the crystallinity of the materials. For a given combination of metal cations and an interlayer anion, a best crystalline LDH material is obtained generally with a M(II)/M(III) ratio of 3:1. Replacement of interlayer carbonate with readily exchangeable nitrate greatly increases the sorption capability of a LDH material for pertechnetate, due to the enhanced adsorption on edge sites and the possible contribution from interlayer anion exchanges. The work reported here will

  12. Aluminium substitution in iron(II III)-layered double hydroxides: Formation and cationic order

    NASA Astrophysics Data System (ADS)

    Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha; Medjahdi, Ghouti; Brunelli, Michela; François, Michel

    2008-09-01

    The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe4IIFe(2-6y)IIIAl6yIII (OH) 12 SO 4, 8H 2O are followed by pH titration curves, Mössbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO 42-), i.e. y=0, in which a bilayer of sulphate anions points to the Fe 3+ species. A cationic order is proposed to occur in both GR(SO 42-) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cell parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO 42-) is preceded by the successive precipitation of Fe III and Al III (oxy)hydroxides. Adsorption of more soluble Al III species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount ( y˜0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe II species of the material.

  13. Enhanced sequestration of Cr(VI) by nanoscale zero-valent iron supported on layered double hydroxide by batch and XAFS study.

    PubMed

    Sheng, Guodong; Hu, Jun; Li, Hui; Li, Jiaxing; Huang, Yuying

    2016-04-01

    Herein, the reduction of nanoscale zero-valent iron (NZVI) and adsorption of layered double hydroxides (LDH) to sequester Cr(VI) were well combined by the immobilization of NZVI onto LDH surface (NZVI/LDH). The characterization results revealed that LDH decreased NZVI aggregation and thus increased Cr(VI) sequestration. The batch results indicated that Cr(VI) sequestration by NZVI/LDH was higher than that of NZVI, and superior to the sum of reduction and adsorption. The LDH with good anion exchange property allowed the adsorption of Cr(VI), facilitating interfacial reaction by increasing the local concentration of Cr(VI) in the NZVI vicinity. X-ray absorption near edge structure (XANES) results indicated that Cr(VI) was almost completely reduced to Cr(III) by NZVI/LDH, but Cr(VI) was partly reduced to Cr(III) by NZVI with a trace of Cr(VI) adsorbed on corrosion products. The coordination environment of Cr from extended X-ray absorption fine structure (EXAFS) analysis revealed that LDH could be a good scavenger for the insoluble products produced during reaction. So, the insoluble products on NZVI could be reduced, and its reactivity could be maintained. These results demonstrated that NZVI/LDH exhibits multiple functionalities relevant to the remediation of Cr(VI)-contaminated sites.

  14. Equilibrium and kinetics studies on As(V) and Sb(V) removal by Fe2+ -doped Mg-Al layered double hydroxides.

    PubMed

    Kameda, Tomohito; Kondo, Eisuke; Yoshioka, Toshiaki

    2015-03-15

    Mg-Al layered double hydroxides (Mg-Al LDHs) doped with Fe(2+) adsorbed As(V) [Formula: see text] and Sb(V) [Formula: see text] from an aqueous solution through anion exchange with Cl(-) intercalated in the LDH interlayer. Fe(2+)-doped Mg-Al LDH exhibited superior As(V) removal compared with Mg-Al LDH. The oxidation of Fe(2+) doped in the Mg-Al LDH host layer to Fe(3+) increased the positive layer charge of the LDH, thus increasing the anion-uptake capacity owing to stronger electrostatic attractive force between the positively charged layer and the anion. However, Fe(2+)-doped Mg-Al LDH was not superior to Mg-Al LDH in terms of Sb(V) removal. This was attributed to the preferential intercalation of OH(-) over [Formula: see text] . The As(V) and Sb(V) removal by LDH followed Langmuir-type adsorption, which proceeded via a pseudo-first-order reaction. The equilibrium and kinetics studies confirm that the adsorption of As(V) and Sb(V) by Fe(2+)-doped Mg-Al LDH was the result of chemical adsorption, involving the anion exchange of [Formula: see text] and [Formula: see text] with the intercalated Cl(-).

  15. Optimization of UV absorptivity of layered double hydroxide by intercalating organic UV-absorbent molecules.

    PubMed

    Mohsin, Sumaiyah Megat Nabil; Hussein, Mohd Zobir; Sarijo, Siti Halimah; Fakurazi, Sharida; Arulselvan, Palanisamy; Taufiq-Yap, Yun Hin

    2014-08-01

    Intercalation of Zn/Al layered double hydroxide (LDH) with benzophenone 9 (B9), a strong ultraviolet (UV) absorber, had been carried out by two different routes; co-precipitation and ion exchange method. Powder X-ray diffraction (PXRD) patterns of co-precipitated (ZB9C) and ion exchanged product (ZB91) showed basal spacing of 15.9 angstrom and 16.6 angstrom, respectively, as a result of the intercalation of B9 anions into the lamellae spaces of LDH. Intercalation was further confirmed by Fourier transform infrared spectra (FTIR), carbon, hydrogen, nitrogen and sulfur (CHNS) and thermogravimetric and differential thermogravimetric (TGA/DTG) studies. UV-vis absorption properties of the nanocomposite was investigated with diffuse reflectance UV-visible spectrometer and showed broader UV absorption range. Furthermore, stability of sunscreen molecules in LDH interlayer space was tested in deionized water, artificial sea water and skin pH condition to show slow deintercalation and high retention in host. Cytotoxicity study of the synthesized nanocomposites on human dermal fibroblast (HDF) cells shows no significant cytotoxicity after 24 h exposure for test concentrations up to 25 microg/mL.

  16. Nickel-cobalt layered double hydroxide nanosheets as high-performance electrocatalyst for oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Jiang, Jing; Zhang, Ailing; Li, Lili; Ai, Lunhong

    2015-03-01

    Developing the first-row transition-metal-based oxygen evolution reaction (OER) catalysts with highly efficient electrocatalytic activity to replace precious catalysts, such as RuO2 and IrO2 have recently attracted considerable attention because of their earth abundant nature, low cost, environmentally friendly, multiple valence state and high theoretical activity. In this work, an advanced integrated electrode for high-performance electrochemical water oxidation has been designed and fabricated by directly growing binary nickel-cobalt layered double hydroxide (NiCo-LDH) nanosheet arrays on nickel foam. Such economical, earth abundant NiCo-LDH nanosheets show excellent OER activity in alkaline medium with an onset overpotential as low as 290 mV, large anodic current density and excellent durability, which makes them comparable to the most active RuO2 catalyst and better than the Pt/C catalyst. The outstanding OER activity of the NiCo-LDH nanosheets can be attributed to their intrinsic layered structure, interconnected nanoarray configuration and unique redox characteristics.

  17. Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers.

    PubMed

    Drenkova-Tuhtan, Asya; Mandel, Karl; Paulus, Anja; Meyer, Carsten; Hutter, Frank; Gellermann, Carsten; Sextl, Gerhard; Franzreb, Matthias; Steinmetz, Heidrun

    2013-10-01

    An innovative nanocomposite material is proposed for phosphate recovery from wastewater using magnetic assistance. Superparamagnetic microparticles modified with layered double hydroxide (LDH) ion exchangers of various compositions act as phosphate adsorbers. Magnetic separation and chemical regeneration of the particles allows their reuse, leading to the successful recovery of phosphate. Based upon the preliminary screening of different LDH ion exchanger modifications for phosphate selectivity and uptake capacity, MgFe-Zr LDH coated magnetic particles were chosen for further characterization and application. The adsorption kinetics of phosphate from municipal wastewater was studied in dependence with particle concentration, contact time and pH. Adsorption isotherms were then determined for the selected particle system. Recovery of phosphate and regeneration of the particles was examined via testing a variety of desorption solutions. Reusability of the particles was demonstrated for 15 adsorption/desorption cycles. Adsorption in the range of 75-97% was achieved in each cycle after 1 h contact time. Phosphate recovery and enrichment was possible through repetitive application of the desorption solution. Finally, a pilot scale experiment was carried out by treating 125 L of wastewater with the particles in five subsequent 25 L batches. Solid-liquid separation on this scale was carried out with a high-gradient magnetic filter (HGMF).

  18. Ultrahigh Enzyme Activity Assembled in Layered Double Hydroxides via Mg(2+)-Allosteric Effector.

    PubMed

    Wang, Min; Huang, Shu-Wan; Xu, Dan; Bao, Wen-Jing; Xia, Xing-Hua

    2015-06-02

    It is well-known that some metal ions could be allosteric effectors of allosteric enzymes to activate/inhibit the catalytic activities of enzymes. In nanobiocatalytic systems constructed based on the positive metal ion-induced allosteric effect, the incorporated enzymes will be activated and thus exhibit excellent catalytic performance. Herein, we present an environmentally friendly strategy to construct a novel allosteric effect-based β-galactosidase/Mg-Al layered double hydroxide (β-gal/Mg-Al-LDH) nanobiocatalytic system via the delamination-reconstruction method. The intercalated β-gal in the LDH galleries changes its conformation significantly due to the Mg(2+)-induced allosteric interactions and other weak interactions, which causes the activation of enzymatic activity. The β-gal/Mg-Al-LDH nanobiocatalytic system shows much higher catalytic activity and affinity toward its substrate and about 30 times higher catalytic reaction velocity than the free β-gal, which suggests that Mg(2+)-induced allosteric effect plays a vital role in the improvement of enzymatic performance.

  19. Methotrexatum intercalated layered double hydroxides: statistical design, mechanism explore and bioassay study.

    PubMed

    Wang, Xiao-Feng; Liu, Su-Qing; Li, Shu-Ping

    2015-04-01

    A series of methotrexatum intercalated layered double hydroxide (MTX/LDH for short) hybrids have been synthesized by a mechanochemical-hydrothermal method, the statistical experiments are planned and conducted to find out the critical factor influencing the physicochemical properties. Four variables, i.e., addition of NaOH solution, grinding duration, hydrothermal temperature and time, are chosen to play as the examined factors in the orthogonal design. Furthermore, three respective levels, i.e., high, medium and low levels, are conducted in the design. The resulting hybrids are then characterized by X-ray diffraction (XRD) patterns, transmission electron microscope (TEM) graphs and Zeta potentials. XRD diffractions indicate that MTX anions have been successfully intercalated into LDH interlayers and the amount of NaOH solution can change the gallery height greatly. The information from TEM graphs and Zeta potentials state that the increase of alkali solution gives rise to regular morphology and the increase of Zeta potentials. As a result of the statistical analysis, addition of alkali solution is the major factor affecting the morphology and drug-loading capacity. At last, the mechanism of particle growth is explored emphatically, and the anticancer efficacy of some MTX/LDH hybrids is estimated by MTT assay on A549 cells as well.

  20. Dependence of bonding interactions in Layered Double Hydroxides on metal cation chemistry

    NASA Astrophysics Data System (ADS)

    Shamim, Mostofa; Dana, Kausik

    2016-12-01

    The evolution of various Infrared bands of Layered Double Hydroxides (LDH) with variable Zn:Al ratio was analyzed to correlate it with the changes in octahedral metal cation chemistry, interlayer carbonate anion and hydroxyl content of LDH. The synthesized phase-pure LDHs were crystallized as hexagonal 2H polytype with a Manasseite structure. The broad and asymmetric hydroxyl stretching region (2400-4000 cm-1) can be deconvoluted into four different bands. With increase in Zn2+:Al3+ metal ratio, the peak position of stretching frequencies of Al3+sbnd OH and carbonate-bridged hydroxyl (water) decrease almost linearly. Individual band's peak position and area under the curve have been successfully correlated with the carbonate and hydroxyl content of LDH. Due to lowering of symmetry of the carbonate anion, the IR-inactive peak νCsbnd O, symm at 1064 cm-1 becomes IR active. The peak position of metal-oxygen bands and carbonate bending modes are practically unaffected by the Zn2+:Al3+ ratio but the area under the individual M-O bands shows a direct correlation.

  1. Layered double hydroxides as supports for intercalation and sustained release of antihypertensive drugs

    NASA Astrophysics Data System (ADS)

    Xia, Sheng-Jie; Ni, Zhe-Ming; Xu, Qian; Hu, Bao-Xiang; Hu, Jun

    2008-10-01

    Zn/Al layered double hydroxides (LDHs) were intercalated with the anionic antihypertensive drugs Enalpril, Lisinopril, Captopril and Ramipril by using coprecipitation or ion-exchange technique. TG-MS analyses suggested that the thermal stability of Ena -, Lis - (arranged with monolayer, resulted from X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) analysis was enhanced much more than Cap - and Ram - (arranged with bilayer). The release studies show that the release rate of all samples markedly decreased in both pH 4.25 and 7.45. However, the release time of Ena -, Lis - were much longer compared with Cap -, Ram - in both pH 4.25 and 7.45, it is possible that the intercalated guests, arranged with monolayer in the interlayer, show lesser repulsive force and strong affinity with the LDH layers. And the release data followed both the Higuchi-square-root law and the first-order equation well. Based on the analysis of batch release, intercalated structural models as well as the TG-DTA results, we conclude that for drug-LDH, stronger the affinity between intercalated anions and the layers is, better the thermal property and the stability to the acid attack of drug-LDH, and the intercalated anions are easier apt to monolayer arrangement within the interlayer, were presented.

  2. Synergistic Effect of Cobalt and Iron in Layered Double Hydroxide Catalysts for the Oxygen Evolution Reaction.

    PubMed

    Yang, Fengkai; Sliozberg, Kirill; Sinev, Ilya; Antoni, Hendrik; Bähr, Alexander; Ollegott, Kevin; Xia, Wei; Masa, Justus; Grünert, Wolfgang; Cuenya, Beatriz Roldan; Schuhmann, Wolfgang; Muhler, Martin

    2017-01-10

    Co-based layered double hydroxide (LDH) catalysts with Fe and Al contents in the range of 15 to 45 at % were synthesized by an efficient coprecipitation method. In these catalysts, Fe(3+) or Al(3+) ions play an essential role as trivalent species to stabilize the LDH structure. The obtained catalysts were characterized by a comprehensive combination of surface- and bulk-sensitive techniques and were evaluated for the oxygen evolution reaction (OER) on rotating disk electrodes. The OER activity decreased upon increasing the Al content for the Co- and Al-based LDH catalysts, whereas a synergistic effect in Co- and Fe-based LDHs was observed, which resulted in an optimal Fe content of 35 at %. This catalyst was spray-coated on Ni foam electrodes and showed very good stability in a flow-through cell with a potential of approximately 1.53 V at 10 mA cm(-2) in 1 m KOH for at least 48 h.

  3. Interlayer intercalation and arrangement of 2-mercaptobenzothiazolate and 1,2,3-benzotriazolate anions in layered double hydroxides: In situ X-ray diffraction study

    NASA Astrophysics Data System (ADS)

    Serdechnova, Maria; Salak, Andrei N.; Barbosa, Filipe S.; Vieira, Daniel E. L.; Tedim, João; Zheludkevich, Mikhail L.; Ferreira, Mário G. S.

    2016-01-01

    2-mercaptobenzothiazole (MBT) and 1,2,3-benzotriazole (BTA) are very promising inhibitors for the corrosion protection of aluminum alloys. These inhibitors can be incorporated in protective coatings in the form of anions intercalated into interlayers of layered double hydroxides (LDHs). Capacity and performance of such LDH-nanocontainers depend on the arrangement of the anions in their interlayers. In this work, intercalation of MBT- and BTA- into Mg-Al-NO3 and Zn-Al-NO3 LDHs were studied in detail using X-ray diffraction (XRD) methods including in situ XRD. The nitrate-to-MBT(BTA) anion exchange is much faster than considered previously. Well-formed Mg-Al-MBT, Zn-Al-MBT, Mg-Al-BTA LDHs were obtained after a 20-min exchange reaction at pH 11.5 at room temperature. It was demonstrated that Zn-Al-BTA LDH cannot be obtained under the same conditions due to the reaction between BTA and the Zn-Al hydroxide layers. Substitution of nitrates by organic anions occurs with the participation of hydroxide anions. Although no intermediate LDH phase intercalated with the combination of NO3 - and OH- appears, formation of the LDH-MBT and LDH-BTA phases results also in appearance of an LDH phase intercalated with OH- at the final stage of the anion exchange. In the LDH interlayer, MBT- and BTA- form a double layer in which these species have a tilted orientation against the layer plane (herringbone-like arrangement). Such an arrangement meets the LDH layer-interlayer electroneutrality and matches well with the observed values of the layer-interlayer distance.

  4. Thermal decomposition behavior of Cu–Al layered double hydroxide, and ethylenediaminetetraacetate-intercalated Cu–Al layered double hydroxide reconstructed from Cu–Al oxide for uptake of Y{sup 3+} from aqueous solution

    SciTech Connect

    Kameda, Tomohito; Hoshi, Kazuaki; Yoshioka, Toshiaki

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► Decomposition of CO{sub 3}·Cu–Al LDH occurred in four stages. ► The edta·Cu–Al LDH was found to take up Y{sup 3+} in aqueous solution. ► The edta·Cu–Al LDH could selectively take up rare earth ions from a mixed solution. -- Abstract: CO{sub 3}{sup 2−}-intercalated Cu–Al layered double hydroxide (CO{sub 3}·Cu–Al LDH) was calcined to yield Cu–Al oxide, and then ethylenediaminetetraacetate-intercalated Cu–Al LDH (edta·Cu–Al LDH) was prepared by reconstructing Cu–Al oxide in edta solution. Decomposition of CO{sub 3}·Cu–Al LDH occurred in four stages. The production of Cu–Al oxide was caused by the thermal decomposition of CO{sub 3}·Cu–Al LDH until the third stage. The first stage was the elimination of adsorbed surface water and interlayer water in CO{sub 3}·Cu–Al LDH. The second and third stages were the dehydroxylation of the brucite-like octahedral layers and the elimination of CO{sub 3}{sup 2−} intercalated in the interlayers. The edta·Cu–Al LDH was found to take up Y{sup 3+} in aqueous solution. The uptake of Y{sup 3+} was caused not only by the chelating function of Hedta{sup 3−} in the interlayer but also by the chemical behavior of Cu–Al LDH itself. The edta·Cu–Al LDH was found to selectively take up rare earth ions from a mixed solution. The degree of uptake was high, in the order Sc{sup 3+} > Y{sup 3+} > La{sup 3+} for all time durations, which was attributable to differences among the stabilities of Sc(edta){sup −}, Y(edta){sup −} and La(edta){sup −}.

  5. Magnesium-containing layered double hydroxides as orthopaedic implant coating materials--An in vitro and in vivo study.

    PubMed

    Weizbauer, Andreas; Kieke, Marc; Rahim, Muhammad Imran; Angrisani, Gian Luigi; Willbold, Elmar; Diekmann, Julia; Flörkemeier, Thilo; Windhagen, Henning; Müller, Peter Paul; Behrens, Peter; Budde, Stefan

    2016-04-01

    The total hip arthroplasty is one of the most common artificial joint replacement procedures. Several different surface coatings have been shown to improve implant fixation by facilitating bone ingrowth and consequently enhancing the longevity of uncemented orthopaedic hip prostheses. In the present study, two different layered double hydroxides (LDHs), Mg-Fe- and Mg-Al-LDH, were investigated as potential magnesium (Mg)-containing coating materials for orthopaedic applications in comparison to Mg hydroxide (Mg(OH)2). In vitro direct cell compatibility tests were carried out using the murine fibroblast cell line NIH 3T3 and the mouse osteosarcoma cell line MG 63. The host response of bone tissue was evaluated in in vivo experiments with nine rabbits. Two cylindrical pellets (3 × 3 mm) were implanted into each femoral condyle of the left hind leg. The samples were analyzed histologically and with μ-computed tomography (μ-CT) 6 weeks after surgery. An in vitro cytotoxicity test determined that more cells grew on the LDH pellets than on the Mg(OH)2-pellets. The pH value and the Mg(2+) content of the cell culture media were increased after incubation of the cells on the degradable samples. The in vivo tests demonstrated the formation of fibrous capsules around Mg(OH)2 and Mg-Fe-LDH. In contrast, the host response of the Mg-Al-LDH samples indicated that this Mg-containing biomaterial is a potential candidate for implant coating.

  6. Kinetics of intercalation of fluorescent probes in magnesium-aluminium layered double hydroxide within a multiscale reaction-diffusion framework

    NASA Astrophysics Data System (ADS)

    Saliba, Daniel; Al-Ghoul, Mazen

    2016-11-01

    We report the synthesis of magnesium-aluminium layered double hydroxide (LDH) using a reaction-diffusion framework (RDF) that exploits the multiscale coupling of molecular diffusion with chemical reactions, nucleation and growth of crystals. In an RDF, the hydroxide anions are allowed to diffuse into an organic gel matrix containing the salt mixture needed for the precipitation of the LDH. The chemical structure and composition of the synthesized magnesium-aluminium LDHs are determined using powder X-ray diffraction (PXRD), thermo-gravimetric analysis, differential scanning calorimetry, solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared and energy dispersive X-ray spectroscopy. This novel technique also allows the investigation of the mechanism of intercalation of some fluorescent probes, such as the neutral three-dimensional rhodamine B (RhB) and the negatively charged two-dimensional 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), using in situ steady-state fluorescence spectroscopy. The incorporation of these organic dyes inside the interlayer region of the LDH is confirmed via fluorescence microscopy, solid-state lifetime, SSNMR and PXRD. The activation energies of intercalation of the corresponding molecules (RhB and HPTS) are computed and exhibit dependence on the geometry of the involved probe (two or three dimensions), the charge of the fluorescent molecule (anionic, cationic or neutral) and the cationic ratio of the corresponding LDH. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  7. Evidences for decarbonation and exfoliation of layered double hydroxide in N,N-dimethylformamide-ethanol solvent mixture

    SciTech Connect

    Gordijo, Claudia R.; Leopoldo Constantino, Vera R.; Oliveira Silva, Denise de

    2007-07-15

    The behavior of a Hydrotalcite-like material (carbonate-containing Mg,Al-layered double hydroxide) in N,N-dimethylformamide (DMF)-ethanol mixture, at ambient temperature, has been investigated. The releasing of CO{sub 2} and production of a formate-containing material occurred mainly for 1:1 (v/v) solvent mixture. Decarbonation of Hydrotalcite is promoted by DMF hydrolysis followed by neutralization of brucite-like layers through HCOO{sup -} intercalation. Translucent colloidal dispersion of LDH nanoparticles from the formate-containing phase was characterized by transmission electron (TEM) and atomic force (AFM) microscopies. The absence of (00l) reflection at X-ray diffraction (XRD) pattern for dried colloidal dispersion indicated delamination of Hydrotalcite. The restacked sample exhibited broad reflections and typical hydroxide ordered layers non-basal (110) diffraction peaks. A LDH-HCOO{sup -} material was also prepared and characterized by FTIR and FT-Raman spectroscopies. Decarbonation and exfoliation of Hydrotalcite in N,N-dimethylformamide-ethanol mixed solvent provide an interesting method for preparation of new intercalated LDH materials. - Graphical abstract: Hydrotalcite suspended in 1:1 (v/v) N,N-dimethylformamide-ethanol solvent mixture, at ambient temperature, undergoes decarbonation and exfoliation. The process is promoted by DMF hydrolysis. Restacking of LDH layers is achieved by evaporating the solvent.

  8. Synthesis and characterization of metal (Core) - layered double hydroxide (Shell) nanostructures

    NASA Astrophysics Data System (ADS)

    Noh, Woo C.

    Layered double hydroxides (LDH) which belong to a class of inorganic ceramic layered materials have been studied since the mid-19th century for a variety of applications including catalysis, anion exchange, adsorbents and antacid, but more recently as a potential drug and gene delivery platform. Drug delivery platforms based on nano-sized geometries are nanovectors which promise a revolutionary impact on the therapy and imaging of various types of cancers and diseases. To date, various polymeric platforms have been the focus of intense research, but the development of inorganic, bio-hybrid nanoparticles for therapeutics and molecular imaging are at a stage of infancy. The hybridization of LDH with bioactive agents or the fabrication of metal (Core)---LDH (Shell) nanostructures could have many beneficial effects including multimodality, active targetability, and efficacy. For example, Core---Shell nanostructures may be designed to have a high scattering optical cross-section for imaging, but may also be tailored to strongly absorb near infrared (NIR) light for hyperthermic ablation. The central theme of this thesis was to demonstrate proof-of-concept of spherical silver and gold metal (Core)---LDH (Shell) nanostructures that have uniform size distribution and are agglomeration free. The effects of processing parameters on the characteristics of LDH as well as LDH-coated spherical metal (Ag, Au) nanoparticles have been evaluated using X-ray Diffraction, Dynamic Light Scattering, Scanning Electron Microscopy, Transmission Electron Microscopy, Rutherford Backscattering Spectrometry, and Inductively Coupled Plasma Emission Spectrometry to arrive at appropriate process windows. The core---shell nanostructures were also characterized for their optical properties in the ultra---violet---visible region, and the data were compared with simulated data, computed by using a quasi static model from Mie scattering theory. Moreover, in order to achieve a strong plasmon resonance

  9. A solid state NMR study of layered double hydroxides intercalated with para-amino salicylate, a tuberculosis drug.

    PubMed

    Jensen, Nicholai Daugaard; Bjerring, Morten; Nielsen, Ulla Gro

    2016-09-01

    Para-amino salicylate (PAS), a tuberculosis drug, was intercalated in three different layered double hydroxides (MgAl, ZnAl, and CaAl-LDH) and the samples were studied by multi-nuclear ((1)H, (13)C, and (27)Al) solid state NMR (SSNMR) spectroscopy in combination with powder X-ray diffraction (PXRD), elemental analysis and IR-spectroscopy to gain insight into the bulk and atomic level structure of these LDHs especially with a view to the purity of the LDH-PAS materials and the concentration of impurities. The intercalations of PAS in MgAl-, ZnAl-, and CaAl-LDH's were confirmed by (13)C SSNMR and PXRD. Moreover, (13)C MAS NMR and infrared spectroscopy show that PAS did not decompose during synthesis. Large amounts (20-41%) of amorphous aluminum impurities were detected in the structure using (27)Al single pulse and 3QMAS NMR spectra, which in combination with (1)H single and double quantum experiments also showed that the M(II):Al ratio was higher than predicted from the bulk metal composition of MgAl-PAS and ZnAl-PAS. Moreover, the first high-resolution (1)H SSNMR spectra of a CaAl LDH is reported and assigned using (1)H single and double quantum experiments in combination with (27)Al{(1)H} HETCOR.

  10. In situ synthesis of poly(methyl methacrylate)/MgAl layered double hydroxide nanocomposite with high transparency and enhanced thermal properties

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Feng, Li; Qu, Baojun

    2004-04-01

    A novel poly(methyl methacrylate)/MgAl layered double hydroxide (LDH) nanocomposite (PMMA-MgAl NC) with high transparency and enhanced thermal properties was synthesized in situ by adding sodium hydroxide aqueous solution to an emulsion consisting of metal ion aqueous solution, sodium dodecyl sulfate, methyl methacrylate, and benzoyl peroxide, then followed by the thermal initiation polymerization. The basal spacing of PMMA-MgAl NC was 2.72 nm determined by X-ray diffraction measurement. The intercalated MgAl LDH particles of 60-120 nm width and 25-40 nm thickness were well dispersed at molecular level in the PMMA matrix. When the 50% weight loss was selected as a comparison point, the decomposition temperature of PMMA-MgAl NC sample with 30 wt% MgAl LDH (including dodecyl sulfate) was ca. 45 °C higher than that of pure PMMA.

  11. Layer-by-layer assembly of bi-protein/layered double hydroxide ultrathin film and its electrocatalytic behavior for catechol.

    PubMed

    Kong, Xianggui; Rao, Xiuying; Han, Jingbin; Wei, Min; Duan, Xue

    2010-10-15

    This paper reports the fabrication of a bi-protein/layered double hydroxide (LDH) ultrathin film in which hemoglobin (HB) and horseradish peroxidase (HRP) molecules were assembled alternately with LDH nanosheets via the layer-by-layer (LBL) deposition technique, and its electrocatalytic performances for oxidation of catechol were demonstrated. The results of XRD indicate that the HB-HRP/LDH ultrathin film possesses a long range stacking order in the normal direction of the substrate, with the two proteins accommodated in the LDH gallery respectively as monolayer arrangement. SEM images show that the film surface exhibits a continuous and uniform morphology, and AFM reveals the Root-Mean-Square (RMS) roughness of ∼10.2 nm for the film. A stable direct electrochemical redox behavior of the proteins was successfully obtained for the HB-HRP/LDH film modified electrode. In addition, it exhibits remarkable electrocatalytic activity towards oxidation of catechol, based on the synergistic effect of the two proteins. The catechol biosensor in this work displays a wide linear response range (6-170 μM, r=0.999), low detection limit (5 μM), high sensitivity and good reproducibility.

  12. Corrosion resistance of Zn-Al layered double hydroxide/poly(lactic acid) composite coating on magnesium alloy AZ31

    NASA Astrophysics Data System (ADS)

    Zeng, Rong-Chang; Li, Xiao-Ting; Liu, Zhen-Guo; Zhang, Fen; Li, Shuo-Qi; Cui, Hong-Zhi

    2015-12-01

    A Zn-Al layered double hydroxide (ZnAl-LDH) coating consisted of uniform hexagonal nano-plates was firstly synthesized by co-precipitation and hydrothermal treatment on the AZ31 alloy, and then a poly(lactic acid) (PLA) coating was sealed on the top layer of the ZnAl-LDH coating using vacuum freeze-drying. The characteristics of the ZnAl-LDH/PLA composite coatings were investigated by means of XRD, SEM, FTIR and EDS. The corrosion resistance of the coatings was assessed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the ZnAl-LDH coating contained a compact inner layer and a porous outer layer, and the PLA coating with a strong adhesion to the porous outer layer can prolong the service life of the ZnAl-LDH coating. The excellent corrosion resistance of this composite coating can be attributable to its barrier function, ion-exchange and self-healing ability.

  13. Layered double hydroxide intercalated with aromatic acid anions for the efficient capture of aniline from aqueous solution.

    PubMed

    Yu, Shujun; Wang, Xiangxue; Chen, Zhongshan; Wang, Jian; Wang, Suhua; Hayat, Tasawar; Wang, Xiangke

    2017-01-05

    Aniline is toxic and hard to be degraded, and thereby causes the environmental pollution seriously. Herein, a practical and green hydrothermal method was applied to fabricate terephthalic acid and pyromellitic acid intercalated layered double hydroxides (LDH) (named as TAL and PAL) for aniline efficient removal. The sorption of aniline on LDH-based materials were investigated at different experimental conditions, and the results indicated that aniline sorption on LDH, TAL and PAL were strongly dependent on pH and independent of ionic strength. The maximum sorption capacities of aniline on TAL and PAL at pH 5.0 and 293K were 90.4 and 130.0mg/g, respectively, which were significantly higher than that of aniline on LDH (52.6mg/g). Based on the BET, FTIR and XPS analysis, the higher sorption capacities of TAL and PAL were mainly due to high surface area and basal spacing as well as the abundant functional groups (e.g. -COO(-)). The interactions of aniline with TAL and PAL were mainly dominated by hydrogen bonds and electrostatic interactions. Such a facile synthesis method, efficient removal performance and superior reusability indicated that the aromatic acid modified LDH materials had potential application for efficient treatment of organic pollutants in environmental pollution cleanup.

  14. Urea biosensors based on immobilization of urease into two oppositely charged clays (laponite and Zn-Al layered double hydroxides).

    PubMed

    de Melo, J V; Cosnier, S; Mousty, C; Martelet, C; Jaffrezic-Renault, N

    2002-08-15

    Enzyme-based field effect transistors (ENFETs) for urea determination were developed based on the immobilization of urease within two different clay matrixes, one cationic (Laponite) and the other anionic (layered double hydroxide (LDH)), cross-linked with glutaraldehyde. The biosensor based on the enzyme immobilized in Laponite shows a greater sensitivity and smaller dynamic linear range, because the enzymatic reaction is protected from the effect of the buffer capacity of the outer medium. The apparent Michaelis-Menten constant, Km(app), is quite similar for both biosensors. Inhibition of the enzyme by sodium tetraborate was investigated. Tetraborate acts as a competitive inhibitor for urease in the two different types of clay, the inhibitor effect being stronger for the LDH/urease biosensor. In particular, the maximum limit of the dynamic linear range extends from 1.4 mM in the absence of the inhibitor to 12 mM in the presence of 0.5 mM tetraborate. The Km(app) values in the presence of 0.5 mM tetraborate for Laponite and LDH biomembranes were 10 and 62 mM, respectively. Comparison of the inhibition constant values, Ki 0.16 and 0.05 mM for Laponite and LDH biosensors, respectively, clearly indicates a stronger enzyme-inhibitor interaction in the LDH/urease biomembrane.

  15. Synthesis and investigation of magnetic nanocomposite of Fe3O4 with cetirizine-intercalated layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Nejati, K.; Davaran, S.; Baggalzadeh, R.

    2014-11-01

    In this research work the nanocomposite CT-LDH/Fe3O4 was prepared by deposition of cetirizine (CT) intercalated-Mg-Al layered double hydroxide (LDH) on Fe3O4 using a co-precipitation method for sustained drug-targeting delivery. The obtained products were characterized by the variety of methods such as (XRD), (FT-IR), (TG) and the elemental analysis. The size and morphology of nanoparticles were examined by the transmission electron microscopy (TEM). The XRD results, showed the coexistence of the strong diffractions of Fe3O4 and cetirizine intercalated LDH. Also, after intercalation, the basal spacing of LDH increased from 0.88 nm to 2.52 nm, indicating that cetirizine anions were successfully intercalated into the interlayer space of LDH as a monolayer. The thermal gravimetric studies indicate the thermal stability of cetirizine molecule has increased with intercalation. In vitro drug release experiments in phosphate buffer solution (pH = 7.4) have been investigated. Magnetic measurements revealed that the nanocomposite displayed superparamagnetic properties at room temperature.

  16. Illustrating the processability of magnetic layered double hydroxides: layer-by-layer assembly of magnetic ultrathin films.

    PubMed

    Coronado, E; Martí-Gastaldo, C; Navarro-Moratalla, E; Ribera, A; Tatay, S

    2013-05-20

    We report the preparation of single-layer layered double hydroxide (LDH) two-dimensional (2D) nanosheets by exfoliation of highly crystalline NiAl-NO3 LDH. Next, these unilamellar moieties have been incorporated layer-by-layer (LbL) into a poly(sodium 4-styrenesulfonate)/LDH nanosheet multilayer ultrathin film (UTF). Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible light (UV-vis), and X-ray diffraction (XRD) profiles have been used to follow the uniform growth of the UTF. The use of a magnetic LDH as the cationic component of the multilayered architecture enables study of the resulting magnetic properties of the UTFs. Our magnetic data show the appearance of spontaneous magnetization at ∼5 K, thus confirming the effective transfer of the magnetic properties of the bulk LDH to the self-assembled film that displays glassy-like ferromagnetic behavior. The high number of bilayers accessible-more than 80-opens the door for the preparation of more-complex hybrid multifunctional materials that combine magnetism with the physical properties provided by other exfoliable layered inorganic hosts.

  17. Layered double hydroxides as effective carrier for anticancer drugs and tailoring of release rate through interlayer anions.

    PubMed

    Senapati, Sudipta; Thakur, Ravi; Verma, Shiv Prakash; Duggal, Shivali; Mishra, Durga Prasad; Das, Parimal; Shripathi, T; Kumar, Mohan; Rana, Dipak; Maiti, Pralay

    2016-02-28

    Hydrophobic anticancer drug, raloxifene hydrochloride (RH) is intercalated into a series of magnesium aluminum layered double hydroxides (LDHs) with various charge density anions through ion exchange technique for controlled drug delivery. The particle nature of the LDH in presence of drug is determined through electron microscopy and surface morphology. The release of drug from the RH intercalated LDHs was made very fast or sustained by altering the exchangeable anions followed by the modified Freundlich and parabolic diffusion models. The drug release rate is explained from the interactions between the drug and LDHs along with order-disorder structure of drug intercalated LDHs. Nitrate bound LDH exhibits greater interaction with drug and sustained drug delivery against the loosely interacted phosphate bound LDH-drug, which shows fast release. Cell viability through MTT assay suggests drug intercalated LDHs as better drug delivery vehicle for cancer cell line against poor bioavailability of the pure drug. In vivo study with mice indicates the differential tumor healing which becomes fast for greater drug release system but the body weight index clearly hints at damaged organ in the case of fast release system. Histopathological experiment confirms the damaged liver of the mice treated either with pure drug or phosphate bound LDH-drug, fast release system, vis-à-vis normal liver cell morphology for sluggish drug release system with steady healing rate of tumor. These observations clearly demonstrate that nitrate bound LDH nanoparticle is a potential drug delivery vehicle for anticancer drugs without any side effect.

  18. Mg-Al and Zn-Fe layered double hydroxides used for organic species storage and controlled release.

    PubMed

    Seftel, E M; Cool, P; Lutic, D

    2013-12-01

    Layered double hydroxides (LDH) containing (Mg and Al) or (Zn and Fe) were prepared by coprecipitation at constant pH, using NaOH and urea as precipitation agents. The most pure LDH phase in the Zn/Fe system was obtained with urea and in Mg/Al system when using NaOH. The incorporation of phenyl-alanine (Phe) anions in the interlayer of the LDH was performed by direct coprecipitation, ionic exchange and structure reconstruction of the mixed oxide obtained by the calcination of the coprecipitated product at 400°C. The reconstruction method and the direct coprecipitation in a medium containing Phe in the initial mixture were less successful in terms of high yields of organic-mineral composite than the ionic exchange method. A spectacular change in sample morphology and yield in exchanged solid was noticed for the Zn3Fe sample obtained by ionic exchange for 6h with Phe solution. A delivery test in PBS of pH=7.4 showed the release of the Phe in several steps up to 25 h indicating different host-guest interactions between the Phe and the LDH matrix. This behavior makes the preparation useful to obtain late delivery drugs, by the incorporation of the anion inside the LDH layer.

  19. Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule

    SciTech Connect

    Abellán, Gonzalo; Jordá, Jose Luis; Atienzar, Pedro; Varela, María; Jaafar, Miriam; Gómez-Herrero, Julio; Zamora, Félix; Ribera, Antonio; García, Hermenegildo; Coronado, Eugenio

    2014-12-04

    In this study, a hybrid magnetic multilayer material of micrometric size, with highly crystalline hexagonal crystals consisting of CoAl–LDH ferromagnetic layers intercalated with thermoresponsive 4-(4 anilinophenylazo)benzenesulfonate (AO5) molecules diluted (ratio 9 : 1) with a flexible sodium dodecylsulphate (SDS) surfactant has been obtained. The resulting material exhibits thermochromism attributable to the isomerization between the azo (prevalent at room temperature) and the hydrazone (favoured at higher temperatures) tautomers, leading to a thermomechanical response. In fact, these crystals exhibited thermally induced motion triggering remarkable changes in the crystal morphology and volume. In situ variable temperature XRD of these thin hybrids shows that the reversible change into the two tautomers is reflected in a shift of the position of the diffraction peaks at high temperatures towards lower interlayer spacing for the hydrazone form, as well as a broadening of the peaks reflecting lower crystallinity and ordering due to non-uniform spacing between the layers. These structural variations between room temperature (basal spacing (BS) = 25.91 Å) and 100 °C (BS = 25.05 Å) are also reflected in the magnetic properties of the layered double hydroxide (LDH) due to the variation of the magnetic coupling between the layers. Finally and in conclusion, our study constitutes one of the few examples showing fully reversible thermo-responsive breathing in a 2D hybrid material. In addition, the magnetic response of the hybrid can be modulated due to the thermotropism of the organic component that, by influencing the distance and in-plane correlation of the inorganic LDH, modulates the magnetism of the CoAl–LDH sheets in a certain range.

  20. Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule

    DOE PAGES

    Abellán, Gonzalo; Jordá, Jose Luis; Atienzar, Pedro; ...

    2014-12-04

    In this study, a hybrid magnetic multilayer material of micrometric size, with highly crystalline hexagonal crystals consisting of CoAl–LDH ferromagnetic layers intercalated with thermoresponsive 4-(4 anilinophenylazo)benzenesulfonate (AO5) molecules diluted (ratio 9 : 1) with a flexible sodium dodecylsulphate (SDS) surfactant has been obtained. The resulting material exhibits thermochromism attributable to the isomerization between the azo (prevalent at room temperature) and the hydrazone (favoured at higher temperatures) tautomers, leading to a thermomechanical response. In fact, these crystals exhibited thermally induced motion triggering remarkable changes in the crystal morphology and volume. In situ variable temperature XRD of these thin hybrids shows thatmore » the reversible change into the two tautomers is reflected in a shift of the position of the diffraction peaks at high temperatures towards lower interlayer spacing for the hydrazone form, as well as a broadening of the peaks reflecting lower crystallinity and ordering due to non-uniform spacing between the layers. These structural variations between room temperature (basal spacing (BS) = 25.91 Å) and 100 °C (BS = 25.05 Å) are also reflected in the magnetic properties of the layered double hydroxide (LDH) due to the variation of the magnetic coupling between the layers. Finally and in conclusion, our study constitutes one of the few examples showing fully reversible thermo-responsive breathing in a 2D hybrid material. In addition, the magnetic response of the hybrid can be modulated due to the thermotropism of the organic component that, by influencing the distance and in-plane correlation of the inorganic LDH, modulates the magnetism of the CoAl–LDH sheets in a certain range.« less

  1. Intercalation of methotrexatum into layered double hydroxides via exfoliation-reassembly process

    NASA Astrophysics Data System (ADS)

    Liu, Su-Qing; Li, Shu-Ping; Li, Xiao-Dong

    2015-03-01

    In this paper, the intercalation of methotrexatum (MTX) into layered double hydroxides (LDHs) via an exfoliation-reassembly process was reported and the resulting hybrids were then characterized by X-ray diffraction (XRD) patterns, Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) patterns etc. In the synthesis procedure, LDHs particles were firstly delaminated into well-dispersed 2D nanosheets in formamide by ultrasonic treatment at room temperature, and then the resulting LDH nanosheets were reassembled in MTX solution to form MTX intercalated LDH (MTX/LDHs) hybrids. AFM images showed that during the exfoliation process a large part of LDHs particles were delaminated into single and double brucite layers. XRD patterns and FTIR investigations manifested the successful intercalation of MTX anions into LDHs interlayers for the final samples. It was also found out that the drug-loading capacity of the hybrids increased with the concentrations of MTX solutions, while the morphology became even aggregated. At last, the cell cytotoxicity of the hybrids was estimated by MTT assays on the human lung cancer cells (A549), and the results stated that MTX/LDHs hybrids had effective suppress role on the proliferation of cancer cells.

  2. Surface-charging behavior of Zn-Cr layered double hydroxide.

    PubMed

    Rojas Delgado, R; Arandigoyen Vidaurre, M; De Pauli, C P; Ulibarri, M A; Avena, M J

    2004-12-15

    A Zn-Cr layered double hydroxide (LDH) having the formula Zn(2)Cr(OH)(6)Cl(0.7)(CO(3))(0.15)2.1H(2)O was synthesized and characterized by powder X-ray diffraction, infrared spectroscopy, acid-base potentiometric titration, mass titration, electrophoretic mobility, and modeling of the electrical double layer. Adsorption of alizarin was also performed in order to show some particular features of the HDL. Net hydroxyl adsorption, which increases with increasing pH and decreasing supporting electrolyte concentration, takes place above pH 5. The electrophoretic mobility of the particles was always positive and it decreased when the pH was higher than 9. An isoelectric point of 12 could be estimated by extrapolating the data. The modified MUSIC model was used to estimate deprotonation constants of surface groups and different adsorption models were compared. Good fit of hydroxyl adsorption and electrophoresis could be achieved by considering both OH(-)/Cl(-) exchange at structural sites and proton desorption from surface hydroxyl groups. The modeling, in agreement with alizarin adsorption, indicates that most of the structural positive charge of the LDH is screened at the surface by exchanged anions and negatively charged surface groups. It also suggests that only structural charge sites initially neutralized by chloride ions are active for anion exchange. The remaining sites are blocked by carbonate and do not participate in the exchange.

  3. Multifunctional organic–inorganic hybrid nanoparticles and nanosheets based on chitosan derivative and layered double hydroxide: cellular uptake mechanism and application for topical ocular drug delivery

    PubMed Central

    Chi, Huibo; Gu, Yan; Xu, Tingting; Cao, Feng

    2017-01-01

    To study the cellular uptake mechanism of multifunctional organic–inorganic hybrid nanoparticles and nanosheets, new chitosan–glutathione–valine–valine-layered double hydroxide (CG-VV-LDH) nanosheets with active targeting to peptide transporter-1 (PepT-1) were prepared, characterized and further compared with CG-VV-LDH nanoparticles. Both organic–inorganic hybrid nanoparticles and nanosheets showed a sustained release in vitro and prolonged precorneal retention time in vivo, but CG-VV-LDH nanoparticles showed superior permeability in the isolated cornea of rabbits than CG-VV-LDH nanosheets. Furthermore, results of cellular uptake on human corneal epithelial primary cells (HCEpiC) and retinal pigment epithelial (ARPE-19) cells indicated that both clathrin-mediated endocytosis and active transport of PepT-1 are involved in the internalization of CG-VV-LDH nanoparticles and CG-VV-LDH nanosheets. In summary, the CG-VV-LDH nanoparticle may be a promising carrier as a topical ocular drug delivery system for the treatment of ocular diseases of mid-posterior segments, while the CG-VV-LDH nanosheet may be suitable for the treatment of ocular surface diseases. PMID:28280329

  4. Synthesis and Characterization of Chitosan-Coated Near-Infrared (NIR) Layered Double Hydroxide-Indocyanine Green Nanocomposites for Potential Applications in Photodynamic Therapy.

    PubMed

    Wei, Pei-Ru; Kuthati, Yaswanth; Kankala, Ranjith Kumar; Lee, Chia-Hung

    2015-09-01

    We designed a study for photodynamic therapy (PDT) using chitosan coated Mg-Al layered double hydroxide (LDH) nanoparticles as the delivery system. A Food and Drug Administration (FDA) approved near-infrared (NIR) fluorescent dye, indocyanine green (ICG) with photoactive properties was intercalated into amine modified LDH interlayers by ion-exchange. The efficient positively charged polymer (chitosan (CS)) coating was achieved by the cross linkage using surface amine groups modified on the LDH nanoparticle surface with glutaraldehyde as a spacer. The unique hybridization of organic-inorganic nanocomposites rendered more effective and successful photodynamic therapy due to the photosensitizer stabilization in the interlayer of LDH, which prevents the leaching and metabolization of the photosensitizer in the physiological conditions. The results indicated that the polymer coating and the number of polymer coats have a significant impact on the photo-toxicity of the nano-composites. The double layer chitosan coated LDH-NH₂-ICG nanoparticles exhibited enhanced photo therapeutic effect compared with uncoated LDH-NH₂-ICG and single layer chitosan-coated LDH-NH₂-ICG due to the enhanced protection to photosensitizers against photo and thermal degradations. This new class of organic-inorganic hybrid nanocomposites can potentially serve as a platform for future non-invasive cancer diagnosis and therapy.

  5. Novel inorganic host layered double hydroxides intercalated with guest organic inhibitors for anticorrosion applications.

    PubMed

    Poznyak, S K; Tedim, J; Rodrigues, L M; Salak, A N; Zheludkevich, M L; Dick, L F P; Ferreira, M G S

    2009-10-01

    Zn-Al and Mg-Al layered double hydroxides (LDHs) loaded with quinaldate and 2-mercaptobenzothiazolate anions were synthesized via anion-exchange reaction. The resulting compounds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. Spectrophotometric measurements demonstrated that the release of organic anions from these LDHs into the bulk solution is triggered by the presence of chloride anions, evidencing the anion-exchange nature of this process. The anticorrosion capabilities of LDHs loaded with organic inhibitors toward the AA2024 aluminum alloy were analyzed by electrochemical impedance spectroscopy. A significant reduction of the corrosion rate is observed when the LDH nanopigments are present in the corrosive media. The mechanism by which the inhibiting anions can be released from the LDHs underlines the versatility of these environmentally friendly structures and their potential application as nanocontainers in self-healing coatings.

  6. Fluorescent vancomycin and terephthalate comodified europium-doped layered double hydroxides nanoparticles: synthesis and application for bacteria labelling

    NASA Astrophysics Data System (ADS)

    Sun, Jianchao; Fan, Hai; Wang, Nan; Ai, Shiyun

    2014-09-01

    Vancomycin (Van)- and terephthalate (TA)-comodified europium-doped layered double hydroxides (Van-TA-Eu-LDHs) nanoparticles were successfully prepared by a two-step method, in which, TA acted as a sensitizer to enhance the fluorescent property and Van was modified on the surface of LDH to act as an affinity reagent to bacteria. The obtained products were characterized by X-ray diffraction, transmission electron microscope and fluorescent spectroscopy. The results demonstrated that the prepared Van- and TA-comodified europium-doped layered double hydroxides (Van-TA-Eu-LDHs) nanoparticles with diameter of 50 nm in size showed highly efficient fluorescent property. Furthermore, due to the high affinity of Van to bacteria, the prepared Van-TA-Eu-LDHs nanoparticles showed efficient bacteria labelling by fluorescent property. The prepared nanoparticles may have wide applications in the biological fields, such as biomolecular labelling and cell imaging.

  7. An optical sensor based on H-acid/layered double hydroxide composite film for the selective detection of mercury ion.

    PubMed

    Sun, Zhiyong; Jin, Lan; Zhang, Shitong; Shi, Wenying; Pu, Min; Wei, Min; Evans, David G; Duan, Xue

    2011-09-19

    A novel optical chemosensor was fabricated based on 1-amino-8-naphthol-3,6-disulfonic acid sodium (H-acid) intercalated layered double hydroxide (LDH) film via the electrophoretic deposition (EPD) method. The film of H-acid/LDH with the thickness of 1 μm possesses a well c-orientation of the LDH microcrystals confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The fluorescence detection for Hg(II) in aqueous solution was performed by using the H-acid/LDH film sensor at pH 7.0, with a linear response range in 1.0 × 10(-7) to 1.0 × 10(-5) mol L(-1) and a detection limit of 6.3 × 10(-8) mol L(-1). Furthermore, it exhibits excellent selectivity for Hg(II) over a large number of competitive cations including alkali, alkaline earth, heavy metal and transitional metals. The specific fluorescence response of the optical sensor is attributed to the coordination between Hg(II) and sulfonic group in the H-acid immobilized in the LDH matrix, which was verified by NMR spectroscopy and UV-vis spectra. In addition, density functional theory (DFT) calculation further confirms that the coordination occurs between one Hg(2+) and two O atoms in the sulfonic group, which is responsible for the significant fluorescence quenching of the H-acid/LDH film. The results indicate that the H-acid/LDH composite film can be potentially used as a chemosensor for the detection of Hg(2+) in the environmental and biomedical field.

  8. Signalling pathways involved in the activation of dendritic cells by layered double hydroxide nanoparticles.

    PubMed

    Li, Ang; Qin, Lili; Zhu, Di; Zhu, Rongrong; Sun, Jing; Wang, Shilong

    2010-02-01

    Layered double hydroxide (LDH) nanoparticles are attractive as potential drug vectors for the targeting not only of tissues, but also of intracellular organelles, and particularly the acidic endolysosomes created after cell endocytosis. The purpose of this study was to investigate the ability of LDH nanoparticles designed as vectors to activate dendritic cells (DCs), as measured by various cellular functions. The study also explored the possible signaling pathway through which the LDH nanoparticles exerted their effects on the cellular functions of DCs. First, LDH nanoparticles with different ratios of Mg(OH)(2) to Al(OH)(3) (1:1, 2:1 and 3:1, called R1, R2 and R3 respectively) were optimized and had a hydrodynamic diameter of 57 nm with a zeta potential of +35 mV. Then, the efficient endocytosis of the optimized LDH nanoparticles by bone marrow-derived dendritic cells (MDDCs) was monitored by fluorescence-activated cell sorting. The effect of R1, R2 and R3 on the expression of the pro- and anti-inflammatory cytokines (TNF-alpha, IL-6, and IL-12) and the co-stimulatory molecules (CD40, CD80, CD86, and MHC class II) in MDDCs was examined. The exposure of R1 caused a dose-dependent increase in the expression of TNF-alpha, IL-12, CD86 and CD40, while R2 and R3 did not up-regulate these cytokines and co-stimulatory molecules. Migration assays showed that R1 could increase the migration capacity of DCs to CCL21 and up-regulate the expression of CCR7. Furthermore, we found that R1 significantly increased the NF-kappaB expression in the nucleus (in a dose-dependent manner) and promoted the degradation of total IkappaBalpha levels, indicating that the NF-kappaB signaling pathway might involve in an R1-induced DC activation. Our results suggested that LDH nanoparticles, in the future, may function as a useful vector for ex vivo engineering to promote vaccine delivery in immune cells.

  9. Synthesis of Cd/(Al+Fe) layered double hydroxides and characterization of the calcination products

    SciTech Connect

    Perez, M.R.; Barriga, C.; Fernandez, J.M.; Rives, V.; Ulibarri, M.A.

    2007-12-15

    Layered double hydroxides (LDHs) containing Cd(II), Al(III), and Fe(III) in the brucite-like layers with different starting Fe/Al atomic ratios and with nitrate as counteranion have been prepared following the coprecipitation method at a constant pH value of 8. An additional Cd(II),Al(III)-LDH sample interlayered with hexacyanoferrate(III) ions has been prepared by ionic exchange at pH 9. The samples have been characterized by elemental chemical analysis, powder X-ray diffraction (PXRD), and FT-IR spectroscopy. Their thermal stability has been assessed by thermogravimetric and differential thermal analyses (TG-DTA) and mass spectrometric analysis of the evolved gases. The PXRD patterns of the solids calcined at 800 deg. C show diffraction lines corresponding to Cd(Al)O and spinel-type materials, which precise nature (CdAl{sub 2}O{sub 4}, Cd{sub 1-x}Fe{sub 2+x}O{sub 4}, or Cd{sub x}Fe{sub 2.66}O{sub 4}) depends on location and concentration of iron in the parent material or precursor. - Graphical abstract: Layered double hydroxides (LDHs) containing Cd(II), Al(III), and Fe(III) in the brucite-like layers with different starting Fe/Al atomic ratios and with nitrate as counteranion have been prepared following the coprecipitation method. An additional Cd(II),Al(III)-LDH sample interlayered with hexacyanoferrate(III) ions has been prepared by ionic exchange. Calcination at 800 deg. C shows diffraction lines corresponding to CdO and to spinel-type materials. SEM micrograph of sample CdAlFe-N-0.

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

    SciTech Connect

    Tsyganok, Andrey; Sayari, Abdelhamid . E-mail: Abdel.Sayari@science.uottawa.ca

    2006-06-15

    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 edta{sup 4-} (edta{sup 4-}=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. - Graphical abstract: Two ways for introducing transition metals M(II) into Mg-Al layered double hydroxides (MY{sup 2-} denotes the edta chelate of transition metal M(II)).0.

  11. Reactivity and applications of layered silicates and layered double hydroxides.

    PubMed

    Selvam, Thangaraj; Inayat, Alexandra; Schwieger, Wilhelm

    2014-07-21

    Layered materials, such as layered sodium silicates and layered double hydroxides (LDHs), are well-known for their remarkable adsorption, intercalation and swelling properties. Their tunable interlayers offer an interesting avenue for the fabrication of pillared nanoporous materials, organic-inorganic hybrid materials and catalysts or catalyst supports. This perspective article provides a summary of the reactivity and applications of layered materials including aluminium-free layered sodium silicates (kanemite, ilerite (RUB-18 or octosilicate) and magadiite) and layered double hydroxides (LDHs). Recent developments in the use of layered sodium silicates as precursors for the preparation of various porous, functional and catalytic materials including zeolites, mesoporous materials, pillared layered silicates, organic-inorganic nanocomposites and synthesis of highly dispersed nanoparticles supported on silica are reviewed in detail. Along this perspective, we have attempted to illustrate the reactivity and transformational potential of LDHs in order to deduce the main differences and similarities between these two types of layered materials.

  12. Tailoring surface properties and structure of layered double hydroxides using silanes with different number of functional groups

    SciTech Connect

    Tao, Qi; He, Hongping; Li, Tian; Frost, Ray L.; Zhang, Dan; He, Zisen

    2014-05-01

    Four silanes, trimethylchlorosilane (TMCS), dimethyldiethoxylsilane (DMDES), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS), were adopted to graft layered double hydroxides (LDH) via an induced hydrolysis silylation method (IHS). Fourier transform infrared spectra (FTIR) and {sup 29}Si MAS nuclear magnetic resonance spectra ({sup 29}Si MAS NMR) indicated that APTES and TEOS can be grafted onto LDH surfaces via condensation with hydroxyl groups of LDH, while TMCS and DMDES could only be adsorbed on the LDH surface with a small quantity. A combination of X-ray diffraction patterns (XRD) and {sup 29}Si MAS NMR spectra showed that silanes were exclusively present in the external surface and had little influence on the long range order of LDH. The surfactant intercalation experiment indicated that the adsorbed and/or grafted silane could not fix the interlamellar spacing of the LDH. However, they will form crosslink between the particles and affect the further surfactant intercalation in the silylated samples. The replacement of water by ethanol in the tactoids and/or aggregations and the polysiloxane oligomers formed during silylation procedure can dramatically increase the value of BET surface area (S{sub BET}) and total pore volumes (V{sub p}) of the products. - Graphical abstract: The replacement of water by ethanol in the tactoids and aggregations of LDHs, and the polysiloxane oligomers formed during silylation process can dramatically increase the BET surface area (S{sub BET}) and the total pore volume (V{sub p}) of the silylated products. - Highlights: • Silanes with multifunctional groups were grafted onto LDH surface in C{sub 2}H{sub 5}OH medium. • The number of hydrolysable groups in silanes affects the structure of grafted LDH. • Replacement of H{sub 2}O by C{sub 2}H{sub 5}OH in aggregations increases S{sub BET} and V{sub p} of grafted LDH. • Polysiloxane oligomers contribute to the increase of S{sub BET} and V{sub p} of grafted LDH.

  13. A novel and easy chemical-clock synthesis of nanocrystalline iron-cobalt bearing layered double hydroxides.

    PubMed

    Hadi, Jebril; Grangeon, Sylvain; Warmont, Fabienne; Seron, Alain; Greneche, Jean-Marc

    2014-11-15

    A novel synthesis of cobalt-iron layered double hydroxide (LDH) with interlayer chlorides was investigated. The method consists in mixing concentrated solutions of hexaamminecobalt(III) trichloride with ferrous chloride at room temperature and in anoxic conditions. Four initial Fe/Co atomic ratios have been tried out (0.12, 0.6, 1.2 and 1.8). Neither heating nor addition of alkali was employed for adjusting the pH and precipitating the metal hydroxides. Still, each mixture led to the spontaneous precipitation of a LDH-rich solid having a crystal-chemistry that depended on the initial solution Fe/Co. These LDHs phases were carefully characterized by mean of X-ray diffraction, (57)Fe Mössbauer spectrometry, transmission electron microscopy and chemical analysis (total dissolution and phenanthroline method). Solution Eh and pH were also monitored during the synthesis. Increasing initial Fe/Co ratio impacted the dynamic of the observed stepwise reaction and the composition of the resulting product. Once the two solutions are mixed, a spontaneous and abrupt color change occurs after an induction time which depends on the starting Fe/Co ratio. This makes the overall process acting as a chemical clock. This spontaneous generation of CoFe-LDH arises from the interplay between redox chemistries of iron and cobalt-ammonium complexes.

  14. In situ oligomerization of 2-(thiophen-3-yl)acetate intercalated into Zn{sub 2}Al layered double hydroxide

    SciTech Connect

    Tronto, Jairo; Pinto, Frederico G.; Costa, Liovando M. da; Leroux, Fabrice; Dubois, Marc; Valim, João B.

    2015-01-15

    A layered double hydroxide (LDH) with cation composition Zn{sub 2}Al was intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers. To achieve in situ polymerization and/or oligomerization of the intercalated monomers, soft thermal treatments were carried out, and subsequent hybrid LDH materials were analyzed by means of several characterization techniques using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), {sup 13}C CP–MAS nuclear magnetic resonance (NMR), electron spin resonance (EPR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and elemental analysis. PXRD analysis suggested that the intercalated monomers formed a bilayer. Thermal treatment of the hybrid LDH assembly above 120 °C provokes partially the breakdown of the layered structure, generating the phase zincite. EPR results indicated that vicinal monomers (oligomerization) were bound to each other after hydrothermal or thermal treatment, leading to a polaron response characteristic of electron conductivity localized on a restricted number of thiophene-based monomer segments. Localized unpaired electrons exist in the material and interact with the {sup 27}Al nuclei of the LDH layers by superhyperfine coupling. These unpaired electrons also interact with the surface of ZnO (O{sup 2−} vacancies), formed during the thermal treatments. - Graphical abstract: We synthesized a layered double hydroxide (LDH) with cation composition Zn{sub 2}Al, intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers, by coprecipitation at constant pH. We thermally treated the material, to achieve in situ polymerization and/or oligomerization of the intercalated monomers. - Highlights: • A Zn{sub 2}Al–LDH was intercalated with 2-(thiophen-3-yl)acetate monomers. • To achieve in situ oligomerization of the monomers, thermal treatments were made.

  15. Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

    SciTech Connect

    Radha, S.; Milius, Wolfgang; Breu, Josef; Kamath, P. Vishnu

    2013-08-15

    The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacing evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.

  16. Immobilization of lipase from Candida rugosa on layered double hydroxides for esterification reaction.

    PubMed

    Rahman, Mohd Basyaruddin A; Basri, Mahiran; Hussein, Mohd Zobir; Rahman, Raja Nor Zaliha A; Zainol, Dara Hatira; Salleh, Abu Bakar

    2004-01-01

    Synthesis of layered double hydroxides (LDHs) of Zn/Al-NO3- hydrotalcite (HIZAN) and Zn/Al-diocytyl sodium sulfosuccinate (DSS) nanocomposite (NAZAD) with a molar ratio of Zn/Al of 4:1 were carried out by coprecipitation through continuous agitation. Their structures were determined using X-ray diffractometer spectra, which showed that basal spacing for LDH synthesized by both methods was about 8.89 A. An expansion of layered structure of about 27.9 A was observed to accommodate the surfactant anion between the interlayer. This phenomenon showed that the intercalation process took place between the LDH interlayer. Lipase from Candida rugosa was immobilized onto these materials by physical adsorption method. It was found that the protein loading onto NAZAD is higher than HIZAN. The activity of immobilized lipase was investigated through esterification of oleic acid and 1-butanol in hexane. The effects of pore size, surface area, reaction temperature, thermostability of the immobilized lipases, storage stability in organic solvent, and leaching studies were investigated. Stability was found to be the highest in the nanocomposite NAZAD.

  17. Potential for layered double hydroxides-based, innovative drug delivery systems.

    PubMed

    Zhang, Kai; Xu, Zhi Ping; Lu, Ji; Tang, Zhi Yong; Zhao, Hui Jun; Good, David A; Wei, Ming Qian

    2014-04-29

    Layered Double Hydroxides (LDHs)-based drug delivery systems have, for many years, shown great promises for the delivery of chemical therapeutics and bioactive molecules to mammalian cells in vitro and in vivo. This system offers high efficiency and drug loading density, as well as excellent protection of loaded molecules from undesired degradation. Toxicological studies have also found LDHs to be biocompatible compared with other widely used nanoparticles, such as iron oxide, silica, and single-walled carbon nanotubes. A plethora of bio-molecules have been reported to either attach to the surface of or intercalate into LDH materials through co-precipitation or anion-exchange reaction, including amino acid and peptides, ATPs, vitamins, and even polysaccharides. Recently, LDHs have been used for gene delivery of small molecular nucleic acids, such as antisense, oligonucleotides, PCR fragments, siRNA molecules or sheared genomic DNA. These nano-medicines have been applied to target cells or organs in gene therapeutic approaches. This review summarizes current progress of the development of LDHs nanoparticle drug carriers for nucleotides, anti-inflammatory, anti-cancer drugs and recent LDH application in medical research. Ground breaking studies will be highlighted and an outlook of the possible future progress proposed. It is hoped that the layered inorganic material will open up new frontier of research, leading to new nano-drugs in clinical applications.

  18. Synthesis, characterization, and controlled release antibacterial behavior of antibiotic intercalated Mg–Al layered double hydroxides

    SciTech Connect

    Wang, Yi; Zhang, Dun

    2012-11-15

    Graphical abstract: The antibiotic anion released from Mg–Al LDHs provides a controlled release antibacterial activity against the growth of Micrococcus lysodeikticus in 3.5% NaCl solution. Highlights: ► Antibiotic anion intercalated LDHs were synthesized and characterized. ► The ion-exchange one is responsible for the release process. ► The diffusion through particle is the release rate limiting step. ► LDHs loaded with antibiotic anion have high antibacterial capabilities. -- Abstract: Antibiotic–inorganic clay composites including four antibiotic anions, namely, benzoate (BZ), succinate (SU), benzylpenicillin (BP), and ticarcillin (TC) anions, intercalated Mg–Al layered double hydroxides (LDHs) were synthesized via ion-exchange. Powder X-ray diffraction and Fourier transform infrared spectrum analyses showed the successful intercalation of antibiotic anion into the LDH interlayer. BZ and BP anions were accommodated in the interlayer region as a bilayer, whereas SU and TC anions were intercalated in a monolayer arrangement. Kinetic simulation of the release data indicated that ion-exchange was responsible for the release process, and the diffusion through the particles was the rate-limiting step. The antibacterial capabilities of LDHs loaded with antibiotic anion toward Micrococcus lysodeikticus growth were analyzed using a turbidimetric method. Significant high inhibition rate was observed when LDH nanohybrid was introduced in 3.5% NaCl solution. Therefore, this hybrid material may be applied as nanocontainer in active antifouling coating for marine equipment.

  19. Removal of Remazol Blue 19 from wastewater by zinc-aluminium-chloride-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Elkhattabi, El Hassan; Lakraimi, Mohamed; Badreddine, Mohamed; Legrouri, Ahmed; Cherkaoui, Omar; Berraho, Moha

    2013-06-01

    Layered double hydroxides (LDHs), also called anionic clays, consist of cationic brucite-like layers and exchangeable interlayer anions. These hydrotalcite-like compounds, with Zn and Al in the layers and chloride in the interlayer space, were prepared following the coprecipitation method at constant pH. The affinity of this material for Remazol Blue 19, RB19 [ 2- (3- (4- Amino- 9,10- dihydro- 3- sulpho- 9,10- dioxoanthracen- 4- yl) aminobenzenesulphonyl) vinyl) disodiumsulphate], was studied as a function of contact time, pH of the solutions LDH dose and the RB19/[Zn-Al-Cl] mass ratio. It was found that 48 h is enough time for the equilibrium state to be reached with maximum RB19 retention at pH of 9 for an LDH dose equal to 100 mg and with an RB19/[Zn-Al-Cl] mass ratio higher than 3. The adsorption isotherm, described by the Langmuir model, is of L-type. The results demonstrate that RB19 retention on LDHs occurs by adsorption on external surface when RB19/[Zn-Al-Cl] mass ratio is equal or <3 and by both adsorption and interlayer ion exchange for ratios higher than 3. A mechanism for removal of RB19 anion has been confirmed by X-ray diffraction, IR spectroscopy and TG analysis (TG and DTG curves).

  20. A novel method to get methotrexatum/layered double hydroxides intercalation compounds and their release properties

    NASA Astrophysics Data System (ADS)

    Qi, Fenglin; Zhang, Xiaoqing; Li, Shuping

    2013-08-01

    In this context, the methotrexatum/layered double hydroxides (MTX/LDHs) intercalation compounds have been synthesized by a mechanochemical-hydrothermal method, which involves a grinding process and subsequent hydrothermal treatment. The influence of R (molar ratio of Mg2+ to Al3+ to MTX) values on the structure and morphology of the intercalation compounds and their release properties were investigated systematically. The resulting compounds were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), inductively coupled plasma (ICP), thermogravimetric (TG) and differential scanning calorimetry (DSC) analysis. All the results indicate that R value has significant influence on the intercalation of MTX anions into LDH interlayer and the optimal R value is 2:1:0.5. Furthermore, four dissolution-diffusion kinetic models were used to fit the in vitro release of MTX from LDH layers. The release process can be divided into two stages: firstly surface diffusion and secondly intraparticle diffusion. The study also revealed that the properties of the intercalation compounds is comparable to that obtained from standard methods such as co-precipitation method, but with time, solvent and energy saving.

  1. Potential for Layered Double Hydroxides-Based, Innovative Drug Delivery Systems

    PubMed Central

    Zhang, Kai; Xu, Zhi Ping; Lu, Ji; Tang, Zhi Yong; Zhao, Hui Jun; Good, David A.; Wei, Ming Qian

    2014-01-01

    Layered Double Hydroxides (LDHs)-based drug delivery systems have, for many years, shown great promises for the delivery of chemical therapeutics and bioactive molecules to mammalian cells in vitro and in vivo. This system offers high efficiency and drug loading density, as well as excellent protection of loaded molecules from undesired degradation. Toxicological studies have also found LDHs to be biocompatible compared with other widely used nanoparticles, such as iron oxide, silica, and single-walled carbon nanotubes. A plethora of bio-molecules have been reported to either attach to the surface of or intercalate into LDH materials through co-precipitation or anion-exchange reaction, including amino acid and peptides, ATPs, vitamins, and even polysaccharides. Recently, LDHs have been used for gene delivery of small molecular nucleic acids, such as antisense, oligonucleotides, PCR fragments, siRNA molecules or sheared genomic DNA. These nano-medicines have been applied to target cells or organs in gene therapeutic approaches. This review summarizes current progress of the development of LDHs nanoparticle drug carriers for nucleotides, anti-inflammatory, anti-cancer drugs and recent LDH application in medical research. Ground breaking studies will be highlighted and an outlook of the possible future progress proposed. It is hoped that the layered inorganic material will open up new frontier of research, leading to new nano-drugs in clinical applications. PMID:24786098

  2. Synthesis of mesoporous silica@Co-Al layered double hydroxide spheres: layer-by-layer method and their effects on the flame retardancy of epoxy resins.

    PubMed

    Jiang, Shu-Dong; Bai, Zhi-Man; Tang, Gang; Song, Lei; Stec, Anna A; Hull, T Richard; Hu, Yuan; Hu, Wei-Zhao

    2014-08-27

    Hierarchical mesoporous silica@Co-Al layered double hydroxide (m-SiO2@Co-Al LDH) spheres were prepared through a layer-by-layer assembly process, in order to integrate their excellent physical and chemical functionalities. TEM results depicted that, due to the electrostatic potential difference between m-SiO2 and Co-Al LDH, the synthetic m-SiO2@Co-Al LDH hybrids exhibited that m-SiO2 spheres were packaged by the Co-Al LDH nanosheets. Subsequently, the m-SiO2@Co-Al LDH spheres were incorporated into epoxy resin (EP) to prepare specimens for investigation of their flame-retardant performance. Cone results indicated that m-SiO2@Co-Al LDH incorporated obviously improved fire retardant of EP. A plausible mechanism of fire retardant was hypothesized based on the analyses of thermal conductivity, char residues, and pyrolysis fragments. Labyrinth effect of m-SiO2 and formation of graphitized carbon char catalyzed by Co-Al LDH play pivotal roles in the flame retardance enhancement.

  3. Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.

    PubMed

    Liu, Zhaoping; Ma, Renzhi; Osada, Minoru; Iyi, Nobuo; Ebina, Yasuo; Takada, Kazunori; Sasaki, Takayoshi

    2006-04-12

    This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.

  4. NiFe layered double hydroxide/reduced graphene oxide nanohybrid as an efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhan, Tianrong; Zhang, Yumei; Liu, Xiaolin; Lu, SiSi; Hou, Wanguo

    2016-11-01

    Highly active and low-cost bifunctional electrocatalysts for oxygen evolution and reduction reactions (OER and ORR) hold a heart position for the renewable energy technologies such as metal-air batteries and fuel cells. Here, we reported the synthesis of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanohybrid via the facile solvothermal method followed by chemical reduction. The template role of surfactant and the hybridization of rGO supplied the NiFe-LDH/rGO catalyst with a porous nanostructure and an enhanced conductivity, favoring both mass transport and charge communication of electrocatalytic reactions. The NiFe-LDH/rGO composite not only displayed highly efficient OER activity in alkaline solution with a low onset overpotential of 240 mV, but also only needed an overpotential of 250 mV to reach the 10 mA cm-2 current density. The NiFe-LDH/rGO nanohybrid also offered excellent ORR catalytic activity with onset potential at 0.796 V in alkaline media. The rotating-disk and rotating-ring-disk electrodes both revealed that the ORR on NiFe-LDH/rGO mainly involved a direct four-electron reaction pathways accompanying part of the two-electron process. The excellent bifunctional activity of the NiFe-LDH/rGO nanohybrid could be attributed to the synergistic effects of rGO and NiFe-LDH components due to the strongly coupled interactions.

  5. A novel injectable thermoresponsive and cytocompatible gel of poly(N-isopropylacrylamide) with layered double hydroxides facilitates siRNA delivery into chondrocytes in 3D culture.

    PubMed

    Yang, Hsiao-yin; van Ee, Renz J; Timmer, Klaas; Craenmehr, Eric G M; Huang, Julie H; Öner, F Cumhur; Dhert, Wouter J A; Kragten, Angela H M; Willems, Nicole; Grinwis, Guy C M; Tryfonidou, Marianna A; Papen-Botterhuis, Nicole E; Creemers, Laura B

    2015-09-01

    Hybrid hydrogels composed of poly(N-isopropylacrylamide) (pNIPAAM) and layered double hydroxides (LDHs) are presented in this study as novel injectable and thermoresponsive materials for siRNA delivery, which could specifically target several negative regulators of tissue homeostasis in cartilaginous tissues. Effectiveness of siRNA transfection using pNIPAAM formulated with either MgAl-LDH or MgFe-LDH platelets was investigated using osteoarthritic chondrocytes. Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) was used as an endogenous model gene to evaluate the extent of silencing. No significant adverse effects of pNIPAAM/LDH hydrogels on cell viability were noticed. Cellular uptake of fluorescently labeled siRNA was greatly enhanced (>75%) in pNIPAAM/LDH hydrogel constructs compared to alginate, hyaluronan and fibrin gels, and was absent in pNIPAAM hydrogel without LDH platelets. When using siRNA against GAPDH, 82-98% reduction of gene expression was found in both types of pNIPAAM/LDH hydrogel constructs after 6 days of culturing. In the pNIPAAM/MgAl-LDH hybrid hydrogel, 80-95% of GAPDH enzyme activity was reduced in parallel with gene. Our findings show that the combination of a cytocompatible hydrogel and therapeutic RNA oligonucleotides is feasible. Thus it might hold promise in treating degeneration of cartilaginous tissues by providing supporting scaffolds for cells and interference with locally produced degenerative factors.

  6. High-performance hybrid supercapacitor with 3D hierarchical porous flower-like layered double hydroxide grown on nickel foam as binder-free electrode

    NASA Astrophysics Data System (ADS)

    Zhang, Luojiang; Hui, Kwun Nam; San Hui, Kwan; Lee, Haiwon

    2016-06-01

    The synthesis of layered double hydroxide (LDH) as electroactive material has been well reported; however, fabricating an LDH electrode with excellent electrochemical performance at high current density remains a challenge. In this paper, we report a 3D hierarchical porous flower-like NiAl-LDH grown on nickel foam (NF) through a liquid-phase deposition method as a high-performance binder-free electrode for energy storage. With large ion-accessible surface area as well as efficient electron and ion transport pathways, the prepared LDH-NF electrode achieves high specific capacity (1250 C g-1 at 2 A g-1 and 401 C g-1 at 50 A g-1) after 5000 cycles of activation at 20 A g-1 and high cycling stability (76.7% retention after another 5000 cycles at 50 A g-1), which is higher than those of most previously reported NiAl-LDH-based materials. Moreover, a hybrid supercapacitor with LDH-NF as the positive electrode and porous graphene nanosheet coated on NF (GNS-NF) as the negative electrode, delivers high energy density (30.2 Wh kg-1 at a power density of 800 W kg-1) and long cycle life, which outperforms the other devices reported in the literature. This study shows that the prepared LDH-NF electrode offers great potential in energy storage device applications.

  7. Comparative X-ray diffraction and infrared spectroscopy study of Zn-Al layered double hydroxides: Vanadate vs nitrate

    NASA Astrophysics Data System (ADS)

    Salak, Andrei N.; Tedim, João; Kuznetsova, Alena I.; Ribeiro, José L.; Vieira, Luís G.; Zheludkevich, Mikhail L.; Ferreira, Mário G. S.

    2012-03-01

    Zn-Al layered double hydroxides (LDH) are promising as nanocontainers of corrosion inhibitors in self-healing corrosion protection coatings. Zn(2)Al-vanadate (Zn/Al = 2:1) is prepared by anion exchange from the parent composition Zn(2)Al-nitrate at pH ˜ 8. Crystal structure and vibrational spectra of both LDHs have been studied in comparison. Their interlayer distances are rather larger than those corresponding to the most compact arrangement of the intercalated anions. Nevertheless, no sign of a turbostratic disorder has been detected in these LDH. Based on the analysis of the spectroscopic data in combination with the XRD results, it has been shown that vanadate anion, which substitutes nitrate at the anion exchange, is pyrovanadate, VO74-. The observed disorder in the hydroxide layers in Zn(2)Al-V2O7 is likely to result from strong interactions between V5+ and Zn2+/Al3. Although Zn(2)Al-NO3 is less disordered than Zn(2)Al-V2O7, it exhibits no long-range order in arrangement of cations in the hydroxide layers.

  8. Photocatalytic property and structural stability of CuAl-based layered double hydroxides

    SciTech Connect

    Lv, Ming; Liu, Haiqiang

    2015-07-15

    Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) were successfully synthesized by coprecipitation. Powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometry (ICP-AES) and UV–Vis diffuse reflectance spectrum (UV–vis) were used to confirm the formation of as-synthesized solids with good crystal structure. The photocatalytic activity of those LDH materials for CO{sub 2} reduction under visible light was investigated. The experimental results show that CuNiAl-LDHs with narrowest band gap and largest surface areas behave highest efficiency for methanol generation under visible light compared with CuMgAl-LDHs and CuZnAl-LDHs. The CuNiAL-LDH showed high yield for methanol production i.e. 0.210 mmol/g h, which was high efficient. In addition, the influence of the different M{sup 2+} on the structures and stability of the CuMAl-LDHs was also investigated by analyzing the geometric parameters, electronic arrangement, charge populations, hydrogen-bonding, and binding energies by density functional theory (DFT) analysis. The theoretical calculation results show that the chemical stability of LDH materials followed the order of CuMgAl-LDHs>CuZnAl-LDHs>CuNiAl-LDHs, which is just opposite with the photocatalytic activity and band gaps of three materials. - Graphical abstract: The host–guest calculation models and XRD patterns of CuMAl-LDHs: CuMgAl-LDHs (a), CuZnAl-LDHs (b) and CuNiAl-LDHs (c). - Highlights: • Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) has been synthesized. • CuMgNi shows narrower band gap and more excellent textural properties than other LDHs. • The band gap: CuMgAl

  9. Effect of MacroRAFT Copolymer Adsorption on the Colloidal Stability of Layered Double Hydroxide Nanoparticles.

    PubMed

    Pavlovic, Marko; Adok-Sipiczki, Monika; Nardin, Corinne; Pearson, Samuel; Bourgeat-Lami, Elodie; Prevot, Vanessa; Szilagyi, Istvan

    2015-11-24

    The colloidal behavior of layered double hydroxide nanoparticles containing Mg(2+) and Al(3+) ions as intralayer cations and nitrates as counterions (MgAl-NO3-LDH) was studied in the presence of a short statistical copolymer of acrylic acid (AA) and butyl acrylate (BA) terminated with 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA) (P(AA7.5-stat-BA7.5)-CTPPA) synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Surface charge properties and aggregation of the particles were investigated by electrophoresis and dynamic light scattering (DLS), respectively. The negatively charged P(AA7.5-stat-BA7.5)-CTPPA adsorbed strongly on the oppositely charged particles, leading to charge neutralization at the isoelectric point (IEP) and charge reversal at higher copolymer concentrations. The dispersions were unstable, i.e., fast aggregation of the MgAl-NO3-LDH occurred near the IEP while high stability was achieved at higher P(AA7.5-stat-BA7.5)-CTPPA concentrations. Atomic force (AFM) and transmission electron (TEM) microscopy imaging revealed that the platelets preferentially adopted a face-to-face orientation in the aggregates. While the stability of the bare particles was very sensitive to ionic strength, the P(AA7.5-stat-BA7.5)-CTPPA copolymer-coated particles were extremely stable even at high salt levels. Accordingly, the limited colloidal stability of bare MgAl-NO3-LDH dispersions was significantly improved by adding an appropriate amount of P(AA7.5-stat-BA7.5)-CTPPA to the suspension.

  10. Atomistic simulation of nanoporous layered double hydroxide materials and their properties. II. Adsorption and diffusion

    NASA Astrophysics Data System (ADS)

    Kim, Nayong; Harale, Aadesh; Tsotsis, Theodore T.; Sahimi, Muhammad

    2007-12-01

    Nanoporous layered double hydroxide (LDH) materials have wide applications, ranging from being good adsorbents for gases (particularly CO2) and liquid ions to membranes and catalysts. They also have applications in medicine, environmental remediation, and electrochemistry. Their general chemical composition is [M1-xIIMxIII(OH-)2]x+[Xn/mm -•nH2O], where M represents a metallic cation (of valence II or III), and Xn/mm - is an m-valence inorganic, or heteropolyacid, or organic anion. We study diffusion and adsorption of CO2 in a particular LDH with MII=Mg, MIII=Al, and x ≃0.71, using an atomistic model developed based on energy minimization and molecular dynamics simulations, together with a modified form of the consistent-valence force field. The adsorption isotherms and self-diffusivity of CO2 in the material are computed over a range of temperature, using molecular simulations. The computed diffusivities are within one order of magnitude of the measured ones at lower temperatures, while agreeing well with the data at high temperatures. The measured and computed adsorption isotherms agree at low loadings, but differ by about 25% at high loadings. Possible reasons for the differences between the computed properties and the experimental data are discussed, and a model for improving the accuracy of the computed properties is suggested. Also studied are the material's hydration and swelling properties. As water molecules are added to the pore space, the LDH material swells to some extent, with the hydration energy exhibiting interesting variations with the number of the water molecules added. The implications of the results are discussed.

  11. Formation of layered single- and double-metal hydroxide precipitates at the mineral/water interface: A multiple-scattering XAFS analysis

    SciTech Connect

    Scheinost, A.C.; Sparks, D.L.

    2000-03-15

    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, a-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 the authors show that an XAFS beat pattern at about 8 {angstrom} {sup {minus}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, the authors 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. The authors 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.

  12. Preferential adsorption of 2,4-dichlorophenoxyacetate from associated binary-solute aqueous systems by Mg/Al-NO3 layered double hydroxides with different nitrate orientations.

    PubMed

    Chao, Yia-Feng; Lee, Jey-Jau; Wang, Shan-Li

    2009-06-15

    Layered double hydroxides (LDHs) are potential scavengers for anionic contaminants. To apply these materials to water treatment, it is essential to understand how the structural properties of LDHs control their preferential binding affinity toward a specific target contaminant in the presence of other anions. In this study, Mg/Al-NO(3) LDHs with different nitrate orientations were investigated for their preferential adsorption of 2,4-dichlorophenoxyacetate (2,4-D). LDH samples containing nitrate ions with parallel (LDH5) and perpendicular (LDH3) orientations exhibited different 2,4-D adsorption characteristics under competition with co-existing anions for surface binding sites. Because 2,4-D is inaccessible to the interlayer region of LDH5, the 2,4-D adsorption occurred mainly on the external surface of LDH5 and was easily subjected to negative effects from increasing concentrations of competing anions, including SO(4)(2-), HCO(3)(-), Cl(-), NO(3)(-) and Br(-). On the contrary, the interlayer nitrate in LDH3 is readily exchanged by 2,4-D. Thus, in conjunction with adsorption on the external surface, 2,4-D can also be adsorbed on the internal surface in the interlayer of LDH3. LDH3 exhibited a much higher 2,4-D adsorption capacity than LDH5, and the 2,4-D adsorption on LDH3 was less affected by the increasing concentration of competing anions. In summary, the selective removal of 2,4-D in solutions with a complex chemical composition may be maximized using Mg/Al-NO(3) LDHs containing perpendicularly oriented interlayer nitrate.

  13. Biochar pyrolyzed from MgAl-layered double hydroxides pre-coated ramie biomass (Boehmeria nivea (L.) Gaud.): Characterization and application for crystal violet removal.

    PubMed

    Tan, Xiao-Fei; Liu, Yun-Guo; Gu, Yan-Ling; Liu, Shao-Bo; Zeng, Guang-Ming; Cai, Xiaoxi; Hu, Xin-Jiang; Wang, Hui; Liu, Si-Mian; Jiang, Lu-Hua

    2016-12-15

    A novel biochar/MgAl-layered double hydroxides composite (CB-LDH) was prepared for the removal of crystal violet from aqueous solution by pyrolyzing MgAl-LDH pre-coated ramie stem (Boehmeria nivea (L.) Gaud.). Pyrolysis played dual role for both converting biomass into biochar and calcining MgAl-LDH during the pyrolysis process. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) and zeta potential analysis were used to characterize the CB-LDH. The results of characterization suggested that the calcined LDH was successfully synthesized and coated on biochar. The resulted CB-LDH had higher total pore volume and more functional groups than the pristine biochar. Adsorption experimental data fitted well with the pseudo-second order kinetics model and the Freundlich isotherm model. The rate-controlled step was controlled by film-diffusion initially and then followed by intra-particle diffusion. Thermodynamic analysis showed that the adsorption of crystal violet was a spontaneous and endothermic process. The higher pH and temperature of the solution enhanced the adsorption performance. CB-LDH could also have excellent ability for the removal of crystal violet from the actual industrial wastewater and groundwater with high ionic strength. LDH adsorption, electrostatic attraction, pore-filling, π-π interaction and hydrogen bond might be the main mechanisms for crystal violet adsorption on CB-LDH. The results of this study indicated that CB-LDH is a sustainable and green adsorbent with high performance for crystal violet contaminated wastewater treatment and groundwater remediation.

  14. Co-intercalation of Acid Red 337 and a UV absorbent into layered double hydroxides: enhancement of photostability.

    PubMed

    Li, Dianqing; Qian, Leilei; Feng, Yongjun; Feng, Junting; Tang, Pinggui; Yang, Lan

    2014-12-10

    Organic-inorganic hybrid pigments with enhanced thermo- and photostability have been prepared by co-intercalating C.I. Acid Red 337 (AR337) and a UV absorbent (BP-4) into the interlayer of ZnAl layered double hydroxides through a coprecipitation method. The obtained compounds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermogravimetric-differential thermal analysis, UV-visible spectroscopy, and the International Commission on Illumination (CIE) 1976 L*a*b* color scales. The results show the successful co-intercalation of AR337 and BP-4 into the interlayer region of layered double hydroxides (LDHs) and reveal the presence of host-guest interactions between LDH host layers and guest anions of AR337 and BP-4 and guest-guest interactions between AR337 and BP-4. The intercalation can improve the thermostability of AR337 due to the protection of LDH layers. Moreover, the co-intercalation of AR337 and BP-4 not only markedly enhances the photostability of AR337 but also significantly influences the color of the hybrid pigment.

  15. Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state {sup 1}H and {sup 71}Ga NMR spectroscopy

    SciTech Connect

    Petersen, Line Boisen; Lipton, Andrew S.; Zorin, Vadim; Nielsen, Ulla Gro

    2014-11-15

    Ordering of gallium(III) in a series of magnesium gallium (MgGa) layered double hydroxides (LDHs), [Mg{sub 1−x}Ga{sub x}(OH){sub 2}(NO{sub 3}){sub x}·yH{sub 2}O] was investigated using solid-state {sup 1}H and {sup 71}Ga NMR spectroscopy as well as powder X-ray diffraction. Three different proton environments from Mg{sub 3}-OH, Mg{sub 2}Ga-OH and intergallery water molecules were assigned and quantified using ({sup 1}H,{sup 71}Ga) HETCOR and {sup 1}H MAS NMR. A single {sup 71}Ga site originating from the unique Ga site in the MgGa LDH's was observed in {sup 71}Ga MAS and 3QMAS NMR spectra. Both {sup 1}H MAS NMR spectra recorded at 21.1 T (900 MHz) and elemental analysis show that the synthesized MgGa LDH's had a lower Mg:Ga ratio than that of the starting reactant solution. The origin of this is the formation of soluble [Ga(OH){sub 4}]{sup −} complexes formed during synthesis, and not due to formation of insoluble gallium (oxy)hydroxides. No sign of Ga-O-Ga connectivities or defects were detected for the MgGa LDH's. - Graphical abstract: Two types of hydroxides groups are observed in magnesium gallium layered double hydroxides revealing an ordering of Ga in the cation layer. - Highlights: • Ga is ordered in our magnesium gallium layered double hydroxides. • Ga depletion due to formation of soluble Ga complexes during synthesis. • No sign of Ga rich regions in magnesium gallium LDHs. • Solid state {sup 1}H and {sup 71}Ga give detailed insight into the structure.

  16. Synthesis and characterization of lawsone-lntercalated Zn-Al-layered double hydroxides.

    PubMed

    Yasin, Yamin; Ismail, Nur Mushirah; Hussein, Mohd Zobir; Aminudin, Norhaniza

    2011-06-01

    A drug-inorganic nanostructured material involving pharmaceutically active compound lawsone intercalated Zn-Al layered double hydroxides (Law-LDHs) with Zn/AI = 4 has been assembled by co-precipitation and ion exchange methods. Powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FTIR) analysis indicate a successful intercalation of lawsone between the layers of layered double hydroxides. It suggests that layered double hydroxides may have application as the basis of a drug delivery system.

  17. Visible-light-responsive photocatalysts toward water oxidation based on NiTi-layered double hydroxide/reduced graphene oxide composite materials.

    PubMed

    Li, Bei; Zhao, Yufei; Zhang, Shitong; Gao, Wa; Wei, Min

    2013-10-23

    A visible-light responsive photocatalyst was fabricated by anchoring NiTi-layered double hydroxide (NiTi-LDH) nanosheets to the surface of reduced graphene oxide sheets (RGO) via an in situ growth method; the resulting NiTi-LDH/RGO composite displays excellent photocatalytic activity toward water splitting into oxygen with a rate of 1.968 mmol g(-1) h(-1) and a quantum efficiency as high as 61.2% at 500 nm, which is among the most effective visible-light photocatalysts. XRD patterns and SEM images indicate that the NiTi-LDH nanosheets (diameter: 100-200 nm) are highly dispersed on the surface of RGO. UV-vis absorption spectroscopy exhibits that the introduction of RGO enhances the visible-light absorption range of photocatalysts, which is further verified by the largely decreased band gap (∼1.78 eV) studied by cyclic voltammetry measurements. Moreover, photoluminescence (PL) measurements indicate a more efficient separation of electron-hole pairs; electron spin resonance (ESR) and Raman scattering spectroscopy confirm the electrons transfer from NiTi-LDH nanosheets to RGO, accounting for the largely enhanced carrier mobility and the resulting photocatalytic activity in comparison with pristine NiTi-LDH material. Therefore, this work demonstrates a facile approach for the fabrication of visible-light responsive NiTi-LDH/RGO composite photocatalysts, which can be used as a promising candidate in solar energy conversion and environmental science.

  18. Facile synthesis of core-shell nanostructured hollow carbon nanospheres@nickel cobalt double hydroxides as high-performance electrode materials for supercapacitors.

    PubMed

    Xu, Juan; Ma, Chaojie; Cao, Jianyu; Chen, Zhidong

    2017-03-07

    Core-shell nanostructured hollow carbon nanospheres@nickel cobalt double hydroxides (HCNs@NiCo-LDH) were fabricated using a facile hydrothermal method and investigated as high-performance electrode materials for supercapacitors. HCNs were acquired by a successive polymerization, carbonization and etching process, which was subsequently wrapped by ultrathin NiCo-LDH nanosheets. The HCNs@NiCo-LDH electrode achieved a high specific capacitance (2558 F g(-1) at 1 A g(-1)) and outstanding rate capability with 74.9% capacitance retention after a 20-fold increase in current density. Capacitances of 2405, 2310, 2168, 2006 and 1916 F g(-1) can be achieved at rates of 3, 5, 10, 15 and 20 A g(-1), respectively, which are much higher than the specific capacitances of most reported carbon loaded NiCo-LDH. Specifically, the assembled HCNs@NiCo-LDH//graphene asymmetric supercapacitor displayed distinguished capacitive behaviors with a prominent specific capacitance of 172.8 F g(-1) and eminent cycling stability with 93.5% capacitance retention after 3000 cycles. These remarkable electrochemical properties indicate that the unique HCNs@NiCo-LDH core-shell electrode is highly promising for application in energy storage fields.

  19. Large-scale fabrication of linear low density polyethylene/layered double hydroxides composite films with enhanced heat retention, thermal, mechanical, optical and water vapor barrier properties

    NASA Astrophysics Data System (ADS)

    Xie, Jiazhuo; Zhang, Kun; Zhao, Qinghua; Wang, Qingguo; Xu, Jing

    2016-11-01

    Novel LDH intercalated with organic aliphatic long-chain anion was large-scale synthesized innovatively by high-energy ball milling in one pot. The linear low density polyethylene (LLDPE)/layered double hydroxides (LDH) composite films with enhanced heat retention, thermal, mechanical, optical and water vapor barrier properties were fabricated by melt blending and blowing process. FT IR, XRD, SEM results show that LDH particles were dispersed uniformly in the LLDPE composite films. Particularly, LLDPE composite film with 1% LDH exhibited the optimal performance among all the composite films with a 60.36% enhancement in the water vapor barrier property and a 45.73 °C increase in the temperature of maximum mass loss rate compared with pure LLDPE film. Furthermore, the improved infrared absorbance (1180-914 cm-1) of LLDPE/LDH films revealed the significant enhancement of heat retention. Therefore, this study prompts the application of LLDPE/LDH films as agricultural films with superior heat retention.

  20. Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

    NASA Astrophysics Data System (ADS)

    Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed

    2017-02-01

    Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

  1. Synthesis of organo cobalt-aluminum layered double hydroxide via a novel single-step self-assembling method and its use as flame retardant nanofiller in PP.

    PubMed

    Wang, De-Yi; Das, Amit; Costa, Francis Reny; Leuteritz, Andreas; Wang, Yu-Zhong; Wagenknecht, Udo; Heinrich, Gert

    2010-09-07

    Synthesis of polypropylene/organo-layered double hydroxide (PP/OLDH) has been carried out based on self-assembled organocobalt-aluminum LDH (O-CoAl-LDH). The novel method of synthesizing self-assembled CoAl-LDH and its characterization have also been reported in details. This method is proven to be very efficient way of producing OLDH in a single step with homogeneous composition and structure. As flame-retardant nanofiller, O-CoAl-LDH shows significant decrease in heat release rate (HRR), the total heat release (THR) and the heat release capacity (HRC) of the PP composites, though the thermal stability of the compounds decreases slightly compared to the base polymer. Morphological analyses show that the LDH particles are dispersed in PP matrix in a partially exfoliated form. The activation energy calculation based on the Kissinger method reveals that O-CoAl-LDH has a positive effect on the activation energy of thermal decomposition of PP. However, in the presence of this filler, decomposition of the composites starts at an earlier stage than that of pure PP.

  2. New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-08-15

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal.

  3. Biodiesel synthesis using calcined layered double hydroxide catalysts

    SciTech Connect

    Schumaker, J. Link; Crofcheck, Czarena; TAckett, S. Adam; Santillan-Jimenez, Eduardo; Morgan, Tonya; Ji, Yaying; Crocker, Mark; Toops, Todd J

    2008-01-01

    The catalytic properties of calcined Li-Al, Mg-Al and Mg-Fe layered double hydroxides (LDHs) were examined in two transesterification reactions, namely, the reaction of glyceryl tributyrate with methanol, and the reaction of soybean oil with methanol. While the Li-Al catalysts showed high activity in these reactions at the reflux temperature of methanol, the Mg-Fe and Mg-Al catalysts exhibited much lower methyl ester yields. CO2 TPD measurements revealed the presence of sites of weak, medium and strong basicity on both Mg-Al and Li-Al catalysts, the latter showing higher concentrations of medium and strong base sites; by implication, these are the main sites active in transesterification catalyzed by calcined Li-Al LDHs. Maximum activity was observed for the Li-Al catalysts when a calcination temperature of 450-500 aC was applied, corresponding to decomposition of the layered double hydroxide to the mixed oxide without formation of crystalline lithium aluminate phases.

  4. In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

    PubMed

    Ghani, Milad; Frizzarin, Rejane M; Maya, Fernando; Cerdà, Víctor

    2016-07-01

    Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35μgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%.

  5. Classical Keggin Intercalated into Layered Double Hydroxides: Facile Preparation and Catalytic Efficiency in Knoevenagel Condensation Reactions.

    PubMed

    Jia, Yueqing; Fang, Yanjun; Zhang, Yingkui; Miras, Haralampos N; Song, Yu-Fei

    2015-10-12

    The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction.

  6. Synthesis, structure refinement and chromate sorption characteristics of an Al-rich bayerite-based layered double hydroxide

    SciTech Connect

    Britto, Sylvia Kamath, P. Vishnu

    2014-07-01

    “Imbibition” of Zn{sup 2+} ions into the cation vacancies of bayerite–Al(OH){sub 3} and NO{sub 3}{sup −} ions into the interlayer gallery yields an Al-rich layered double hydroxide with Al/Zn ratio ∼3. NO{sub 3}{sup −} ions are intercalated with their molecular planes inclined at an angle to the plane of the metal hydroxide slab and bonded to it by hydrogen bonds. Rietveld refinement of the structure shows that the monoclinic symmetry of the precursor bayerite is preserved in the product, showing that the imbibition is topochemical in nature. The nitrate ion is labile and is quantitatively replaced by CrO{sub 4}{sup 2−} ions from solution. The uptake of CrO{sub 4}{sup 2−} ions follows a Langmuir adsorption isotherm, thus showing that the hydroxide is a candidate material for green chemistry applications for the removal of CrO{sub 4}{sup 2−} ions from waste water. Rietveld refinement of the structure of the hydroxide after CrO{sub 4}{sup 2−} inclusion reveals that the CrO{sub 4}{sup 2−} ion is intercalated with one of its 2-fold axes parallel to the b-crystallographic axis of the crystal, also the principal 2 axis of the monoclinic cell. - Graphical abstract: The structure of the [Zn–Al4-nitrate] LDH viewed along the a-axis. - Highlights: • Synthesis of Al-rich layered double hydroxide with Al/Zn ratio ∼3. • Rietveld refinement indicates that the imbibition of Zn into Al(OH){sub 3} is topochemical in nature. • The uptake of CrO{sub 4}{sup 2−} ions follows a Langmuir adsorption isotherm.

  7. How the method of synthesis governs the local and global structure of zinc aluminum layered double hydroxides

    SciTech Connect

    Pushparaj, Suraj Shiv Charan; Forano, Claude; Prevot, Vanessa; Lipton, Andrew S.; Rees, Gregory; Hanna, John V.; Nielsen, Ulla Gro

    2015-11-10

    A series of zinc aluminum layered double hydroxides (ZnAl LDHs), [Zn1-xAlx (OH)2Ax,nH2O with A = NO3-, Cl- or CO3] were prepared by the urea and co-precipitation synthesis methods, which allowed for a detailed investigation on how synthesis parameters such as pH, metal ion concentration and post synthesis treatment influence the local and global structure of the LDH product. Information about sample composition, purity, defects and other structural aspects of the LDH products were obtained from powder X-ray diffraction, transmission electron microscopy, micro-Raman, and elemental analysis, as well as solid state 1H, 27Al and 67Zn NMR spectroscopy. Our results show that the urea method results in LDHs, which on the global scale are highly crystalline LDHs, whereas solid state NMR shows the different local environments indicating local disorder most likely linked to the presence of Al-rich phases. However, these Alrich phases are not detected by global range techniques, as they either defects within the LDH particles or separate phase(s) associated with LDHs. In contrast, samples prepared by coprecipitation especially synthesized under careful pH control and subsequently hydrothermal treated have high local order and good crystallinity (particle size). Our results show that both molecular level and macroscopic techniques are needed to assess the composition of LDHs, as the conventional PXRD and TEM analysis of LDHs failed to identify the many structural defects and/or amorphous phases.

  8. Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

    NASA Astrophysics Data System (ADS)

    Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

    2017-01-01

    Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation.

  9. Nanoincorporation of layered double hydroxides into a miscible blend system of cellulose acetate with poly(acryloyl morpholine).

    PubMed

    Yoshitake, Sachi; Suzuki, Tetsuya; Miyashita, Yoshiharu; Aoki, Dan; Teramoto, Yoshikuni; Nishio, Yoshiyuki

    2013-03-01

    Blend miscibility of cellulose acetate (CA) with poly(acryloyl morpholine) (PACMO) was examined by thermal transition measurements and solid-state (13)C NMR spectroscopy, in which CA materials of acetyl DS=1.80-2.95 were used. All the blends prepared gave a single Tg and formed an amorphous monophase homogeneous within a distance of ∼2.0nm. An Al/Mg-based, layered double hydroxide (LDH) was modified with different ionic oligomers, and an attempt was made to incorporate the respective organophilic LDHs (3-3.5wt%) into blend films of the miscible PACMO/CA pair, via bulk polymerization of an ACMO monomer/organo-LDH mixture and then blending CA with the polymer/inorganic hybrid precursor. Particularly, 12-hydroxystearic acid-modified LDH was well exfoliated and ultimately dispersed in the PACMO/CA matrix on a scale of less than a few tens of nanometers in thickness. This gave rise to a successful reinforcement effect leading to the improvement in thermo-mechanical property of the polymer blends.

  10. Removal of boron from oilfield wastewater via adsorption with synthetic layered double hydroxides.

    PubMed

    Delazare, Thais; Ferreira, Letícia P; Ribeiro, Nielson F P; Souza, Mariana M V M; Campos, Juacyara C; Yokoyama, Lídia

    2014-01-01

    Hydrotalcite is a layered double hydroxide (LDH) consisting of brucite-like sheets of metal ions (Mg-Al). In this work, hydrotalcites were synthesized, and boron removal from oilfield wastewater was evaluated. LDHs were synthesized using the co-precipitation method. The calcined products (CLDHs) were obtained by heating at 500°C and characterized using X-ray diffraction, X-ray fluorescence, thermogravimetric analysis and the specific surface area (BET). The affinity of LDHs for borate ions was evaluated for calcined and uncalcined LDHs as a function of contact time, initial pH of the oilfield wastewater (pH ∼ 9) and the LDH surface area. The tests were conducted at room temperature (approximately 25ºC). The results indicated that 10 min were needed to reach a state of equilibrium during boron removal for calcined LDHs due to the high surface area (202.3 m(2) g(-1)) regardless of the initial pH of the oilfield wastewater, which resulted from the high buffering capacity of the LDHs. The adsorption capacity increased as the adsorbents levels increased for the range studied. After treatment of the oilfield wastewater containing 30 mg L(-1) of boron with Mg-Al-CO3-LDHs, the final concentration of boron was within the discharge limit set by current Brazilian environmental legislation, which is 5 mg L(-1). Pseudo-first-order and pseudo-second-order kinetic models were tested, and the latter was found to fit the experimental data better. Isotherms for boron adsorption by CLDHs were well described using the Langmuir and Freundlich equations.

  11. Carboxylate-intercalated layered double hydroxides aged under microwave-hydrothermal treatment

    SciTech Connect

    Benito, P.; Labajos, F.M.; Mafra, L.; Rocha, J.; Rives, V.

    2009-01-15

    Carboxylate-intercalated (terephthalate, TA and oxalate, ox) layered double hydroxides (LDHs) are aged under a microwave-hydrothermal treatment. The influence of the nature of the interlayer anion during the ageing process is studied. Characterization results show that the microwave-hydrothermal method can be extended to synthesize LDHs with anions different than carbonate, like TA. LDH-TA compounds are stable under microwave irradiation for increasing periods of time and the solids show an improved order both in the layers and in the interlayer region as evidenced by powder X-ray diffraction (PXRD), {sup 27}Al MAS NMR and FT-IR spectroscopy. Furthermore, cleaning of the surface through removal of some organic species adsorbed on the surface of the particles also occurs during the microwave-hydrothermal treatment. Conversely, although the expected increase in crystallinity is observed in LDH-ox samples, the side-reaction between Al{sup 3+} and ox is also enhanced under microwave irradiation, and a partial destruction of the structure takes place with an increase in the M{sup 2+}/M{sup 3+} ratio and consequent modification of the cell parameters. - Graphical Abstract: The influence of the nature of the interlayer anion during the ageing process of carboxylate-intercalated (TA and ox) hydrotalcite-like compounds (HTlcs) is studied. Well crystallized for TA-containing compounds were obtained. However, the non-desired side-reaction of ox with the aluminum of the layers is enhanced by the microwaves and a partial destruction of the structure takes place.

  12. Development of an Immunosensor Based on Layered Double Hydroxides for MMR Cancer Biomarker Detection.

    PubMed

    Hammami, M; Soussou, A; Idoudi, F; Cohen-Bouhacina, T; Bouhaouala-Zahar, B; Baccar, Z M

    2015-10-01

    As a potential biomarker for the investigation of cancer inflammatory profiles, macrophage mannose receptor (MMR, CD206) is herein selected to develop an immunosensor based on layered double hydroxide (LDH). Like an endocyte C-type lectin receptor, MMR plays an important role in immune homeostasis by scavenging unwanted mannose glycoproteins. It attracts a progressive attention thanks to its particularly high expression within the tumor microenvironment. There is a great of interest to develop an immunosensor based on an antibody specific to MMR for detection of stroma versus tumor cells. In this work, we studied the feasibility of high sensitive MMR cancer Screen Printed Electrode (SPE) immunosensor. Working electrode of commercialized SPE was modified by immobilization of specific antibody (anti-MMR) into thin layer of LDH nanomaterials. Structural, morphological, and surface properties of LDHs were studied by X-Ray diffraction, atomic force microscopy and Infrared spectroscopy in ATR. Cyclic Voltammetry technique was used to study interaction between the human recombinant MMR protein (rHu-MMR, NSO derived) and an immobilized antibody into developed immunosensor. High specific response of -11.72 μA/ng.mL(-1) (with a correlation coefficient of R(2)=0.994 ) were obtained in linear range of 0.05 ng/mL to 10.0 ng/mL of specific recombinant antigen. The limit of detection (LOD) was less than 15.0 pg/mL. From these attractive results, the feasibility of an electrochemical immunosensor for cancer was proved. Additional experiments to study stability and reproducibility the immunosensor should be completed in perspective to use these anti-MMR based immunosensors for sensing human MMR in patient biopsies and sera.

  13. A novel thermotropic elastomer based on highly-filled LDH-SSB composites.

    PubMed

    Das, Amit; George, Jinu Jacob; Kutlu, Burak; Leuteritz, Andreas; Wang, De-Yi; Rooj, Sandip; Jurk, René; Rajeshbabu, Ramanujam; Stöckelhuber, Klaus Werner; Galiatsatos, Vassilios; Heinrich, Gert

    2012-02-27

    Elastomeric composites are prepared based on solution styrene butadiene elastomer and zinc-aluminium layered double hydroxides (LDH), using a conventional sulphur cure system. Up to 100 parts per hundred rubber of LDH are incorporated into the elastomer matrix. The composites exhibit an interesting phenomenon of thermoreversible transparency, i.e. the transparent sample becomes opaque at warm condition and restores the transparency at room temperature. The transparency is found to be increased as the amount of LDH was increased. The addition of LDH gradually improved the mechanical, dynamic mechanical performance and thermal stability of the base elastomer. These developped elastomers could be utilised as smart materials in different applications.

  14. Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

    NASA Astrophysics Data System (ADS)

    Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

    2016-08-01

    Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as ‑0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at ‑0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under ‑0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination.

  15. Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

    PubMed Central

    Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

    2016-01-01

    Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as −0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at −0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under −0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination. PMID:27487918

  16. Aluminium substitution in iron(II-III)-layered double hydroxides: Formation and cationic order

    SciTech Connect

    Ruby, Christian Abdelmoula, Mustapha; Aissa, Rabha; Medjahdi, Ghouti; Brunelli, Michela; Francois, Michel

    2008-09-15

    The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe{sub 4}{sup II}Fe{sub (2-6y)}{sup III}Al{sub 6y}{sup III} (OH){sub 12} SO{sub 4}, 8H{sub 2}O are followed by pH titration curves, Moessbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO{sub 4}{sup 2-}), i.e. y=0, in which a bilayer of sulphate anions points to the Fe{sup 3+} species. A cationic order is proposed to occur in both GR(SO{sub 4}{sup 2-}) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cell parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO{sub 4}{sup 2-}) is preceded by the successive precipitation of Fe{sup III} and Al{sup III} (oxy)hydroxides. Adsorption of more soluble Al{sup III} species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount (y{approx}0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe{sup II} species of the material. - Graphical abstract: (a) Crystallographical structure of sulphated green rust: SO{sub 4}{sup 2-} point to the Fe{sup 3+} cations (red) that form an ordered array with the Fe{sup 2+} cations (green). (b) Width and asymmetry of the synchrotron XRD peaks increase rapidly when some Al{sup 3+} species substitute the Fe{sup 3+} cations; z is molar ratio Al{sup 3+}/Fe{sup 3+}.

  17. Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene

    NASA Astrophysics Data System (ADS)

    Ma, Wei; Ma, Renzhi; Wu, Jinghua; Sun, Pengzhan; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

    2016-05-01

    Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery.Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade

  18. Immobilization of layered double hydroxides in the fluidic system for nanoextraction of specific DNA molecules

    NASA Astrophysics Data System (ADS)

    Chen, Jem-Kun; Chan, Chia-Hao; Chang, Feng-Chih

    2008-02-01

    The purpose of this study was to immobilize inorganic layered double hydroxides (LDHs) on the poly(methylmethacrylate) substrate as the media to extract the specific DNA molecules through fluidic system to enhance the efficiency of extract specific DNA molecules from extremely low concentration in sample solution. LDH immobilized through solvent swelling and plasma treatment on the polymer surface captured the specific DNA molecules lysed from Escherichia coli (E. coli) cells as the target DNA molecules with 2×10-4g/l of concentration in sample solution mixed biomacromolecules lysed from human blood. The encapsulated DNA molecules released through dissolving of LDHs by slight acid (pH=4-5) solution then amplified by polymerase chain reaction (PCR) process through the primers for E. coli cells. The DNA molecules amplified by PCR process were characterized by gel electrophoresis to recognize the existence of E. coli cells. The results show that immobilized LDHs could be regarded as the specific DNA detector for rapid disease diagnosis through fluidic system.

  19. Synthesis of protocatechuic acid-zinc/aluminium-layered double hydroxide nanocomposite as an anticancer nanodelivery system

    NASA Astrophysics Data System (ADS)

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Gani, Shafinaz Abd; Fakurazi, Sharida; Zainal, Zulkarnain

    2015-01-01

    Protocatechuic acid, an active anticancer agent, has been intercalated into Zn/Al-layered double hydroxide at Zn/Al=2) using two different preparation methods, co-precipitation and ion-exchange, which are labelled as PZAE and PZAC, respectively. The release of protocatechuate from the nanocomposites occurred in a controlled manner and was fitted satisfactorily to pseudo-second order kinetics. The basal spacing of the resulting nanocomposites PZAE and PZAC was 10.2 and 11.0 Å, respectively, indicating successful intercalation of protocatechuate anions into the interlayer galleries of Zn/Al-NO3-LDH in a monolayer arrangement with angles of 24 and 33° from the z-axis in PZAE and PZAC, respectively. The formation of nanocomposites was further confirmed by a Fourier transform infrared study. Thermogravimetric and differential thermogravimetric analyses indicated that the thermal stability of the intercalated protocatechuic acid was significantly enhanced compared to its free protocatechuic acid, and the drug content in the nanocomposites was estimated to be approximately 32.6% in PZAE and 29.2% in PZAC. Both PZAE and PZAC nanocomposites inhibit the growth of human cervical, liver and colorectal cancer cell lines and exhibit no toxic effects towards normal fibroblast 3T3 cell after 72 h of treatment.

  20. Bacteria encapsulated in layered double hydroxides: towards an efficient bionanohybrid for pollutant degradation.

    PubMed

    Halma, Matilte; Mousty, Christine; Forano, Claude; Sancelme, Martine; Besse-Hoggan, Pascale; Prevot, Vanessa

    2015-02-01

    A soft chemical process was successfully used to immobilize Pseudomonas sp. strain ADP (ADP), a well-known atrazine (herbicide) degrading bacterium, within a Mg2Al-layered double hydroxide host matrix. This approach is based on a simple, quick and ecofriendly direct coprecipitation of metal salts in the presence of a colloidal suspension of bacteria in water. It must be stressed that by this process the mass ratio between inorganic and biological components was easily tuned ranging from 2 to 40. This ratio strongly influenced the biological activity of the bacteria towards atrazine degradation. The better results were obtained for ratios of 10 or lower, leading to an enhanced atrazine degradation rate and percentage compared to free cells. Moreover the biohybrid material maintained this biodegradative activity after four cycles of reutilization and 3 weeks storage at 4°C. The ADP@MgAl-LDH bionanohybrid materials were completely characterized by X-ray diffraction (XRD), FTIR spectroscopy, thermogravimetric analysis and scanning and transmission electronic microscopy (SEM and TEM) evidencing the successful immobilization of ADP within the inorganic matrix. This synthetic approach could be readily extended to other microbial whole-cell immobilization of interest for new developments in biotechnological systems.

  1. Synthesis and Characterization of Layered Double Hydroxides and Their Potential as Nonviral Gene Delivery Vehicles

    PubMed Central

    Balcomb, Blake; Singh, Moganavelli; Singh, Sooboo

    2015-01-01

    Layered double hydroxides (LDHs) exhibit characteristic anion-exchange chemistry making them ideal carriers of negatively charged molecules like deoxyribonucleic acid (DNA). In this study, hydrotalcite (Mg−Al) and hydrotalcite-like compounds (Mg−Fe, Zn−Al, and Zn−Fe), also known as LDHs, were evaluated for their potential application as a carrier of DNA. LDHs were prepared by coprecipitation at low supersaturation and characterized by Powder X-ray diffraction (XRD), infrared (IR), Raman, and inductively coupled plasma—optical emission spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRD patterns showed strong and sharp diffraction peaks for the (003) and (006) planes indicating well-ordered crystalline materials. TEM images yielded irregular circular to hexagonal-shaped particles of 50–250 nm in size. Varying degrees of DNA binding was observed for all the compounds, and nuclease digestion studies revealed that the LDHs afford some degree of protection to the bound DNA. Minimal toxicity was observed in human embryonic kidney (HEK293), cervical cancer (HeLa) and hepatocellular carcinoma (HepG2) cell lines with most showing a cell viability in excess of 80 %. All LDH complexes promoted significant levels of luciferase gene expression, with the DNA:Mg−Al LDHs proving to be the most efficient in all cell lines. PMID:25969811

  2. Influence of emulsification process on the properties of Pickering emulsions stabilized by layered double hydroxide particles.

    PubMed

    Zhang, Nana; Zhang, Li; Sun, Dejun

    2015-04-28

    This paper reports the influence of emulsification process on the packing of layered double hydroxide (LDH) particles at the aqueous/oil phase interface and the properties of the resulting Pickering emulsions. Emulsions prepared by ultrasonication display superior long-term stability and gel-like characteristics at the dispersed phase volume fraction well below the random close packing limit, whereas emulsions with same compositions prepared by vortex mixing show some extent of sedimentation and liquid-like behaviors. Rheological measurements demonstrate that the zero-shear elastic modulus and yield stress of gel-like emulsions exhibit power-law dependences on particle concentration and independence on aqueous/oil phase ratio. The microstructural origin of this behavior is investigated by optical microscopy, revealing the droplets become strongly adhesive and a heterogeneous percolating network is formed among neighboring droplets. Fluorescent confocal microscopy measurements further confirm that the droplet adhesion is due to particle layers bridging opposite interfaces. In contrast, homogeneous, isolated, and densely packed droplets are present in emulsions prepared by vortex mixing, which results in these systems being dominantly viscous like the suspending fluid. This study shows that the emulsification process can be used as a trigger to modify long-term stability and rheology of solid-stabilized multiphase mixtures, which greatly expands their potential technological applications.

  3. Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

    SciTech Connect

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; and others

    2016-01-15

    A mechanochemical method (grinding the components without added water – dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution – wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic–inorganic nanocomposites: LDHs intercalated with amino acid anions. - Graphical abstract: Amino acid anion-Ca(II)Fe(III)-LDHs were successfully prepared by a two-step milling procedure. - Highlights: • Synthesis of pristine and amino acid intercalated CaFe-LDHs by two-step milling. • Identifying the optimum synthesis and intercalation parameters. • Characterisation of the samples with a range of instrumental methods.

  4. Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; Pálinkó, I.

    2016-01-01

    A mechanochemical method (grinding the components without added water - dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution - wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic-inorganic nanocomposites: LDHs intercalated with amino acid anions.

  5. Organo-layered double hydroxides composite thin films deposited by laser techniques

    NASA Astrophysics Data System (ADS)

    Birjega, R.; Vlad, A.; Matei, A.; Dumitru, M.; Stokker-Cheregi, F.; Dinescu, M.; Zavoianu, R.; Raditoiu, V.; Corobea, M. C.

    2016-06-01

    We used laser techniques to create hydrophobic thin films of layered double hydroxides (LDHs) and organo-modified LDHs. A LDH based on Zn-Al with Zn2+/Al3+ ratio of 2.5 was used as host material, while dodecyl sulfate (DS), which is an organic surfactant, acted as guest material. Pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) were employed for the growth of the films. The organic anions were intercalated in co-precipitation step. The powders were subsequently used either as materials for MAPLE, or they were pressed and used as targets for PLD. The surface topography of the thin films was investigated by atomic force microscopy (AFM), the crystallographic structure of the powders and films was checked by X-ray diffraction. FTIR spectroscopy was used to evidence DS interlayer intercalation, both for powders and the derived films. Contact angle measurements were performed in order to establish the wettability properties of the as-prepared thin films, in view of functionalization applications as hydrophobic surfaces, owing to the effect of DS intercalation.

  6. Molecular modeling of layered double hydroxide intercalated with benzoate, modeling and experiment.

    PubMed

    Kovár, Petr; Pospísil, M; Nocchetti, M; Capková, P; Melánová, Klára

    2007-08-01

    The structure of Zn4Al2 Layered Double Hydroxide intercalated with benzencarboxylate (C6H5COO-) was solved using molecular modeling combined with experiment (X-ray powder diffraction, IR spectroscopy, TG measurements). Molecular modeling revealed the arrangement of guest molecules, layer stacking, water content and water location in the interlayer space of the host structure. Molecular modeling using empirical force field was carried out in Cerius(2) modeling environment. Results of modeling were confronted with experiment that means comparing the calculated and measured diffraction pattern and comparing the calculated water content with the thermogravimetric value. Good agreement has been achieved between calculated and measured basal spacing: d(calc) = 15.3 A and d(exp) = 15.5 A. The number of water molecules per formula unit (6H2O per Zn4Al2(OH)12) obtained by modeling (i.e., corresponding to the energy minimum) agrees with the water content estimated by thermogravimetry. The long axis of guest molecules are almost perpendicular to the LDH layers, anchored to the host layers via COO- groups. Mutual orientation of benzoate ring planes in the interlayer space keeps the parquet arrangement. Water molecules are roughly arranged in planes adjacent to host layers together with COO- groups.

  7. Ion exchange and intercalation properties of layered double hydroxides towards halide anions.

    PubMed

    Costantino, Umberto; Vivani, Riccardo; Bastianini, Maria; Costantino, Ferdinando; Nocchetti, Morena

    2014-08-14

    A layered double hydroxide (LDH) obtained by the urea method, having an empirical formula [Zn(0.61)Al(0.39)(OH)2](CO3)(0.195)·0.50H2O, has been converted into the corresponding chloride form [Zn(0.61)Al(0.39)(OH)2]Cl(0.39)·0.47H2O by making the solid come into contact with a suitable HCl solution. The intercalation of the other halide anions (X(-) = F(-), Br(-), I(-)) via the Cl(-)/X(-) anion exchange has been attained and the respective anion exchange isotherms have been obtained with the batch method. The analysis of the isotherms indicates that the selectivity of LDH towards the halides decreases with the increase of the X(-) ionic radius, the selectivity order being F(-) > Cl(-)≥ Br(-) > I(-). The CO3(2-)/Cl(-) isotherm has also been reported to highlight the extraordinary selectivity of LDH towards carbonate anions. Samples taken from the isotherms at different exchange degrees were analyzed by X-ray diffraction, thermogravimetry and thermodiffractometry to obtain information about the ion exchange mechanism. The Cl(-)/Br(-) and the reverse Br(-)/Cl(-) exchanges occur with the formation of solid solutions, very likely because of the similar ionic radius of the exchanging anions. In contrast, in the Cl(-)/F(-) and Cl(-)/I(-) exchange, the co-existence of the Cl(-) and F(-) (or I(-)) phases in the same sample was detected, indicating the occurrence of a first order phase transition, in which the starting phase is transformed into the final phase, as the process goes on. The variation of the interlayer distances of ZnAl-X intercalation compounds with the hydration degree has been interpreted with a structural model based on the nesting of the guest species into the trigonal pockets of the brucite-like layer surface. Rietveld refinements of the phases with the maximum F(-), Br(-) and I(-) content were also performed and compared with the above model, giving indications of the arrangement and order/disorder of the halide anions in the interlayer region.

  8. Abatement of aqueous anionic contaminants by thermo-responsive nanocomposites: (poly(N-isopropylacrylamide))-co-silylanized magnesium/aluminun layered double hydroxides.

    PubMed

    Chen, Hua; Qian, Guangren; Ruan, Xiuxiu; Frost, Ray L

    2015-06-15

    A series of novel thermo-responsive composite sorbents, were prepared by free-radical co-polymerization of N-isopropylacrylamide (NIPAm) and the silylanized Mg/Al layered double hydroxides (SiLDHs), named as PNIPAm-co-SiLDHs. For keeping the high affinity of Mg/Al layered double hydroxides towards anions, the layered structure of LDHs was assumed to be reserved in PNIPAm-co-SiLDHs by the silanization of the wet LDH plates as evidenced by the X-ray powder diffraction. The sorption capacity of PNIPAm-co-SiLDH (13.5 mg/g) for Orange-II from water was found to be seven times higher than that of PNIPAm (2.0mg/g), and the sorption capacities of arsenate onto PNIPAm-co-SiLDH are also greater than that onto PNIPAm, for both As(III) and As(V). These sorption results suggest that reserved LDH structure played a significant role in enhancing the sorption capacities. NO3(-) intercalated LDHs composite showed the stronger sorption capacity for Orange-II than that of CO3(2-). After sorption, the PNIPAm-co-SiLDH may be removed from water because of its gel-like nature, and may be easily regenerated contributing to the accelerated desorption of anionic contaminants from PNIPAm-co-SiLDHs by the unique phase-transfer feature through slightly heating (to 40 °C). These recyclable and regeneratable properties of thermo-responsive nanocomposites facilitate its potential application in the in-situ remediation of organic and inorganic anions from contaminated water.

  9. Nickel-aluminum layered double hydroxide as a nanosorbent for selective solid-phase extraction and spectrofluorometric determination of salicylic acid in pharmaceutical and biological samples.

    PubMed

    Abdolmohammad-Zadeh, H; Kohansal, S; Sadeghi, G H

    2011-04-15

    The nickel-aluminum layered double hydroxide (Ni-Al LDH) was synthesized by a simple co-precipitation method and used as a solid-phase extraction (SPE) sorbent for separation and pre-concentration of trace levels of salicylic acid (SA) from aqueous solutions. Extraction of analyte is based on the adsorption of salicylate ions on the Ni-Al (NO(3)(-)) LDH and/or their exchanging with LDH interlayer NO(3)(-) ions. The retained analyte on the LDH was stripped by 3 mol L(-1) NaOH solution and its concentration was subsequently determined spectrofluorometrically at λ(em)=400 nm with excitation at λ(ex)=270 nm. Various parameters affecting the extraction efficiency of SA on the Ni-Al (NO(3)(-)) LDH, such as pH, amount of nano-sorbent, sample loading flow rate, elution conditions, sample volume and matrix effects were investigated. In the optimum experimental conditions, the limit of detection (3s) and enrichment factor were 0.12 μg L(-1) and 40, respectively. The relative standard deviation (RSD) for six replicate determinations of 10 μg L(-1) SA was 2.3%. The calibration graph using the pre-concentration system was linear in the range of 0.3-45 μg L(-1) with a correlation coefficient of 0.9985. The optimized method was successfully applied to the determination of SA in blood serum, willow leaf and aspirin tablet.

  10. Highly Enhanced Photoelectrochemical Water Oxidation Efficiency Based on Triadic Quantum Dot/Layered Double Hydroxide/BiVO 4 Photoanodes

    SciTech Connect

    Tang, Yanqun; Wang, Ruirui; Yang, Ye; Yan, Dongpeng; Xiang, Xu

    2016-08-03

    The water oxidation half-reaction is considered to be a bottleneck for achieving highly efficient solar-driven water splitting due to its multiproton-coupled four-electron process and sluggish kinetics. Herein, a triadic photoanode consisting of dual-sized CdTe quantum dots (QDs), Co-based layered double hydroxide (LDH) nanosheets, and BiVO4 particles, that is, QD@LDH@BiVO4, was designed. Two sets of consecutive Type-II band alignments were constructed to improve photogenerated electron-hole separation in the triadic structure. The efficient charge separation resulted in a 2-fold enhancement of the photocurrent of the QD@LDH@BiVO4 photoanode. A significantly enhanced oxidation efficiency reaching above 90% in the low bias region (i.e., E < 0.8 V vs RHE) could be critical in determining the overall performance of a complete photoelectrochemical cell. The faradaic efficiency for water oxidation was almost 90%. The conduction band energy of QDs is -1.0 V more negative than that of LDH, favorable for the electron injection to LDH and enabling a more efficient hole separation. The enhanced photon-to-current conversion efficiency and improved water oxidation efficiency of the triadic structure may result from the non-negligible contribution of hot electrons or holes generated in QDs. Such a band-matching and multidimensional triadic architecture could be a promising strategy for achieving high-efficiency photoanodes by sufficiently utilizing and maximizing the functionalities of QDs.

  11. Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

    PubMed Central

    Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

    2015-01-01

    The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field. PMID:26670467

  12. Three dimensionally honeycomb layered double hydroxides framework as a novel fiber coating for headspace solid-phase microextraction of phenolic compounds.

    PubMed

    Abolghasemi, Mir Mahdi; Yousefi, Vahid

    2014-06-06

    A new solid phase microextraction (SPME) fiber based on high-temperature three dimensionally honeycomb layered double hydroxide (TDH-LDH) material is presented. The fiber coating can be prepared easily, it is mechanically stable and exhibits relatively high thermal stability. This study shows that three dimensionally honeycomb layered double hydroxide generated porous morphology. The TDH-LDH material was tested for the extraction of some phenolic and polycyclic aromatic hydrocarbon compounds from aqueous sample solutions in combination with gas chromatography-mass spectrometry (GC-MS). The TDH-LDH fiber contains polar groups and its efficiency for non-polar polycyclic aromatic hydrocarbon compounds was lower than phenolic compounds. On the other hand, a high tendency towards the adsorption of polar phenolic compounds was observed for the proposed fiber. The effects of the extraction and desorption parameters including extraction temperature, extraction time, ionic strength, stirring rate, pH and desorption temperature and time have been studied. In optimum conditions, the repeatability for one fiber (n=5), expressed as relative standard deviation (R.S.D. %), was between 2.8% and 7.1% for the phenolic compounds. The detection limits for the studied phenolic compounds were between 0.02 and 5.8 ng mL(-1). The developed method offers the advantage of being simple to use, with shorter analysis time, lower cost of equipment, thermal stability of fiber and high relative recovery in comparison to conventional methods of analysis.

  13. Magnetic-field-assisted assembly of layered double hydroxide/metal porphyrin ultrathin films and their application for glucose sensors.

    PubMed

    Shao, Mingfei; Xu, Xiangyu; Han, Jingbin; Zhao, Jingwen; Shi, Wenying; Kong, Xianggui; Wei, Min; Evans, David G; Duan, Xue

    2011-07-05

    The ordered ultrathin films (UTFs) based on CoFe-LDH (layered double hydroxide) nanoplatelets and manganese porphyrin (Mn-TPPS) have been fabricated on ITO substrates via a magnetic-field-assisted (MFA) layer-by-layer (LBL) method and were demonstrated as an electrochemical sensor for glucose. The XRD pattern for the film indicates a long-range stacking order in the normal direction of the substrate. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images of the MFA LDH/Mn-TPPS UTFs reveal a continuous and uniform surface morphology. Cyclic voltammetry, impedance spectroscopy, and chronoamperometry were used to evaluate the electrochemical performance of the film, and the results show that the MFA-0.5 (0.5 T magnetic field) CoFe-LDH/Mn-TPPS-modified electrode displays the strongest redox current peaks and fastest electron transfer process compared with those of MFA-0 (without magnetic-field) and MFA-0.15 (0.15 T magnetic field). Furthermore, the MFA-0.5 CoFe-LDH/Mn-TPPS exhibits remarkable electrocatalytic activity toward the oxidation of glucose with a linear response range (0.1-15 mM; R(2) = 0.999), low detection limit (0.79 μM) and high sensitivity (66.3 μA mM(-1) cm(-2)). In addition, the glucose sensor prepared by the MFA LBL method also shows good selectivity and reproducibility as well as resistance to poisoning in a chloride ion solution. Therefore, the novel strategy in this work creates new opportunities for the fabrication of nonenzyme sensors with prospective applications in practical detection.

  14. Intercalation of papain enzyme into hydrotalcite type layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Zou, N.; Plank, J.

    2012-09-01

    Intercalation of proteolytic enzyme papain into hydrotalcite type LDH structure was achieved by controlled co-precipitation at pH=9.0 in the presence of papain. Characterization of the MgAl-papain-LDH phase was carried out using X-ray powder diffraction (XRD), elemental analysis, infrared spectroscopy (IR) and thermogravimetry (TG). According to XRD, papain was successfully intercalated. The d-value for the basal spacing of MgAl-papain-LDH was found at ˜5.3 nm. Consequently, original papain (hydrodynamic diameter ˜7.2 nm) attains a compressed conformation during intercalation.Formation of MgAl-papain-LDH was confirmed by elemental analysis and transmission electron microscopy (TEM). Under SEM, MgAl-papain-LDH phases appear as nanothin platelets which are intergrown to flower-like aggregates. Steric size and activity of the enzyme was retained after deintercalation from MgAl-LDH framework, as was evidenced by light scattering and UV/vis measurements. Thus, papain is not denatured during intercalation, and LDH is a suitable host structure which can provide a time-controlled release of the biomolecule.

  15. Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

    PubMed Central

    Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

    2015-01-01

    Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm−2 or 1734 F g−1 at 5 mA cm−2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application. PMID:26278334

  16. Exchange of interlayer terephthalate anions from a Mg Al layered double hydroxide: formation of intermediate interstratified phases

    NASA Astrophysics Data System (ADS)

    Kaneyoshi, Masami; Jones, William

    1998-10-01

    The exchange of interlayer terephthalate (TA) anions from a Mg-Al layered double hydroxide (LDH) by carbonate, sulfate, chloride and nitrate anions is reported. It is shown that TA is readily exchanged by CO 32- and SO 42- but only partly by Cl - and NO 3-. We demonstrate that during the exchange process interstratified phases are observed. Such interstratification has previously been reported only for directly synthesised materials. The origin of the interstratification is believed to be associated with two preferred orientations of TA anions within the layers, i.e. vertical or horizontal to the clay sheets. Two models for the possible exchange mechanism which is operating in these systems are proposed.

  17. 3D Hierarchical Co-Al Layered Double Hydroxides with Long-Term Stabilities and High Rate Performances in Supercapacitors

    NASA Astrophysics Data System (ADS)

    Zai, Jiantao; Liu, Yuanyuan; Li, Xiaomin; Ma, Zi-feng; Qi, Rongrong; Qian, Xuefeng

    2017-04-01

    Three-dimensional (3D) flower-like Co-Al layered double hydroxide (Co-Al-LDH) architectures composed of atomically thin nanosheets were successfully synthesized via a hydrothermal method in a mixed solvent of water and butyl alcohol. Owing to the unique hierarchical structure and modification by butyl alcohol, the electrochemical stability and the charge/mass transport of the Co-Al-LDHs was improved. When used in supercapacitors, the obtained Co-Al-LDHs deliver a high specific capacitance of 838 F g-1 at a current density of 1 A g-1 and excellent rate performance (753 F g-1 at 30 A g-1 and 677 F g-1 at 100 A g-1), as well as excellent cycling stability with 95% retention of the initial capacitance even after 20,000 cycles at a current density of 5 A g-1. This work provides a promising alternative strategy to enhance the electrochemical properties of supercapacitors.

  18. The structure and stability of CaFe layered double hydroxides with various Ca:Fe ratios studied by Mössbauer spectroscopy, X-ray diffractometry and microscopic analysis

    NASA Astrophysics Data System (ADS)

    Sipiczki, M.; Kuzmann, E.; Homonnay, Z.; Megyeri, J.; Pálinkó, I.; Sipos, P.

    2013-07-01

    The effects of the Ca(II)/Fe(III) ratios on the structure and Fe microenvironments have been studied in layered double hydroxides comprising of Ca(II) and Fe(III) (CaFe-LDH) prepared by the co-precipitation method. The Ca(II)/Fe(III) ratios were varied systematically from 2 to 6 and for characterisation 57Fe Mössbauer spectroscopy, powder X-ray diffractometry and scanning electron microscopy were applied. XRD patterns of the samples at all Ca(II)/Fe(III) ratios exhibited reflections corresponding to CaFe-LDH and 57Fe Mössbauer measurements revealed that Fe(III) was in a high-spin, somewhat disordered octahedral environment. Above the Ca(II)/Fe(III) ratio of 2 the reflections of Ca(OH)2 also appeared. This phase was found to stabilise the LDH phase, while the phase-pure LDH decomposed on ageing.

  19. Mesoporous layer-by-layer ordered nanohybrids of layered double hydroxide and layered metal oxide: highly active visible light photocatalysts with improved chemical stability.

    PubMed

    Gunjakar, Jayavant L; Kim, Tae Woo; Kim, Hyo Na; Kim, In Young; Hwang, Seong-Ju

    2011-09-28

    Mesoporous layer-by-layer ordered nanohybrids highly active for visible light-induced O(2) generation are synthesized by self-assembly between oppositely charged 2D nanosheets of Zn-Cr-layered double hydroxide (Zn-Cr-LDH) and layered titanium oxide. The layer-by-layer ordering of two kinds of 2D nanosheets is evidenced by powder X-ray diffraction and cross-sectional high resolution-transmission electron microscopy. Upon the interstratification process, the original in-plane atomic arrangements and electronic structures of the component nanosheets remain intact. The obtained heterolayered nanohybrids show a strong absorption of visible light and a remarkably depressed photoluminescence signal, indicating an effective electronic coupling between the two component nanosheets. The self-assembly between 2D inorganic nanosheets leads to the formation of highly porous stacking structure, whose porosity is controllable by changing the ratio of layered titanate/Zn-Cr-LDH. The resultant heterolayered nanohybrids are fairly active for visible light-induced O(2) generation with a rate of ∼1.18 mmol h(-1) g(-1), which is higher than the O(2) production rate (∼0.67 mmol h(-1) g(-1)) by the pristine Zn-Cr-LDH material, that is, one of the most effective visible light photocatalysts for O(2) production, under the same experimental condition. This result highlights an excellent functionality of the Zn-Cr-LDH-layered titanate nanohybrids as efficient visible light active photocatalysts. Of prime interest is that the chemical stability of the Zn-Cr-LDH is significantly improved upon the hybridization, a result of the protection of the LDH lattice by highly stable titanate layer. The present findings clearly demonstrate that the layer-by-layer-ordered assembly between inorganic 2D nanosheets is quite effective not only in improving the photocatalytic activity of the component semiconductors but also in synthesizing novel porous LDH-based hybrid materials with improved chemical

  20. Utilization of Mg2Al-layered double hydroxide as an effective sequestrator to trap Cu(II) ions from aqueous solution impacted by water quality parameters

    NASA Astrophysics Data System (ADS)

    Xu, Meng; Linghu, Wensheng; Hu, Jun; Jiang, Gongyi; Sheng, Jiang

    2016-11-01

    Recently, Mg2Al-layered double hydroxide (Mg2Al-LDH) has been extensively studied as promising candidates to trap metal ions due to their high complexation and adsorption capacity. Herein, Mg2Al-LDH was utilized as an effectiveness sequestrator to trap Cu(II) ions from aqueous solution by an adsorption process using batch technique under ambient conditions. The results showed that Cu(II) adsorption on Mg2Al-LDH increases with pH increasing and maintains a high level at pH>7.0. The adsorption of Cu(II) was obviously affected by ionic strength at low pH, which was not dependent on ionic strength at high pH. The presence of HA or FA promotes the adsorption of Cu(II) on Mg2Al-LDH at low pH values, while reduces the adsorption of Cu(II) at high pH values. The adsorption isotherms of Cu(II) on Mg2Al-LDH at three different temperatures were simulated by the Langmuir, Freundlich, and Dubinin-Radushkevitch (D-R) models very well. The thermodynamic parameters were determined from the temperature-dependent adsorption, and the results showed that Cu(II) adsorption on Mg2Al-LDH was exothermic and the process was favored at high temperature. The results suggest that Mg2Al-LDH is suitable as a sorbent material for the recovery and attenuation of Cu(II)-polluted wastewater.

  1. Synthesis and Characterization of Chitosan-Coated Near-Infrared (NIR) Layered Double Hydroxide-Indocyanine Green Nanocomposites for Potential Applications in Photodynamic Therapy

    PubMed Central

    Wei, Pei-Ru; Kuthati, Yaswanth; Kankala, Ranjith Kumar; Lee, Chia-Hung

    2015-01-01

    We designed a study for photodynamic therapy (PDT) using chitosan coated Mg–Al layered double hydroxide (LDH) nanoparticles as the delivery system. A Food and Drug Administration (FDA) approved near-infrared (NIR) fluorescent dye, indocyanine green (ICG) with photoactive properties was intercalated into amine modified LDH interlayers by ion-exchange. The efficient positively charged polymer (chitosan (CS)) coating was achieved by the cross linkage using surface amine groups modified on the LDH nanoparticle surface with glutaraldehyde as a spacer. The unique hybridization of organic-inorganic nanocomposites rendered more effective and successful photodynamic therapy due to the photosensitizer stabilization in the interlayer of LDH, which prevents the leaching and metabolization of the photosensitizer in the physiological conditions. The results indicated that the polymer coating and the number of polymer coats have a significant impact on the photo-toxicity of the nano-composites. The double layer chitosan coated LDH–NH2–ICG nanoparticles exhibited enhanced photo therapeutic effect compared with uncoated LDH–NH2–ICG and single layer chitosan-coated LDH–NH2–ICG due to the enhanced protection to photosensitizers against photo and thermal degradations. This new class of organic-inorganic hybrid nanocomposites can potentially serve as a platform for future non-invasive cancer diagnosis and therapy. PMID:26340627

  2. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    SciTech Connect

    Chang Zheng; Zhao Na; Liu Junfeng; Li Feng; Evans, David G.; Duan Xue; Forano, Claude; Roy, Marie de

    2011-12-15

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N{sub 2} adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide. - Graphical Abstract: Cu-Ce-O mixed oxides calcined from [Ce(dipic){sub 3}]{sup 3-}- intercalated Cu/Zn/Al layered double hydroxides were synthesized and displayed good catalytic performances in phenol oxidation due to the Cu-Ce interactions. Highlights: Black-Right-Pointing-Pointer [Ce(dipic){sub 3}]{sup 3-}-intercalated Cu/Zn/Al layered double hydroxides were synthesized. Black-Right-Pointing-Pointer Cu-Ce-O mixed oxides derivated from the LDHs were characterized as catalysts. Black-Right-Pointing-Pointer Presence of Ce influenced physicochemical property and catalytic performance. Black-Right-Pointing-Pointer Cu-Ce interaction was largely responsible for enhanced catalytic ability.

  3. Closing the Phosphorus Loop by Recovering Phosphorus From Waste Streams With Layered Double Hydroxide Nanocomposites and Converting the Product into an Efficient Fertilizer

    NASA Astrophysics Data System (ADS)

    Yan, H.; Shih, K.

    2015-12-01

    Phosphorus (P) recovery has been frequently discussed in recent decades due to the uncertain availability and uneven distribution of global phosphate rock reserves. Sorption technology is increasingly considered as a reliable, efficient and environmentally friendly P removal method from aqueous solution. In this study, a series of Mg-Al-based layered double hydroxide nanocomposites and their corresponding calcined products were fabricated and applied as phosphate adsorbents. The prepared samples were with average size at ~50 nm and self-assembled into larger particles in irregular shapes. The results of batch adsorption experiments demonstrated that calcination significantly enhanced the adsorption ability of LDHs for phosphorus, and the maximum adsorption capacity of calcined Mg-Al-LDH was as high as 100.7 mg-P/g. Furthermore, incorporation of Zr4+ and La3+ into LDH materials increases the sorption selectivity as well as sorption amount of phosphorus in LDHs, which was confirmed by experiments operated in synthetic human urine. For the first time ammonia (NH4OH) and potassium hydroxide (KOH) solutions were employed to desorb the P-loaded LDH. Identification of solids derived from two eluting solutions showed that struvite (MgNH4PO4•6H2O, MAP) was precipitated in ammonia solution while most phosphate was desorbed into liquid phase in KOH system without crystallization of potassium struvite (MgKPO4•6H2O) due to its higher solubility. Quantitative X-ray diffraction technique was used to determine struvite contents in obtained solids and the results revealed that ~ 30% of adsorbed P was transferred into struvite form in the sample extracted by 0.5M NH4OH. Leaching tests suggested that the phosphorus releasing kinetics of ammonia treated LDH was comparable to that of pure struvite product, indicating that postsorption Mg-Al-LDH desorbed with ammonia could serve as a slow-releasing fertilizer in agriculture (see Figure 1).

  4. Synthesis of 4-chlorophenoxyacetate-zinc-aluminium-layered double hydroxide nanocomposite: physico-chemical and controlled release properties.

    PubMed

    Hussein, Mohd Zobir Bin; Sarijo, Siti Halimah; Yahaya, Asmah Hj; Zainal, Zulkarnain

    2007-08-01

    Layered organic-inorganic hybrid nanocomposite material was synthesised using 4-chlorophenoxyacetate (4CPA) as guest anion intercalated into the Zn-Al layered double hydroxide inorganic host by direct co-precipitation method at pH = 7.5 and Zn to Al molar ratio of 4. Both PXRD and FTIR results confirmed that the 4CPA was successfully intercalated into the Zn-AI-LDH interlayer. As a result, a well-ordered nanolayered organic-inorganic hybrid nanocomposite, with the expansion of the basal spacing from 8.9 angstroms in the layered double hydroxide to 20.1 angstroms in the resulting nanocomposite was observed. The FTIR spectrum of the nanocomposite (ZAC) showed that it composed spectral features of Zn-AI-LDH (ZAL) and 4CPA. The nanocomposites synthesized in this work are of mesoporous-type containing 39.8% (w/w) of 4CPA with mole fraction of Al3+ in the inorganic brucite-like layers (xAI) of 0.224. The release studies showed a rapid release of the 4CPA for the first 600 min, and more sustained thereafter. The total amount of 4CPA released from the nanocomposite interlayer into the aqueous solution were 21%, 66%, and 72% in 0.0001, 0.00025, and 0.0005 M sodium carbonate, respectively. In distilled water, about 75, 35, and 57% of 4CPA could be released in 1000 min, when the pH of the release media was set at 3, 6.25, and 12, respectively. In comparison with a structurally similar organic moiety with one more chlorine atom at the 2-position of the aromatic ring, namely 2,4-dichlorophenoxyacetate (24D), the 4CPA showed a slower release rate. The slightly bulkier organic moiety of 24D together with the presence of chlorine atom at the 2-position presumably had contributed to its higher release rate, and it seems that these factors may be exploited for tuning the release rate of intercalated guest anions with similar properties. This study suggests that layered double hydroxide can be used as a carrier for an active agent and the chemical structure of the intercalated moiety

  5. Luminescent ultrathin film of anionic styrylbiphenyl derivative-layered double hydroxide and its reversible sensing for heavy metal ions.

    PubMed

    Yan, Dongpeng; Lu, Jun; Wei, Min; Li, Shuangde; Evans, David G; Duan, Xue

    2012-06-28

    Ordered ultrathin films (UTFs) with blue luminescence based on a styrylbiphenyl derivative (BTBS) and Mg-Al-layered double hydroxide (LDH) nanosheets have been constructed employing the layer-by-layer assembly technique. UV-visible absorption and fluorescence spectroscopy showed a stepwise and regular growth of the films upon increasing the number of deposition cycles. XRD, AFM and SEM indicated that the films possess a periodic layered structure with a period of ca. 1.5 nm, and uniform surface morphology. The film thickness can be precisely controlled in the range ca. 15-53 nm. The BTBS-LDH UTFs exhibit improved UV-light resistance capability compared with the pristine BTBS and show well-defined polarized photoemission, with anisotropy of ca. 0.24. The UTFs show a fast, selective and reversible luminescent response to aqueous solutions containing different heavy metal ions, with the most significant luminescent quenching occurring for the Hg(2+) solution, shedding light on the fact that these films can serve as a new type of selective solid luminescent metal-ion sensor.

  6. A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides.

    PubMed

    Theiss, Frederick L; Couperthwaite, Sara J; Ayoko, Godwin A; Frost, Ray L

    2014-03-01

    The application of layered double hydroxides (LDHs) and thermally activated LDHs for the removal of various fluorine (F(-),BF4(-)), chlorine (Cl(-),ClO4(-)), bromine (Br(-),BrO3(-)) and iodine (I(-),IO3(-)) species from aqueous solutions has been reviewed in this article. LDHs and thermally activated LDHs were able to significantly reduce the concentration of selected anions in laboratory scale experiments. The M(2+):M(3+) cation ratio of the LDH adsorbent was an important factor which influenced anion uptake. Though LDHs were able to remove some target anion species through anion exchange and surface adsorption thermal activation and reformation generally produced better results. The presence of competing anions including carbonate, phosphate and sulphate had a significant impact on uptake of the target anion as LDHs typically exhibit lower affinity towards monovalent anions compared to anions with multiple charges. The removal of fluoride and perchlorate from aqueous solution by a continuous flow system utilising fixed bed columns packed with LDH adsorbents has also been investigated. The adsorption capacity of the columns at breakpoint was heavily dependent on the flow rate and lower than result reported for the corresponding batch methods. There is still considerable scope for future research on numerous topics summarised in this article.

  7. Layered double hydroxides as efficient drug delivery system of ciprofloxacin in the middle ear: an animal study in rabbits.

    PubMed

    Hesse, Daniela; Badar, Muhammad; Bleich, André; Smoczek, Anna; Glage, Silke; Kieke, Marc; Behrens, Peter; Müller, Peter Paul; Esser, Karl-Heinz; Stieve, Martin; Prenzler, Nils Kristian

    2013-01-01

    Chronic otitis media is a common disease often accompanied by recurrent bacterial infections. These may lead to the destruction of the middle ear bones such that prostheses have to be implanted to restore sound transmission. Surface coatings with layered double hydroxides (LDHs) are evaluated here as a possibility for drug delivery systems with convenient advantages such as low cytotoxicity and easy synthesis. Male New Zealand White rabbits were implanted with Bioverit(®) II middle ear prostheses coated with the LDH Mg(4)Al(2)(OH)(12)(SO(4))(2)·6H(2)O impregnated with ciprofloxacin. 12 (group 1) were directly infected with Pseudomonas aeruginosa and another 12 (group 2) 1 week after the implantation. Clinical outcome, blood counts, histological analyses and microbiological examination showed an excellent antimicrobial activity for group 1, whereas this effect was attenuated in animals where infection was performed 1 week after implantation. This is the first study to demonstrate an efficient drug delivery system with an LDH coating on prostheses in the middle ear.

  8. Thermodynamical and structural insights of orange II adsorption by Mg RAlNO 3 layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Mustapha Bouhent, Mohamed; Derriche, Zoubir; Denoyel, Renaud; Prevot, Vanessa; Forano, Claude

    2011-05-01

    [Mg 1- x Al x(OH) 2][(NO 3) x, nH 2O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar ( R=(1- x)/ x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg 2AlNO 3 displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg 2AlNO 3 at 40 °C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption (Δ G°), enthalpy (Δ H°) and entropy (Δ S°) were calculated. The experimental values for Δ G° in temperature range between 10 and 40 °C were found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange.

  9. A comparative study of supercapacitive performances of nickel cobalt layered double hydroxides coated on ZnO nanostructured arrays on textile fibre as electrodes for wearable energy storage devices.

    PubMed

    Trang, Nguyen Thi Hong; Ngoc, Huynh Van; Lingappan, Niranjanmurthi; Kang, Dae Joon

    2014-02-21

    We demonstrated an efficient method for the fabrication of novel, flexible electrodes based on ZnO nanoflakes and nickel-cobalt layered double hydroxides (denoted as ZnONF/NiCoLDH) as a core-shell nanostructure on textile substrates for wearable energy storage devices. NiCoLDH coated ZnO nanowire (denoted as ZnONW/NiCoLDH) flexible electrodes are also prepared for comparison. As an electrode for supercapacitors, ZnONF/NiCoLDH exhibits a high specific capacitance of 1624 F g(-1), which is nearly 1.6 times greater than ZnONW/NiCoLDH counterparts. It also shows a maximum energy density of 48.32 W h kg(-1) at a power density of 27.53 kW kg(-1), and an excellent cycling stability with capacitance retention of 94% and a Coulombic efficiency of 93% over 2000 cycles. We believe that the superior performance of the ZnONF/NiCoLDH hybrids is due primarily to the large surface area of the nanoflake structure and the open spaces between nanoflakes, both of which provide a large space for the deposition of NiCoLDH, resulting in reduced internal resistance and improved capacitance performance. Our results are significant for the development of electrode materials for high-performance wearable energy storage devices.

  10. Formation of Zn-rich phyllosilicate, Zn-layered double hydroxide and hydrozincite in contaminated calcareous soils

    SciTech Connect

    Jacquat, Olivier; Voegelin, Andreas; Villard, Andre; Marcus, Matthew A.; Kretzschmar, Ruben

    2007-10-15

    Recent studies demonstrated that Zn-phyllosilicate- and Zn-layered double hydroxide-type (Zn-LDH) precipitates may form in contaminated soils. However, the influence of soil properties and Zn content on the quantity and type of precipitate forming has not been studied in detail so far. In this work, we determined the speciation of Zn in six carbonate-rich surface soils (pH 6.2 to 7.5) contaminated by aqueous Zn in the runoff from galvanized power line towers (1322 to 30090 mg/kg Zn). Based on 12 bulk and 23 microfocused extended X-ray absorption fine structure (EXAFS) spectra, the number, type and proportion of Zn species were derived using principal component analysis, target testing, and linear combination fitting. Nearly pure Zn-rich phyllosilicate and Zn-LDH were identified at different locations within a single soil horizon, suggesting that the local availabilities of Al and Si controlled the type of precipitate forming. Hydrozincite was identified on the surfaces of limestone particles that were not in direct contact with the soil clay matrix. With increasing Zn loading of the soils, the percentage of precipitated Zn increased from {approx}20% to {approx}80%, while the precipitate type shifted from Zn-phyllosilicate and/or Zn-LDH at the lowest studied soil Zn contents over predominantly Zn-LDH at intermediate loadings to hydrozincite in extremely contaminated soils. These trends were in agreement with the solubility of Zn in equilibrium with these phases. Sequential extractions showed that large fractions of soil Zn ({approx}30% to {approx}80%) as well as of synthetic Zn-kerolite, Zn-LDH, and hydrozincite spiked into uncontaminated soil were readily extracted by 1 M NH{sub 4}NO{sub 3} followed by 1 M NH{sub 4}-acetate at pH 6.0. Even though the formation of Zn precipitates allows for the retention of Zn in excess to the adsorption capacity of calcareous soils, the long-term immobilization potential of these precipitates is limited.

  11. Preparation of an anionic azo pigment-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

    NASA Astrophysics Data System (ADS)

    Guo, Shengchang; Li, Dianqing; Zhang, Weifeng; Pu, Min; Evans, David G.; Duan, Xue

    2004-12-01

    A large anionic pigment has been intercalated into a layered double hydroxide (LDH) host by ion-exchange of an Mg/Al LDH-nitrate precursor with a solution of C.I. Pigment Red 48:2 (the calcium salt of 4-((5-chloro-4-methyl-2-sulfophenyl)azo)-3-hydroxy-2-naphthalene-carboxylic acid), in ethane-1,2-diol. After intercalation of the pigment, the interlayer distance in the LDH increases from 0.86 to 1.72 nm. Infrared spectra and TG-DTA curves reveal the presence of a complex system of supramolecular host-guest interactions. The UV-visible diffuse reflectance spectra of C.I. Pigment Red 48:2 show marked changes after heating at 200 °C and above, whereas there are no significant changes in the spectra of the intercalated pigment after heating at temperatures up to 300 °C, showing that the thermostability is markedly enhanced by intercalation in the LDH host. The pigment-intercalated LDHs exhibits much higher photostability to UV light than the pristine pigment, in the case of both the pure solids and their composites with polypropylene, as shown by measurement of CIE 1976 L*a*b* color difference ( ΔE) values.

  12. Synthesis of highly efficient flame retardant high-density polyethylene nanocomposites with inorgano-layered double hydroxides as nanofiller using solvent mixing method.

    PubMed

    Gao, Yanshan; Wang, Qiang; Wang, Junya; Huang, Liang; Yan, Xingru; Zhang, Xi; He, Qingliang; Xing, Zipeng; Guo, Zhanhu

    2014-04-09

    High-density polyethylene (HDPE) polymer nanocomposites containing Zn2Al-X (X= CO3(2-), NO3(-), Cl(-), SO4(2-)) layered double hydroxide (LDH) nanoparticles with different loadings from 10 to 40 wt % were synthesized using a modified solvent mixing method. Synthesized LDH nanofillers and the corresponding nanocomposites were carefully characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, etc. The thermal stability and flame retardancy behavior were investigated using a thermo gravimetric analyzer and microscale combustion calorimeter. Comparing to neat HDPE, the thermal stability of nanocomposites was significantly enhanced. With the addition of 15 wt % Zn2Al-Cl LDH, the 50% weight loss temperature was increased by 67 °C. After adding LDHs, the flame retardant performance was significantly improved as well. With 40 wt % of LDH loading, the peak heat release rate was reduced by 24%, 41%, 48%, and 54% for HDPE/Zn2Al-Cl, HDPE/Zn2Al-CO3, HDPE/Zn2Al-NO3, and HDPE/Zn2Al-SO4, respectively. We also noticed that different interlayer anions could result in different rheological properties and the influence on storage and loss moduli follows the order of SO4(2-) > NO3(-) > CO3(2-) > Cl(-). Another important finding of this work is that the influence of anions on flame retardancy follows the exact same order on rheological properties.

  13. Structure of oxides prepared by decomposition of layered double Mg–Al and Ni–Al hydroxides

    SciTech Connect

    Cherepanova, Svetlana V.; Leont’eva, Natalya N.; Arbuzov, Aleksey B.; Drozdov, Vladimir A.; Belskaya, Olga B.; Antonicheva, Nina V.

    2015-05-15

    Abstracts: Thermal decomposition of Mg–Al and Ni–Al layered double hydroxides LDH at temperatures lower than 800 °C leads to the formation of oxides with different structures. Mg–Al oxide has a very defective structure and consists of octahedral layers as in periclase MgO and mixed octahedral–tetrahedral layers as in spinel MgAl{sub 2}O{sub 4}. Mixed Ni–Al oxide has a sandwich-like structure, consisting of a core with Al-doped NiO-like structure and some surface layers with spinel NiAl{sub 2}O{sub 4} structure epitaxial connected with the core. Suggested models were verified by simulation of X-ray diffraction patterns using DIFFaX code, as well as HRTEM, IR-, UV-spectroscopies, and XPS. - Graphical abstract: In the Mg–Al layered double hydroxide Al{sup 3+} ions migrate into interlayers during decomposition. The Mg–Al oxide represents sequence of octahedral and octahedral–tetrahedral spinel layers with vacancies. The Ni–Al oxide has a sandwich-like structure with NiO-like core and surface spinel layers as a result of migration of Al{sup 3+} ions on the surface. The models explain the presence and absence of “memory effect” for the Mg–Al and Ni–Al oxides, respectively. - Highlights: • We study products of Mg(Ni)–Al LDH decomposition by calcination at 500(400)–800 °C. • In Mg–Al/Ni–Al LDH Al ions migrate into interlayers/on the surface during decomposition. • Mg–Al oxide represents sequence of periclase- and spinel-like layers with vacancies. • Ni–Al oxide has a sandwich-like structure with NiO-like core and surface spinel layers. • The models explain the presence/absence of “memory effect” for Mg–Al/Ni–Al oxides.

  14. Synthesis, characterization, and immune efficacy of layered double hydroxide@SiO2 nanoparticles with shell-core structure as a delivery carrier for Newcastle disease virus DNA vaccine.

    PubMed

    Zhao, Kai; Rong, Guangyu; Guo, Chen; Luo, Xiaomei; Kang, Hong; Sun, Yanwei; Dai, Chunxiao; Wang, Xiaohua; Wang, Xin; Jin, Zheng; Cui, Shangjin; Sun, Qingshen

    2015-01-01

    Layered double hydroxide (LDH)@SiO2 nanoparticles were developed as a delivery carrier for the plasmid DNA expressing the Newcastle disease virus F gene. The LDH was hydrotalcite-like materials. The plasmid DNA encapsulated in the LDH@SiO2 nanoparticles (pFDNA-LDH@SiO2-NPs) was prepared by the coprecipitation method, and the properties of pFDNA-LDH@SiO2-NPs were characterized by transmission electron microscopy, zeta potential analyzer, Fourier transform infrared spectroscopy, and X-ray diffraction analysis. The results demonstrated that the pFDNA-LDH@SiO2-NPs had a regular morphology and high stability with a mean diameter of 371.93 nm, loading capacity of 39.66%±0.45%, and a zeta potential of +31.63 mV. A release assay in vitro showed that up to 91.36% of the total plasmid DNA could be sustainably released from the pFDNA-LDH@SiO2-NPs within 288 hours. The LDH@SiO2 nanoparticles had very low toxicity. Additionally, their high transfection efficiency in vitro was detected by fluorescent microscopy. Intranasal immunization of specific pathogen-free chickens with pFDNA-LDH@SiO2-NPs induced stronger cellular, humoral, and mucosal immune responses and achieved a greater sustained release effect than intramuscular naked plasmid DNA, and the protective efficacy after challenge with the strain F48E9 with highly virulent (mean death time of chicken embryos ≤60 hours, intracerebral pathogenicity index in 1 -day-old chickens >1.6) was 100%. Based on the results, LDH@SiO2 nanoparticles can be used as a delivery carrier for mucosal immunity of Newcastle disease DNA vaccine, and have great application potential in the future.

  15. Synthesis of protocatechuic acid–zinc/aluminium–layered double hydroxide nanocomposite as an anticancer nanodelivery system

    SciTech Connect

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Gani, Shafinaz Abd; Fakurazi, Sharida; Zainal, Zulkarnain

    2015-01-15

    Protocatechuic acid, an active anticancer agent, has been intercalated into Zn/Al–layered double hydroxide at Zn/Al=2) using two different preparation methods, co-precipitation and ion-exchange, which are labelled as PZAE and PZAC, respectively. The release of protocatechuate from the nanocomposites occurred in a controlled manner and was fitted satisfactorily to pseudo-second order kinetics. The basal spacing of the resulting nanocomposites PZAE and PZAC was 10.2 and 11.0 Å, respectively, indicating successful intercalation of protocatechuate anions into the interlayer galleries of Zn/Al–NO{sub 3}–LDH in a monolayer arrangement with angles of 24 and 33° from the z-axis in PZAE and PZAC, respectively. The formation of nanocomposites was further confirmed by a Fourier transform infrared study. Thermogravimetric and differential thermogravimetric analyses indicated that the thermal stability of the intercalated protocatechuic acid was significantly enhanced compared to its free protocatechuic acid, and the drug content in the nanocomposites was estimated to be approximately 32.6% in PZAE and 29.2% in PZAC. Both PZAE and PZAC nanocomposites inhibit the growth of human cervical, liver and colorectal cancer cell lines and exhibit no toxic effects towards normal fibroblast 3T3 cell after 72 h of treatment. - Graphical abstract: Protocatechuate anions were arranged in monolayer mode with the angle of 24° for PZAE and 33° for PZAC from Z axis to maximize interaction between carboxylate groups and brucite-like layers. - Highlights: • Two methods gave nanocomposites with slightly different physico-chemical properties. • PZAE and PZAC have the potential to be used as a controlled release formulation. • The thermal stability of PA is markedly enhanced upon the intercalation process. • Higher cancer cell growth inhibition for PZAE and PZAC nanocomposites than for PA.

  16. Layered double hydroxide catalyst for the conversion of crude vegetable oils to a sustainable biofuel

    NASA Astrophysics Data System (ADS)

    Mollaeian, Keyvan

    Over the last two decades, the U.S. has developed the production of biodiesel, a mixture of fatty acid methyl esters, using chiefly vegetable oils as feedstocks. However, there is much concern about the availability of high-quality vegetable oils for longterm biodiesel production. Problems have also risen due to the production of glycerol, an unwanted byproduct, as well as the need for process wash water. Therefore, this study was initiated to produce not only fatty acid methyl esters (FAMEs) but also fatty acid glycerol carbonates (FAGCs) by replacing methanol with dimethyl carbonate (DMC). The process would have no unnecessary byproducts and would be a simplified process compared to traditional biodiesel. In addition, this altering of the methylating agent could convert triglycerides, free fatty acids, and phospholipids to a sustainable biofuel. In this project, Mg-Al Layered Double Hydroxide (LDH) was optimized by calcination in different temperature varied from 250°C to 450°C. The gallery between layers was increased by intercalating sodium dodecylsulfate (SDS). During catalyst preparation, the pH was controlled ~10. In our experiment, triazabicyclodecene (TBD) was attached with trimethoxysilane (3GPS) as a coupling agent, and N-cetyl-N,N,N-trimethylammonium bromide (CTAB) was added to remove SDS from the catalyst. The catalyst was characterized by XRD, FTIR, and Raman spectroscopy. The effect of the heterogeneous catalyst on the conversion of canola oil, corn oil, and free fatty acids was investigated. To analyze the conversion of lipid oils to biofuel an in situ Raman spectroscopic method was developed. Catalyst synthesis methods and a proposed mechanism for converting triglycerides and free fatty acids to biofuel will be presented.

  17. Coexistence of adsorption and coagulation processes of both arsenate and NOM from contaminated groundwater by nanocrystallined Mg/Al layered double hydroxides.

    PubMed

    Wu, Xilin; Tan, Xiaoli; Yang, Shitong; Wen, Tao; Guo, Hongli; Wang, Xiangke; Xu, Anwu

    2013-08-01

    In this study, nanocrystallined Mg/Al layered double hydroxides (LDH-CO3) and chloridion intercalated nanocrystallined Mg/Al LDHs (LDH-Cl) were synthesized and used for simultaneous removal of arsenic and natural organic matter (NOM) from contaminated groundwater. Humic acid (HA) was selected as a model compound of NOM. The maximum adsorption capacities of arsenate (As(V)) on LDH-CO3 and LDH-Cl are 44.66 and 88.30 mg/g, respectively, and those of HA on LDH-CO3 and LDH-Cl are 53.16 and 269.24 mg/g, respectively. It was found that more than 98% of arsenic and 94% of NOM were eliminated by LDH-Cl from both arsenic and NOM-rich groundwater, which is used as drinking water in Togtoh County, Inner Mongolia, China. The arsenic concentration declined from 231 to 4 μg/L, which meets the drinking water standard. The adsorption mechanisms were determined by using X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and extended X-ray absorption fine structure spectroscopy techniques (EXAFS). The results showed that the removal of HA was mainly via surface complexation as well as coagulation at the surface of LDHs, while the adsorption of As(V) was mainly via ion-exchange process. The presence of HA exhibited little inhibiting effect on As(V) adsorption by occupying partial binding sites on LDH surfaces. Nevertheless, it could not affect the ion-exchange process of As(V) with the interlayer anions of LDHs. The removal of As(V) and HA can be carried out independently due to the different adsorption mechanisms. By integrating the experimental results, it is clear that LDH-Cl can be potentially used as a cost-effective material for the purification of both arsenic and NOM contaminated groundwater.

  18. Anion exchange reaction potentials as approximate estimates of the relative thermodynamic stabilities of Mg/Al layered double hydroxides containing different anions.

    PubMed

    Prasad, Belavalli E; Kamath, P Vishnu; Vijayamohanan, K

    2011-11-15

    Coatings of hydrotalcite-like nitrate-intercalated Mg/Al layered double hydroxides are electrochemically deposited on a Pt electrode by electrogeneration of base by reduction of a mixed metal nitrate aqueous solution. As-prepared coatings are stable to workup and function as rugged electrodes. The voltammetric response generated by anion exchange of intercalated nitrate for dissolved anions from solution under equilibrium conditions is employed to estimate the thermodynamic stabilities of the Mg/Al layered double hydroxides comprising different anions relative to the nitrate-containing phase. Among monovalent anions, the most stable is the fluoride-containing LDH (ΔG° = -48.7 kJ mol(-1)) relative to the nitrate-containing LDH. The stability in aqueous phase decreases as F(-) > Cl(-) > Br(-) > NO(2)(-) > NO(3)(-), whereas, among divalent anions, SO(4)(2-) (ΔG° = -8.7 kJ mol(-1)) > CO(3)(2-) (ΔG° = 14.3 kJ mol(-1)). The results of monovalent ions match well with the Miyata series, whereas the divalent anion series is at variance with the commonly held belief that carbonate-LDHs are more stable than sulfate-LDHs.

  19. Study of 2,4-dichlorophenoxyacetic acid (2,4-D) removal by Cu-Fe-layered double hydroxide from aqueous solution

    NASA Astrophysics Data System (ADS)

    Nejati, Kamellia; Davary, Soheila; Saati, Marziye

    2013-09-01

    The hydrotalcite-like compound of Cu-Fe-layered double hydroxide was studied as a potential adsorbent of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The nanoparticles of Cu-Fe layered double hydroxide were prepared by Cu/Fe molar ratio of 2:1 using a coprecipitation method at pH 8.5 and characterized by the X-ray powder diffraction (XRD), the Fourier transform infrared spectroscopy (FT-IR), the thermal gravimetric analysis (TGA) and the elemental analysis. The size and morphology of nanoparticles were examined by the transmission electron microscopy (TEM). The adsorption experiments on LDH, on the other hand, were conducted in three different procedures, namely, time-dependent, pH-dependent and temperature-dependent. Characterization of the adsorption products by the XRD method indicates that the intercalation of 2,4-D between the LDH layers has not occurred and the surface adsorption had taken place. The adsorption kinetic was tested for pseudo-first-order, pseudo-second-order, Elovich and Intra-particle diffusion kinetic models and the rate constants were calculated. The equilibrium adsorption data were described by Langmuir and Freundlich equations. It was observed that, the Langmuir isotherm slightly better fitted to the experimental data rather than that of Freundlich. In the adsorption experiments, the Gibbs free energy values, ΔG°, the enthalpy, ΔH°, and the entropy, ΔS° were also determined.

  20. Nickel–cobalt layered double hydroxide ultrathin nanoflakes decorated on graphene sheets with a 3D nanonetwork structure as supercapacitive materials

    SciTech Connect

    Yan, Tao; Li, Ruiyi; Li, Zaijun

    2014-03-01

    Graphical abstract: The microwave heating reflux approach was developed for the fabrication of nickel–cobalt layered double hydroxide ultrathin nanoflakes decorated on graphene sheets, in which ammonia and ethanol were used as the precipitator and medium for the synthesis. The obtained composite shows a 3D flowerclusters morphology with nanonetwork structure and largely enhanced supercapacitive performance. - Highlights: • The paper reported the microwave synthesis of nickel–cobalt layered double hydroxide/graphene composite. • The novel synthesis method is rapid, green, efficient and can be well used to the mass production. • The as-synthesized composite offers a 3D flowerclusters morphology with nanonetwork structure. • The composite offers excellent supercapacitive performance. • This study provides a promising route to design and synthesis of advanced graphene-based materials with the superiorities of time-saving and cost-effective characteristics. - Abstract: The study reported a novel microwave heating reflux method for the fabrication of nickel–cobalt layered double hydroxide ultrathin nanoflakes decorated on graphene sheets (GS/NiCo-LDH). Ammonia and ethanol were employed as precipitant and reaction medium for the synthesis, respectively. The resulting GS/NiCo-LDH offers a 3D flowerclusters morphology with nanonetwork structure. Due to the greatly enhanced rate of electron transfer and mass transport, the GS/NiCo-LDH electrode exhibits excellent supercapacitive performances. The maximum specific capacitance was found to be 1980.7 F g{sup −1} at the current density of 1 A g{sup −1}. The specific capacitance can remain 1274.7 F g{sup −1} at the current density of 15 A g{sup −1} and it has an increase of about 2.9% after 1500 cycles. Moreover, the study also provides a promising approach for the design and synthesis of metallic double hydroxides/graphene hybrid materials with time-saving and cost-effective characteristics, which can be

  1. Mg/Al double-metal hydroxide regeneration of anion exchange resin by electric field intensification.

    PubMed

    Wang, Ying; Li, Zhun; Li, Yansheng; Liu, Zhigang

    2017-03-01

    Fouled anion exchange resins were regenerated by electric field intensification of Mg/Al double-metal hydroxides. Regenerative experiments were performed with varying voltages (10-30 V) and dosages of Mg/Al hydroxides (0.045-0.135 mol and 0.015-0.045 mol, respectively) for 1-5 h. Optimal results were obtained under the following regenerative conditions: 20 V, 4 h, and 0.09/0.03 mol of Mg/Al hydroxides. The maximum regenerative capacity of resins was increased to 41.07%. The regenerative mechanism was presented by Fourier-transform infrared spectrum of resins and Mg/Al hydroxides, and the regenerative degree was analyzed with respect to conductivity, pH value, and electric current. Mg/Al hydroxides were also recycled after the regeneration. This method was proven to be cost-effective and environmentally friendly.

  2. Preparation and enhanced properties of polyaniline/grafted intercalated ZnAl-LDH nanocomposites

    NASA Astrophysics Data System (ADS)

    Hu, Jinlong; Gan, Mengyu; Ma, Li; Zhang, Jun; Xie, Shuang; Xu, Fenfang; Shen, JiYue Zheng Xiaoyu; Yin, Hui

    2015-02-01

    The polymeric nanocomposites (PANI/AD-LDH) were prepared by in situ polymerization based on polyaniline (PANI) and decavanadate-intercalated and γ-aminopropyltriethoxysilane (APTS)-grafted ZnAl-layered double hydroxide (AD-LDH). FTIR and XRD studies confirm the grafting of APTS with decavanadate-intercalated LDH (D-LDH). The extent of grafting (wt%) has also been estimated on the basis of the residue left in nitrogen atmosphere at 800 °C in TGA. SEM and XPS studies show the partial exfoliation of grafted LDH in the PANI matrix and the interfacial interaction between PANI and grafted LDH, respectively. The grafted intercalated layered double hydroxide in reinforcing the properties of the PANI nanocomposites has also been investigated by open circuit potential (OCP), tafel polarization curves (TAF), electrochemical impendence spectroscopy (EIS), salt spray test and TGA-DTA. The experimental results indicate that the PANI/AD-LDH has a higher thermal stability and anticorrosion properties relative to the PANI.

  3. Synthesis of Li-Al layered double hydroxide intercalated with amino tris(methylene phosphonic acid) and kinetic and equilibrium studies of the uptake of Nd3+ and Sr2+ ions

    NASA Astrophysics Data System (ADS)

    Kameda, Tomohito; Shinmyou, Tetsu; Yoshioka, Toshiaki

    2016-03-01

    A Li-Al layered double hydroxide intercalated with amino tris(methylene phosphonic acid) (AMP·Li-Al LDH) was synthesized by the drop-wise addition of an Al-containing solution to a Li-AMP solution at a constant pH of 8.0. The AMP·Li-Al LDH was found to take up Nd3+ and Sr2+ ions from aqueous solutions; this phenomenon was attributable to the metal-chelating functionality of the AMP ions in the interlayers of the AMP·Li-Al LDH. Further, the AMP·Li-Al LDH was found to take up Nd3+ ions preferentially than Sr2+ ions. This was attributable to the stability of the Nd-AMP complex being higher than that of the Sr-AMP complex. The mass-transfer-controlled shrinking-core model could describe the uptake behavior better than the surface-reaction-control model. The AMP ions in the AMP·Li-Al LDH interlayers rapidly formed chelate complexes with the Nd3+ or Sr2+ ions. As a result, the transfer of Nd3+ and Sr2+ ions through the product layer was the rate-limiting step. Furthermore, this reaction could be explained by a Langmuir-type adsorption mechanism, indicating that it involved chemical adsorption; this was consistent with the formation of chelate complexes between Nd3+ and Sr2+ ions and the AMP ions in the interlayers of the AMP·Li-Al LDH.

  4. Enhanced Removal of Arsenic and Antimony in the Mining Site by Calcined γ-Fe2O3/Layered Double Hydroxide Nanocomposite

    NASA Astrophysics Data System (ADS)

    Lee, Sang-Ho; Choi, Heechul; Kim, Kyoung-Woong

    2016-04-01

    Arsenic (As) and Antimony (Sb) have been recognized as harmful contaminants in aquatic environment due to its high toxicity and carcinogenicity. Especially, the contamination of arsenic in the mining areas is considered as a serious emerging environmental issue in Korea. Due to the hazardous effect of arsenic, the United States Environmental Protection Agency (US EPA) regulated maximum contamination level of arsenic to 10 μg/L in drinking water. The harmful effect on human health by excessive intake of antimony was also reported by previous studies, and severe contamination level (100 - 7,000 μg/L) of antimony reported in surface and groundwater of abandoned mining area in China and Slovakia. Therefore, US EPA regulated maximum contaminants level of antimony in drinking water to 6 μg/L. In order to remove anionic contaminants in drinking water, various type of nanomaterials have been developed. Layered double hydroxide (LDH) is the artificial anionic clay that is based on the layered structure of positively charged brucite-like layers with interlayers of anions. The LDH is one of the promising nanomaterials for the removal of anionic contaminants because it has high selectivity for arsenic, phosphate, chromium and antimony. However, the biggest problem of LDH for wastewater treatment is that the particles cannot be easily separated after the removal of contaminants. In this study, magnetic nanoparticles (γ-Fe2O3) supported LDH nanocomposite (γ-Fe2O3/LDH) was investigated to enhance magnetic particle recovery and removal efficiency for arsenic and antimony. The calcined γ-Fe2O3/LDH nanocomposites synthesized by co-precipitation method, and the crystallographic properties of maghemite (γ-Fe2O3) and layered structure of LDH were confirmed by X-ray diffraction. The nano-sized γ-Fe2O3 (30 to 50 nm) was stably attached on the surface of LDH (100 to 150 nm) and O1s spectrum by X-ray photoelectron spectroscopy (XPS) explained that there are both physical and

  5. Nickel–vanadium monolayer double hydroxide for efficient electrochemical water oxidation

    PubMed Central

    Fan, Ke; Chen, Hong; Ji, Yongfei; Huang, Hui; Claesson, Per Martin; Daniel, Quentin; Philippe, Bertrand; Rensmo, Håkan; Li, Fusheng; Luo, Yi; Sun, Licheng

    2016-01-01

    Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel–vanadium-layered double hydroxide that shows a current density of 27 mA cm−2 (57 mA cm−2 after ohmic-drop correction) at an overpotential of 350 mV for water oxidation. Such performance is comparable to those of the best-performing nickel–iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel–vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting. PMID:27306541

  6. Nickel-vanadium monolayer double hydroxide for efficient electrochemical water oxidation

    NASA Astrophysics Data System (ADS)

    Fan, Ke; Chen, Hong; Ji, Yongfei; Huang, Hui; Claesson, Per Martin; Daniel, Quentin; Philippe, Bertrand; Rensmo, Håkan; Li, Fusheng; Luo, Yi; Sun, Licheng

    2016-06-01

    Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel-vanadium-layered double hydroxide that shows a current density of 27 mA cm-2 (57 mA cm-2 after ohmic-drop correction) at an overpotential of 350 mV for water oxidation. Such performance is comparable to those of the best-performing nickel-iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel-vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting.

  7. Swelling and gel/sol formation of perchlorate-type layered double hydroxides in concentrated aqueous solutions of amino acid-related zwitterionic compounds.

    PubMed

    Iyi, Nobuo; Ishihara, Shinsuke; Kaneko, Yoshiro; Yamada, Hirohisa

    2013-02-26

    ClO(4)(-)MgAl-LDH3, a MgAl (Mg/Al = 3) layered double hydroxide (LDH) containing perchlorate, swells and forms colloidal suspensions (sols) via the gel state in concentrated aqueous solutions of zwitterionic compounds related to amino acids. In total, 36 zwitterionic compounds with different molecular structures and additional functional groups were examined at various concentrations, and the sol-formation ability was judged by the transmittance (at λ = 589 nm) of the resulting suspensions. At low concentration, the obtained suspensions were turbid, with transmittances of ~0%. However, above the threshold concentration (0.3-1.0 M), osmotic swelling occurred and the transmittances of the suspensions increased sharply with increases in concentration to reach maximum values of 70-95%. The threshold concentration and maximum transmittance value depended on the structure and the location of the functional groups. The enhancement of the permittivity of water by the zwitterions and the formation of H-bond networks were assumed to be the reasons for the swelling phenomenon. Similar gel/sol formation was observed for ClO(4)(-)LDHs with Mg/Al = 2, Ni/Al = 2, 3, and Co/Al = 2 and some NO(3)(-)LDHs. Large ClO(4)(-)LDH films could be prepared by filtration of the colloidal suspensions followed by washing and drying processes.

  8. Gold Nanoclusters@Ru(bpy)₃²⁺-Layered Double Hydroxide Ultrathin Film as a Cathodic Electrochemiluminescence Resonance Energy Transfer Probe.

    PubMed

    Yu, Yingchang; Lu, Chao; Zhang, Meining

    2015-08-04

    Herein, it is the first report that a cathodic electrochemiluminescence (ECL) resonance energy transfer (ERET) system is fabricated by layer-by-layer (LBL) electrostatic assembly of CoAl layered double hydroxide (LDH) nanosheets with a mixture of blue BSA-gold nanoclusters (AuNCs) and Ru(bpy)3(2+) (denoted as AuNCs@Ru) on an Au electrode. The possible ECL mechanism indicates that the appearance of CoAl-LDH nanosheets generates a long-range stacking order of the AuNCs@Ru on an Au electrode, facilitating the occurrence of the ERET between BSA-AuNC donors and Ru(bpy)3(2+) acceptors on the as-prepared AuNCs@Ru-LDH ultrathin films (UTFs). Furthermore, it is observed that the cathodic ECL intensity can be quenched efficiently in the presence of 6-mercaptopurine (6-MP) in a linear range of 2.5-100 nM with a detection limit of 1.0 nM. On the basis of these interesting phenomena, a facile cathodic ECL sensor has successfully distinguished 6-MP from other thiol-containing compounds (e.g., cysteine and glutathione) in human serum and urine samples. The proposed sensing scheme opens a way for employing the layered UTFs as a platform for the cathodic ECL of Ru(bpy)3(2+).

  9. Synthesis of Zn–Fe layered double hydroxides via an oxidation process and structural analysis of products

    SciTech Connect

    Morimoto, Kazuya; Tamura, Kenji; Anraku, Sohtaro; Sato, Tsutomu; Suzuki, Masaya; Yamada, Hirohisa

    2015-08-15

    The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn–Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species. - Graphical abstract: The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. - Highlights: • Iron valency affected the generation of Zn–Fe layered double hydroxides. • Zn–Fe layered double hydroxides were successfully synthesized using Fe(II). • Fe(II) species were likely to form trioctahedral hydroxide layers with Zn species.

  10. Aluminum doped nickel oxide thin film with improved electrochromic performance from layered double hydroxides precursor in situ pyrolytic route

    NASA Astrophysics Data System (ADS)

    Shi, Jingjing; Lai, Lincong; Zhang, Ping; Li, Hailong; Qin, Yumei; Gao, Yuanchunxue; Luo, Lei; Lu, Jun

    2016-09-01

    Electrochromic materials with unique performance arouse great interest on account of potential application values in smart window, low-power display, automobile anti-glare rearview mirror, and e-papers. In this paper, high-performing Al-doped NiO porous electrochromic film grown on ITO substrate has been prepared via a layered double hydroxides(LDHs) precursor in situ pyrolytic route. The Al3+ ions distributed homogenously within the NiO matrix can significantly influence the crystallinity of Ni-Al LDH and NiO:Al3+ films. The electrochromic performance of the films were evaluated by means of UV-vis absorption spectroscopy, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry(CA) measurements. In addition, the ratio of Ni3+/Ni2+ also varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range (58.4%), fast switching speed (bleaching/coloration times are 1.8/4.2 s, respectively) and excellent durability (30% decrease after 2000 cycles). The improved performance was owed to the synergy of large NiO film specific surface area and porous morphology, as well as Al doping stifled the formation of Ni3+ making bleached state more pure. This LDHs precursor pyrolytic method is simple, low-cost and environmental benign and is feasible for the preparation of NiO:Al and other Al-doped oxide thin film.

  11. Multiple and configurable optical logic systems based on layered double hydroxides and chromophore assemblies.

    PubMed

    Shi, Wenying; Fu, Yi; Li, Zhixiong; Wei, Min

    2015-01-14

    Multiple and configurable fluorescence logic gates were fabricated via self-assembly of layered double hydroxides and various chromophores. These logic gates were operated by observation of different emissions with the same excitation wavelength, which achieve YES, NOT, AND, INH and INHIBIT logic operations, respectively.

  12. Acid and redox properties of mixed oxides prepared by calcination of chromate-containing layered double hydroxides

    SciTech Connect

    Arco, M. del; Carriazo, D.; Martin, C.; Perez-Grueso, A.M.; Rives, V. . E-mail: vrives@usal.es

    2005-11-15

    Layered double hydroxides (LDHs) with Mg and Al in the layers and carbonate, nitrate or chloride in the interlayer, or with Zn and Al in the layers and chloride in the interlayer, have been prepared by coprecipitation, and have been used as precursors to prepare chromate-containing LDHs. All these systems, as well as those obtained upon their calcination up to 800 deg. C, have been characterised by powder X-ray diffraction, FT-IR and vis-UV spectroscopies, temperature-programmed reduction (TPR), nitrogen adsorption at -196 deg. C for surface texture and porosity assessment, and FT-IR monitoring of pyridine adsorption for surface acidity determination. The results obtained show that the crystallinity of the chromate-containing LDH depends on the precursor used. The layered structure of the Mg, Al systems is stabilised up to 400 deg. C upon incorporation of chromate; however, the Zn,Al-chromate samples collapse between 200 and 300 deg. C, with simultaneous formation of ZnO. Calcination of the samples above 400 deg. C gives rise to a reduction of Cr(VI) to Cr(III), as concluded from vis-UV spectroscopic studies. The TPR profiles show that chromate in ZnAl hydrotalcite is more easily reduced than that incorporated in the magnesium ones. Moderately strong surface Lewis acid sites exist in all samples calcined below 500 deg. C.

  13. The alternative use of layered double hydroxides as extraction medium coupled with microcomplexation for determination of phosphate in water samples

    NASA Astrophysics Data System (ADS)

    Gissawong, Netsirin; Sansuk, Sira; Srijaranai, Supalax

    2017-02-01

    A simple, rapid, in situ, and green extraction combined with a microcomplexation has been developed for the spectrophotometric determination of phosphate in water samples. Through their formation, layered double hydroxides (LDHs) were employed as the extraction medium, instantly commenced by a rapid addition of a mixed solution of Mg2 + and Al3 + ions into alkaline phosphate solution. After the extraction, LDH precipitate containing phosphate was dissolved by sulfuric acid and the released phosphate was subsequently detected via its complexation with molybdate in the presence of antimonyl and ascorbic acid. Under optimum conditions, the linearity in the range of 5-200 μg L- 1, with the correlation coefficient (r2) of 0.9969, and the enrichment factor (EF) of 14 were obtained. The limit of detection (LOD) of 5 μg L- 1 and good precision, with the relative standard deviations (RSDs) less than 8.16%, were achieved. The proposed method was successfully applied to determine phosphate in water samples and the relative recoveries of 72.97-115.32% were obtained.

  14. The alternative use of layered double hydroxides as extraction medium coupled with microcomplexation for determination of phosphate in water samples.

    PubMed

    Gissawong, Netsirin; Sansuk, Sira; Srijaranai, Supalax

    2017-02-15

    A simple, rapid, in situ, and green extraction combined with a microcomplexation has been developed for the spectrophotometric determination of phosphate in water samples. Through their formation, layered double hydroxides (LDHs) were employed as the extraction medium, instantly commenced by a rapid addition of a mixed solution of Mg(2+) and Al(3+) ions into alkaline phosphate solution. After the extraction, LDH precipitate containing phosphate was dissolved by sulfuric acid and the released phosphate was subsequently detected via its complexation with molybdate in the presence of antimonyl and ascorbic acid. Under optimum conditions, the linearity in the range of 5-200μgL(-1), with the correlation coefficient (r(2)) of 0.9969, and the enrichment factor (EF) of 14 were obtained. The limit of detection (LOD) of 5μgL(-1) and good precision, with the relative standard deviations (RSDs) less than 8.16%, were achieved. The proposed method was successfully applied to determine phosphate in water samples and the relative recoveries of 72.97-115.32% were obtained.

  15. A combined FTIR and infrared emission spectroscopy investigation of layered double hydroxide as an effective electron donor

    NASA Astrophysics Data System (ADS)

    Zhang, Jia; Wei, Feng; Liang, Ying; Zhou, Jizhi; Xi, Yunfei; Qian, Guangren; Frost, Ray

    2016-02-01

    A novel method has been presented to characterize electron transfer in layered double hydroxides (LDHs) utilizing an investigation combing FTIR and infrared emission spectroscopy. At room temperature, electron could transfer to interlayer Fe3 + through monodentate ligand cyanide, and resulted in a reduction of 40% Fe3 + to Fe2 +. When the environmental temperature increased from 25 to 300 °C, reduction of Fe3 + and Ni2 + increased to 94% and 42%. Furthermore, electron also transferred to interlayer cation through multidentate ligand EDTA. As a result, LDHs has been proven to be an effective electron donor, and FTIR was a feasible tool in characterizing this property by monitoring the valence state of cations. It was also concluded that octahedral units with OH- groups in LDH layer functioned as electron donor centers. Driving force for electron transfer is attributed to the charge density difference between cation layer and probe anion. These results could help to explain the mechanism of various applications of LDHs in catalysis and photocatalysis.

  16. Sorption mechanisms of arsenate on Mg-Fe layered double hydroxides: A combination of adsorption modeling and solid state analysis.

    PubMed

    Hudcová, Barbora; Veselská, Veronika; Filip, Jan; Číhalová, Sylva; Komárek, Michael

    2017-02-01

    Layered double hydroxides have been proposed as effective sorbents for As(V), but studies investigating adsorption mechanisms usually lack a comprehensive mechanistic/modeling approach. In this work, we propose coupling surface complexation modeling with various spectroscopic techniques. To this end, a series of batch experiments at different pH values were performed. Kinetic data were well fitted by a pseudo-second order kinetic model, and the equilibrium data were fitted by the Freundlich model. Moreover, the pH-dependent As(V) sorption data were satisfactorily fitted by a diffuse layer model, which described the formation of >SOAsO3H(-) monodentate and >(SO)2AsO2(-) bidentate inner-sphere complexes (">S" represents a crystallographically-bound group on the surface). Additionally, XPS analyses confirmed the adsorption mechanisms. The sorption mechanisms were affected by anion exchange, which was responsible for the formation of outer sphere complexes, as identified by XRD and FTIR analyses. Furthermore, a homogenous distribution of As(V) was determined by HR-TEM with elemental mapping. Using low-temperature Mössbauer spectroscopy on isotope (57)Fe, a slight shift of the hyperfine parameters towards higher values following As(V) sorption was measured, indicating a higher degree of structural disorder. In general, mechanistic adsorption modeling coupled with solid state analyses presents a powerful approach for investigating the adsorption mechanism of As(V) on Mg-Fe LDH or other sorbents.

  17. Acid and redox properties of mixed oxides prepared by calcination of chromate-containing layered double hydroxides

    NASA Astrophysics Data System (ADS)

    del Arco, M.; Carriazo, D.; Martín, C.; Pérez-Grueso, A. M.; Rives, V.

    2005-11-01

    Layered double hydroxides (LDHs) with Mg and Al in the layers and carbonate, nitrate or chloride in the interlayer, or with Zn and Al in the layers and chloride in the interlayer, have been prepared by coprecipitation, and have been used as precursors to prepare chromate-containing LDHs. All these systems, as well as those obtained upon their calcination up to 800 °C, have been characterised by powder X-ray diffraction, FT-IR and vis-UV spectroscopies, temperature-programmed reduction (TPR), nitrogen adsorption at -196 °C for surface texture and porosity assessment, and FT-IR monitoring of pyridine adsorption for surface acidity determination. The results obtained show that the crystallinity of the chromate-containing LDH depends on the precursor used. The layered structure of the Mg, Al systems is stabilised up to 400 °C upon incorporation of chromate; however, the Zn,Al-chromate samples collapse between 200 and 300 °C, with simultaneous formation of ZnO. Calcination of the samples above 400 °C gives rise to a reduction of Cr(VI) to Cr(III), as concluded from vis-UV spectroscopic studies. The TPR profiles show that chromate in ZnAl hydrotalcite is more easily reduced than that incorporated in the magnesium ones. Moderately strong surface Lewis acid sites exist in all samples calcined below 500 °C.

  18. CO₂ sorbents with scaffold-like Ca-Al layered double hydroxides as precursors for CO₂ capture at high temperatures.

    PubMed

    Chang, Po-Hsueh; Lee, Tai-Jung; Chang, Yen-Po; Chen, San-Yuan

    2013-06-01

    A highly stable high-temperature CO₂ sorbent consisting of scaffold-like Ca-rich oxides (Ca-Al-O) with rapid absorption kinetics and a high capacity is described. The Ca-rich oxides were prepared by annealing Ca-Al-NO₃ layered double hydroxide (LDH) precursors through a sol-gel process with Al(O(i)P)₃ and Ca(NO₃)₂ with Ca(2+)/Al(3+) ratios of 1:1, 2:1, 4:1, and 7:1. XRD indicated that only LDH powders were formed for Ca(2+)/Al(3+) ratios of 2:1. However, both LDH and Ca(OH)₂ phases were produced at higher ratios. Both TEM and SEM observations indicated that the Ca-Al-NO₃ LDHs displayed a scaffold-like porous structure morphology rather than platelet-like particles. Upon annealing at 600 °C, a highly stable porous network structure of the CaO-based Ca-Al-O mixed oxide (CAMO), composed of CaO and Ca₁₂Al₁₄O₃₃, was still present. The CAMO exhibited high specific surface areas (up to 191 m(2)g(-1)) and a pore size distribution of 3-6 nm, which allowed rapid diffusion of CO₂ into the interior of the material, inducing fast carbonation/calcination and enhancing the sintering-resistant nature over multiple carbonation/calcination cycles for CO₂ absorption at 700 °C. Thermogravimetric analysis results indicated that a CO₂ capture capacity of approximately 49 wt% could be obtained with rapid absorption from the porous 7:1 CAMO sorbents by carbonation at 700 °C for 5 min. Also, 94-98% of the initial CO₂ capture capability was retained after 50 cycles of multiple carbonation/calcination tests. Therefore, the CAMO framework is a good isolator for preventing the aggregation of CaO particles, and it is suitable for long-term cyclic operation in high-temperature environments.

  19. Selective oxidation catalysts obtained by immobilization of iron(III) porphyrins on thiosalicylic acid-modified Mg-Al layered double hydroxides.

    PubMed

    de Freitas Castro, Kelly Aparecida Dias; Wypych, Fernando; Antonangelo, Ariana; Mantovani, Karen Mary; Bail, Alesandro; Ucoski, Geani Maria; Ciuffi, Kátia Jorge; Cintra, Thais Elita; Nakagaki, Shirley

    2016-09-15

    Nitrate-intercalated Mg-Al layered double hydroxides (LDHs) were synthesized and exfoliated in formamide. Reaction of the single layer suspension with thiosalicylic acid under different conditions afforded two types of solids: LDHA1, in which the outer surface was modified with the anion thiosalicylate, and LDHA2, which contained the anion thiosalicylate intercalated between the LDH layers. LDHA1 and LDHA2 were used as supports to immobilize neutral (FeP1 and FeP2) and anionic (FeP3) iron(III) porphyrins. For comparison purposes, the iron(III) porphyrins (FePs) were also immobilized on LDH intercalated with nitrate anions obtained by the co-precipitation method. Chemical modification of LDH facilitated immobilization of the FePs through interaction of the functionalizing groups in LDH with the peripheral substituents on the porphyrin ring. The resulting FePx-LDHAy solids were characterized by X-ray diffraction (powder) and UV-Vis and EPR spectroscopies and were investigated as catalysts in the oxidation of cyclooctene and cyclohexane. The immobilized neutral FePs and their homogeneous counterparts gave similar product yields in the oxidation of cyclooctene, suggesting that immobilization of the FePs on the thiosalicylate-modified LDHs only supported the catalyst species without interfering in the catalytic outcome. On the other hand, in the oxidation of cyclohexane, the thiosalicylate anions on the outer surface of LDHA1 or intercalated between the LDHA2 layers influenced the catalytic activity of FePx-LDHAy, leading to different efficiency and selectivity results. FeP1-LDHA2 performed the best (29.6% alcohol yield) due to changes in the polarity of the surface of the support and the presence of FeP1. Interestingly, FeP1 also performed better in solution as compared to the other FePs. Finally, it was possible to recycle FeP1-LDHA2 at least three times.

  20. Synthesis and Characterization of Layered Double Hydroxides Containing Optically Active Transition Metal Ion

    NASA Astrophysics Data System (ADS)

    Tyagi, S. B.; Kharkwal, Aneeta; Nitu; Kharkwal, Mamta; Sharma, Raghunandan

    2017-01-01

    The acetate intercalated layered double hydroxides of Zn and Mn, have been synthesized by chimie douce method. The materials were characterized by XRD, TGA, CHN, IR, XPS, SEM-EDX and UV-visible spectroscopy. The photoluminescence properties was also studied. The optical properties of layered hydroxides are active transition metal ion dependent, particularly d1-10 system plays an important role. Simultaneously the role of host - guest orientation has been considered the basis of photoluminescence. Acetate ion can be exchanged with iodide and sulphate ions. The decomposed product resulted the pure phase Mn doped zinc oxide are also reported.

  1. Cu2+ ions as a paramagnetic probe to study the surface chemical modification process of layered double hydroxides and hydroxide salts with nitrate and carboxylate anions.

    PubMed

    Arizaga, Gregorio Guadalupe Carbajal; Mangrich, Antonio Salvio; Wypych, Fernando

    2008-04-01

    A layered zinc hydroxide nitrate (Zn5(OH)8(NO3)2.2H2O) and a layered double hydroxide (Zn/Al-NO3) were synthesized by coprecipitation and doped with different amounts of Cu2+ (0.2, 1, and 10 mol%), as paramagnetic probe. Although the literature reports that the nitrate ion is free (with D3h symmetry) between the layers of these two structures, the FTIR spectra of two zinc hydroxide nitrate samples show the C2v symmetry for the nitrate ion, whereas the g ||/A || value in the EPR spectra of Cu2+ is high. This fact suggests bonding of some nitrate ions to the layers of the zinc hydroxide nitrate. The zinc hydroxide nitrate was used as matrix in the intercalation reaction with benzoate, o-chlorobenzoate, and o-iodobenzoate ions. FTIR spectra confirm the ionic exchange reaction and the EPR spectroscopy reveals bonding of the organic ions to the inorganic layers of the zinc hydroxide nitrate, while the layered double hydroxides show only exchange reactions.

  2. Zn-Al layered double hydroxide prepared at different molar ratios: Preparation, characterization, optical and dielectric properties

    SciTech Connect

    Ahmed, Abdullah Ahmed Ali; Talib, Zainal Abidin; Zobir bin Hussein, Mohd; Zakaria, Azmi

    2012-07-15

    The co-precipitation method was used to prepare Zn-Al-NO{sub 3}-LDH at different Zn{sup 2+}/Al{sup 3+} molar ratios (2, 3, 4, 5 and 6) and pH value of 7.5. The structure, textural, composition and morphological properties were investigated using powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) and scanning electron microscope (SEM), respectively. The crystallinity of LDH samples were found to improve as molar ratio decreased which is attributed to the distortion of the hydroxide layers networks of the LDH crystal by the larger difference in ionic radii of Zn{sup 2+} and Al{sup 3+}. The optical band gap energy of LDH samples were evaluated using absorbance data from UV-Vis-NIR Diffuse reflectance spectroscopy. Band gaps were affected by the variation of the Zn{sup 2+}/Al{sup 3+} molar ratio is due to the formation of the low crystalline phases (ZnO and ZnAl{sub 2}O{sub 4}). The water molecules and anionic NO{sub 3}{sup -} in the LDH interlayer were responsible for the generation of the dielectric response. This response can be described by an anomalous low frequency dispersion using the second type of Universal Power Law. The dominance of ZnO dipoles and charge carriers (NO{sub 3}{sup -} ions) in the dielectric relaxation increases with the increasing molar ratio. - Graphical abstract: (a) Schematic diagram of Zn-Al- NO{sub 3}-LDH shows the LDH structure, (b) Kubelka-Munk transformed reflectance spectra and c. The dielectric constant versus frequency of Zn-Al- NO{sub 3}-LDH samples. Highlights: Black-Right-Pointing-Pointer Zn-Al-NO{sub 3}-LDH was prepared at different Zn{sup 2+}/Al{sup 3+} molar ratios (2, 3, 4, 5 and 6). Black-Right-Pointing-Pointer The crystallinity of LDH phase decreased with increase of Zn{sup 2+}/Al{sup 3+} molar ratio. Black-Right-Pointing-Pointer The optical band gaps of LDH samples have been measured. Black-Right-Pointing-Pointer Dielectric response of LDH can be described by anomalous low

  3. Removal of SO2 with a Mg-Al oxide slurry via reconstruction of a Mg-Al layered double hydroxide.

    PubMed

    Kameda, Tomohito; Kodama, Aki; Fubasami, Yuki; Kumagai, Shogo; Yoshioka, Toshiaki

    2012-06-01

    Although effective treatments of SO(x) are essential for preventing air pollution, current methods pose other environmental problems such as increased amounts of desulfurized gypsum and reduced landfill lifetimes. We report a process for removing SO(2) from waste streams using a Mg-Al oxide slurry. The ability of the mixed oxide to remove SO(2) increased with slurry quantity and temperature but decreased with time. SO(2) was removed through the reconstruction of a Mg-Al layered double hydroxide (Mg-Al LDH) intercalated with SO(3)(2-), which was derived from the dissociation of H(2)SO(3) upon dissolution of SO(2) in the slurry. SO(2) was not adsorbed onto the surface of the Mg-Al oxide. These results suggest that SO(2) removal using a Mg-Al oxide slurry may be possible without the concomitant problems of conventional treatment methods.

  4. Thermal decomposition and reconstruction of CaFe-layered double hydroxide studied by X-ray diffractometry and 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Bugris, Valéria; Ádok-Sipiczki, Mónika; Anitics, Tamás; Kuzmann, Ernő; Homonnay, Zoltán; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

    2015-06-01

    In spite of numerous investigations on the various processes of the thermal decomposition and rehydration of layered double hydroxides (LDHs) by a variety sophisticated experimental means, many details are still unexplored and some contradictions are still unresolved. In this work, our efforts were focussed on clarifying the composition, structure and properties of thermally decomposed metaphases originating from CaFe-LDH, heat treated in the 373-973 K temperature range. The structure reconstruction ability of mixed metal oxide phases obtained after heat treatments was also investigated, mainly concentrating on the changes in the microenvironment of Fe(III), in the presence of controlled amount of water vapour (i.e., at different relative humidities). All samples were characterised by X-ray diffractometry, and the iron-containing phases were studied by 57Fe Mössbauer spectroscopy.

  5. Transesterification of edible, non-edible and used cooking oils for biodiesel production using calcined layered double hydroxides as reusable base catalysts.

    PubMed

    Sankaranarayanan, Sivashunmugam; Antonyraj, Churchil A; Kannan, S

    2012-04-01

    Fatty acid methyl esters (FAME) were produced from edible, non-edible and used cooking oils with different fatty acid contents by transesterification with methanol using calcined layered double hydroxides (LDHs) as solid base catalysts. Among the catalysts, calcined CaAl2-LDH (hydrocalumite) showed the highest activity with >90% yield of FAME using low methanol:oil molar ratio (<6:1) at 65 °C in 5 h. The activity of the catalyst was attributed to its high basicity as supported by Hammett studies and CO(2)-TPD measurements. The catalyst was successfully reused in up to four cycles. Some of the properties such as density, viscosity, neutralization number and glycerol content of the obtained biodiesel matched well with the standard DIN values. It is concluded that a scalable heterogeneously catalyzed process for production of biodiesel in high yields from a wide variety of triglyceride oils including used oils is possible using optimized conditions.

  6. Direct coating for layered double hydroxide/4,4'-diaminostilbene-2,2'-disulfonic acid nanocomposite with silica by seeded polymerization technique

    NASA Astrophysics Data System (ADS)

    El-Toni, Ahmed Mohamed; Yin, Shu; Sato, Tsugio

    2004-09-01

    Organic ultraviolet (UV) ray absorbents have been used as sunscreen materials, but may pose a safety problem when used at high concentration. In order to prevent direct contact of organic UV rays absorbent by the human skin, an organic UV absorbent such as 4,4'-diaminostilbene-2,2'-disulfonic acid (DASDSA) was intercalated into Zn 2Al-layered double hydroxide (Zn 2Al-LDHs) by coprecipiation reaction. The problem of deintercalation of organic molecules from LDHs by the anion exchange reaction with carbonate ion could be greatly depressed by forming a protection film of silica on the surface. Zn 2Al-LDH/DASDSA was directly coated with silica by means of a polymerization technique based on the Stöber method. The deintercalation behavior as well as UV-shielding properties were investigated for coated particles.

  7. Synthesis and characterisation of a new stable organo-mineral hybrid nanomaterial: 4-Chlorobenzenesulfonate in the zinc-aluminium layered double hydroxide

    SciTech Connect

    Lakraimi, Mohamed; Legrouri, Ahmed . E-mail: legrouri@aui.ma; Barroug, Allal; De Roy, Andre; Besse, Jean Pierre

    2006-09-14

    4-Chlorobenzenesulfonate (4-CBS) was intercalated between layers of Zn-Al layered double hydroxides (LDHs). Two methods of incorporation were applied: (1) direct synthesis by coprecipitation of metal nitrates and sodium 4-CBS and (2) ion exchange of the LDH nitrate with the organic ion. The solids were characterized by X-ray diffraction and infrared spectroscopy. The direct method, effected at different pH values, led to a hybrid material with good degree of intercalation. In order to optimise the exchange conditions, particular attention was given to the effect of solution pH, 4-CBS/NO{sub 3} ratio and exchange temperature. The total exchange was successful and a new stable hybrid nanostructured material was obtained at pH 8 and with a 4-CBS concentration of 0.0028 M. This solid was further characterised by chemical and thermal analyses.

  8. Structural characterization and thermal and chemical stability of bioactive molecule-hydrotalcite (LDH) nanocomposites.

    PubMed

    Conterosito, Eleonora; Croce, Gianluca; Palin, Luca; Pagano, Cinzia; Perioli, Luana; Viterbo, Davide; Boccaleri, Enrico; Paul, Geo; Milanesio, Marco

    2013-08-28

    Layered double hydroxides (LDH) are versatile materials used for intercalating bioactive molecules, both in pharmaceutical and cosmetic fields, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability, and/or obtaining modified release properties. The properties of the intercalation compounds of Mg/Al_LDH and Zn/Al_LDH with different drugs and sunscreens, namely diclofenac, ketoprofen, gliclazide, retinoic acid, furosemide, para-aminobenzoic acid and 2-phenylbenzimidazolsulfonic (Eusolex) acid, have been studied by crystallographic, spectroscopic and thermogravimetric techniques and by solid state NMR, to shed light on their structure, their molecular interactions and their stability from the thermal and chemical viewpoint. The structural features were described with particular attention to the interaction between the organic and inorganic components and to the stability of the intercalation products. For the first time two synchrotron radiation powder diffraction patterns of organic-containing LDH were solved and refined by Rietveld methods to obtain an experimental crystal structure.

  9. Nickel-Aluminum Layered Double Hydroxide Coating on the Surface of Conductive Substrates by Liquid Phase Deposition.

    PubMed

    Maki, Hideshi; Takigawa, Masashi; Mizuhata, Minoru

    2015-08-12

    The direct synthesis of the adhered Ni-Al LDH thin film onto the surface of electrically conductive substrates by the liquid phase deposition (LPD) reaction is carried out for the development of the positive electrode. The complexation and solution equilibria of the dissolved species in the LPD reaction have been clarified by a theoretical approach, and the LPD reaction conditions for the Ni-Al LDH depositions are shown to be optimized by controlling the fluoride ion concentration and the pH of the LPD reaction solutions. The yields of metal oxides and hydroxides by the LPD method are very sensitive to the supersaturation state of the hydroxide in the reaction solution. The surfaces of conductive substrates are completely covered by the minute mesh-like Ni-Al LDH thin film; furthermore, there is no gap between the surfaces of conductive substrates and the deposited Ni-Al LDH thin film. The active material layer thickness was able to be controlled within the range from 100 nm to 1 μm by the LPD reaction time. The high-crystallinity and the arbitrary-thickness thin films on the conductive substrate surface will be beneficial for the interface control of charge transfer reaction fields and the internal resistance reduction of various secondary batteries.

  10. Intercalation studies of zinc hydroxide chloride: Ammonia and amino acids

    SciTech Connect

    Arizaga, Gregorio Guadalupe Carbajal

    2012-01-15

    Zinc hydroxide chloride (ZHC) is a layered hydroxide salt with formula Zn{sub 5}(OH){sub 8}Cl{sub 2}{center_dot}2H{sub 2}O. It was tested as intercalation matrix for the first time and results were compared with intercalation products of the well-known zinc hydroxide nitrate and a Zn/Al layered double hydroxide. Ammonia was intercalated into ZHC, while no significant intercalation occurred in ZHN. Aspartic acid intercalation was only achieved by co-precipitation at pH=10 with ZHC and pH=8 with zinc hydroxide nitrate. Higher pH resistance in ZHC favored total deprotonation of both carboxylic groups of the Asp molecule. ZHC conferred more thermal protection against Asp combustion presenting exothermic peaks even at 452 Degree-Sign C while the exothermic event in ZHN was 366 Degree-Sign C and in the LDH at 276 Degree-Sign C. - Graphical abstract: The zinc hydroxide chloride (ZHC) with formula Zn{sub 5}(OH){sub 8}Cl{sub 2}{center_dot}2H{sub 2}O was tested as intercalation matrix. In comparison with the well-known zinc hydroxide nitrate (ZHN) and layered double hydroxides (LDH), ZHC was the best matrix for thermal protection of Asp combustion, presenting exothermic peaks even at 452 Degree-Sign C, while the highest exothermic event in ZHN was at 366 Degree-Sign C, and in the LDH it was at 276 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Zinc hydroxide chloride (ZHC) was tested as intercalation matrix for the first time. Black-Right-Pointing-Pointer ZHC has higher chemical and thermal stability than zinc hydroxide nitrate and LDH. Black-Right-Pointing-Pointer NH{sub 3} molecules can be intercalated into ZHC. Black-Right-Pointing-Pointer The amino group of amino acids limits the intercalation by ion-exchange.

  11. Removal of perchlorate in water by calcined MgAl-CO3 layered double hydroxides.

    PubMed

    Yang, Yiqiong; Gao, Naiyun; Deng, Yang; Yu, Guoping

    2013-04-01

    Perchlorate is widely known as an inorganic endocrine disruptor. In this study, MgAl-CO3 layered double hydroxides with different Mg/Al molar ratios were prepared using a coprecipitation method and followed by a calcination process at a temperature range of 300 to 700 degrees C. Results showed that the best synthesis conditions were a calcination temperature of 550 degrees C and Mg/Al molar ratio of 3. Further, the adsorbent and its adsorption product were characterized by x-ray diffraction, Fourier transform-infrared spectroscopy, and thermogravimetric-differential thermal analysis. The layered double hydroxides structures in the adsorbent were lost during calcination at 550 degrees C but were reconstructed subsequent to adsorption of perchlorate, indicating that the "memory effect" appeared to play an important role in perchlorate adsorption. The perchlorate adsorption pattern was best described by the pseudo-second-order kinetics model, while the Freundlich isotherms appropriately explained perchlorate adsorption data.

  12. Synthesis and properties of Mg{sub 2}Al layered double hydroxides containing 5-fluorouracil

    SciTech Connect

    Wang Zhongliang; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Gao Lei; Xu Lin

    2005-03-15

    A pharmaceutically active compound, 5-fluorouracil (5-FU) has been firstly intercalated into layered double hydroxide with the restructure method. Powder X-ray diffraction and spectroscopic analysis indicate that 5-FU molecule is stabilized in the host interlayer by electrostatic interaction and intermolecular interaction, and that the orientation of 5-FU is different when changing the pattern of aging treatment or the swelling agent. The release studies show that a rapid release of the drug during the first 40min is followed by a more sustained one, and that the total amount of drug released from hybrid material into the aqueous solution is almost 87% and 74% at pH 4 and 7, respectively. The studies mentioned above suggest that layered double hydroxide might be used as the basis of a tunable drug delivery carrier.

  13. Aniosotropically organized LDH on PVDF: a geometrically templated electrospun substrate for advanced anion conducting membranes.

    PubMed

    Sailaja, G S; Zhang, Peilin; Anilkumar, Gopinathan M; Yamaguchi, Takeo

    2015-04-01

    A bioinspired geometric templating of an electrospun PVDF substrate with hexagonal platelets of Mg-Al layered double hydroxide (LDH), an intrinsic anion conductor, is presented. The distinctive morphology restructures the internal pore geometry and modulates the dynamic wetting profile of PVDF, transforming it into a highly functional substrate for SAFC anion conducting membranes. The membrane fabricated with PVDF-LDH substrate exhibited exceptionally high durability (>140 °C), high anionic conductivity, ion exchange capacity (IEC), restricted swelling, and improved tensile strength, overcoming critical challenges associated with PVDF electrospun substrates and validating its immense potential as a high-temperature-stable and durable substrate for advanced fuel cell membrane applications.

  14. Synthesis, characterization, and efficacy of antituberculosis isoniazid zinc aluminum-layered double hydroxide based nanocomposites.

    PubMed

    Saifullah, Bullo; El Zowalaty, Mohamed Ezzat; Arulselvan, Palanisamy; Fakurazi, Sharida; Webster, Thomas J; Geilich, Benjamin Mahler; Hussein, Mohd Zobir

    2016-01-01

    The chemotherapy for tuberculosis (TB) is complicated by its long-term treatment, its frequent drug dosing, and the adverse effects of anti-TB drugs. In this study, we have developed two nanocomposites (A and B) by intercalating the anti-TB drug isoniazid (INH) into Zn/Al-layered double hydroxides. The average size of the nanocomposites was found to bê164 nm. The efficacy of the Zn/Al-layered double hydroxides intercalated INH against Mycobacterium tuberculosis was increased by approximately three times more than free INH. The nanocomposites were also found to be active against Gram-positive and -negative bacteria. Compared to the free INH, the nanodelivery formulation was determined to be three times more biocompatible with human normal lung fibroblast MRC-5 cells and 3T3 fibroblast cells at a very high concentration of 50 µg/mL for up to 72 hours. The in vitro release of INH from the Zn/Al-layered double hydroxides was found to be sustained in human body-simulated buffer solutions of pH 4.8 and 7.4. This research is a step forward in making the TB chemotherapy patient friendly.

  15. Synthesis, characterization, and efficacy of antituberculosis isoniazid zinc aluminum-layered double hydroxide based nanocomposites

    PubMed Central

    Saifullah, Bullo; El Zowalaty, Mohamed Ezzat; Arulselvan, Palanisamy; Fakurazi, Sharida; Webster, Thomas J; Geilich, Benjamin Mahler; Hussein, Mohd Zobir

    2016-01-01

    The chemotherapy for tuberculosis (TB) is complicated by its long-term treatment, its frequent drug dosing, and the adverse effects of anti-TB drugs. In this study, we have developed two nanocomposites (A and B) by intercalating the anti-TB drug isoniazid (INH) into Zn/Al-layered double hydroxides. The average size of the nanocomposites was found to bê164 nm. The efficacy of the Zn/Al-layered double hydroxides intercalated INH against Mycobacterium tuberculosis was increased by approximately three times more than free INH. The nanocomposites were also found to be active against Gram-positive and -negative bacteria. Compared to the free INH, the nanodelivery formulation was determined to be three times more biocompatible with human normal lung fibroblast MRC-5 cells and 3T3 fibroblast cells at a very high concentration of 50 µg/mL for up to 72 hours. The in vitro release of INH from the Zn/Al-layered double hydroxides was found to be sustained in human body-simulated buffer solutions of pH 4.8 and 7.4. This research is a step forward in making the TB chemotherapy patient friendly. PMID:27486322

  16. Hybrid Materials Based on Magnetic Layered Double Hydroxides: A Molecular Perspective.

    PubMed

    Abellán, Gonzalo; Martí-Gastaldo, Carlos; Ribera, Antonio; Coronado, Eugenio

    2015-06-16

    Design of functional hybrids lies at the very core of synthetic chemistry as it has enabled the development of an unlimited number of solids displaying unprecedented or even improved properties built upon the association at the molecular level of quite disparate components by chemical design. Multifunctional hybrids are a particularly appealing case among hybrid organic/inorganic materials. Here, chemical knowledge is used to deploy molecular components bearing different functionalities within a single solid so that these properties can coexist or event interact leading to unprecedented phenomena. From a molecular perspective, this can be done either by controlled assembly of organic/inorganic molecular tectons into an extended architecture of hybrid nature or by intercalation of organic moieties within the empty channels or interlamellar space offered by inorganic solids with three-dimensional (MOFs, zeolites, and mesoporous hosts) or layered structures (phosphates, silicates, metal dichalcogenides, or anionic clays). This Account specifically illustrates the use of layered double hydroxides (LDHs) in the preparation of magnetic hybrids, in line with the development of soft inorganic chemistry processes (also called "Chimie Douce"), which has significantly contributed to boost the preparation hybrid materials based on solid-state hosts and subsequent development of applications. Several features sustain the importance of LDHs in this context. Their magnetism can be manipulated at a molecular level by adequate choice of constituting metals and interlayer separation for tuning the nature and extent of magnetic interactions across and between planes. They display unparalleled versatility in accommodating a broad range of anionic species in their interlamellar space that encompasses not only simple anions but chemical systems of increasing dimensionality and functionalities. Their swelling characteristics allow for their exfoliation in organic solvents with high

  17. Ethylene Glycol Intercalated Cobalt/Nickel Layered Double Hydroxide Nanosheet Assemblies with Ultrahigh Specific Capacitance: Structural Design and Green Synthesis for Advanced Electrochemical Storage.

    PubMed

    Wang, Changhui; Zhang, Xiong; Xu, Zhongtang; Sun, Xianzhong; Ma, Yanwei

    2015-09-09

    Because of the rapid depletion of fossil fuels and severe environmental pollution, more advanced energy-storage systems need to possess dramatically improved performance and be produced on a large scale with high efficiency while maintaining low-enough costs to ensure the higher and wider requirements. A facile, energy-saving process was successfully adopted for the synthesis of ethylene glycol intercalated cobalt/nickel layered double hydroxide (EG-Co/Ni LDH) nanosheet assembly variants with higher interlayer distance and tunable transitional-metal composition. At an optimized starting Co/Ni ratio of 1, the nanosheet assemblies display a three-dimensional, spongelike network, affording a high specific surface area with advantageous mesopore structure in 2-5 nm containing large numbers of about 1.2 nm micropores for promoting electrochemical reaction. An unprecedented electrochemical performance was achieved, with a specific capacitance of 4160 F g(-1) at a discharge current density of 1 A g(-1) and of 1313 F g(-1) even at 50 A g(-1), as well as excellent cycling ability. The design and optimization of EG-Co/Ni LDH nanosheets in compositions, structures, and performances, in conjunction with the easy and relatively "green" synthetic process, will play a pivotal role in meeting the needs of large-scale manufacture and widespread application for advanced electrochemical storage.

  18. Insight of an easy topochemical oxidative reaction in obtaining high performance electrochemical capacitor based on CoIICoIII monometallic cobalt Layered Double Hydroxide

    NASA Astrophysics Data System (ADS)

    Vialat, Pierre; Rabu, Pierre; Mousty, Christine; Leroux, Fabrice

    2015-10-01

    A series of monometallic Layered Double Hydroxides (LDH) using electroactive cation, i.e. divalent or trivalent cobalt, was prepared by Topochemical Oxidation Reaction (TOR) under O2 atmosphere at 40 °C from pristine β-Co(OH)2 platelets. The oxidation state of the ill-defined layered materials was evaluated by coupling thermal measurements and chemical titration (iodometry). Their characterization by ancillary techniques was completed by the study of their magnetic behavior. The obtained magnetic moments suggest the presence of structural local deformation around the CoII ions, unhomogeneous charge distribution yielding to clustering effects cannot be discarded. Their pseudo-faradic properties as supercapacitor in KOH solution was thoroughly investigated by using Cyclic Voltammetry (CV), Galvanostatic Cycling with Potential Limitation (GCPL) and Electrochemical Impedance Spectroscopy (EIS) techniques. As a function of the oxygen treatment, the relative amount of CoII/CoIII was found to range into 5.3 and 13.3, which is unusually high when compared to classical LDH charge distribution. Pseudocapacitance as high as 1540 F g-1 was obtained underlining a high percentage of CoII, ≈40%, involved in electrochemical process. This high percentage is tentatively explained by an extended outer-active electrochemical surface which demonstrates that TOR is a quick and easy process to get a high pseudocapacitive performance.

  19. Enhanced photocatalytic performances of hierarchical ZnO/ZnAl2O4 microsphere derived from layered double hydroxide precursor spray-dried microsphere.

    PubMed

    Huo, Ruijie; Kuang, Ye; Zhao, Zhiping; Zhang, Fazhi; Xu, Sailong

    2013-10-01

    Layered double hydroxides (LDHs), also called hydrotalcites, have been widely investigated for degradation of dye molecules, in the forms of direct photocatalysts, supports or precursors to ZnO-containing photocatalysts. LDH precursor-derived ZnO/ZnAl2O4 photocatalytic nanostructures have hitherto been created, involving ZnO/ZnAl2O4 powder and templated hierarchical frameworks with laboratory-scale preparations. We herein report a scalable preparation of ZnO/ZnAl2O4 microsphere derived from ZnAl-LDH precursor spray-dried microsphere. Survey of textural properties shows that ZnO/ZnAl2O4 microspheres maintain the hierarchically spherical feature and the relatively large surface area. Photocatalytic evaluation under UV irradiation shows that the ZnO/ZnAl2O4 microspheres exhibit highly enhanced photodegradation performance to methylene blue (MB) in comparison with the commercial ZnO powder. A preferential photodegradation to methyl orange (MO) of the MO/MB mixture was also observed, which was illustrated experimentally in terms of the favorable interaction and distribution between basic MO molecules and the acidic-site ZnO/ZnAl2O4 photocatalyst. Our results may initiate large-scale production of microspheres with promising photocatalytic performances.

  20. Synthesis and characterization of chitosan/Mg-Al layered double hydroxide composite for the removal of oil particles from oil-in-water emulsion.

    PubMed

    Elanchezhiyan, S Sd; Meenakshi, Sankaran

    2017-01-23

    The recovery of oil from oil-in-water emulsion has been investigated using chitosan/magnesium-aluminium layered double hydroxide hybrid composite (CS-LDHCs) by a single co-precipitation method. Resulting better adsorption efficiency of CS-LDHCs could be observed, indicating the synthesized material was effective to adsorb oil particles from oil-in-water emulsion at acidic pH (pH 3.0) than as-prepared LDH and raw chitosan. The enhancement of adsorption properties by CS-LDHCs material were attributed to the high content of LDH in chitosan, which makes the material more effective towards immobilization of oily particles. Batch experiment study has been elucidated by varying different physicochemical parameters such as time, pH, dose, initial oil concentration and temperature. The as-synthesized CS-LDHCs was characterized by various spectro analytical techniques viz., FTIR, SEM with EDAX, XRD, TGA and DSC analysis. To find out the best fit for the sorption process, the obtained adsorption equilibrium data was explained with Freundlich, Langmuir, Dubinin-Radushkevich and Tempkin isotherm models. The mechanism of adsorption process was demonstrated by calculating ΔG°, ΔH° and ΔS° values from thermodynamic parameters in order to understand the nature of sorption process. The schematic representation of oil removal using CS-LDHCs was explored in detail. This work provides an apparent proposal for the growth of oil removal technology.

  1. Layered double hydroxide of Cd-Al/C for the Mineralization and De-coloration of Dyes in Solar and Visible Light Exposure

    NASA Astrophysics Data System (ADS)

    Khan, Shahid Ali; Khan, Sher Bahadar; Asiri, Abdullah M.

    2016-11-01

    Cd-Al/C layered double hydroxide (Cd-Al/C-LDH) and Cd-Sb/C nanocatalyst are reported here for the de-coloration and mineralization of organic dyes. These catalysts were largely characterized by FESEM, EDS, XRD, FTIR, XPS, PL and DRS. The diffuse reflectance data showed a band gap at 2.92 and 2.983 eV for Cd-Al/C-LDH and Cd-Sb/C respectively. The band gap suggested that both catalysts work well in visible range. The photoluminescence spectra indicated a peak at 623 nm for both the catalysts which further support the effectiveness of the respective catalyst in visible range. Both catalysts also showed good recyclability and durability till 4th cycle. Five dyes, acridine orange (AO), malachite green (MG), crystal violet (CV), congo red (CR) and methyl orange (MO) were used in this experiment. Various parameters of different light intensity such as visible, ultraviolet, sunlight and dark condition are observed for the de-coloration of these dyes. The de-coloration phenomenon was proceeded through adsorption assisted phot-degradation. The low cost, abundant nature, good recyclability and better dye removal efficiency make these catalysts suitable candidates for the de-coloration and mineralization of organic dyes.

  2. Layered double hydroxide of Cd-Al/C for the Mineralization and De-coloration of Dyes in Solar and Visible Light Exposure

    PubMed Central

    Khan, Shahid Ali; Khan, Sher Bahadar; Asiri, Abdullah M.

    2016-01-01

    Cd-Al/C layered double hydroxide (Cd-Al/C-LDH) and Cd-Sb/C nanocatalyst are reported here for the de-coloration and mineralization of organic dyes. These catalysts were largely characterized by FESEM, EDS, XRD, FTIR, XPS, PL and DRS. The diffuse reflectance data showed a band gap at 2.92 and 2.983 eV for Cd-Al/C-LDH and Cd-Sb/C respectively. The band gap suggested that both catalysts work well in visible range. The photoluminescence spectra indicated a peak at 623 nm for both the catalysts which further support the effectiveness of the respective catalyst in visible range. Both catalysts also showed good recyclability and durability till 4th cycle. Five dyes, acridine orange (AO), malachite green (MG), crystal violet (CV), congo red (CR) and methyl orange (MO) were used in this experiment. Various parameters of different light intensity such as visible, ultraviolet, sunlight and dark condition are observed for the de-coloration of these dyes. The de-coloration phenomenon was proceeded through adsorption assisted phot-degradation. The low cost, abundant nature, good recyclability and better dye removal efficiency make these catalysts suitable candidates for the de-coloration and mineralization of organic dyes. PMID:27841277

  3. Preparation and controlled-release studies of a protocatechuic acid-magnesium/aluminum-layered double hydroxide nanocomposite

    PubMed Central

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Hussein-Al-Ali, Samer Hasan; Arulselvan, Palanisamy; Fakurazi, Sharida; Zainal, Zulkarnain

    2013-01-01

    In the study reported here, magnesium/aluminum (Mg/Al)-layered double hydroxide (LDH) was intercalated with an anticancer drug, protocatechuic acid, using ion-exchange and direct coprecipitation methods, with the resultant products labeled according to the method used to produce them: “PANE” (ie, protocatechuic acid-Mg/Al nanocomposite synthesized using the ion-exchange method) and “PAND” (ie, protocatechuic acid-Mg/Al nanocomposite synthesized using the direct method), respectively. Powder X-ray diffraction and Fourier transform infrared spectroscopy confirmed the intercalation of protocatechuic acid into the inter-galleries of Mg/Al-LDH. The protocatechuic acid between the interlayers of PANE and PAND was found to be a monolayer, with an angle from the z-axis of 8° for PANE and 15° for PAND. Thermogravimetric and differential thermogravimetric analysis results revealed that the thermal stability of protocatechuic acid was markedly enhanced upon intercalation. The loading of protocatechuic acid in PANE and PAND was estimated to be about 24.5% and 27.5% (w/w), respectively. The in vitro release study of protocatechuic acid from PANE and PAND in phosphate-buffered saline at pH 7.4, 5.3, and 4.8 revealed that the nanocomposites had a sustained release property. After 72 hours incubation of PANE and PAND with MCF-7 human breast cancer and HeLa human cervical cancer cell lines, it was found that the nanocomposites had suppressed the growth of these cancer cells, with a half maximal inhibitory concentration of 35.6 μg/mL for PANE and 36.0 μg/mL for PAND for MCF-7 cells, and 19.8 μg/mL for PANE and 30.3 μg/mL for PAND for HeLa cells. No half maximal inhibitory concentration for either nanocomposite was found for 3T3 cells. PMID:23737666

  4. Thermodynamical and structural insights of orange II adsorption by Mg{sub R}AlNO{sub 3} layered double hydroxides

    SciTech Connect

    Mustapha Bouhent, Mohamed; Derriche, Zoubir; Denoyel, Renaud; Prevot, Vanessa; Forano, Claude

    2011-05-15

    [Mg{sub 1-x} Al{sub x}(OH){sub 2}][(NO{sub 3}){sub x}, nH{sub 2}O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar (R=(1-x)/x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}) and entropy ({Delta}S{sup o}) were calculated. The experimental values for {Delta}G{sup o} in temperature range between 10 and 40 {sup o}C were found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange. -- Graphical Abstract: Structural and thermodynamical insight of adsorption/Intercalation of OII in Mg{sub R}Al LDH Display Omitted Highlights: {yields} The nitrate containing hydrotalcite-like compounds (Mg{sub R}AlNO{sub 3} LDH) were prepared by the coprecipitation method. {yields} Adsorption of anionic orange dye(OII) is studied on LDHs at different temperatures. {yields} The adsorption process is well described by the Langmuir isotherm model. {yields} Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. {yields} Adsorption process does not occur on the surface of the LDH only but an intercalation process is also occurring concomitantly according to the thermodynamical values.

  5. Biomass-Derived Nitrogen-Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel-Cobalt Layered Double Hydroxide Nanosheets as High-Performance Asymmetric Supercapacitor Electrode.

    PubMed

    Lai, Feili; Miao, Yue-E; Zuo, Lizeng; Lu, Hengyi; Huang, Yunpeng; Liu, Tianxi

    2016-06-01

    The development of biomass-based energy storage devices is an emerging trend to reduce the ever-increasing consumption of non-renewable resources. Here, nitrogen-doped carbonized bacterial cellulose (CBC-N) nanofibers are obtained by one-step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio-template for further deposition of ultrathin nickel-cobalt layered double hydroxide (Ni-Co LDH) nanosheets. The as-obtained CBC-N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g(-1) at a discharge current density of 1 A g(-1) , based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g(-1) and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC-N@LDH composites as positive electrode materials and CBC-N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC-N@LDH composites and 3D nitrogen-doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg(-1) at the power density of 800.2 W kg(-1) . Therefore, this work presents a novel protocol for the large-scale production of biomass-derived high-performance electrode materials in practical supercapacitor applications.

  6. Ni/Ti layered double hydroxide: synthesis, characterization and application as a photocatalyst for visible light degradation of aqueous methylene blue.

    PubMed

    Roy Chowdhury, Priyadarshi; Bhattacharyya, Krishna G

    2015-04-21

    Visible light responsive 2 : 1 Ni/Ti layered double hydroxide (LDH) was synthesized by a single step hydrothermal route using commercially available Ni(NO3)2·6H2O, TiCl4 and urea. The material exhibited significant absorption in the visible range with a very narrow band gap (2.68 eV). This could be attributed to structural defects as confirmed by diffuse reflectance spectroscopy (DRS), photoluminescence (PL), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. FT-IR, TGA, DTA, DSC, HR-TEM and SEM-EDX measurements yielded information about structural aspects, thermal stability and surface morphology. Surface and pore characteristics of the material were obtained from the BET isotherm for N2 adsorption at 77 K. Zeta potential measurements were used to characterize the electrical properties of the surface while XPS revealed changes in surface states and oxygen deficiencies. The material was found to be an excellent photocatalyst for the degradation of aqueous methylene blue in visible light. The photocatalytic properties of the material were explained on the basis of the narrow band gap, the high surface area and the presence of surface defects. The photocatalytic activity improved in alkaline media [pH 11.0, catalyst load 15 mg in 200 ml dye solution, dye concentration 1 × 10(-6) M (= 0.3198 mg L(-1))] due to the electrostatic attractions between the dye cations and the negative charges on the Ni/Ti LDH surface. The catalytic activity was found to be higher than the common commercial catalysts like ZnO, ZnS, NiO, TiO2 and Degussa P25. The catalytic activity was retained even after five methylene blue degradation cycles, demonstrating that the LDH could be an important addition to the field of wastewater treatment.

  7. [Removal of PO4(3-) from solution, wastewater and seawater by modification and granulation magnesium and aluminium layered double hydroxide].

    PubMed

    Xing, Kun; Wang, Hai-Zeng

    2013-04-01

    Powder layered double hydroxide of Mg-Al LDH were prepared by hydrothermal technology with 500 kg x batch(-1), modified and granulated (MG Mg-Al CLDH) by deposition method. After the modification and granulation, the fixed bed can not be accumulated and clogged by the adsorbents. The PO4(3-) is removed from aqueous solution, wastewater and seawater by MG Mg-Al CLDH with column experiments. It shows that MG Mg-Al CLDH is an effective adsorbent. After removal, the water quality can satisfy with the first degree of integrated wastewater discharge or seawater standards. The mechanism of removal PO4(3-) is ion exchange and 'memory effect'. The breakthrough adsorption capacity of PO4(3-) from solution is 13.49 mg x g(-1), more than 6 times higher than that by Mg-Al LDH without modification. The exhausted MG Mg-Al CLDH can be desorbed with 0.1 mol x L(-1) NaOH and 3 mol x L(-1) NaCl and regenerated with 25% MgCl2. The regeneration rate is 126.24%. The breakthrough curves are influenced by bed depth, flow rate, initial concentration and initial pH. The adsorption processes are controlled by film diffusion. When the initial concentration is as low as 0.38 micromol x L(-1), PO4(3-) can be removed from seawater to satisfy with the first degree of seawater quality. So this work is very useful for the practical application of Mg-Al LDH and the removal of phosphorus.

  8. Evaluation of layered zinc hydroxide nitrate and zinc/nickel double hydroxide salts in the removal of chromate ions from solutions

    NASA Astrophysics Data System (ADS)

    de Oliveira, Henrique Bortolaz; Wypych, Fernando

    2016-11-01

    Layered zinc hydroxide nitrate (ZnHN) and Zn/Ni layered double hydroxide salts were synthesized and used to remove chromate ions from solutions at pH 8.0. The materials were characterized by many instrumental techniques before and after chromate ion removal. ZnHN decomposed after contact with the chromate solution, whereas the layered structure of Zn/Ni hydroxide nitrate (Zn/NiHN) and Zn/Ni hydroxide acetate (Zn/NiHA) remained their layers intact after the topotactic anionic exchange reaction, only changing the basal distances. ZnHN, Zn/NiHN, and Zn/NiHA removed 210.1, 144.8, and 170.1 mg of CrO42-/g of material, respectively. Although the removal values obtained for Zn/NiHN and Zn/NiHA were smaller than the values predicted for the ideal formulas of the solids (194.3 and 192.4 mg of CrO42-/g of material, respectively), the measured capacities were higher than the values achieved with many materials reported in the literature. Kinetic experiments showed the removal reaction was fast. To facilitate the solid/liquid separation process after chromium removal, Zn/Ni layered double hydroxide salts with magnetic supports were also synthesized, and their ability to remove chromate was evaluated.

  9. Interplay between chemical composition and cation ordering in the magnetism of Ni/Fe layered double hydroxides.

    PubMed

    Abellán, Gonzalo; Coronado, Eugenio; Martí-Gastaldo, Carlos; Waerenborgh, Joao; Ribera, Antonio

    2013-09-03

    We report the synthesis of a family of ferrimagnetic NiFe layered double hydroxides (LDHs) with a variable Ni(2+)/Fe(3+) in-plane composition of [Ni(1-x)Fe(x)(OH)2](CO3)(x/2)·yH2O (x = 0.20, 0.25, and 0.33) by following a modified homogeneous precipitation. These layered magnets display high crystallinity, homogeneous hexagonal morphologies, and micrometric size that enable their quantitative exfoliation into single layers by sonomechanical treatment of the solids in polar solvents. This was confirmed by dynamic light scattering, UV-vis spectroscopy, high-resolution transmission electron miscroscopy, and atomic force microscopy methodologies to study the resulting steady suspensions. Our magnetic study reflects that the iron content in the LDH layers controls the overall magnetism of these lamellae. Hence, the gradual replacement of Ni(2+) with Fe(3+) centers introduces a larger amount of antiferromagnetically coupled Fe-OH-Fe pairs across the layers, provoking that the compound with the highest Fe/Ni ratio displays spontaneous magnetization at higher temperatures (T(irr) = 15.1 K) and the hardest coercive field (3.6 kG). Mössbauer spectroscopy confirms that the cation distribution in the layers is not random and reflects the occurrence of Fe clustering due to the higher affinity of Fe(3+) ions to accommodate other homometallic centers in their surroundings. In our opinion, this clarifies the origin of the glassy behavior, also reported for other magnetic LDHs, and points out spin frustration as the most likely cause.

  10. Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

    SciTech Connect

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Arulselvan, Palanisamy; Fakurazi, Sharida; Zainal, Zulkarnain

    2014-09-15

    A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the properties of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro. - Highlights: • We intercalated chlorogenic into Zn/Al-layered double hydroxide by ion-exchange and coprecipitation methods. • The two methods gave nanocomposites

  11. The investigation of Ni-Al and Co-Al based layered double hydroxides and their derived mixed oxides thin films deposited by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Birjega, R.; Matei, A.; Filipescu, M.; Stokker-Cheregi, F.; Luculescu, C.; Colceag, D.; Zavoianu, R.; Pavel, O. D.; Dinescu, M.

    2013-08-01

    Layered Double Hydroxides (LDHs) are host-guest materials consisting of positively charged metal/hydroxides sheets with intercalated anions and water molecules. LDHs can be described by the generic formula [[ṡmHO and their structure is formed by layers containing divalent cations (M2+: Mg, Zn, Ni, Co,…) and trivalent cations (M3+: Al, Ga, Cr,…) with an octahedral coordination. LDH films with well-oriented structure and controlled thickness are needed for numerous applications like sensors, protective coatings, catalysts, components for optoelectronics etc. In this work, we report on the deposition of Ni-Al and Co-Al based LDHs and their derived mixed oxides by pulsed laser deposition as a new approach to fabricate oriented LDHs or highly dispersed metallic mixed oxides. The influence of the laser characteristics, such as wavelength and fluence, on the films properties was studied. The films investigation techniques were X-Ray Diffraction, Atomic Force Microscopy, Scanning Electron Microscopy combined with energy dispersive X-ray analysis, and Secondary Ions Mass Spectrometry.

  12. New layered double hydroxides by prepared by the intercalation of gibbsite

    SciTech Connect

    Rees, Jennifer R.; Burden, Chloe S.; Fogg, Andrew M.

    2015-04-15

    New layered double hydroxides (LDHs) with the composition [MAl{sub 4}(OH){sub 12}]Cl{sub 2}·1.5H{sub 2}O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH){sub 3}, with the appropriate chloride salt in a synthesis in which the water of crystallization is the only solvent present and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature making them comparable to other LDHs in this respect. Reactions under the same conditions with CuCl{sub 2}·2H{sub 2}O and ZnCl{sub 2} failed to form the desired LDHs but those with nitrate salts did lead to the formation of the previously reported [MAl{sub 4}(OH){sub 12}](NO{sub 3}){sub 2}·1.5H{sub 2}O (M=Co, Ni) compounds. - Graphical abstract: New layered double hydroxides (LDHs) with the composition [MAl{sub 4}(OH){sub 12}]Cl{sub 2}·1.5H{sub 2}O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH){sub 3}, with the appropriate chloride salt in a synthesis in which no additional solvent is used and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature. - Highlights: • Synthesis of new layered double hydroxides, [MAl{sub 4}(OH){sub 12}]Cl{sub 2}·1.5H{sub 2}O (M=Co, Ni). • Demonstration of the anion exchange capacity with both organic and inorganic anions. • Demonstration of the generality of the synthesis for LDHs.

  13. Removal of borate by coprecipitation with Mg/Al layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Kurashina, Masashi; Inoue, Tatsuki; Tajima, Chihiro; Kanezaki, Eiji

    2015-03-01

    Borate has been used for various industrial products and excessive dose of boron is harmful to humans. We investigated the removal of borate by direct coprecipitation with Mg/Al layered double hydroxide. In this study, the maximum removal of boron was 90% when Mg 30 mmol and Al 15 mmol at pH = 10 were used for 498 mg/l as B. The boron adsorption isotherms could be fitted to Langmuir model. The calculated constant Ws, saturation limit of boron adsorption, is 25 ± 2 mg/g and it is larger than that of ion exchange reaction (Ws = 15±1 mg/g).

  14. Structure and thermal decomposition of sulfated β-cyclodextrin intercalated in a layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Wang, Ji; Wei, Min; Rao, Guoying; Evans, David G.; Duan, Xue

    2004-01-01

    The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.

  15. Mössbauer and XRD study of intercalated CaFe-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Sipiczki, Mónika; Kuzmann, Ernő; Pálinkó, István; Homonnay, Zoltán; Sipos, Pál; Kukovecz, Ákos; Kónya, Zoltán

    2014-04-01

    N-containing fully saturated (L-prolinate) or aromatic (indole-2-carboxylate) heterocyclic anions were immobilised in CaFe-layered double hydroxide with the dehydration-rehydration method from aqueous ethanol or acetone. The structure of the resulting organic-inorganic hybrids was characterised mainly with powder X-ray diffraction and 57Fe Mössbauer spectroscopy, and as supplementary analysis scanning electron microscopy, energy dispersive X-ray spectroscopy with elemental mapping and molecular modelling were also applied. It was found that the solvent mixture used for the synthesis caused enormous difference in the interlayer spacings of the obtained inorganic-organic hybrids.

  16. Structural characterization and thermal properties of polyamide 6.6/Mg, Al/adipate-LDH nanocomposites obtained by solid state polymerization

    SciTech Connect

    Herrero, M.; Benito, P.; Labajos, F.M.; Rives, V.; Zhu, Y.D.; Allen, G.C.; Adams, J.M.

    2010-07-15

    A new nanocomposite was obtained by dispersing an adipate-modified layered double hydroxide (Ad-LDH) with adipic acid and hexamethylene diamine. These samples were polymerized in the solid phase under a nitrogen flow for 200 min at 190 {sup o}C. The structural and compositional details of the nanocomposite were determined by powder X-ray diffraction (PXRD), fourier transform infrared (FTIR) spectroscopy, focused ion beam (FIB), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The PXRD patterns and FIB images show a partially intercalated and partially exfoliated dispersion of layered crystalline materials in the polyamide 6.6 matrix. The best dispersion level is achieved in polyamide 6.6/LDH nanocomposites with low LDH loading. Some residual tactoids and particle agglomerates are also evident at high concentration. The best thermal stability of the nanocomposites is shown by the sample with 0.1% LDH content, for which it is higher than that of pure polyamide. - Graphical abstract: A new nanocomposite was obtained by compounding an adipate-modified layered double hydroxides (LDH) with adipic acid and hexamethylene diamine. These samples were polymerized in the solid phase under a nitrogen flow for 200 min at 190 {sup o}C. The nanodispersion of LDH in polyamide 6.6 may be qualitatively estimated from the analysis and PXRD patterns and FIB images. The decomposition temperature in the nanocomposite with 0.1 % LDH increases significantly compared to that for pristine PA6.6. .

  17. Double layer hydroxide minerals as host structures for bioorganic molecules. [Abstract only

    NASA Technical Reports Server (NTRS)

    Lee, Ton; Arrhenius, Meichia L.; Hui, Stella S.-Y.; Ring, Ken M.; Gedulin, Benjamin I.; Orgel, Leslie E.; Arrhenius, Gustaf

    1994-01-01

    A central problem in molecular evolution concerns the selective concentration from dilute, multicomponent solution of source molecules into a reactive environment, where formation of larger molecular assemblages can take place. Minerals consisting of positively charged, separable metal hydroxide sheets have proven capable of these functions. This common structural type is represented by minerals such as pyroaurite (Mg-Fe(3+) hydroxide), hydrotalcite (Mg-Al), green rust Fe(2+)-Fe(3+) and others. Effective interlayer sorption is demonstrated for orthophosphate and condensed phosphates, anionic alkyl compounds, polypeptides, nucleic acids, cyanide complexes and glycolaldehyde phosphate, the latter shown to readily oligomerize to form and selectively retain racemic hexose -2, 4, 6-phosphates, preferentially of altrose (Pitsch, et al, 1993). The selective aldomerization and retention effects correlate with the charge distribution in the host mineral structure and the stereochemistry of the substrate molecules. Interaction between nucleic acid bases, and between the cyanide groups of glycolaldehyde phosphate nitrile at the low water activity in the mineral interlayer is indicated by doubling of the monomeric separation of the hydroxide mineral sheets.

  18. Adsorption of charged protein residues on an inorganic nanosheet: Computer simulation of LDH interaction with ion channel

    NASA Astrophysics Data System (ADS)

    Tsukanov, Alexey A.; Psakhie, Sergey G.

    2016-08-01

    Quasi-two-dimensional and hybrid nanomaterials based on layered double hydroxides (LDH), cationic clays, layered oxyhydroxides and hydroxides of metals possess large specific surface area and strong electrostatic properties with permanent or pH-dependent electric charge. Such nanomaterials may impact cellular electrostatics, changing the ion balance, pH and membrane potential. Selective ion adsorption/exchange may alter the transmembrane electrochemical gradient, disrupting potential-dependent cellular processes. Cellular proteins as a rule have charged residues which can be effectively adsorbed on the surface of layered hydroxide based nanomaterials. The aim of this study is to attempt to shed some light on the possibility and mechanisms of protein "adhesion" an LDH nanosheet and to propose a new direction in anticancer medicine, based on physical impact and strong electrostatics. An unbiased molecular dynamics simulation was performed and the combined process free energy estimation (COPFEE) approach was used.

  19. Preparation of Tween 80-Zn/Al-Levodopa-Layered Double Hydroxides Nanocomposite for Drug Delivery System

    PubMed Central

    Kura, Aminu Umar; Hussein-Al-Ali, Samer Hasan; Hussein, Mohd Zobir; Fakurazi, Sharida

    2014-01-01

    We incorporated anti-Parkinsonian drug, levodopa (dopa), in Zn/Al-LDH by coprecipitation method to form dopa-LDH nanocomposite. Further coating of Tween-80 on the external surfaces of dopa-LDH nanocomposite was achieved through the oxygen of C=O group of Tween-80 with the layer of dopa-LDH nanocomposite. The final product is called Tween-dopa-LDH nanocomposite. The X-ray diffraction indicates that the Tween-dopa-LDH nanocomposite was formed by aggregation structure. From the TGA data, the Tween-80 loading on the surface of LDH and dopa-LDH was 8.6 and 7.4%, respectively. The effect of coating process on the dopa release from Tween-dopa-LDH nanocomposite was also studied. The release from Tween-dopa-LDH nanocomposite shows slower release compared to the release of the drug from dopa-LDH nanocomposite as done previously in our study, presumably due to the retarding shielding effect. The cell viability study using PC12 showed improved viability with Tween-80 coating on dopa-LDH nanocomposite as studied by mitochondrial dehydrogenase activity (MTT assay). PMID:24782658

  20. Preparation of Tween 80-Zn/Al-levodopa-layered double hydroxides nanocomposite for drug delivery system.

    PubMed

    Kura, Aminu Umar; Hussein-Al-Ali, Samer Hasan; Hussein, Mohd Zobir; Fakurazi, Sharida

    2014-01-01

    We incorporated anti-Parkinsonian drug, levodopa (dopa), in Zn/Al-LDH by coprecipitation method to form dopa-LDH nanocomposite. Further coating of Tween-80 on the external surfaces of dopa-LDH nanocomposite was achieved through the oxygen of C=O group of Tween-80 with the layer of dopa-LDH nanocomposite. The final product is called Tween-dopa-LDH nanocomposite. The X-ray diffraction indicates that the Tween-dopa-LDH nanocomposite was formed by aggregation structure. From the TGA data, the Tween-80 loading on the surface of LDH and dopa-LDH was 8.6 and 7.4%, respectively. The effect of coating process on the dopa release from Tween-dopa-LDH nanocomposite was also studied. The release from Tween-dopa-LDH nanocomposite shows slower release compared to the release of the drug from dopa-LDH nanocomposite as done previously in our study, presumably due to the retarding shielding effect. The cell viability study using PC12 showed improved viability with Tween-80 coating on dopa-LDH nanocomposite as studied by mitochondrial dehydrogenase activity (MTT assay).

  1. Degradability Enhancement of Poly(Lactic Acid) by Stearate-Zn3Al LDH Nanolayers

    PubMed Central

    Eili, Mahboobeh; Shameli, Kamyar; Ibrahim, Nor Azowa; Yunus, Wan Md Zin Wan

    2012-01-01

    Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn3Al LDH. A solution casting method was used to prepare PLA/stearate-Zn3Al LDH nanocomposites. The anionic clay Zn3Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn3Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn3Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn3Al LDH nanocomposites showed that the presence of around 1.0–3.0 wt % of the stearate-Zn3Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn3Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA. PMID:22942682

  2. Degradability enhancement of poly(lactic acid) by stearate-Zn(3)Al LDH nanolayers.

    PubMed

    Eili, Mahboobeh; Shameli, Kamyar; Ibrahim, Nor Azowa; Yunus, Wan Md Zin Wan

    2012-01-01

    Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn(3)Al LDH. A solution casting method was used to prepare PLA/stearate-Zn(3)Al LDH nanocomposites. The anionic clay Zn(3)Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn(3)Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn(3)Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn(3)Al LDH nanocomposites showed that the presence of around 1.0-3.0 wt % of the stearate-Zn(3)Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn(3)Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA.

  3. LDH isoenzyme blood test

    MedlinePlus

    ... body tissues such as the heart, liver, kidney, skeletal muscle, brain, blood cells, and lungs. LDH exists in ... LDH-5 is highest in the liver and skeletal muscle. All of these can be measured in the ...

  4. A molecular dynamic study of layered hydroxide induced depletion of mobile anions within the extracellular medium

    NASA Astrophysics Data System (ADS)

    Tsukanov, Alexey A.; Psakhie, Sergey G.

    2015-10-01

    The strong surface electric charge density of clay mineral host nanolayers enables their use as host-guest nanohybrids in many different areas of application. In particular, layered double hydroxides (LDH) of metals have found applications in medicine. Drug-LDH or gene-LDH nanohybrids are used for targeted delivery of biomedical agents to diseased cells or cancer cells. Fragments of the LDH host nanolayers may remain both within the cell and in the extracellular medium after drug delivery. How these charged nanosheets affect the cell electrostatics is still poorly understood. In the present paper, the idealized case of a single pure Mg2/Al-LDH nanolayer interacting with the extracellular anion environment was investigated to estimate the order of magnitude of a possible shift of the cell membrane equilibrium potential. An approximate dependence of the change in the chloride equilibrium membrane potential on the concentration of pure Mg2/Al-LDH nanosheets was determined.

  5. Thermal Diffusivity Measurement of Zinc-Aluminum-Layered Double Hydroxide using Photoflash Technique

    NASA Astrophysics Data System (ADS)

    Ranjbar, Maryam; Yunus, W. Mahmood Mat.; Hussein, Mohd Zobir bin; Moksin, Mohd Maarof H. A.; Haydari, Mehdi

    2008-05-01

    The photoflash technique has been widely used for measuring thermal diffusivity of various types of materials. In this report thermal diffusivity of Zn-Al layered double hydroxide synthesized at different ratios of Zn to Al composition is presented. The samples were prepared using Zn(NO3)2 and Al(NO3)3 solutions at pH of 10 by drop wise addition of NaOH solution with vigorous stirring under nitrogen atmosphere. Different compositions of Zn to Al molar ratios were obtained by changing the molar ratio of Zn(NO3)2 to Al(NO3)3. The slurry formed was kept at 70 °C in an oil bath shaker for 18 h, filtered, washed and dried in an oven for 18 h at 70 °C. A simple photo flash and polyvinlidene diflouride (PVDF) film was used as light source and thermal wave detector, respectively. Thermal diffusivity of Zn-Al layered double hydroxide measure at room temperature was found increase with different compositions for Zn-Al ratio of 3-5.

  6. Sandwich-like graphene/polypyrrole/layered double hydroxide nanowires for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Li, Xuejin; Zhang, Yu; Xing, Wei; Li, Li; Xue, Qingzhong; Yan, Zifeng

    2016-11-01

    Electrode design in nanoscale is considered to be ultra-important to construct a superb capacitor. Herein, a sandwich-like composite was made by combining graphene/polypyrrole (GPPY) with nickel-aluminum layered double hydroxide nanowires (NiAl-NWs) via a facile hydrothermal method. This sandwich-like architecture is promising in energy storage applications due to three unique features: (1) the conductive GPPY substrate not only effectively prevents the layered double hydroxides species from aggregating, but also considerably facilitates the electron transmission; (2) the ultrathin NiAl-NWs ensure a maximum exposure of active Ni2+, which can improve the efficiency of rapid redox reactions even at high current densities; (3) the sufficient space between anisotropic NiAl-NWs can accommodate a large volume change of the nanowires to avoid their collapse or distortion during the reduplicative redox reactions. Keeping all these unique features in mind, when the as-prepared composite was applied to supercapacitors, it presented an enhanced capacitive performance in terms of high specific capacitance (845 F g-1), excellent rate performance (67% retained at 30 A g-1), remarkable cyclic stability (92% maintained after 5000 cycles) and large energy density (40.1 Wh·Kg-1). This accomplishment in the present work inspires an innovative strategy of nanoscale electrode design for high-rate performance supercapacitor electrodes containing pseuducapacitive metal oxide.

  7. Organo/layered double hydroxide nanohybrids used to remove non ionic pesticides.

    PubMed

    Chaara, D; Bruna, F; Ulibarri, M A; Draoui, K; Barriga, C; Pavlovic, I

    2011-11-30

    The preparation and characterization of organo/layered double hydroxide nanohybrids with dodecylsulfate and sebacate as interlayer anion were studied in detail. The aim of the modification of the layered double hydroxides (LDHs) was to change the hydrophilic character of the interlayer to hydrophobic to improve the ability of the nanohybrids to adsorb non-ionic pesticides such as alachlor and metolachlor from water. Adsorption tests were conducted on organo/LDHs using variable pH values, contact times and initial pesticide concentrations (adsorption isotherms) in order to identify the optimum conditions for the intended purpose. Adsorbents and adsorption products were characterized several physicochemical techniques. The adsorption test showed that a noticeable increase of the adsorption of the non-ionic herbicides was produced. Based on the results, the organo/LDHs could be good adsorbents to remove alachlor and metolachlor from water. Different organo/LDHs complexes were prepared by a mechanical mixture and by adsorption. The results show that HTSEB-based complex displays controlled release properties that reduce metolachlor leaching in soil columns compared to a technical product and the other formulations. The release was dependent on the nature of the adsorbent used to prepare the complexes. Thus, it can be concluded that organo/LDHs might act as suitable supports for the design of pesticide slow release formulations with the aim of reducing the adverse effects derived from rapid transport losses of the chemical once applied to soils.

  8. On the dielectric response of complex layered oxides: Mica-type silicates and layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Mehrotra, Vivek; Giannelis, Emmanuel P.

    1992-08-01

    The dielectric properties of mica-type silicates and layered double hydroxides have been studied in the pristine and various intercalated forms in the frequency range 101-107 Hz. A relaxation peak has been observed for the pristine silicate, whereas the pristine layered double hydroxide exhibits an anomalous low-frequency dispersion. The dielectric response is rationalized in terms of structural ordering and fluctuation of charge carriers as well as models invoking fractal time processes and fractal structure. The response is also related to the structure and mobility of the intercalated water molecules. In both pristine hosts, the predominant conduction mechanism is proton hopping between sites generated by a network of intercalated water molecules. Silicate intercalated with the insulating form of polyaniline exhibits an almost frequency-independent response. In the case of conducting polyaniline intercalated silicate, where polarons are the majority charge carriers, an anomalous low-frequency dispersion is observed and the response is typical of a metal-insulator composite. Finally, impedance measurements have been used to calculate the spatial disorder and/or surface irregularity of the host layers, expressed by the fractal dimension ds. The changes observed in ds upon intercalation of high-charge ions are correlated to the stacking disorder of the host layers.

  9. Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

    NASA Astrophysics Data System (ADS)

    Barahuie, Farahnaz; Hussein, Mohd Zobir; Arulselvan, Palanisamy; Fakurazi, Sharida; Zainal, Zulkarnain

    2014-09-01

    A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the properties of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro.

  10. Controlled release of ketorolac through nanocomposite films of hydrogel and LDH nanoparticles

    NASA Astrophysics Data System (ADS)

    Xu, Zhi Ping; Gu, Zi; Cheng, Xiaoxi; Rasoul, Firas; Whittaker, Andrew K.; Lu, Gao Qing Max

    2011-03-01

    A novel nanocomposite film for sustained release of anionic ophthalmic drugs through a double-control process has been examined in this study. The film, made as a drug-loaded contact lens, consists principally of a polymer hydrogel of 2-hydroxyethyl methacrylate (HEMA), in whose matrix MgAl-layered double hydroxide (MgAl-LDH) nanoparticles intercalated with the anionic drug are well dispersed. Such nanocomposite films (hydrogel-LDH-drug) contained 0.6-0.8 mg of MgAl-LDH and 0.08-0.09 mg of the ophthalmic drug (ketorolac) in 1.0 g of hydrogel. MgAl-drug-LDH nanoparticles were prepared with the hydrodynamic particle size of 40-200 nm. TEM images show that these nanoparticles are evenly dispersed in the hydrogel matrix. In vitro release tests of hydrogel-LDH-drug in pH 7.4 PBS solution at 32 °C indicate a sustained release profile of the loaded drug for 1 week. The drug release undergoes a rapid initial burst and then a monotonically decreasing rate up to 168 h. The initial burst release is determined by the film thickness and the polymerization conditions, but the following release rate is very similar, with the effective diffusion coefficient being nearly constant (3.0 × 10-12 m2/s). The drug release from the films is mechanistically attributed to anionic exchange and the subsequent diffusion in the hydrogel matrix.

  11. Microwave-assisted melt reaction method for the intercalation of carboxylic acid anions into layered double hydroxides.

    PubMed

    Rosa, Roberto; Leonelli, Cristina; Villa, Carla; Priarone, Giulia

    2013-01-01

    Carboxylic acid anions intercalated layered double hydroxides are currently gaining increasing interest due to their potential applications in pharmaceutical field for controlled drug release in novel tunable drug delivery systems. In this work different aliphatic carboxylic acid anions were intercalated into the interlayers of commercial as well as synthetically prepared layered double hydroxides, through a novel microwave mediated melt reaction approach. The volumetric nature of microwave dielectric heating was exploited in order to rapidly heat the intimate mixture of the lamellar inorganic precursor and the appropriate organic acid, at the melting temperature of the particular mono- or dicarboxylic acid used, reaching the intercalation in approximately two hours treatment.

  12. Spontaneous magnetization in Ni-Al and Ni-Fe layered double hydroxides.

    PubMed

    Coronado, Eugenio; Galán-Mascarós, José R; Martí-Gastaldo, Carlos; Ribera, Antonio; Palacios, Elías; Castro, Miguel; Burriel, Ramón

    2008-10-06

    Layered double hydroxides containing paramagnetic Ni (II) and diamagnetic/paramagnetic Al (III)/Fe (III) ions have been prepared and characterized. Ni 2Al(OH) 6(NO 3). nH 2O ( 1), Ni 2Fe(OH) 6(NO 3). nH 2O ( 2), Ni 2Fe(OH) 6(C 6H 8O 4) 0.5. nH 2O ( 3), and Ni 2Fe(OH) 6(C 10H 16O 4) 0.5. nH 2O ( 4) were prepared by coprecipitation at controlled pH as polycrystalline materials with the typical brucite-like structure, with alternating layers of hydroxide and the corresponding anions, which determine the interlayer separation. Magnetic studies show the appearance of spontaneous magnetization between 2 and 15 K for these compounds. Interestingly, the onset temperature for spontaneous magnetization follows a direct relationship with interlayer separation, since this is the only magnetic difference between compounds 2, 3, and 4. Magnetic and calorimetric data indicate that long-range magnetic ordering is not occurring in any of these materials, but rather a freezing of the magnetic system in 3D due to the magnetic disorder and competing intra- and interlayer interactions. Thus, these hydrotalcite-like magnetic materials can be regarded as spin glasses.

  13. Phosphate adsorption from sewage sludge filtrate using zinc-aluminum layered double hydroxides.

    PubMed

    Cheng, Xiang; Huang, Xinrui; Wang, Xingzu; Zhao, Bingqing; Chen, Aiyan; Sun, Dezhi

    2009-09-30

    A series of layered double hydroxides (LDHs) with different metal cations were synthesized to remove phosphate in waste sludge filtrate from a municipal wastewater treatment plant for phosphorus recovery and to help control eutrophication. The highest phosphate adsorption capacity was obtained by using Zn-Al-2-300, that is LDHs with Zn/Al molar ratio of 2 and calcined at 300 degrees C for 4h. Circumneutral and mildly alkaline waters appeared suitable for the possible application of Zn-Al LDHs due to the amphoteric nature of aluminum hydroxide. Phosphate adsorption from the sludge filtrate by the LDHs followed pseudo-second-order kinetics, and the adsorption capacity at equilibrium was determined to be approximately 50 mg P/g. Adsorption isotherms showed that phosphate uptake in this study was an endothermic process and had a good fit with a Langmuir-type model. The absorbed phosphate can be effectively desorbed (more than 80%) from LDHs particles by a 5 wt% NaOH solution. The regeneration rate of used LDHs was approximately 60% after six cycles of adsorption-desorption-regeneration.

  14. The intercalation of bicyclic and tricyclic carboxylates into layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Khan, Aamir I.; Williams, Gareth R.; Hu, Gang; Rees, Nicholas H.; O'Hare, Dermot

    2010-12-01

    Twenty-four nanocomposites built from layered double hydroxides and bicyclic and tricyclic carboxylates have been synthesised for the first time. Eight carboxylates were successfully intercalated into [LiAl 2(OH) 6]Cl· yH 2O, [Ca 2Al(OH) 6]NO 3· yH 2O, and [Mg 2Al(OH) 6]NO 3· yH 2O, and the products fully characterised. Guest species incorporated include 1-adamantane carboxylate (1- AC) and 5-norbornene-2- endo-3- exo-dicarboxylate. In some cases, carbonate anions were co-intercalated with the organic guest, and in others poorly crystalline aluminium hydroxides formed as by-products. Sharper resonances were observed in the 13C solid-state NMR spectra of the 1- AC intercalates than in the spectrum of pure 1- AC, suggesting increased order in the arrangement of the cyclic cages in the intercalates. Where possible, time-resolved in situ X-ray diffraction was employed to study the nanoscopic steps involved in the intercalation reactions. These investigations showed that the reactions are one-step processes, proceeding directly to the fully exchanged intercalate with no intermediate phases. The intercalation processes were found to be nucleation controlled.

  15. Double-blind clinical, endoscopic and histological comparison of hydrotalcite/dimethicone suspension and magnesium hydroxide/aluminum hydroxide suspension in the treatment of symptomatic gastritis.

    PubMed

    Cobden, I; McMahon, M J; Dixon, M F; Axon, A T

    1981-01-01

    A double-blind, randomized trial was undertaken to compare the clinical, endoscopic and histological response to 6-weeks' treatment with hydrotalcite/dimethicone suspension or magnesium hydroxide/aluminum hydroxide suspension in 36 patients with symptomatic gastritis. Significantly more patients (P less than 0.05) showed symptomatic improvement in the antacid-treated group than in the hydrotalcite/dimethicone-treated group and more had a reduction in histological inflammatory scores (P less than 0.01), although there was little correlation between histology and symptoms. There was no evidence from this study that the bile acid binding and anti-foaming properties of hydrotalcite/dimethicone suspension were of any benefit in the treatment of patients with symptomatic gastritis.

  16. Intercalation of luminescent Europium(III) complexes in layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Sarakha, L.; Forano, C.; Boutinaud, P.

    2009-01-01

    Anionic Europium(III) complexes EuL1, EuL2 and EuL3 (L1 = tris (dipicolinate), L2 = diethylenetriaminepentaacetate, L3 = disulfonated bathophenanthroline tris(dibenzoylmethanate) were intercalated in Zn 2Al(OH) 6Cl, nH 2O and Zn 4Al(OH) 10Cl, nH 2O layered double hydroxides (LDHs). Intercalation was confirmed by X-ray diffraction, vibration spectroscopy and photoluminescence measurements, using Eu(III) as a local structural probe. Information on host-guest interactions in the hybrid materials were deduced by analyzing the intensity parameter Ω 2, the energy position of the 5D 0- 7F 0 transition and the emission decay profile of the prominent hypersensitive red 5D 0- 7F 2 emission.

  17. Stabilization of Co{sup 2+} in layered double hydroxides (LDHs) by microwave-assisted ageing

    SciTech Connect

    Herrero, M.; Benito, P.; Labajos, F.M.; Rives, V.

    2007-03-15

    Co-containing layered double hydroxides at different pH have been prepared, and aged following different routes. The solids prepared have been characterized by element chemical analysis, powder X-ray diffraction, thermogravimetric and differential thermal analyses (both in nitrogen and in oxygen), FT-IR and Vis-UV spectroscopies, temperature-programmed reduction and surface area assessment by nitrogen adsorption at -196 deg. C. The best conditions found to preserve the cobalt species in the divalent oxidation state are preparing the samples at controlled pH, and then submit them to ageing under microwave irradiation. - Graphical abstract: The use of microwave-hydrothermal treatment, controlling both temperature and ageing time, permits to synthesize well-crystallized nanomaterials with controlled surface properties. An enhancement in the crystallinity degree and an increase in the particle size are observed when the irradiation time is prolonged.

  18. Preparation and characterization of trans-RhCl(CO)(TPPTS){sub 2}-intercalated layered double hydroxides

    SciTech Connect

    Zhang Xian; Wei Min; Pu Min; Li Xianjun; Chen Hua; Evans, David G.; Duan Xue . E-mail: duanx@mail.buct.edu.cn

    2005-09-15

    trans-RhCl(CO)(TPPTS){sub 2} (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and {sup 31}P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS){sub 2} was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS){sub 2} is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins.

  19. Methotrexate intercalated layered double hydroxides with the mediation of surfactants: Mechanism exploration and bioassay study.

    PubMed

    Dai, Chao-Fan; Tian, De-Ying; Li, Shu-Ping; Li, Xiao-Dong

    2015-12-01

    Methotrexatum intercalated layered double hydroxides (MTX/LDHs) hybrids were synthesized by the co-precipitation method and three kinds of nonionic surfactants with different hydrocarbon chain lengths were used. The resulting hybrids were then characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). XRD and FTIR investigations manifest the successful intercalation of MTX anions into the interlayer of LDHs. TEM graphs indicate that the morphology of the hybrids changes with the variation of the chain length of the surfactants, i.e., the particles synthesized using polyethylene glycol (PEG-7) present regular disc morphology with good monodispersity, while samples with the mediation of alkyl polyglycoside (APG-14) are heavily aggregated and samples with the addition of polyvinylpyrrolidone (PVP-10) exhibit irregular branches. Furthermore, the release and bioassay experiments show that monodisperse MTX/LDHs present good controlled-release and are more efficient in the suppression of the tumor cells.

  20. [Adsorption of perchlorate by calcined Mg/Zn/Al layered double hydroxides].

    PubMed

    Wang, Hong-Yu; Liu, Yan

    2014-07-01

    The adsorption capacity of perchlorate by Mg/Zn/Al layered double hydroxides was investigated. The samples were characterized by X-ray diffraction (XRD) and the adsorption isothermal model and dynamic model were discussed. The effect of calcination temperature, Mg/Zn/Al molar ratio, pH value of solution, adsorption time and dosage on the adsorption capacity of samples were studied. The experiment results showed that the removal ratio and adsorption capacity reached the highest and the pH value had good applicability when the molar ratio was Mg/Zn/Al = 2: 1 : 1. The adsorption of perchlorate basically conformed to the pseudo-second kinetics and Langmuir, Freundlich isotherm model.

  1. Atomistic simulation of nanoporous layered double hydroxide materials and their properties. I. Structural modeling.

    PubMed

    Kim, Nayong; Kim, Yongman; Tsotsis, Theodore T; Sahimi, Muhammad

    2005-06-01

    An atomistic model of layered double hydroxides, an important class of nanoporous materials, is presented. These materials have wide applications, ranging from adsorbents for gases and liquid ions to nanoporous membranes and catalysts. They consist of two types of metallic cations that are accommodated by a close-packed configuration of OH- and other anions in a positively charged brucitelike layer. Water and various anions are distributed in the interlayer space for charge compensation. A modified form of the consistent-valence force field, together with energy minimization and molecular dynamics simulations, is utilized for developing an atomistic model of the materials. To test the accuracy of the model, we compare the vibrational frequencies, x-ray diffraction patterns, and the basal spacing of the material, computed using the atomistic model, with our experimental data over a wide range of temperature. Good agreement is found between the computed and measured quantities.

  2. Atomistic simulation of nanoporous layered double hydroxide materials and their properties. I. Structural modeling

    NASA Astrophysics Data System (ADS)

    Kim, Nayong; Kim, Yongman; Tsotsis, Theodore T.; Sahimi, Muhammad

    2005-06-01

    An atomistic model of layered double hydroxides, an important class of nanoporous materials, is presented. These materials have wide applications, ranging from adsorbents for gases and liquid ions to nanoporous membranes and catalysts. They consist of two types of metallic cations that are accommodated by a close-packed configuration of OH- and other anions in a positively charged brucitelike layer. Water and various anions are distributed in the interlayer space for charge compensation. A modified form of the consistent-valence force field, together with energy minimization and molecular dynamics simulations, is utilized for developing an atomistic model of the materials. To test the accuracy of the model, we compare the vibrational frequencies, x-ray diffraction patterns, and the basal spacing of the material, computed using the atomistic model, with our experimental data over a wide range of temperature. Good agreement is found between the computed and measured quantities.

  3. A study on the structure and electrochemical characteristics of a Ni/Al double hydroxide

    NASA Astrophysics Data System (ADS)

    Zhen, Fu Zhong; Quan, Jiang Wen; Min, Yu Li; Peng, Zhang; Jun, Jiang Li

    2004-10-01

    Aluminium-substituted nickel based layered double hydroxides (LDHs), Ni0.78Zn0.04Co0.04Co0.02Al0.16(OH)2(CO3)0.08· 1.0H2O, were synthesized by a chemical co-precipitating process. It was shown that the structure of the LDHs is similar with that of α-Ni(OH)2 investigated by X-ray diffraction and transmission electron microscopy. The electrode comprising the LDHs was charged/discharged according to a galvanostatic model, and displayed better discharge capacity than the common β-Ni(OH)2 electrode. In addition, the effects of losing structure water on structure and electrochemical performance were investigated.

  4. Preparation and characterization of trans-RhCl(CO)(TPPTS) 2-intercalated layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, Xian; Wei, Min; Pu, Min; Li, Xianjun; Chen, Hua; Evans, David G.; Duan, Xue

    2005-09-01

    trans-RhCl(CO)(TPPTS) 2 (TPPTS= tris( m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and 31P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS) 2 was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS) 2 is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins.

  5. Intercalation of Layered Silicates, Layered Double Hydroxides, and Lead Iodide: Synthesis, Characterization and Properties.

    NASA Astrophysics Data System (ADS)

    Mehrotra, Vivek

    Layered silicates, layered double hydroxides, and lead iodide are lamellar solids that can incorporate guest species into the galleries between their layers. Various intercalated forms of these layered materials have been synthesized and their properties studied. The dielectric behavior of pristine fluorohectorite, a typical layered silicate, and Zn-Al layered double hydroxide is explained by considering the structural ordering and mobility of the intercalated water molecules, as well as models invoking fractal time processes and fractal structure. Intercalative polymerization of aniline and pyrrole into fluorohectorite leads to a multilayered structure consisting of single polymer chains alternately stacked with the 9.6 A thick silicate layers. The polymer chains are confined to the quasi two-dimensional interlayer space between the rigid host layers. The hybrid films exhibit highly anisotropic properties. The optical, electrical and mechanical behavior is discussed in terms of the molecular confinement of the polymer chains. Ethylenediamine functionalized C _{60} clusters have also been intercalated into fluorohectorite via an ion-exchange procedure. Intercalation results in an improved thermal stability of the functionalized C_{60} clusters. Rutherford backscattering spectrometry has been used to elucidate the mechanism of intercalative ion exchange of silver in muscovite mica, a layered silicate with a layer charge density of 2e per unit cell. It is proposed that ion-exchange progresses by intercalating successive galleries through the edges of the mica layers. Guest-host interactions have been studied in the system aniline-PbI_2. The optical and structural effects of aniline intercalation in lead iodide thin films is discussed. Intercalation leads to a large shift in the optical band gap of PbI_2. The observed change in band gap is not only due to the increased separation between the PbI_2 layers but also because of an electrostatic interaction between the

  6. Ordered poly(p-phenylene)/layered double hydroxide ultrathin films with blue luminescence by layer-by-layer assembly.

    PubMed

    Yan, Dongpeng; Lu, Jun; Wei, Min; Han, Jingbin; Ma, Jing; Li, Feng; Evans, David G; Duan, Xue

    2009-01-01

    Lavender layers: A poly(p-phenylene) anionic derivate and exfoliated Mg-Al layered double hydroxide monolayers were assembled into ultrathin films with well-defined blue fluorescence (see picture; the numbers indicate the number of bilayers), long-range order, and high photostability. These films work as multiple quantum-well structures for valence electrons.

  7. Combined chemotherapy and photodynamic therapy using a nanohybrid based on layered double hydroxides to conquer cisplatin resistance.

    PubMed

    Wang, Zhigang; Ma, Rong; Yan, Li; Chen, Xianfeng; Zhu, Guangyu

    2015-07-25

    A nanohybrid is assembled by ratiometrically co-loading Pt(IV) prodrugs and photosensitizers into layered double hydroxide nanoparticles. The nanohybrid shows synergistic cell-killing effects and is significantly active against the proliferation of cisplatin-resistant human cancer cells with nanomolar IC50 values. Profound mechanistic investigations confirm its action mode of combined chemo- and photodynamic therapy.

  8. Synthesis of Zn/Co/Fe-layered double hydroxide nanowires with controllable morphology in a water-in-oil microemulsion

    SciTech Connect

    Wu Hongyu; Jiao Qingze; Zhao Yun; Huang Silu; Li Xuefei; Liu Hongbo; Zhou Mingji

    2010-02-15

    The Zn/Co/Fe-layered double hydroxide nanowires were synthesized via a reverse microemulsion method by using cetyltrimethyl ammonium bromide (CTAB) /n-hexane/n-hexanol/water as Soft-Template. ZnSO{sub 4}, CoSO{sub 4}, Fe{sub 2}(SO{sub 4}){sub 3} and urea were used as raw materials. The influence of reaction temperature, time, urea concentration and Cn (molar ratio of cetyltrimethyl ammonium bromide to water) on the structure and morphology of Zn/Co/Fe-layered double hydroxides was investigated. The samples were characterized using Transmission Electron Microscopy (TEM), Inductively Coupled Plasma (ICP), X-ray Diffraction (XRD) and Infrared Absorption Spectrum (IR). The results indicate that higher temperature is beneficial to the formation of layered double hydroxides, but particles apart from nanowires could be produced if temperature is up to 120 deg. C. By varying the temperature, reaction time, urea concentration and Cn, we got the optimum conditions of synthesizing uniform Zn/Co/Fe-layered double hydroxide nanowires: 100 deg. C, more than 12 h, Cn: 30-33, urea concentration: 0.3 M.

  9. Radiation induced topotactic [2 + 2] dimerisation of acrylate derivatives among the layers of a CaFe layered double hydroxide followed by IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Srankó, D. F.; Canton, S.; Enghdahl, A.; Muráth, Sz.; Kukovecz, Á.; Kónya, Z.; Sipiczki, M.; Sipos, P.; Pálinkó, I.

    2013-07-01

    Various acrylates [E-phenylpropenoate, E-3(4‧-nitrophenyl)propenoate, E-3(2‧,5‧-difluorphenyl)propenoate, E-3(2‧-thienyl)propenoate, E-3(4‧-imidazolyl)propenoate or E-2,3-dimethylpropenoate] were successfully intercalated into Ca(II)Fe(III) layered double hydroxide (CaFe-LDH) verified by a range of instrumental methods. The possible arrangements for the organic anions were suggested on the basis of basal spacing data, layer thickness and the dimensions of the quantum chemically optimised structures of the acrylate ions. Using the acrylate-CaFe-LDHs as reactant-filled nanoreactors, photoinitiated topotactic [2 + 2] cyclisation reactions followed by IR spectroscopy could be performed with many representatives [E-phenylpropenoate-, E-3(4‧-nitrophenyl)propenoate-, E-3(2‧,5‧-difluorphenyl)propenoate- or E-3(2‧-thienyl)propenoate-CaFe-LDHs] resulting in cyclobutane derivatives within the layers of the host material indicating that there were domains where the intercalated anions were in close proximity to each other and in proper arrangement for the reaction to occur.

  10. Zinc/Aluminum layered double hydroxide-titanium dioxide composite nanosheet film as novel solid phase microextraction fiber for the gas chromatographic determination of valproic acid.

    PubMed

    Matin, Amir Abbas; Biparva, Pourya; Amanzadeh, Hatam; Farhadi, Khalil

    2013-01-15

    A nanosheet thin film based on Zn/Al layered double hydroxide (LDH) and TiO(2) composite was prepared via sol-gel process on capillary glass rod. Characterization of the fiber coating using X-ray diffraction (XRD) pattern and scanning electron microscopy (SEM) images showed that it consists of a large number of intercrossed and curved nanosheets with hexagonal architecture. The thickness of these plates is about few nanometers, and the lateral dimension is varying from 400 to 1000 nm. Application of the proposed coating as a solid phase microextraction fiber was investigated. As a model analyte, valproic acid (VPA, antiepileptic drug) was selected and its extraction from biological (human serum) and pharmaceutical (tablet and syrup) samples were performed without any considerable matrix effect. Analytical merits of the method, under optimum conditions (extraction temperature: 50 ± 1°C, extraction time: 15 min, desorption temperature: 250°C, desorption time: 2 min, solution pH: 1.5, salt concentration: 5 mol L(-1)), are 70 μg L(-1) and 0.20-100 mg L(-1) for LOD and LDR, respectively.

  11. Enhanced photocatalytic activity of TiO2-impregnated with MgZnAl mixed oxides obtained from layered double hydroxides for phenol degradation

    NASA Astrophysics Data System (ADS)

    de Almeida, Marciano Fabiano; Bellato, Carlos Roberto; Mounteer, Ann Honor; Ferreira, Sukarno Olavo; Milagres, Jaderson Lopes; Miranda, Liany Divina Lima

    2015-12-01

    A series of TiO2/MgZnAl photocatalysts were successfully synthesized from ternary (Mg, Zn and Al) layered double hydroxides impregnated with TiO2 nanoparticles by the co-precipitation method at variable pH with different Zn2+/Mg2+ molar ratios. The composite photocatalysts were calcined at 500 °C resulting in the incorporation of oxide zinc, in the calcined MgZnAl LDH structure. Synergistic effect between ZnO and TiO2 lead to significant enhancement of TiO2/MgZnAl photocatalytic activity. Composite photocatalysts were characterized by ICP-MS, N2 adsorption-desorption, XRD, SEM, EDS, IR and UV-vis DRS. Phenol in aqueous solution (50 mg/L) was used as a model compound for evaluation of UV-vis (filter cut-off for λ > 300 nm) photocatalytic activity. The most efficient photocatalyst composite was obtained at a 5% Zn2+/Mg2+ molar ratio, in the catalyst identified as TiO2/MgZnAl-5. This composite catalyst had high photocatalytic activity, completely destroying phenol and removing 80% of total organic carbon in solution after 360 min. The TiO2/MgZnAl-5 catalyst remained relatively stable, presenting a 15% decrease in phenol degradation efficiency after five consecutive photocatalytic cycles.

  12. DOUBLE SHELL TANK (DST) HYDROXIDE DEPLETION MODEL FOR CARBON DIOXIDE ABSORPTION

    SciTech Connect

    OGDEN DM; KIRCH NW

    2007-10-31

    This document generates a supernatant hydroxide ion depletion model based on mechanistic principles. The carbon dioxide absorption mechanistic model is developed in this report. The report also benchmarks the model against historical tank supernatant hydroxide data and vapor space carbon dioxide data. A comparison of the newly generated mechanistic model with previously applied empirical hydroxide depletion equations is also performed.

  13. Efficient delivery of anticancer drug MTX through MTX-LDH nanohybrid system

    NASA Astrophysics Data System (ADS)

    Oh, Jae-Min; Park, Man; Kim, Sang-Tae; Jung, Jin-Young; Kang, Yong-Gu; Choy, Jin-Ho

    2006-05-01

    We have been successful to intercalate anticancer drug, methotrexate (MTX), into layered double hydroxides (LDHs), Mg2Al(OH)6(NO3)·0.1H2O, through conventional co-precipitation method. Layered double hydroxides (LDHs) are endowed with great potential for delivery vector, since their cationic layers lead to safe reservation of biofunctional molecules such as drug molecules or genes. And their ion exchangeability and solubility in acidic media (pH<4) give rise to the controlled release of drug molecules. Moreover, it has been partly confirmed that LDH itself is non-toxic and facilitate the cellular permeation. To check the toxicity of LDHs, the osteosarcoma cell culture lines (Saos-2 and MG-63) and the normal one (human fibroblast) were used for in vitro test. The anticancer efficacy of MTX intercalated LDHs (MTX-LDH nanohybrids) was also estimated in vitro by the bioassay such as MTT and BrdU (5-bromo-2-deoxyuridine) with the bone cancer cell culture lines (Saos-2 and MG-63). According to the toxicity test results, LDHs do not harm to both the normal and cancer cells upto the concentration of 500 ug/mL. The anticancer efficacy test for the MTX-LDH nanohybrids turn out to be much more effective in cell suppression compared to the MTX itself. According to the cell-line tests, the MTX-LDH shows same drug efficacy to the MTX itself in spite of the low concentration by ˜5000 times. Such a high cancer suppression effect of MTX-LDH hybrid is surely due to the excellent delivery efficiency of inorganic delivery vector, LDHs.

  14. Structure models for the hydrated and dehydrated nitrate-intercalated layered double hydroxide of Li and Al.

    PubMed

    Nagendran, Supreeth; Periyasamy, Ganga; Kamath, P Vishnu

    2016-11-15

    Imbibition of LiNO3 into gibbsite results in the formation of a single phase layered double hydroxide of the composition LiAl2(OH)6(NO3)·1.2H2O. This phase undergoes reversible dehydration along with the compression of the basal spacing accompanied by the reorientation of the nitrate in the interlayer gallery. The hydrated phase is a solid solution of two lattices: (i) a hexagonal lattice defining the ordering of atoms within the metal hydroxide layer, and (ii) a lattice of orthorhombic symmetry defining the ordering of atoms within the interlayer. DFT calculations of the hydration behaviour show that there is no registry between the two sublattices. In the dehydrated phase, the nitrate ion is intercalated with its molecular plane parallel to the metal hydroxide layer and the crystal adopts a structure of hexagonal symmetry.

  15. Structural characterization and thermal properties of polyamide 6.6/Mg, Al/adipate-LDH nanocomposites obtained by solid state polymerization

    NASA Astrophysics Data System (ADS)

    Herrero, M.; Benito, P.; Labajos, F. M.; Rives, V.; Zhu, Y. D.; Allen, G. C.; Adams, J. M.

    2010-07-01

    A new nanocomposite was obtained by dispersing an adipate-modified layered double hydroxide (Ad-LDH) with adipic acid and hexamethylene diamine. These samples were polymerized in the solid phase under a nitrogen flow for 200 min at 190 °C. The structural and compositional details of the nanocomposite were determined by powder X-ray diffraction (PXRD), fourier transform infrared (FTIR) spectroscopy, focused ion beam (FIB), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The PXRD patterns and FIB images show a partially intercalated and partially exfoliated dispersion of layered crystalline materials in the polyamide 6.6 matrix. The best dispersion level is achieved in polyamide 6.6/LDH nanocomposites with low LDH loading. Some residual tactoids and particle agglomerates are also evident at high concentration. The best thermal stability of the nanocomposites is shown by the sample with 0.1% LDH content, for which it is higher than that of pure polyamide.

  16. Photophysical properties of donor- N-Ary-Product -acceptor azoic chromophores adsorbed and intercalated into Mg--Al--LDH

    SciTech Connect

    Li, Lei; Liu, Pengfei; Zhang, Li; Chen, Dazhou

    2013-02-15

    Ethyl Orange (EO) and 4-aminoazobenzene-4-sulfonic (AS) anions with Donor- N-Ary-Product -Acceptor structure have been intercalated into the layered double hydroxide (LDH), [Mg{sub 0.66} Al{sub 0.34} (OH){sub 2}] (CO{sub 3}){sub 0.17}{center_dot}0.67H{sub 2}O or adsorbed on the external surface of the host by the method of ion-exchange procedures. The photoabsorption and fluorescence properties of the obtained compounds were different from the pure solid phase of EO and AS. It was suggested that the photophysical properties of guests were closely related to the geometry and electrical structure of the guest molecule, which can affect the distribution and orientation of the guests in the layers or on the surface of the host. The host-guest interactions modulate photophysical properties of guest. In addition, the guest having higher molecular dipole moments surface exchanged on Mg--Al--CO{sub 3}--LDH are beneficial to the enhancement of the blue emission than that of intercalation into LDH. - Graphical abstract: Emission spectra of (a) EO (b) EO surface exchanged on Mg--Al--CO{sub 3}--LDH (c) Mg--Al--EO--LDH. Emission spectra of (a) AS (b) Mg--Al--AS--LDH (c) AS surface exchanged on Mg--Al--CO{sub 3}--LDH. The guests having higher molecular dipole moments surface exchanged on Mg--Al--CO{sub 3}--LDH are beneficial to the enhancement of the blue emission than that of intercalation into LDH. Highlights: Black-Right-Pointing-Pointer EO and AS are intercalated into LDHs or adsorbed on the external surface of LDHs. Black-Right-Pointing-Pointer The host-guest interactions modulate photophysical properties of the guest. Black-Right-Pointing-Pointer The guests having higher molecular dipole moments can enhance the blue emission.

  17. Enhanced photocatalytic properties of the 3D flower-like Mg-Al layered double hydroxides decorated with Ag{sub 2}CO{sub 3} under visible light illumination

    SciTech Connect

    Ao, Yanhui Wang, Dandan; Wang, Peifang; Wang, Chao; Hou, Jun; Qian, Jin

    2016-08-15

    Highlights: • 3D flower-like Ag{sub 2}CO{sub 3}/Mg-Al layered double hydroxide composite was prepared. • The nanocomposites exhibited high photocatalytic activities on different organic pollutants. • The mechanism of the enhanced activity were investigated. - Abstract: A facile anion-exchange precipitation method was employed to synthesize 3D flower-like Ag{sub 2}CO{sub 3}/Mg-Al layered double hydroxide composite photocatalyst. Results showed that Ag{sub 2}CO{sub 3} nanoparticles dispersed uniformly on the petals of the flower-like Mg-Al LDH. The obtained nanocomposites exhibited high photocatalytic activities on different organic pollutants (cationic and anionic dyes, phenol) under visible light illumination. The high photocatalytic activity can be ascribed to the special structure which accomplishes the wide-distribution of Ag{sub 2}CO{sub 3} nanoparticles on the surfaces of the 3D flower-like nanocomposites. Therefore, it can provide much more active sites for the degradation of organic pollutant. Then the photocatalytic mechanism was also verified by reactive species trapping experiments in detail. The work would pave a facile way to prepare LDHs based hierarchical photocatalysts with high activity for the degradation of wide range organic pollutants under visible light irradiation.

  18. Universal biomimetic preparation and immobilization of layered double hydroxide films and adsorption behavior

    NASA Astrophysics Data System (ADS)

    Zhou, Wei; Zhang, Wenpeng; Chen, Zilin

    2017-01-01

    Preparation and immobilization of layered double hydroxides (LDHs) film onto multiple substrates is important and challenging in functional materials fields by date. In this work, a simple and universal polydopamine (PD)-based layer-by-layer assembly strategy was developed for the immobilization of LDHs film onto surfaces such as polypropylene chip, glass slides and metal coins. The surface of substrates was firstly modified by polydopamine functionalization, and then LDHs film was synthesized via urea method and directly immobilized on the PD layer by in situ growing strategy in one step. The PD layer as well as the final LDHs film was characterized by energy dispersive X-ray spectroscopy, scanning electron microscope, infrared spectroscopy, X-ray diffraction pattern and X-ray photoelectron spectra. It has been demonstrated the formation of the dense and homogeneous nanoscaled LDHs film with 400 nm thickness. Adsorption behavior of the fabricated NiAl-LDHs film toward anionic dyes and pharmaceuticals was further assessed. To demonstrate their extensive application, fast and high efficient adsorption of anionic dyes and pharmaceuticals was achieved by NiAl-LDHs-modified polypropylene centrifugal tube.

  19. Formation of nematic liquid crystals of sterically stabilized layered double hydroxide platelets.

    PubMed

    Mourad, Maurice C D; Devid, Edwin J; van Schooneveld, Matti M; Vonk, Chantal; Lekkerkerker, Henk N W

    2008-08-21

    Colloidal platelets of hydrotalcite, a layered double hydroxide, have been prepared by coprecipitation at pH 11-12 of magnesium nitrate and aluminum nitrate at two different magnesium to aluminum ratios. Changing the temperature and ionic strength during hydrothermal treatment, the platelets were tailored to different sizes and aspect ratios. Amino-modified polyisobutylene molecules were grafted onto the platelets following a convenient new route involving freeze-drying. Organic dispersions in toluene were prepared of the particles with the largest size and highest aspect ratio. The colloidal dispersions prepared in this way showed isotropic-nematic phase transitions above a limiting concentration in a matter of days. The number density at the transition and the width of the biphasic region were determined and compared to theory. The orientation of the platelets in nematic droplets (tactoids) and at the isotropic-nematic interface were analyzed by polarization microscopy. It was observed that sedimentation induces a nematic layer in samples that are below the limiting concentration for isotropic-nematic phase separation. No nematic phase was observed in the initial aqueous suspensions of the ungrafted particles.

  20. Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides

    NASA Astrophysics Data System (ADS)

    García-García, J. M.; Pérez-Bernal, M. E.; Ruano-Casero, R. J.; Rives, V.

    2007-12-01

    Layered double hydroxides with the hydrotalcite-like structures, containing Mg 2+ and Al 3+, doped with Cr 3+ and Y 3+, have been prepared by precipitation at constant pH. The weight percentages of Cr 3+ and Y 3+ were 1, 2, or 3%, and 0.5 or 1%, respectively. Single phases were obtained in all cases, whose crystallinity decreased as the content in Cr and Y was increased. The solids have been characterised by element chemical analysis, powder X-ray diffraction, thermal analyses (differential, thermogravimetric and programmed reduction), FT-IR and UV-vis spectroscopies; the specific surface areas have been determined from nitrogen adsorption isotherms at -196 °C. Upon calcination at 1200 °C for 5 h in air all solids display a mixed structure (spinel and rock salt for MgO); these solids have also been characterised by these techniques and their chromatic coordinates (CIE - L∗a∗b∗) have been determined. Their pink colour makes these solids suitable for being used as ceramic pigments.

  1. Morphologies developed by the drying of droplets containing dispersed and aggregated layered double hydroxide platelets.

    PubMed

    Zhang, Yan; Evans, Julian R G

    2013-04-01

    Despite much interest in the structures formed from droplets of suspension as they dry, there are few studies involving plate-like particles. Layered double hydroxide suspensions were prepared with pH adjusted to give well-dispersed and flocculated variants that were characterised by sedimentation and rheology measurements. In the well-dispersed suspension, the three-phase boundary was pinned and radial flow created a peripheral wall. The platelet structure involved local flat packing but was replete with scrolls that result from the recirculation flows in the droplets as they dry. In contrast, the flocculating suspension produced flatter droplet relics and the microstructure consisted of ordered domains which were disoriented with respect to each other. Although of scientific interest, the control of these structures will make it possible to use direct ink-jet printing to build 3D shapes for the preparation of aligned, ordered nanocomposites based on plate-like particles in which platelet preferred orientation mimics the structures found in nacre.

  2. Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

    NASA Technical Reports Server (NTRS)

    Pitsch, S.; Krishnamurthy, R.; Arrhenius, G.; Bada, J. L. (Principal Investigator)

    2000-01-01

    Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

  3. Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered double hydroxides

    SciTech Connect

    Wang Jun; Zhou Jideng; Li Zhanshuang; He Yang; Lin Shuangshuang; Liu Qi; Zhang Milin; Jiang Zhaohua

    2010-11-15

    We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs having different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted

  4. Study on the adsorption of DNA on the layered double hydroxides (LDHs).

    PubMed

    Li, Bin; Wu, Pingxiao; Ruan, Bo; Liu, Paiyu; Zhu, Nengwu

    2014-01-01

    Four kinds of layered double hydroxides (LDHs) were prepared by chemical coprecipitation method and used as DNA adsorbents. Multiple characterization tools such as power X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and Standard electronic modules (SEM) were employed to characterize the LDHs. By examining the effect of initial concentration, solution pH, adsorption experiments were carried out to investigate the adsorption capacities of LDHs for DNA. The results revealed that the LDHs with Mg/Al=3 had higher ability on adsorbing the DNA and were not affected by pH values. The LDHs exhibited excellent adsorption properties and completely adsorbed DNA within 2h. The adsorption equilibrium data were fitted to the Langmuir and Freundlich models, showing that the Langmuir model which represented monolayer adsorption had better correlation with the adsorption linear equation. In addition, Circular dichroism (CD) spectrum, UV-vis spectorscopy and agarose gel electrophoresis revealed the integrity of DNA structure, suggesting that there had no damage on the DNA structure during the adsorption process.

  5. Anion-intercalated layered double hydroxides modified test strips for detection of heavy metal ions.

    PubMed

    Wang, Nan; Sun, Jianchao; Fan, Hai; Ai, Shiyun

    2016-01-01

    In this work, a novel approach for facile and rapid detection of heavy metal ions using anion-intercalated layered double hydroxides (LDHs) modified test strips is demonstrated. By intercalating Fe(CN)6(4-) or S(2-) anions into the interlayers of LDHs on the filter paper, various heavy metal ions can be easily detected based on the color change before and after reaction between the anions and the heavy metal ions. Upon the dropping of heavy metal ions solutions to the test strips, the colors of the test strips changed instantly, which can be easily observed by naked eyes. With the decrease of the concentration, the color depth changed obviously. The lowest detection concentration can be up to 1×10(-6) mol L(-1). Due to the easily intercalation of anions into the interlayer of the LDHs on test trips, this procedure provides a general method for the construction of LDHs modified test strips for detection of heavy metal ions. The stability of the prepared test strips is investigated. Furthermore, all the results were highly reproducible. The test strips may have potential applications in environmental monitoring fields.

  6. Methotrexate intercalated layered double hydroxides with different particle sizes: structural study and controlled release properties.

    PubMed

    Zhang, Xiao-Qing; Zeng, Mei-Gui; Li, Shu-Ping; Li, Xiao-Dong

    2014-05-01

    To study the influence of particle size on release properties, drug efficacy and other properties, a series of methotrexate intercalated layered double hydroxides (MTX/LDHs) nanohybrids with different particle sizes were synthesized through traditional coprecipitation method, by using the mixture of water and polyethylene glycol (volume ratio is 3:1) as solvent. The relationship between particle size and hydrothermal treatment conditions (i.e., time and temperature) had been systematically investigated, and the results indicate that the particle size can be precisely controlled between 70 and 300 nm. Elemental C/H/N and inductive coupled plasma (ICP) analysis indicated that different hydrothermal treatment almost has no effect on compositions of the nanohybrids. X-ray diffraction (XRD) patterns and fourier transform infrared spectroscopy (FTIR) investigations manifested the successful intercalation of MTX anions. MTX/LDHs particles exhibited hexagonal platelet morphology with round corner, due to the adsorption of MTX anions on positively charged LDHs surface. In addition, the crystallinity of MTX/LDHs increased with the particle diameters and the thermal stability of MTX anions was enhanced by holding together with LDHs layers. The in vitro release showed that bigger particles have much longer release duration, and the bioassay tests indicated that bigger particles are more efficient in the suppression of the tumor cells.

  7. Heterogeneous photocatalytic degradation of pesticides using decatungstate intercalated macroporous layered double hydroxides.

    PubMed

    Da Silva, Eliana S; Prevot, Vanessa; Forano, Claude; Wong-Wah-Chung, Pascal; Burrows, Hugh D; Sarakha, Mohamed

    2014-10-01

    Decatungstate W10O32(4-) was efficiently intercalated between the layers of three-dimensionally ordered macroporous Mg2Al-layered double hydroxide. The structural and textural properties of as-prepared intercalated compound were characterized using different solid-state characterization techniques such as X-ray powder diffraction, FTIR and Raman spectroscopies and electronic microscopy. The photocatalytic properties of immobilized W10O32 (4-) within Mg2Al structure were investigated using 2-(1-naphthyl) acetamide (NAD) as a model of pesticide. The influence of different parameters such as amount of catalyst, pH and oxygen concentration were investigated. An optimal NAD degradation was obtained for a photocatalyst concentration of 60 mg l(-1). Under our experimental conditions, this heterogeneous photocatalyst induces photodegradation of 60 % of NAD after 17 h of irradiation at 365 nm and at pH 6.6. Interestingly, pesticide photodegradation leads to the mineralization of substrates to H2O and CO2 and the photocatalyst can be recycled and reused without any loss of activity over four cycles.

  8. Structure, molecular simulation, and release of aspirin from intercalated Zn-Al-layered double hydroxides.

    PubMed

    Meng, Zilin; Li, Xiaowei; Lv, Fengzhu; Zhang, Qian; Chu, Paul K; Zhang, Yihe

    2015-11-01

    Aspirin or acetylsalicylic acid (AA), a non-steroidal anti-inflammatory drug, is intercalated into Zn-Al-layered double hydroxides (ZnAl-LDHs) by co-precipitation and reconstruction methods. The composition, structure, and morphology of the intercalated products as well as their release behavior are determined experimentally and theoretically by Material Studio 5.5. Experimental results disclose the strong interaction between the LDHs sheets and AA in the intercalated ZnAl-LDHs produced by co-precipitation and slow release of AA from the intercalated ZnAl-LDHs in both phosphate buffered saline (PBS) and borate buffered saline (BBS) solutions. The percentage of AA released from the ZnAl-LDHs prepared by both methods in PBS (96.87% and 98.12%) are much more than those in BBS (68.59% and 81.22%) implying that both H4BO4(-) and H2PO4(-) can exchange with AA in the ZnAl-LDHs. After AA is released to PBS, ZnAl-LDHs break into small pieces. The experimental results are explained theoretically based on the calculation of the bonding energy between the anions and LDHs sheets as well as the AlO bond length change in the LDHs sheets.

  9. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    SciTech Connect

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-05-01

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the other catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.

  10. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    DOE PAGES

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; ...

    2016-03-09

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

  11. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    SciTech Connect

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-03-09

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the other catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.

  12. Ephemeral Fe(II)/Fe(III) layered double hydroxides in hydromorphic soils: A review

    NASA Astrophysics Data System (ADS)

    Vodyanitskii, Yu. N.; Shoba, S. A.

    2015-03-01

    Ephemeral green rust is formed seasonally in some hydromorphic soils. It consists of Fe(II)/Fe(III) layered double hydroxides with different types of interlayer anions and different oxidation degrees of iron ( x). In synthetized stoichiometric green rust, x = 0.25-0.33; in soil fougerite, it may reach 0.50-0.66. The mineral stability is provided by the partial substitution of Mg2+ for Fe2+. The ephemeral properties of the green rust are manifested in the high sensitivity to the varying redox regime in hydromorphic soils. Green rust disappears during oxidation stages, which complicates its diagnostics in soils. For green rust formation, excessively moist mineral soil needs organic matter as a source of energy for the vital activity of iron-reducing bacteria. In a gleyed Cambisol France, where fougerite is formed in the winter, the index of hydrogen partial pressure rH2 is 7.0-8.2, which corresponds to highly reducing conditions; upon the development of oxidation, fougerite is transformed into lepidocrocite. In the mineral siderite horizon of peatbogs in Belarus, where green rust is formed in the summer, rH2 is 11-14, which corresponds to the lower boundary of reducing conditions ( rH2 = 10-18); magnetite is formed in these soils in the winter season upon dehydration of the soil mass.

  13. From layered double hydroxide to spinel nanostructures: facile synthesis and characterization of nanoplatelets and nanorods.

    PubMed

    Sun, Genban; Sun, Lingna; Wen, He; Jia, Zhiqian; Huang, Kunlin; Hu, Changwen

    2006-07-13

    Mg-Al spinel (MgAl2O4) nanorods and nanoplatelets transformed from Mg-Al layered double hydroxide (Mg-Al-LDHs) were synthesized via a combined hydrothermal method and calcination route using Al(NO3).9H2O and Mg(NO3)2.6H2O as raw materials. The nanorods and nanoplatelets were characterized by means of physical techniques, including powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microcopy (HRTEM), selected-area electron diffraction (SAED), Fourier transform infrared spectra (FT-IR), thermogravimetric (TG), and nitrogen adsorption-desorption isotherms. XRD patterns reveal that the Mg-Al-LDHs nanostructures were obtained under a hydrothermal reaction temperature of 200 degrees C and Mg-Al spinel nanostructures were fabricated via calcination of the Mg-Al-LDHs nanostructures at 750 degrees C. It can be seen from TEM that the sizes of the Mg-Al-LDHs nanoplatelets were about 20-40 nm and the diameters of the MgAl2O4 nanorods were ca. 6 nm. The HRTEM images indicate that the crystal lattice spaces of the MgAl2O4 nanorods and nanoplatelets are 0.282 and 0.287 nm, respectively.

  14. Computer simulation of interlayer arrangement in cinnamate intercalated layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Greenwell, H. C.; Jones, W.; Newman, S. P.; Coveney, P. V.

    2003-02-01

    The interlayer arrangements of Mg-Al layered double hydroxides (LDHs) containing trans-cinnamate anions have been studied using molecular dynamics computer simulations. A modified version of the Dreiding forcefield was used to perform simulations of models with Mg/Al ratios of 2,3 and 6. For each Mg/Al ratio, two hydration states of 20 and 30 wt% water content were modelled. Close contacts between the olefinic carbons of the anion were analysed in an attempt to rationalize the potential outcome of the [2+2] photo-induced dimerization of the anions. In all instances, except for the model with Mg/Al=6 and 20 wt% water, the arrangement of the dimer pairs showed that syn-head-to-tail dimer formation was unfavourable. Preferred orientation of dimer pairs towards formation of head-to-head dimers was observed to undergo a transition from strongly favouring the syn-head-to-head dimer at low Mg/Al ratios to greater selectivity for the anti-head-to-head dimer with increasing Mg/Al ratio. The model with Mg/Al=6 and 20 wt% water content was observed to have a very disordered interlayer arrangement, with preference towards anion-pair arrangements favouring syn-head-to-tail dimer formation. The model with Mg/Al=6 and 30 wt% water content was predicted to exhibit only trans- cis isomerisation.

  15. Preparation of layered double hydroxide/chlorophyll a hybrid nano-antennae: a key step.

    PubMed

    Sommer Márquez, Alicia E; Lerner, Dan A; Fetter, Geolar; Bosch, Pedro; Tichit, Didier; Palomares, Eduardo

    2014-07-21

    In the first step to obtain an efficient nano-antenna in a bottom-up approach, new hybrid materials were synthesized using a set of layered double hydroxides (LDHs) with basic properties and pure chlorophyll a (Chl a). The stability of the adsorbed monolayer of Chl a was shown to be dependent on the nature and the ratio of the different metal ions present in the LDHs tested. The hybrid materials turned out to be adequate for stabilizing Chl a on Mg/Al LDHs for more than a month under ambient conditions while a limited catalytic decomposition was observed for the Ni/Al LDHs leading to the formation of pheophytin. These changes were followed by namely XRD, DR-UV-vis and fluorescence spectroscopies of the hybrid antennae and of the solutions obtained from their lixiviation with acetone or diethylether. On Mg/Al hydrotalcites the stability of the adsorbed Chl a was equivalent for values of the metal atom ratio ranging from 2 to 4. The latter hybrids should constitute a good basis to form efficient nanoscale light harvesting units following intercalation of selected dyes. This work describes an efficient preparation of Chl a that allows scale-up as well as the obtention of a stable Chl a monolayer on the surface of various LDHs.

  16. Deconstruction of Lignin Model Compounds and Biomass-Derived Lignin using Layered Double Hydroxide Catalysts

    SciTech Connect

    Chmely, S. C.; McKinney, K. A.; Lawrence, K. R.; Sturgeon, M.; Katahira, R.; Beckham, G. T.

    2013-01-01

    Lignin is an underutilized value stream in current biomass conversion technologies because there exist no economic and technically feasible routes for lignin depolymerization and upgrading. Base-catalyzed deconstruction (BCD) has been applied for lignin depolymerization (e.g., the Kraft process) in the pulp and paper industry for more than a century using aqueous-phase media. However, these efforts require treatment to neutralize the resulting streams, which adds significantly to the cost of lignin deconstruction. To circumvent the need for downstream treatment, here we report recent advances in the synthesis of layered double hydroxide and metal oxide catalysts to be applied to the BCD of lignin. These catalysts may prove more cost-effective than liquid-phase, non-recyclable base, and their use obviates downstream processing steps such as neutralization. Synthetic procedures for various transition-metal containing catalysts, detailed kinetics measurements using lignin model compounds, and results of the application of these catalysts to biomass-derived lignin will be presented.

  17. Study on the adsorption of DNA on the layered double hydroxides (LDHs)

    NASA Astrophysics Data System (ADS)

    Li, Bin; Wu, Pingxiao; Ruan, Bo; Liu, Paiyu; Zhu, Nengwu

    2014-03-01

    Four kinds of layered double hydroxides (LDHs) were prepared by chemical coprecipitation method and used as DNA adsorbents. Multiple characterization tools such as power X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and Standard electronic modules (SEM) were employed to characterize the LDHs. By examining the effect of initial concentration, solution pH, adsorption experiments were carried out to investigate the adsorption capacities of LDHs for DNA. The results revealed that the LDHs with Mg/Al = 3 had higher ability on adsorbing the DNA and were not affected by pH values. The LDHs exhibited excellent adsorption properties and completely adsorbed DNA within 2 h. The adsorption equilibrium data were fitted to the Langmuir and Freundlich models, showing that the Langmuir model which represented monolayer adsorption had better correlation with the adsorption linear equation. In addition, Circular dichroism (CD) spectrum, UV-vis spectorscopy and agarose gel electrophoresis revealed the integrity of DNA structure, suggesting that there had no damage on the DNA structure during the adsorption process.

  18. Evolution of rheological properties of the nanofluids composed of laponite particles and Mg–Fe layered double hydroxide nanosheets

    SciTech Connect

    Hur, Tae-Bong; Phuoc, Tran X.; Chyu, Minking K.; Romanov, Vyacheslav

    2011-05-01

    The thixotropic clay suspensions composed of laponite particles and Mg-Fe layered double hydroxide nanosheets were examined. By adding a very small amount of the layered double hydroxide nanosheets overall theological properties of the host laponite suspension have been changed. Though the particle concentration of the mixture suspension is only about 1 wt%, the mixture quickly becomes a gel in a day by the electrostatic attraction between nano-materials. When a constant shear rate is applied to the mixture gel suspension, at short time, stress increases linearly with elastic deformation of the mixture. Beyond the maximum of stress, while the solid-like gel structure is being broken down with time of shearing, the stress increases again by reflecting shear enhanced association of solid phase. This is likely that the mixture suspension shows partially the behavior of memory effect.

  19. Layered double hydroxides as drug carriers and for controlled release of non-steroidal antiinflammatory drugs (NSAIDs): a review.

    PubMed

    Rives, Vicente; Del Arco, Margarita; Martín, Cristina

    2013-07-10

    Non-steroidal anti-inflammatory drugs constitute one of the groups most widely currently used, but show several problems for administration due to low solubility and delivery control. For this reason, several matrices have been tested to support them in order to overcome these drawbacks. Among them, layered double hydroxides have been used in recent years. The aim of this review is to update the current knowledge and findings on this hybrid system, namely, layered double hydroxides intercalated with different NSAIDs. The basic nature of the matrix introduces an additional advantage, i.e., to decrease ulceration damages. We have focused our review mostly on the preparation procedures, as these control, define and determine the performance of the systems in vitro and also in living organisms.

  20. Control of crystallite and particle size in the synthesis of layered double hydroxides: Macromolecular insights and a complementary modeling tool.

    PubMed

    Galvão, Tiago L P; Neves, Cristina S; Caetano, Ana P F; Maia, Frederico; Mata, Diogo; Malheiro, Eliana; Ferreira, Maria J; Bastos, Alexandre C; Salak, Andrei N; Gomes, José R B; Tedim, João; Ferreira, Mário G S

    2016-04-15

    Zinc-aluminum layered double hydroxides with nitrate intercalated (Zn(n)Al-NO3, n=Zn/Al) is an intermediate material for the intercalation of different functional molecules used in a wide range of industrial applications. The synthesis of Zn(2)Al-NO3 was investigated considering the time and temperature of hydrothermal treatment. By examining the crystallite size in two different directions, hydrodynamic particle size, morphology, crystal structure and chemical species in solution, it was possible to understand the crystallization and dissolution processes involved in the mechanisms of crystallite and particle growth. In addition, hydrogeochemical modeling rendered insights on the speciation of different metal cations in solution. Therefore, this tool can be a promising solution to model and optimize the synthesis of layered double hydroxide-based materials for industrial applications.

  1. Facile synthesis of nickel-cobalt double hydroxide nanosheets with high rate capability for application in supercapacitor

    NASA Astrophysics Data System (ADS)

    Wang, Minmin; Xue, Junying; Zhang, Fangming; Ma, Wenle; Cui, Hongtao

    2015-02-01

    In this work, nickel-cobalt double hydroxide nanosheets with high rate capability are prepared by a facile epoxide precipitation route. The synthetic procedure includes an oxidization step using ammonium persulfate as oxidant and a precipitation step using propylene oxide as precipitation agent. As shown in the results of electrochemical characterization, high specific capacitance of 2548 F g-1 for this material can be obtained at current density of 0.9 A g-1 in aqueous solution of 3 mol L-1 KOH. It is surprising to notice that the capacitance of material still remains 1587 F g-1 at high current density of 35.7 A g-1. These results demonstrate that the as-prepared nickel-cobalt double hydroxide nanosheets are promising electrode material for supercapacitor application as a primary power source.

  2. Effect of monobutylether ethylene glycol on Mg/Al layered double hydroxide: a physicochemical and conductivity study

    NASA Astrophysics Data System (ADS)

    Paulo, Maria Joao; de Matos, Bruno Ribeiro; Ntais, Spyridon; Fonseca, Fabio Coral; Tavares, Ana C.

    2013-02-01

    Mg-Al hydrotalcite-like compounds with OH- ions intercalated in the gallery and modified with monobutylether ethylene glycol ( mbeeg) were prepared from Mg6Al2(CO3)(OH)16·4H2O by the reconstruction method. The effect of the ethylene glycol, a moderate surfactant, on the textural properties and on the vapor water sorption of the layered double hydroxides was investigated by transmission electron microscopy and nitrogen and water sorption techniques. The ion conductivity of the samples was measured at 98 % RH up to 180 °C. The compounds are formed by nanoplatelets with a lateral size inferior to 20 nm. The addition of the ethylene glycol was found to increase the specific surface area, total pore volume, and water sorption capacity of the Mg-Al layered double hydroxide. However, it also decreased the average pore diameter, and the ion conductivity of the ethylene glycol modified layered double hydroxide was lower than expected based on the samples' specific surface area and water content.

  3. Removal of boron and fluoride in wastewater using Mg-Al layered double hydroxide and Mg-Al oxide.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2017-03-01

    Mg-Al layered double hydroxide intercalated with NO3(-) and Mg-Al oxide were found to remove hazardous materials such as B and As, as well as Cl(-) and SO4(2-), from artificial and real hot spring wastewater. However, compared with the mixture of Al2(SO4)3 and Ca(OH)2, both adsorbents were inferior for the removal of B from real hot spring wastewater. Both adsorbents were also found to remove F(-) and PO4(3-) from artificial semiconductor plant wastewater. Both adsorbents have the same ability to remove B from landfill wastewater as the mixture of Al2(SO4)3 and Ca(OH)2; furthermore, both remove Cl(-), Br(-), and SO4(2-). The benefit of Mg-Al layered double hydroxide intercalated with NO3(-) is that it does not require neutralization after the treatment. Overall, it can be stated that among the materials tested, Mg-Al layered double hydroxide intercalated with NO3(-) is the most suitable adsorbent for the treatment of hot spring and landfill wastewater.

  4. Ultrathin nanoflakes of cobalt-manganese layered double hydroxide with high reversibility for asymmetric supercapacitor

    NASA Astrophysics Data System (ADS)

    Jagadale, Ajay D.; Guan, Guoqing; Li, Xiumin; Du, Xiao; Ma, Xuli; Hao, Xiaogang; Abudula, Abuliti

    2016-02-01

    CoMn LDH electrode is successfully prepared via facile and cost-effective electrodeposition method. The effect of Co2+/Mn2+ molar ratio on supercapacitive performance is systematically investigated. It is found that the presence of Mn(OH)6 unit in CoMn LDH offers an excellent reversibility as well as highly electrochemical activity for supercapacitor application. The CoMn LDH film with a Co2+/Mn2+ molar ratio of 9:1 loaded on Ni foam electrode exhibits the maximum specific capacitance of 1062.6 F/g at the current density of 0.7 A/g with an excellent cyclic stability of 96.3% over 5000 CD cycles. It indicates that CoMn LDH nanoflakes loaded on Ni foam can minimize the lattice mismatch which leads to an excellent cyclic stability. The asymmetric supercapacitor assembled with CoMn LDH/Ni foam and AC electrodes shows an excellent cyclic life of 84.2% and an energy density of 4.4 Wh/kg with a power density of 2500 W/kg.

  5. Intercalation of sulfonated melamine formaldehyde polycondensates into a hydrocalumite LDH structure

    NASA Astrophysics Data System (ADS)

    von Hoessle, F.; Plank, J.; Leroux, F.

    2015-05-01

    A series of sulfonated melamine formaldehyde (SMF) polycondensates possessing different anionic charge amounts and molecular weights was synthesized and incorporated into a hydrocalumite type layered double hydroxide structure using the rehydration method. For this purpose, tricalcium aluminate was dispersed in water and hydrated in the presence of these polymers. Defined inorganic-organic hybrid materials were obtained as reaction products. All SMF polymers tested intercalated readily into the hydrocalumite structure, independent of their different molecular weights (chain lengths) and anionic charge amounts. X-ray diffraction revealed typical patterns for weakly ordered, highly polymer loaded LDH materials which was confirmed via elemental analysis and thermogravimetry. IR spectroscopy suggests that the SMF polymers are interleaved between the [Ca2Al(OH)6]+ main sheets via electrostatic interaction, and that no chemical bond between the host matrix and the guest anion is formed. The SMF polymers well ensconced within the LDH structure exhibit significantly slower thermal degradation.

  6. Evaluation of layered double hydroxide/graphene hybrid as a sorbent in membrane-protected stir-bar supported micro-solid-phase extraction for determination of organochlorine pesticides in urine samples.

    PubMed

    Sajid, Muhammad; Basheer, Chanbasha; Daud, Muhammad; Alsharaa, Abdulnaser

    2017-03-17

    In this work, the potential of layered double hydroxide/graphene (LDH-G) hybrid as a sorbent for extraction and preconcentration of fifteen organochlorine pesticides (OCPs) in urine samples was evaluated. The LDH-G hybrid was synthesized by co-precipitation method and it was then characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The sorbent was then employed in membrane-protected stir-bar supported micro-solid-phase extraction (SB-μ-SPE) of OCPs in urine samples. This extraction approach is highly suitable for the samples representing matrix complexity such as urine because the sorbent is effectively protected inside the membrane. The extracted samples were analyzed by gas chromatography mass spectrometry. The factors that affect the performance of SB-μ-SPE were suitably optimized. This method demonstrated good linearity with coefficients of determination up to 0.9996. The limits of detection ranged between 0.22 and 1.38ngmL(-1). The RSD values for intra and inter-day precision were also in a satisfactory range (2.7-9.5%).

  7. Synthesis, structure refinement and chromate sorption characteristics of an Al-rich bayerite-based layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Britto, Sylvia; Kamath, P. Vishnu

    2014-07-01

    “Imbibition” of Zn2+ ions into the cation vacancies of bayerite-Al(OH)3 and NO3- ions into the interlayer gallery yields an Al-rich layered double hydroxide with Al/Zn ratio ~3. NO3- ions are intercalated with their molecular planes inclined at an angle to the plane of the metal hydroxide slab and bonded to it by hydrogen bonds. Rietveld refinement of the structure shows that the monoclinic symmetry of the precursor bayerite is preserved in the product, showing that the imbibition is topochemical in nature. The nitrate ion is labile and is quantitatively replaced by CrO42- ions from solution. The uptake of CrO42- ions follows a Langmuir adsorption isotherm, thus showing that the hydroxide is a candidate material for green chemistry applications for the removal of CrO42- ions from waste water. Rietveld refinement of the structure of the hydroxide after CrO42- inclusion reveals that the CrO42- ion is intercalated with one of its 2-fold axes parallel to the b-crystallographic axis of the crystal, also the principal 2 axis of the monoclinic cell.

  8. Selenium adsorption and speciation with Mg-FeCO₃ layered double hydroxides loaded cellulose fibre.

    PubMed

    Chen, Ming-Li; An, Myog-Il

    2012-06-15

    A novel adsorbent was developed by coating Mg-FeCO(3) layered double hydroxides (LDHs) on cellulose fibre. The LDHs take up significant amount of selenite and selenate in a wide pH range with similar sorption capacities (pH 3.8-8.0 for selenite and pH 5.8-7.0 for selenate). A mini-column packed with Mg-FeCO(3) LDHs layer coated cellulose fibre particles was incorporated into a sequential injection system for uptake of selenite at pH 6.0. The retained selenite was afterwards collected with 70 μ L of 0.8%(m/v) NaOH as eluent, followed by hydride generation and atomic fluorescence spectrometric detection. Total inorganic selenium was adsorbed at pH 6.0 by the LDHs-cellulose fibre mini-column after selenate was pre-reduced to selenite by 2.0 mol L(-1) HCl at 80°C, and selenium speciation was performed by difference. With a sample volume of 1.0 mL, an enrichment factor of 13.3 was derived with a detection limit of 11 ng L(-1) within a linear range of 0.04-4.0 μg L(-1). A relative standard deviation (RSD) of 3.3% (0.5 μg L(-1), n=11) was achieved. The procedure was validated by analyzing selenium in a certified reference material GBW 10010 (rice), and speciation of inorganic selenium in natural water samples.

  9. Arsenate removal by layered double hydroxides embedded into spherical polymer beads: Batch and column studies.

    PubMed

    Nhat Ha, Ho Nguyen; Kim Phuong, Nguyen Thi; Boi An, Tran; Mai Tho, Nguyen Thi; Ngoc Thang, Tran; Quang Minh, Bui; Van Du, Cao

    2016-01-01

    In this study, the performance of poly(layered double hydroxides) [poly(LDHs)] beads as an adsorbent for arsenate removal from aqueous solution was investigated. The poly(LDHs) beads were prepared by immobilizing LDHs into spherical alginate/polyvinyl alcohol (PVA)-glutaraldehyde beads (spherical polymer beads). Batch adsorption studies were conducted to assess the effect of contact time, solution pH, initial arsenate concentrations and co-existing anions on arsenate removal performance. The potential reuse of these poly(LDHs) beads was also investigated. Approximately 79.1 to 91.2% of arsenic was removed from an arsenate solution (50 mg As L(-1)) by poly(LDHs). The adsorption data were well described by the pseudo-second-order kinetics model and the Langmuir isotherm model, and the adsorption capacities of these poly(LDHs) beads at pH 8 were from 1.64 to 1.73 mg As g(-1), as calculated from the Langmuir adsorption isotherm. The adsorption ability of the poly(LDHs) beads decreased by approximately 5-6% after 5 adsorption-desorption cycles. Phosphates markedly decreased arsenate removal. The effect of co-existing anions on the adsorption capacity declined in the following order: HPO4 (2-) > HCO3 (-) > SO4 (2-) > Cl(-). A fixed-bed column study was conducted with real-life arsenic-containing water. The breakthrough time was found to be from 7 to 10 h. Under optimized conditions, the poly(LDHs) removed more than 82% of total arsenic. The results obtained in this study will be useful for further extending the adsorbents to the field scale or for designing pilot plants in future studies. From the viewpoint of environmental friendliness, the poly(LDHs) beads are a potential cost-effective adsorbent for arsenate removal in water treatment.

  10. Selectivity of layered double hydroxides and their derivative mixed metal oxides as sorbents of hydrogen sulfide.

    PubMed

    Othman, Mohamed A; Zahid, Waleed M; Abasaeed, Ahmed E

    2013-06-15

    In the context of finding high efficient sorbent materials for removing hydrogen sulfide (H2S) from air stream, a screening study was performed to find the best combination of metals for the synthesis of layered double hydroxides (LDHs) and their derivative mixed metal oxides. Based on selectivity of 998 natural mineral species of sulfur-containing compounds, Cu(2+), Ni(2+) and Zn(2+) were selected as divalent metals, and Fe(3+), Al(3+) and Cr(3+) as trivalent metals to synthesis the LDHs sorbents. 10 LDHs materials and their calcined mixed metal oxides, Ni(0.66)Al(0.34), Cu(0.35)Ni(0.32)Al(0.33), Zn(0.66)Al(0.34), Cu(0.36)Zn(0.32)Al(0.32), Ni(0.64)Fe(0.36), Cu(0.35)Ni(0.31)Fe(0.34), Ni(0.66)Cr(0.34), Cu(0.35)Ni(0.31)Cr(0.34), Zn(0.66)Cr(0.34), Cu(0.33)Zn(0.32)Cr(0.35) were synthesized, characterized chemically and physically, and then tested using breakthrough test to determine their sulfur uptake. Ni(0.64)Fe(0.36) mixed metal oxides was found to have the best uptake of hydrogen sulfide (136 mg H₂S/g). Regeneration of spent Ni(0.64)Fe(0.36) mixed metal oxides was studied using two different mixture solutions, NaCl/NaOH and acetate-buffer/NaCl/NaOH. The latter mixture successfully desorbed the sulfur from the Ni0.64Fe0.36 sorbent for 2 cycles of regeneration/sorption.

  11. Pathways of phosphate uptake from aqueous solution by ZnAl layered double hydroxides.

    PubMed

    Cheng, X; Wang, Y; Sun, Z; Sun, D; Wang, A

    2013-01-01

    ZnAl layered double hydroxides (LDHs) were prepared by urea hydrolysis-based coprecipitation for removing phosphate from aqueous solutions. The chemical formula of the product was determined as Zn5.54Al3.02(OH)8.73(CO3)0.57Cl5.66·7.84H2O. Chloride ion was the major interlayer anion of the ZnAl LDHs. Adsorption of phosphate onto the ZnAl sorbent over the entire study period was not in close agreement with pseudo-first-order or pseudo-second-order models. The adsorption can be divided into two steps. A fast adsorption was observed during the first 10 h with a marked increase in the concentration of Cl(-) in the bulk solution. This indicated that the adsorption of phosphate was largely attributed to the ion exchange between phosphate and the interlayer Cl(-). A second fast adsorption of phosphate occurred after 10 h. During this period, the pH increased slowly, whereas the Cl(-) concentration was stable. The uptake of phosphate was likely attributed to OH(-)-H2PO4(-)/HPO4(2-) ion exchange as well as surface adsorption/complexation. Acidic conditions favored adsorption of phosphate by ZnAl LDHs, which is consistent with the pH increases during the adsorption. Coexisting anions, e.g., SO4(2-) and CO3(2-), are competitive ions for the adsorption of phosphate. The results verify the contribution of ion exchange and surface adsorption/complexation in the removal of phosphate by ZnAl LDHs.

  12. Synthesis of magnetite-graphene oxide-layered double hydroxide composites and applications for the removal of Pb(II) and 2,4-dichlorophenoxyacetic acid from aqueous solutions.

    PubMed

    Zhang, Fengrong; Song, Yawen; Song, Shue; Zhang, Renjie; Hou, Wanguo

    2015-04-08

    Magnetic composites consisting of magnetite (Fe3O4), graphene oxide (GO), and Mg3Al-OH layered double hydroxide (LDH), denoted as MGL composites, with varying GO contents (RGO) were synthesized by a mechano-hydrothermal (MHT) route using Fe3O4, Mg(OH)2, and Al(OH)3 as the inorganic starting materials. The application of the synthesized MGLs for removing the heavy-metal Pb(II) and the hydrophobic organic pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solutions was investigated. Chemical bonding among the GO, Fe3O4, and LDH components was observed in the MGLs. The MGL composites showed good water-dispersity, strong magnetic response, and high sorption capacities and removal efficiencies for both Pb(II) and 2,4-D pollutants. The sorption capacities of the MGL for the pollutants significantly increased with an increase in RGO. Increasing pH could increase the removal efficiency for Pb(II) but decrease that for 2,4-D. The MGLs showed more affinity for Pb(II) than for 2,4-D in the competitive sorption. In addition, the MGLs could remain almost constant removal efficiency for the pollutants after reuse over six cycles, indicating their potential use as sorbents in wastewater treatment. Furthermore, a Cs effect was observed in the sorption equilibriums, which could be described using the Langmuir-SCA and Freundlich-SCA isotherms. The removal mechanisms of the MGL for Pb(II) and 2,4-D were discussed. The MHT method provided a simple and environmentally friendly route for synthesizing GO-LDH composite materials.

  13. Enhanced photocatalytic activity of Ce-doped Zn-Al multi-metal oxide composites derived from layered double hydroxide precursors.

    PubMed

    Zhu, Jianyao; Zhu, Zhiliang; Zhang, Hua; Lu, Hongtao; Qiu, Yanling; Zhu, Linyan; Küppers, Stephan

    2016-11-01

    In this work, a series of novel Zn-Al-Ce multi-metal oxide (Zn-Al-Ce-MMO) photocatalysts with different Ce doping contents were prepared by calcination of Ce-doped Zn-Al layered double hydroxide (Zn-Al-Ce-LDH) precursors at various temperatures in air atmosphere. The synthesized Zn-Al-Ce-MMO materials were characterized by XRD, FTIR, TGA, BET, SEM, TEM, XPS and UV-vis DRS. The photocatalytic activities of the Zn-Al-Ce-MMO materials were evaluated by the photodegradation of rhodamine B (RhB) dye and paracetamol in aqueous solution under simulated solar light irradiation. The result of photodegradation of RhB showed that the Zn-Al-Ce-MMO samples exhibit much higher photocatalytic activity than that of Zn-Al-MMO, and the optimal Ce doping content is 5% of mole ratio (nCe/n(Zn+Al+Ce)). The enhanced photocatalytic activity of the Zn-Al-Ce-MMO was mainly attributed to the increasing in the separation efficiency of electrons and holes. The effect of calcination temperature was also studied. The photocatalytic activity of Zn-Al-Ce-MMO increased with increasing calcination temperature up to 750°C, which can be ascribed to the formation of well-crystallized metal oxides during calcination. Under experimental conditions, 97.8% degradation efficiency of RhB and 98.9% degradation efficiency of paracetamol were achieved after 240min. Active species trapping and EPR experiments suggested that hole (h(+)), superoxide radical (O2(-)) and hydroxyl radical (OH) played important roles during the RhB photocatalytic process. Moreover, the results indicated that the synthesized Zn-Al-Ce-MMO materials had good stability and reusability.

  14. Molecular modeling of the structure and dynamics of the interlayer species of ZnAlCl layered double hydroxide.

    PubMed

    Pisson, J; Morel, J P; Morel-Desrosiers, N; Taviot-Guého, C; Malfreyt, P

    2008-07-03

    Molecular dynamics simulations of the ZnAl layered double hydroxide containing interlayer chloride anions have been performed in the NpT and Np(zz)T statistical ensembles for metal Zn/Al ratios of 2 and 3. We have monitored the interlayer spacing as a function of the number of intercalated water molecules for each statistical ensemble. We have studied how these profiles are affected by the method of calculation of the charges of the hydroxide layer atoms. Diffusion coefficients of the interlayer water molecules have been calculated for different Zn/Al ratios. The calculation of the chemical potential of the interlayer water molecules has been carried out for three amounts of interlayer water molecules. The calculation showed a qualitative agreement with the bulk water chemical potential within a range of interlayer water molecule contents.

  15. Ni adsorption and Ni-Al LDH precipitation in a sandy aquifer: an experimental and mechanistic modeling study.

    PubMed

    Regelink, Inge C; Temminghoff, Erwin J M

    2011-03-01

    Mining activities and industries have created nickel (Ni) contaminations in many parts of the world. The objective of this study is to increase our understanding of Ni adsorption and Nickel-Aluminium Layered Double Hydroxide (Ni-Al LDH) precipitation to reduce Ni mobility in a sandy soil aquifer. At pH ≥ 7.2 both adsorption and Ni-Al LDH precipitation occurred. In batch experiments with the sandy soil up to 70% of oxalate-extractable Al was taken up in LDH formation during 56 days. In a long term column experiment 99% of influent Ni was retained at pH 7.5 due to Ni adsorption (≈ 34%) and Ni-Al LDH precipitation (≈ 66%) based on mechanistic reactive transport modeling. The subsequent leaching at pH 6.5 could be largely attributed to desorption. Our results show that even in sandy aquifers with relatively low Al content, Ni-Al LDH precipitation is a promising mechanism to immobilize Ni.

  16. Electrochemiluminescence detection of reduced and oxidized glutathione ratio by quantum dot-layered double hydroxide film.

    PubMed

    Yu, Yingchang; Shi, Jingjing; Zhao, Xiaocen; Yuan, Zhiqin; Lu, Chao; Lu, Jun

    2016-05-23

    The ratio of reduced and oxidized glutathione (GSH/GSSG ratio) is a greater first indication of disease risk than the total concentration of GSH. However, the interferences from thiolated biomolecules, especially cysteine (Cys), make the accurate detection of GSH/GSSG ratio a technical problem. In this work, we successfully used a mixture of quantum dots (QDs) and ZnAl-LDH nanosheets to fabricate a high electrochemiluminescence resonance energy transfer (ERET) efficiency sensor for GSH from the disturbances of amino acids, especially Cys and GSSG. The mechanisms of high ERET efficiency and selectivity were well investigated with spectroscopy analysis and theoretical calculation. The results showed that the interaction force between ZnAl-LDH nanosheets and molecules proved a long-range-ordered space and selective transmission for molecules. On the basis of these interesting phenomena, we successfully measured the GSH/GSSG ratio in whole blood and serum samples.

  17. Thermal evolution of Mg-Al and Ni-Al layered double hydroxides: the structure of the dehydrated phase.

    PubMed

    Cherepanova, Svetlana; Leont'eva, Natalya; Drozdov, Vladimir; Doronin, Vladimir

    2016-11-01

    Simulation of X-ray diffraction patterns on the basis of the models of one-dimensional disordered crystals was used to investigate the structure of the dehydrated phase produced by dehydration of Mg-Al and Ni-Al layered double hydroxides at a temperature of ∼473-498 K. It was found that the removal of water molecules transforms the initial structure, which is a mixture of 3R1 and 2H1 polytypes, into a structure that comprises preferentially fragments of 3R2 and 1H polytypes and has some turbostratic disorder.

  18. Organo-modified ZnAl layered double hydroxide as new catalyst support for the ethylene polymerization.

    PubMed

    He, Fu-An; Zhang, Li-Ming

    2007-11-15

    Organo-modified ZnAl layered double hydroxide was used for the first time to support a nickel a-diimine catalyst for the ethylene polymerization, and its effects on the catalytic activity, the morphology, thermal stability, and dynamic viscoelastic properties of the resultant polyethylene material were investigated. Different from the homogeneous nickel a-diimine catalyst, the supported catalyst system was found to have a long-lasting polymerization activity. Moreover, the resultant polyethylene material showed good particle morphology, improved thermal stability, as well as enhanced storage modulus and complex viscosity.

  19. Structural features of intercalated CaFe-layered double hydroxides studied by X-ray diffractometry, infrared spectroscopy and computations

    NASA Astrophysics Data System (ADS)

    Ferencz, Zs.; Ádok-Sipiczki, M.; Hannus, I.; Sipos, P.; Pálinkó, I.

    2015-06-01

    The intercalation of various N-containing carboxylic acid anions into CaFe-layered double hydroxides was performed by the dehydration-rehydration method. Particular attention was paid to the effect of solvent mixture used during preparation. It was found that various solvent mixtures resulted in different interlayer distances and, thus, different arrangements of the anions between the layers. The dimensions of the intercalated anions and detailed analysis of the infrared spectra gave clues for the reasonable prediction of the spatial arrangements of the anions in the interlamellar space.

  20. Synthesis of a novel green fluorescent material Ca3Al2O6:Tb3+ based on a layered double hydroxide precursor

    NASA Astrophysics Data System (ADS)

    Gao, Xiaorui; Jiang, Kangle; Hao, Yongjing; Chang, Tao; Yin, Yaobing

    2015-08-01

    A novel green light emitting material, Ca3Al2O6:Tb3+ was synthesized by calcination of a terbium doped Ca/Al layered double hydroxide precursor at 1350°C. The precursor was prepared by coprecipitation from metal nitrates with sodium hydroxide. The material shows characteristic green emission at 543 nm when excited with 266 nm UV source. The photoluminescence intensity reaches its maximum at Tb3+ concentration of 0.5 mol %.

  1. Photocatalytic O{sub 2} evolution from water over Zn–Cr layered double hydroxides intercalated with inorganic anions

    SciTech Connect

    Hirata, Naoya; Tadanaga, Kiyoharu; Tatsumisago, Masahiro

    2015-02-15

    Graphical abstract: The photocatalytic activity of Zn–Cr LDHs intercalated with various inorganic anions was studied by O{sub 2} evolution from aqueous solution of AgNO{sub 3} as a sacrificial agent. All the prepared LDHs showed photocatalytic activity under either UV and/or visible light irradiation. The interlayer anions affected the photocatalytic activity of the LDHs. - Highlights: • Zn–Cr layered double hydroxides intercalated with inorganic anions were synthesized. • Photocatalytic activity of the LDHs was studied by O{sub 2} evolution. • All the prepared LDHs showed photocatalytic activity under either UV and/or visible light irradiation. • The interlayer anions affected the photocatalytic activity of the LDHs. - Abstract: Zn–Cr layered double hydroxides (LDHs) intercalated with inorganic anions (CO{sub 3}{sup 2−}, Cl{sup −}, SO{sub 4}{sup 2−} and NO{sub 3}{sup −}) were synthesized by the co-precipitation method and the anion exchange process. The photocatalytic activity of the LDHs was studied by O{sub 2} evolution from aqueous solution of AgNO{sub 3} as a sacrificial agent. All the prepared LDHs showed photocatalytic activity under either UV and/or visible light irradiation. Besides, the interlayer anions affected the photocatalytic activity of the LDHs. After irradiation, Ag particles were formed on the LDHs by accepting the electrons generated during the photocatalytic reaction.

  2. An ethylene glycol intercalated monometallic layered double hydroxide based on iron as an efficient bifunctional catalyst.

    PubMed

    Nagarajan, Rajamani; Gupta, Pankaj; Singh, Poonam; Chakraborty, Pinki

    2016-11-01

    Given the fact that the literature describing the intercalation of organic molecules in monometallic LDH systems is scarce, the present investigation is aimed at the generation of ethylene glycol intercalated Fe(II)-Fe(III) LDH with the objective of enhancing the surface area for further catalytic applications of industrially important and environmentally harmful organics. The solvothermal reaction of FeCl3 with urea in an ethylene glycol medium yielded a brown colored powder which was characterized employing a wide range of analytical techniques including high resolution powder X-ray diffraction (PXRD), scanning electron microscopy, thermal analysis, X-ray photo electron spectroscopy (XPS), elemental (C, H, N and S) analysis, UV-visible, photoluminescence spectroscopy measurements, BET surface area and pore-size analysis. The observed reflections in the PXRD pattern were indexed in a rhombohedral symmetry with a = 3.175 and c = 31.9 Å. Combining the results from the Fe 2p core level analysis and anion contents from elemental and thermogravimetric analysis, a formula of Fe(2+)1.06 Fe(3+)0.94 (O2C2H4) (OH)4 was deduced for the sample. The intercalation of EG in the interlayer was confirmed from FTIR and Raman spectroscopy measurements. The d-d transitions of the Fe(3+)-ion and the charge transfer transition of the Fe(ii)-Fe(iii) lattice were evident in the UV-visible spectrum. Blue indigoid emission bands arising from the transitions present in the Fe(3+)-ion were noticed in the photoluminescence spectrum. The measured BET surface area and pore diameter of the sample were 144 m(2) g(-1) and 12.5 nm, respectively. Almost instant decolourisation of the Xylenol Orange (XO) dye occurred in the presence of H2O2 and the LDH sample as catalyst. Similar observations were encountered for Methyl Orange (MO) and Methylene Blue (MB) dyes. All these reactions followed pseudo first-order kinetics. The industrially important reductive conversion of nitro aromatics was catalyzed

  3. Efficient fluorinating agent through topochemical fluorination of Co-Fe layered double hydroxides.

    PubMed

    Louvain, Nicolas; Peyroux, Jérémy; Dubois, Marc; Simond, Wikenson; Leroux, Fabrice

    2014-01-21

    Mixed-metal inorganic fluoride, Co0.60Fe0.40F3, solid solutions are obtained through topochemical reactions of Co2FeCl(OH)6·2H2O LDH with molecular fluorine, F2, at temperatures as low as 100 °C. This solid solution possesses interesting F(•)-releasing ability, and its efficiency as a solid-state fluorinating agent is demonstrated on a commercial polyethylene film. (19)F solid state NMR and contact angle measurements underline the efficient fluorination of this polymer.

  4. Layered double hydroxides as efficient photocatalysts for visible-light degradation of Rhodamine B.

    PubMed

    Xia, Sheng-Jie; Liu, Feng-Xian; Ni, Zhe-Ming; Xue, Ji-Long; Qian, Ping-Ping

    2013-09-01

    A series of Zn/M-NO3-LDHs (M=Al, Fe, Ti, and Fe/Ti) have been synthesized by two different methods, and their activities for visible-light photocatalytic degradation on Rhodamine B (RB) were tested. Solids were analyzed by XRD, FT-IR, and ICP characterization, confirming the formation of pure LDH phase with good crystal structure. It was observed that the band gap of these nitrate LDH materials was following this order: Zn/Fe-NO3-LDHs (2.55 eV)>Zn/Fe/Ti-NO3-LDHs (2.88 eV)>Zn/Ti-NO3-LDHs (3.0 3eV)>Zn/Al-NO3-LDHs (3.23 eV); however, the degradation performance of RB by four materials followed the order: Zn/Ti-NO3-LDHs (98%)>Zn/Al-NO3-LDHs (96%)>Zn/Fe/Ti-NO3-LDHs (88%)>Zn/Fe-NO3-LDHs (72%). In addition, a possible mechanism for photocatalytic degradation on RB has also been presumed. Moreover, after three regeneration cycles, the percentage of RB degradation rate was still close to 90%.

  5. Efficient Fluorinating Agent through Topochemical Fluorination of Co-Fe Layered Double Hydroxides

    SciTech Connect

    Louvain, Nicolas; Peyroux, Jérémy; Dubois, Marc; Simond, Wikenson; Leroux, Fabrice

    2014-02-13

    Mixed-metal inorganic fluoride, Co0.60Fe0.40F3, solid solutions are obtained through topochemical reactions of Co2FeCl(OH)6·2H2O LDH with molecular fluorine, F2, at temperatures as low as 100 °C. This solid solution possesses interesting F-releasing ability, and its efficiency as a solid-state fluorinating agent is demonstrated on a commercial polyethylene film. 19F solid state NMR and contact angle measurements underline the efficient fluorination of this polymer.

  6. A facile approach for synthesizing Fe-based layered double hydroxides with high purity and its exfoliation.

    PubMed

    Wang, Yinling; Li, Fajun; Dong, Shengye; Liu, Xiaowang; Li, Maoguo

    2016-04-01

    Transition metal (e.g., Fe, Co, Ni)-based layered double hydroxides (LDHs) and their exfoliated nanosheets have great potential applications due to their redox and magnetic properties. Here we report a facile approach for the preparation of Co-Fe LDHs with good crystallinity and high purity. The proposed approach includes two steps: (1) The mixed divalent metal (e.g., Co(2+), Fe(2+)) hydroxides were first synthesized using a homogeneous precipitation without piping N2 into the system; hexamethylenetetramine (HMT) was the hydrolysis agent providing OH(-), and hydroxylamine hydrochloride (HAH) was used as both a reducing and a complexing reagent. (2) Then the as-prepared hydroxides were slowly oxidated by air and simultaneously intercalated by CO3(2-) to form CO3-intercalated LDHs. The Co-Fe LDHs were roundly characterized by XRD, SEM, EDX and FT-IR. The effect of HAH on the morphology and structure of the Co-Fe LDHs was also studied. The magnetism of Co-Fe LDHs at room temperature was investigated and the results showed that the LDHs displayed a low saturation magnetization value of 6.3emug(-1), suggesting that the purity of the products was very high. In addition, the intercalated CO3(2-) in the Co-Fe LDHs could be successfully exchanged with other anions such as Cl(-) and ClO4(-). Furthermore, the exchanged-LDHs could be exfoliated in formamide. This work establishes a new method for the synthesis of Fe-based LDHs with good crystallinity and high purity under mild conditions, and can accelerate the development of applications using these layered materials.

  7. Antibiofilm efficacy of photoactivated curcumin, triple and double antibiotic paste, 2% chlorhexidine and calcium hydroxide against Enterococcus fecalis in vitro

    PubMed Central

    Devaraj, Sharmila; Jagannathan, Nithya; Neelakantan, Prasanna

    2016-01-01

    Root canal disinfection is one of the most important factors governing success of root canal treatment, especially when regenerative strategies are used. This study evaluated the efficacy of 5 intracanal medicaments against mature biofilms of Enterococcus fecalis in vitro: Light activated curcumin, triple antibiotic paste (TAP), double antibiotic paste (DAP), chlorhexidine, calcium hydroxide. Untreated teeth with biofilms served as controls. Confocal microscopy was used to analyse the biofilm mass and percentage of live/dead bacteria within the root canal as well as dentinal tubules. Dentinal shavings obtained from the root canal walls (at 200 and 400 microns depth) were used to quantify the colony forming units/mL. The results showed that light activated curcumin and triple antibiotic paste brought about complete disruption of the biofilm structure (P < 0.05) while chlorhexidine and calcium hydroxide were not significantly different from the control (P > 0.05). Light activated curcumin brought about the highest percentage of dead cells at both depths, but this was not significantly different from triple antibiotic paste (P > 0.05). Curcumin, TAP and DAP brought about a significant reduction of CFU/mL at both depths compared to the control and other groups (P < 0.05). Light activated curcumin brought about a 7 log reduction of bacteria at both depths. PMID:27097667

  8. Bioinspired design and assembly of layered double hydroxide/poly(vinyl alcohol) film with high mechanical performance.

    PubMed

    Shu, Yingqi; Yin, Penggang; Liang, Benliang; Wang, Hao; Guo, Lin

    2014-09-10

    Inspired by the hierarchical structure and excellent mechanical performance of nacre, LDH nanosheets with an appropriate aspect ratio to withstand significant loads and at the same time allow for rupture under the pull-out mode were synthesized as artificial building blocks for the fabrication of nacre-like films. Multilayered PVA/LDH films with a high tensile strength and ductility were prepared for the first time by bottom-up layer-by-layer assembly of pretreated LDH nanosheets and spin-coating of PVA. The weight fraction of inorganic LDH platelets in the hybrid PVA/LDH films (wp) was controlled by changing the concentration of PVA solution applied in the spin-coating process. The resulting films revealed that the PVA/LDH hybrid films were piled close together to form a well-defined stratified structure resembling the brick-and-mortar structure of natural nacre. In the hybrid films, the content of inorganic LDH platelets was comparable to the value in nacre, up to 96.9 wt %. It could be clearly seen that the mechanical performance of the as-prepared PVA/LDH films was greatly improved by increasing the rigid building-block LDHs. The tensile strength of the 2 wt % PVA/LDH hybrid film reached a value of 169.36 MPa, thus exceeding the strength of natural nacre and reaching 4 times that of a pure PVA film. Meanwhile, its elastic modulus was comparable to that of lamellar bone.

  9. Development of a biocompatible nanodelivery system for tuberculosis drugs based on isoniazid-Mg/Al layered double hydroxide

    PubMed Central

    Saifullah, Bullo; Arulselvan, Palanisamy; El Zowalaty, Mohamed Ezzat; Fakurazi, Sharida; Webster, Thomas J; Geilich, Benjamin M; Hussein, Mohd Zobir

    2014-01-01

    The primary challenge in finding a treatment for tuberculosis (TB) is patient non-compliance to treatment due to long treatment duration, high dosing frequency, and adverse effects of anti-TB drugs. This study reports on the development of a nanodelivery system that intercalates the anti-TB drug isoniazid into Mg/Al layered double hydroxides (LDHs). Isoniazid was found to be released in a sustained manner from the novel nanodelivery system in humans in simulated phosphate buffer solutions at pH 4.8 and pH 7.4. The nanodelivery formulation was highly biocompatible compared to free isoniazid against human normal lung and 3T3 mouse fibroblast cells. The formulation was active against Mycobacterium tuberculosis and gram-positive bacteria and gram-negative bacteria. Thus results show significant promise for the further study of these nanocomposites for the treatment of TB. PMID:25336952

  10. Insights into the behaviour of biomolecules on the early Earth: The concentration of aspartate by layered double hydroxide minerals

    NASA Astrophysics Data System (ADS)

    Grégoire, Brian; Erastova, Valentina; Geatches, Dawn L.; Clark, Stewart J.; Greenwell, H. Christopher; Fraser, Donald G.

    2016-03-01

    The role of mineral surfaces in concentrating and facilitating the polymerisation of simple protobiomolecules during the Hadean and Archean has been the subject of much research in order to constrain the conditions that may have led to the origin of life on early Earth. Here we examine the adsorption of the amino acid aspartate on layered double hydroxide minerals, and use a combined computer simulation - experimental spectroscopy approach to gain insight into the resulting structures of the host-aspartate material. We show that the uptake of aspartate occurs in alkaline solution by anion exchange of the dianion form of aspartate, rather than by surface adsorption. Anion exchange only occurs at values of pH where a significant population of aspartate has the amino group deprotonated, and is then highly efficient up to the mineral anion exchange capacity.

  11. ANTS-anchored Zn-Al-CO3-LDH particles as fluorescent probe for sensing of folic acid

    NASA Astrophysics Data System (ADS)

    Liu, Pengfei; Liu, Dan; Liu, Yanhuan; Li, Lei

    2016-09-01

    A novel fluorescent nanosensor for detecting folic acid (FA) in aqueous media has been developed based on 8-aminonaphthalene-1,3,6-trisulfonate (ANTS) anchored to the surface of Zn-Al-CO3-layered double hydroxides (LDH) particles. The nanosensor showed high fluorescence intensity and good photostability due to a strong coordination interaction between surface Zn2+ ions of Zn-Al-CO3-LDH and N atoms of ANTS, which were verified by result of X-ray photoelectron spectroscopy (XPS). ANTS-anchored on the surface of Zn-Al-CO3-LDH restricted the intra-molecular rotation leading to ANTS-anchored J-type aggregation emission enhancement. ANTS-anchored Zn-Al-CO3-LDH particles exhibited highly sensitive and selective response to FA over other common metal ions and saccharides present in biological fluids. The proposed mechanism was that oxygen atoms of -SO3 groups in ANTS-anchored on the surface of Zn-Al-CO3-LDH were easily collided by FA molecules to form potential hydrogen bonds between ANTS-anchored and FA molecules, which could effectively quench the ANTS-anchored fluorescence. Under the simulated physiological conditions (pH of 7.4), the fluorescence quenching was fitted to Stern-Volmer equation with a linear response in the concentration range of 1 μM to 200 μM with a limit of detection of 0.1 μM. The results indicate that ANTS-anchored Zn-Al-CO3-LDH particles can afford a very sensitive system for the sensing FA in aqueous solution.

  12. Clarification of possible ordered distributions of trivalent cations in layered double hydroxides and an explanation for the observed variation in the lower solid-solution limit

    PubMed Central

    Richardson, Ian G.

    2013-01-01

    The sequence of hexagonal ordered distributions of trivalent cations that are possible in the octahedral layer of layered double hydroxides is clarified, including the link between the composition and the supercell a parameter. A plausible explanation is provided for the observed variation in the lower solid-solution limit. PMID:24253089

  13. Clarification of possible ordered distributions of trivalent cations in layered double hydroxides and an explanation for the observed variation in the lower solid-solution limit.

    PubMed

    Richardson, Ian G

    2013-12-01

    The sequence of hexagonal ordered distributions of trivalent cations that are possible in the octahedral layer of layered double hydroxides is clarified, including the link between the composition and the supercell a parameter. A plausible explanation is provided for the observed variation in the lower solid-solution limit.

  14. Zn- and Co-based layered double hydroxides: prediction of the a parameter from the fraction of trivalent cations and vice versa.

    PubMed

    Richardson, Ian G

    2013-08-01

    A recently proposed method to calculate the a parameter of the unit cell of layered double hydroxides from the fraction of trivalent cations is extended to Zn- and Co-based phases. It is shown to be useful as a sanity test for extant and future structure determinations and computer-simulation studies.

  15. Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

    PubMed

    Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

    2014-06-25

    We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

  16. Synthesis and characterization of a mixture of CoFe2O4 and MgFe2O4 from layered double hydroxides: Band gap energy and magnetic responses

    NASA Astrophysics Data System (ADS)

    Agú, Ulises A.; Oliva, Marcos I.; Marchetti, Sergio G.; Heredia, Angélica C.; Casuscelli, Sandra G.; Crivello, Mónica E.

    2014-11-01

    A mixture of nanocrystals of cobalt ferrite and magnesium ferrite was obtained from Layered Double Hydroxides (LDH) through a co-precitation method with a theoretical molar ratio M2+:Fe3+=3:1, where M2+represents Mg2+ and/or Co2+. The molar ratios between Co2+:Fe3+ were 0.0 (0Co), 0.2 (5Co), and 0.4 (10Co). In order to assess the effect on the properties of the LDH and their oxides, the molar percentages were 0, 5 and 10%. Two different synthesis methods were evaluated; (i) ageing at room temperature (rt), and (ii) hydrothermal ageing at 200 °C in autoclave (ht), both methods needed 15 h of ageing. Then, these LDH were calcined in air atmosphere at 550 °C for 10 h. The calcined materials were characterized by X-ray diffraction (XRD), thermogravymetric analysis (TGA), temperature-programmed reduction (TPR), infrared spectroscopy with Fourier transform (FTIR), Diffuse Reflectance UV-visible spectroscopy (UV-vis-DRS), Mössbauer spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). The magnetic response was analyzed using a vibrating sample magnetometer (VSM). The band gap energy of the iron oxides was determined through the UV-vis-DRS analysis. Through these studies it was possible to identify the presence of a mixture of cobalt ferrite and magnesium ferrite. Samples did not show hematite and cobalt oxides, but the presence of MgO in the periclase phase was determined. This magnesium oxide promoted a good dispersion of the ferrites. Moreover, when a single ferrite phase of Co or Mg was formed, a diminution of the crystal size with consequent enlarged values of band gap energy was observed. Thus, materials synthesized by room temperature ageing promoted the superparamagnetic behaviour of samples, attributed to the content of the cobalt ferrite structure in nanocrystals. In regard to the estimated band gap energy, all samples exhibited low levels. These results indicate that these solids would be suitable for photocatalysts use in all

  17. Impact of size, secondary structure, and counterions on the binding of small ribonucleic acids to layered double hydroxide nanoparticles.

    PubMed

    Rodriguez, Blanca V; Pescador, Jorge; Pollok, Nicole; Beall, Gary W; Maeder, Corina; Lewis, L Kevin

    2015-12-30

    Use of ribonucleic acid (RNA) interference to regulate protein expression has become an important research topic and gene therapy tool, and therefore, finding suitable vehicles for delivery of small RNAs into cells is of crucial importance. Layered double metal hydroxides such as hydrotalcite (HT) have shown great promise as nonviral vectors for transport of deoxyribose nucleic acid (DNA), proteins, and drugs into cells, but the adsorption of RNAs to these materials has been little explored. In this study, the binding of small RNAs with different lengths and levels of secondary structure to HT nanoparticles has been analyzed and compared to results obtained with small DNAs in concurrent experiments. Initial experiments established the spectrophotometric properties of HT in aqueous solutions and determined that HT particles could be readily sedimented with near 100% efficiencies. Use of RNA+HT cosedimentation experiments as well as electrophoretic mobility shift assays demonstrated strong adsorption of RNA 25mers to HT, with twofold greater binding of single-stranded RNAs relative to double-stranded molecules. Strong affinities were also observed with ssRNA and dsRNA 54mers and with more complex transfer RNA molecules. Competition binding and RNA displacement experiments indicated that RNA-HT associations were strong and were only modestly affected by the presence of high concentrations of inorganic anions.

  18. Analysis of ldh genes in Lactobacillus casei BL23: role on lactic acid production.

    PubMed

    Rico, Juan; Yebra, María Jesús; Pérez-Martínez, Gaspar; Deutscher, Josef; Monedero, Vicente

    2008-06-01

    Lactobacillus casei is a lactic acid bacterium that produces L-lactate as the main product of sugar fermentation via L-lactate dehydrogenase (Ldh1) activity. In addition, small amounts of the D-lactate isomer are produced by the activity of a D-hydroxycaproate dehydrogenase (HicD). Ldh1 is the main L-lactate producing enzyme, but mutation of its gene does not eliminate L-lactate synthesis. A survey of the L. casei BL23 draft genome sequence revealed the presence of three additional genes encoding Ldh paralogs. In order to study the contribution of these genes to the global lactate production in this organism, individual, as well as double mutants (ldh1 ldh2, ldh1 ldh3, ldh1 ldh4 and ldh1 hicD) were constructed and lactic acid production was assessed in culture supernatants. ldh2, ldh3 and ldh4 genes play a minor role in lactate production, as their single mutation or a mutation in combination with an ldh1 deletion had a low impact on L-lactate synthesis. A Deltaldh1 mutant displayed an increased production of D-lactate, which was probably synthesized via the activity of HicD, as it was abolished in a Deltaldh1 hicD double mutant. Contrarily to HicD, no Ldh1, Ldh2, Ldh3 or Ldh4 activities could be detected by zymogram assays. In addition, these assays revealed the presence of extra bands exhibiting D-/L-lactate dehydrogenase activity, which could not be attributed to any of the described genes. These results suggest that L. casei BL23 possesses a complex enzymatic system able to reduce pyruvic to lactic acid.

  19. Effect of added zinc on the properties of cobalt-containing ceramic pigments prepared from layered double hydroxides

    SciTech Connect

    Perez-Bernal, M.E.; Ruano-Casero, R.J.; Rives, V.

    2009-09-15

    Layered double hydroxides (LDHs) with the hydrotalcite-type structure containing Co and Al, or Zn, Co and Al in the brucite-like layers and carbonate in the interlayer have been prepared by coprecipitation. The Zn/Co molar ratio was kept to 1 in all samples, while the divalent/trivalent molar ratio was varied from 2/1 to 1/2. The samples have been characterised by element chemical analysis, powder X-ray diffraction, differential thermal and thermogravimetric analysis, temperature-programmed reduction and FT-IR spectroscopy. A single hydrotalcite-like phase is formed for samples with molar ratio 2/1, which crystallinity decreases as the Al content is increased, developing small amounts of diaspore and dawsonite and probably an additional amorphous phase. Calcination at 1200 deg. C in air led to formation of spinels; a small amount of NaAlO{sub 2} was observed in the Al-rich samples, which was removed by washing. The nature of the spinels formed (containing Co{sup II}, Co{sup III}, Al{sup III} and Zn{sup II}) strongly depends on the cations molar ratio in the starting materials and the calcination treatment, leading to a partial oxidation of Co{sup II} species to Co{sup III} ones. Colour properties (L*a*b*) of the original and calcined solids have been measured. While the original samples show a pink colour (lighter for the series containing Zn), the calcined Co,Al samples show a dark blue colour and the Zn,Co,Al ones a green colour. Changes due to the different molar ratios within a given calcined series are less evident than between samples with the same composition in different series. These calcined materials could be usable as ceramic pigments. - Abstract: Mixed oxides from layered double hydroxides (LDHs) with the hydrotalcite-type structure containing Co and Al or Zn, Co and Al in the brucite-like layers are potential candidates for ceramic pigments with tunable colour properties. Display Omitted

  20. Water decontamination via the removal of Pb (II) using a new generation of highly energetic surface nano-material: Co(+2)Mo(+6) LDH.

    PubMed

    Mostafa, Mohsen S; Bakr, Al-Sayed A; El Naggar, Ahmed M A; Sultan, El-Sayed A

    2016-01-01

    CoMo(CO3(2-)) layered double hydroxide of a highly energetic surface, as a new LDH consisting of divalent and hexavalent cations (M(+2)/M(+6)-LDH), was prepared by a homogeneous co-precipitation method. The structure and morphology of the prepared material was confirmed by several analytical techniques namely; X-ray diffraction analysis (XRD), X-ray fluorescence (XRF), Fourier transform infra-red (FT-IR) spectroscopy, differential scanning calorimetry and thermal gravimetric analysis (DSC-TGA), N2 adsorption-desorption isotherm and scanning electron microscope (SEM). The highly energetic surface of the prepared LDH was demonstrated via the X-ray photoelectron spectroscopy (XPS). The surface energy is due to the formation of +4 surface charges in the brucite layer between Co(+2) and Mo(+6). The prepared LDH was applied as a novel adsorbent for the removal of Pb (II) from its aqueous solution at different experimental conditions of time, temperature and initial Pb (II) concentrations. The change of the Pb (II) concentrations; due to adsorption, was monitored by atomic absorption spectrophotometer (AAS). The maximum uptake of Pb (II) by the Co Mo LDH was (73.4 mg/g) at 298 K. The Pb (II) adsorption was found to follow Langmuir isotherm and pseudo second order model. The adsorption process was spontaneous and endothermic. The interference of other cations on the removal of the Pb (II) was studied. Na(+) and K(+) were found to increase the adsorption capacity of the Co Mo LDH toward Pb (II) while it was slightly decreased by the presence of Mn(+2) and Cu(+2). The synthesized LDH showed a great degree of recoverability (7 times) while completely conserving its parental morphology and adsorption capacity. The mechanism of the lead ions removal had exhibited more reliability through a surface adsorption by the coordination between the Mo(+6) of the brucite layers and the oxygen atoms of the nitrates counter ions.

  1. Reversible intercalation of ammonia molecules into a layered double hydroxide structure without exchanging nitrate counter-ions

    SciTech Connect

    Carbajal Arizaga, Gregorio Guadalupe; Wypych, Fernando; Castillon Barraza, Felipe; Contreras Lopez, Oscar Edel

    2010-10-15

    A zinc/aluminum LDH was precipitated with recycled ammonia from a chemical vapor deposition reaction. The LDH presented a crystalline phase with basal distance of 8.9 A, typical for nitrate-containing LDHs, and another phase with a basal distance of 13.9 A. Thermal treatment at 150 {sup o}C eliminated the phase with the bigger basal distance leaving only the anhydrous nitrate-intercalated LDH structure with 8.9 A. Intense N-H stretching modes in the FTIR spectra suggested that the expansion was due to intercalation of ammonia in the form of [NH{sub 4}(NH{sub 3}){sub n}]{sup +} species. When additional samples were precipitated with pure ammonia, the conventional LDH nitrate structure was obtained (8.9 A basal distance) at pH=7, as well as a pure crystalline phase with 13.9 A basal distance at pH=10 due to ammonia intercalation that can be removed by heating at 150 {sup o}C or by stirring in acetone, confirming a unusual sensu stricto intercalation process into a LDH without exchanging nitrate ions. - Graphical abstract: LDH-nitrate precipitated with ammonia expands the interlayer space if ammonia is bubbled up to pH 10. The basal distance decreased when the compound was heated at 150 {sup o}C or stirred in acetone. Nitrate ions are not exchanged.

  2. Removal of chloride ion from aqueous solution by ZnAl-NO(3) layered double hydroxides as anion-exchanger.

    PubMed

    Lv, Liang; Sun, Peide; Gu, Zhengyu; Du, Hangeng; Pang, Xiangjun; Tao, Xiaohong; Xu, Rufeng; Xu, Lili

    2009-01-30

    The layered double hydroxides (LDHs) containing nitrate as the interlayer anion has a high anion-exchange capacity in the presence of appropriate anions. In the light of this, ZnAl-NO(3) LDHs have been employed to remove chloride ion from aqueous solution in a batch mode. The influences of conditions for chloride ion uptake, including dosage of LDHs, pH of aqueous solution, and temperature on anion-exchange have been investigated, respectively. The thermodynamic parameters including Gibbs free energy (DeltaG(0)), standard enthalpy change (DeltaH(0)), and standard entropy change (DeltaS(0)) for the process were calculated using the Langmuir constants. It was found from kinetics test that the pseudo-second order kinetics model could be used to well describe the uptake process. An E(a) value of 10.27 kJ/mol provides evidence the anion-exchange process. The explanation of anion-exchange phenomenon has also been supported by X-ray diffraction and FT-IR spectra.

  3. Effect of Rare Earth Ions on the Properties of Composites Composed of Ethylene Vinyl Acetate Copolymer and Layered Double Hydroxides

    PubMed Central

    Wang, Lili; Li, Bin; Zhao, Xiaohong; Chen, Chunxia; Cao, Jingjing

    2012-01-01

    Background The study on the rare earth (RE)-doped layered double hydroxides (LDHs) has received considerable attention due to their potential applications in catalysts. However, the use of RE-doped LDHs as polymer halogen-free flame retardants was seldom investigated. Furthermore, the effect of rare earth elements on the hydrophobicity of LDHs materials and the compatibility of LDHs/polymer composite has seldom been reported. Methodology/Principal Findings The stearate sodium surface modified Ni-containing LDHs and RE-doped Ni-containing LDHs were rapidly synthesized by a coprecipitation method coupled with the microwave hydrothermal treatment. The influences of trace amounts of rare earth ions La, Ce and Nd on the amount of water molecules, the crystallinity, the morphology, the hydrophobicity of modified Ni-containing LDHs and the adsorption of modifier in the surface of LDHs were investigated by TGA, XRD, TEM, contact angle and IR, respectively. Moreover, the effects of the rare earth ions on the interfacial compatibility, the flame retardancy and the mechanical properties of ethylene vinyl acetate copolymer (EVA)/LDHs composites were also explored in detail. Conclusions/Significance S-Ni0.1MgAl-La displayed more uniform dispersion and better interfacial compatibility in EVA matrix compared with other LDHs. Furthermore, the S-Ni0.1MgAl-La/EVA composite showed the best fire retardancy and mechanical properties in all composites. PMID:22693627

  4. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting.

    PubMed

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G; Duan, Xue

    2015-07-15

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm(2) at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting.

  5. Flexible Fiber-Shaped Supercapacitor Based on Nickel-Cobalt Double Hydroxide and Pen Ink Electrodes on Metallized Carbon Fiber.

    PubMed

    Gao, Libo; Surjadi, James Utama; Cao, Ke; Zhang, Hongti; Li, Peifeng; Xu, Shang; Jiang, Chenchen; Song, Jian; Sun, Dong; Lu, Yang

    2017-02-15

    Flexible fiber-shaped supercapacitors (FSSCs) are recently of extensive interest for portable and wearable electronic gadgets. Yet the lack of industrial-scale flexible fibers with high conductivity and capacitance and low cost greatly limits its practical engineering applications. To this end, we here present pristine twisted carbon fibers (CFs) coated with a thin metallic layer via electroless deposition route, which exhibits exceptional conductivity with ∼300% enhancement and superior mechanical strength (∼1.8 GPa). Subsequently, the commercially available conductive pen ink modified high conductive composite fibers, on which uniformly covered ultrathin nickel-cobalt double hydroxides (Ni-Co DHs) were introduced to fabricate flexible FSSCs. The synthesized functionalized hierarchical flexible fibers exhibit high specific capacitance up to 1.39 F·cm(-2) in KOH aqueous electrolyte. The asymmetric solid-state FSSCs show maximum specific capacitance of 28.67 mF·cm(-2) and energy density of 9.57 μWh·cm(-2) at corresponding power density as high as 492.17 μW·cm(-2) in PVA/KOH gel electrolyte, with demonstrated high flexibility during stretching, demonstrating their potential in flexible electronic devices and wearable energy systems.

  6. Influence of nature of precursors on the formation and structure of Cu Ni Cr mixed oxides from layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, Lihong; Zhu, Jia; Jiang, Xiaorui; Evans, David G.; Li, Feng

    2006-08-01

    Analogous layered double hydroxides (LDHs) with the Cu2+/Ni2+/Cr3+ molar ratio of 1/2/1 on the brucite-like layers and interlayer anions (viz sulfate, nitrate and carbonate, respectively) were synthesized by a coprecipitation method. For the first time, the effects of interlayer anions on the structural properties of as-synthesized LDHs and resulting calcined products at 773 K were investigated by means of powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), simultaneous thermogravimetric and differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The results indicate that the nature of interlayer anions involved within the hydrotalcite (HT)-like structure has a larger influence on the thermal stability of LDHs precursors. Calcination of well-crystallized LDHs leads to the formation of mixed metal oxides including CuO, NiO and Cu2+-, Ni2+- and Cr3+-containing spinel phases, the composition distributions of which obtained from LDHs precursors depend on the nature of interlayer anions, thus resulting in the difference of the reducibility of reducible metal species in the calcined LDHs. Moreover, the surface basicity of the calcined material, which is related to the different behaviour of LDHs precursors during the thermal decomposition depending on the interlayer anions, increases progressively following the order of calcined LDHs from sulfate to nitrate and carbonate.

  7. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

    PubMed Central

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

    2015-01-01

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

  8. Tribological performance of Mg/Al/Ce layered double hydroxides nanoparticles and intercalated products as lubricant additives

    NASA Astrophysics Data System (ADS)

    Li, Shuo; Qin, Haojing; Zuo, Ranfang; Bai, Zhimin

    2015-10-01

    Mg/Al/Ce ternary layered double hydroxides (LDHs) were synthesized via coprecipitation and intercalated by succinic acid and lauric acid through ion exchange method respectively. The LDHs products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transform infrared (FT-IR). Tribological properties of LDHs as lubricant additives were evaluated by four-ball friction and air compressor test. The results indicated that Mg/Al/Ce LDHs were prepared successfully with Ce/Al molar ratio of 0.05 and crystallization temperature of 140 °C. The interlayer spacing of LDHs precursor was expanded by succinic acid and lauric acid to 8.838 and 17.519 Å respectively. All the three LDHs products can reduce friction and wear of engine lubricating oil in the tests. LDHs intercalated with lauric acid showed best tribological performance among them which was attributed to sliding each other between laminates, good dispersibility in oil medium and a protective tribofilm formed on the worn surface.

  9. The decomposition of the layered double hydroxides of Co and Al: phase segregation of a new single phase spinel oxide.

    PubMed

    Babay, Salem; Bulou, Alain; Mercier, Anne Marie; Toumi, Mouhamed

    2015-04-15

    Monophasic Co-Al-CO3-like layered double hydroxides has been prepared by the coprecipitation method. It has been characterised by Rietveld refinement of the X-ray powder diffraction pattern, DTA-TGA, infrared and Raman spectroscopies. Its structure is trigonal, R3̅m with cell parameters a=0.3061(4) nm and c=2.252 (3) nm. The decomposition of this hydrotalcite-like structure on heating up to 800 °C yields to a single phase spinel oxide. Besides, infrared and Raman spectroscopies showed the presence of spinel-like domains. The results of Rietveld refinement have revealed that this compound has the Fd3̅m space group (a=0.8088(4) nm), with crystallographic formula [Co(II)0.75Al0.25](8a)[Co(II)0.252Co(III)0.77Al0.98](16d)O4, which is of the general formula Co1.77Al1.23O4. This structure is also validated by the charge distribution (CD) analysis.

  10. Competitive adsorption characteristics of fluoride and phosphate on calcined Mg-Al-CO3 layered double hydroxides.

    PubMed

    Cai, Peng; Zheng, Hong; Wang, Chong; Ma, Hongwen; Hu, Jianchao; Pu, Yubing; Liang, Peng

    2012-04-30

    With synthetic wastewater, competitive adsorption characteristics of fluoride and phosphate on calcined Mg-Al-CO(3) layered double hydroxides (CLDH) were investigated. A series of batch experiments were performed to study the influence of various experimental parameters, such as pH, contact time, and order of addition of the anions on the competitive adsorption of fluoride and phosphate on CLDH. It was found that the optimal pH is around 6 and it took 24 h to attain equilibrium when fluoride and phosphate were simultaneous added. The order of addition of anions influenced the adsorption of fluoride and phosphate on CLDH. The kinetic data were analyzed using the pseudo first-order and pseudo second-order models and they were found to fit very well the pseudo second-order kinetic model. Data of equilibrium experiments were fitted well to Langmuir isotherm and the competitive monolayer adsorption capacities of fluoride and phosphate were found to be obviously lower than those of single anion at 25 °C. The results of X-ray diffraction, Scanning Electron Microscopy with energy-dispersive X-ray analyses, and ATR-FTIR demonstrate that the adsorption mechanism involves the rehydration of mixed metal oxides and concomitant intercalation of fluoride and phosphate ions into the interlayer to reconstruct the initial LDHs structure.

  11. Preparation of a polymer monolith modified with delaminated layered double hydroxides for the microextraction of β-agonists.

    PubMed

    Zhou, Yufeng; Zheng, Haijiao; Ma, Jiutong; Jia, Qiong

    2017-04-01

    In the present study, a novel poly(acrylamide-co-N-isopropylacrylamide-co-ethylene dimethacrylate) monolithic column modified with saline-modified delaminated layered double hydroxides was developed and exploited as the stationary phase in the polymer monolith microextraction of β-agonists. Transmission electron microscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and thermal gravimetric analysis with derivative thermogravimetric determination were employed to characterize the monoliths. By coupling with high-performance liquid chromatography determinations, extraction parameters affecting the extraction efficiency, including sample volume, flow rate, sample pH, eluent volume, and eluent flow rate were investigated with an orthogonal experiment design, L16 (4(5) ). Results demonstrated that under the optimal experimental conditions, low limits of detection in the range of 0.025-0.280 ng/mL were obtained with relative standard deviations in the range of 4.3-7.6% (intraday) and 6.7-8.8% (interday). When the developed method was applied to the analysis of β-agonists in pork samples, recovery values were obtained in the range of 80.5-108.6%.

  12. Biosensor based on acetylcholinesterase immobilized onto layered double hydroxides for flow injection/amperometric detection of organophosphate pesticides.

    PubMed

    Gong, Jingming; Guan, Zhangqiong; Song, Dandan

    2013-01-15

    We developed a highly sensitive flow injection/amperometric biosensor for the detection of organophosphate pesticides (OPs) using layered double hydroxides (LDHs) as the immobilization matrix of acetylcholinesterase (AChE). LDHs provided a biocompatible microenvironment to keep the bioactivity of AChE, due to the intrinsic properties of LDHs (such as a regular structure, good mechanical, chemical and thermal stabilities, and swelling properties). By integrating the flow injection analysis (FIA) with amperometric detection, the resulting AChE-LDHs modified electrode greatly catalyzed the oxidation of the enzymatically generated thiocholine product, and facilitated the detection automation, thus increasing the detection sensitivity. The analytical conditions for the FIA/amperometric detection of OPs were optimized by using methyl parathion (MP) as a model. The inhibition of MP was proportional to its concentration ranging from 0.005 to 0.3μg mL(-1) and 0.3 to 4.0μg mL(-1) with a detection limit 0.6ng mL(-1) (S/N=3). The developed biosensor exhibited good reproducibility and acceptable stability.

  13. Enhanced removal performance by the core-shell zeolites/MgFe-layered double hydroxides (LDHs) for municipal wastewater treatment.

    PubMed

    Guo, Lu; Zhang, Xiangling; Chen, Qiaozhen; Ruan, Congying; Leng, Yujie

    2016-04-01

    The application of powdered layer double hydroxides (LDHs) in constructed rapid infiltration system (CRIS) appears to be an appreciable problem still unsolved due to the small particle size and the low density. Therefore, the core-shell zeolites/MgFe-LDHs composites were prepared via using co-precipitation method in present study. To investigate the practical applicability, a detailed organics, ammonia, and total phosphorus removal study were carried out in columns to treat the municipal wastewater. The scanning electron microscope (SEM) and energy dispersive spectrometer (EDS) results confirmed the successful synthesis of core-shell zeolites/MgFe-LDHs through coating on the surface of zeolites. Accordingly, the zeolites/MgFe-LDHs largely reduced the COD by 81.14 %, NH4 (+)-N by 81.50%, and TP by 83.29%. Phosphate adsorption study revealed that the equilibrium adsorption data were better fitted by Langmuir isothermal model, with the maximum adsorption capacity of 79.3651 mg/kg for zeolites/MgFe-LDHs and 38.4615 mg/kg for the natural zeolites. In addition, economic analysis indicated that the reagent cost of synthesis of zeolites/MgFe-LDHs was economical. Herein, the zeolites/MgFe-LDHs solved the natural zeolites problem for poor P removal and the application of powdered LDHs in the solid/liquid separation process, suggesting that it was applicable as potential substrates for the removal of organics, ammonia, and total phosphorus in CRIS.

  14. Synthesis of higher alcohols over highly dispersed Cu-Fe based catalysts derived from layered double hydroxides.

    PubMed

    Han, Xinyou; Fang, Kegong; Zhou, Juan; Zhao, Lu; Sun, Yuhan

    2016-05-15

    Highly dispersed Cu-Fe based catalysts with Fe/Cu molar ratios ranging from 0.2 to 1 were prepared via thermal decomposition of layered double hydroxides (LDHs) precursors and tested for higher alcohol synthesis (HAS) via CO hydrogenation. The catalysts were characterized using different techniques such as XRD, TEM, XPS, and H2-TPR. It was demonstrated that the Cu and Fe ions were highly dispersed in the brucite-like layers of the LDHs. With increased Fe/Cu atomic ratio, the tetrahedrally coordinated Cu ion content, Cu reduction temperatures, and the spacing of layers initially increase until the Fe/Cu ratio reaches 0.5 and then decrease. In addition to the catalytic evaluation for CO hydrogenation and catalyst characterization, the relationships between the physical-chemical properties of the catalysts and their catalytic performances were also investigated. It was also found that the alcohols/hydrocarbons ratios correlate linearly with the tetrahedrally coordinated Cu ion content. Moreover, higher reduction temperatures of Cu species as well as larger spacing between the layers in the catalyst are favorable for the synthesis of alcohols. The incorporation of a suitable amount of Fe is beneficial for the production of higher alcohols, with the best catalytic performance (alcohol selectivity of 20.77% and C2+ alcohol selectivity of 48.06%) obtained from a Fe/Cu atomic ratio of 0.5.

  15. Adsorption and photodegradation kinetics of herbicide 2,4,5-trichlorophenoxyacetic acid with MgFeTi layered double hydroxides.

    PubMed

    Nguyen, Thi Kim Phuong; Beak, Min-wook; Huy, Bui The; Lee, Yong-Ill

    2016-03-01

    The calcined layered double hydroxides (cLDHs) Ti-doped and undoped MgFe for this study were prepared by co-precipitation method followed by calcination at 500 °C. The as-prepared samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET) and UV-Vis diffuse reflectance spectrum (DRS) techniques and tested for adsorption and photodegradation (including photocatalytic and photo-Fenton-like) of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solutions under visible light irradiation. In the range of studied operating conditions, the as-prepared samples exhibited excellent photo-Fenton-like activity, leading to more than 80-95% degradation of 2,4,5-T at initial concentration of 100 mg L(-1) with 4 g calcined LDHs per liter, was accomplished in 360 min, while 2,4,5-T half-life time was as short as 99-182 min. The kinetics of adsorption and photodegradation of 2,4,5-T were also discussed. These results offered a green, low cost and high efficiency photocatalyst for environmental remediation.

  16. Horseradish peroxidase immobilization on carbon nanodots/CoFe layered double hydroxides: direct electrochemistry and hydrogen peroxide sensing.

    PubMed

    Wang, Yinling; Wang, Zhangcui; Rui, Yeping; Li, Maoguo

    2015-02-15

    Carbon nanodots and CoFe layered double hydroxide composites (C-Dots/LDHs) were prepared via simply mixing C-Dots and CoFe-LDHs. The as-prepared composites were used for the immobilization of horseradish peroxidase (HRP) on the glass carbon (GC) electrode. The electrochemical behavior of the HRP/C-Dots/LDHs/GC electrode and its application as a H2O2 biosensor were investigated. The results indicated that HRP immobilized by C-Dots/LDHs retained the activity of enzyme and displayed quasi-reversible redox behavior and fast electron transfer with an electron transfer rate constant ks of 8.46 s(-1). Under optimum experimental conditions, the HRP/C-Dots/LDHs/GC electrode displayed good electrocatalytic reduction activity and excellent analytic performance toward H2O2. The H2O2 biosensor showed a linear range of 0.1-23.1 μM (R(2) = 0.9942) with a calculated detection limit of 0.04 μM (S/N = 3). In addition, the biosensor exhibited high sensitivity, good selectivity, acceptable reproducibility and stability. The superior properties of this biosensor are attributed to the synergistic effect of HRP, C-Dots and CoFe-LDHs, which has been proved by investigating their electrochemical response to H2O2. Thus the C-Dots and LDHs composites provide a promising platform for the immobilization of redox enzymes and construction of sensitive biosensors.

  17. Vertically Aligned FeOOH/NiFe Layered Double Hydroxides Electrode for Highly Efficient Oxygen Evolution Reaction.

    PubMed

    Chi, Jun; Yu, Hongmei; Qin, Bowen; Fu, Li; Jia, Jia; Yi, Baolian; Shao, Zhigang

    2017-01-11

    Employing a low-cost and highly efficient electrocatalyst to replace Ir-based catalysts for oxygen evolution reaction (OER) has drawn increasing interest in renewable energy storage. In this work, a vertically aligned FeOOH/NiFe layered double hydroxides (LDHs) nanosheets supported on Ni foam (VA FeOOH/NiFe LDHs-NF) is prepared as a highly effective OER electrode in alkaline electrolyte. The VA FeOOH/NiFe LDHs-NF represents nanosheet arrays on nickel foam with some interspace among them. The vertically aligned and interlayer-structured architecture is binder-free and contributes to facile strain relaxation, relieving the exfoliation of the catalysts layer caused by the oxygen evolution process. The as-prepared electrode shows current densities of 10 and 500 mA cm(-2) at overpotentials of 208 and 288 mV, and good stability in a half-cell electrolyzer. Besides, the alkaline polymer electrolyte water electrolyzer (APEWE) with this electrode showed 1.71 V at 200 mA cm(-2), and 2.041 V at 500 mA cm(-2), exhibiting the corresponding energy efficiency of 86.0% and 72.0% (based on the lower heating value of hydrogen), which is better than the typical commercial alkaline water electrolyzer.

  18. Chemiluminescence flow biosensor for glucose using Mg-Al carbonate layered double hydroxides as catalysts and buffer solutions.

    PubMed

    Wang, Zhihua; Liu, Fang; Lu, Chao

    2012-01-01

    In this work, serving as supports in immobilizing luminol reagent, catalysts of luminol chemiluminescence (CL), and buffer solutions for the CL reaction, Mg-Al-CO(3) layered double hydroxides (LDHs) were found to trigger luminol CL in weak acid solutions (pH 5.8). The silica sol-gel with glucose oxidase and horseradish peroxidase was immobilized in the first half of the inside surface of a clear quartz tube, and luminol-hybrid Mg-Al-CO(3) LDHs were packed in the second half. Therefore, a novel CL flow-through biosensor for glucose was constructed in weak acid solutions. The CL intensity was linear with glucose concentration in the range of 0.005-1.0mM, and the detection limit for glucose (S/N=3) was 0.1 μM. The proposed biosensor exhibited excellent stability, high reproducibility and high selectivity for the determination of glucose and has been successfully applied to determine glucose in human plasma samples with satisfactory results. The success of this work has broken the bottleneck of the pH incompatibility between luminol CL and enzyme activity.

  19. A new route for local probing of inner interactions within a layered double hydroxide/benzene derivative hybrid material.

    PubMed

    Fleutot, S; Dupin, J C; Baraille, I; Forano, C; Renaudin, G; Leroux, F; Gonbeau, D; Martinez, H

    2009-05-14

    This paper presents the preparation and characterization of hybrid hydrotalcite-type layered double hydroxides (Zn1-xAlx(OH)2HBSx.nH2O, with x=0.33) where HBS is the 4-phenol sulfonate, with a detailed analysis of the grafting process of this organic entity onto the host lattice. As a set of the usual techniques (XRD, TG-DT/MS, FTIR and 27Al MAS NMR) was used to characterize the hybrid materials, this work focuses on a joint study by X-ray photoelectron spectroscopy and some quantum-calculation modeling in order to highlight the nature of the interactions between the organic and the mineral sub-systems. For the as-prepared hybrid material, the main results lead to a quasi-vertical orientation of the organic molecules within the mineral sheets via H-bond stabilization. By heating the hybrid material up to 200 degrees C, the structure shrinks with the condensation of the organics; the different theoretical modeling done gives an energy-stable situation when a direct attachment of the HBS sulfonate group sets up with the mineral layers, in agreement with the recorded XPS experimental data.

  20. A magnetic organic inorganic composite: Synthesis and characterization of magnetic 5-aminosalicylic acid intercalated layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Zou, Kang; Sun, Hui; Duan, Xue

    2005-11-01

    A core-shell structured magnetic layered organic-inorganic material involving 5-aminosalicylic acid (5-ASA) intercalated Zn-Al layered double hydroxides (LDHs) and magnesium ferrite (MgFe 2O 4) is assembled by a coprecipitation method. The powder X-ray diffraction results show the coexistence of the clear but weak diffractions of MgFe 2O 4 and ordered relatively stronger reflections of 5-ASA intercalated LDHs. The TEM image of magnetic 5-ASA intercalated LDHs reveals that the LDHs layer covers the MgFe 2O 4 particles or their aggregates with particle size of 50-80 nm. The vibration sample magnetization (VSM) measurements exhibit the increase in saturation magnetization of magnetic 5-ASA intercalated LDHs samples with increasing amount of magnetic core. The XPS analyses account for a majority of Zn, Al and O atoms on the surface of magnetic particles. It is suggested that the magnetic core MgFe 2O 4 was coated with LDHs layer probably through Zn-O-Mg and Al-O-Mg linkages, and a core-shell structured model is tentatively proposed.

  1. Layered double hydroxides as carriers for quantum dots@silica nanospheres.

    PubMed

    Stoica, Georgiana; Castelló Serrano, Iván; Figuerola, Albert; Ugarte, Irati; Pacios, Roberto; Palomares, Emilio

    2012-09-07

    Quantum dot-hydrotalcite layered nanoplatforms were successfully prepared following a one-pot synthesis. The process is very fast and a priori delamination of hydrotalcite is not a prerequisite for the intercalation of quantum dots. The novel materials were extensively characterized by X-ray diffraction, thermogravimetry, infrared spectroscopy, transmission electron microscopy, true color fluorescence microscopy, photoluminescence, and nitrogen adsorption. The quantum dot-hydrotalcite nanomaterials display extremely high stability in mimicking physiological media such as saline serum (pH 5.5) and PBS (pH 7.2). Yet, quantum dot release from the solid structure is noted. In order to prevent the leaking of quantum dots we have developed a novel strategy which consists of using tailor made double layered hydrotalcites as protecting shells for quantum dots embedded into silica nanospheres without changing either the materials or the optical properties.

  2. Studies on the intercalation of naproxen into layered double hydroxide and its thermal decomposition by in situ FT-IR and in situ HT-XRD

    NASA Astrophysics Data System (ADS)

    Wei, Min; Shi, Shuxian; Wang, Ji; Li, Yong; Duan, Xue

    2004-07-01

    Layered double hydroxides, novel anionic clay, meet the first requirement as inorganic matrices for encapsulating functional drugs or biomolecules with negative charge in aqueous media. In this study, naproxen has been intercalated into Mg-Al layered double hydroxide by the methods of ion exchange. The structure and composition of the intercalated material have been studied by X-ray diffraction (XRD), UV-vis spectroscopy and inductively coupled plasma emission spectroscopy. A schematic model has been proposed. Furthermore, in situ Fourier transform infrared spectroscopy, in situ high-temperature XRD, and thermogravimetry (TG) have been used to characterize the thermal decomposition of the hybrid material. It has been found that the thermal stability of the intercalated naproxen is significantly enhanced compared with the pure form before intercalation, which suggests that this drug-inorganic layered material may have prospective application as the basis of a novel drug delivery system.

  3. Synthesis, sustained release properties of magnetically functionalized organic-inorganic materials: Amoxicillin anions intercalated magnetic layered double hydroxides via calcined precursors at room temperature

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Liu, Qi; Zhang, Guangchun; Li, Zhanshuang; Yang, Piaoping; Jing, Xiaoyan; Zhang, Milin; Liu, Tianfu; Jiang, Zhaohua

    2009-09-01

    Zinc-aluminum-carbonate-layered double hydroxides (ZnAl-CO 3-LDHs), loaded with magnetic substrates (Fe 3O 4), were prepared for sustained drug-targeting delivery. From the X-ray diffraction results, it was found that the magnetic substrates were successfully incorporated with LDHs and highly dispersed in the hydrotalcite structure. After intercalation with an antibiotic drug (amoxicillin) by using a calcinations-reconstruction method, the basal spacing of layered double hydroxides increased from 7.51 Å to 12.35 Å, indicating that amoxicillin was successfully intercalated into the interlay space of LDHs as a monolayer. Furthermore, in vitro drug release experiments in pH 7.4 phosphate buffer solution (PBS) showed sustained release profiles with amoxicillin as a model drug. Magnetic measurements revealed that the composite possessed paramagnetic properties at room temperature.

  4. Preparation of layered double hydroxides and their applications as additives in polymers, as precursors to magnetic materials and in biology and medicine.

    PubMed

    Evans, David G; Duan, Xue

    2006-02-07

    In recent years layered double hydroxides (LDHs), also known as hydrotalcite-like materials, have attracted considerable interest from both industry and academia. In this article, we discuss methods of preparing LDHs with an emphasis on the way in which particle size and morphology can be controlled with regard to specific target applications; scale-up of one such preparation procedure is also described. In addition, we review selected applications of LDHs developed by our own and other laboratories.

  5. Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state 1H and 71Ga NMR spectroscopy

    SciTech Connect

    Petersen, Line B.; Lipton, Andrew S.; Zorin, Vadim; Nielsen, Ulla Gro

    2014-11-01

    Ordering of gallium(III) in a series of magnesium gallium layered double hydroxides (LDH’s), [Mg1-xGax(OH)2(NO3)x yH2O], was determined using solid-state 1H and 71Ga NMR spectroscopy. Depletion of Ga in these LDH’s is demonstrated to be the result of soluble [Ga(OH)4]-complexes formed during synthesis.

  6. Cu sbnd Al sbnd Fe layered double hydroxides with CO32- and anionic surfactants with different alkyl chains in the interlayer

    NASA Astrophysics Data System (ADS)

    Trujillano, Raquel; Holgado, María Jesús; González, José Luis; Rives, Vicente

    2005-08-01

    Layered double hydroxides (LDHs), with the hydrotalcite-like structure containing Cu(II), Al(III) and Fe(III) in the layers, and different alkyl sulfonates in the interlayer, have been prepared and characterized by powder X-ray diffraction, FT-IR spectroscopy, differential thermal analysis and thermogravimetric analysis. Pure crystalline phases have been obtained in all cases. Upon heating, combustion of the organic chain takes place at lower temperature than the corresponding sodium salts.

  7. Self-Assembly of Single-Layer CoAl-Layered Double Hydroxide Nanosheets on 3D Graphene Network Used as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction.

    PubMed

    Ping, Jianfeng; Wang, Yixian; Lu, Qipeng; Chen, Bo; Chen, Junze; Huang, Ying; Ma, Qinglang; Tan, Chaoliang; Yang, Jian; Cao, Xiehong; Wang, Zhijuan; Wu, Jian; Ying, Yibin; Zhang, Hua

    2016-09-01

    A non-noble metal based 3D porous electrocatalyst is prepared by self-assembly of the liquid-exfoliated single-layer CoAl-layered double hydroxide nanosheets (CoAl-NSs) onto 3D graphene network, which exhibits higher catalytic activity and better stability for electrochemical oxygen evolution reaction compared to the commercial IrO2 nanoparticle-based 3D porous electrocatalyst.

  8. Comparative study of Mg/Al- and Zn/Al-layered double hydroxide-perindopril erbumine nanocomposites for inhibition of angiotensin-converting enzyme

    PubMed Central

    Hussein Al Ali, Samer Hasan; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Ismail, Maznah; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

    2012-01-01

    The intercalation of a drug active, perindopril, into Mg/Al-layered double hydroxide for the formation of a new nanocomposite, PMAE, was accomplished using a simple ion exchange technique. A relatively high loading percentage of perindopril of about 36.5% (w/w) indicates that intercalation of the active took place in the Mg/Al inorganic interlayer. Intercalation was further supported by Fourier transform infrared spectroscopy, and thermal analysis shows markedly enhanced thermal stability of the active. The release of perindopril from the nanocomposite occurred in a controlled manner governed by pseudo-second order kinetics. MTT assay showed no cytotoxicity effects from either Mg/Al-layered double hydroxide or its nanocomposite, PMAE. Mg/Al-layered double hydroxide showed angiotensin-converting enzyme inhibitory activity, with 5.6% inhibition after 90 minutes of incubation. On incubation of angiotensin-converting enzyme with 0.5 μg/mL of the PMAE nanocomposite, inhibition of the enzyme increased from 56.6% to 70.6% at 30 and 90 minutes, respectively. These results are comparable with data reported in the literature for Zn/Al-perindopril. PMID:22904631

  9. Comparative study of Mg/Al- and Zn/Al-layered double hydroxide-perindopril erbumine nanocomposites for inhibition of angiotensin-converting enzyme.

    PubMed

    Hussein Al Ali, Samer Hasan; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Ismail, Maznah; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

    2012-01-01

    The intercalation of a drug active, perindopril, into Mg/Al-layered double hydroxide for the formation of a new nanocomposite, PMAE, was accomplished using a simple ion exchange technique. A relatively high loading percentage of perindopril of about 36.5% (w/w) indicates that intercalation of the active took place in the Mg/Al inorganic interlayer. Intercalation was further supported by Fourier transform infrared spectroscopy, and thermal analysis shows markedly enhanced thermal stability of the active. The release of perindopril from the nanocomposite occurred in a controlled manner governed by pseudo-second order kinetics. MTT assay showed no cytotoxicity effects from either Mg/Al-layered double hydroxide or its nanocomposite, PMAE. Mg/Al-layered double hydroxide showed angiotensin-converting enzyme inhibitory activity, with 5.6% inhibition after 90 minutes of incubation. On incubation of angiotensin-converting enzyme with 0.5 μg/mL of the PMAE nanocomposite, inhibition of the enzyme increased from 56.6% to 70.6% at 30 and 90 minutes, respectively. These results are comparable with data reported in the literature for Zn/Al-perindopril.

  10. Determination of haloacetic acids in water using layered double hydroxides as a sorbent in dispersive solid-phase extraction followed by liquid chromatography with tandem mass spectrometry.

    PubMed

    Alsharaa, Abdulnaser; Sajid, Muhammad; Basheer, Chanbasha; Alhooshani, Khalid; Lee, Hian Kee

    2016-09-01

    In the present study, highly efficient and simple dispersive solid-phase extraction procedure for the determination of haloacetic acids in water samples has been established. Three different types of layered double hydroxides were synthesized and used as a sorbent in dispersive solid-phase extraction. Due to the interesting behavior of layered double hydroxides in an acidic medium (pH˂4), the analyte elution step was not needed; the layered double hydroxides are simply dissolved in acid immediately after extraction to release the analytes which are then directly introduced into a liquid chromatography with tandem mass spectrometry system for analysis. Several dispersive solid-phase extraction parameters were optimized to increase the extraction efficiency of haloacetic acids such as temperature, extraction time and pH. Under optimum conditions, good linearity was achieved over the concentration range of 0.05-100 μg/L with detection limits in the range of 0.006-0.05 μg/L. The relative standard deviations were 0.33-3.64% (n = 6). The proposed method was applied to different water samples collected from a drinking water plant to determine the concentrations of haloacetic acids.

  11. NiMn layered double hydroxides as efficient electrocatalysts for the oxygen evolution reaction and their application in rechargeable Zn-air batteries.

    PubMed

    Sumboja, Afriyanti; Chen, Jingwei; Zong, Yun; Lee, Pooi See; Liu, Zhaolin

    2017-01-05

    High performance catalysts for the oxygen evolution reaction (OER) are in demand to improve the re-chargeability of Zn-air batteries. In this work, atomically dispersed NiMn layered double hydroxides are prepared via simple hydrothermal synthesis and tested as the OER catalyst in rechargeable Zn-air batteries. NiMn layered double hydroxides with the optimized Ni : Mn molar feeding ratio have good crystallinity, big interlayer spacing, and large surface area, which are beneficial to enhance their catalytic activity. They are highly active and stable during the OER, showing an overpotential of 0.35 V, a Tafel slope of 40 mV dec(-1), and remarkable stability during 16 h of a chronopotentiometry test. Rechargeable Zn-air batteries with NiMn layered double hydroxides as the OER catalyst exhibit a low charge voltage of ≈2 V which is stable for up to 200 cycles. This study illustrates a platform to enhance the catalytic activity of the OER catalyst via fine-tuning the composition and physical properties of the materials and their application for rechargeable metal-air batteries.

  12. Synergetic effect of SLN-curcumin and LDH-5-Fu on SMMC-7721 liver cancer cell line.

    PubMed

    Zhu, Rongrong; Wu, Xianzheng; Xiao, Yu; Gao, Bo; Xie, Qian; Liu, Hui; Wang, Shilong

    2013-10-01

    Curcumin and 5-Fluorouracil (5-Fu) have been reported to have anticancer potentials and show certain synergetic effect on some cancer cell lines. However, the poor bioavailability and rapid metabolism limited their medical application. In this study, we encapsulated curcumin with solid lipid nanoparticles (SLN), 5-Fu with Layered double hydroxides (LDHs) separately and tested its properties and anticancer potentials. SLN-curcumin and LDH-5-Fu were determined to be 100 and 60 nm by Transmission Electron Microscopy detection, and the loading efficiency were 28%±2.5% and 16.7%±1.8%, individually. Furthermore, SLN-curcumin and LDH-5-Fu showed a significantly synergetic effect on SMMC-7721 cell stronger than plain drugs together, of which the Idrug loaded nano-carriers was only 0.315. FACS analysis revealed that the combination of SLN-curcumin and LDH-5-Fu induced 80.1% apoptosis in SMMC-7721 cells, which were 1.7-folds of the sum of the two plain drug loaded carriers. The results demonstrated the significant synergetic anticancer potentials of nano-encapsulated curcumin and 5-Fu, which could be further explored for the treatment of other carcinoma.

  13. Synergetic Effect of SLN-Curcumin and LDH-5-Fu on SMMC-7721 Liver Cancer Cell Line

    PubMed Central

    Zhu, Rongrong; Wu, Xianzheng; Xiao, Yu; Gao, Bo; Xie, Qian

    2013-01-01

    Abstract Curcumin and 5-Fluorouracil (5-Fu) have been reported to have anticancer potentials and show certain synergetic effect on some cancer cell lines. However, the poor bioavailability and rapid metabolism limited their medical application. In this study, we encapsulated curcumin with solid lipid nanoparticles (SLN), 5-Fu with Layered double hydroxides (LDHs) separately and tested its properties and anticancer potentials. SLN-curcumin and LDH-5-Fu were determined to be 100 and 60 nm by Transmission Electron Microscopy detection, and the loading efficiency were 28%±2.5% and 16.7%±1.8%, individually. Furthermore, SLN-curcumin and LDH-5-Fu showed a significantly synergetic effect on SMMC-7721 cell stronger than plain drugs together, of which the Idrug loaded nano-carriers was only 0.315. FACS analysis revealed that the combination of SLN-curcumin and LDH-5-Fu induced 80.1% apoptosis in SMMC-7721 cells, which were 1.7-folds of the sum of the two plain drug loaded carriers. The results demonstrated the significant synergetic anticancer potentials of nano-encapsulated curcumin and 5-Fu, which could be further explored for the treatment of other carcinoma. PMID:23808828

  14. Pectins filled with LDH-antimicrobial molecules: preparation, characterization and physical properties.

    PubMed

    Gorrasi, Giuliana; Bugatti, Valeria; Vittoria, Vittoria

    2012-06-05

    Nanohybrids of layered double hydroxide (LDH) with intercalated active molecules: benzoate, 2,4-dichlorobenzoate, para-hydroxybenzoate and ortho-hydroxybenzoate, were incorporated into pectins from apples through high energy ball milling in the presence of water. Cast films were obtained and analysed. X-ray diffraction analysis showed a complete destructuration of all nanohybrids in the pectin matrix. Thermogravimetric analysis showed a better thermal resistance of pectin in the presence of fillers, especially para-hydroxybenzoate and ortho-hydroxybenzoate. Mechanical properties showed an improvement of elastic modulus in particular for LDH-para-hydroxybenzoate nanohybrid, due probably to a better interaction between pectin matrix and nanohybrid layers. Barrier properties (sorption and diffusion) to water vapour showed improvement in the dependence on the intercalated active molecule, the best improvement was achieved for composites containing para-hydroxybenzoate molecules, suggesting that the interaction between the filler phase and the polymer plays an important role in sorption and diffusion phenomena. Incorporation of these active molecules gave antimicrobial properties to the composite films giving opportunities in the field of active packaging.

  15. Chemical reactive features of novel amino acids intercalated layered double hydroxides in As(III) and As(V) adsorption.

    PubMed

    Shen, Liang; Jiang, Xiuli; Chen, Zheng; Fu, Dun; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

    2017-06-01

    Layered double hydroxides (LDHs) intercalated with amino acids such as methionine (Met) were synthesized as new adsorbents to remediate arsenic-polluted water. This Zn2Al-Met-LDHs, identified with the formula of Zn0.7Al0.3(OH)2(Met)0.3·0.32H2O, has good thermal stability. Adsorption experiments with Zn2Al-Met-LDHs showed that the residual arsenic in solution could be reduced below the regulation limit, and this adsorption process fitted Langmuir isotherm and the pseudo-second-order kinetics well. A remarkably high removal efficiency and the maximum adsorption capacity for As(III) were achieved, 96.7% and 94.1 mg/g, respectively, at 298 K. The desorption efficiency of As(III) from the arsenic-saturated Zn2Al-Met-LDHs (<8.7%), far less than that of As(V), promises a specific and reliable uptake of As(III) in sorts of solutions. More importantly, a complete and in-depth spectra analysis through FTIR, XPS and NMR was conducted to explain the excellent performance of Zn2Al-Met-LDHs in arsenic removal. Herein, two special chemical reactions were proposed as the dominant mechanisms, i.e., hydrogen bonding between the carboxyl group of the host Met and the hydroxyl group of As(III) or As(V), and the formation of a chelate ring between the guest As(III) and the S, N bidentate ligands of the intercalated Met in the LDHs.

  16. Effect of added zinc on the properties of cobalt-containing ceramic pigments prepared from layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Pérez-Bernal, M. E.; Ruano-Casero, R. J.; Rives, V.

    2009-09-01

    Layered double hydroxides (LDHs) with the hydrotalcite-type structure containing Co and Al, or Zn, Co and Al in the brucite-like layers and carbonate in the interlayer have been prepared by coprecipitation. The Zn/Co molar ratio was kept to 1 in all samples, while the divalent/trivalent molar ratio was varied from 2/1 to 1/2. The samples have been characterised by element chemical analysis, powder X-ray diffraction, differential thermal and thermogravimetric analysis, temperature-programmed reduction and FT-IR spectroscopy. A single hydrotalcite-like phase is formed for samples with molar ratio 2/1, which crystallinity decreases as the Al content is increased, developing small amounts of diaspore and dawsonite and probably an additional amorphous phase. Calcination at 1200 °C in air led to formation of spinels; a small amount of NaAlO 2 was observed in the Al-rich samples, which was removed by washing. The nature of the spinels formed (containing Co II, Co III, Al III and Zn II) strongly depends on the cations molar ratio in the starting materials and the calcination treatment, leading to a partial oxidation of Co II species to Co III ones. Colour properties ( L* a* b*) of the original and calcined solids have been measured. While the original samples show a pink colour (lighter for the series containing Zn), the calcined Co,Al samples show a dark blue colour and the Zn,Co,Al ones a green colour. Changes due to the different molar ratios within a given calcined series are less evident than between samples with the same composition in different series. These calcined materials could be usable as ceramic pigments.

  17. Anti‐Metastatic and Anti‐Angiogenic Activities of Core–Shell SiO2@LDH Loaded with Etoposide in Non‐Small Cell Lung Cancer

    PubMed Central

    Zhu, Yanjing; Wang, Mei; Wu, Bin; He, Xiaolie

    2016-01-01

    Currently, nanoparticles have gained a great attention in the anti‐tumor research area. However, to date, studies on the anti‐metastasis action of core–shell SiO2@LDH (LDH: layered double hydroxide) nanoparticles remain untouched. Two emerging aspects considered are establishing research on the controlling delivery effect of SiO2@LDH combined with anti‐cancer medicine from a new perspective. The fine properties synthetic SiO2@LDH‐VP16 (VP16: etoposide) are practiced to exhibit the nanoparticle's suppression on migration and invasion of non‐small cell lung cancer (NSCLC). Both in vitro and in vivo inspection shows that SiO2@LDH can help VP16 better function as an anti‐metastasis agent. On the other hand, anti‐angiogenic efficiency, co‐localization, as well as western blot are investigated to explain the possible mechanism. A clear mergence of SiO2@LDH‐VP16 and cytomembrane/microtubule may be observed from co‐location images. Results offer evidence that SiO2@LDH‐VP16 plays positions on cytomembrane and microtubules. It efficiently inhibits metastasis on NSCLC by reducing vascularization, and eliciting depression of the PI3K‐AKT and FAK‐Paxillin signaling pathways. SiO2@LDH‐VP16, the overall particle morphology, and function on anti‐metastasis and anti‐angiogenic may be tuned to give new opportunities for novel strategies for cancer therapy. PMID:27980999

  18. [Mg/Al layered double hydroxides prepared by microwave-assisted co-precipitation method for the removal of bromate].

    PubMed

    Zhong, Qiong; Li, Huan

    2014-04-01

    In this paper, Mg/Al layered double hydroxides (Mg/Al LDHs) were prepared by the microwave-assisted co-precipitation method and the conventional co-precipitation method. The samples were labeled as Mg/Al LDHs-MW and Mg/Al LDHs-H, respectively. Mg/Al LDHs were characterized by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR). The results showed that the application of microwave in the preparation process promoted the formation of smaller pore diameter and higher crystallinity particles. The pore size and particle size of Mg/Al LDHs-MW were 41.13 nm and 427.08 nm, respectively. Batch experiments were investigated to evaluate the effect of dosage, initial pH and regeneration frequencies for bromate removal. The conclusion showed that the process of bromate removal on Mg/Al LDHs could be described by the pseudo-second kinetic model. The Langmuir isotherm well described the experimental data, and the Mg/Al LDHs-MW has a stronger adsorption capacity while the maximum adsorption capacity (q(0)) of Mg/Al LDHs-MW for bromate was 321.26 microg x g(-1) which was larger than the q(0) (288.74 microg x g(-1)) of Mg/Al LDHs-H. For the continuous fixed-bed column, model simulations using the Thomas model showed that the experimental data obtained at three different columns packed with Mg/Al LDHs-MW were able to predict breakthrough curves. Simulating the maximum adsorption capacity of adsorption column for bromate removal was 288.81 microg x g(-1). When the bed depth was 10 cm, inlet concentration was 800 microg x L(-1) and flow rate was 4.0 mL x min, the correlation coefficient of model was 0.92, indicating that the experimental data was described well by the Thomas model.

  19. Adsorption and subsequent partial photodegradation of methyl violet 2B on Cu/Al layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Guzmán-Vargas, Ariel; Lima, Enrique; Uriostegui-Ortega, Gisselle A.; Oliver-Tolentino, Miguel A.; Rodríguez, Esaú E.

    2016-02-01

    Uncalcined Cu/Al LDH was studied as adsorbent and photocatalyst in the adsorption and subsequent photodegradation of methyl violet 2B dye (MV2B). Physicochemical characterization was carried out by XRD, FTIR, UV-vis, including photoactive properties, DSC/TGA and SEM. Kinetic and thermodynamic models showed great affinity and sorption capacity, the maximum adsorption capacity was 361.0 mg g-1 obtained by Langmuir model, in addition, the results showed that the dye was adsorbed on the LDH surface. Photocatalytic activity was evaluated in the MV2B dye photodegradation process, and it was confirmed by the presence rad OH radicals monitored by EPR spin trapping technique, additionally, COD and TOC parameters were measured, 13C NMR showed differences for the adsorbed and photodegraded samples.

  20. Aluminum Hydroxide

    MedlinePlus

    Aluminum hydroxide is used for the relief of heartburn, sour stomach, and peptic ulcer pain and to ... Aluminum hydroxide comes as a capsule, a tablet, and an oral liquid and suspension. The dose and ...

  1. One-pot synthesis of carbon supported calcined-Mg/Al layered double hydroxides for antibiotic removal by slow pyrolysis of biomass waste

    NASA Astrophysics Data System (ADS)

    Tan, Xiaofei; Liu, Shaobo; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Cai, Xiaoxi; Yan, Zhili; Yang, Chunping; Hu, Xinjiang; Chen, Bo

    2016-12-01

    A biochar supported calcined-Mg/Al layered double hydroxides composite (CLDHs/BC) was synthesized by a one-pot slow pyrolysis of LDHs preloaded bagasse biomass. Multiple characterizations of the product illustrated that the calcined-Mg/Al layered double hydroxides (CLDHs) were successfully coated onto the biochar in slow pyrolysis of pre-treated biomass. The as-synthesized CLDHs/BC could efficiently remove antibiotic tetracycline from aqueous solutions. The coating of CLDHs significantly increased the adsorption ability of biochar, and CLDHs/BC exhibited more than 2 times higher adsorption capacity than that of the pristine biochar (BC) in the tested pH range. The maximum adsorption capacity of CLDHs/BC for tetracycline was 1118.12 mg/g at 318 K. The experimental results suggested that the interaction with LDHs on biochar played a dominant role in tetracycline adsorption, accompanied with π–π interaction and hydrogen bond. This study provides a feasible and simple approach for the preparation of high-performance material for antibiotics contaminated wastewater treatment in a cost-effective way.

  2. One-pot synthesis of carbon supported calcined-Mg/Al layered double hydroxides for antibiotic removal by slow pyrolysis of biomass waste

    PubMed Central

    Tan, Xiaofei; Liu, Shaobo; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Cai, Xiaoxi; Yan, ZhiLi; Yang, Chunping; Hu, Xinjiang; Chen, Bo

    2016-01-01

    A biochar supported calcined-Mg/Al layered double hydroxides composite (CLDHs/BC) was synthesized by a one-pot slow pyrolysis of LDHs preloaded bagasse biomass. Multiple characterizations of the product illustrated that the calcined-Mg/Al layered double hydroxides (CLDHs) were successfully coated onto the biochar in slow pyrolysis of pre-treated biomass. The as-synthesized CLDHs/BC could efficiently remove antibiotic tetracycline from aqueous solutions. The coating of CLDHs significantly increased the adsorption ability of biochar, and CLDHs/BC exhibited more than 2 times higher adsorption capacity than that of the pristine biochar (BC) in the tested pH range. The maximum adsorption capacity of CLDHs/BC for tetracycline was 1118.12 mg/g at 318 K. The experimental results suggested that the interaction with LDHs on biochar played a dominant role in tetracycline adsorption, accompanied with π–π interaction and hydrogen bond. This study provides a feasible and simple approach for the preparation of high-performance material for antibiotics contaminated wastewater treatment in a cost-effective way. PMID:28000759

  3. In Vitro Inhibition of Histamine Release Behavior of Cetirizine Intercalated into Zn/Al- and Mg/Al-Layered Double Hydroxides

    PubMed Central

    Hussein-Al-Ali, Samer Hasan; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Ismail, Maznah; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

    2012-01-01

    The intercalation of cetirizine into two types of layered double hydroxides, Zn/Al and Mg/Al, has been investigated by the ion exchange method to form CTZAN and CTMAN nanocomposites, respectively. The basal spacing of the nanocomposites were expanded to 31.9 Å for CTZAN and 31.2 Å for CTMAN, suggesting that cetirizine anion was intercalated into Layered double hydroxides (LDHs) and arranged in a tilted bilayer fashion. A Fourier transform infrared spectroscopy (FTIR) study supported the formation of both the nanocomposites, and the intercalated cetirizine is thermally more stable than its counterpart in free state. The loading of cetirizine in the nanocomposite was estimated to be about 57.2% for CTZAN and 60.7% CTMAN. The cetirizine release from the nanocomposites show sustained release manner and the release rate of cetirizine from CTZAN and CTMAN nanocomposites at pH 7.4 is remarkably lower than that at pH 4.8, presumably due to the different release mechanism. The inhibition of histamine release from RBL2H3 cells by the free cetirizine is higher than the intercalated cetirizine both in CTZAN and CTMAN nanocomposites. The viability in human Chang liver cells at 1000 μg/mL for CTZAN and CTMAN nanocomposites are 74.5 and 91.9%, respectively. PMID:22754339

  4. Controlled release and angiotensin-converting enzyme inhibition properties of an antihypertensive drug based on a perindopril erbumine-layered double hydroxide nanocomposite

    PubMed Central

    Al Ali, Samer Hasan Hussein; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Ismail, Maznah; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

    2012-01-01

    Background The intercalation of perindopril erbumine into Zn/Al-NO3-layered double hydroxide resulted in the formation of a host-guest type of material. By virtue of the ion-exchange properties of layered double hydroxide, perindopril erbumine was released in a sustained manner. Therefore, this intercalated material can be used as a controlled-release formulation. Results Perindopril was intercalated into the interlayers and formed a well ordered, layered organic-inorganic nanocomposite. The basal spacing of the products was expanded to 21.7 Å and 19.9 Å by the ion-exchange and coprecipitation methods, respectively, in a bilayer and a monolayer arrangement, respectively. The release of perindopril from the nanocomposite synthesized by the coprecipitation method was slower than that of its counterpart synthesized by the ion-exchange method. The rate of release was governed by pseudo-second order kinetics. An in vitro antihypertensive assay showed that the intercalation process results in effectiveness similar to that of the antihypertensive properties of perindopril. Conclusion Intercalated perindopril showed better thermal stability than its free counterpart. The resulting material showed sustained-release properties and can therefore be used as a controlled-release formulation. PMID:22619549

  5. Incorporation of rare-earth ions in Mg-Al layered double hydroxides: intercalation with an [Eu(EDTA)]{sup -} chelate

    SciTech Connect

    Li Cang; Wang Ge; Evans, David G.; Duan Xue . E-mail: duanx@mail.buct.edu.cn

    2004-12-01

    Reaction of an aqueous slurry of an Mg{sub 2}Al-NO{sub 3} layered double hydroxide with a four-fold excess of Na[Eu(EDTA)] gives a material which analyses for Mg{sub 0.68}Al{sub 0.32}(OH){sub 2}[Eu(EDTA)]{sub 0.10}(CO{sub 3}){sub 0.11}.0.66H{sub 2}O. The interlayer spacing of the material is 13.8A, corresponding to a gallery height of 9.0A, which accords with the maximal dimensions (9-10A) of the anion in metal-EDTA complex salts as determined by single crystal X-ray diffraction. Geometrical considerations show that the charge density on the layered double hydroxide layers is too high to be balanced by intercalation of [Eu(EDTA)]{sup -} alone, necessitating the co-intercalation of carbonate ions which have a much higher charge density.

  6. In vitro inhibition of histamine release behavior of cetirizine intercalated into Zn/Al- and Mg/Al-layered double hydroxides.

    PubMed

    Hussein-Al-Ali, Samer Hasan; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Ismail, Maznah; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

    2012-01-01

    The intercalation of cetirizine into two types of layered double hydroxides, Zn/Al and Mg/Al, has been investigated by the ion exchange method to form CTZAN and CTMAN nanocomposites, respectively. The basal spacing of the nanocomposites were expanded to 31.9 Å for CTZAN and 31.2 Å for CTMAN, suggesting that cetirizine anion was intercalated into Layered double hydroxides (LDHs) and arranged in a tilted bilayer fashion. A Fourier transform infrared spectroscopy (FTIR) study supported the formation of both the nanocomposites, and the intercalated cetirizine is thermally more stable than its counterpart in free state. The loading of cetirizine in the nanocomposite was estimated to be about 57.2% for CTZAN and 60.7% CTMAN. The cetirizine release from the nanocomposites show sustained release manner and the release rate of cetirizine from CTZAN and CTMAN nanocomposites at pH 7.4 is remarkably lower than that at pH 4.8, presumably due to the different release mechanism. The inhibition of histamine release from RBL2H3 cells by the free cetirizine is higher than the intercalated cetirizine both in CTZAN and CTMAN nanocomposites. The viability in human Chang liver cells at 1000 μg/mL for CTZAN and CTMAN nanocomposites are 74.5 and 91.9%, respectively.

  7. Fenton-Like Catalysis and Oxidation/Adsorption Performances of Acetaminophen and Arsenic Pollutants in Water on a Multimetal Cu-Zn-Fe-LDH.

    PubMed

    Lu, Hongtao; Zhu, Zhiliang; Zhang, Hua; Zhu, Jianyao; Qiu, Yanling; Zhu, Linyan; Küppers, Stephan

    2016-09-28

    Acetaminophen can increase the risk of arsenic-mediated hepatic oxidative damage; therefore, the decontamination of water polluted with coexisting acetaminophen and arsenic gives rise to new challenges for the purification of drinking water. In this work, a three-metal layered double hydroxide, namely, Cu-Zn-Fe-LDH, was synthesized and applied as a heterogeneous Fenton-like oxidation catalyst and adsorbent to simultaneously remove acetaminophen (Paracetamol, PR) and arsenic. The results showed that the degradation of acetaminophen was accelerated with decreasing pH or increasing H2O2 concentrations. Under the conditions of a catalyst dosage of 0.5 g·L(-1) and a H2O2 concentration of 30 mmol·L(-1), the acetaminophen in a water sample was completely degraded within 24 h by a Fenton-like reaction. The synthesized Cu-Zn-Fe-LDH also exhibited a high efficiency for arsenate removal from aqueous solutions, with a calculated maximum adsorption capacity of 126.13 mg·g(-1). In the presence of hydrogen peroxide, the more toxic arsenite can be gradually oxidized into arsenate and adsorbed at the same time by Cu-Zn-Fe-LDH. For simulated water samples with coexisting arsenic and acetaminophen pollutants, after treatment with Cu-Zn-Fe-LDH and H2O2, the residual arsenic concentration in water was less than 10 μg·L(-1), and acetaminophen was not detected in the solution. These results indicate that the obtained Cu-Zn-Fe-LDH is an efficient material for the decontamination of combined acetaminophen and arsenic pollution.

  8. In-situ intercalation of NiFe LDH materials: An efficient approach to improve electrocatalytic activity and stability for water splitting

    NASA Astrophysics Data System (ADS)

    Li, Xiumin; Hao, Xiaogang; Wang, Zhongde; Abudula, Abuliti; Guan, Guoqing

    2017-04-01

    Intercalation and exfoliation are effective approaches for enlarging the interlayer distance and increasing ion exchange capacity of layered materials. Here, an in-situ intercalation method is demonstrated to expand the inter-layer spacing of electrodeposited NiFe Layered Double Hydroxides (LDH) electrodes. Compared with traditional electrode fabrication method, in which intercalation/exfoliation of LDH powders is performed first followed by coating it on substrate, better interface connection and stability are maintained in the present method. It is found that the inter-layer distance of NiFe LDH material can be increased from 7.8 to 9.5 Å by immersing the electrode in formamide at 80 °C for 3 h, and the required overpotential of oxygen evolution reaction (OER) for sustaining 10 mA cm-2 current density is reduced from 256 to 210 mV. Moreover, with the assistance of ultrasound treatment, the required intercalation time is reduced drastically and the overpotential@10 mA cm-2 current density is further decreased to 203 mV.

  9. Synthesis of layered double hydroxides containing Mg2+, Zn2+, Ca2+ and Al3+ layer cations by co-precipitation methods-A review

    NASA Astrophysics Data System (ADS)

    Theiss, Frederick L.; Ayoko, Godwin A.; Frost, Ray L.

    2016-10-01

    Co-precipitation is a common method for the preparation of layered double hydroxides (LDHs) and related materials. This review article is aimed at providing newcomers to the field with some examples of the types of co-precipitation reactions that have been reported previously and to briefly investigate some of the properties of the products of these reactions. Due to the sheer volume of literature on the subject, the authors have had to limit this article to the synthesis of Mg/Al, Zn/Al and Ca/Al LDHs by co-precipitation and directly related methods. LDHs have been synthesised from various reagents including metal salts, oxides and hydroxides. Co-precipitation is also useful for the direct synthesis of LDHs with a wide range of interlayer anions and various bases have been successfully employed to prepare LDHs. Examples of other synthesis techniques including the urea method, hydrothermal synthesis and various mechanochemical methods that are undoubtedly related to co-precipitation have also been included in this review. The effect of post synthesis hydrothermal has also been summarised.

  10. Metal composition of layered double hydroxides (LDHs) regulating ClO(-)4 adsorption to calcined LDHs via the memory effect and hydrogen bonding.

    PubMed

    Lin, Yajie; Fang, Qile; Chen, Baoliang

    2014-03-01

    A series of calcined carbonate layered double hydroxides (CLDHs) with various metal compositions and different M(2+)/M(3+) ratios were prepared as adsorbents for perchlorate. Adsorption isotherms fit Langmuir model well, and the adsorption amount followed the order of MgAl-CLDHs ≥ MgFe-CLDHs > ZnAl-CLDHs. The isotherms of MgAl-CLDHs and MgFe-CLDHs displayed a two-step shape at low and high concentration ranges and increased with an increase in the M(2+)/M(3+) ratio from 2 to 4. The two-step isotherm was not observed for ZnAl-CLDHs, and the adsorption was minimally affected by the M(2+)/M(3+) ratio. The LDHs, CLDHs and the reconstructed samples were characterized by X-ray diffraction, SEM, FT-IR and Raman spectra to delineate the analysis of perchlorate adsorption mechanisms. The perchlorate adsorption of MgAl-CLDHs and MgFe-CLDHs was dominated by the structural memory effect and the hydrogen bonds between the free hydroxyl groups on the reconstructed-LDHs and the oxygen atoms of the perchlorates. For ZnAl-CLDHs, the perchlorate adsorption was controlled by the structural memory effect only, as the hydroxyl groups on the hydroxide layers preferred to form strong hydrogen bonds with carbonate over perchlorate, which locked the intercalated perchlorate into a more confined nano-interlayer. Several distinct binding mechanisms of perchlorate by CLDHs with unique M(2+) ions were proposed.

  11. Enhancing selectivity in stripping voltammetry by different adsorption behaviors: the use of nanostructured Mg-Al-layered double hydroxides to detect Cd(II).

    PubMed

    Xu, Ren-Xia; Yu, Xin-Yao; Gao, Chao; Liu, Jin-Huai; Compton, Richard G; Huang, Xing-Jiu

    2013-03-21

    We report the use of nanostructured layered double hydroxides (LDHs) for the highly selective and sensitive detection of Cd(2+) using anodic stripping voltammetry (ASV). In particular, the modification of a glassy carbon electrode promotes the sensitivity and selectivity towards Cd(2+) in the presence of Pb(2+), Hg(2+), Cu(2+) and Zn(2+). The electrochemical characterization and anodic stripping voltammetric performance of Cd(2+) were evaluated using cyclic voltammetry (CV) and square wave anodic stripping voltammetry (SWASV) analysis. Operational parameters, including supporting electrolytes, pH value, deposition potential and deposition time were optimized. In addition, the selectivity, interference and stability were also investigated under the optimized conditions. The results showed that the fabricated electrode possessed good selectivity, stability and reproducibility. The proposed electrochemical sensing strategy is thus expected to open new opportunities to broaden the use of ASV in analysis for detecting heavy metal ions in the environment.

  12. Precipitation of Zn2Al LDH by urease enzyme.

    PubMed

    Vial, Stephanie; Ghanbaja, Jaafar; Forano, Claude

    2006-01-21

    A biomineralization process based on the promotion of precipitating agent by the urea-urease enzymatic system is developed to prepare ZnAl layered double hydroxide materials and the effects of the enzymatic reaction parameters on the structural and textural properties of the materials are investigated on the basis of XRD and EM analysis.

  13. Role of the synthesis route on the properties of hybrid LDH-graphene as basic catalysts

    NASA Astrophysics Data System (ADS)

    Álvarez, Mayra G.; Tichit, Didier; Medina, Francesc; Llorca, Jordi

    2017-02-01

    Layered double hydroxides (LDH or HT) or their derived mixed oxides present marked acid-base properties useful in catalysis, but they lead to agglomerate inducing a weak accessibility to the active sites. In this study we report the preparation and characterization of HT/Graphene (HT/rGO) nanocomposites as active and selective basic catalysts for the acetone condensation reaction. The graphene high specific surface area and structural compatibility with the HT allowed increasing the number and accessibility of the active sites and activity of this later. Two series of HT/rGO nanocomposites with 0.5 ≤ HT/rGO ≤ 10 mass ratio were prepared by: i) direct HT coprecipitation in the presence of GO; ii) self-assembly of preformed HT with GO. The prepared HT/rGO nanocomposites were dried either in air at 80 °C or freeze-dried. A series of characterizations showed the great influence of the preparation method and HT/rGO mass ratio on both the nanocomposite structure and catalytic activity. An optimum activity was observed for a HT/rGO = 10 catalyst. Particularly, the highest catalytic activity was found in those nanocomposites obtained by coprecipitation and freeze dried (3 times more active than bulk HT) which can be connected to their structure with a better accessibility to the basic sites.

  14. Superb adsorption capacity of hierarchical calcined Ni/Mg/Al layered double hydroxides for Congo red and Cr(VI) ions.

    PubMed

    Lei, Chunsheng; Zhu, Xiaofeng; Zhu, Bicheng; Jiang, Chuanjia; Le, Yao; Yu, Jiaguo

    2017-01-05

    The preparation of hierarchical porous materials as catalysts and sorbents has attracted much attention in the field of environmental pollution control. Herein, Ni/Mg/Al layered double hydroxides (NMA-LDHs) hierarchical flower-like hollow microspheres were synthesized by a hydrothermal method. After the NMA-LDHs was calcined at 600°C, NMA-LDHs transformed into Ni/Mg/Al layered double oxides (NMA-LDOs), which maintained the hierarchical flower-like hollow structure. The crystal phase, morphology, and microstructure of the as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy elemental mapping, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption methods. Both the calcined and non-calcined NMA-LDHs were examined for their performance to remove Congo red (CR) and hexavalent chromium (Cr(VI)) ions in aqueous solution. The maximum monolayer adsorption capacities of CR and Cr(VI) ions over the NMA-LDOs sample were 1250 and 103.4mg/g at 30°C, respectively. Thermodynamic studies indicated that the adsorption process was endothermic in nature. In addition, the addition of coexisting anions negatively influenced the adsorption capacity of Cr(VI) ions, in the following order: CO3(2-)>SO4(2-)>H2PO4(-)>Cl(-). This work will provide new insight into the design and fabrication of advanced adsorption materials for water pollutant removal.

  15. Estimation of the solubility product of hydrocalumite-hydroxide, a layered double hydroxide with the formula of [Ca2Al(OH)6]OH·nH2O

    NASA Astrophysics Data System (ADS)

    Gácsi, Attila; Kutus, Bence; Kónya, Zoltán; Kukovecz, Ákos; Pálinkó, István; Sipos, Pál

    2016-11-01

    From aqueous NaOH/Ca(OH)2/NaAl(OH)4 mixtures, after allowing short reaction times we observed the precipitation of Ca(OH)2(s) at lower, and a mixture of Ca(OH)2(s) and a layered double hydroxide, hydrocalumite (HC) at higher aluminate concentrations. From the maximum aluminate concentration, at which the equilibrium solid phase is still portlandite (i.e., further increase in the aluminate concentration results in HC appearing in the precipitate beside the portlandite), the concentration based solubility products of two polymorphs of HC with the formula of [Ca2Al(OH)6]OH·nH2O (differing in n) has been estimated and was found to be log LHC=-11.4 at 25 °C and -12.1 at 75 °C, respectively (where LHC=[Ca2+]2[Al(OH)4-][OH-]3) and at constant ionic strength (I=1 M NaCl). To the best of our knowledge, this is the first published estimate for the solubility product of hydrocalumite. Additionally, from the composition obtained for NaOH/Ca(OH)2/NaAl(OH)4 mother liquors in equilibrium with Ca(OH)2(s), attempts were made to extract the formation constant of the ion pair CaAl(OH)4+. It was found, that the effects caused by the supposed formation of this solution species are too small to be reliably determined, which allowed an upper estimate for its formation constant, K, to be suggested in the temperature range of 25-75 °C (K<200 and 40 M-1 at 25 and 75 °C, respectively).

  16. NICKEL HYDROXIDES

    SciTech Connect

    MCBREEN,J.

    1997-11-01

    Nickel hydroxides have been used as the active material in the positive electrodes of several alkaline batteries for over a century. These materials continue to attract a lot of attention because of the commercial importance of nickel-cadmium and nickel-metal hydride batteries. This review gives a brief overview of the structure of nickel hydroxide battery electrodes and a more detailed review of the solid state chemistry and electrochemistry of the electrode materials. Emphasis is on work done since 1989.