Enhanced Defluoridation Using Novel Millisphere Nanocomposite of La-Doped Li-Al Layered Double Hydroxides Supported by Polymeric Anion Exchanger.
ABSTRACT: A novel nanocomposite bead LaLiAl-LDH@201 was fabricated by doping a small amount of La into nanocrystalline Li/Al layered double hydroxides (LDHs) pre-confined inside polystyrene anion exchanger D201 (LiAl-LDH@201). A systematic characterisation of the resultant LaLiAl-LDH@201 (XRD, SEM-EDS, TEM-EDS, and XPS) evidenced the successful incorporation of La into the Li/Al LDHs, with their interlayer distance expanded to allow more exchangeable sites for fluoride uptake. The resultant LaLiAl-LDH@201 showed high and stable defluoridation performance over a wide range of pH from 4 to 9. The superior uptake capacity and affinity for fluoride of LaLiAl-LDH@201 over LiAl-LDH@201 were driven by both the increased anion exchange capacity of the embedded LDHs and the specific La-F interaction evidenced via XPS and TEM-EDS characterisation. Fixed-bed column test confirmed that the working capacity of LaLiAl-LDH@201 for defluoridation of authentic fluoride-rich groundwater was nearly twice that of LiAl-LDH@201. The fluoride-loaded LaLiAl-LDH@201 could be conveniently regenerated in situ by using NaOH?+?NaCl binary solution, achieving desorption efficiency above 98%. Moreover, negligible capacity loss, La leaching, or structure alteration was observed after five adsorption-regeneration cycles, indicating the high stability of LaLiAl-LDH@201. Therefore, the novel millisphere nanocomposite LaLiAl-LDH@201 was promising for efficient defluoridation from water and wastewater.
Project description:Lithium extraction from salt lake brine is critical for satisfying the increasing demand of a variety of lithium products. We report lithium recovery from pre-synthesized LiAl-layered double hydroxides (LDHs) via a mild solution reaction. Lithium ions were released from solid LiAl-LDHs to obtain a lithium-bearing solution. The LiAl-LDHs phase was gradually transformed into a predominantly Al(OH)3 phase with lithium recovery to the aqueous solution. The lithium recovery percentage and the concentration of the lithium-bearing solution were dependent on the crystallinity of LiAl-LDHs, the initial concentration of the LiAl-LDHs-1 slurry, the reaction temperature, and the reaction time. Under optimized conditions, the lithium recovery reached 86.2% and the Li+ concentration in the filtrate is 141.6 mg/L. Interestingly, no aluminum ions were detected in the filtrate after solid-liquid separation with high crystallinity LiAl-LDHs, which indicated the complete separation of lithium and aluminum in the liquid and solid phases, respectively. The 27Al NMR spectra of the solid products indicate that lithium recovery from the lattice vacancies of LiAl-LDHs affects the AlO6 coordination in an octahedral configuration of the ordered Al(OH)3 phase. The XPS O 1s spectra show that the Oad peak intensity increased and the OL peak intensity decreased with the increasing lithium recovery, which indicated that the Al-OH bond was gradually formed and the metal-oxygen-metal bond was broken.
Project description:In this work, potassium fluoride-doped Ca-Mg-Al layered double hydroxides (CaMgAl-LDHs) were synthesized by a coprecipitation method, after which they were further used as strong adsorbents for HCl gas adsorption in a quartz reactor at high temperature. The physiochemical properties of the as-prepared KF/CaMgAl-LDHs and CaMgAl-LDHs were investigated by X-ray diffraction, thermogravimetric, scanning electron microscopy, energy-dispersive system, and Brunauer-Emmett-Teller. The HCl adsorption test showed that 25 wt % KF loading of the KF/CaMgAl-LDOs was the optimal adsorbent for HCl removal. The highest adsorption capacity of the KF/CaMgAl-LDH adsorbent was achieved with 0.2968 g at 600 °C, 500 ppm HCl concentration, and 0.5 g adsorbent. Furthermore, the microstructure of the adsorbents after the reaction revealed that the adsorbents were encapsulated by dense chloride. The adsorption process was mainly dominated by chemical adsorption, strong acid-base properties, specific surface area, and mesopore number.
Project description:In this paper, Co-Al layered double hydroxides (LDHs), Co-Al LDHs/poly(o-phenylenediamine) (PoPD) and Ag nanoparticles decorated Co-Al LDHs/PoPD (Ag@Co-Al LDH/PoPD) samples were prepared. The as-prepared samples were characterized by XRD, Raman, XPS, FT-IR, DRS-UV-Vis, PL and TGA techniques. The salient features of morphology and size of the samples were determined using FESEM, and HR-TEM. Then, the samples were coated on glassy carbon electrode (GCE) and employed for sensing of 4-nitrophenol (4-NP), 2,4-dinitrophenol (2,4-DNP)) and uric acid (UA). It was found that Ag@Co-Al LDH/PoPD/GCE showed superior electrochemical sensing behaviour than other modified electrodes. It exhibits the detection limit (DL) of 63 nM, 50 nM and 0.28 µM for 4-NP, 2,4-DNP and UA respectively.
Project description:Polybutylene succinate (PBS) nanocomposite materials were prepared using a melt compounding process. The Mg2Al-based PBS nanocomposites, dispersed with inorganic-organic hybrid materials (layered double hydroxides, LDHs), were functionalized with the amino acids L-histidine (HIS) and L-phenylalanine (PHE). The rheological and anti-ultraviolet (anti-UV) properties were investigated and compared to filler-free PBS as well as LDH Mg2Al/nitrate as references. Both organo-modified LDHs exhibited a remarkable chain-extension effect for PBS with an outstanding increase in the zero-shear viscosity η0 for PBS-Mg2Al/PHE (two order of magnitude increase as compared to filler-free PBS). These results were compared to data found in the literature. Moreover, HIS and PHE anions embedded into the LDH structure can successfully prevent the chain scission reactions that usually occur during photo-ageing of PBS under UV radiation exposure. This highlights the outstanding performance of the LDH hybrid materials, and in particular, their application as a polymer chain extender and UV stabilizer for PBS, which can likely be extended to other biodegradable polymers.
Project description:γ-(2,3-Epoxypropoxy)propyltrimethoxy silane surface modified layered double hydroxides (KH560-LDHs) were prepared and used to improve the ultraviolet ageing resistance of asphalt. The results of X-ray photoelectron spectrometry (XPS) indicated that KH560 has been successfully grafted onto the surface of LDHs. The agglomeration of LDHs particles notably reduced after KH560 surface modification according to scanning electron microscopy (SEM), which implied that the KH560 surface modification was helpful to promote the dispersibility of LDHs in asphalt. Then, the influence of KH560-LDHs and LDHs on the physical and rheological properties of asphalt before and after UV ageing was thoroughly investigated. The storage stability test showed that the difference in softening point (ΔS) of LDHs modified asphalt decreased from 0.6 °C to 0.2 °C at an LDHs content of 1% after KH560 surface modification, and the tendency became more pronounced with the increase of LDH content, indicating that KH560 surface modification could improve the stability of LDHs in asphalt. After UV ageing, the viscous modulus (G'') of asphalt significantly reduced, and correspondingly, the elastic modulus (G') and rutting factor (G*/sin δ) rapidly increased. Moreover, the asphaltene increased and the amount of "bee-like" structures of the asphalt decreased. Compared with LDHs, KH560-LDHs obviously restrained performance deterioration of the asphalt, and helped to relieve the variation of the chemical compositions and morphology of asphalt, which suggested that the improvement of KH560-LDHs on UV ageing resistance of asphalt was superior to LDHs.
Project description:The layered double hydroxides (LDHs) of Ca2+ and trivalent cations, Al3+ and Fe3+, are single-source precursors to generate supported CaO, which picks up CO2 from the gas phase in the temperature range 350-550 °C. The supports are ternary oxides, mayenite, and Ca2Fe2O5. The uptake capacity of the Fe3+-containing LDH at 1.9 mmol g-1 is two times the capacity of the Al3+-containing LDH. The product of CO2 uptake is calcite CaCO3. It is observed that the intercalated chloride ions reduce the thermal penalty by inducing the early decomposition of CaCO3. In the case of the chloride-intercalated LDHs of Ca2+ and Fe3+, the CaCO3 formed is completely decomposed at 900 °C. This is in contrast with the CaCO3 formed from bare CaO, which shows no sign of decomposition at 900 °C under similar conditions. This work shows that the hydrocalumite-like LDHs are candidate materials for CO2 mineralization.
Project description:Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (?50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T 0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.
Project description:The synthesis method of layered double hydroxides (LDHs) determines nanoparticles' performance in biomedical applications. In this study, hydrothermal treatment as an important synthesis technique has been examined for its influence on the physicochemical properties and the drug release rate from drug-containing LDHs. We synthesised MgAl-LDHs intercalated with non-steroidal anti-inflammatory drugs (i.e., naproxen, diclofenac and ibuprofen) using a co-precipitation method with or without hydrothermal treatment (150 °C, 4 h). After being hydrothermally treated, LDH-drug crystallites increased in particle size and crystallinity, but did not change in the interlayer anion orientation, gallery height and chemical composition. The drug release patterns of all studied LDH-drug hybrids were biphasic and sustained. LDHs loaded with diclofenac had a quicker drug release rate compared with those with naproxen and ibuprofen, and the drug release from the hydrothermally-treated LDH-drug was slower than the freshly precipitated LDH-drug. These results suggest that the drug release of LDH-drugs is influenced by the crystallite size of LDHs, which can be controlled by hydrothermal treatment, as well as by the drug molecular physicochemical properties.
Project description: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.
Project description:We found in our previous study that layered double hydroxides (LDHs) which undergo aqueous miscible organic solvent treatment (AMOST) can tune the hydrophobicity surface of LDHs to be hydrophobic, and then the solvent mixing method can be used to prepare polymer/LDH nanocomposites. However, flame retardant property is not very high if LDHs are only used. In this present work, ammonium polyphosphate (APP) intercalated LDHs and zinc borate (ZB) was incorporated into a polypropylene (PP) matrix using the solvent mixing method. The structures, morphologies, and performance of the composites were characterized carefully. The peak heat release rate (PHRR) reduction of PP containing 10 and 20 wt % APP-LDH reached 27% and 55%, respectively, which increased up to 63% compared with PP/CO₃-LDH. After incorporating 2 wt % ZB in the PP/APP-LDH system, the flame retardant property was further improved. Polypropylene composites with 20 wt % APP-LDH and 2 wt % ZB showed a 58% PHRR reduction. In addition, thermogravimetric analyzer (TGA) results indicated that the addition of APP-LDH and ZB improved the temperature at 50% weight loss (T50%) and the char formation of the materials significantly.