Formation Of Layered Double Hydroxides Research Articles

NiCo layered double hydroxides/carbon dots composites with S-doing for high-performance asymmetric supercapacitors

The pursuit of high-performance electrode materials for supercapacitors has led to the exploration of transition metal layered double hydroxides (LDH), which boast an impressive theoretical specific capacitance. However, their intrinsic limitations, such as poor electronic conductivity and slow diffusion kinetics, have posed significant challenges for their practical implementation. In this work, a NiCo LDH/carbon dots (CDs) composite with S-doping has been meticulously designed to overcome the aforementioned limitations through a synergistic combination of heteroatom doping and carbon incorporation. Utilizing a one-pot hydrothermal method, the composite electrode for the application of asymmetric supercapacitors have been in-situ growth on Ni foam substrate, which not only serves as a robust support but also contributes to the formation of NiCo LDH by providing a uniform Ni source, thereby ensuring strong adhesion and structural integrity. The morphology and microstructures of composites could be finely modulated by adjusting CDs amount. With moderate CDs contents, the optimum electrode S-LDH/CDs-2 exhibits distinctive 3D needle-like spherical morphology, coupled with the ample space for ion diffusion. Consequently, the electrode demonstrates outstanding electrochemical performance, featuring a high areal capacitance of 5157 mF cm−2 at a current density of 2 mA cm−2. Additionally, it exhibits noteworthy rate performance and maintains excellent cycling stability. Integrating the innovative electrode into asymmetric supercapacitors configuration, superior energy density (0.24–0.45 mWh cm−2) and power density (4–20 mW cm−2) as well as good stability have been achieved for the S-LDH/CDs-2//AC device. These results indicate that S-doped NiCo LDH/CDs composite electrode has the desirable potential to be a candidate for energy storage devices.

Chelating agent stimulated LDH post-treatment of PEO coated AA2024

Layered double hydroxides (LDHs) are well known and broadly investigated on bare aluminum alloys, but not on PEO treated aluminum where source of aluminum ions is restricted. The additions of the chelating agents were tested in this work to stimulate the LDH formation on PEO (plasma electrolytic oxidation) coated aluminum alloy AA2024. 1,3-diamino-2-hydroxipropane-N,N,N’,N’-tetraacetic acid (DHPTA) was identified as the most effective one among tested additives. Its performance in terms of LDH growth stimulation was investigated. The DHPTA additive provides an increase of the pH of the LDH synthesis compared to previously known methods to achieve hydration of aluminum oxide from PEO as the initial stage of PEO etching, as well as the formation of soluble complex compounds of Zn-DHPTA, necessary for the formation of ZnAl LDH. The process of LDH formation was also followed by intercalation of DHPTA ions into LDH galleries. It was shown that LDH was formed both on the surface and insight the pores of parental PEO coating. Moreover, it imparted lubricating properties to the hybrid coating. Finally, PEO-LDH coating demonstrated higher corrosion resistance and long-term stability comparing to the PEO coated aluminum alloy.

Interface engineering of 2D NiFe LDH/NiFeS heterostructure for highly efficient 5-hydroxymethylfurfural electrooxidation

The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to valuable chemicals is an efficient way to upgrade biomass molecules and replace traditional catalytic synthesis. It is crucial to develop efficient and low-cost earth-abundant electrocatalysts to enhance catalytic performance of HMF oxidation. Herein, a new type of two-dimensional (2D) hybrid arrays consisting of NiFe layered double hydroxides (LDH) nanosheets and bimetallic sulfide (NiFeS) is constructed via interface engineering for efficient electrocatalytic oxidation of HMF to 2,5-furandicarboxylic acid (FDCA). The preparation process of 2D NiFe LDH/NiFeS with ultrathin heterostructure involves in anchoring a Co-based metal-organic framework (Co MOF) as template onto the carbon cloth (CC) via in-situ growth, formation of NiFe LDH on the surface of Co MOF and subsequent partial sulfidation. The electrocatalyst of NiFe LDH/NiFeS exhibits outstanding performance towards HMF oxidation, about 98.5% yield for FDCA and 97.2% Faraday efficiency (FE) in the alkaline electrolyte with 10 mmol/L HMF, as well as excellent stability retaining 90.1% FE for FDCA after six cycles test. Moreover, even at an HMF concentration of 100 mmol/L, the yield and FE for FDCA remain high at 83.6% and 93.6%, respectively. These findings highlight that 2D heterostructure containing abundant interfaces between NiFe LDH nanosheets and NiFeS can enhance the intrinsic activity of LDH and thus promote the oxidation reaction kinetics. Additionally, the synergistic effect of the bimetallic NiFe compounds also improved the selectivity of HMF conversion to FDCA. Our present work demonstrates that constructing 2D ultrathin heterostructure of NiFe LDH/NiFeS is a facile strategy via interface engineering to enhance the intrinsic activity of LDH electrocatalysts, which would open new avenues toward low-cost and advanced 2D nanocatalysts for sustainable energy conversion and electrochemical valorization of biomass derivatives.

Insights into in-situ synthesis of PEO-LDH composite film on AM50 Mg alloy: The effect of final voltage

MgAl layered double hydroxide (LDH) layer was in-situ grown on PEO coatings formed at different voltages. Influence of thickness, phase composition and stability of the initial PEO coating on LDH formation was investigated. A PEO layer consisting of thin and unstable amorphous phase can be recrystallized into LDH, while a dense coating slows down LDH growth. Balancing the dissolution of the PEO structure with formation of LDH nanocontainers can dramatically enhance the corrosion resistance of the resultant coating. The superior corrosion properties can be attributed to the intact parent PEO layer, the uniform coverage of the LDH film and its ion-exchange effect.

Synthesis of layered double hydroxides: Investigating the impact of stirring conditions and reactor design parameters

The synthesis by coprecipitation of Layered Double Hydroxides (LDHs) is governed by the stages of nucleation and crystal growth associated with the efficiency of the mixing and dispersion process of the reagents. Mixing efficiency is related to process variables, such as agitation speed, type of impeller and baffles presence, among others. In this context, this work proposes an analysis of these variables in a batch reactor, using a 23 factorial design employing the factors: acceleration speed (200 and 1000 rpm), mixing time (2 and 18 h) and presence or absence of baffles. The results were evaluated quantitatively (amount of LDH produced, time and amount of base for the formation of LDHs to begin) and qualitatively (mixing aspects, sedimentation ad grinding). The significant factors affecting the amount of LDH produced (51.94–80.81 g) were agitation speed and aging time. These factors were also correlated with the structural characteristics of the materials produced, such as crystallinity, crystallite size (70.99–174.79 nm), surface area (69.81–97.62 m2/g), pore volume (0.28–0.59 cm3/g), and pore diameter (11.40–34.66 nm). LDHs produced at higher agitation rates (1000 rpm) and longer aging times (18 h) yielded higher quantities of materials (80.81 g) with improved structural characteristics. The study highlights the importance of systematically exploring the synergistic effect between process variables, emphasizing the research potential in this area.

Resource utilization of field acid mine drainage: Formation of layered double hydroxides, its removal capacity and mechanism for antimony

Although acid mine drainage (AMD) has been recognized as a major environmental pollutant, it is also a potential source of valuable metals and sulfate. In this study, a resource utilization approach of field AMD for the formation of iron-based layered double hydroxides (LDHs) with sulfate intercalation was proposed and its capacity for removing antimonate [Sb(V)] was examined. Layered double hydroxides derived from field AMD possesses a more rapid equilibration time (<120 min) and a larger removal capacity (78 mg g−1) for Sb(V) compared with other LDHs from chemical reagents. Following the treatment of field AMD containing 10.7 mg L−1 Sb, a residual Sb concentration of 4.0 μg L−1 was achieved using a dose of 1 g L−1 LDHs, which meets the drinking water standard of 5 μg L−1 recommended by China's Ministry of Health. Leaching tests showed negligible metal(loid)s dissolution in Sb-loaded LDHs over a short period. The interactions between Sb(V) and LDHs include anion exchange and formation of brandholzite, which were further investigated at the electronic scale using density functional theory (DFT) calculations. It is envisaged that this approach for preparing LDHs will provide theoretical support for the remediation and resource recovery of AMD.

Improvement of solubility, dissolution, and bioavailability of phenytoin intercalated in Mg-Al layered double hydroxide.

Layered double hydroxides (LDHs) are highly effective drug delivery systems, owing to their capacity to intercalate or adsorb biomaterials, flexible structure, swelling property, high stability, good biocompatibility, and ease of synthesis. Phenytoin (PHT) is an antiseizure BCS (Biopharmaceutics Classification System) class II drug, presenting low aqueous solubility. Therefore, the current study aimed at increasing its solubility, dissolution, and bioavailability. PHT was intercalated to the MgAl-LDH formed in situ and successful intercalation to form MgAl-PHT-LDH was confirmed by FTIR, PXRD, DSC, and TGA. Examination of particle size and morphology (by photon correlation spectroscopy and electron microscopy, respectively) confirmed the formation and intercalation of nanostructured LDH. Intercalation enhanced the saturation solubility of PHT at 25°C in 0.1N HCl and phosphate buffer (pH 6.8) by 6.57 and 10.5 times respectively. The selected drug excipient powder blend for the formulation of MgAl-PHT-LDH tablets exhibited satisfactory properties in both pre-compression parameters (angle of repose, bulk density, tapped density, Carr's index, and Hausner ratio) and tablet characteristics (weight variation, thickness, hardness, friability, content uniformity, and disintegration time). MgAl-PHT-LDH tablets showed better dissolution of PHT compared to unprocessed PHT tablets at all time points. Oral bioavailability of MgAl-PHT-LDH tablets and unprocessed PHT tablets was tested in two groups of Sprague Dawley rats based on analysis of serum levels of both forms of PHT by UPLC-ESI-MS/MS serum. MgAl-PHT-LDH tablets demonstrated a relative bioavailability of 130.15% compared to unprocessed PHT tablets, confirming a significantly higher oral bioavailability of MgAl-PHT-LDH. In conclusion, MgAl-PHT-LDH could provide a strategy for enhancing solubility, dissolution, and thereby bioavailability of PHT, enabling the evaluation of theclinical efficacy of MgAl-PHT-LDH tablets for the treatment of seizures at lower PHT doses.

Synthesis of layered double hydroxides from municipal solid waste incineration fly ash for heavy metal adsorption

The process of urbanization has resulted in a continuous growth of the production of municipal solid waste, consequently leading to the increase of municipal solid waste incineration fly ash (MSWI FA) over time. This has prompted the need for effective disposal and value-added utilization strategies for MSWI FA. In this study, a hydrothermal method was employed to synthesize CaAl layered double hydroxides (LDHs) using MSWI FA as the raw material. The main objective was to investigate how different synthesis parameters affect the crystallinity of the layered bimetallic hydroxides. Subsequently, the synthesized LDHs were characterized using various techniques such as BET, SEM, XRD, FT-IR, and XPS. The results revealed the presence of calcium and aluminum cations in the interlayer region of the synthesized material, with chloride ions, sulfate ions, and acetate ions being the predominant anions. Moreover, the formation of LDHs presents an effective approach for the self-purification of leachates derived from MSWI FA. The LDHs exhibited excellent adsorption capacity for Cd2+ and Cu2+ in wastewater, with maximum values of 730 mg·g−1 and 446 mg·g−1, respectively. The adsorption mechanisms involved isomorphous substitution, complexation, as well as the precipitation of hydroxides or interlayer anions. This method presents a novel approach for effectively utilizing MSWI FA to produce environmentally friendly value-added adsorbents.

Intercalation vs Adsorption Strategies of Myo-Inositol Hexakisphosphate into Zn-Fe Layered Double Hydroxide: A Tiff between Anion Exchange and Coprecipitation.

Myo-inositol hexakisphosphates (IHPs) or phytates are the most abundant organic phosphates having the potential to serve as a phosphorus reserve in soil. Understanding the fate of IHP interaction with soil minerals tends to be crucial for its efficient storage and utilization as a slow-release organic phosphate fertilizer. We have systematically compared the effective intercalation strategy of a phytate onto Zn-Fe layered double hydroxide (LDH) acting as storage/carrier material through coprecipitation and anion exchange. Powder X-ray diffraction, X-ray photoelectron spectroscopy, elemental analysis, thermogravimetric analysis, FTIR spectra, and molecular modeling demonstrated the formation of phytate-intercalated Zn-Fe LDH through coprecipitation with a maximum loading of 41.34% (w/w) in the pH range of ∼9-10 in a vertical alignment through monolayer formation. No intercalation product was obtained from the anion exchange method, which was concluded based on the absence of shifting in the XRD (003) peak. A change in the zeta potential values from positive to negative and subsequent increase in solution pH, with decreasing phytate concentration, are suggestive of adsorption of IHP onto the LDH surface. The batch adsorption data were best fitted with Langmuir isotherm equation and followed the pseudo-second-order kinetic model. The maximum adsorption capacity was found to be 45.87 mg g-1 at a temperature of 25 ± 0.5 °C and pH 5.63.

Enhancing rural drinking water safety using an Mg–Al-type layered double hydroxide foil as a new point-of-use disinfection tool

Abstract Point-of-use (POU) drinking water treatment is crucial for residents in resource-constrained areas. This study introduces a layered double hydroxide (LDH) foil, an innovative POU device that eliminates waterborne pathogens via adsorption. It is an aluminum foil coated with magnesium–aluminum (Mg–Al)-type LDH, a recognized human-safe pathogen adsorbent. Its sheet-like morphology enables easy retrieval of inherently powdered LDH from post-disinfected water. Coating with Mg–Al LDH foils was accomplished by immersing aluminum foils in alkaline magnesium solutions, resulting in the on-surface formation of LDH. Using 12 distinct alkaline magnesium solutions, 12 types of LDH foils were prepared. Most LDH foils demonstrated &amp;gt;99% removal of Escherichia coli (DH5α strain) within 3–24 h when 100 mL of water was inoculated with DH5α at approximately 103 colony-forming units (CFU)/mL agitated with a 25-cm2 LDH foil piece. The LDH foil with the highest efficacy had a maximum adsorption capacity of approximately 1.3 × 106 CFU per 1-cm2 LDH foil. Furthermore, the LDH foil was regenerated by submersing it in the alkaline solution during its preparation, enabling multiple reuses. Owing to its straightforward production and application, the LDH foil holds substantial promise as a convenient-to-use adsorbent for batch water disinfection, such as jug water, in rural households.

Comparative study of in-situ formation process of Mg-Al layered double hydroxides though two pathways to remove Cr(VI) and As(V) from wastewater

The method of direct synthesis of layered double hydroxide (LDHs) in wastewater has attracted wide attention, but the formation process and removal mechanism are still unclear. In this study, two different paths of alkali solution (NaOH) dropped to salt solution (Mg2+/Al3+) (A-S process) and salt solution dropped to alkali solution (S-A process) were proposed to directly synthesize LDHs in wastewater and remove contaminants Cr(VI)/As(V) simultaneously. In A-S process, the formation of LDHs could be divided into three stages: initial formation of amorphous Al(OH)3, crystal phase transformation, and the complete formation of LDHs crystal. There was a gradual incorporation of Mg into Al(OH)3, and the removal of Cr(VI)/As(V) significantly increased upon the formation of LDHs structure. However, in S-A process, the formation of LDHs primarily involved crystal structure optimization. The layered structure was constantly growing and optimizing, accompanied by the removal of Cr(VI)/As(V). The Competition removal experiment of Cr(VI)/As(V) indicated that As(V) preferentially possess active sites and occupied more high-energy sites analyzed by molecular simulation and site energy distribution theory. The experimental investigation of co-existing ions, pH and recycle experiment for practical performance were also examined and demonstrated a high stability and a good recyclability.

Process and mechanism of recovering layered double hydroxides (LDHs) from acid mine drainage (AMD) and synergetic removal of manganese

The neutralization-precipitation method is widely used for treating acid mine drainage (AMD). However, the accumulation of sludge and the requirement for a high pH for the precipitation of Mn2+ limit the widespread application of this technology. In this work, layer double hydroxides (LDHs) were obtained by chemical neutralization of AMD, and the mechanism of LDHs for synergistic removal of Mn2+ was investigated by studying the morphological of metal elements during the neutralization process. The results showed that pH=8.5 was the critical condition for the formation of LDHs, and the sludge mainly consisted of Mg-Al-LDHs and manganese oxides. With increasing pH, Mn2+ was synergistically removed by LDHs through ion exchange (at the site 6) and complexation (with Mg-O). At pH=9.0, the concentration of Mn2+ was reduced to 1.5 mg/L, but it should be noted that high pH could destroy the structure of LDHs. Moreover, LDHs recovered from actual AMD were also found to have the ability to remove environmental pollutants. These findings not only enhance our understanding of the morphological change of metal elements during the neutralization process and the mechanism of Mn2+ removal, but also provide new insights for the recycling and utilization of neutralized sludge.

Synthesis of bifunctional nanostructured adsorbents based on anionic/cationic clays: effect of arrangement on simultaneous adsorption of cadmium and arsenate.

The development of bifunctional hybrid materials based on natural clays and layered double hydroxide (LDH) and their application on the simultaneous adsorption of Cd(II) and As(V) was investigated in this work. Two different synthesis routes, in situ and assembly, were employed to obtain the hybrid materials. Three types of natural clays, namely bentonite (B), halloysite (H), and sepiolite (S), were used in the study. These clays are characterized by a laminar, tubular, and fibrous structural arrangement, respectively. The physicochemical characterization results indicate that the hybrid materials were formed through interactions between the Al-OH and Si-OH groups present in the natural clays, and the Mg-OH and Al-OH groups present in the LDH for both synthesis routes. However, the "in situ" route yields a more homogenous material because the LDH formation is performed on the natural clay surface. The hybrid materials showed an anion and cation exchange capacity up to 200.7meq/100g and an isoelectric point near 7. The arrangement of natural clay has no impact on the properties of hybrid material but influences the adsorption capacity. The adsorption of Cd(II) onto hybrid materials was enhanced in comparison with natural clays, obtaining adsorption capacities of 80, 74, 65, and 30mg/g for 15:1 (LDH:H)INSITU, 1:1 (LDH:S)INSITU, 1:1 (LDH:B)INSITU, and 1:1 (LDH:H)INSITU, respectively. The adsorption capacities of hybrid materials to adsorb As(V) were between 20 and 60μg/g. The 15:1 (LDH:H)INSITU sample showed the best adsorption capacity being ten folds greater than halloysite and LDH. In all cases, the hybrid materials showed a synergistic effect for Cd(II) and As(V) adsorption. The adsorption study of Cd(II) onto hybrid materials showed that the primary adsorption mechanism is cation exchange between the interlayer cations in natural clay and Cd(II) in the aqueous solution. The adsorption of As(V) showed that the adsorption mechanism is attributed to anion exchange between CO23- in the interlayer space of LDH and H2ASO4- in the solution. The simultaneous adsorption of As (V) and Cd (II) shows that, during the As(V) adsorption, there is no competition by the adsorption sites. Still, the adsorption capacity towards Cd(II) was enhanced 1.2-folds. This study ultimately revealed that the arrangement of clay has a significant influence on the adsorption capacity of the hybrid material. This can be attributed to the similar morphology between the hybrid material and natural clays, as well as the important diffusion effects observed in the system.

Synthesis of CuAl-LDHs by Co-Precipitation and Mechanochemical Methods and Selective Hydrogenation Catalysts Based on Them

The paper presents the results of the synthesis and study of CuAl layered double hydroxides (LDHs) as well as their application as catalysts for the selective hydrogenation of crotonaldehyde. Phase-homogeneous LDHs were obtained by co-precipitation and mechanochemical methods, and critical parameters ensuring the formation of the target product were identified. In the case of coprecipitation, the formation of LDH is most affected by the pH of the reaction medium and the CO32−/Al3+ ratio. The optimal CO32−/Al3+ ratio is ca. 0.5–0.8 and pH 9.5–10.0. When mechanochemical synthesis is used, at 500 m·s−2 and 60 min, it is possible to obtain a single-phase CuAl LDH, whereas at higher energies, LDH is destroyed. The mechanochemical method makes it possible not only to reduce the synthesis time and the amount of alkaline wash water but also to obtain more dispersed copper particles with a higher hydrogenating activity. The conversion of 2-butenal (T = 80 °C, P = 0.5 MPa, 180 min, ethanol) for this sample was 99.9%, in contrast to 50.5% for the catalyst obtained by co-precipitation. It is important that, regardless of the conversion, both catalysts showed high selectivity (S = 90–95%) for the double bond hydrogenation.

Role of Anions in Stabilizing the [Zn–Al] Layered Double Hydroxides: A Thermodynamic Study

Room-temperature acid solution calorimetry, high-temperature oxide melt solution calorimetry, and low-temperature heat capacity measurements were employed to calculate the thermodynamic stabilities of the [Zn–Al–X] layered double hydroxides (LDH) containing different anions (X = Cl–, CO32–, and SO42–). Cryogenic heat capacity measurements demonstrated a Schottky-type anomaly in the heat capacity of all three LDHs below 11 K. This anomaly is attributed to the tunneling of protons between adjacent oxygen atoms in the LDH interlayer as this creates an energy system similar to a two-level system modeled with a Schottky term. These heat capacity measurements were also used to determine vibrational entropies which, when combined with configurational entropies, provide standard entropies of these LDHs. Enthalpies of formation of LDHs from binary components were determined and combined with the entropies of formation to calculate Gibbs free energies. Based on these values, the order of stability is [Zn–Al–SO4] > [Zn–Al–CO3] > [Zn–Al–Cl]. This trend results from a combination of the interlayer spacing, amount of water in the interlayer, interactions among the interlayer species, and interactions between the metal hydroxide layer and the interlayer.

Characterization and sorption study of Zn2[FeAl]-CO3 layered double hydroxide for Cu(II) and Pb(II) removal

This study reports the synthesis of a ternary layered double hydroxide (LDH) from ZnII, FeIII, and AlIII (Zn2[FeAl]-CO3) for the efficient removal Cu(II) and Pb(II) from water samples. Herein, Zn2[FeAl]-CO3 was prepared by a co-precipitation method and characterized using X-ray powder diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, N2 adsorption-desorption isotherms and differential scanning calorimetry analysis. The characterization results ensured the formation of a mesoporous LDH with carbonate as the interlayer anion and the presence of Zn, Fe and Al on the surface with a MII/MIII molar ratio of about 1.82. The Cu(II) and Pb(II) sorption process has been thoroughly studied for different parameters. The kinetic data showed that the process is very fast and follows a pseudo-first-order model. In addition, both surface sorption and intraparticle diffusion contributed to the rate-limiting steps in the sorption system. The sorption isotherms were evaluated quantitatively with four different isotherm models. It was found that the Redlich-Peterson and Freundlich models showed better correlation with the experimental data. The thermodynamics study indicates the endothermic, disorder-increasing and spontaneous nature of the sorption process. In conclusion, these results suggest that the synthesized Zn2[FeAl]-CO3 is favorable and useful for the removal of the studied metal ions and the high sorption capacity makes it a promising candidate material for the removal of heavy metals from water.

Efficient ZnCr LDH/monoclinic‐WO3 composites for Degradation of Tetracycline under Visible Light

AbstractRecently, efficient removal of antibiotics like Tetracycline (TC) from wastewater is emerging as a crucial problem. However, low adsorption capacity and high cost of photocatalysts limit their utility. In this context, monoclinic tungsten trioxide (WO3) loaded ZnCr layered double hydroxide (LDH) composites (ZnCr‐xWO3 x=10 and 20 %) are prepared by co‐precipitation method and characterized by several techniques viz. X‐Ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Raman, Photoluminescence (PL), Field‐Emission Scanning Electron Microscopy (FE‐SEM), Brunauer Emmett Teller (BET), Diffuse Reflectance Spectroscopy (DRS) and Dynamic Light Scattering (DLS). The XRD pattern confirms the formation of ZnCr LDH and its composites with monoclinic‐WO3. Bond vibrations and phase transitions were explored with the help of FTIR and Raman spectra. The BET analysis for ZnCr LDH and ZnCr‐10WO3 composite shows surface area as 27.439 m2/g and 47.691 m2/g. The higher photocatalytic performance of the composites formed is due to enhanced specific surface area and better separation efficiency of photo‐generated electrons and holes through conventional class II hetero junction between ZnCr LDH and monoclinic‐WO3. The kinetics studies performed shows better fit for pseudo first order reaction with maximum degradation efficiency and rate constant for ZnCr‐10WO3 (i. e., 86.7 % and 1.5×10−2 min−1).

Activation-induced layered structure in NiCoAl by atomic modulation for energy storage application

The surface activation of alloys favors their electrochemical interactions, ion diffusivity, and the rapid kinetics of ions and electrons, leading to the formation of self-supported layered double hydroxides (LDHs) in them. However, the formation of LDHs at different depths in the alloy upon activation, their electronic/atomic structures, and their electrochemical charge storage mechanism, have not been thoroughly explored. Herein, Ni ion-substituted CoAl alloys are prepared by arc melting and activated by KOH electrolyte, which is responsible for the modulation of the atomic configuration as confirmed by XRD. Raman depth mapping demonstrates how the LDHs vary with depth upon activation and that the octahedral and tetrahedral symmetry sites of CoO and Co3O4 are responsible for the formation of the layered structures of CoOOH and Co(OH)2, respectively. The activated Ni10Co85Al5 has a superior volumetric capacitance of 4.15 F/cm3 at 0.5 mA/g, which is 38.6 times that of an unactivated one, and excellent cyclic stability up to 5000 cycles, and a voltage of 0.54 V generated from a fabricated supercapacitor cell. X-ray Absorption Spectroscopy (XAS) analysis indicates greater charge transfer by Co than by Ni and the modulation of the local atomic structures facilitates electrochemical charge storage in Ni10Co85Al5. This work presents an easy route for the development of advanced LDHs, and the mechanism of electrochemical charge storage in them.

A facile synthesis of MgAl/layered double hydroxides from aluminum wastes

This work aimed to study the synthesis of Mg/Al layered double hydroxides (LDH) from aluminum residues. LDH was produced by co-precipitation and hydrothermal methods using Al(OH)3 synthesized from aluminum residue. It was possible to confirm the formation of LDH, with an increase in crystallinity for the hydrothermal synthesis. The FTIR indicates no influence regarding the Al(OH)3 origin (synthesized or commercial). N2 adsorption/desorption isotherms indicate a mesoporous structure with non-rigid aggregates of plate-shaped particles creating slit pores of varying shapes and sizes. The synthesized materials presented surface area ranging from 27.66 to 96.08 m2/g and pore diameter between 20 and 500 Å. Finally, it can be affirmed that LDHs were satisfactorily synthesized using aluminum residue as a source of aluminum hydroxide.

Coupling Molecular-Scale Spectroscopy with Stable Isotope Analyses to Investigate the Effect of Si on the Mechanisms of Zn-Al LDH Formation on Al Oxide.

While silicate has been known to affect metal sorption on mineral surfaces, the mechanisms remain poorly understood. We investigated the effects of silicate on Zn sorption onto Al oxide at pH 7.5 and elucidated the mechanisms using a combination of X-ray absorption fine structure (XAFS) spectroscopy, Zn stable isotope analysis, and scanning transmission electron microscopy (STEM). XAFS analysis revealed that Zn-Al layered double hydroxide (LDH) precipitates were formed in the absence of silicate or at low Si concentrations (≤0.4 mM), whereas the formation of Zn-Al LDH was inhibited at high silicate concentrations (≥0.64 mM) due to surface-induced Si oligomerization. Significant Zn isotope fractionation (Δ66Znsorbed-aqueous = 0.63 ± 0.03‰) was determined at silicate concentrations ≥0.64 mM, larger than that induced by sorption of Zn on Al oxide (0.47 ± 0.03‰) but closer to that caused by Zn bonding to the surface of Si oxides (0.60-0.94‰), suggesting a presence of Zn-Si bonding environment. STEM showed that the sorbed silicates had a close spatial coupling with γ-Al2O3, indicating that >Si-Zn inner-sphere complexes (">" denotes surface) likely bond to the γ-Al2O3 surface to form >Al-Si-Zn ternary inner-sphere complexes. This study not only demonstrates that dissolved silicate in the natural environment plays an important role in the fate and bioavailability of Zn but also highlights the potential of coupled spectroscopic and isotopic methods in probing complex environmental processes.