Magnesium-aluminum Layered Double Hydroxide Research Articles

Effect of relative humidity on the interlayer spacing of phosphate intercalated Mg, Al layered double hydroxide (hydrotalcite‐like) crystals

AbstractThe availability of water and the type of interlayer anions present affect the arrangement and interlayer spacing of layered double hydroxide (LDH). A systematic study of the effect of relative humidity (RH) on the basal spacing of phosphate intercalated, magnesium aluminum LDHs (MgAl–PO4 LDH) was conducted, confirming that MgAl‐PO4 LDH exhibit distinct interlayer spacing corresponding to separate low‐ and high‐hydration states produced when exposed to low and high humidity conditions. The transition from the low‐ to high‐hydration form begins when RH exceeds 33% and is accompanied by the transition from one to two interlayers of water. An improved understanding of the effect of RH on MgAl–PO4 LDHs will enable more accurate atomistic modeling and experimental characterization of MgAl–PO4 LDHs and may lead to improvements in the tunability of MgAl‐PO4 LDHs for commercial applications such as slow‐release fertilizer.

Mechanism of carbonized humic acid and magnesium aluminum-layered double hydroxide promoting biohydrogen generation

Dark fermentation (DF) is prone to low hydrogen (H2) yield. In this work, magnesium aluminum-layered double hydroxide and carbonized humic acid (MgAl-LDH/CHA) was synthesized by co-precipitation to reveal the mechanism in rising bioH2 generation. The results indicated that MgAl-LDH released Mg and Al ions slowly in DF system, improving the activity of H2-producing microbes (HPM) for more H2. The H2 yield increased from 169.3 mL/g glucose to 244.9 mL/g glucose, which was 44.7 % higher than that for the control yield. MgAl-LDH/CHA increased Proteobacteria content from 30.9 % to 43.7 %, making it form a complex microbial community and participate in DF metabolism with Firmicutes and other microbes together. Besides, MgAl-LDH/CHA could serve as an electron shuttle that likely effectively promotes electron transfer in DF, significantly reduced the energy requirements of HPM, thus raising metabolic activity. It provides direction for the multi-element composite applied in DF system.

Investigation on the Preparation and Performance of a Novel Sustained-Release Type Fluid Loss Agent for High-Temperature Resistant Oil Well Cement

Fluid loss agents (FLA) can reduce the fluid loss of cement paste by adsorption on the surface of the cement particles during cementing and decreasing the permeability of the cement cake, ensuring the safety of the cementing. As the exploration of the use of cement is progressing toward deeper and ultra-deeper layers, the use of FLA at high temperatures is urgently necessary. Hence, in this article, we describe the preparation of FLA with an organic/inorganic intercalated microstructure to meet the requirements of cementing at 210 °C. The anionic polymer FLA (ASDA) consists of 2-acrylamido-2-methylpropane sulfonic acid, sodium p-styrenesulfonate, N, N-dimethylacrylamide, and sodium 3-allyloxy-1-hydroxy-1-propylene. Organic-inorganic hybrid FLA, magnesium/aluminum-ASDA-hydrotalcite (Mg/Al-ASDA-LDHs) was prepared by intercalating ASDA into the interlayers of magnesium/aluminum layered double hydroxides (Mg/Al-LDHs) via an anion-exchange reaction. The results of thermal stability analysis showed that Mg/Al-ASDA-LDHs had better thermal stability than ASDA, with a decomposition temperature of 416 °C. In addition, the structure effectively mitigated the decrease in compressive strength of the mud caused by the carboxyl groups in the polymer. The Mg/Al-LDHs structure avoids the problem of reduced compressive strength of hardened cements due to conventional polymer FLA. The compressive strength of the cement containing Mg/Al-ASDA-LDHs increased by 57.4% after 7 days of curing compared with the cement containing 3% bwoc (“% bwoc” is defined as “by the weight of cement”) ASDA.

Synthesis of graphene oxide/layered double hydroxides hybrids via co-precipitation and their polypropylene composites

A series of hybrid particles consisting of graphene oxide and magnesium–aluminium-layered double hydroxides (GO/Mg–Al-LDHs) were prepared by the co-precipitation method and then modified by allyltrimethoxysilane (ATMS). X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, Raman spectra and field emission scanning electron microscope (FESEM) micrograph results showed the modified GO/Mg–Al-LDHs were synthesised with a smaller particle size and better dispersion. The polypropylene (PP) composites were prepared via the reactive extrusion method, and the effects of GO content in hybrids on the mechanical properties, processability, thermal stability, flame retardation, melting and crystallisation behaviour of composites were investigated in detail. The comprehensive properties of composites containing GO/Mg–Al-LDHs were excellent compared to those of Mg–Al-LDHs under the same filler concentration. Compared with pure PP, 20 wt-% of GO/Mg–Al-LDHs-2.5 increased the limiting oxygen index (LOI) value of composites from 16.4% to 28.8% with a V-0 level of U-94 testing and decreased the heat release rate (HRR) and total heat release (THR) values from 1206.4 kW/m2 and 133.9 MJ/m2 to 146.9 kW/m2 and 69.6 MJ/m2. Meanwhile, the tensile, impact strength and elongation at break were 36.2 MPa, 3.0 kJ/m2 and 68.6%, respectively. This work provided an effective strategy for enhancing the dispersion and comprehensive properties of GO/LDHs-based composites.

Novel three-dimensional architectured ZnMgAl ternary layered double hydroxide@reduced graphene oxide nanocomposites as electrode material for high-performance supercapacitor

Ternary layered double hydroxides (LDH) have recently attracted immense attention owing to their stupendous features, such as fine compositional tuning, multiple valence states, and superior electrochemical activity. Moreover, their intriguing structures and distinctive physiochemical properties delineate them as an exemplary material to serve as electrodes for high-performance supercapacitors (SCs). The present work reports the in-situ synthesis of Zinc Magnesium Aluminium LDH (ZMA) integrated with reduced graphene oxide (rGO) through a single-step hydrothermal approach. The resulting novel ternary ZMA@rGO nanocomposite (ZMAG) possesses a unique architecture incorporating hierarchical 3D nanoflowers of ZMA embedded on graphene nanosheets. The porous morphology of LDH improves interfacial charge transport, which results in more faradaic reactions at the electrochemically active sites. In addition, the conductive graphene nanosheets render a high specific surface area, endowing excellent capacitive behavior. The amalgamated electrochemical properties of ZMA and rGO develop a competent electrode material (ZMAG) for SCs. The ZMAG2 nanocomposite having ZMA and rGO in 1:1, evinces a specific capacitance (Cs) of 656.7 F/g at a current density (Id) of 1 A/g. Furthermore, the asymmetric supercapacitor (ASC) features admirable cycle stability (retains 89% of initial capacitance after 15,000 charge/discharge cycles). Herein, the real-time application of ZMA@rGO//AC ASC has also been demonstrated. Therefore, hierarchical porous nanostructure proclaims new prospects for fabricating proficient electrode materials for energy storage devices.

Step-by-step in-situ preparation of magnesium-aluminum layered double hydroxide film to improve the corrosion resistance of AZ31 magnesium alloy

In this study, a hydrothermal method was employed to cultivate Mg(OH)2 precursor layers on the surface of AZ31 magnesium alloy samples. Subsequently, Mg-Al LDHs films were successfully synthesized through an in-situ growth approach. The phase composition of the films were analyzed using X-ray diffraction and infrared spectroscopy. The growth process and surface morphology of the films at the microstructure level were examined and interpreted using scanning electron microscopy and EDS. The corrosion resistance of the films was assessed through potentiodynamic polarization curves, electrochemical impedance spectroscopy, and hydrogen evolution tests. The findings indicate that the Mg(OH)2 precursor effectively mitigates defects in the Mg-Al LDHs films and improves the LDHs microstructure. Moreover, the precursor synthesized at a pH range of 10–12 better enhances the corrosion resistance of the Mg-Al LDHs film.

Efficient enrichment of uranium (VI) in aqueous solution using magnesium–aluminum layered double hydroxide composite phosphate-modified hydrothermal biochar: Mechanism and adsorption

This study presents the successful synthesis of Magnesium-aluminum layered double hydroxide composite phosphate-modified hydrothermal biochar for efficient removal of U(VI) from aqueous solutions. A novel synthesis approach involving phosphate thermal polymerization-hydrothermal method was employed, deviating from conventional pyrolysis methods, to produce hydrothermal biochar. The combination of solvent thermal polymerization technique with hydrothermal process facilitated efficient loading of layered double hydroxide (LDH) components onto the biochar surface, ensuring simplicity, low energy consumption and enhanced modifiability. Bamboo waste was utilized as the precursor for biochar, highlighting its superior green and sustainable characteristics. Additionally, this study elucidated the interactions between phosphate-modified hydrothermal biochar and LDH components with U(VI). Physicochemical analysis demonstrated that the composite biochar possessed a high surface area and abundant oxygen-containing functional groups. XPS and FTIR analyses confirmed the efficient adsorption of U(VI), attributed to chelation interactions between phosphate groups, magnesium hydroxyl groups, hydroxyl groups and U(VI), as well as the co-precipitation of U(VI) with multi-hydroxyl aluminum cations captured by LDH. The composite biochar reached adsorption equilibrium with U(VI) within 80 min and exhibited excellent fitting to the pseudo-second-order kinetic model and Langmuir model. Under conditions of pH = 4 and 298 K, it displayed significantly high maximum adsorption capacity of approximately 388.81 mg g⁻1, surpassing untreated biochar by 17-fold. The adsorption process was found to be endothermic and spontaneous and even after five consecutive adsorption-desorption cycles, the removal efficiency of U(VI) remained stable at 75.46%. These findings underscore the promising application prospects of Magnesium-aluminum layered double hydroxide composite phosphate-modified hydrothermal biochar in efficiently separating U(VI) from uranium-containing wastewater, emphasizing its environmental and economic value.

Shape Self-Adaptive Liquid Embolic Agent for Ultrafast and Durable Vascular Embolization.

Minimally invasive embolization greatly decreases the mortality resulting from vascular injuries while still suffering from a high risk of recanalization and systematic thrombosis due to the intrinsic hydrophobicity and poor adhesion of the clinically used liquid embolic agent of Lipiodol. In this study, a shape self-adaptive liquid embolic agent was developed by mixing biocompatible poly(acrylic acid) (PAA), two-dimensional magnesium-aluminum layered double hydroxide (LDH), and poly(ethylene glycol)200 (PEG200). Upon contact with blood, the injectable PAA-LDH@PEG200 would quickly absorb water to form an adhesive and mechanically strong PAA-LDH thin hydrogel within 5 s, which could firmly adhere to the blood vessel wall for ultrafast and durable embolization. In addition, benefiting from the "positively charged nucleic center effect" of LDH nanosheets, the liquid PAA-LDH@PEG200 could avoid vascular distension by PAA overexpansion and possess high shock-resistant mechanical strength from the blood flow. Furthermore, both in vitro and in vivo embolization experiments demonstrated the complete embolic capacity of liquid PAA-LDH@PEG200 without the occurrence of recanalization for 28 days and also the great potential to act as a platform to couple with chemotherapeutic drugs for the minimized transcatheter arterial chemoembolization (TACE) treatment of VX2 tumors without recurrence for 18 days. Thus, liquid PAA-LDH@PEG200 developed here possesses great potential to act as a shape self-adaptive liquid embolic agent for ultrafast and durable vascular embolization.

Design and preparation of a novel Mg–Al LDH@EDTA-Melamine nanocomposite for effective adsorptive removal of methylene blue and rhodamine B dyes from water

This paper deals with the preparation of a novel nanocomposite consisted of magnesium-aluminum layered double hydroxide (Mg–Al LDH) and ethylenediaminetetraacetic acid (EDTA) as well as melamine (MA) as an adsorbent. This nanocomposite was utilized to adsorb different dyes such as rhodamine B (RhB) and methylene blue (MB) from water. The prepared adsorbent was characterized using FT-IR, EDS, XRD, TGA, and FE-SEM analyses. The effects of various parameters such as concentration, time, adsorbent dosage, temperature, and pH were tested to investigate their influence on adsorption conditions. Both methylene blue and rhodamine B dyes showed pseudo-second-order adsorption kinetics, and their adsorption followed the Langmuir isotherm. Moreover, the maximum adsorption capacities for methylene blue and rhodamine B were found to be 1111.103 mg/g at 45 °C and 232.558 mg/g at 60 °C, respectively. Additionally, the adsorption processes were found to be spontaneous (ΔG°< 0, for both dyes) and exothermic (ΔH° = −12.42 kJ/mol for methylene blue and ΔH° = −25.84 kJ/mol for rhodamine B) for both dyes. Hydrogen bonding and electrostatic forces are responsible for the interactions occur between the nanocomposite and the functional groups in the dyes. The experimental findings demonstrated a greater adsorption rate of MB than RhB, suggesting the adsorbent's stronger affinity for MB. This preference is likely due to MB's size, specific functional groups, and smaller molecule size, enabling stronger interactions and more efficient access to adsorption sites compared to RhB. Even after recycling 4 times, the dye adsorption percentages of the adsorbent for MB and RhB dyes were 90 % and 87 %, but the desorption percentages of the adsorbate dyes were 85 % and 80 %, respectively. The prepared adsorbent boasts several unique properties, such as the swift and effortless adsorption of MB and RhB dyes, straightforward synthesis, mild adsorption conditions, remarkable efficiency, and the ability to be recycled up to 4 times without a significant decrease in activity.

Biodegradable chelator GLDA intercalated magnesium/aluminum layered double hydroxides for efficient phosphate capture and removal from wastewater

Phosphate removal and recovery from wastewater play a vital role in controlling water eutrophication and facilitating resource recycling. Adsorbents of layered double hydroxides (LDHs) exhibit promising potential in the removal of phosphate; however, the removal efficiency often suffers insufficient as easy aggregation and inevitable loss of LDHs. Herein, a novel N, N–bis (carboxymethyl)–L–glutamic acid intercalated magnesium–aluminum LDH (GLDA@MgAl–LDH) were successfully synthesized. Intercalating with GLDA spawned dual functionality, i.e., the layer spacing expansion elevated the loading of phosphate, while GLDA also acted as additional binding sites toward phosphate. A higher phosphate capture (＞90%) was obtained in pH 5.0–8.0. Phosphate uptake was predominantly observed within the first1h, reaching equilibrium in approximately 4 h. The maximum adsorption capacity of 44.17 mg g–1 was attained for GLDA@MgAl–LDH at pH 6.70, which are far higher than that of pristine MgAl–LDH. GLDA@MgAl–LDH also had the excellent stability and reusability in five adsorption/desorption experiments. The GLDA@MgAl–LDH demonstrated significant efficacy in treating actual phosphate-containing wastewater in the fixed–bed adsorption column. Spectroscopic analysis, in conjunction with density functional theory, elucidated that GLDA intercalation enhanced the adsorption efficiency of MgAl–LDH. The key mechanisms facilitating phosphate removal included electrostatic attraction, anion and ligand exchange, and surface complexation. The above results highlight that GLDA@MgAl–LDH could serve as a promising and environmentally friendly candidate for phosphate treatment from the real wastewater.

Size-Optimized Layered Double Hydroxide Nanoparticles Promote Neural Progenitor Cells Differentiation of Embryonic Stem Cells Through the Regulation of M6A Methylation.

The committed differentiation fate regulation has been a difficult problem in the fields of stem cell research, evidence showed that nanomaterials could promote the differentiation of stem cells into specific cell types. Layered double hydroxide (LDH) nanoparticles possess the regulation function of stem cell fate, while the underlying mechanism needs to be investigated. In this study, the process of embryonic stem cells (ESCs) differentiate to neural progenitor cells (NPCs) by magnesium aluminum LDH (MgAl-LDH) was investigated. MgAl-LDH with diameters of 30, 50, and 100 nm were synthesized and characterized, and their effects on the cytotoxicity and differentiation of NPCs were detected in vitro. Dot blot and MeRIP-qPCR were performed to detect the level of m6A RNA methylation in nanoparticles-treated cells. Our work displayed that LDH nanoparticles of three different sizes were biocompatible with NPCs, and the addition of MgAl-LDH could significantly promote the process of ESCs differentiate to NPCs. 100 nm LDH has a stronger effect on promoting NPCs differentiation compared to 30 nm and 50 nm LDH. In addition, dot blot results indicated that the enhanced NPCs differentiation by MgAl-LDH was closely related to m6A RNA methylation process, and the major modification enzyme in LDH controlled NPCs differentiation may be the m6A RNA methyltransferase METTL3. The upregulated METTL3 by LDH increased the m6A level of Sox1 mRNA, enhancing its stability. This work reveals that MgAl-LDH nanoparticles can regulate the differentiation of ESCs into NPCs by increasing m6A RNA methylation modification of Sox1.

Protecting Mg-sites from hydration by embedding magnesium-aluminium layered double hydroxide in halloysite and using as pickering catalysts in Baeyer-Villiger oxidation

A facile strategy was developed via thermal treatment to get hierarchically structured magnesium-aluminium layered double hydroxide (MgAl-LDH) selectively loaded on the inner and external surfaces of halloysite nanotubes, respectively. The loaded MgAl-LDH was found to have active centers for Baeyer-Villiger (BV) oxidation that was protected from hydration by embedding in halloysite lumens. The BV oxidation of cyclohexanone was observed to have better performance by using the halloysite impregnated MgAl-LDH (MgAl-LDH@Hal) as catalysts than that of external surface modified MgAl-LDH (MgAl-LDH@Hal600). A conversion 57.0% of cyclohexanone was achieved, and the yield of ε-caprolactone was 22.0% when the MgAl-LDH@Hal was used as catalysts. Density Functional Theory (DFT) calculations as well as high-resolution of X-ray photoelectron spectrum (XPS) measurements revealed the charge depletion occurred in the Mg-sites of sample MgAl-LDH@Hal in comparison with MgAl-LDH@Hal600, which benefited the activation of H2O2 oxidants, and thus assisting the BV reaction. The prepared composites were able to work as phase-transfer catalysts as Pickering emulsions in oxidation of cyclohexanone.

RETRACTED: Construction of self-repairing polyethersulfone membrane with high density hydrophilic microregions by two dimensional restricted channels for enhanced dyes/salts selective separation

Based on the dye/salts separation efficiency and membrane injury caused by serious pollution of dye/salts wastewater, this study constructed a 2D tight ultrafiltration membrane that could both solve the membrane injury problem and improve the dye/salts separation efficiency, the compatibility of good self-healing performance and penetration performance by 2D material magnesium-aluminum Layered double hydroxide (MgAl-LDH). The self-repairing of physical injury was achieved through the swelling effect of AMPS-PAN, this property was proved by permeate flux, the retention performance of salts in dye/salts solution, the comparison of scanning electron microscope (SEM), and the mechanical strength after physical injury. The healing of chemical injury occured through the reaction of CC and polyethersulfone chain breakage, which was confirmed by X-ray photoelectron spectroscopy (XPS), permeate flux, the retention performance of salts in dye/salts solution, and mechanical property. The high separation efficiency of dye/salts was achieved through 2D material MgAl-LDH, which was proved by separation selectivity ɑ. The compatibility of good self-healing performance and penetration performance was obtained by 2D material MgAl-LDH, which was proved by the penetration and self-healing performance. Morever, the membrane illustrated excellent both permeability and dye/sals separation efficiency, just like the permeate flux, the retention performance of sodium sulfate in methyl blue/sodium sulfate solution, the retention performance of Na2SO4 in methyl blue/Na2SO4 solution, the retention rate of methyl blue were 99.1 L/m2h, 12.5%, 7.9%, 97.7%, respectively. The results of pollution index and contact angle also proved that the membrane had anti-pollution performance.

A flame-retardant wood-based composite with magnesium–aluminium layered double hydroxides for efficient daytime radiative cooling

The incorporation of magnesium–aluminium layered double hydroxide (MgAl-LDH) nanoflakes into delignified wood sawdust is effective in providing simultaneous passive daytime radiative cooling and flame-retardant properties.

Impedance spectroscopy of solids for monitoring the adsorption kinetic of chromate ions from aqueous solution by a synthesized clay

The adsorption kinetic of chromate ions from aqueous solution was monitored by analyzing the electrical response of the adsorbent at various contact times. This process was also monitored by XRD and FTIR which confirmed the retention of chromate ions on the absorbent surface. The adsorbent used was a synthesized clay based on nitrate intercalated magnesium–aluminum layered double hydroxide (LDH). The adsorption kinetic of chromates was found to follow a pseudo-second order model. Through the contact time dependence, it was found a good correlation between the adsorbed quantity of chromates and the electrode-sample interface conductivity of the adsorbent, which showed a quasi-symmetry achieved by a plateau leading to a same equilibrium time of 60 min. A similar result was observed for the percentage removal of chromates and the relative change in capacitance of the electrode-sample interface of the adsorbent that exhibited a same maximum rate of approximately 93 %.

Enhancing adsorption capacity of magnetic magnesium-aluminum layered double hydroxide by surface modification with sodium dodecyl sulfate for efficient removal of organic contaminants

A magnetic magnesium-aluminum layered double hydroxide (Mag-MgAl) was prepared, and its surface was modified using surfactant sodium dodecyl sulfate (SDS) and utilized as adsorbents for antibiotic ciprofloxacin (CIP) and dyes ponceau red (PR) and methylene blue (MB). Mag-MgAl/SDS demonstrated twice the adsorption capacity for CIP compared to Mag-MgAl, confirming that the surface modification by SDS aided the adsorption capacity. At pH 3.5, Mag-MgAl removed CIP and PR, attributed to electrostatic effect and hydrogen bonding, whereas it did not interact with MB. Conversely, Mag-MgAl/SDS successfully removed both MB and CIP, suggesting that SDS micelles acted as nanoreactors attracting cationic contaminants. The PR removal efficiency was low, possibly due to electrostatic repulsion. A binary dye system adsorption assessment was performed by mixing MB and PR aqueous solutions with Mag-MgAl and Mag-MgAl/SDS as selective adsorbents. Mag-MgAl removed around 80% of PR and 45% of MB, whereas Mag-MgAl/SDS removed less than 40% of PR and 80% of MB. SDS remains adsorbed on the surface of Mag-MgAl/SDS after the adsorption process of CIP, MB, or PR. The inversion in the affinity for the target molecules suggests that the surface of the composite can be adjusted to modulate the behavior of the adsorbent toward organic contaminants.

Dental material based on poly(methyl methacrylate) with magnesium-aluminum layered double hydroxide (MgAl-LDH) on bio-silica particles

The MgAl-LDH@SiO2 particles are prepared by the coprecipitation of LDH on silica originating from plants. Particles are of submicron size and are well dispersed in the matrix. Composites consisting of PMMA reinforced with MgAl-LDH@SiO2 particles have improved hardness and resistance to viscoelastic deformation, as tested by microhardness measurements.

Synthesis of High-Crystallinity Mg-Al Hydrotalcite with a Nanoflake Morphology and Its Adsorption Properties for Cu2+ from an Aqueous Solution

A magnesium–aluminum-layered double hydroxide (Mg-Al LDH) with a nano-lamellar morphology was prepared by using a homogeneous precipitation and hydrothermal method, and a calcination product (Mg-Al LDO) of the Mg-Al LDH was also obtained in this work. The XRD, TEM, SEM, FTIR, N2 ad/desorption, and TG-DTG techniques were employed to characterize the microstructures, morphologies, and thermostability levels of these two materials in detail. The results showed that both the Mg-Al LDH and Mg-Al LDO had mesoporous structures and nanoplate morphologies, with diameters of 50~200 nm. The Mg-Al LDH was transformed into Mg-Al LDO at 773 K in an air atmosphere. The adsorption properties of the Mg-Al LDH were investigated systematically with a copper chloride solution as a simulated waste. The experimental results demonstrated that the pH value of the solution had an obvious influence on its Cu2+ adsorption capacity, and the optimal pH value was approximately 5.0. The adsorption kinetics results showed that the Mg-Al LDH had a rapid adsorption rate, and the equilibrium adsorption capacity was 62.11 mg/g. Additionally, the Cu2+ adsorption could be commendably described using a pseudo-second-order model, demonstrating that the adsorption behavior is regulated by chemical sorption. The adsorption thermodynamic results indicated that the adsorption process was spontaneous at temperatures above 318 K. Moreover, the ΔG0 values decreased as the temperature was raised, which indicated that a higher temperature can cause a greater impetus for Cu2+adsorption. In addition, the positive values of the ΔH0 indicated that the Cu2+ adsorption was endothermic, and the positive ΔS0 values revealed an increase in the confusion at the solid–liquid interface of the adsorbent.

The effect of Zr(IV) addition on the phosphate removal properties of MgAl-LDH

Recovery of phosphate from wastewater represents a sustainable alternative to phosphate rock, a limited resource. Magnesium aluminum layered double hydroxides (MgAl-LDH), are promising sorbents due to their high phosphate removal capacity by anion-exchange (26–124 mgP/g). Furthermore, an increased sorption capacity has been reported by the addition of zirconium (Zr(IV)) into the LDH lattice. However, ambiguity exists especially in relation to the incorporation of Zr and the stability of the MgAl-LDH. To understand how Zr(IV)-addition affects the phosphate sorption properties (both capacity and mechanism) on the atomic level, solid state multi-nuclear NMR spectroscopy was combined with complimentary characterization techniques to study a series of MgAl-LDH with Zr to Al ratios of 1:9 and 1:1, which had the Mg to (Al + Zr) ratio fixed at 2:1. The LDH were synthesized by coprecipitation and subsequently aged or hydrothermally treated to improve the crystallinity (particle size). No evidence of Zr(IV) incorporation in the LDH was observed, instead Zr was present as Zr(IV)-hydroxide (X-ray amorphous) and crystalline Zr(IV) oxide after aging and hydrothermal treatment, respectively. The segregation of Zr(IV) and resulting lower Al content in the MgAl-LDH decreased the phosphate sorption capacity from 45 to 54 to 16–20 mgP/g. Zr (hydr)oxide impurities removed <3 mgP/g. Moreover, 31P MAS NMR spectroscopy quantified that the MgAl-LDH contributed to <62% of the total P removal capacity.

Smart Inhibition Action of Amino Acid-Modified Layered Double Hydroxide and Its Application on Carbon Steel.

Surface impregnation of concrete structures with a migrating corrosion inhibitor is a promising and non-invasive technique for increasing the lifetime of existing structures that already show signs of corrosion attack. The main requirement for inhibitors is their ability to diffuse the rebar at a sufficient rate to protect steel. The use of smart nanocontainers such as layered double hydroxides (LDH) to store corrosion inhibitors significantly increases efficiency by providing an active protection from chloride-induced corrosion. The addition of LDH to reinforced mortar can also improve the compactness and mechanical properties of this matrix. Here, we report the synthesis of a magnesium-aluminum LDH storing glutamine amino acid as a green inhibitor (labeled as Mg-Al-Gln), which can be used as a migrating inhibitor on mortar specimens. The corrosion behavior of the specimens was determined via electrochemical techniques based on measurements of corrosion potential and electrochemical impedance spectroscopy. A cell containing a 3.5% NaCl solution was applied to the mortar surface to promote the corrosion of embedded rebars. The specimens treated with Mg-Al-Gln presented an improved corrosion protection performance, exhibiting an increase in polarization resistance (Rp) compared to the reference specimens without an inhibitor (NO INH). This effect is a consequence of a double mechanism of protection/stimuli-responsive release of glutamine and the removal of corrosive chloride species from the medium.