Layered Double Hydroxide Nanosheets Research Articles

Fabrication of new in‐situ ternary nano/microcomposite LDH/Ag2O/Bayerite in trimetallic NiAg/Al layered double hydroxides for CO2 capture material

AbstractWe reported new in‐situ ternary nano/microcomposite layered double hydroxides/Ag2O/bayerite in trimetallic NiAg/Al layered double hydroxides (LDH) via hydrothermal technique; and characterization by powder X‐ray diffraction (XRD), Fourier transforms infrared spectroscopy (FT‐IR), field emission scanning electron microscopy (FE‐SEM), energy dispersive spectroscopy (EDS), and N2 adsorption‐desorption. The formation of bayerite and silver oxide species on the LDH nanosheet depended on the excess of Al3+ and Ag+ in the solution under alkaline and hydrothermal conditions. The nitrogen isotherm adsorption profile for all ternary composites exhibited uniformity with mesoporous and lamellar characteristics. The surface area of all the composites ranged from 81.17 to 150.23 m2. g−1, the Barret‐Joyner‐Halenda (BJH) pore volume from 0.22 to 0.27 cm3. g−1, and the average pore diameter ranged from 3.47 to 5.78 nm. All composites show a laminar plate‐like structure covered with elongated pieces. The particle size of the composites ranged from 54.86 to 115.96 nm, indicating the size changed from nano to microcomposite because of the different molar ratios of Ag and Ni in the solid. The ternary composite reveals CO2 capture activity with adsorption capacity ranging from 13.93 to 19.61 mmol g−1. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Hydrogen bond-modulated copper nanocluster-aggregation-induced enhanced ECL with layered double hydroxides-sensing interface for miRNA-135b detection in colorectal cancer

Herein, we developed a novel electrochemiluminescence (ECL) sensing interface based on Mg/Fe layered double hydroxides nanosheets (LDHs) for miRNA-135b detection in human colorectal cancer tissues. The LDHs nanosheet with large specific surface area and abundant active sites can work as the electrode sensing interface to effectively catalyze the electrochemical reactions. Furthermore, the formation of hydrogen bonds between 4-carboxyphenylboronic acid (CBPA) on the copper nanoclusters (Cu NCs) and fluorine ions limited the intramolecular vibration and accelerated electron transfer, greatly improving the luminescence signal. Due to the catalysis of LDH and the aggregation-induced enhanced electrochemiluminescence (AIECL) effect, the ECL quantum yield of Cu NCs has been significantly amplified. The Mg/Fe LDH-based sensing system for miRNA-135b detection had a linear detection range of 10 fM to 10 μM with a detection limit of 3.5 fM. Finally, the cancer tissue extracted from colorectal cancer patients have been successfully detected. The result indicated that the Mg/Fe LDHs sensing interface provided a new and reliable pathway for ECL analysis performance.

Production of H2 and Glucaric Acid Using Electrocatalyst Glucose Oxidation by the Ta NiFe LDH Electrode.

The slow anodic oxygen evolution reaction (OER) significantly limits electrocatalytic water splitting for hydrogen production. We proposed the electrocatalyst for glucose oxidation by Ta-doping NiFe LDH nanosheets to simultaneously obtain glucaric acid (GRA) and hydrogen gas as a useful byproduct. Superior glucose oxidation reaction (GOR) activity is demonstrated by the optimized Ta-NiFe LDH, which has a low overpotential of 192 mV, allowing for a small Tafel slope of 70 mV dec-1 and a current density of 50 mA cm-2. The Ta NiFe LDH-oxidized glucose to GRA with a 72.94% yield and 64.3% Faradaic efficiency at 1.45 VRHE. Herein, we report the Ta NiFe LDH/NF electrode for the GOR&hydrogen evolution reaction (HER), which exhibits a cell voltage of 1.62 V to reach a current density of 10 mA cm-2, which is 250 mV lower compared to OER&HER (1.87 V). This study reveals that GOR is an energy-efficient and cost-effective method for producing H2 and valorizing biomass.

Magnetron Sputtered SnO₂ Layer Combined with NiCo−LDH Nanosheets for High‐Performance All‐Solid‐State Supercapacitors

AbstractNickel‐cobalt layered double hydroxide (NiCo−LDH) has attracted much attention because of its excellent electrochemical properties and regulability. And it is a potential pseudocapacitive electrode material, which is commonly used in supercapacitors and lithium‐ion batteries. Its application in the field of supercapacitors can improve the energy density, power density and cycle life of devices. However, NiCo−LDH still faces some challenges, such as poor electrical conductivity and the capacity attenuation caused by agglomeration of layered structures, which require further research and optimization. In this paper, SnO2 films were prepared on carbon cloth (CC) by magnetron sputtering method, and Ni−Co LDH nanosheets were grown by hydrothermal reaction to obtain NiCo−LDH@SnO2 composites. Due to the synergistic effect between NiCo−LDH and SnO2, NiCo−LDH@SnO2 composites exhibit high Cs and good cyclic stability. In addition, an all‐solid‐state flexible asymmetric supercapacitor (ASC) was assembled with activated carbon (AC) anodes, showing good specific capacitance(Cs) and energy density. And a high initial capacitance can still be retained after 10,000 cycles. This paper shows that NiCo−LDH@SnO2 shows excellent application potential in supercapacitors.

Ti3C2 mediates the NiFe-LDH layered electrocatalyst to enhance the OER performance for water splitting

Oxygen evolution reaction (OER) is a very complex process with slow reaction kinetics and high overpotential, which is the main limitation for the commercial application of water splitting. Thus, it is of necessary to design high-performance OER catalysts. NiFe based layered double hydroxides (NiFe-LDHs) have recently gained a lot of attention due to their high reaction activity and simple manufacturing process. In this study, a novel electrocatalyst based on NiFe-LDH was constructed by introducing Ti3C2, which was utilized to modulate the structural and electronic properties of the electrocatalysts. Structural examinations reveal that the Ti3C2 of 2D structure successfully dope the NiFe-LDHs nanosheets, forming NiFe-LDH/Ti3C2 heterojunctions. Firstly, the heterojunction substantially reduces the charge transfer resistance, promoting the electron migration between the LDH nanosheets. Secondly, theoretical calculations demonstrate that the energy barrier between the rate-determining step from *OH to *O is lowered, favoring the formation of the reaction intermediates and thus the occurrence of OER. As a result, the composite electrocatalyst exhibits a low overpotential of 334 mV at a current density of 10 mA/cm2 and a small Tafel slope of 55 mV/dec, which are superior to those of the NiFe-LDH by 11.2 % and 38.5 %, respectively. This study provides inspiration for promoting the performances of NiFe based electrocatalysts by utilizing 2D materials.

Efficient photocatalytic hydrogen production of Ni-Co layered double hydroxides (Ni-Co LDHs) anchored with reduced graphene oxide (rGO) hybrid composite

Using a suitable co-catalyst to boost photocatalytic H2 evolution from water splitting is crucial. Herein, we designed pristine NiCo-LDH and reduced graphene-oxide supported nickel-cobalt layered double hydroxide nanosheets (NiCo-LDH/rGO) as photocatalyst for the first time to evaluate the hydrogen production performance. Adding graphene has the potential to significantly increase electrical conductivity, and the supported NiCo-LDH has the potential to significantly reduce the likelihood of graphene self-aggregation. The effectiveness of its photocatalytic hydrogen generation was analyzed using a set of characterizations. The H2 evolution rates for pure rGO were 345.2 μmolh-1g-1, whereas those for Ni-Co LDH/rGO were 578.2 μmolh-1g-1. Average hydrogen generation per hour for the Ni-Co LDH/rGO composite material was 2032.1 μmolh-1g-1, which was 5.8 and 3.5 times that of rGO and Ni-Co LDH/rGO, respectively, NiCo-LDH@rGO's synergistic impact on the NiCo-LDH boosts the H2 generation pathway by increasing the catalyst's stability as well as performance by exposing active sites and speeding up electron transport. The produced nanocomposite shows excellent spatial charge separation and quicker electron transport across the conductive network of rGO, as shown by the photocurrent response test and photoluminescence (PL) spectra. The results of this study provide a fresh perspective on the practical use and synthesis of the inexpensive and effective NiCo-LDH/rGO, demonstrating the standard deviation of logical planning and preparation of high-performance photocatalysts.

Tribological Behavior of GTL Base Oil Improved by Ni-Fe Layered Double Hydroxide Nanosheets

The layered double hydroxide (LDH) has been practically applied in the field of tribology and materials science due to its unique physicochemical properties, weak bonding, flexible structural composition, and adjustable interlayer space. In this work, a series of ultrathin and flexible composition of Ni-Fe LDH samples were prepared via a cost-effective room-temperature co-precipitation process. Then, they were mechanically dispersed into GTL base oil and their lubricating performance were tested by a four-ball tribometer. It is found that the variation of Ni-Fe ratio of Ni-Fe LDH has a great influence on the improvement of lubricating performance of GTL base oil. At the same concentration (0.3 mg/mL), the Ni-Fe LDH with Ni/Fe ratio of 6 was demonstrated to exhibit the best lubricating performance and the AFC, WSD, the wear volume, surface roughness and average wear scar depth decreased 51.3%, 30.8%, 78.4%, 6.7% and 50.0%, respectively. SEM-EDS and X-ray photoelectron spectra illustrated that the tribo-chemical film consisting of iron oxides and NiO with better mechanical properties formed and slowly replaced the physical film, which resists scuffing and protect solid surface from severe collisions.

Green delamination of 2D LDH nanosheets incorporated in mixed matrix membrane for CO2 capture

Carbon capture is a critical issue due to worsening global warming. Mixed matrix membranes incorporating 2D fillers have been attractive since they exhibit superior separation performance. In this study, the synthesis of ALDH was adjusted by sodium dodecyl sulfate (SDS) intercalation and 3-aminopropyltrimethoxysilane (APTMS) surface functionalization. Owing to this modification, the ALDH was delaminated in Pebax solutions, leading to a green process for fabricating 2D ALDH nanosheets incorporated in mixed matrix membranes. Due to the increased filler-polymer interfacial area produced by the ALDH nanosheets, CO2 passed through the membrane more quickly, which endowed the membrane with efficient CO2 separation performance. The optimal performance was obtained by adding 50 % PEGDME and 4 % ALDH to Pebax-1657, and the CO2 permeability and CO2/N2 selectivity were 460 barrer and 63, respectively. No toxic solvent was used in the process, providing an environmentally friendly method for fabricating 2D ALDH MMMs for efficient CO2 capture.

Short-time potentiostatic assisted borate to induce the generation of ultrathin NiFe LDH active phase for industrial-level water oxidation

Self-supported NiFe-based oxygen evolution reaction (OER) catalysts with high activity and durability are essential for the industrialization of green hydrogen. Herein, Boron-interfered NiFe LDH nanosheets (B2-NiFe-(a-10)) with abundant wrinkle structure are prepared by introducing nonmetallic sources into the surface reconstruction of layered double hydroxide (NiFe LDH) through a novel short-time potential constant activation strategy. It enhances interactions with the electrolyte, decreases Arrhenius activation energy (Ea), accelerates efficient charge transfer and O2 escape rate. The as-reconstructed B2-NiFe-(a-10) exhibits outstanding alkaline OER activity with an ultralow overpotential of 290 mV at 100 mA cm−2 and excellent durability (100 h). Additionally, density functional theory calculations further reveal that the interaction optimizes the adsorption of oxygenated intermediates (*OH→*O), induces the center of the d-band toward the Fermi energy level, and lowers the dissociation barrier of H2O. Moreover, the anion-exchange membrane water electrolyzer (AEMWE) achieves a current density of 1 A cm−2 at 1.97 V.

Enhancing the Performance of 2D Ni-Fe Layered Double Hydroxides by Cabbage-Inspired Carbon Conjunction for Oxygen Evolution Reactions.

Layered double hydroxide (LDH) nanosheets as one type of two-dimensional materials have garnered increasing attention in the field of oxygen evolution reaction (OER) in recent decades. To address the challenges associated with poor conductivity and limited electron and charge transfer capability in LDH materials, we have developed a straightforward one-pot synthesis method to successfully fabricate a composite material with a microstructure resembling cabbage, which encompasses NiFe-LDH and nanocarbon (referred as NiFe-LDH@C). Atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM) revealed that the monolayer NiFe-LDH with a height of ~ 0.5-0.8 nm is uniformly distributed and closely bonded to the carbon support, leading to a significant enhancement in conductivity and facilitating faster electron and charge transfer. Moreover, the NiFe-LDH@C exhibits a substantial number of surface defect sites, which enhances the interaction with oxygen species. This dual enhancement in charge transfer and oxygen species-mediated transfer greatly improves the catalytic OER performance, which is further corroborated by theoretical calculations. Notably, the Ni10Fe6-LDH@C with the highest concentration of surface oxygen vacancies demonstrated superior water oxidation performance, surpassing commercially available RuO2 catalysts; an OER overpotential of 231 mV@10 mA cm-2 with a Tafel slope of 71 mV dec-1 was achieved.

Ultra-flexible inorganic coating realized by scale-like nanosheets

Rapid development of foldable devices poses a challenging requirement on functional inorganic coatings with high flexibility. However, the inherent brittleness often renders inorganic coatings incompatible with flexibility. How to make flexible inorganic coatings remains challenging. Here, inspired by the scale structure of animal skins, we realize ultra-flexible scale-like coatings on polyimide (PI) film with layered double hydroxide (LDH) nanosheets. The adhesion is enhanced without peeling due to the bonding of polyimide with amino group attached to nanosheets. LDH nanosheets parallel to the substrate form scale-like structure that absorbs and releases stress to prevent coatings from cracking. And the coatings exhibit ultra-flexibility by surviving from 20,000 cycles of bending fatigue test. We apply the LDH-coated PI for atomic oxygen protection, which has important applications in aerospace industry. The coatings are designed as this special scale-like structure to release stress while possessing protection ability. Due to the barrier and adsorption of this flexible LDH coating, the erosion yield of the PI under an exposure of ~5 × 1021 atoms/cm2 is decreased by about 4 orders of magnitude to 0.015 % (~5 × 10−28 cm3/atom), which can satisfy the requirement for applications in harsh space environment of low earth orbit. Our work provides a general solution for simultaneously realizing high mechanical strength and flexibility in the coating technology, which may find applications in other areas, such as flexible electronics.

Cu3P Nanoarrays Fabricated on Copper Foam Substrates Followed by Coating with CoFe Layered Double Hydroxide Nanosheets as Electrocatalysts for Water Splitting

Cu₃P Nanoarrays Fabricated on Copper Foam Substrates Followed by Coating with CoFe Layered Double Hydroxide Nanosheets as Electrocatalysts for Water Splitting

Bioactive Layered Double Hydroxides for Synergistic Sonodynamic/Cuproptosis Anticancer Therapy with Elicitation of the Immune Response.

Sonodynamic therapy (SDT) has promising application prospects in tumor therapy. However, SDT does not eradicate metastatic tumors. Herein, Cu-substituted ZnAl ternary layered double hydroxide nanosheets (ZCA NSs) were developed as both sonosensitizers and copper nanocarriers for synergistic SDT/cuproptosis cancer therapy. An optimized electronic structure more conducive to the sonodynamic process was obtained from ZCA NSs via the Jahn-Teller effect induced by the introduction of Cu2+, and the synthesized ZCA NSs regulated the intricate tumor microenvironment (TME) by depleting endogenous glutathione (GSH) to amplify oxidative stress for further enhanced SDT performance. Furthermore, cuproptosis was evoked by intracellular overload of Cu2+ and amplified by SDT, leading to irreversible proteotoxicity. In vitro results showed that such synergetic SDT/cuproptosis triggered immunogenic cell death (ICD) and promoted the maturation of dendritic cells (DCs). Furthermore, the as-synthesized ZCA NS-mediated SDT/cuproptosis thoroughly eradicated the in vivo solid tumors and simultaneously elicited antitumor immunity to suppress lung and liver metastasis. Overall, this work established a nanoplatform for synergistic SDT/cuproptosis with a satisfactory antitumor immunity.

Active corrosion protection of micro-arc oxidation-based composite coating on magnesium alloy: Multiple roles of ionic liquid modified layered double hydroxide

Multifunctional composite coatings have been extensively used to protect metal substrates from corrosion. However, the use of ionic liquids (ILs) to modify the micro-arc oxidation/layered double hydroxides (MAO/LDHs) composite coating, to our best knowledge, has not been reported for the corrosion protection on metal substrates. It is thus necessary to prepare the ILs-modified MAO/LDHs composite coatings and understand in depth their corrosion resistance and active anticorrosive mechanism. Herein, a composite coating is constructed by introducing the MgAl-LDH modified by a choline 3-morpholinopropanesulfonate [Ch][MOPS] ionic liquid on an MAO film (CM-LDH/MAO). It is found that the CM-LDH/MAO composite coating shows the optimal corrosion protection on magnesium alloy, with a corrosion current density of 8.38 × 10−10 A cm−2, clearly lower than those of the MAO and LDH/MAO coatings. More importantly, a small pitting appears at the edge of the CM-LDH/MAO film only after long-term exposure of 216 h in 3.5 wt% NaCl solution. Such an improvement of corrosion resistance can be ascribed to the synergetic mechanism including the physical barrier of the composite coating, the self-repairing ability of the LDH nanosheets on the microporous flaws of the MAO film, as well as the formation effect of the Mg-based chelates by the adsorption of the [Ch]+ cations and the re-adsorption of the [MOPS]– anions released from the LDH interlayers.

Investigation of Ag nanoparticles decorated Ni-Al layered double hydroxide as a gas sensor

Chemiresistive gas sensors based on LDH structure were investigated for the detection of widely used volatile organic compounds (VOCs) including methanol, ethanol, and acetone at room temperature. In order to increase the surface active sites and subsequently improve the detection sensitivity of gas molecules, the use of Ag decoration method along with the creation of porosity on the surface of LDH structures were investigated. In this method, methanol solvent was used as a hole scavenger and UV radiation as a catalyst for binding Ag to the surface of LDH sheets. The microstructure and morphology of the composites were investigated by FESEM, HRTEM, EDS, EDS mapping, XRD, and MS analysis. The investigated parameters included relative humidity, calibration curve, repeatability, selectivity, and response/recovery times. According to the obtained results, the creations of surface corrosion by methanol and decorating the structure with Ag have both affected the sensitivity of the sensors. The pure Ni-Al LDH sensor has a response value of 6.8–250 ppm of ethanol. By increasing the specific surface area and creating LDH nanosheets, the response value can be increased up to 8.52. Also, the addition of Ag NP (Ni-Al LDH decorated with Ag NP) has increased the response up to 10.89. It was also observed that the response times in different modes have the least difference. At the end, the response mechanism was investigated based on the heterojunction theory.

Layered assembly of PEGylated graphene oxide and Mg–Al layered double hydroxide nanosheets with superior adsorption capacity and selective isolation of hemoglobin

This study developed a novel organic-inorganic hybrid composite, shortly as GO-PEG-LDHs, by self-assembly of exfoliated Mg–Al layer double hydroxide (LDHs) on the polyethylene glycol (PEG) grafted graphene oxide (GO) to achieve the selective adsorption of hemoglobin (Hb). The prepared GO-PEG-LDHs has a hierarchical structure with a homogeneous loading of exfoliated LDHs nano-sheets on its surface. The adsorption test reveals that GO-PEG-LDHs exhibits an adsorption efficiency of 95.03% for Hb and 3.45% for bovine serum albumin (BSA). The adsorption of Hb follows the Langmuir model, with an ultrahigh adsorption capacity of 55248.6 mg/g, which is higher than any previously reported materials. Meanwhile, the adsorbed Hb can be efficiently recovered through elution with a 50 mM Tris-HCl buffer, with an elution efficiency of 80.77%. Circular dichroism (CD) spectra indicate no conformational change for Hb during the process of adsorption/desorption. Furthermore, the composite demonstrates the ability to selectively isolate Hb in the presence of interfering protein BSA, indicating its potential for practical applications.

Zn–Al LDH nanosheets exfoliated in a LiOH/urea solution in situ: an effective strategy for fabricating cellulosic fibres with enhanced mechanical properties

Zn–Al LDH nanosheets exfoliated in a LiOH/urea solution in situ: an effective strategy for fabricating cellulosic fibres with enhanced mechanical properties

Intracellular Delivery of Therapeutic Protein via Ultrathin Layered Double Hydroxide Nanosheets.

The therapeutic application of biofunctional proteins relies on their intracellular delivery, which is hindered by poor cellular uptake and transport from endosomes to cytoplasm. Herein, we constructed a two-dimensional (2D) ultrathin layered double hydroxide (LDH) nanosheet for the intracellular delivery of a cell-impermeable protein, gelonin, towards efficient and specific cancer treatment. The LDH nanosheet was synthesized via a facile method without using exfoliation agents and showed a high loading capacity of proteins (up to 182%). Using 2D and 3D 4T1 breast cancer cell models, LDH-gelonin demonstrated significantly higher cellular uptake efficiency, favorable endosome escape ability, and deep tumor penetration performance, leading to a higher anticancer efficiency, in comparison to free gelonin. This work provides a promising strategy and a generalized nanoplatform to efficiently deliver biofunctional proteins to unlock their therapeutic potential for cancer treatment.

High-Performance Catalytic Reduction of 4-Nitrophenol to 4-Aminophenol over Pt Nanoparticles Supported on Co-Al LDH Nanosheets

In this study, a Pt@Co-Al LDH hybrid structure was fabricated by assembling the metal precursor PtCl62− with the exfoliated LDH nanosheets followed by in situ reduction by NaBH4. The morphology, composition and microstructure of the hybrid were characterized by FESEM, HRTEM, XRD, XPS and BET techniques. Pt nanoparticles (NPs) with an average particle size of 3.1 nm were successfully and uniformly loaded on the surface of LDH nanosheets. The catalytic activity of the Pt@Co-Al LDH hybrid was tested for the reduction of 4-nitrophenol, which is one of the most frequent pollutants in wastewater effluent from the pharmaceutical and textile industries. The hybrid displays superior catalytic activity and stability in the reduction of 4-NP under environmental conditions with NaBH4 as a reducing agent. The hybrid can be recovered in a simple way and still shows high catalytic activity after five reuses.

Mixed matrix membranes based on morpholinium-functionalized CardoPES and MgAl-LDH: Structures, properties and electrodialysis performance

A simple, inexpensive, and effective method based on the MMMs prepared from morpholinium-functionalized CardoPES and MgAl-LDHs is proposed to improve the ED capabilities of AEMs. The microphase separation and ED performance of mixed matrix AEMs were substantially enhanced by LDH introduction, which was attributed to the surface OH groups of the LDH nanosheets; these interactions induced polymer chain self-assembly. The AEM with 8 % LDH exhibited the highest salt flux (92.5 mg/m2·s) during ED, which was 19.6 % and 14.1 % greater than those of the commercial Type 10 membrane and the mixed matrix AEM, respectively. Hydrogen bonding interactions and the ED capabilities of the AEMs were readily regulated by adjusting the feed ratios of the LDH and morpholinium groups. With increasing LDH content, the Rm and ED performance increased, while the hydrophilicity and mechanical properties initially decreased. When the OH content of an LDH nanosheet was higher than the morpholinium content, as the LDH content increased, the Rm and ED performance decreased, while the hydrophilicity and mechanical properties increased, which may be attributed to internal structural discrepancies between the complete and incomplete core-shell structures of the AEMs caused by different hydrogen bonding patterns.