Recent advances in flat sheet mixed matrix membrane modified by Mg-based layered double hydroxides(LDHs)for salt and organic compound separations

Magnesium(Mg)is a widely used and attractive metal,known for its unique physical and chemical properties,and it has been employed in the manufacture of many practical materials.Layered Double Hydroxides(LDHs),particularly Mg-based LDHs,rank among the most prevalent two-dimensional materials utilized in separation processes,which include adsorption,extraction,and membrane technology.The high popularity of Mg-based LDHs in separation applications can be attributed to their properties,such as excellent hydrophilicity,high surface area,ion exchangeability,and adjustable interlayer space.Currently,polymer membranes play a pivotal role in semi-industrial and industrial separation processes.Consequently,the development of polymer membranes and the mitigation of their limitations have emerged as compelling topics for researchers.Several methods exist to enhance the separation performance and anti-fouling properties of polymer membranes.Among these,incorporating additives into the membrane polymer matrix stands out as a cost-effective,straightforward,readily available,and efficient approach.The use of Mg-based LDHs,either in combination with other materials or as a standalone additive in the polymer membrane matrix,represents a promising strategy to bolster the separation and anti-fouling efficacy of flat sheet mixed matrix polymer membranes.This review highlights Mg-based LDHs as high-potential additives designed to refine flat sheet mixed matrix polymer membranes for applications in wastewater treatment and brackish water desalination.

Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

Effective multifunctional coatings with polyvinylpyrrolidone-enhanced ZIF-67 and zinc iron layered double hydroxide on microarc oxidation treated AZ31 magnesium alloy

Modulating metal-organic framework’s(MOF)crystallinity and size using a polymer,in conjunction with a high surface area of layered double hydroxide,yields an effective strategy for concurrently enhancing the electrochemical and photocatalytic performance.In this study,we present the development of an optimized nanocomposite,denoted as 0.5PVP/ZIF-67,developed on AZ31 magnesium alloy,serving as an efficient and durable multifunctional coating.This novel strategy aims to enhance the overall performance of the porous coating through the integration of microarc oxidation(MAO),ZnFe LDH backbone,and ZIF-67 formation facilitated by the addition of polyvinylpyrrolidone(PVP),resulting in a three-dimensional,highly efficient,and multifunctional material.The incorporation of 0.5 g of PVP proved to be effective in the size modulation of ZIF-67,which formed a corrosion-resistant top layer,improving the total polarization resistance(R_(p)=8.20×10^(8)).The dual functionality exhibited by this hybrid architecture positions it as a promising candidate for mitigating environmental pollution,degrading 97.93%of Rhodamine B dye in 45 min.Moreover,the sample displayed exceptional degradation efficiency(96.17%)after 5 cycles.This study illuminates the potential of nanocomposites as electrochemically stable and photocatalytically active materials,laying the foundation for the advancements of next-generation multifunctional frameworks.

Defective Nickel-Iron Layered Double Hydroxide for Enhanced Photocatalytic NO Oxidation with Significant Alleviation of NO2 Production

Photocatalysis offers a sustainable means for the oxidative removal of low concentrations of NOx(NO,NO2,N2O,N2O5,etc.)from the atmosphere.Layered double hydroxides(LDHs)are promising candidate photocatalysts owing to their unique layered and tunable chemical structures and abundant surface hydroxide(OH)moieties,which are hydroxyl radical(OH)precursors.However,the practical applications of LDHs are limited by their poor charge-separation ability and insufficient active sites.Herein,we developed a facile N_(2)H_(4)-driven etching approach to introduce dual Ni^(2+)and OHvacancies(Niv and OHv,respectively)into NiFe-LDH nanosheets(hereafter referred to as NiFe-LDH-et)to facilitate improved charge-carrier separation and active Lewis acidic site(Fe^(3+)and Ni^(2+)exposed at OHv)formation.In contrast to inert pristine LDH,NiFe-LDH-et actively removed NO under visible-light illumination.Specifically,Ni_(76)Fe_(24)-LDH-et etched with 1.50 mmol·L^(-1)N_(2)H_(4)solution removed 32.8%of the NO in continuously flowing air(NO feed concentration:500 parts per billion(ppb))under visible-light illumination,thereby outperforming most reported catalysts.Experimental and theoretical data revealed that the dual vacancies promoted the production of reactive oxygen species(O_(2)·^(-)andOH)and the adsorption of NO on the LDH.In situ spectroscopy demonstrated that NO was preferentially adsorbed at Lewis acidic sites,particularly exposed Fe^(3+)sites,converted into NO+,and subsequently oxidized to NO3without the notable formation of the more toxic intermediate NO2,thereby alleviating risks associated with its production and emission.

Layered double hydroxides as electrode materials for flexible energy storage devices

To prevent and mitigate environmental degradation,high-performance and cost-effective electrochemical flexible energy storage systems need to be urgently developed.This demand has led to an increase in research on electrode materials for high-capacity flexible supercapacitors and secondary batteries,which have greatly aided the development of contemporary digital communications and electric vehicles.The use of layered double hydroxides(LDHs)as electrode materials has shown productive results over the last decade,owing to their easy production,versatile composition,low cost,and excellent physicochemical features.This review highlights the distinctive 2D sheet-like structures and electrochemical characteristics of LDH materials,as well as current developments in their fabrication strategies for expanding the application scope of LDHs as electrode materials for flexible supercapacitors and alkali metal(Li,Na,K)ion batteries.

Self-supported ultrathin NiCo layered double hydroxides nanosheets electrode for efficient electrosynthesis of formate

Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.

Identification and comparison of the local physicochemical structures of transition metal-based layered double hydroxides for high performance electrochemical oxygen evolution reactions

Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.

Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides

ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.

Design, synthesis, and nanoengineered modification of spherical graphene surface by layered double hydroxide (LDH) for removal of As (Ⅲ) from aqueous solutions

In this study, new nano spherical graphene modified with LDH(Layered Double Hydroxide) was prepared and used to remove As(Ⅲ) ion from aqueous solutions. At first, graphene oxide was synthesized from graphite using a well-known Hammer method. The obtained graphene oxide solution was sprayed in octanol solution under different temperatures and sprayed speed as influenced variables. The structure and physical characterization of synthesized spherical graphene oxide were determined by various techniques,including FT-IR, N_(2) adsorption–desorption, SEM, TEM, and EDX. In the next step, the hydrothermal method was applied to deposition LDH on the spherical graphene oxide. The synthesized spherical graphene modified by LDH was used to remove As(Ⅲ) as a toxic heavy metal ion. The effect of influenced variables including p H, contact time, amount of sorbent, and type eluent studied and the optimum values were as 8, 30, 50, and HCl(0.5 mol·L^(-1)), respectively. After optimization, the studied sorbent was shown a high adsorption capacity(149.3 mg·g^(-1)). The adsorption mechanism and kinetic models exhibited good agreement with the Langmuir isotherm and pseudo-second-order trends, respectively. Besides, the synthesized product was tested for seven times without significant loss in its sorption efficiency.

Synthesis and characterization of colored layered double hydroxides for thermal stabilizer

Colored layered double hydroxides （LDHs） can be synthesized by introducing colored cations such as Fe^3＋ and Cr^3 ＋, which call be used as thermal stabilizers for polyvinyl chloride （PVC）. The yellowish Mg/Fe and bluish Mg/Cr LDHs are prepared by the co-precipitation method. The results show that the MgsCr_ CO3 and Mg3Fe_ CO3 colored layered double hydroxides can stabilize PVC for more than 30 min under the thermal aging temperature of 180 ℃. The preparation can use cheap Mg（OH） 2 instead of MgCl2, which produces a much smaller amount of the by-product NH4Cl. It is known that NH4Cl is a cheap fertilizer that is difficult to sell; therefore, the preparation is much greener and more economic than the one using magnesium salt.

Advances in efficient electrocatalysts based on layered double hydroxides and their derivatives

The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water splitting cells. Layered double hydroxides（LDHs） and their derivatives（e.g., transition metal alloys, oxides, sulfides, nitrides and phosphides） have been adopted as catalysts for various electrochemical reactions, such as oxygen reduction, oxygen evolution, hydrogen evolution, and COreduction, which show excellent activity and remarkable durability in electrocatalytic process. In this review, the synthesis strategies, structural characters and electrochemical performances for the LDHs and their derivatives are described. In addition, we also discussed the effect of electronic and geometry structures to their electrocatalytic activity. The further development of high-performance electrocatalysts based on LDHs and their derivatives is covered by both a short summary and future outlook from the viewpoint of the material design and practical application.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

Selenium(Ⅵ) removal from caustic solution by synthetic Ca-Al-Cl layered double hydroxides

To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were synthesized.A plate-like morphology and hexagonal crystal structure with typical mineral phases and functional groups were identified by the FESEM,XRD,FTIR,BET and XPS analysis.The forward feeding sample exhibits the best adsorption capacity of Se(Ⅵ).The factor experiments then reveal a favorable adsorption process with low temperature,low NaOH concentration and high adsorbent dosage.Furthermore,the adsorption kinetics and isotherm parameters can be well described by the Langmuir isotherm and the pseudo-second-order models,respectively.Accordingly,the maximum adsorption amount of Se(Ⅵ)onto Ca-Al-Cl-LDHs reaches188.6 mg/g at 50 ℃.

Electronic structure regulation on layered double hydroxides for oxygen evolution reaction

Oxygen evolution reactions(OERs)as core components of energy conversion and storage technology systems,such as water splitting and rechargeable metal–air batteries,have attracted considerable attention in recent years.Transition metal compounds,particularly layered double hydroxides(LDHs),are considered as the most promising electrocatalysts owing to their unique two-dimensional layer structures and tunable components.However,heir poor intrinsic electrical conductivities and the limited number of active sites hinder their performances.The regulation of the electronic structure is an effective approach to improve the OER activity of LDHs,including cationic and anionic regulation,defect engineering,regulation of intercalated anions,and surface modifications.In this review,we summarize recent advances in the regulation of the electronic structures of LDHs used as electrocatalysts in OERs.In addition,we discuss the effects of each regulation type on OER activities.This review is expected to shed light on the development and design of effective OER electrocatalysts by summarizing various electronic structure regulation pathways and the effects on their catalytic performances.

Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

Synergistic cerium doping and MXene coupling in layered double hydroxides as efficient electrocatalysts for oxygen evolution

Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.

2D materials modulating layered double hydroxides for electrocatalytic water splitting

Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered double hydroxides(LDHs)have been proved to be one of the most efficient materials for oxygen evolution reaction(OER),however,still suffered from low conductivity and sluggish kinetics for hydrogen evolution reaction(HER),which largely inhibited the overall water splitting efficiency.To address this dilemma,enormous approaches including doping regulation,intercalation tuning and defect engineering are therefore rationally designed and developed.Herein,we focus on the recent exciting progress of LDHs hybridization with other two‐dimensional(2D)materials for water splitting reactions,not barely for enhancing OER efficiency but also for boosting HER activity.Particularly,the structural features,morphologies,charge transfer and synergistic effects for the heterostructure/heterointerface that influence the electrocatalytic performance are discussed in details.The hybrid 2D building blocks not only serve as additional conductivity and structural supported but also promote electron transfer at the interfaces and further enhance the electrocatalytic performance.The construction and application of the nanohybrid materials will guide a new direction in developing multifunctional materials based on LDHs,which will contribute to energy conversion and storage.

Layered double hydroxides:Scale production and application in soil remediation as super-stable mineralizer

Soil contamination by heavy metals has presented severe risks to human health through food chain.As one of the most promising remediation technologies,in-situ immobilization strategy has been widely adopted in practice.However,considering the large quantities of contaminated soil,it is still a huge challenge to design low-cost amendments with strong and long-term immobilization ability.Layered double hydroxides(LDHs)have drawn tremendous attention in fundamental research and practical application because of their unique properties.Moreover,owing to its super-stable mineralization effect to heavy metal ions,LDHs have exhibited great potential in the field of soil remediation.In this work,we mainly focused on the scale production strategy of LDHs with low-cost,and its application in soil remediation.Besides,several key challenges in using LDHs as amendments for immobilization of heavy metal ions are presented.We hope that this mini-review could shed light on the sustainable development of LDHs as amendment for heavy metals in future research directions.

Effect of Layered Double Hydroxides on Ultraviolet Aging Resistance of SBS Modified Bitumen Membrane

Layered double hydroxides （LDHs）/styrene-butadiene-styrene （SBS） eopolymer modified bitumen was prepared by melt blending. The effect of LDHs on the ultraviolet （UV） aging behavior of SBS modified bitumen was investigated. The changes of chemical structures of modified bitumen before and after UV aging were characterized by Fourier transform infrared spectroscopy （FTIR）. The results show that LDHs obviously reduce the variation of softening point and low temperature flexibility of SBS modified bitumen under different UV radiation intensities, which indicates that the UV aging resistance performance of SBS modified bitumen is improved effectively by LDHs. Compared with SBS modified bitumen, the changes of carbonyl, sulfoxide and butadienyl of LDHs/SBS modified bitumen decrease significantly after UV aging according to FTIR analysis, demonstrating that the oxidation and degradation reactions of SBS modified bitumen were restrained effectively by adding LDHs.

Structured NiFe catalysts derived from in-situ grown layered double hydroxides on ceramic monolith for CO_(2) methanation

Monolithic catalysts for CO_(2) methanation have become an active research area for the industrial development of Power-to-Gas technology.In this study,we developed a facile and reproducible synthesis strategy for the preparation of structured NiFe catalysts on washcoated cordierite monoliths for CO_(2) methanation.The NiFe catalysts were derived from in-situ grown layered double hydroxides(LDHs)via urea hydrolysis.The influence of different washcoat materials,i.e.,alumina and silica colloidal suspensions on the formation of LDHs layer was investigated,together with the impact of total metal concentration.NiFe LDHs were precipitated on the exterior surface of cordierite washcoated with alumina,while it was found to deposit further inside the channel wall of monolith washcoated with silica due to different intrinsic properties of the colloidal solutions.On the other hand,the thickness of in-situ grown LDHs layers and the catalyst loading could be increased by high metal concentration.The best monolithic catalyst(COR-AluCC-0.5M)was robust,having a thin and well-adhered catalytic layer on the cordierite substrate.As a result,high methane yield was obtained from CO_(2) methanation at high flow rate on this structured NiFe catalysts.The monolithic catalysts appeared as promising structured catalysts for the development of industrial methanation reactor.