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.

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.

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.

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.

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.

Adsorption of glutamic acid from aqueous solution with calcined layered double Mg-Fe-CO_3 hydroxide

Layered double Mg-Fe-CO3 hydroxide （Mg-Fe-LDH） with a mole ratio of Mg to Fe of 3 was synthesized by coprecipitation method and calcined product Mg-Fe-CLDH was obtained by heating Mg-Fe-LDH at 500 ℃ for 6 h. The as prepared Mg-Fe-LDH and calcined Mg-Fe-CLDH were used for removal of glutamic acid （Glu） from aqueous solution, respectively. Batch studies were carried out to address various experimental parameters such as contact time, pH, initial glutamic acid （Glu） concentration, co-existing anions and temperature. Glu was removed effectively （99.9%） under the optimized experimental conditions with Mg-Fe-CLDH. The adsorption kinetics follows the Ho’s pseudo second-order model. Isotherms for adsorption with Mg-Fe-CLDH at different solution temperatures were well described using the Langmuir model with a good correlation coefficient. The intraparticle diffusion model fitted the data well, which suggests that the intraparticle diffusion is not only the rate-limiting step.

Removal of vanadate anion by calcined Mg/Al-CO_3 layered double hydroxide in aqueous solution

Mg/Al-CO3 layered double hydroxide （LDH2） with Mg（II）：Al（III） molar ratio of 2：1 was synthesized by co-precipitation method and its calcined product Mg2Al-CLDH（CLDH2） was prepared by heating Mg2Al-LDH at 773 K for 6 h. Removal of vanadate anion （ 3-4VO ） from aqueous solution on CLDH2 was studied. Batch studies were carried out to address various experimental parameters such as Mg/Al molar ratio, adsorbent dosage, initial concentration of solution, contact time and temperature. Vanadate was removed effectively at the optimized experimental conditions. The adsorption kinetics data fitted the pseudo-first-order model. Isotherms for adsorption vanadate by CLDH2 at different solution temperatures were well described using the Langmuir and Freundlich equations, and the isotherm parameters were calculated using linear regression analysis. The adsorption data fitted the langmuir model with good values of the correlation coefficient （R2〉0.999）. The negative value ofΔGΘand the positive value ofΔHΘindicate that the adsorption processes are spontaneous endothermic in nature. The mechanism of adsorption suggests that the surface adsorption is the main process.

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.

Ultrafine monolayer Co-containing layered double hydroxide nanosheets for water oxidation

For many two-dimensional(2D)materials,low coordination edges and corner sites offer greatly enhanced catalytic performance compared to basal sites,motivating the search for new synthetic approaches towards ultrathin and ultrafine 2D nanomaterials with high specific surface areas.To date,the synthesis of catalysts that are both ultrathin(monolayer)and ultrafine(lateral size<10nm)has proven extremely challenging.Herein,using a facile ultrasonic exfoliation procedure,we describe the successful synthesis of ultrafine ZnCo-LDH nanosheets(denoted as ZnCo-UF)with a size^3.5 nm and thickness^0.5 nm.The single layer ZnCo-UF nanosheets possess an abundance of oxygen vacancies(Vo)and unsaturated coordination s让es,thereby affording outstanding electrocatalytic water oxidation performance.DFT calculations confirmed that Vo on the surface of ZnCo-UF enhanced H20 adsorption via increasing the electropositivity of the nanosheets.

Ternary NiCoFe-layered double hydroxide hollow polyhedrons as highly efficient electrocatalysts for oxygen evolution reaction

With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1],fuel cells[2]and water splitting devices[3].Electrocatalytic oxidation of water to O2(oxygen evolution reaction,OER)is a vital chemical process involved in energy storage and conversion from renewable sources in form of molecular fuels such as H2 via water electrolysis,which has attracted a great amount of research efforts in the past few years[4,5].Nowadays,RuO2 and IrO2 are widely used as typical excellent OER electrocatalysts.However,their high-cost and scarce nature restricts the broadly commercial application of those materials[6,7].Hence,there is an urgent demand to develop low cost,highly efficient,and superb stable OER catalysts.

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.

2D Layered Double Hydroxide Nanosheets and Their Derivatives Toward E cient Oxygen Evolution Reaction

Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.

Recent progress in functionalized layered double hydroxides and their application in efficient electrocatalytic water oxidation

Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable compositi on and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional (2D) materials, and controlled growth on conductive supports (e.g., nanowire arrays, nano tubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nano structures and functionalized composites toward the applications in energy conversion, especially for water oxidation.

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg-Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.

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.

Fe-doped Co3O4@C nanoparticles derived from layered double hydroxide used as efficient electrocatalyst for oxygen evolution reaction

Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still remains a huge challenge. Herein, we demonstrate a feasible approach through oxidation of CoFe layered double hydroxide (CoFe-LDH) to synthesize Fe-doped Co3O4@C nanopmrticles with size of about 30-50 nm. As OER catalyst, the as-synthesized Fe-doped Co3O4@C nanoparticles exhibited superior OER performance with a small overpotential of 260 mV at the current density of 20 mA cm^-2, a small Tafel slope of 70 mV dec^-1 and long-term durability (there was no obviously OER current density degradation for 100 h) in alkaline solution. The present work opens a new avenue to the exploration of cost-effective and excellent electrocatalysts based on transition metal oxide materials to substitute precious metal materials for water splitting.

Preparation and Anti-ultraviolet Aging Performance of Organic Layered Double Hydroxides/Bitumen Composites

Layered double hydroxides(LDHs) with the physical property of high ultraviolet(UV)reflectance were used to enhance the anti-UV aging performance of bitumen. In view of the poor compatibility of LDHs with bitumen, three organic anions, namely, sodium dodecyl benzenesulfonate(SDBS), sodium dodecyl sulfate(SDS) and sodium dodecyl sulfonate(SDSO), were used as modifiers to prepare organic LDHs(OCLDHs) through regeneration process, and the crystal structure, chemical composition, morphological feature and UV shielding capability of synthesized OCLDHs were analyzed. Then the OCLDHs were added into bitumen to evaluate the storage stability and anti-UV aging property of OCLDHs/bitumen composites.The results show that the organic anions are inserted into the interlayers of LDHs, the intercalation expands the interlayer distance of LDHs, makes the particle shapes become more irregular and complicated, and enhances the absorption ability within the range from 200 to 300 nm while has little influence on the UV reflection ability.Result of high temperature storage stability indicates the organic modification ameliorates the compatibility of LDHs with bitumen. Compared with LDHs, OCLDHs decrease the deteriorations of bitumen’s properties during UV exposure test, exhibiting better effect in enhancing anti-UV aging performance of bitumen. Furthermore,among the three OCLDHs, LDHs intercalated by SDBS exhibit the most effective improvement due to the best compatibility with bitumen and comparatively good UV shielding effect.

Layered double hydroxide(LDH)-based materials:A mini-review on strategies to improve the performance for photocatalytic water splitting

The high energy demand we currently face in society and the subsequent large consumption of fossil fuels cause its depletion and increase the pollution levels.The quest for the production of clean energy from renewable and sustainable sources remains open.The conversion of solar energy into hydrogen via the water-splitting process,assisted by pho tores pons ive semiconductor catalysts,is one of the most promising technologies.Significant progress has been made on water splitting in the past few years and a variety of photocatalysts active not only under ultra-violet(UV) light but especially with the visible part of the electromagnetic spectrum have been developed.Layered double hydroxides(LDH)-based materials have emerged as a promising class of nanomaterials for solar energy applications owing to their unique layered structure,compositional flexibility,tunable bandgaps,ease of synthesis and low manufacturing costs.This review covers the most recent research dedicated to LDH materials for photocatalytic water-splitting applications and encompasses a range of synthetic strategies and post-modifications used to enhance their performance.Moreover,we provide a thorough discussion of the experimental conditions crucial to obtaining improved photoactivity and highlight the impact of some specific parameters,namely,catalysts loading,cocatalysts,sacrificial agents,and irradiation sources.This review provides the necessary tools to select the election technique for adequately enhancing the photoactivity of LDH and modified LDH-based materials and concludes with a critical summary that outlines further research directions.

The tuning of pore structures and acidity for Zn/Al layered double hydroxides:The application on selective hydrodesulfurization for FCC gasoline

Co–Mo catalysts applied on the hydrodesulfurization（HDS） for FCC gasoline were prepared with Zn–Al layered double hydroxides（LDHs） to improve their performances,and the effects of pore structures and acidity on HDS performances were studied in detail. A series of Zn–Al/LDHs samples with different pore structures and acidities are synthesized on the bases of co-precipitation of OH-,CO2-,Al3＋,and Zn2＋. The neutralization p H is a main factor to affect the pore structures and acidity of Zn–Al/LDHs,and a series of Zn–Al/LDHs with different pore structures and acidities are obtained. Based on the representative samples with different specific surface areas（SBET） and acidities,three Co Mo/LDHs catalysts were prepared,and their HDS performances were compared with traditional Co Mo/Al2O3 catalysts. The results indicated that catalysts prepared with high SBETpossessed high HDS activity,and Br？nsted acid sites could reduce the thiol content in the product to some extent. All the three catalysts prepared with LDHs displayed little lower HDS activity but higher selectivity than Co Mo/Al2O3,and could restrain the reactions of re-combination between olefin and H2 S which could be due to the existence of Br？nsted acid sites.

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 ℃.