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.

Self-assembling organomodified Co/Al based layered double hydroxides (LDH) via one-step route

The preparation of self-assembling organomodified Co/Al-layered double hydroxide(LDH)via one-step route was studied. A common surfactant,sodium dodecylbenzenesulfonate(DBS),was employed as an organic modifier.The behavior and structure of self-assembled intercalated organic Co/Al-LDH were investigated by FTIR,SEM,WAXS,element analysis and TGA.Based upon the WAXS results and calculation by Bragg equation,the interlayer distance(d value)for organic Co/Al-LDH is enlarged from 0.75 nm to 3.10 nm,showing that the self-assembling behavior has been carried out successfully.Considering the observation from SEM, the product shows the morphology of organic Co/Al-LDH of a layered structure.In addition,FTIR,element analysis and TGA analysis show that the modifier is intercalated into the gallery of the Co/Al-LDH.Since organic modification for nanofiller is deemed to be necessary before applying it into polymer,the successful preparation of organomodified Co/Al-LDH will be significantly beneficial to the preparation and investigation of novel polymer/LDH nanocomposite.

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.

Colloid of Delaminated Layered Double Hydroxides:a Novel Type of LDH-based Catalyst

The colloid of delaminated layered double hydroxides(LDHs), a new LDH-based catalyst, is described. The semi-heterogeneous delaminated colloidal MgPdA1-LDH, in which the total surface of catalytic site-bearing lamellae was rendered accessible for chemical reactivity, showed excellent catalysis toward Suzuki reaction. The turnover frequency of this catalyst for Suzuki reaction between bromobenzene and phenylboronic acid is about 8000 h^-1.

3D Hierarchical Co–Al Layered Double Hydroxides with Long-Term Stabilities and High Rate Performances in Supercapacitors

Three-dimensional(3D) flower-like Co–Al layered double hydroxide(Co–Al-LDH) architectures composed of atomically thin nanosheets were successfully synthesized via a hydrothermal method in a mixed solvent of water and butyl alcohol. Owing to the unique hierarchical structure and modification by butyl alcohol, the electrochemical stability and the charge/mass transport of the Co–Al-LDHs was improved. When used in supercapacitors, the obtained Co–Al-LDHs deliver a high specific capacitance of 838 Fg^(-1) at a current density of 1 Ag^(-1)and excellent rate performance(753 Fg^(-1) at 30 Ag^(-1) and 677 Fg^(-1) at 100 Ag^(-1)), as well as excellent cycling stability with 95% retention of the initial capacitance even after 20,000 cycles at a current density of 5 Ag^(-1). This work provides a promising alternative strategy to enhance the electrochemical properties of supercapacitors.

Porous Cobalt Oxide@Layered Double Hydroxide Core-Shell Architectures on Nickel Foam as Electrode for Supercapacitor

The high performance of an electrode relies largely on a scrupulous design of nanoarchitectures and smart hybridization of electroactive materials.A porous core-shell architecture in which one-dimensional cobalt oxide(Co_3O_4)nanowire cores are grown on nickel foam prior to the growth of layered double hydroxide(LDH)shells is fabricated.Hydrothermal precipitation and thermal treatment result in homogeneous forests of 70-nm diameter Co_3O_4 nanowire,which are wrapped in LDH-nanosheet-built porous covers through a liquid phase deposition method.Due to the unique core-shell architecture and the synergetic effects of Co_3O_4and NiAl-LDH,the obtained Co_3O_4@LDH electrode exhibits a capacitance of 1 133.3F/g at a current density of 2A/g and 688.8F/g at 20A/g(5.3F/cm^(2 )at 9.4mA/cm^(2 )and 3.2F/cm^(2 )at 94mA/cm^2),which are better than those of the individual Co_3O_4nanowire.Moreover,the electrode shows excellent cycling performance with a retention rate of 90.4%after 3 000cycles at a current density of 20A/g.

Synthesis of Ni/Mg/Al Layered Double Hydroxides and Their Use as Catalyst Precursors in the Preparation of Carbon Nanotubes

Ni/Mg/Al layered double hydroxides(LDHs) with different n(Ni)∶n(Mg)∶n(Al) ratio values were prepared via a coprecipitation reaction. Then Ni/Mg/Al mixed oxides were obtained by calcination of these LDHs precursors. Carbon nanotubes were produced in the catalytic decomposition of propane over the Ni/Mg/Al mixed oxide catalysts. The quality of as-made nanotubes was investigated by SEM and TEM. The nanotubes were multiwall with a high length-diameter ratio and appeared to be flexible. The catalytic activities of these mixed oxides increased with increasing the Ni content. The Ni/Mg/Al mixed oxide with the highest Ni content [n(Ni)/n(Mg)/n(Al)=1/1/1] showed the highest activity and the carbon nanotubes grown on its surface had the best quality.

Advances in Mg-Al-layered double hydroxide steam coatings on Mg alloys:A review

Layered double hydroxide(LDH)coatings on magnesium(Mg)alloys shine brightly in the field of corrosion protection because of their special ion-exchange function.State-of-the-art steam coating as a type of LDH film preparation technique has emerged in recent years because only pure water is required as the steam source and its environmentally friendly LDH coating fits the current need for green development.Moreover,this coating can effectively inhibit the corrosion of the Mg alloy substrate due to the chemical bonding between the coating and the Mg alloy substrate.This review systematically explains cutting-edge advancements in the growth mechanism and corrosion behavior of LDH steam coatings,and analyzes the advantages and limitations of the steam-coating method.The influencing factors including pressure,CO_(2)/CO_(3)^(2-),aluminum content of the substrate alloy,solution type,and acid-pickling pretreatment,as well as the post-treatment of steam-coating defects,are comprehensively elucidated,providing new insights into the development of the in situ steam-coating technique.Finally,existing issues and future prospects are discussed to further accelerate the widespread application of Mg alloys.

Disposal of wastewater containing Congo Red by synthesizing layer double hydroxide in-situ

Based on the principle of synthesis, a new method was put forward to dispose Congo Red anion-containing dyestuff from wastewater and its feasibility was also examined. The principle of the method is described as follows: Mg2+ and Al3+ are hydrolyzed to form Mg/Al-LDH by adding Mg2+, Al3+ and NaOH in wastewater containing anion dyestuff, which is selectively intercalated with the interlayer of LDH in order to balance positive structural charge. While Mg2+ and Al3+ are co-precipitated to form LDH, the anion dyestuff in wastewater will be removed by LDH synthesized in-situ, as is confirmed by X-ray diffraction analysis of settlings and chemical analysis of aqueous samples. In this work, we studied the influence of Mg/Al mole ratio, pH value, time and temperature of reaction on the removal of anion dyestuff and the use of Mg and Al. The experimental results showed the maximum removal efficiency of anion dyestuff could be attained when pH value was 9.0, and Mg/Al mol ratio was 2∶1, reaction duration was 2 hours, and the effect of temperature was not remarkable, and the removal efficiency could reach 100%. Meanwhile, the Mg and Al added could be made good use of. This technology has the advantage of extraordinary efficiency of wastewater disposal.

Structure Engineering of Layered Double Hydroxides(LDHs)for Heterogeneous Catalysis

Layered double hydroxide(LDH)is regarded as an advanced platform material in catalysis and attracts vast attrition recently.As a kind of two-dimensional layered material,it exhibits great advantages including cation-tunability in layer,lattice limitation,topological transformation,ion exchange and intercalation characteristics.It also can be used as building blocks for composite catalytic materials.Over 100 years,a large number of works have been accomplished and researchers made great progress on investigating the LDH-based catalytic materials.In this review,we summarize representative achievements and significant progress in recent years,which mainly include constructing high entropy catalytic material,high dispersion/stability and interfacial supported catalytic material,composite catalytic materials and nano-reactor based on LDH.Furthermore,through collecting the excellent works,we conclude the future development potential of LDH and provide a perspective.

镍铁比对Fe_3O_4/Ni-Fe-LDHs复合结构吸附性能影响研究

采用原位生长法,控制组成金属离子配合比,在四氧化三铁(Fe_3O_4)表面垂直生长镍铁(Ni-Fe)层状双金属氢氧化物(LDHs),制得Fe_3O_4/Ni-Fe-LDHs复合结构,并考察其对有机染料(甲基橙和亚甲基蓝)的吸附规律。结果表明:制得的Fe_3O_4/Ni-Fe-LDHs的饱和磁化强度为41.2emu/g,在室温,镍:铁的摩尔配合比为2∶1,吸附平衡时间为48h,Fe_3O_4/Ni-Fe-LDHs用量为25mg/L的条件下,Fe_3O_4/Ni-Fe-LDHs对甲基橙和亚甲基蓝的吸附量分别达到188mg/g和175mg/g。

Bimetallic Ni-Fe catalysts derived from layered double hydroxides for CO methanation from syngas

Carbon deposition and sintering of active components such as nano particles are great challenges for Ni-based catalysts for CO methanation to generate synthetic natural gas from syngas. Facing the challenges, bimetallic catalysts with different Fe content derived from layered double hydroxide containing Ni, Fe, Mg, A1 elements were prepared by co-precipitation method. Nanoparticles of Ni-Fe alloy were supported on mixed oxides of aluminium and magnesium after calcination and reduction. The catalysts were characterized by Brunner- Emmett-Teller （BET）, X-ray diffraction, hydrogen tem- perature programmed reduction, inductively coupled plasma, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric techniques, and their catalytic activity for CO methanation was investigated. The results show that the Ni-Fe alloy catalysts exhibit better catalytic performance than mono- metallic catalysts except for the Ni4Fe-red catalyst. The Ni2Fe-red catalyst shows the highest CO conversion （100% at 260-350 ~C）, as well as the highest CH4 selectivity （over 95% at 280-350 ~C）, owing to the formation of Ni-Fe alloy. In stability test, the Ni2Fe-red catalyst exhibits great improvement in both anti-sintering and resistance to carbon formation compared with the Ni0Fe-red catalyst. The strong interaction between Ni and Fe element in alloy and surface distribution of Fe element not only inhibits the sintering ofnanoparticles but restrains the formation of Ni clusters.

Construction of 3D hollow NiCo-layered double hydroxide nanostructures for high-performance industrial overall seawater electrolysis

Green hydrogen production via seawater electrolysis holds a great promise for carbon-neutral energy production. However, the development of efficient and low-cost bifunctional electrocatalysts for seawater electrolysis at an industrial level remains a significant challenge. Herein, we report a facile approach based on one-dimensional (1D) cobalt carbonate hydroxide (CCH) nanoneedles (NNs) as skeleton and zeolitic imidazolate framework-67 (ZIF-67) as a sacrificial template to construct a self-supported NiCo layered double hydroxide (NiCo LDH) heterostructure nanocage (CCH@NiCo LDH) anchoring on the carbon felt (CF). The NiCo LDHs have hollow features, consisting of ultrathin layered hydroxide nanosheets. Benefiting from the structural advantages, unique carbon substrate and desirable composition, three-dimensional (3D) NiCo LDH nanocages exhibit superior performance as a bifunctional catalyst for overall seawater splitting at an industrial level and good corrosion resistance in alkaline media. In the alkaline seawater (1 M KOH + 0.5 M NaCl), it exhibits low overpotentials of 356 mV for hydrogen evolution reaction (HER) and 433 mV for oxygen evolution reaction (OER) at 400 mA·cm^(−2), much better than most of reported non-noble metal catalysts. Consequently, the obtained CF electrode loading of CCH@NiCo LDH exhibits outstanding performance as anodes and cathodes for overall alkaline seawater splitting, with remarkably low cell voltages of 1.56 and 1.89 V at current densities of 10 and 400 mA·cm^(−2), respectively. Moreover, the robust stability of 100 h is also demonstrated at above 200 mA·cm^(−2) in alkaline seawater. Our present work demonstrates significant potential for constructing effective cost-efficient and non-noble-metal bifunctional electrocatalyst and electrode for industrial seawater splitting.

Hierarchical cobalt-molybdenum layered double hydroxide arrays power efficient oxygen evolution reaction

Transition metal-based layered double hydroxides(LDHs)have been capable of working efficiently as catalysts in the basic oxygen evolution reaction(OER)for sustaining hydrogen production of alkaline water electrolysis.Nevertheless,exploring new LDH-based electrocatalysts featuring both remarkable activity and good stability is still in high demand,which is pivotal for comprehensive understanding and impressive improvement of the sluggish OER kinetics.Here,a series of bimetallic(Co and Mo)LDH arrays were designed and fabricated via a facile and controlled strategy by incorporating a Mo source into presynthesized Co-based metal-organic framework(MOF)arrays on carbon cloth(CC),named as ZIF-67/CC arrays.We found that tuning the Mo content resulted in gradual differences in the structural properties,surface morphology,and chemical states of the resulting catalysts,namely CoMox-LDH/CC(x representing the added weight of the Mo source).Gratifyingly,the best-performing CoMo_(0.20)-LDH/CC electrocatalyst demonstrates a low overpotential of only 226 mV and high stability at a current density of 10 mA·cm^(−2),which is superior to most LDH-based OER catalysts reported previously.Furthermore,it only required 1.611 V voltage to drive the overall water splitting device at the current density of 10 mA·cm^(−2).The present study represents a significant advancement in the development and applications of new OER catalysts.

A composite of Ni-Fe-Zn layered double hydroxides/biochar for atrazine removal from aqueous solution

This study assembled corn stalk-derived biochar(BC)with layered double hydroxide(LDH)through a rapid coprecipitation of biochar and metal(Ni/Fe/Zn)hydroxide precipitates.A BC and LDH composite(BC-LDH)and modified BC-LDH material after heating(BC-LDH-P)were prepared successfully for atrazine adsorptive removal.The physicochemical properties of the synthesized samples were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),Fourier transform infrared(FT-IR),and X-ray photoelectron spectroscopy(XPS).Batch experiments were conducted to study the sorption of atrazine onto BC,BC-LDH,and BC-LDH-P from the aqueous solution.The adsorption of atrazine onto BC-LDH and BC-LDH-P were performed following with the pseudo-second-order kinetic model,and the sorption isotherms agreed well with the Freundlich fitting model.The adsorption amounts of the three materials are arranged in descending order is as follows:BC-LDH-P>BC-LDH>BC(143.15>123.10>95.93 mg g−1,respectively).Due to the high crystallinity of the LDH material and the high binding degree with biochar,Ni/Fe/Zn-LDH biochar composites offer a potential alternative to a carbon-based adsorbent for atrazine removal from aqueous solution.

Ni-Fe层状双金属氢氧化物的制备及性能研究

采用水热法制备了Ni-Fe层状双金属氢氧化物(Ni-Fe LDHs),研究了反应温度、反应时间、镍铁比和柠檬酸三钠用量对Ni-Fe LDHs生长的影响,并研究其对甲基橙和亚甲基蓝的吸附性能。利用X-射线衍射、扫描电镜和交变梯度磁强计等测试方法研究了工艺条件对Ni-Fe-LDHs形貌、粒径、结晶性和磁性能的影响。实验结果表明:延长反应时间或升高反应温度都不利于得到结晶性好的Ni-Fe-LDHs。镍铁比对样品的结晶性和形貌有重要影响;镍铁比为2∶1,样品的结晶性和磁性能最好,增加镍铁比,得到片层组装形成得花状结构;镍铁比为3∶1时,Ni-Fe-LDHs对甲基橙和亚甲基蓝表现出良好的吸附性。

Corrosion resistance of Mg（OH）2/Mg-Al-layered double hydroxide coatings on magnesium alloy AZ31:influence of hydrolysis degree of silane

Mg(OH)2/Mg-Al-layered double hydroxide (LDH) coatings were modified with methyltrimethoxysilane (MTMS) on magnesium alloys. Effect of hydrolysis degree of silane solution on coating formation was investigated. Chemical compositions and surface morphologies of the coatings were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electronic microscopy (FESEM). Results indicated that the composite coatings consisted of polymethyltrimethoxysilane (PMTMS), LDH and Mg(OH)2. Electrochemical and hydrogen evolution measurements revealed that the composite coatings possessed good corrosion resistance, especially the ones prepared in a high hydrolysis degree of silane. The optimum corrosion resistance of the composite coati ng was LDH/PMTMS-3 coating, which had the lowest value of corrosion current density (5.537×10^-9 A·cm^-2) and a dense surface.Plausible mechanism for coating formation and corrosion process of MTMS-modified Mg(OH)2/Mg-Al-LDH coatings were discussed.

Corrosion resistance of Zn-AI layered double hydroxide/ poly（lactic acid） composite coating on magnesium alloy AZ31

A Zn-AI layered double hydroxide （ZnAI-LDH） coating consisted of uniform hexagonal nano-plates was firstly synthesized by co-precipitation and hydrothermal treatment on the AZ31 alloy, and then a poly（lactic acid） （PLA） coating was sealed on the top layer of the ZnAI-LDH coating using vacuum freeze-drying. The characteristics of the ZnAI-LDH/PLA composite coatings were investigated by means of XRD, SEM, FTIR and EDS. The corrosion resistance of the coatings was assessed by potentiodynamic polarization and electrochemical impedance spectroscopy （EIS）. The results showed that the ZnAI-LDH coating contained a compact inner layer and a porous outer layer, and the PLA coating with a strong adhesion to the porous outer layer can prolong the service life of the ZnAI-LDH coating. The excellent corrosion resistance of this composite coating can be attributable to its barrier function, ion-exchange and self-healing ability.

Layered double hydroxide-based core-shell nanoarrays for efficient electrochemical water splitting

Electrochemical water splitting is an efficient and clean strategy to produce sustainable energy produc- tions （especially hydrogen） from earth-abundant water. Recently, layered double hydroxide （LDH）-based materi- als have gained increasing attentions as promising electrocatalysts for water splitting. Designing LDHs into hierarchical architectures （e.g., core-shell nanoarrays） is one of the most promising strategies to improve their electrocatalytic performances, owing to the abundant exposure of active sites. This review mainly focuses on recent progress on the synthesis of hierarchical LDH-based core-shell nanoarrays as high performance electrocatalysts for electrochemical water splitting. By classifying different nanostructured materials combined with LDHs, a number of LDH-based core-shell nanoarrays have been developed and their synthesis strategies, structural characters and electrochemical performances are rationally described. Moreover, further developments and challenges in devel- oping promising electrocatalysts based on hierarchical nanostructured LDHs are covered from the viewpoint of fundamental research and practical applications.

Removal efficiency of fluoride by novel Mg-Cr-Cl layered double hydroxide by batch process from water

The fluoride ion removal from aqueous solution using synthesized Mg-Cr-Cl layered double hydroxide has been reported.Mg-Cr-Cl was characterized by X-ray powder diffraction,Fourier-transform infrared,thermo-gravimetric analysis,differential thermal analysis,and scanning electron microscope.Adsorption experiments were carried out in batch mode as a function of adsorption dosages,contact time,pH,and initial fluoride concentration to get optimum adsorption capacity.The adsorption kinetic study showed that the adsorption process followed first order kinetics.The fluoride removal was 88.5% and 77.4% at pH 7 with an adsorbent dose of 0.6 g/100 mL solution and initial fluoride concentration of 10 mg/L and 100 mg/L,respectively.The equilibrium was established at 40 min.Adsorption experiment data were fitted well with Langmuir isotherm with R 2 = 0.9924.Thermodynamic constants were also measured and concluded that the adsorption process was spontaneous and endothermic in nature.The removal percentage decreased slowly with increasing pH.This process is suitable for industrial effluents.The regeneration of the material is not possible.