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.

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.

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.

Synthesis and Characterization of LDHs （Layered Double Hydroxides） Intercalated with EDTA （Ethylenediaminetetracetic Acid） or EDDS （N, N＇-1, 2-Ethanediylbis-l-Aspartic Acid）

The hydrotalcite-like compound [Zn2Al·（OH）6] NO3·nH2O and [Mg2Al·（OH）6] NO3·nH2O （shorted as ZnA1-NO3 and MgAl-NO3） was intercalated with the chelating agent EDTA （Ethylenediaminetetraacetic Acid） and EDDS （N, N＇-1, 2-Ethanediylbis-1-Aspartic Acid） by anion exchange. The materials synthesized in this work were characterized by chemical analysis, FT-IR （Fourier Transform Infrared Spectroscopy）, SEM （Scanning Electron Microscopy） and XRD （Powder X-ray Diffraction） to confirm their properties. In order to discuss the adsorption capacity of LDHs （Layered Double Hydroxides）, the adsorption experiment was investigated under the optimum condition （10 mg, 25℃ and 100 μg·L-1）. The amount of metallic ions adsorbed by LDHs intercalated with EDTA and precursor LDHs were determined by ICP-AES （Inductively Coupled Plasma-Atomic Emission Spectrometry） and AAS （Atomic Absorption Spectrometry）. The intercalation of EDTA leads to improve the adsorption capacity of LDHs. LDHs intercalated with chelating agents have generally high affinity for removing metallic ions, and they can be efficient adsorbents for metallic ions.

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.

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.

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.

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.

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.

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.

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.

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.

LDHs覆膜改性活性炭对水中磷的吸附特性研究

采用水热共沉淀法合成两种层状双金属氢氧化物(MgAl-LDHs和MgFe-LDHs)覆膜于活性炭,并研究了其对水中磷的吸附特性。结果表明,在pH=7、温度为298.15 K、吸附时间为4 h时,MgAl-LDHs和MgFe-LDHs改性基质对磷酸盐最大理论吸附容量分别为3.158 mg/g和4.557 mg/g。吸附过程更加符合Langmuir等温模型和拟二级动力学吸附模型,以均匀单分子层化学吸附为主。当磷酸盐初始浓度为0.5 mg/L和2 mg/L时,MgAl-LDHs改性基质的饱和吸附容量接近MgFe-LDHs改性基质的2倍,MgAl-LDHs改性基质更适合作为吸附剂。LDHs改性基质吸附磷酸盐的热力学参数ΔG_(0)<0、ΔH_(0)<0,说明吸附过程是自发的放热过程,低温更有利于提高吸附效果。

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.

层状双金属氢氧化物(LDHs)对SBS改性沥青抗老化性能的影响研究

为了增强SBS改性沥青(SMB)的抗老化性能,利用层状双金属氢氧化物(LDHs)的独特结构对SMB进行改性。研究了LDHs对SMB的物理性能、高低温流变性能和化学结构的影响规律。研究结果表明:LDHs的加入有助于提高SMB的弹性性能,提升SMB的高温稳定性能;老化后,沥青分子发生氧化反应导致SMB中含氧官能团(S=O和C=O)含量增加,同时SBS分子链发生断裂引起SMB中碳碳双键官能团(C=C)含量减少,这些变化使SMB的物理性能、高温抗车辙性能和低温抗疲劳开裂性能发生劣化,导致其变硬变脆;LDHs的加入可以阻止沥青分子的氧化反应和SBS分子链断裂,减缓沥青分子的老化和SBS老化降解,减轻老化对SMB物理性能和高低温流变性能的破坏,增强SMB的抗老化能力,为建设长寿命的SMB路面提供技术支持。

Polyoxometalate-Incorporated Host-Guest Framework Derived Layered Double Hydroxide Composites for High-Performance Hybrid Supercapacitor

Metal organic frameworks have been employed as high-performance layered double hydroxide(LDH)composite supercapacitor electrode materials but have shown unsatisfactory redox ability and stability.Herein,a host-guest CuMo-based polyoxomet-alate-based metal organic framework(POMOF)with copious electrochemically active sites and strong electrochemical redox activi-ties has been effectively coupled with POM-incorporated CoNi-LDH to develop a nanocomposite(NENU-5@CoNi-LDH)by a simple solvothermal method.The designed electrode shows a high specific capacity of 333.61 mAh·g^(-1) at 1 A·g^(-1).In addition,the novel hy-brid symmetric supercapacitor NENU-5@CoNi-LDH/active carbon(AC)demonstrated a high energy density of 80.8 Wh·kg^(-1) at a power density of 750.7 W·kg^(-1).Interestingly,the nanocomposite of NENU-5@CoNi-LDH exhibits an outstanding capacitance reten-tion of 79%after 5000 charge-discharge cycles at 10 A·g^(-1).This work provides a new strategy and will be the backbone for future energy storage research.

ZnAl-LDHs覆膜改性湿地基质强化氮磷吸附性能

传统湿地基质存在吸附作用单一的缺陷,采用LDHs覆膜定向改性具有一定氨氮吸附优势的人工湿地基质,通过冷场发射扫描电镜、X射线衍射仪对改性基质进行物理表征,研究无机磷(In-P)溶液初始浓度、吸附时间等因素对改性基质吸附In-P的影响,结合吸附等温线和吸附动力学分析除磷特性及吸附机理。结果表明,ZnAl-LDHs改性蛭石拟合得到的最大吸附量达74.239 mg/g,高于同类改性的沸石(4.133 mg/g)和砖渣(11.937 mg/g);吸附强度和吸附容量(K f=5.022)均大于改性沸石(0.633)和改性砖渣(0.971);ZnAl-LDHs改性基质对In-P的吸附动力学与准二级动力学模型拟合度(R2>0.980)更高,以化学吸附为控制步骤的吸附过程为主。利用蛭石进行ZnAl-LDHs覆膜改性可实现氨氮与In-P的同步高效吸附,有望弥补传统人工湿地基质吸附功能单一的不足。