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.

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.

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.

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.

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.

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.

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.

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.

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。

Phase control of 2D binary hydroxides nanosheets via controlling-release strategy for enhanced oxygen evolution reaction and supercapacitor performances

An OH^--slow-release strategy was established to controllably tune the( α-and β-) phase of nickel cobalt binary hydroxide in the presence of ammonium chloride. Ammonium chloride is added to the ionic solution to regulate the p H of the solution and slow down the release of OH^-, effectively regulating the phase, nanostructure, interlayer spacing, surface area, thickness, and the performance of binary Ni –Co hydroxide. The ion-slow-release mechanism is conducive to the formation of α-phase with larger interlayer spacing and thinner flakes rather than β-phase. Attributed to the enlarged interlayer spacing, thinner nanosheets, and more exposed active sites, the resultant α-phase hydroxides(NCNS-5.2), displayed much lower over potential of 285 mV with respect to the dense-stacked β-phase hydroxides(362 mV) for OER at 10 mA/cm^2. It also exhibited high specific capacitance of 1474.2 F/g, when tested at 0.5 A/g within a voltage range of 0–0.45 Vvs. Hg/Hg O. This composite was also stable for water oxidation reaction and supercapacitor. The proof-of-concept of using controlled-release agent may provide suggestive insights for the material innovation and a variety of applications.

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。

LDHs材料的结构、性质及其应用研究进展

LDHs(layered double hydroxides)是一类具有双金属氢氧化物层结构的新型无机材料,其酸碱性、热稳定性、层间阴离子可交换性以及结构记忆效应等特性在诸多领域中得到了广泛应用,成为当前研究的热点。针对国内外研究现状,本文综述了LDHs材料的基本性质、层间不同种阴离子及插层阴离子的化学作用。在此基础上,概括了LDHs材料的制备、表征方法和相关领域的应用,介绍了其在不同溶剂中进行剥离的研究进展,指出能否将其工业化扩大生产是制约其应用的重要因素,同时也分析了当前需要解决的相关问题,为今后LDHs材料的研究提供借鉴。

Synergistic effect of V and Fe in Ni/Fe/V ternary layered double hydroxides for efficient and durable oxygen evolution reaction

High-performance and stable electrocatalysts are vital for the oxygen evolution reaction(OER).Herein,via a one-pot hydrothermal method,Ni/Fe/V ternary layered double hydroxides(NiFeV-LDH)derived from Ni foam are fabricated to work as highly active and durable electrocatalysts for OER.By changing the feeding ratio of Fe and V salts,the prepared ternary hydroxides were optimized.At an Fe:V ratio of 0.5:0.5,NiFeV-LDH exhibits outstanding OER activity superior to that of the binary hydroxides,requiring overpotentials of 269 and 274 mV at 50 mA·cm^(−2)in the linear sweep voltammetry and sampled current voltammetry measurements,respectively.Importantly,NiFeV-LDH shows extraordinary long-term stability(≥75 h)at an extremely high current density of 200 mA·cm^(−2).In contrast,the binary hydroxides present quick decay at 200 mA·cm^(−2)or even reduced current densities(150 and 100 mA·cm^(−2)).The outstanding OER performance of NiFeV-LDH benefits from the synergistic effect of V and Fe while doping the third metal into bimetallic hydroxide layers:(a)Fe plays a crucial role as the active site;(b)electron-withdrawing V stabilizes the high valence state of Fe,thus accelerating the OER process;(c)V further offers great stabilization for the formed intermediate of FeOOH,thus achieving superior durability.

纳米双羟基复合金属氧化物(LDHs)对聚氯乙烯(PVC)阻燃抑烟研究

总结了聚氯乙烯(PVC)塑料燃烧时产生烟雾的机理及其阻燃抑烟原理,并且在已开发出的常用无机阻燃抑烟剂的基础上研究了一种新型的无毒环保型无机纳米级阻燃抑烟剂———纳米双羟基复合金属氧化物(LDHs)。分析了其对PVC的阻燃抑烟机理,并且试验证实了它的阻燃抑烟效果。试验结果表明,该阻燃剂只需少量添加就有明显的阻燃抑烟效果,并且克服了以往由于大量添加无机阻燃剂而造成的力学性能下降的缺点,是一种很有发展前景的新型阻燃抑烟剂。

LDHs耐紫外老化沥青的光学与老化性能研究

采用熔融共混法制备了层状双羟基复合金属氧氧化物LDHs耐老化沥青,研究了LDHs对沥青耐老化性能的影响。制备了LDHs耐老化沥青薄膜,通过沥青薄膜光学性能研究揭示了LDHs与沥青的作用机理。结果表明,LDHs可有效提高沥青的抗紫外老化性能。

类水滑石Ti/Li/Al-LDHs的制备及其CO_2吸附性能

采用共沉淀法制备了一系列新型的类水滑石Ti/Li/Al-LDHs材料,通过原子吸收光谱(AAS)、X射线衍射(XRD)、扫描电镜(SEM)、热重分析(TG)和傅里叶变换红外光谱(FT-IR)等技术对其进行了表征,研究了不同金属元素比例和焙烧温度对该Ti/Li/Al-LDHs材料的结构、形貌及其CO_2吸附性能的影响。结果表明,当Ti/Li/Al比为1∶3∶4时,水滑石Ti/Li/AlLDHs的结晶度最好,形貌最规整,而Ti/Li/Al比为1∶3∶2、300℃下焙烧后得到的Ti_1Li_3Al_2-LDHs_(300)的CO_2吸附性能最好。Ti_1Li_3Al_2-LDHs_(300)上CO_2吸附量可达53.5 mg/g,10次循环吸附后,CO_2吸附量仅下降了2.4%。

Fe_3O_4/LDHs复合结构的制备及吸附性能研究

分别采用两种方式(一步合成法和二步合成法)在Fe3O4表面生长层状双金属氢氧化物(LDHs),得到了Fe3O4/LDHs复合材料。利用X-射线衍射、电子显微分析、红外光谱和交变梯度磁强计等测试方法研究了LDHs和Fe3O4的复合方式对复合材料形貌、粒径、结晶性、磁性能和吸附性能的影响。同时对比分析了LDHs和Fe3O4/LDHs复合材料对Cr(VI)离子的平衡吸附规律。结果表明,采用一步合成法制备的Fe3O4/LDHs复合材料具有良好的磁性能和吸附性能。

离子交换法制备LDHs纳米复合材料及其影响因素研究

以层状双金属氢氧化物(LDHs)、氯化镁和氯化铝为原料,通过液相非稳态共沉淀法制备MgAl-Cl-LDHs溶胶,通过离子交换引入己基磺酸钠(SHS),制备SHS-LDHs纳米复合材料,研究了混合溶胶pH值、SHS的初始浓度、碳链长度以及LDHs的浓度对材料性能的影响。研究发现,当混合溶液的pH 7.25,LDHs的浓度不大于0.50%,且SHS的浓度高于20 mmol/L时,CH_3(CH_2)_5SO_3^-才能通过离子交换反应进入LDHs层间,得到SHS-LDHs纳米复合材料。