类水滑石制备及其功能改性的研究进展

目的 为了探索类水滑石的低成本制备方法及插层改性增加其新功能的方法,提出类水滑石制备及其功能改性的环保新方向。方法 基于类水滑石的常规制备方法以及矿物原料和固废制备类水滑石的方法,综述类水滑石常规制备方法的优缺点,同时综述增强阻燃性能、吸附性能、催化性能、润滑性能、光催化、抗菌抗肿瘤、抗紫外线等性能的类水滑石的功能改性方法。结论 认为目前类水滑石制备及改性应加强2个方面的研究：利用矿物原料和钢渣、矿渣、粉煤灰等固体废弃物直接制备类水滑石,以降低其制备成本;利用水滑石和类水滑石的层状结构,以及层间阴离子的可交换的特性,加强其多种性能的改性。     

亚铁铝类水滑石吸附铀的性能与吸附机制

运用超声共沉淀制备了亚铁铝类水滑石(Fe(Ⅱ)-Al LDH),用于处理含U(Ⅵ)废水。实验考察了初始pH、吸附剂投加量、温度、吸附时间以及U(Ⅵ)初始浓度对Fe(Ⅱ)-Al LDH吸附U(Ⅵ)的影响。采用SEM、FTIR、XRD与XPS等手段分析了相关机制。试验表明,Fe(Ⅱ)-Al LDH吸附U(Ⅵ)的最佳pH为6,当温度为25℃,投加量为1.0g/L,U(Ⅵ)初始质量浓度为10mg/L时,对U(Ⅵ)的去除率达到99.98%,反应在120min达到平衡,饱和吸附量为117.13mg/g。Langmuir等温吸附模型和准二级动力学模型(R~2≈1)较好地拟合了吸附过程,Fe(Ⅱ)-Al LDH对U(Ⅵ)的吸附是自发的吸热反应。SEM、FTIR、XPS分析结果表明,吸附前后的Fe(Ⅱ)-Al LDH结构没有发生改变,Fe(Ⅱ)-Al LDH对U(Ⅵ)的吸附是化学吸附为主,氧化还原作用为辅。     

镁铝水滑石纳米片可控制备及其吸附性能研究

在聚乙二醇(PEG)存在的条件下,通过一步水热法合成了晶相单一的六方片状镁铝水滑石层状双氢氧化物(LDH)。采用XRD、SEM、TEM、FT-IR、N2吸附、UV-Vis紫外-分光光度计和zeta电位仪等对产物进行了表征。考察了PEG活性剂对水滑石形貌及性能的影响。结果表明,添加活性剂改性后制备的六边形水滑石纳米片形貌规整均一,宽约几微米,厚度约为100~200 nm,纳米片间易形成交叉支撑结构,分散性好,比表面积为203.5 m2/g。在室温,焙烧后的Mg AlLDO对浓度为100 mg/L的刚果红30 min内去除率可达97%,饱和吸附量为243.5 mg/g。     

水滑石类材料在污染治理中的应用及研究进展

水滑石类材料是一类双金属层柱状化合物,因具有特殊的层间离子交换性能和结构记忆效应,在环境污染治理中可作为催化剂、吸附剂和螯合剂,分别用于低温催化还原气态污染物、修复阴离子污染水体和螯合重金属阳离子.针对国内外研究现状,讨论了水滑石类材料在环境污染治理中的应用及最新研究进展.具有螯合性能的水滑石类材料有可能发展为一种新的处理重金属污染的水体净化剂.     

NiMgAl类水滑石制备条件研究

采用共沉淀法合成了不同摩尔投料比的NiMgAl类水滑石化合物.测定了Ni、Mg、Al单盐以及不同摩尔比的混合硝酸盐溶液的滴定曲线,考察了加料方式、晶化温度、晶化时间、原料配比对类水滑石合成的影响.通过XRD、IR对合成物进行表征,结果表明,在恒定pH值为8～9,n(Mg Ni)/n(Al)=1～3,n(Mg)/n(Ni)=8～16,晶化温度为65℃,晶化时间6h的条件下即得到晶相单=的NiMgAl-HTLcs;随n(Mg Ni)/n(Al)的增加,类水滑石结构的规整性提高,n(Mg)/n(Ni)比增加,层间距略有减小.     

二元金属类水滑石的合成及其作为前驱体对NOx的吸附性能研究

用共沉淀法合成了多种二元金属类水滑石化合物,对其进行了XRD、IR表征,并测试了焙烧产物对NOx的吸附性能.结果表明,合成的样品都具有典型的水滑石层状结构;二元金属类水滑石化合物MAl-HTlcs(M=Cu,Mg,Zn,Co,Ni)对NOx均具有良好的吸附性能,其中锌铝型类水滑石(摩尔比Zn/Al=3)对NOx的吸附速率及饱和吸附量最大,饱和吸附量为1851mg/g.     

类水滑石的制备与改性及其在聚丙烯阻燃中的应用

采用共沉淀法制备了镁铝类水滑石（LDHs）前驱体,加入少量聚磷酸铵（APP）制得APP-LDHs,探讨了不同质量分数APP对LDHs晶体生长的影响;当APP在LDHs前驱浆液中添加量为0.8wt%时,将APP-LDHs与季戊四醇（PER）、硅烷偶联剂KH-550进行球磨混合,制备插层包覆改性的LDHs;通过XRD、FTIR、SEM和TG等对改性前后的LDHs进行了表征;采用极限氧指数（LOI）、垂直燃烧测试（UL-94）、缺口冲击和弯曲实验等方法研究了LDHs改性前后LDHs/聚丙烯（PP）复合材料的阻燃性能及力学性能的差异。研究结果表明：APP的加入,未显著影响LDHs的层板生长,但其层板堆叠受到抑制;SEM观察表明,所制备的LDHs为片状,且经插层包覆改性后的LDHs粉体形貌较为规整,颗粒粒径为100~250 nm;改性LDHs在较高温度下的热稳定性显著优于未改性的LDHs;当PP中加入质量分数为20%的LDHs及改性LDHs时,可抑制PP燃烧时产生的熔滴,并促使LDHs/PP复合材料表面形成炭层;改性LDHs/PP复合材料具有更好的阻燃性能,且其冲击强度、弯曲强度等力学性能下降不明显。     

水滑石除磷的吸附动力学研究

采用共沉淀法制备了Mg/Al水滑石,研究了不同Mg/Al物质的量比、材料用量、不同pH条件下Mg/Al水滑石吸附除磷的动力学特征,从而对吸附速率的控制过程进行分析。结果表明水滑石对磷的吸附能较好地符合准二级动力学方程、Elovich动力学方程和内扩散模型。n(Mg)/n(Al)=3是水滑石最理想配比,水滑石投加量越大,外扩散过程越慢;一定范围内pH的升高能促进水滑石对磷吸附速率和吸附容量的提升。     

磁性水滑石复合材料的制备及其对曙红Y的吸附性能

为了解决水滑石型（LDH）吸附剂在污水处理中难回收的问题,采用双滴沉淀法将磁性Fe₃O₄颗粒与具有吸附性能的Ni-Mg-Al-LDH水滑石相结合,合成了Fe₃O₄@Ni-Mg-Al-LDH磁性水滑石复合吸附材料,利用SEM、XRD、FT-IR和氮气吸附脱附等表征对Fe₃O₄@Ni-Mg-Al-LDH材料的形貌和结构进行测试,并将其用于曙红Y染料废水处理。结果表明,Fe₃O₄@Ni-Mg-Al-LDH对曙红Y染料的吸附在20 min内较为迅速,120 min后吸附趋于平衡,且随着曙红Y初始浓度的升高,Fe₃O₄@Ni-Mg-Al-LDH对曙红Y染料的吸附量也逐渐增加,最大吸附量达到108.6 mg·g^-1。同时,Fe₃O₄@Ni-Mg-Al-LDH对曙红Y的吸附过程符合Langmuir等温吸附模型和伪二级动...     

Mg-Al-Ce水滑石吸附去除水中的硼

用共沉淀法成功制备了镁铝铈水滑石(Mg-Al-Ce-HT), 采用不同分析手段对材料进行表征。通过静态吸附实验研究了Mg-Al-Ce-HT的吸附效率与初始pH、吸附剂剂量、初始硼酸浓度和接触时间的关系。当pH小于8.0时, 溶液的pH对硼吸附几乎没有影响, 当pH超过8.0时, 吸附容量降低。吸附剂的最佳用量为200 mg, 最大吸附容量为32.52 mg·g ^-1。 硼去除量在160 min内达到平衡。吸附等温线表明吸附过程是一个非自发的吸热过程。吸附数据与Langmuir模型拟合良好, 表明吸附是单层吸附。     

层状双氢氧化物析氧催化剂的研究进展

层状双氢氧化物具有制备简单,层间客体可调节,合成成本较低,稳定性较好等优点,因此成为析氧催化剂的研究热点,但仍存在电荷传输速率低,过电位相对较高等问题,因此需要对其改性来加快其大规模应用。首先介绍了层状双氢氧化物的结构特点,简述了其析氧反应的催化机理,然后总结了不同种类的优化改性策略来增强其催化活性。优化改性方法分别包括:与导电基材复合;合成超薄纳米片法;与石墨烯复合法;杂化改性法。重点探讨了层状双氢氧化物析氧催化剂在电解水制氢方面的应用,提出了不同改性方法的优缺点,阐明将其适当结合,有利于制备更高效的析氧催化剂,最后指出了这类催化剂仍面临的问题:回收率较低,催化剂稳定性和可实现的电流密度尚未达到工业化需求,无法实现大规模制备等难点。     

Chloride adsorption by calcined layered double hydroxides in hardened Portland cement paste

This study investigated the feasibility of using calcined layered double hydroxides (CLDHs) to prevent chloride-induced deterioration in reinforced concrete. CLDHs not only adsorbed chloride ions in aqueous solution with a memory effect but also had a much higher binding capacity than the original layered double hydroxides (LDHs) in the cement matrix. We investigated this adsorption in hardened cement paste in batch cultures to determine adsorption isotherms. The measured and theoretical binding capacities (153 mg g⁻¹ and 257 mg g⁻¹, respectively) of the CLDHs were comparable to the theoretical capacity of Friedel's salt (2 mol mol⁻¹ or 121 mg g⁻¹), which belongs to the LDH family among cementitious phases. We simulated chloride adsorption by CLDHs through the cement matrix using the Fickian model and compared the simulation result to the X-ray fluorescence (XRF) chlorine map. Based on our results, it is proposed that the adsorption process is governed by the chloride transport through the cement matrix; this process differs from that in an aqueous solution. X-ray diffraction (XRD) analysis showed that the CLDH rebuilds the layered structure in a cementitious environment, thereby demonstrating the feasibility of applying CLDHs to the cement and concrete industries.     

Synthesis of layered double hydroxides from eggshells

Ca-Al and Ca-Fe layered double hydroxides (LDHs) were successfully synthesized from chicken eggshells by an ultrasonic wave assistant method. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) techniques. XRD and TEM analyses showed that the 4Ca-Al LDHs were of high purity but other samples were not. The present study provides a simple, efficient and environmental friendly method to obtain LDHs from biowaste eggshells, in which additional alkaline solution is not required for synthesis. Moreover, eggshells provide all the requisite bivalent metal ions, which are needed to form layered double hydroxides.     

Effect of salicylic acid intercalated layered double hydroxides on ultraviolet aging properties of bitumen

Salicylic acid intercalated layered double hydroxides (Sa-LDHs) were prepared by ion-exchange method. X-ray diffraction (XRD), Fourier transform infrared (FTIR) and ultraviolet and visible (UV–Vis) spectrum were applied to characterize the Sa-LDHs. The increase of basal spacing illustrated in XRD and presence of characteristic peak of salicylic acid observed in FTIR demonstrate that the salicylic acid is favorably intercalated into the interlayers of LDHs. UV–Vis curves of Sa-LDHs reveal the salicylic acid intercalated in LDHs dramatically improves the UV absorption ability, therefore, Sa-LDHs possess both excellent physical reflection and chemical absorption to UV rays. And then the effects of Sa-LDHs and LDHs on UV aging properties of bitumen were investigated. Compared with LDHs modified bitumen after UV aging, Sa-LDHs modified bitumen exhibits smaller changes in physical indexes (softening point and viscosity) and rheological parameters (complex modulus and phase angle), indicating Sa-LDHs can further improve the UV aging resistance of bitumen. The enhanced anti UV aging performance of bitumen mainly attribute to the dramatic improvement in UV absorption ability.     

Stearate intercalated layered double hydroxides: effect on the physical properties of dextrin-alginate films

Glycerol-plasticized dextrin-alginate films were prepared by solution casting. They contained a fixed amount (16.6% mass/dry film mass) of functional filler based on the reaction products of the LDH, Mg₄Al₂(OH)₁₂CO₃·3H₂O, and stearic acid (SA). The films were characterized using infrared (IR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effect of filler composition on water vapour permeability and film stiffness was determined. The ratio of stearic acid (SA) to the LDH (Mg₄Al₂(OH)₁₂CO₃·3H₂O) was varied over the full composition range. Infrared spectroscopy and X-ray diffraction studies confirmed that the SA intercalated into the LDH. The Young’s modulus of films attained a maximum value (more than double the value for the neat film) at a filler composition of 60% SA. The water vapour permeability showed a broad minimum at filler compositions of 50–80% SA. Scanning electron microscopy revealed that in this composition range the filler assumes a high-aspect-ratio platelet morphology. This contrasts with the sand rose morphology of the LDH starting material and the globular dispersion of 100% SA in the film.     

Facile preparation of poly(vinyl alcohol) nanocomposites with pristine layered double hydroxides

In this paper, nano-sized Mg–Al layered double hydroxide (LDH) was synthesized by a fast nucleation and slow aging method. The structures of LDH were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM) and photon correlation spectroscopy (PCS). Poly(vinyl alcohol) (PVA) nanocomposites with different LDH loadings were prepared by water solution casting method. TEM observations show that the LDH nanoplatelets are uniformly dispersed in the PVA matrix. Tensile tests indicate that the elastic modulus and the tensile strength of PVA are improved by about 15% and 54%, respectively, when incorporating with 2 wt% LDH. The improvement of mechanical properties of PVA can be attributed to fine dispersion of LDH, good compatibility and strong interaction between PVA and LDH. In addition, the presence of LDH decreases the decomposition rates at the second stage and improves the amount of residues of PVA. Meanwhile, the transparency of the nanocomposite films is maintained compared with neat PVA.     

Sorption study of an acid dye from an aqueous solution on modified Mg-Al layered double hydroxides

In this paper, experimental methods and results are reported on the removal of the dye Green Bezanyl-F2B (an acid dye) from MgAlCO(3) (HT) and from intercalated anionic surfactant, "sodium dodecylsulfate (SDS)", into the Mg-Al layered double hydroxides by the calcination-rehydration reaction using Mg-Al oxide precursors calcined at 773 K. Dodecylsulfate hydrotalcite was prepared by the calcination-rehydration method. The surfactant intercalation in the interlayer space of hydrotalcite was investigated by XRD and FT-IR spectroscopy where the resulting materials were found to be similar to those reported in the literature and were used to remove an acid dye from an aqueous solution. Equilibrium time and rate-determining step of the dye Green Bezanyl-F2B sorption were determined. Two simplified kinetic models were tested to investigate the sorption. The adsorption capacity data were also fitted to Langmuir and Freundlich equation as well. The sorption data fitted to the Langmuir model gave good values of the determination coefficient.     

Surfactant-assisted fatty acid intercalation of layered double hydroxides

Surfactant-mediated intercalation of aliphatic carboxylic acids into a commercial layered double hydroxide (LDH) with approximate composition ] was explored. The reaction was conducted at elevated temperatures with the LDH powder as a suspension in a stearic acid oil-in-water emulsion. The acidic fatty acid, e.g., stearic acid, reacts with the basic carbonate anions, CO₂ is released and the fatty acid is intercalated as a bilayer. High-concentration anionic or nonionic surfactants, i.e., sodium dodecylsulfate or Tween 60, aid the intercalation process by emulsifying the molten acid and dispersing the hydrotalcite particles. X-ray diffraction, thermal analysis, and infrared spectroscopy confirmed that a bilayer-intercalated hydrotalcite was formed and that the surfactant is not co-intercalated. The method is convenient, economical, and environmentally friendly: It employs the readily available carbonate form as starting reagent; water is used as medium rather than organic solvents; low reaction temperatures suffice, i.e., calcinations of the clay are superfluous and there is no need for working under a CO₂-free atmosphere.     

基于NiMoCo层状双金属氢氧化物的电催化剂和超级电容器电极

本文通过调控Ni,Mo,Co三种元素的摩尔比得到一系列高效双功能电催化剂.其中,Co元素特定的氧吸附位点(Co^2+-O-Co^3+)可有效提高催化剂的活性.Mo元素在温和反应条件下具有较好的氧化还原能力.Ni是另一种高活性过渡金属.与其他材料结合可有效增强催化剂的氧化还原活性和储氧能力.所制备的NiMoCo层状双金属...