Electrochemical behaviour of thin films of Co/Al layered double hydroxide prepared by electrodeposition

Thin films of controlled thickness of Co/Al layered double hydroxide with different Co and Al percentages have been electrosynthesized by the cathodic reduction of a 0.03 M Co and Al nitrate solution. The electrochemical behaviour of the films deposited on Pt or ITO electrodes has been deeply studied in 0.1 M NaOH solution. Our findings demonstrate that as soon as a potential is applied in the anodic direction, the films undergo an irreversible change of phase.     

Polydimethylsiloxane based polyurethane and its composite with layered double hydroxide: Synthesis and its thermal properties

This investigation reports the synthesis of a new class of polyurethane (PU) based on bis(hydroxyalkyl) polydimethylsiloxane (PDMS) as diol and isophorone diisocyanate as diisocyanate followed by the preparation of PU/layered double hydroxide (PU/LDH) nanocomposite via ex-situ technique. Nuclear magnetic resonance and Fourier-transform infrared spectroscopy studies confirm the formation of PU and incorporation of PDMS into the PU backbone. Thermogravimetry analysis revealed that thermal stability of the composite improves significantly with incorporation of LDH into the PU matrix. This may be accredited to the barrier effect rendered by the LDH layers. Differential scanning calorimetry study reveals that with the incorporation of LDH, glass transition temperature (T_g) of the composite increases for an optimum level of loading beyond which it remains constant.     

Preparation and characterization of polyimide/modified layered double hydroxide nanocomposites

Polyimide (PI)/modified layered double hydroxide (m‐LDH) nanocomposites were prepared in this study. For this work, m‐LDHs were prepared from layered double hydroxides (LDHs) through an anionic exchange reaction with pyromellitic dianhydride (PMDA), succinic acid or terephthalic acid. PMDA and 4,4′‐oxydianiline were used to make the poly(amic acid) precursor for PI. X‐ray diffraction and transmission electron microscopy measurements confirmed that the PMDA‐modified LDH (PMH) and terephthalic acid‐modified LDH (TMH) were well dispersed in the PI matrix. For the succinic acid‐modified LDH, some of the LDH was intercalated with the succinic acid molecules but most maintained its original structure. Thus, the PI/PMH and PI/TMH nanocomposites exhibited improved mechanical, thermal and electrical properties compared to pure PI. The PMH has aromatic groups and is expected to have better π–π interactions with the PI chains than the other m‐LDHs. Thus, the PI/PMH nanocomposites exhibited the best properties among the nanocomposites investigated. Copyright © 2010 Society of Chemical Industry     

层状双氢氧化物材料在染料废水中的应用进展

层状双氢氧化物(LDH)凭借其特殊的层状结构、极强的可调控性等,已在水处理领域得到广泛关注.LDH除用于重金属吸附外,处理染料废水也表现出独特的优势.但由于单一的LDH存在耐酸碱性差、表面官能团少、化学稳定性差等缺陷,严重制约了其在处理染料废水方面的应用,为此,越来越多的研究者通过对LDH进行改性提高材料的吸附性能.首先归纳总结了LDH材料的常用制备及改性方法并比较了各方法的优缺点;其次,介绍了改性LDH材料对染料废水中离子的去除效果及其吸附机理,同时分析了不同环境条件(pH、接触时间、吸附剂用量等)对LDH基吸附材料吸附性能的影响;最后,对改性LDH材料的应用现状作出总结并对其未来发展方向作出展望.     

聚丙烯腈/水滑石插层共混体系的结构和性能研究

采用原位聚合法,以过氧化二苯甲酰为引发剂,在形成水滑石的同时单体丙烯腈进入其层间并发生聚合反应,制备出聚丙烯腈/水滑石插层复合材料.用红外光谱、扫描电镜和X射线衍射对这种插层复合材料的结构进行了分析和表征,并对其燃烧性能和热性能进行了初步研究.结果表明:在水滑石片层之间通过原位聚合的方法生成了聚丙烯腈大分子,使水滑石层间距有一定程度的增大.聚丙烯腈/水滑石共混复合物的阻燃性能有一定提高,其极限氧指数(LOI)从18%提高到了21%;耐热性能得到一定程度改善.     

泡沫镍表面原位生长纳米花锌钴氢氧化物电极材料及电化学性能研究

层状双金属氢氧化物（LDH）由于其丰富的活性位点和双金属的协同效应等优点已得到广泛关注。然而,制备具有高倍率性能、低电阻的新颖LDH电极材料仍是一个挑战。通过共沉淀法,在泡沫镍（NF）集流体上原位生长三维纳米花层状锌钴氢氧化物（ZnCo LDHs）电极材料。ZnCo LDHs@NF有较大的可及表面积以及较低的固有电阻（0.56 Ω）。同时该电极材料有较高的比容量（1 A/g的电流密度下为1 583 F/g）,并且在20 A/g的电流密度下仍能保持81%的比容量（1 280 F/g）。这些优异的电化学性能表明制备的ZnCo LDHs@NF电极材料在储能设备中具有较大的应用前景。     

Ni(OH)2 versus Ni/Al layered double hydroxides as matrices to immobilize glucose oxidase

Ni hydroxide and Ni/Al layered double hydroxide (LDH) were electrochemically deposited on Pt electrodes in the presence of glucose oxidase in the electrolytic solution, in order to verify if the performances of the two biosensors were dependent on the Ni content of the inorganic matrix used to entrap the enzyme. The comparative study was conducted by recording the current response due to the oxidation of H₂O₂, produced enzymatically after glucose additions, at +0.45 V versus SCE, pH 7.0 and T = 25 °C.A higher sensitivity and a narrower linearity range were observed for nickel hydroxide based biosensor (up to 5 mM against 15 mM exhibited when LDH was the immobilizing matrix). These results suggested that the amount of the enzyme entrapped on the electrode surface was higher when the matrix was Ni(OH)₂ and they were confirmed by EQCM measurements. On the contrary, the selectivity displayed by the two biosensors in the presence of interfering compounds, such as acetaminophen, citric, uric and ascorbic acids, was almost the same.     

Synthesis of Ni-Al layered double hydroxide via coprecipitation: Formation mechanism,synthesis intensification,and catalytic application

Herein, the formation mechanism of Ni-Al layered double hydroxide (NiAl-LDH) synthesized by coprecipitation was explored. Moreover, NiAl-LDH was prepared in a rotating packed bed (RPB) under different rotation speeds, which shows that increasing the rotation speed decreases the lateral size and thickness of NiAl-LDH, since high rotation speed accelerates the nucleation of NiAl-LDH. Additionally, the Ni/mixed metal oxides (MMO) catalysts derived from NiAl-LDH were prepared for maleic anhydride (MA) hydrogenation. Result shows that Ni/MMO catalyst obtained from NiAl-LDH prepared under a higher rotation speed exhibits higher MA conversion due to its larger surface area and smaller nickel particle size. The Ni/MMO catalyst obtained from NiAl-LDH prepared under 500 rpm exhibits 100% MA conversion and 100% succinic anhydride selectivity under 30°C and 2 MPa within 1 h. This work provides fundamental insight to understand the formation of NiAl-LDH. Moreover, RPB as an effective technique to synthesize NiAl-LDH and Ni-based catalysts was validated.     

水滑石的制备及其阻燃性能研究进展

由于聚合物受热易燃烧,常存在火灾风险,通常需要引入阻燃剂来提升其阻燃性能。水滑石(LDHs)因其无卤、无毒且抑烟性能优异,在阻燃领域受到了越来越多的关注。基于此,对LDHs的结构、制备方法及其阻燃机理进行了介绍,特别是对提高LDHs阻燃性能的途径即从层板阳离子掺杂、层间阴离子插层和表面改性进行了重点综述,并对不同结构LDHs的阻燃机理及阻燃性能进行了总结,最后展望了LDHs作为阻燃剂今后的发展趋势。     

水滑石的制备及其阻燃性能研究进展

由于聚合物受热易燃烧,常存在火灾风险,因此通常需要引入阻燃剂来提升其阻燃性能。水滑石（LDHs）因其无卤、无毒且抑烟性能优异,在阻燃领域受到了越来越多的关注。基于此,本文对LDHs的结构、制备方法及其阻燃机理进行了总结,特别是对提高水滑石阻燃性能的途径即从层板阳离子掺杂、层间阴离子插层和表面改性等方面进行了重点综述,并对不同结构水滑石的阻燃机理及阻燃性能进行了归纳总结,最后展望了水滑石作为阻燃剂今后的发展趋势,以期为水滑石类阻燃剂的发展及相关研究者提供指导作用。     

可光助再生二氧化钛/层状双氢氧化物去除水体中有机染料

利用吸附-光催化技术去除水体中有机染料,是高效节能的方法之一。然而,碳基吸附剂在光催化降解污染物过程中,由于活性氧的攻击会发生自身的逐渐氧化。本研究中,采用尿素水解水热法制备二氧化钛/层状双氢氧化物(TiO₂/LDH)非碳基复合材料,不仅对水体中有机染料具有较高的吸附容量,也在光辐射后具有可重复的再生能力。对甲基橙的吸附量为527.5 mg/g,在4轮循环再生后仍具有88.6%的再生率;对亚甲基蓝的吸附量为208.3 mg/g,在4轮循环再生后仍具有94.7%的再生率。在吸附-光再生过程中,LDH基底自身具有强抗氧化能力和高吸附能力,同时提高了负载剂TiO₂的光吸收效率,为水中有机污染物去除和吸附-光催化复合材料设计优化提供了可行的策略。     

Second staging of tartrate and carbonate anions in Mg–Al layered double hydroxide

The intercalation of tartrate was performed through ion exchange using carbonate Mg–Al layered double hydroxide (LDH) as precursor. The intermediate crystalline phase (so-called second-staging phase) was observed during the intercalation process. The pure second-staging LDH, in which alternate interlayer regions are occupied by carbonate and tartrate anions, was obtained by the deintercalation of interlayer tartrate with carbonate. It was also found that the interlayer tartrates are so stable that they are difficult to exchange by carbonate at room temperature.     

Preparation and properties of in‐situ polymerized polyurethane/stearate intercalated layer double hydroxide nanocomposites

The present work deals with the effect of stearate intercalated layered double hydroxide (St‐LDH) loadings on the morphological, mechanical, thermal, adhesive and flame retardant properties of polyurethane (PU)/St‐LDH nanocomposites prepared by the in situ polymerization method. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation takes place at 3 wt% loading followed by intercalation at higher filler loadings in the PU matrix. The exfoliated structure has been further verified by atomic force microscopy. The measurements of stress‐strain, thermogravimetric analysis, dynamic mechanical analysis, lap shear strength and peel strength analysis showed that the nanocomposites containing 3 wt% St‐LDH exhibit excellent improvement in tensile strength (ca 175%) and log storage modulus (ca 14%), while PU/St‐LDH (5 wt%) possesses optimum improvement in glass transition temperature (ca 6 °C), lap shear strength (200%) and peel strength (130%) over neat PU. In addition, the gradual improvements in limiting oxygen index value with St‐LDH loading indicated the higher effectiveness in providing better barrier properties as well as better flame retardant behavior. Copyright © 2012 Society of Chemical Industry     

氨基改性层状双氢氧化物的制备及其二氧化碳吸附机理

以氨基硅烷为改性剂,采用超声剥脱的方法合成了氨基改性的层状双氢氧化物。利用元素分析、X射线衍射(XRD)、漫反射红外傅里叶变换光谱(DRIFTS)和热重分析(TGA)等技术对样品进行了表征。研究了样品在25～150℃温度范围内的二氧化碳吸附能力。在80℃下,NiMgAl N2在纯CO₂和15% CO₂/N₂混合气中达到最大吸附容量,分别为2.02 mmol·g^-1和1.89 mmol·g^-1。吸附/脱附再生实验显示140℃为最佳的脱附温度。利用原位漫反射傅里叶红外光谱对二氧化碳在样品上的吸附进行了机理研究。     

In situ microwave‐assisted polymerization of polyethylene terephtalate in layered double hydroxides

The synthesis of poly(ethylene terephthalate) (PET)/layered double hydroxide (LDH) nanocomposites through microwave methods has been investigated. To enhance the compatibility between the PET polymer and the LDH, dodecyl sulfate was intercalated in the lamellar structure. The organo‐LDH structure was confirmed by powder X‐ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR). PET nanocomposites were prepared with 0–10 wt % of LDH content by in situ microwave‐assisted polymerization. PXRD was used to detect the formation of the exfoliated PET/LDH nanocomposites. Transmission electron microscopy was used to observe the dispersed layers and to confirm the exfoliation process. FTIR spectroscopy confirmed that the polymerization process had occurred. TG and DTA are used to study changes in thermal stability of the nanocomposites, which resulted enhanced by well dispersed LDHs layers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of 5‐sulfosalicylic acid‐intercalated layered double hydroxide and its effects on wood flour/polypropylene composites during accelerated UV weathering

In this study, 5‐sulfosalicylic acid (SA) anions have been intercalated into Mg₃Al‐NO₃ layered double hydroxide (LDH) to synthesize SA‐intercalated Mg₃Al‐NO₃‐LDH (LDH‐SA) by ion‐exchange reaction. Then, the effects of LDH, SA, and LDH‐SA on the photostability of wood flour/polypropylene (WF/PP) composites during accelerated ultraviolet (UV) weathering were investigated. The surface color, surface gloss, and mechanical properties of the composites during weathering were tested, accompanied by characterizations using SEM, ATR‐FTIR, and TG. The results showed that (1) SA anions completely replaced the anions in LDH and the thermal stability of LDH‐SA was considerably enhanced; (2) composites with LDH or LDH‐SA exhibited less color change, fewer surface cracks, better thermal stability, and less losses of mechanical properties than the control group; (3) LDH‐SA showed a long‐term efficiency and alleviated the photo‐oxidation of WF/PP composites successfully; (4) LDH‐SA blocked UV light by physical shield effect of the layer sheets, as well as the chemical absorbability of the interlayer anions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44597.     

原位共聚合改性HIPS/氢氧化镁复合材料的性能

采用乙烯基硅烷在氢氧化镁(MH)表面引入乙烯基后与苯乙烯原位聚合,制备苯乙烯原位共聚合改性MH。将改性前后的MH、微胶囊红磷(MRP)、高抗冲聚苯乙烯(HIPS)按不同配比熔融复合制备HIPS/MH和HIPS/MH/MRP复合材料。研究了复合材料的力学性能和阻燃性能。结果表明:改性后的MH能显著提高复合材料的冲击强度。改性前后的MH与MRP的协同阻燃效应使HIPS/MH复合材料极限氧指数提高到28.9%,UL 94垂直燃烧达到V-0级。MH与MRP的协同作用增加了HIPS/MH复合材料的点燃难度,有效抑制了HIPS的热释放速率和烟释放速率,对HIPS起到良好的阻燃作用。     

Effect of phytic acid–modified layered double hydroxide on flammability and mechanical properties of intumescent flame retardant polypropylene system

Phytic acid–modified layered double hydroxide (Ph‐LDH) was synthesized via coprecipitation method and subsequently was used in polypropylene (PP) by combining with an ammonium polyphosphate (APP) via melt compounding method. The synergistic effect between APP and Ph‐LDH on the thermal stability, flammability, and mechanical properties of the resultant PP composites was investigated by thermogravimetric analysis, limiting oxygen index, vertical burning test (UL‐94), cone calorimeter tests, tensile test, and impact test. Morphologies of the chars obtained from the samples after the cone calorimeter tests were studied by scanning electron microscopy. The combination of APP and Ph‐LDH slightly influenced the impact and tensile properties of PP. Also, the synergistic effect between APP and Ph‐LDH occurred in the cone calorimeter test. Moreover, the combination of APP and Ph‐LDH produced better quality char that effectively suppressed the spread of the flame and volatile and finally extinguished the fire.     

Fabrication of an anionic polythiophene/layered double hydroxide ultrathin film showing red luminescence and reversible pH photoresponse

Luminescent ordered ultrathin films (UTFs) based on a sulfonated polythiophene (SPT) and Mg–Al‐layered double hydroxide (LDH) nanosheets have been fabricated by the layer‐by‐layer assembly method. UV‐visible absorption and fluorescence spectroscopy showed that there was a stepwise and regular growth of the films with increasing number of deposition cycles. XRD, AFM, and SEM showed that the films had a periodic layered structure with a period of ca. 3.0 nm, and that the thickness can be finely controlled within the range ca. 26–100 nm. The SPT/LDH UTFs show well‐defined polarized photoemission with an anisotropy of ca. 0.3, and they show a reversible luminescence response to changes in pH. Periodic density functional theoretical calculations gave a band energy of 1.85 eV for the SPT/LDH system and showed that the valence electrons of SPT can be confined in the energy wells formed by the LDH monolayers, which effectively inhibits both the nonradiative relaxation and the π–π stacking interaction of the polymer chromophores. © 2010 American Institute of Chemical Engineers AIChE J, 2011