Chemical Modifications of Layered Double Hydroxides in the Supercapacitor

Layered double hydroxides are one class or kind of 2 D layered materials that are considered promising for use in the supercapacitor.Although there have been many studies on the structure,composition,properties,and electrode fabrication of layered double hydroxides,none summarize the effects of various modification methods on the structure and performance of layered double hydroxides in the supercapacitor.In a bid to fill this gap,in this review,we summarize the progress of modification methods such as exfoliation,intercalation,vacancy,doping,phase transformation,and composition regulation of layered double hydroxides in the field of the supercapacitor and put forward some opinions regarding the progress of research on the methods used in modifying the layered double hydroxides.

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.

USING COLLOIDAL LAYERED DOUBLE HYDROXIDES AS CATIONIC MICROPARTICULATE COMPONENT

Layered double hydroxides consisting of layers with cationic charges may be potential candidates of cationic microparticles forming synergetic retention effect with anionic polyacrylamide. In this work, the layered double hydroxides with various molar ratios of Mg/Al were synthesized by co-precipitation of magnesium chloride and aluminum chloride and peptized by intense washing with water. The chemical formula, particle size, Zeta potential of the layered double hydroxide were analyzed. It was found that positively charged magnesium aluminum hydroxide with particle diameter in nanoparticle size could be prepared. The Zeta potential and particle size vary with the feed molar ratio of Mg/Al and the peptizing process, respectively. The Zeta potential is also pH dependent. The retention experiments carried out on DDJ show that when used together with anionic polyacrylamide, the positively charged colloidal double hydroxide greatly improves the retention of reed pulps. The chemical formula, particle size and Zeta potential of the colloidal double hydroxide all affect its retention behavior.

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides (LDHs), is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/Al-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of (Mg, Al)-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like (Mg, Al)-oxide is transformed into a composite with periclase (MgO) and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.

Structural Analysis of Magnesium-Aluminium Hydrotalcites Modified with Iron III Obtained by Hydroxide Precipitation Method

Hydrotalcite-type anionic clays are a group of important materials used in adsorption processes, mainly for organic pollutants removal due the layered double hydroxide structure. The layer-interlayer interactions provide a structural memory even after dehydration and dehydroxylation process, since a very stable interlayer anions are part of material composition, like the carbonate one. A limited numbers of trivalent modifier cations can replace the aluminium cation due the ionic radii mismatch or oxidation state restrictions. Transition metal cations can replace the aluminium one in octahedral site of hydroxide lamellas in order to improve the adsorptive behaviors. In this work, we have investigate three compositions of carbonated magnesium-aluminium hydrotalcite with dif-ferent iron (III) contents through the co-precipitation method at pH 11 and aging step at 60°C for 6 hours. Thermal analysis was performed aiming the determination of the hydration water and hydroxyl amounts in dried precipitate samples, taking in account the results obtained for X-ray diffractometry, infrared spectroscopy, and nitrogen adsorption-desorption characterization for several thermally treated samples. All of synthesized samples showed high surface areas, even for high temperature of thermal treatment. The co-substitution with iron (III) reduced the temperature of dehydration and dehydroxylation process, but the co-substitution at 5 mol% provides other desirables characteristics, like a more amount of rhombohedral HDL phase and higher porosity, even after the thermal treatment at 500°C for 4 hours. This result makes that composition very applicable as a reusable adsorbent material in order to removal several types of micro-pollutant compounds in aqueous media.

Preparation,Characterization and Application of ZnAlLa-Hydrotalcite-Like Compounds

The preparation of ZnAlLa-hydrotalcite-like compounds [ZnAlLa-HTLcs] was studied.ZnAlLa-HTLcs were synthesized by a method of variable pH with the raw materials of Zn(NO3)2,Al(NO3)3, La(NO3)3, and NaOH. The effects of some factors (i.e. pH values, the mole ratio of Al3+ to La3+,temperature and the period of hydrothermal treatment) on the preparation of HTLcs were discussed systematically. XRD, TG-DTA, FT-IR spectroscopy, and ICP were performed to characterize ZnAlLa-HTLcs samples, and the thermal stability of HTLcs was also discussed. It was shown that unique ZnAlLa-HTLcs with high crystallinity can be prepared, under the conditions of pH=5.5-6.5, n(Zn2+)/n(Al3++La3+)=2and the atomic ratio of La3+ to Al3+ ranging from 0.07 to 2, hydrothermal treatment at 120 ℃ for 5h. When the calcination of the HTLcs is performed at temperatures above 200 ℃, ZnO phase is detected with Al2O3 and La2O3 spreading on its top. The complex metal oxides derived from ZnAlLa-HTLcs at 500 ℃ have higher catalytic activity and selectivity than those from ZnAl-HTLcs for the esterification of acetic acid with n-butanol under the same reaction conditions.

The photoluminescence of Co-Al-layered double hydroxide

我们报导纯 Co-Al-layered 双氢氧化物(LDH ) 的新光行为。没有任何荧光灯的物质， Co-Al-LDH 样品能射出荧光，这被发现设置。它的刺激光谱在波长附近显示出一座最大的山峰 370 nm，最大的排放山峰在 430 nm 出现， Co-Al-LDH 样品的光致发光颜色是蓝的。这个新光性质将被期望在光材料地里扩大 LDH 的潜在的应用。

原位合成LDHs@地聚物复合材料的矿物组成及除磷效果

以高铝粉煤灰、粒化高炉矿渣为前驱体,以氢氧化钠-碳酸钠、氢氧化钙-二水硫酸钙为混合激发剂,原位合成了两种富含层状双金属氢氧化物(LDHs)的粉煤灰-矿渣地聚物复合材料(LDHs@地聚物)。采用XRD、SEM-EDS微观测试手段,分析了LDHs@地聚物的主要矿物组成;以LDHs@地聚物复合材料为吸附剂,采用静态吸附试验考察了其除磷效果。研究结果表明:以氢氧化钠-碳酸钠为激发剂、活性氧化镁为调节材料,原位合成了CO_(3)^(2-)-LDHs@地聚物复合材料;以氢氧化钙-二水硫酸钙为激发剂,原位合成了SO_(4)^(2-)-LDHs@地聚物复合材料。在H_2PO_4~-初始浓度为100 mg·L^(-1)、固液比为1∶100的吸附条件下,掺8%的活性MgO制备的CO_(3)^(2-)-LDHs@地聚物复合材料经热处理后对H_(2)PO_(4)^(-)的吸附容量、去除率分别为9.51 mg·g^(-1)和95.1%;以质量比1∶1的氢氧化钙-二水硫酸钙为激发剂制备的SO_(4)^(2-)-LDHs@地聚物复合材料对H_2PO_(4)^(-)的吸附容量、去除率分别为9.99 mg·g^(-1)和99.9%;相同条件下,SO_(4)^(2-)-LDHs@地聚物复合材料比CO_(3)^(2-)-LDHs@地聚物复合材料具有更优异的除磷效果。

镍钴水滑石纳米笼/GO复合材料在锂离子电池负极中的应用

近年来,水滑石(LDH)材料因其组成、结构和形貌易于调节,具有丰富的活性位点,被认为是高性能锂离子电池(LIBs)负极的替代材料,然而水滑石作为负极仍存在电导率差和结构易聚集等问题.于此同时,金属有机框架(MOFs)及碳基材料也由于其优秀的孔隙率、比表面积以及良好的电导率在储能领域得到了广泛的关注.考虑到这二者有望对LDH的主要缺陷有所改进,提出了将原位沉淀、化学刻蚀法和静电吸附法相结合,使镍钴水滑石纳米笼(H-(Ni,Co)-LDHP)能够固定在GO上,从而得到镍钴水滑石纳米笼/氧化石墨烯复合材料(H-(Ni,Co)-LDHP/GO).这种GO上密集分布的中空纳米结构更能有效抑制水滑石纳米片的聚集,并有利于锂离子的脱嵌.H-(Ni,Co)-LDHP/GO纳米复合材料作为锂离子电池的负极,在电流密度为50m A·g^(-1)下,循环第一圈库伦效率可达68%,循环50圈后电容保留率为68.4%.

Salt freezing resistance improvement of cement-based materials incorporated with calcined layered double hydroxide

Salt freezing damage has severe impacts on durability of cement-based materials(CBMs).Calcined layered double hydroxide(CLDH),as an efficient environmental-friendly adsorption material,can impart excellent salt freezing resistance to CBMs.In this work,salt freezing resistance improvement of CBMs incorporated with CLDH was experimentally evaluated by chloride binding capacity,mass loss rate,relative dynamic elastic modulus,setting time,compressive strength,and micro structure tests.Beside these,the salt freezing damage model was established to effectively express the quantitative relationship between influencing factors and evaluation indexes of the salt freezing resistance of CBMs.Results show that CLDH can reconstruct its original layered structure to form reconstructed layered double hydroxide(RLDH).RLDH combines with chloride ions to form RLDH-Cl recrystallization,which can improve chloride binding capacity and pore structures of CBMs to relieve the salt freezing damage.The salt freezing damage model indicates that the suitable CLDH content can evidently alleviate the salt freezing damage,which facilitates the quantitative analysis of the effect of CLDH on the salt freezing resistance of CBMs.

Co金属有机骨架模板制备NiCo水滑石/泡沫镍复合材料及电容性能

通过两步法先在泡沫镍(nickel foam,NF)上原位生长Co金属有机骨架(Co metal-organic framework,Co-MOF)纳米片阵列,再浸入不同浓度Ni^(2+)离子溶液刻蚀Co-MOF纳米片,在NF表面得到NiCo水滑石(NiCo layered double hydroxide,NiCo-LDH)。NiCo-LDH/NF继承了Co-MOF纳米片结构形成一级纳米片阵列,并在一级纳米片表面形成次级纳米片褶皱。在2 mmol Ni(NO_(3))2·6H_(2)O溶液中刻蚀得到的NiCo-LDH/NF表现出高容量、高倍率性能,在电流密度为5 mA·cm^(-2)时比电容为7 764.5 mF·cm^(-2),电流密度为20 mA·cm^(-2)时比电容为6 098.2 mF·cm^(-2),容量保持率为78.5%,在20 A·g^(-1)电流密度下经过5 000次长循环后,容量保持率为85.9%。与活性炭组装的混合电容器达到38.9 Wh·kg^(-1)的最大能量密度和8 000.0 W·kg^(-1)的最大功率密度。

Zn-Mg-Al LDO的制备及其除氟性能研究

半导体、电镀、冶金和陶瓷行业排放高浓度含氟废水,因此天然水中的氟化物污染已成为一个全球性问题,而Zn-Mg-Al LDO是很好的吸附材料。在n(Zn^(2+))/n(Mg^(2+))/n(Al^(3+))、反应温度不同的条件下,采用共沉淀法合成Zn-Mg-Al LDH,并将Zn-Mg-Al LDH在不同温度下焙烧制得Zn-Mg-Al LDO;利用X射线衍射(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)、BET比表面积测试法等方法,探究了Zn-Mg-Al LDO的结构和性质;对50 mL质量浓度为20.0 mg/L的NaF溶液进行吸附实验,考察了Zn-Mg-Al LDO吸附去除氟离子的性能。结果表明,在n(Zn^(2+))/n(Mg^(2+))/n(Al^(3+))=2∶1∶1、反应温度为75℃、焙烧温度为400℃的条件下制备的Zn-MgAl LDO吸附去除氟离子的性能最好,氟离子的吸附去除率达到85.39%;Zn-Mg-Al LDO具有水滑石特征峰,晶型良好,呈层状结构;Zn-Mg-Al LDO为介孔材料,其比表面积为103.15 m2/g。此外,还研究了吸附过程的动力学和吸附机理。结果表明,吸附过程符合Langmuir吸附等温线和准二级动力学方程。

基于亚硝酸根插层LDHs的高效水泥降铬剂研究

基于层状双氢氧化物(LDHs)结构可重建性,制备亚硝酸根插层的LDHs。将亚硝酸根插层的LDHs作为新型降铬外加剂掺入水泥,研究LDHs降铬效率、耐存储性和球磨温度处理条件下的稳定性,并揭示其还原和固化水泥中可溶性Cr^(6+)的作用机理。结果表明,与水拌和后LDHs-NO_(2)层间释放的亚硝酸根离子能够快速还原水泥中的Cr^(6+),有效降低可溶性Cr^(6+)含量。掺入0.2%(质量分数)LDHs-NO_(2)可使水泥中可溶性Cr^(6+)含量从40.26 mg/kg降至9.36 mg/kg,同时水泥3 d抗压强度增加约2 MPa。还原后的Cr^(3+)与层板中的Al^(3+)进行离子交换进入LDHs层板,从而实现稳定的化学固化。亚硝酸根插层LDHs的还原效率优于FeSO_(4)·7H_(2)O,并且在长时间储存和球磨温度处理条件下仍能保持优异的还原能力。

超级电容器用NiCo-LDH电极材料研究进展

镍钴层状双金属氢氧化物(NiCo-LDH)具有理论比电容大、成本低等优势,作为超级电容器电极材料得到广泛研究,但导电性能和电化学性能较差,限制了实际应用。简要介绍NiCo-LDH电极材料的储能原理、电化学性能影响因素(如比表面积、孔径和导电性等)和制备方法,其中包括水热法(溶剂热法)、微波法、电化学沉积法、化学共沉淀法和牺牲模板法等。重点介绍NiCo-LDH电极材料的改性研究(如改变形貌、制备复合材料等),并对研究方向进行展望。

水滑石类化合物在水处理和气体净化领域中的应用

水滑石类化合物(Layered double hydroxides,LDHs)是一种阴离子型层状纳米材料,具有良好结构稳定性、离子交换性、记忆效应及酸碱双功能等特性,作为吸附剂和催化材料广泛应用于环境治理领域。向单一LDHs晶体结构中引入客体分子以制备多功能杂化材料,不仅拓宽了晶体元素组成范畴,还可以提升晶体结构性能甚至引入新的功能,从而有效扩大其应用领域。基于此,本文首先综述了LDHs的基本结构性能特点,以及两种典型生长机理。另外,还简要介绍了水滑石类杂化材料的结构性能特点。最后,根据国内外研究现状,介绍了LDHs及其杂化材料在染料/持久性有机物降解、污水除磷、重金属吸附等水处理以及酸性气体净化等领域的应用。

水滑石及其衍生物处理水中污染物的研究进展

水滑石(LDH)由于具有记忆效应、内部结构可调性、层间阴离子可交换性等优良性质,而在水处理领域具有广阔应用前景。综述了水滑石及其衍生物处理水中污染物的最新研究进展。介绍了LDH处理重金属废水和有机废水,利用催化氧化性能或通过与不同材料复合处理废水。此外,还简述了LDH的规模化生产现状及存在问题,对LDH材料在水处理领域的未来发展方向进行了展望。

类水滑石/蒙脱土复合材料的研究进展

类水滑石(LDHs)和蒙脱土(MMT)都属于二维层状黏土,通过将LDHs与MMT复合可得到不同结构的LDHs/MMT复合材料,如板对板交替结构、花状结构及板层混合交替结构,已应用于吸附、催化、荧光、油水分离领域。介绍了LDHs/MMT复合材料的制备方法,对其在各领域的研究进展进行了综述,最后对其发展前景进行了展望。

用于电解水制氢的镍铁层状双氢氧化物改性研究进展

镍铁层状双氢氧化物(NiFe-LDH)具有独特的化学组成和结构特性,因其价格低廉,比表面积大、层状结构可控,而且表现出较为突出的催化析氧活性,被认为是有开发潜质的非贵金属析氧催化剂。但NiFe-LDH存在电导率低、表面活性位点不足等问题,限制了电子转移效率,影响了析氧反应的进行,目前还无法满足电解水制氢的实用性要求。因此,对NiFe-LDH在合成方法改进和本征活性改进2个方面进行综述,为深入探索NiFe-LDH的合成及应用提供思路,并对NiFe-LDH在电解水析氧反应中的应用发展进行展望。