锌铝水滑石微米球的合成及吸附性能研究

采用多步法合成锌铝复合氧化物（LDO）与锌铝水滑石（LDHs）,通过XRD、SEM、TEM、N2吸附等对合成的试样进行了表征;研究了甲基橙（MO）在LDO及LDHs上的吸附性能,考察了pH值和温度对吸附性能的影响,并结合红外光谱和XRD对吸附机理进行探讨.结果表明：所制备的LDO和LDHs呈空心球状,直径为3～5 μm,分散性较好,LDO比表面积高达210.2 m2/g;LDO对甲基橙具有优异的吸附性能,在25℃,初始pH=3的条件下,0.2 g/L LDO对100 mg/L甲基橙的吸附容量和去除率分别达497 mg/g和99.4％,其吸附等温线和吸附动力学分别符合Langmuir方程和准二级速率方程.     

Differently aged gallium-containing layered double hydroxides

Ni–Ga layered double hydroxides with the hydrotalcite-like structure have been prepared by coprecipitation of the metal cations with NaOH or by urea hydrolysis; the use of different aging treatments, under air, reflux and or microwave radiation, permits to modify their chemical composition and textural properties. Slight variations of the different parameters in the aging treatments, namely, pressure (atmospheric or autogenous), heating conditions (conventional or microwave) and time, have been tested to develop a suitable method to obtain solids with tailored characteristics. Original and calcined solids have been fully characterized by means of PXRD, FT-IR, TG–DTA, S_BET and particle size distribution measurements. After calcination, well-dispersed oxides with a high specific surface area have been obtained.     

Dendrimer intercalation in layered double hydroxides

New organic/inorganic (O/I) hybrid assemblies based on Layered Double Hydroxide (LDH) with polyamide amine dendrimer (PAMAM, generation −0.5 and generation +0.5) were prepared by two different routes using either the direct coprecipitation at constant pH or the anion exchange procedure in double surfactant S⁺S⁻ phases. The obtained materials were characterized by means of powder X-ray diffraction, thermal gravimetric analysis associated with mass spectrometry, and Fourier-transform infrared spectroscopy. X-ray powder diffraction pattern of the O/I LDH assembly exhibit characteristic profiles of LDH-based materials with basal spacing depending on the nature of the dendrimer. Indeed, for both synthetic procedures, interleaved PAMAM −0.5 gives rise to an interlayer space in agreement with a perpendicular molecular arrangement against the layer of the host structure. For PAMAM+0.5, considering its spherical dimension, a much smaller basal spacing was observed. This observation was interpreted as shrinkage of the molecule to accommodate the interlayer LDH gap, which was rendered possible by the bond angle twisting within PAMAM−0.5. FTIR spectra confirm the presence of both moieties inside both Zn₂Al/PAMAM G−0.5 and Zn₂Al/PAMAM G+0.5 assemblies. Finally, thermal analysis associated with mass spectrometry confirm this composition, and in situ temperature XRD data reveal that the highly constrained arrangement for the generation +0.5 is not accompanied by a gain in thermal structural stability; in fact, the assembly prepared from PAMAM −0.5 is more stable. Both O/I PAMAM LDH assemblies constitute well-defined materials which are candidate for catalytic applications.     

Adsorption mechanism of humic and fulvic acid onto Mg/Al layered double hydroxides

The adsorption of humic and fulvic acids onto nitrate, chloride and carbonate intercalated layered double hydroxides with Mg/Al ratios ranging from 85/15 to 60/40 was studied by adsorption isotherms at different ionic strengths and the characterization of the preferentially adsorbed humic substance size fractions. The adsorption of humic and fulvic acids onto LDHs occurred by ion exchange with both the intercalated and surface anions of the LDH and ligand exchange reactions with surface groups. The contribution of both mechanisms to the total HA and FA adsorption was estimated. Lower molecular weight humic and fulvic acids were preferentially adsorbed because these fractions can more easily enter the mesoporous LDHs and contain more carboxylic groups, which are known to be involved in ligand exchange reactions with e.g. surface Al-OH groups. Intercalation of the entire HA or FA molecules in-between the LDH sheets is unlikely to occur.     

Sn-containing layered double hydroxides as precursors for nano-sized ZnO/SnO2 photocatalysts

Sn⁴⁺-containing LDH was prepared using the co-precipitation method at constant pH, and characterized using X-ray diffraction, UV–vis diffuse reflectance spectroscopy and TG/DTG methods. The obtained product was further exposed to different thermal treatments in order to obtain nano-sized coupled ZnO/SnO₂ systems with enhanced photocatalytic performances than the ones obtained by mixing the two semiconductor oxides. The formation of a well-defined ZnO/SnO₂ system and the crystallite size, fully investigated using XRD, micro-Raman scattering and UV–vis DR techniques, were found to be influenced by the nature of the precursors and the calcination temperature. The photocatalytic activity of the ZnO/SnO₂ systems, evaluated for the photodegradation of methyl orange (MO) dye, was studied as a function of the initial pH, catalyst loading and the calcination temperature. The metal dispersion supplied by layered structures proved to be an advantage when preparing coupled ZnO/SnO₂ systems, the photocatalytic activity being 2.3 times higher comparing with the physical mixtures performances. The maximum photocatalytic activity of the coupled ZnO/SnO₂ system having a layered precursor was observed when using neutral pH, at a catalyst loading of 1 g/L calcined at 600 °C for 4 h.     

Alkoxylation reaction catalysed by layered double hydroxides

Layered double hydroxides (LDHs) are extensively studied as precursors for catalysts, following a calcination at high temperatures to yield mixed oxides. However, these materials are less used as layered materials, i.e., without undergoing thermal activation. We have focused in this work on the use of a series of as-synthesised LDHs for the catalytic preparation of glycol ethers, which is a reaction of primary commercial importance. Two main systems are considered, namely the [Cu–Cr] and [Mg–Al] LDHs. The [Cu–Cr–Cl] LDH is obtained by the coprecipitation method, then through the appropriate chimie douce exchange reactions the original chloride anions are replaced by a variety of oxo- and polyoxometallates, (CrO₄)²⁻, (Cr₂O₇)²⁻, (V₂O₇)²⁻, (V₁₀O₂₈)⁶⁻ and (Mo₇O₂₄)⁶⁻. On the other hand, the [Mg–Al] hydrotalcites, intercalated by (V₂O₇)²⁻, (V₁₀O₂₈)⁶⁻ and [Fe^III(CN)₆]³⁻ anions, are obtained by structure regeneration. This was done by rehydration of a commercial calcined material (Kyowa) in aqueous solutions containing the desired anion. The different materials have been fully characterised by conventional analytical techniques to evidence their lamellar properties and chemical nature. They were then tested in the catalytic reaction involving butan-1-ol and one or more units of ethylene oxide to make butyl-monoglycol ether (BMGE), di-glycol ether (BDGE), tri-glycol ether (BTGE), etc. The reactions were carried out between 80 and 120°C, temperature range in which no collapse of the lamellar structure is normally observed. In this paper it is shown that decavanadate exchanged LDHs proved to be very selective catalysts for the preparation of the monoglycol adduct, some samples achieving up to 100% selectivity in the screening tests.     

水滑石纳米材料特性及其在电化学生物传感器方面的应用

阐述了水滑石纳米材料结构和性能之间的关系及近年来水滑石纳米材料在电化学生物传感器方面应用的最新进展。重点介绍了水滑石纳米材料在吸附生物酶制备电化学传感器、水滑石纳米片固定生物酶制备电化学传感器、水滑石纳米片固定其它活性组分制备电化学传感器、水滑石自构筑电化学传感器等方面的应用。着重对水滑石纳米材料制备电化学传感器的机理和制备方法进行了系统概述。提出了水滑石纳米材料构筑电化学生物传感器应用研究的发展趋势：对水滑石纳米材料进行多层、多组分、微型化和阵列化等多样化设计,指出高选择性和高灵敏度检测是未来新型电化学生物传感器应用研究的主要发展方向。     

Electrocatalysis of gold nanoparticles/layered double hydroxides nanocomposites toward methanol electro-oxidation in alkaline medium

A nanocomposite based on layered double hydroxides (LDHs) and gold nanoparticles (AuNPs) was prepared via hydrothermal treatment followed by a reduction procedure. The AuNPs were obtained in Mg-Al LDHs, and they maintained good stability. The electrocatalytic activities of AuNPs/LDH-modified glassy carbon electrodes for methanol oxidation in alkaline medium were investigated in detail. Under the same conditions, the modified electrode exhibited higher electrocatalytic activity than both the pure AuNPs-modified electrode and LDH-modified electrode. The role of the AuNPs and LDHs in this composite system was explored by cyclic voltammetry and chronoamperometry, respectively. Further studies demonstrated that the promoting effect of LDHs could be due to its strong adsorption and partly to the discharge of OH⁻ during methanol oxidation. This work indicates that LDHs is expected to be a good supporting material in the development of methanol anode catalysts.     

Size control and optimisation of intercalated layered double hydroxides

Two types of organo-layered double hydroxides (LDH), with adipate or dodecyl sulfate in the interlayer space, have been prepared by the coprecipitation. In order to improve the homogeneity and to obtain well crystallised solids, the samples were submitted to microwave (MW) irradiation. Hydrotalcite (HT)-like compounds were obtained in all cases. The TEM and particle size distribution point out that even short irradiation times led to homogeneous and well defined solids with small particle size.     

硝酸根型镁铁水滑石的合成及其离子交换性能研究

采用共沉淀法合成出了层间阴离子为NO-3的镁铁水滑石(MgFe-NO3-LDHs),当滴料终点pH值为9.5,反应温度为100℃,反应时间为4h时,可得到晶体结构规整的层状结构产物。通过离子交换将有机阴离子CH2CHC6H4SO-3和CH3(CH2)11SO-3引入层间,形成以双分子层垂直于层板的交错有序的排布结构模式。     

镁铝钡三元水滑石的制备及吸附性能研究

以Al(NO3)3·9H2O、Mg(NO3)2·6H2O、Ba(NO3)2为原料,用共沉淀法制备了Mg/Al/Ba三元水滑石(Mg/Al/Ba-LDHs),经过傅里叶红外光谱仪和比表面及孔径分析仪进行表征。考察了该水滑石对重金属铬离子(Ⅲ)的吸附行为及干扰离子,优化了浓度、时间、温度、酸度(pH)等因素对Mg/Al/Ba-LDHs吸附性能的影响。结果表明,在最佳浓度13mg/mL、时间150 min、温度30℃、pH=6时吸附容量最大达到400mg/g。     

水滑石材料用于催化脱氢的研究进展

催化脱氢反应广泛应用于化工生产和制氢工艺领域,因此,开发高效且适应苛刻反应条件的脱氢催化剂十分关键.水滑石材料(LDHs)由于具有特殊二维层状结构、金属阳离子的灵活可调性以及插层阴离子的易交换性等特点,可为催化脱氢的应用开展许多智能化设计策略.首先,介绍了LDHs的催化用途及其作用机制,主要介绍了LDHs及其插层材料作...     

A new method for preparation of nanoplates of Zn-Al layered double hydroxides

Methods for preparation of nanoplates of layered double hydroxides (LDHs) have been intensively investigated for the purpose of making nanocomposites. The present study provides a new simple method of nanoplate preparation for Zn-Al LDHs. Zn-Al LDHs containing lactate or combinations of lactate and simple inorganic anions were synthesized by a coprecipitation method, and water-washed and undried LDHs were dispersed in water. Among them, suspensions of Zn-Al LDHs containing both lactate and bicarbonate were unique in that they rapidly became translucent colloidal dispersions when the molar ratio of added bicarbonate to added Al was ≤ 0.5. The resulting LDH nanoplates in the dispersions were delaminated single layers or nanoplates with a thickness of several layers, depending on the amount of bicarbonate.     

Cation ordering and superstructures in natural layered double hydroxides

Layered double hydroxides (LDHs) constitute an important group of materials with many applications ranging from catalysis and absorption to carriers for drug delivery, DNA intercalation and carbon dioxide sequestration. The structures of LDHs are based upon double brucite-like hydroxide layers [M(2+)(n)M(3+)(m)(OH)(2(m+n)](m+), where M(2+) = Mg(2+), Fe(2+), Mn(2+), Zn(2+), etc.; M(3+) = Al(3+), Fe(3+), Cr(3+), Mn(3+), etc. Structural features of LDHs such as cation ordering, charge distribution and polytypism have an immediate influence upon their properties. However, all the structural studies on synthetic LDHs deal with powder samples that prevent elucidation of such fine details of structure architecture as formation of superstructures due to cation ordering. In contrast to synthetic materials, natural LDHs are known to form single crystals accessible to single-crystal X-ray diffraction analysis, which provides a unique possibility to investigate 3D cation ordering in LDHs that results in formation of complex superstructures, where 2D cation order is combined with a specific order of layer stacking (polytypism). Therefore LDH minerals provide an indispensable source of structural information for modeling of structures and processes happening in LDHs at the molecular and nanoscale levels.     

Stretchable single-walled carbon nanotube double helices derived from molybdenum-containing layered double hydroxides

Single-walled carbon nanotube (SWCNT) double helices were fabricated with directly synthesized FeMoMgAl layered double hydroxide flakes as the catalyst precursor. The as-obtained SWCNT double helices were closely packed, while the screw pitches of the double helices were tunable from 2 to 10 μm. Straight millimeter-length SWCNT yarns can be obtained by further stretching the SWCNT double helices.     

Adsorption of phosphate by layered double hydroxides in aqueous solutions

Adsorption of phosphate by various calcined layered double hydroxides (LDHs) such as Mg–Al, Zn–Al, Ni–Al, Co–Al, Mg–Fe, Zn–Fe, Ni–Fe and Co–Fe was investigated. LDHs were found to have high anion exchange capacity that enhances their capability to remove anionic contaminants from aqueous system. The nature and content of di- and trivalent cations in LDH have strong influence on the adsorption process. Calcined Mg–Al LDH (CLDH) with Mg–Al molar ratio of 2.0 showed higher adsorption capacity compared to other calcined LDHs as it possessed higher Al³⁺ content. Results indicate that the adsorption isotherm could be fitted to a linearised form of Langmuir and Freundlich equations. The adsorption phenomenon has been well supported by XRD study. The adsorption process was spontaneous and exothermic in nature and followed first order kinetics. Competitive anions were found to have detrimental effect on the percentage of adsorption.     

One-pot green hydrothermal synthesis of stearate-intercalated MgAl layered double hydroxides

A convenient one-pot green hydrothermal synthesis method has been developed to obtain stearate-intercalated layered double hydroxide (LDH-St), an important nanofiller for polymer/LDH nanocomposites. Various factors of the hydrothermal synthesis conditions, including reaction time, temperature and solid content, were taken into account. The resulting products were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), inductively coupled plasma (ICP) atomic emission spectrophotometry, CHN elemental analysis, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The increase of reaction time or solid content is helpful to the formation of LDH-St, whereas high reaction temperature had little effect. Deduced from PXRD and the composition analysis results, prolonging of reaction time led to a packing arrangement transformation from a bilayer-like structure with stearate acids co-intercalated to monolayer for the intercalated stearate anions in the interlayer space. In addition the prepared LDH-St crystallites showed flower-like aggregates with a diameter of about 8–10 μm consisting of sheets with irregular shape.     

酒石酸根阴离子柱撑Mg-Al-LDHs水滑石的合成

采用共沉淀法制备纳米Mg-Al-LDHs水滑石,并以纳米Mg-Al水滑石为前体,采用返混沉淀法进行插层组装,合成酒石酸根阴离子柱撑水滑石。采用红外光谱、X射线衍射对样品进行了表征。结果表明,酒石酸根阴离子可以插入纳米Mg-Al水滑石层间,完全取代CO32-,形成具有超分子结构的稳定酸根阴离子柱撑水滑石,其尺寸达到纳米级。     

层状双氢氧化物的可控合成及功能化研究进展

层状双氢氧化物（LDHs）作为一种低成本、表面带正电荷、结构与组成高度可调变并能进行插层反应的二维无机材料备受关注。目前合成出分散性良好、粒径分布范围窄以及可调结构和组成的LDHs具有一定挑战性,再加上为了满足不同应用的实际需求,需要将其他功能组分与含有复杂结构（化学修饰）的LDHs进行组装形成功能化LDHs材料,这对其结构设计和制备方法的策略提出了新的挑战。因此,本文将目光聚焦在LDHs的可控合成、表面化学修饰、功能化复合材料方面的研究上,归类总结了研究者们在设计制备功能化LDHs方面所做的贡献,分析了功能化LDHs复合材料在不同领域应用的特点和作用,提出进行创新结构设计和合成方案简易化将是今后构建功能化LDHs复合材料的研究重点。     

Heteropoly blue-intercalated layered double hydroxides for cationic dye removal from aqueous media

Heteropoly blue-intercalated layered double hydroxide (HB-LDH) was obtained by aqueous ion exchange of a Zn–Al LDH precursor in nitrate form with the reduced polyoxometalate anions [PW₁₀Mo₂O₄₀]^5?. The physicochemical properties of the product were characterized by the methods of powder X-ray diffraction, infrared spectroscopy, and cyclic voltammetry. The HB-LDH has been used for the removal of cationic dye methylene blue (MB) from aqueous solutions via adsorption. The intercalation of large cluster anion [PW₁₀Mo₂O₄₀]^5? into LDH could induce the adsorption to cationic dye of MB, obviously. The HB-LDH shows much higher cationic dye adsorption capacity than pure LDH and the maximum adsorption capacity Q_max of MB onto ZnAl–PW₁₀Mo₂ is 30.87 mg/g.