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ISSN 1996-1944 www.mdpi.com/journal/materials Review
Morphologies, Preparations and Applications of Layered Double Hydroxide Micro-/Nanostructures
Ye Kuang 1, Lina Zhao 1, Shuai Zhang 2, Fazhi Zhang 1, Mingdong Dong 2,* and Sailong Xu 1,*
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, 15 Beisanhuan East Road, Chaoyang District, Beijing, 100029, China Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, DK-8000 Aarhus C, Denmark
* Author to whom correspondence should be addressed; E-Mails: email@example.com (S.X.); firstname.lastname@example.org (M.D.). Received: 28 October 2010; in revised form: 29 November 2010 / Accepted: 3 December 2010 / Published: 9 December 2010
Abstract: Layered double hydroxides (LDHs), also well-known as hydrotalcite-like layered clays, have been widely investigated in the fields of catalysts and catalyst support, anion exchanger, electrical and optical functional materials, flame retardants and nanoadditives. This feature article focuses on the progress in micro-/nanostructured LDHs in terms of morphology, and also on the preparations, applications, and perspectives of the LDHs with different morphologies. Keywords: layered double hydroxides; morphology; preparation; application
1. Introduction Nanostructured materials have generated diverse scientific and technological interest in many potential areas of applications such as energy conversion, electronics, catalysis, optics, chemical sensing, and medicine. As one type of layered material, such as anionic clays (e.g., layered double hydroxides) and cationic clays (e.g., montmorillonite), layered double hydroxides (LDHs) [1-4] are a class of anionic clays with the structure based on brucite (Mg(OH)2)-like layers in which some of the divalent cations have been replaced by trivalent cations yielding positively charged sheets. LDHs can be represented by the general formula [MII1–xMIIIx(OH)2]x+(An–)x/n· 2O, where MII and MIII cations yH
The obtained LDH platelets had the dimensional sizes ranging from 50 to 300 nm.Materials 2010.  also prepared colloidal MgAl-LDH by a fast coprecipitation followed by controlled hydrothermal treatment (Figure 2). In addition. acid residue scavengers. Important advances in LDH morphology have been made in the past years. typically show preferential growth of ab faces (i.e. nanosized LDH platelets can be synthesized in a large-amount production using a method involving separate nucleation and aging steps (SNAS) [32-34]. Fe3+. this suggests the preferential growth of ab faces (i.12]. we focus on the applications of LDHs and offer some perspectives for future multifunctional LDH materials. LDHs are widely used in commercial products as adsorbents. may be varied over a wide range. the key features of which are a very rapid mixing and nucleation process in a modified colloid mill followed by a separate aging process. To control the growth environment of LDH. 2. Gursky et al. including transition metal such as Ni2+. perpendicular to the stacking direction).e.. In this feature article. fibrous structure . and Gd3+. and NiAl-LDH.1. Powdery LDHs Powdery LDHs typically show the brucite (Mg(OH)2)-like layered structure via a conventional co-precipitation process. The microsized platelets can be fairly well prepared into nanosized crystals. The approach was extended to prepare Al3+-based LDHs. ZnAl-. Xu et al. The platelets are often observed to aggregate . [28-31] prepared very small LDH particles in isooctane-sodium dodecyl sulfate/aqueous solution and also obtained LDH monolayer with a thickness of 14 Å. thus leading to limitations in their technical applicability. flame retardants and polymer stabilizers. In addition. 3 5221 occupy octahedral holes in a brucite-like layer and An− anion is located in the hydrated interlayer galleries. to 2-D films. LDH powders are spontaneously ready to aggregate during storage and application. O’Hare et al. The approach was also extended to prepare other types of LDHs. ranging from LDH powders [11. such as by using microemulsion. LDH powders. such as CoAl-.. spheres [13-18]. one-dimensional (1-D) belt/fiber. The identities of the divalent and trivalent cations (MII and MIII. The major advantages of this method for the preparation of LDHs can be summarized as follows: (1) the synthesis process is simple to carry out. Therefore. anion exchangers. to LDH films on substrates [21-27]. it is of great interest and importance to generate alternative predefined structures. prepared by conventional coprecipitation. When synthesized by a hydrothermal approach induced by slow hydrolysis of urea. nanosized LDH belt .  obtained nanosized colloidal MgAl-LDH particles through coprecipitation from metal salts dissolved in methanol in the presence of NaOH. together with the value of the stoichiometric coefficient (x). (2) small crystallite sizes can be obtained. (3) the crystallite size . giving rise to a large class of isostructural materials. catalyst support precursors. perpendicular to the stacking direction) and microscale hexagonal platelet morphology . we summarize the progress in fabrication of LDH structure materials with different morphologies from powder/sphere. Due to the highly active surface atoms. Considered generally as promising materials [5-9] in view of their high chemical versatility associated with a tunable anionic exchange capacity. Fe2+. the resulting MgAl-LDH usually exhibits hexagonal platelet morphology at the micro scale (Figure 1). respectively) and the interlayer anion (An–). LDH Morphology 2.
Spherical LDHs Spherical structure is of interest for a number of different applications. Reprinted with permission from . 2005. One main synthesis route—template-directed synthesis—has been performed to prepare spherical LDH structure. The soft templates. even in an organic/water solvent system for preparation of CaAl-LDH nanoplatelets without byproduct of calcium carbonate.Materials 2010. (b) Scanning electron microscope (SEM) image of typical LDH crystals. (a) Schematic illustration of the layered double hydroxide (LDH) structure showing the metal hydroxide octahedra stacked along the crystallographic c axis (indicated as a red arrow). lithium-ion battery electrodes.2. which could be attributed to the ability of organic media (such as ethanol) to prevent carbon dioxides from entering the reaction solution . for example spherical vesicle . The green parts correspond to MII cations and the red dots to MIII cations. With regard to types of LDHs. numerous nanosized LDH building blocks were prepared. sorbents. general LDHs are able to be prepared. Using this method. involving either soft templates or hard templates. Water (grey) and anions (pink) are present in the interlayer region. 3 5222 distribution of the product is much narrower than that obtained using conventional coprecipitation methods. Dispersion of an LDH aggregate (A) into several smaller LDH aggregates (B) via an aging process. © American Chemical Society. and carriers for cellular drug and gene delivery. 2. or (C) both (A and B) into individual LDH nanosheet crystallites via the new hydrothermal treatment method. such as catalysts. such as Al 3+-based and transmission metal cation-based LDHs. Figure 1. Figure 2.
3 5223 formed by sodium dodecanesulfonate (SDS). by urea hydrolysis under high-temperature hydrothermal treatment of 150 ° .3. Synthesis of the magnetic Fe3O4 core/LDH shell composite structure. the hard template could have advantages in facile preparation of size-controllable hollow spheres due to the rich functional groups on the surface. Zhang et al. a three-dimension open macroporous (3DOM) LDH framework was prepared during a process of coprecipitation [39. giving the LDH shell walls. note that with the aid of the template of 3-D close-packed PS array. and therefore it is still a challenge to engineer microsized LDH platelet into 1-D structures. and then deposited or assembled as building block on the surface of PS latex . ZnAl-LDH. using hard cores such as polystyrene (PS) beads as templates.40]. were used to synthesize micrometer-sized rosette-like solid LDH spherical aggregates with SDS anions intercalated already in the LDH galleries. involves formation of the LDH hollow sphere with nanoshell face-on orientation. Furthermore. In such a method. 1-D LDHs Nanostructures LDHs are well-known to show preferential growth perpendicular to the stacking direction. Coral-like MgAl-LDH solid C microsphere was also synthesized using ethylene glycol/methanol/dodecyl sulfate nonaqueous polar solvent/surfactant system . Compared with the soft template approach. Zhao et al. and silica  (Figure 3). and MgAl-LDH) in formamide [35-38]. 2. carbon . synthesized MgAl-LDHs with a high aspect ratio via calcination and rehydrolysis under hydrothermal conditions . or by obtaining LDH nanosheets via delamination of Al3+-based types of LDHs (such as CoAl-. such as nanobelt and fibrous structure. 2009.43]. O’Hare’ group obtained MgAl-LDH belt structure in a water-in-oil reverse . The hard template method. In few previous studies [41-43].Materials 2010. 1-D LDH structures were obtained through the control of nucleation and growth of LDH crystal. Interestingly. positively charged colloidal LDH nanoplatelets were necessarily prepared. © Wiley-VCH. Reprinted with permission from . prepared MgAl-LDH nanowires and nanorods via hydrothermal treatment at a high temperature and ZnCoFe-LDH nanowires with controllable morphology in a water-in-oil microemulsion [42. The necessity of preparing positively charged LDH was achieved either by synthesizing LDH nanoparticles using a protocol involving a fast coprecipitation followed by controlled hydrothermal treatment . This type of rigid platelet is not similar to a graphene sheet which is able to be rolled into a tube. Figure 3.
a HRTEM image of this structure is shown in the inset. Lima et al. (B) TEM image of one belt reveals the lamellar structure. 3 5224 microemulsion system (Figure 4) . . Al)-O) recover the layered structure typical of hydrotalcites in the presence of SDS solutions.Materials 2010. Figure 4. since the weak liquid confinements are easily deformed and coalesced during synthesis. Comparison of all the 1-D LDH structures in the above studies shows the dependence of the formation on relatively restricted conditions necessary to form vesicles. The local disturbance in the layered structure was thereby proposed as an evolution from platelet-like to fibrous pipe. (A) SEM image of a belt-like LDH structure with the parallel linear pattern highlighted in the white rectangle. The reverse system involved was considered to offer two important water pools in the confined nucleation and growth: small spheroidal microemulsion spontaneously formed by SDS act as microreactors for the nucleation and crystallization of LDHs. micelles. The possible mechanism is that mixed oxides ((Mg. Reprinted with permission from . and (C) spectrum of the chemical compositions analyzed by energy dispersive X-ray (EDX). (F) The corresponding selective area electron diffraction pattern. and then the most external layers in a particle of LDH fold to give rise to a mesostructured material by the formation of small amounts of Al-OH-Al groups (Figure 5). and large branching reservoirs contributing to confine LDH growth that is distinctly different from the traditional coprecipitation with a preferred orientation along the c axis . The belts were easily exfoliated to give structures shown by the SEM image in (D) and TEM image in (E). or reverse emulsions. 2005. Recently. © American Chemical Society. fabricated fibular LDH via folding of LDH layers by the aid of SDS surfactant .
electrochemical deposition [51-53]. Parallel-Oriented LDH Films Parallel-oriented LDH films usually consist of face-on oriented building blocks of platelet-like LDHs. Using colloid deposition. Iyi et al. Itaya et al. prepared the monolayer [47. Layer-by-layer (LbL) technique [35-38]. and in-situ growth . ethanol. such as solvent evaporation [44-50]. and transparent hybrid layer  on substrates—all were assembled from LDH nanoplatelets. 2. 2008. By the aid of this method. The face-on orientation of the building blocks of LDH platelets are achieved through various methods. Previous studies have shown the fabrications of LDH films with microsized LDH platelets oriented perpendicularly or horizontally to the underlying metal or surface-modified substrates [21-26.4.and m NiAl-LDH films by solvent evaporation of LDH powder obtained by the SNAS method .1. 2-D LDH Films LDH films have increasingly attracted attention due to advantages in the context of immobilization of LDH structures.Materials 2010. Similarly. prepared water-swellable MgAl-LDH film by solvent evaporation on polyethylene (PE) substrate and obtained self-supported film of thickness in the range from 10 to 25 µ . the multilayer  (Figure 6). ZnAl-LDH. CoAl-LDH. Spin coating is another effective approach for fabrication of inorganic ﬁlms with controlled structure and crystal orientation. spin-coating technique .44-62]. With regards to orientation. 5225 2. 2-D LDH films can be classified into two main types: perpendicular and parallel oriented.4. Reprinted with permission from . Lee et al. Zhang et al. One advantage of fabrication of well-oriented or self-supporting LDH ﬁlms is to avoid spontaneous aggregation of LDH powders. Langmuir-Blodgett (LB) technique . © American Chemical Society. 3 Figure 5. Wang et al. and water) and assembled with the solvent evaporation. prepared film of 100 nm thickness on a SnO2 electrode . reported that MgAl-LDH films was readily . Possible mechanism for the folding of layers of LDH to give fibrous hydrotalcites.48]. Solvent evaporation and colloid deposition technique are the direct ways to prepare LDH films. LDH platelets or exfoliated LDH nanosheets are evenly dispersed in solvent (such as methanol. fabricated transparent ZnAl. Electrochemical deposition technique is also used to prepare LDH films due to the positive charge of LDH colloid. and NiAl-LDH films were prepared on different electrode surfaces [51-53].
3 5226 prepared by spin coating nanodispersed MgAl-LDH solution on a magnesium-containing alloy substrate . to which Sasaki and co-workers have made a pioneer contribution. Reprinted with permission from . 3 L (b). 4 L (g) and 5 L (h) samples. © American Chemical Society. In addition. SEM images of the monolayer of LbL LDH nanocrystals: 1 layer (L) (a). 2 L (e). Figure 6. or via hydrogen bonding . © American Chemical Society. Compared with the above methods. Figure 7. Reprinted with permission from . 2006. and 5 L MgAl-LDH/Si (c). Through assembly of positively charged LDH building blocks and negatively charged polyelectrolytes. LbL assembly is a commonly used approach to prepare LDH films. Schematic illustration of the possible delamination mechanism for LDHs in formamide. This approach is based on assembly of alternating deposition of oppositely charged building blocks either mainly via electrostatic interaction . such as CoAl-LDH/poly(sodium 4styrenesulfonate) [35.Materials 2010.37] (Figure 7) and MgAl-LDH/poly(p-phenylene) anionic derivate ultrathin films . Cross-sectional views of 1 L (d). LB technique was utilized to fabricate MgAl-LDH film using an anionic Ru(II) cyanide polypyridyl complex as template . a serials of LDH nanosheet/polyelectrolyte heterogeneous ultrathin films were successfully prepared [35-37]. 2007. 3 L (f). which were used as positively charged building block to prepare multilayer film of (LDH/PSS)n assembled on a quartz glass substrate.
using two substrates (Al and Zn or Cu foils) as trivalent and bivalent resources. reported the preparation of a ZnAl-LDH film on single Al substrate . as mentioned in Section 2. The hydrogen bonding between PVA and the hydroxyl groups of LDH crystallites orientation was proposed for the formation of the orientation. reported the edge-on oriented MgAl-LDH thin films with microscale thickness on the sulfonated PS flat substrates by urea hydrolysis reaction at 70–80 ° over more than eight days . . Using the approach. typically microsized LDH platelets. We have recently shown a parallel-oriented LDH structure with LDH c-axis perpendicular to the glass substrate upon surface modification of poly(vinyl alcohol) (PVA) . k ≠ 0) at high angle. were observed perpendicular to the underlying surfaces of the substrates. Perpendicular-Oriented LDH Films Perpendicular-oriented LDH films are usually composed of edge-on oriented LDH platelets. strong lines at low angles. with (Figure 8) or without the necessity of the pre-treatment of anodization to Al substrate [25. show the different results of the presence or absence of basal and higher order (00l) reflections at low angle. Such films were typically prepared using in situ growth based on a hydrothermal synthesis. presented the preparation of NiAl-LDH films by using single porous anodic alumina/aluminum (PAO/Al) foil as both substrate and sole source of aluminum . Lei et al. Typically. respectively. Zhao et al. the LDH nanosheets utilized were obtained via exploitation of Al3+-based type (such as CoAl.and CuAl-LDH films on the Al substrates . symmetric. cloth and sponge) through a combined procedure of sol-gel process and in situ growth method . Further investigation of growth C kinetics of LDH microcrystals supported the possibility of templating the formation of the edge-on orientated MgAl-LDH film . reported the fabrication of hierarchical ZnAl-. The X-Ray diffraction (XRD) pattern of the LDH film showed the absence of any non-basal reflections (h. Zhang et al. 3 5227 . which is mentioned in Section 2.2. NiAl-. Gao et al. which could deserve further research in the field of inorganic materials. Recently. Huang’s group fabricated ZnAl.26].2.4. In situ growth is also an effective method to fabricate parallel-oriented LDH films whose crystal is directly formed on the surface of the substrate. The XRD patterns involved.Materials 2010.4. and MgAl-LDH films on intriguing man-made supports (article. As an alternative. All the involved LDH structures observed by scanning electron microscope (SEM) in the above studies showed that the building blocks. 2. however. instead of basal (00l) reflections with a series of LDH peaks appearing as narrow. further demonstrated the possibilities of micro/nanostructured ZnAl-LDH film precursors. One feature of the approach lies in the strong adhesion between the LDHs and the substrates. This opened up the possibility of growing large-scale uniform LDH films directly from substrates.1 to fabricate parallel oriented LDH films. Chen et al. This could be attributed to the difference in orientations between vertically oriented and titled LDH platelets.and MgAl-LDH) in formamide. More interestingly.
ZnAl-LDH-La/Al. LbL. such . LDH film. and reported that the array of active Cu2+ centers on the surface of CuZnAl-CLDH is ordered net shaped. 5228 On the basis of the above-mentioned LDH micro-/nanostructures. LB. 3. The advantages of novel LDH films are able to overcome the problems of use of powdery catalysts on an industrial scale. hydrothermal LbL.Materials 2010. coprecipitation hydrothermal calcination and rehydrolysis. Application of LDHs The nanostructures involved often combine fascinating shapes with remarkable properties.1. SEM of the ZnAl-LDH-laurate hybrid film showing the hemispherical protrusions. which is influenced by the effect of ordered cross trap. and activated rehydrated LDH (RLDH) structures are well-known as effective solid catalysts. 43 19 20 44-59 21-26. electrochemical deposition spin-coating. together with the requirements of practical applications. Catalysts LDH powder. 60-62 39-40 SNAS. in-situ growth in-situ growth coprecipitation 1-D 3-D 3. used the Cu2+-based LDH powder as a catalyst for wet oxidation . various studies focus on the properties and applications of nanostructured LDHs. coprecipitation. 3 Figure 8. hydrothermal coprecipitation coprecipitation solvent evaporation. Dimension 0-D Morphology powder sphere high aspect ratio nanowire nanobelt nanotube parallel-oriented 2-D perpendicularoriented 3DOM Method References 28-34 15-18 41 42. With the introduction of new techniques and novel concepts for preparation of LDH structures. an overview of the morphologies in terms of dimension is given in Table 1. Table 1. Zhang et al. Overview of the LDH micro-/nanostructures with different dimensions and synthesis. The inset shows the image of contact angle of a water droplet on the surface of the ZnAl-LDH-laurate hybrid film.
Br–. being composed of positively charged layers [Ca2Al(OH)6]+. exhibited a greatly enhanced performance in respect to early compressive strength and early flexural strength. reported that the activated MgAl-LDH film was promising to be used as precursor to synthesize monolithic catalyst for the aldol condensation of acetone and other base catalyzed reactions . halogen-free alternatives are one active research area. Structured LDHs are one new type of promising material due to their ability to capture organic and inorganic anions which can be used in water treatment. demonstrated that the activated MgAl-LDH. Water Treatment Waste water often contains oxyanions such as F–.Materials 2010. We recently reported that the specimens containing pure CaAl-LDHs. and concluded that the rate constant for exchange of nitrate anions by halide decreases in the order of F– > Cl– > Br– > I–. thyroid. following pseudo-second order kinetic models. the edge-on LDH films prepared on man-made supports exhibited the enhanced performances of regeneration for water treatment and membrane separation in comparison with the corresponding powdery LDH . since LDH can afford mixed metal oxides and has a special property called memory effect. . The novel and well-dispersed nanocrystals of LDH on the paper substrate without aggregation was considered to provide large specific surface area as well as good accessibility. compared to the pristine concrete specimen . Calcined LDH powder is also an important type of material used in water treatment. 6-dimethylphenol with control of the corresponding coprecipitated LDH material . Powdery LDH is also commercially promising as an additive in flame retardants. Enhanced ability to remove oxyanions is of importance in environment protection. montmorillonite) have been widely investigated as additives in this context. The main advantages of LDHs over the conventional anionic exchange resins include their higher anion exchange capacity for certain oxyanions and their good thermal stability. PO43–. and naphthalene-2 sulfonic acid. 6-disulfonic acid. Currently. Furthermore. LDHs can be fully regenerated in a short time for reuse. Gé raud et al. therefore. used MgAl-NO3-LDH powder  and calcined powder  to remove F–. and I–. As described above in Section 2. AFm phase is generally believed nH to act as a crystal seed accelerating cement hydration. which were promising for future applications in cement and concrete science . 3. Many flame retardants are considered harmful. and neurological effects.2. and the values increased by 61% and 71%. which are harmful to both humans and wildlife. Lv et al. Basically.3. synthesized CaAl-LDHs intercalated with nitrobenzoic acid.g. Cl–. CaAl-LDH has a general formula very similar to the AFm phase occurring in hydrated cement. due to the high specific surface of the novel 3DOM structure. underlying the superior adsorption performances of the film sample . Lv et al.. Raki et al. naphthalene-2. 3. respectively. CaAl-LDHs have been. free of contamination by CaCO3. Br–. reproductive/developmental. For the interesting 3DOM LDH structure. and negatively charged interlayers [X−· 2O]−. with decatungstate anion intercalated exhibited the enhanced photocatalytic activity for the photodegradation of 2. proposed as potential concrete hardening accelerators. LDHs and cationic clays (e.4. 3 5229 as high pressure drop and difficult catalyst separation. having been linked to liver. Additives in Concrete and Flame Retardants Powdered LDH are one types of additives in concrete. Cl–.
Basically. Some perspectives could focus on preparing novel LDH micro-/nanostructures and developing novel applications in many fields such as separation. 3. Lin et al. ternary ZnMgAl-LDH showed better flame retarding properties than binary MgAl-CO32–-LDHs . Wei et al. and as nanocarriers for drugs.and photo-stabilities for L-Dopa  and L-Tyrosine . catalyst. still remain. Conclusions In this feature article we have reviewed the morphology. found that a borate-pillared MgAl-LDH with ethylene vinyl acetate (EVA) as the polymer component was a promising flame retardant . preparation.8]. 4. For example. involving dedication to the problem of well-dispersed LDH nanoplatelets as additives in flame retardants and also to realize non-toxic. biocompatible and biodegradable LDH carries into practical applications for drug and gene delivery. as well as further understanding the specific structures . and functional molecules. In the point of view of applications. Comprehensive investigations have been performed in Choy’s group on the toxicity of LDH nanoparticles in vitro and in vivo in practical biological applications . By tuning the composition of the layers. LDH powders and films are widely explored as catalysts and adsorbed materials. Lu’s group recently reported an efficient LDH-based delivery for siRNA to mammalian cells in vitro. The edge-on oriented LDH spheres (perpendicular to the tangent plane at the spherical surface) and films are fabricated via in situ growth. and electrode modifier energy harvesting devices. demonstrated that LDH was able to be used as an effective nanocarrier by greatly enhancing the thermal. whereas the preparation of the face-on oriented LDH spheres and films is achieved by physical deposition methods (mainly consisting of LbL assembly. or as nanocarriers for delivery of drug and genes into cells [5. the flame retardancy of LDHs was steered. LDH is a new type of material due to high smoke suppression. nontoxicity or low toxicity. conventional coprecipitation or scalable SNAS. drug and gene delivery. Powdery LDHs are typically used as addictives in flame retardants and concrete. gene molecules. Interestingly. the resulting activated structures exhibit enhanced performances. sol-gel spin-coating and the solvent evaporation technique) and hydrogen-bonding-based in situ growth. and also on the relationship between the novel structures and the enhanced properties of LDH micro-/nanostructures. and application of LDH structures. A few big challenges. which is actually performed on the basis of hydrothermal synthesis.4. MgAl-LDH is used as an important component of drugs. micro-/nanosized LDH powder is prepared through hydrothermal synthesis. which are both unstable agents in storage or transport. however. biomedical products. 1-D structured LDHs can be synthesized via control of LDH nucleation and growth in confined microsystems. 3 5230 Compared to other flame retardants.Materials 2010. A pronounced down-regulation of protein expression upon LDH mediated siRNA transfection of HEK293T cells was observed . upon calcination and rehydration. LDH is currently explored as a second generation flame retardant with enhanced properties by either modification of the layers or intercalation of different anions. LDHs in Biology and Medicine Powdered LDHs have demonstrated to be one type of important and green carrier or host for genes and drugs due to the excellent biocompatibility and nontoxicity or low toxicity.
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