Applied Clay Science 53 (2011) 139150

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Review Article

Catalytic applications of layered double hydroxides and derivatives

Zhi Ping Xu a,, Jia Zhang b, Moses O. Adebajo a, Hong Zhang c, Chunhui Zhou d
a Australian Research Council Centre of Excellence for Functional Nanomaterials, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072, Australia b School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200072, PR China c Centre for Computational Molecular Science, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072, Australia d Breeding Base of State Key Laboratory of Green Chemistry Synthesis Technology, Research Group for Advanced Materials and Sustainable Catalysis, 6 College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou, 310032, PR China

a r t i c l e

i n f o

a b s t r a c t
The review paper has briey summarized the development of the use of layered double hydroxides (LDHs) and their derivatives as heterogeneous and recyclable catalysts/catalyst supports for various reactions in the period of 2005 to early 2010. The catalysis reactions involve a number of important elds, such as organic/ pharmaceutical synthesis (e.g. the formation of several types of organic bonds), clean energy (e.g. the production of hydrogen and popular carbon nanotubes), and environmental pollution control (e.g. total decomposition of volatile organic compounds, photodecomposition of organic wastes, DeNOx and DeSOx). The authors have also commented on the state of the art of research and pointed out the potential future directions in developing LDH-based catalysts. This review has thus indicated that LDH-based catalysts are important materials useful in these elds and it is worthwhile making more efforts towards the development of LDH-based catalysts. 2011 Elsevier B.V. All rights reserved.

Article history: Received 22 June 2010 Received in revised form 4 February 2011 Accepted 8 February 2011 Available online 15 February 2011 Keywords: Layered double hydroxides Mixed oxide catalysts Heterogeneous catalysts Organic bond formation Pollution control

1. LDH materials: Structure features Layered double hydroxides (LDHs), also known as hydrotalcite-like compounds (HTlcs), are anionic clay materials (Braterman et al., 2004; Cavani et al., 1991). Unlike silicate-based cationic clays most of which occur naturally on the Earth, only a few anionic clays have been found in nature, and most can be readily and articially synthesized in the laboratory. This group of clay materials has attracted much attention worldwide because they nd a wide range of potential applications in the incipient or derived form, such as many catalysts in pharmaceutical industries and organic synthesis, anion scavengers in wastewater treatments, medicine and health (Braterman et al., 2004; Carretero and Lagaly, 2007; Cavani et al., 1991; Costantino et al., 2008a; Xu et al., 2006; Zhou, 2010). A few books (Rives, 2001; Wypych and Satyanarayana, 2004) and special issues in Appl. Clay Sci. (Basile et al., 2001; Carretero and Lagaly, 2007; Tichit and Vaccari, 1998; Vaccari, 1995; Zhou, 2010) have been published on the development of these materials in such applications. In particular, these materials have been intensively investigated in recent years as catalysts and catalyst supports in many aspects, such as organic synthesis, (photo)degradation of organic wastes, greenhouse gas control emission and H2 production by taking advantages of their specic physicochemical features. Therefore, in this review, we can only present an overview of what we regard as the most

Corresponding author. Tel.: + 61 7 33463809. E-mail address: gordonxu@uq.edu.au (Z.P. Xu). 0169-1317/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.clay.2011.02.007

signicant progress in this eld through published documents known to us mostly from 2005 to early 2010. The layered structure of the representative of LDH materials, e.g. hydrotalcite ([Mg3Al(OH)8][(CO3)1/2 2H2O]) is closely related to that of brucite, Mg(OH)2. The 2-D brucite layer is constructed with octahedrons by sharing their edges, with charges being balanced. Each octahedron consists of one MgII in the centre and six OH groups at vertexes. Partial replacement of MgII ions by AlIII in hydrotalcite gives the brucite-like layer ([Mg3Al(OH)8]+) a positive charge, which is balanced by carbonate anions, located in the interlayer region (gallery) between the two brucite-like layers [(CO3)1/2 2H2O], as shown in Fig. 1 (Braterman et al., 2004; Taylor, 1973). This gallery also contains water molecules, hydrogen bonded to layer OH groups and/ or the interlayer anions. The electrostatic interactions and hydrogen bonds between the layers and the contents of the gallery hold the layers together, forming the crystal structure, as shown in Fig. 1. There are mainly two ways for brucite-like layers to stack on top of one another (Bookin and Drits, 1993). One is hexagonal polytypes (2H) with a two-layer repeat, and the other is rhombohedral polytypes with a three-layer repeat (3R1 and 3R2) (18). Natural LDHs are known in both 2H and 3R forms, and synthetic LDHs are usually assigned to 3R1 as well as 3R2 form. All LDH materials found in nature or synthesized in the laboratory have a structure similar to that of hydrotalcite, as shown in Fig. 1, even though different combinations of cations in the brucite-like layers and intercalation of anions with different sizes and charges sometimes distort this regular structure to a small extent. The majority of LDH materials adhere

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PW12O403, PW6Mo6O403 etc.) (Braterman et al., 2004; Cavani et al., 1991; Rives and Ulibarri, 1999). LDH materials can be directly synthesized using precipitation at a varied or constant pH (Braterman et al., 2004; Cavani et al., 1991). This process involves nucleating and growing the metal hydroxide layer by mixing an aqueous solution containing the salts of two or more metal ions with a base solution with the desired anion. It has been demonstrated that LDH materials form in preference to a mixture of the individual metal hydroxides (Boclair and Braterman, 1999). Anion exchange and rehydration methods are often used to prepare LDHs with some particular anion intercalated into the interlayer. Many other preparation methods can be referred to in review papers (Braterman et al., 2004; Cavani et al., 1991). Moreover, an LDH compound can be readily transferred to the corresponding mixed oxide by heating to a certain temperature, which typically involves dehydration, dehydroxylation, decomposition of anions and oxide segregation in series or in overlapping style:
Fig. 1. Schematic of crystal structure of hydrotalcite ([Mg3Al(OH)8][(CO3)1/2 2H2O]).

to the general formula where M represents a divalent metal, M a trivalent metal and A an anion. The value of x is reported to be 0.2 to 0.4 in forming a pure LDH phase. If x values are outside this range, hydroxides or other compounds as impurities may be formed. The divalent (MII) and trivalent cations (MIII) listed in Table 1 are all found to form LDHs through replacing MgII or AlIII in full or in part in the brucite-like layer. For these ions, the only requirement is that their radii in the case of octahedral coordination are not too much different from those of MgII and AlIII. In view of the cation size, many transition metal ions in divalent and trivalent states and lanthanide ions (0.0860.103 nm) could in principle replace MgII/AlIII, at least in part to form a very wide range of LDH materials in composition. In addition, some tetravalent cations, such as TiIV (Silva et al., 2009), ZrIV (Saber, 2007) and SnIV (Saber and Tagaya, 2003), have also been claimed to incorporate into the brucite-like layer, with a general formula of ([MII1xMIVx/2(OH)2]x+(An)x/n mH2O), while some evidences reveal that MIV cations form amorphous MIV-oxide particles instead of incorporating into the brucite-like layer (Intissar et al., 2003, 2006). A more outstanding feature is that multi-metal cations can be incorporated simultaneously into the brucite-like layer to prepare multi-component LDHs, only if x is in the valid range. The anion located in the interlayer gallery can be any one as long as the anion does not abstract the metal ions from the brucite-like layer and has a sufcient charge density. Up to now, many kinds of anions have been intercalated into the LDH interlayer, including (1) common inorganic anions (Cl, F, CO32, NO3 etc.); (2) organic anions (carboxylates, dicarboxylates, alkylsulfates, alkanesulfonates etc.); (3) complex anions (Fe(CN)64/Fe(CN)63, metal-porphyrin and phthalocyanine complexes); and (4) Iso- and hetero-polyoxometalates (POMs) (Mo7O246, W7O246, V10O286, OsO42, PMo12O403,

[MII1xMIIIx(OH)2]x+(An)x/n mH2O, III n

II

(1) Dehydration: [MII1xMIIIx(OH)2]x+(An)x/n mH2O [MII1xMIIIx(OH)2]x+(An)x/n (2) Dehydroxylation: [MII1xMIIIx(OH)2]x+(An)x/n [MII1xMIIIxO]x+(An)x/n (3) Decomposition of anion: [MII1xMIIIxO]x+(An)x/n MII1xMIIIxO1 + x/2(BOy) (4) Oxide reformation: MII1xMIIIxO1 + x/2(BOy) MIIO + MIIMIII2O4+ BOy where MIIO is an oxide with rock salt phase, MIIMIII2O4 is a mixed oxide with spinel phase, and BOy denotes the species of decomposed anion. These decomposition processes are of great importance in deriving oxide and oxide-supported catalysts. Specically, hydrotalcite [Mg3Al(OH)8][(CO3)1/2 2H2O] rst undergoes dehydration (100250 C), then dehydroxylation (350450 C), and in the later stage of step (2) decarbonation (420470 C), giving rise to rock salt phase MgO (~ 450 C) and mixed oxides (rock salt + spinel) at N 700 C (Braterman et al., 2004; Cavani et al., 1991). However, for LDHs containing oxidizable divalent cations, such as CoII, FeII, NiII and MnII, a spontaneous oxidation reaction occurs during heating in air. In this case, dehydroxylation is facilitated and takes place at temperatures below 250300 C, or even overlaps with dehydration. During the decomposition process, rock salt oxide may not be formed, while pure spinel phase mixed oxide is readily produced at relatively low temperature (e.g. 300 C) (Xu and Zeng, 1999, 2000; Zhang et al., 2010). Oxidation of MIII can also occur, for instance during calcination of LDHs containing CrIII, or MnIII cations. Thus calcination of MgCr-, NiCr-, and ZnCr-LDHs at intermediate temperatures (i.e., 350 C) results in the formation of chromate-like (CrO42) species, and that of MgMn-LDH would lead to the formation of MnO2. The decomposed anion (BOy) could be nothing if CO32 or NO3 is intercalated, or some kind of oxide, such as WO3 or MoO3 if Wo7O246 or Mo7O246 is intercalated. It is worth mentioning that the cations in most LDHs are evenly distributed in the brucite-like layers after suitable post-treatment. More remarkably, as Markov et al. (1990) have shown, dehydroxylation of the brucite-like layer, i.e., the collapse of the layered structure, occurs topotactically at temperatures less than 500 C. This means that the diffusion of metal ions to occupy other metal sites during this stage of calcination can be ignored. Very interestingly, the mixed oxide obtained at the intermediate calcination temperature (b 600 C) can easily regain the layered structure to become a similar LDH compound upon exposure to aqueous solution; this is called the memory effect (Miyata, 1983; Reichle, 1986). During the reconstruction, anions in the solution can be intercalated into the interlayer, which is a method often used to load anions with a weak afnity for LDH. Even upon calcination at 600 to 700 C, the diffusion of cations should be minimal. Therefore, the calcined LDHs (b 700 C) usually

Table 1 Ionic radii of some cations with coordinate number of 6 (Lide, 1999). MII Fe Co Ni Mg Cu Zn Mn Pd Cd Ca (TiIV (SnIV Radius (nm) 0.061 0.065 0.069 0.072 0.073 0.074 0.083 0.086 0.095 0.100 0.061) 0.069) MIII Al Co Fe Mn Ga Rh Ru Cr V Y La (ZrIV Radius (nm) 0.054 0.055 0.055 0.058 0.062 0.067 0.068 0.069 0.074 0.090 0.103 0.072)

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inherit a good cationic dispersion from the pristine LDHs, a characteristic actively sought after in the development of many multi-metal mixed oxide catalysts. Therefore, incorporation of a range of different cations into the brucite-like layer makes these materials suitable for ne tuning the chemical composition and hence for catalytic properties, which have been widely examined in various reactions, as reviewed in the following section. For the sake of convenience, the original LDH(s) (dried below 150 C) are denoted as LDH(s), and the calcined LDH(s) as LDO(s) (layered double oxide). LDH-POM means the LDH intercalated with polyoxomatalate and LDO-POM the calcined LDH-POM. 2. LDH-based catalysts 2.1. Formation of C\C and C_C bonds 2.1.1. As catalyst supports In 1973, LDHs with different combinations of metal ions (mainly NiAl, MgZnAl, MgMnAl, MgCoMnCuAl, CoCr, MgAlCr and MgAl), calcined at 473723 K and partially or completely chlorinated, were reported to be effective supports for Ziegler catalysts for olen polymerization (Basile and Vaccari, 2001; Frielingsdorf et al., 1973). The highest catalytic activity of polyethylene production was observed for MgMnAlCO3-LDH heated at 473 K (Frielingsdorf et al., 1973). Some newer applications have included vanadium oxide catalysts supported on calcined MgAl-LDHs for oxidative dehydrogenation of butane (Blasko et al., 1995; Lpez Nieto et al., 1995) and the vapor phase synthesis of isobutyraldehyde from methanol and n-propanol (Dinka et al., 1998). In the former reaction (Blasko et al., 1995; Lpez Nieto et al., 1995), the activity was found to be lower than that of analogous MgO- or Al2O3-supported vanadium oxide catalysts. However, a high selectivity to alkenes, especially 1-butene and butadiene, was achieved for V-contents of about 30 wt.% (as V2O5). In the latter reaction (Dinka et al., 1998), the activity was found to depend mainly on the acidbase properties since the synthesis of isobutyraldehyde took place through metal enolate intermediates, while selectivity was observed to be strongly inuenced by the method of vanadium loading (impregnation or intercalation). It has also been demonstrated that both calcined and uncalcined LDHs are effective supports for noble metal catalysts (Bennur et al., 2002; Chen et al., 1998; Choudary et al., 2002a; Das et al., 2001). For example, palladium supported on calcined MgAl-LDH has been used for one-pot synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK) from acetone and hydrogen at an atmospheric pressure (Das et al., 2001). In this reaction, the performance depended on the interplay between the acidbase and hydrogenation properties. In the other example, Pd-containing LDH and LDH-supported Pd(TPPS)2Cl2 (TPPS = triphenylphosphine trisulfate, sodium salt) have been reported to be efcient and re-usable catalysts in the Heck reaction between aryl halides and olens to give good to moderate yields of C\C coupled products (Bennur et al., 2002; Choudary et al., 2002a). Choudary et al., (2002b) studied Pd(0) catalysts supported on MgAl-LDHs prepared by ion-exchange with PdCl42 and followed by reduction. They observed that the catalysts, used in ionic liquids, not only exhibited higher activity and selectivity than the homogeneous PdCl2 system in the Heck olenation of electron-poor and electronrich chloroarenes, but also showed superior activity in the C\C coupling reactions of chloroarens compared with other heterogeneous catalysts involving Pd(0) on supports such as silica, alumina or Merrield resin. In a later study, a cooperative effect between Ru species and the surface base sites was observed when a multifunctional ruthenium-grafted MgAl-LDH catalyst was used in the direct -alkylation of a variety of nitriles with primary alcohols (Motokura et al., 2004). It was shown that the use of the same catalyst system can be extended to the one-pot synthesis of ,-dialkylated phenylacetonitriles via a base-catalyzed Michael addition of alkylated phenylacetonitrile with activated olens. A more recent

investigation demonstrated that an LDH-supported Rh(0) catalyst was very effective for Heck, Suzuki and Stille cross-coupling reactions of haloarenes, providing an excellent yield of coupling products. The catalyst was found to be easily recovered by simple ltration and reused for several cycles with consistent activity (Kantam et al., 2007). 2.1.2. As solid base catalysts Heterogeneous solid base catalysts such as calcined LDHs, e.g. LDOs, are currently receiving considerable attention from the viewpoint of environmental and economical concerns because of their unique properties such as simple handling, easy separation and recyclability, and low cost (Nishimura et al., 2000). In particular, mixed oxide LDOs, due to their unique ability to provide Brnsted type base sites, are well suited to replace homogeneous base catalysts as more environmentally benign and recyclable catalysts for several important organic reactions. These reactions involve C\C and C_C bond formations, such as Knoevenagel condensations (Choudary et al., 2001b; Costantino et al., 2003; Kantam et al., 2006; Veloso et al., 2008), Michael additions (Choudary et al., 2001b; Kantam et al., 2006), aldol and ClaisenSchmidt condensations (Abell et al., 2007a, 2007b, 2008; An et al., 2006; erven et al., 2008; Liu et al., 2010; Sharma et al., 2007), and Henry reaction (Kantam et al., 2006), as will be presented herein. Furthermore, LDOs with rock-salt like phase possess both acid and base sites, the nature, strength and relative amounts of which depend mainly on the nature and molar ratio of cations and calcination temperature. Brief reviews of recent development of LDHs as catalytic materials and precursors of multifunctional catalysts have also been presented (Tichit et al., 2006). Among the previous work on applying LDHs as catalysts for organic reactions involving C\C and C_C bond formations, Choudary et al. (2001b) reported that LDHs containing highly polarized basic uoride ions are very efcient, environmentally attractive and selective solid base catalysts for 1,4-Michael addition and also for simple synthesis of ,-unsaturated esters and nitriles by Knoevenagel condensation, as illustrated in Schemes 1 and 2:

R1 O + H2C R2

CN LDH-F R3
Schemes 1

R1

CN

R2

R3

O R1 + H 2C

O X LDH-F Y MeCN, RT Y
Schemes 2

R1 X

The LDH-F catalyst was found to display unprecedented catalytic activity for both reactions under mild liquid phase conditions at a greater rate than that with any known solid base and uoride catalysts. Such an eco-friendly catalyst was therefore recommended as a potential alternative to soluble bases. In an earlier work, Choudary et al. reported the rst example of a catalyst derived from MgAl-LDH (Mg/Al = 2.5:1), which was used for selective Michael addition

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reactions on methyl vinyl ketone, methyl acrylate, and simple and substituted chalcones by donors such as nitroalkanes, malononitrile, diethyl malonate, cyanoacetamide and thiols, with comparative yields obtained under mild reaction conditions (Choudary et al., 1999). In recent investigations, LDH catalysts modied with Sn(IV) incorporation (Costantino et al., 2008b) or diisopropylamide loading (Kantam et al., 2006) for C\C bond formation were developed and found to be efcient and selective solid base for aldol, Knoevenagel, Henry, Michael and other organic reactions at mild or ambient temperature. Veloso et al. (2008) recently reported that MgAl-LDOs derived from MgAl-LDHs with different Mg/Al molar ratios were active for the Knoevenagel reaction between glyceraldehyde acetonide ((R)-(+)2,2-Dimethyl-1,3-dioxolane-4-carboxaldehyde) and ethyl acetoacetate to produce the corresponding carbonyl compound, an important intermediate for ne chemicals. All the catalysts studied were found to be 100% selective to the condensation product (Scheme 3):

COCH3 + CHO H2C CO2C2H5

Cat

COCH3 CO2C2H5

at 4731073 K exhibited high catalytic activity for the benzylation of benzene and substituted benzenes with benzyl chloride as the alkylating agent. Iron oxides on the catalyst surface were found to be the most active sites of the catalytically active species in the catalyst. A more recent investigation has demonstrated the catalytic activity of LDOs for the side chain methylation of toluene with methanol (Manivannan and Pandurangan, 2009). MgAl-LDO yielded mainly ethyl benzene and styrene in the side chain alkylation reaction while the other LDOs (CuAl-, NiAl-, CoAl- and ZnAl-LDOs) yielded mainly nuclear alkylated products, namely xylenes and mesitylene. Calcined MgAl-LDH was found to be the most active catalyst for the side chain methylation of toluene under the chosen conditions. Nanosized LDHs synthesized within mesoporous materials have recently been developed for use as catalysts for aldol and Claisen Schmidt condensation reactions (Dubey, 2007; Li and Shi, 2008). For example, Dubey synthesized nanosized LDH inside mesoporous carbon (CMK-1), known as CMK-LDH nanocomposite, by simple impregnation and precipitation techniques (Dubey, 2007). These nanocomposites were found to exhibit remarkably high activity and selectivity to the desired product in ClaisenSchmidt condensation between benzaldehyde and 2-hydroxyacetophenone under environmentally friendly conditions (Scheme 4).
HO Cat CHO + CH3CO CH CHCO HO

Scheme 3 A decrease in Al content in MgAl-LDOs was found to increase the conversion of glyceraldehyde acetonide and consequently the product yield, a trend that reects both the basic site density as measured by TPD of CO2 and the mesoporous characteristics of the mixed oxides. The rehydration of MgAl-LDOs was also found to increase the conversion of glyceraldehyde acetonide without changing the selectivity. Although this activation procedure decreased the basic sites density, it converted Lewis basic sites into Brnsted ones that favored the condensation reaction under the conditions studied. Corma and colleagues previously studied an MgAl-LDH for the synthesis of chalcones of pharmaceutical interest through the ClaisenSchmidt condensation between benzaldehyde and acetophenone (Climent et al., 2004). It was observed that an MgAl-LDO (Mg/ Al = 3:1) with a water content of 35 wt.% was the optimized solid base catalyst that can be used in the synthesis of several chalcones with anti-inammatory, antineoplastic, and diuretic activities, with an excellent activity and selectivity. The rehydrated MgAl-LDO has also been very recently reported to be active for the aldol condensation of furfural with acetone to give 4-(2-furyl)-3-buten-2-one, one of the most important processes in the aqueous-reforming of oxygencontaining biomass derivatives (Liu et al., 2010). The rehydrated LDO with Mg/Al = 2.5 (calcined at 400 C and rehydrated decarbonate water at 70 C) was found to show the best catalytic performance. The catalytic activity of rehydrated LDO has also been found to be relevant to the calcination temperature and rehydration temperature, mainly attributed to the formation of MgAl spinel (Liu et al., 2010). The relative stability, reutilization and scalability of LDOs in aldol condensation were recently demonstrated using the aldol condensation of citral and acetone to produce pseudoionone as an example (Abell et al., 2008). There have also been some recent reports on applications of LDOs as catalysts for alkylation reactions of aromatics (Manivannan and Pandurangan, 2009; Shimada and Ogoshi, 2005; Tahir et al., 2008). For example, amorphous oxides, formed upon calcination of Zn2Al-LDHs with interlayer chloride or carbonate, were found to exhibit high catalytic activity for benzylation of benzene with benzyl chloride (Shimada and Ogoshi, 2005). The IR spectra of pyridine adsorbed on the amorphous oxides showed that the benzylation activity was due to the formation of zinc chloride on the surface. In the other example, Tahir et al. (2008) demonstrated that MgFe-LDH (Mg/Fe = 2) calcined

Scheme 4 In a more recent investigation (Li and Shi, 2008), MgAl-LDH nanocrystallites with a lateral size less than 9 nm were synthesized in situ within the pore channels of mesoporous silica materials (such as SBA-15) and found to be very active heterogeneous base catalysts for aldol condensation reactions. It was concluded that a combination of nanosized LDH crystallites and open structure of the mesoporous support provided the excellent catalytic activities for these reactions. 2.2. Formation of C\O bond: Epoxidation Epoxides are very important intermediates for the chemical synthesis of complex molecules. They are normally prepared by oxidizing C_C double bonds with H2O2 or oxygen over a homogeneous or heterogeneous catalyst. Intensively investigated are two kinds of catalysts, i.e. polyoxometalates (POM)-based and sulfonato-salen (Salen)-based catalysts in organic solvent-free system. These two catalytic anions can be intercalated and thus conned in the interlayer spacing of LDHs, which leads to high activity and selectivity for epoxidation of various olens, as demonstrated in the following part. In our previous review paper (Braterman et al., 2004), epoxidation of various alkenes over POM-intercalating LDH was already summarized. Recently, Liu et al. (2009) used Mg3Al- and Zn3Al-LDHs to host a few Mo-based POMs to catalyze epoxidation of various allylic alcohols (Scheme 5):

R2 H2O2 R1 OH Cat
Scheme 5

R2 O R1 OH

They found that [WZn3(ZnW9O34)2]12-intercalating Mg3Al-LDH heterogeneous catalyst leads to a high conversion of prenol (95%) and a very high selectivity to epoxide (98%), in comparison with Na[WZn3(ZnW9O34)2] homogeneous catalyst with 98% conversion but

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only 27% selectivity. The high selectivity to epoxide is largely attributed to avoiding epoxide hydrolysis, a major side reaction in the homogeneous epoxidation. This catalyst has also shown a comparable or higher activity and selectivity than a homogeneous one for epoxidation of several other allylic alcohols. The most economical point is that the heterogeneous catalyst (POM-LDH) can be readily recovered and reused, without any noticeable activity loss (Liu et al., 2008; Rives and Ulibarri, 1999). Since POM is restricted in the interlayer or on the surface, so only part of the anion is exposed to reactants, which probably causes regioselective epoxidation of one C_C bond over another in the same organic molecule, and stereoselective epoxidation of a C_C bond to form a specic stereo-structure. Levecque et al. (2009) loaded WO42 into NiAl-LDH (Ni/Al= 1.7, 2.8 and 3.6) and noted that Ni1.7AlWO42LDH is the most active one for terpene epoxidation with the bromide assistance. In particular for (+)-limonene epoxidation (Scheme 6), 1,2epoxidation (78%) is much preferred to 8,9-epoxidation (22%). In 1,2epoxidation, the cis-epoxidation (90%) is much more selective than the trans-epoxidation (10%). The similar stereo- and regioselectivities have been also observed in the epoxidation of 3-carene, squalene and ()carveol (Levecque et al., 2009).

2.3. Formation of C\N bond: N-arylation N-arylation of amines is an important reaction in chemical synthesis because N-arylated compounds constitute the subunits of many biologically active molecules. Using Cu-containing LDH materials as the catalyst, the following N-arylation occurs in a good to excellent yield at 100 to 160 C with K2CO3 doped into Cu-containing LDH as the base (Scheme 8):

Ar-X + R1NHR2

Ar-N(R1)R2 + HX
Scheme 8

O 1 2
H2O2 +Br-

+ Cat 8 9 Limonene cis-1,2-epoxide

trans-1,2-epoxide 8,9-epoxide

Scheme 6 On the other hand, ZnAl-LDHs intercalated with sulfonato-salenMn, Fe or Co complex anion have also demonstrated high activity and selectivity in the epoxidation of various olens. For instance, Bhattacharjee et al. (2004) found that ZnAl-LDH-Salen-Mn catalyst is able to convert 95100% of (+)-limonene and ()--pinene with nearly 90% selectivity to epoxidation in various solvents with O2 or air as the oxidant at room temperature. In their further research (Bhattacharjee and Anderson, 2006a), they noted that the epoxidation of dicyclopentadiene is regioselective when the reaction is catalyzed with ZnAl-LDH-Salen-Mn using pivalaldehyde as the additive (Scheme 7):

where X = Cl, Br, I, and Ar can be one of substituted phenyl rings. R1 and R2 can be either substituted phenyl, or benzyl, or cycloalkyl (or H). For example, Likhar et al. (2007) noted that CuAl-LDH based catalyst (Cu/Al = 2.5) with K2CO3 doped has the highest activity for pnitrochlorobenzene amination with benzylamine at 160 C, with 77% yield. Then they investigated the N-arylation of benzylamine and cycloalkylamines with several chlorobenzenes that were substituted with an electron-withdrawing group over catalyst CuAl-LDH-K2CO3. In general, the reaction yield is good to excellent (4593%) at 100160 C for 816 h. They also noted that the presence of the electronwithdrawing group in chlorobenzene is essential for this reaction to take place. On the other hand, Jadhav et al. (2007) prepared CuFe-LDH (Cu/ Fe = 3) and used it to catalyze the N-arylation of aniline, benzylamine, cyclohexylamine and indole with bromobenzene and iodobenzene, with the yield of 7487% at 130 C for 1216 h. Their results indicated that (1) the catalyst is very selective toward the primary amines so that no further N-arylation of the secondary amines occurs; (2) the substituent in bromobenzene and iodobenzene is not necessarily electron-withdrawing, as \OCH3 does not interfere this reaction, unlike the case for chlorobenzene (Likhar et al., 2007); and (3) bromobenzene seems to react more readily than chlorobenzene because only Br joins the reaction to produce HBr with CuFe-LDH as the catalyst when 4-bromo-chlorobenzene reacts with aniline. It is worth mentioning that the catalysts were readily recovered from the liquid mixtures and reused for the next time, without loss of activity (Likhar et al., 2007). 2.4. Formation of N\O bond: N-oxidation of secondary and tertiary amines The secondary and tertiary amines can be oxidized with various oxidizing reagents over the catalyst with a certain alkalinity (Schemes 9 and 10):

O2/aldehyde
O Cat + O

R1 CH R2 NH R3

Cat

R1 C R2

O N+

(A)
Scheme 7

(B)

R3

where A (81%) is preferred to B (19%) with 9697% conversion of dicyclopentadiene. The catalyst activity is kept unchanged after 3time reuse (Bhattacharjee and Anderson, 2006a). In addition, they intercalated chiral sulfonato-salen-Mn complex anion into ZnAl-LDH to asymmetrically epoxide styrenes and cyclic alkenes, giving rise to 2070% of enantiomeric excess (ee) (Bhattacharjee and Anderson, 2006b). It is noted that pinene epoxidation over this catalyst at room temperature results in an enantiomeric excess (ee) up to 98%, much higher than that for limonene (3040%), showing a high stereoselectivity (Bhattacharjee et al., 2004).

Schemes 9

R1 N R2 R3

Cat

R1

+ O N R2

R3

Schemes 10

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MgAl-LDH is a weak base, and can be made stronger by intercalating OBu anion, as reported by Choudary et al. (2004). They found that MgAl-OBu-LDH (Mg/Al = 3) showed an activity similar or superior to KOBu and NaOH for N-oxidation of Nmethylmorpholine and dibutylamine using H2O2 as the oxidant in benzonitrile-methanol at 6575 C. Several secondary and tertiary amines were readily N-oxidized with a high yield (7298%). It seems that N-oxidation of tertiary amines is much faster than secondary amines as the tertiary amines are almost quantitatively N-oxidized with H2O2 over MgAl-WO4-LDH under similar conditions (95% yield) (Choudary et al., 2001a). These LDH-based catalysts are all recyclable, without any obvious loss of activity. 2.5. Formation of S\O bond: Oxidation of organic sulde In general, organic suldes can be oxidized with various polyoxometalates (POMs), which normally occur in two steps to form sulfoxide and sulfone, respectively, as schematically shown below (Scheme 11):

S R1 R2

Cat R1

O S R2 Cat R1

O S

O R2

Sulfide

Sulfoxide
Scheme 11

Sulfone

where R1 and R2 can be aromatic and/or alkyl groups. For this oxidation, LDH is designed as a support to host POM in the interlayer. It is extremely interesting that POM intercalation into the LDH interlayer results in a fast reaction, a high yield, a high selectivity and an asymmetric oxidation (Choudary et al., 2003; Kantam et al., 2005). Choudary et al. (2003) intercalated osmate (OsO42) into the MgAl-LDH interlayer and used it to oxidize various organic suldes directly to sulfone, with a yield of 9599% and without formation of intermediate sulfoxide in the t-butanol phosphate buffer at 55 C for 524 h. They attributed this to the 3 + 1 cycloaddition catalytic process. Very surprisingly, LDH-OsO4 was found to selectively and asymmetrically catalyze organic suldes to sulfoxides in t-butanol with the presence of a chiral ligand (Kantam et al., 2005). When MgAl-OsO4-LDH (Mg/Al = 3) was used in the oxidation of methyl phenyl sulde at 025 C for 3 h in tbutanol with hydroquinidine 1,4-phthalazinediyl diether as the chiral ligand, 7580% of methyl phenyl sulde was selectively oxidized to sulfoxide with N-methyl morpholine N-oxide as the co-oxidant, in which there was up to 50% enantiomeric excess. Some other organic suldes were also found to be selectively oxidized to sulfoxides with a yield of about 80% and a moderate enantiomeric excess (1030%) (Kantam et al., 2005). Recently, V-, Mo- and W-containing LDHs were investigated for oxidation of various suldes by Hulea and co-workers using H2O2 as the oxidant at 2550 C (Hulea et al., 2006, 2009; Maciuca et al., 2008a, 2008b). Their results indicate that (1) W-LDH is the most active catalyst for oxidation of methyl phenyl sulde, benzyl phenyl sulde, di-phenyl sulde, benzothiophene, dibenzothiophene, tetrahydrothiophene, dimethyl sulde; (2) sulfoxide is detected in the early stage of reaction (normally within the rst 30 min) and then gradually transferred to sulfone; (3) sulfone is the predominant product after 1-hr reaction; and (4) the conversion can be up to 100% in most cases under the suitable conditions. 2.6. CNT formation Carbon nanotubes (CNTs) have received much attention for various potential applications such as transistors, eld-emission

tips, sensors, supercapacitors and biomedical agents because of their superior mechanical, thermal and electrical properties, and can be prepared in many methods, such as arc-discharge, laser ablation, catalytic chemical vapor deposition (CCVD), and hydrocarbon pyrolysis (Baughman et al., 2002; Kitiyanan et al., 2000; Thess et al., 1996). However, CCVD appears the most promising one for largescale production at a lower energy cost. In this method, CNTs are normally formed through catalytic decomposition of a hydrocarbon gas and subsequent carbon deposition on catalytic nanosized transition metal particles supported on metal oxides, silica or zeolites. As transition metal cation(s) can be readily incorporated and well dispersed in the brucite-like layers, so the physicochemical properties of such metal nanoparticles (such as size, surface reactivity, and chemical composition) can be nely tuned through careful selection of the metal cation combination, controllable calcination of LDH precursors and manageable reduction of transition metal cation(s). The nely-tuned metal particles can be used to control the growth of nanotubes, as demonstrated by various research efforts in recent years. Li et al. (2005) for the rst time synthesized multi-walled CNTs at 700 C in this method by decomposing/depositing acetylene over reduced Co1.7Al-LDO catalyst. As-prepared CNTs showed a uniform size with the diameter ranging from 20 to 30 nm. Benito et al. (2009) utilized microwave to enhance Co dispersion in CoZnAl-LDH precursor and then used the calcined/reduced LDO as the catalyst to produce multi-walled CNTs (diameter = ~ 2030 nm) via CCVD of methane. In contrast, the similar catalyst derived from the normally co-precipitated LDH precursor just gave rise to herringbone carbon nanobers (diameter = ~ 14 nm). Ni- and Fe-containing reduced MgAl-LDOs were also able to produce CNTs, where NiMgAl-LDO shows the higher activity (Zhao et al., 2005). Li and colleagues further investigated the composition effect of NiMgAl-LDHs with (Ni2++ Mg2+)/Al3+ = 2.0 but varying Mg2+/Ni2+ from 0, 0.5, 1 to 2. They noted that the carbon yield was enhanced with more Mg, which could be attributed to the good dispersion of active Ni particles with small sizes that mainly resulted from the inhibition effect of spinel phases (Ni1xMgxAl2O4) formed in calcined LDHs (Zhang et al., 2009). In addition, Zhao et al. (2007) noted that Fe0.1Mg2Al0.9-LDO was able to produce single-walled CNTs. In a more detailed study, Zhao et al. (2010) prepared the single/ double-walled CNTs over FeMgAl-LDO in a controllable way that were interlinked between LDO akes. Such a composite (LDOCNT) shows a much greater enhancement in the tensile strength and the Young's modulus in comparison with pure CNTs at the similar loading in the polyimide matrix. A few LDOs with multiple transition metals were used to produce CNTs or carbon nanobers (CNFs). Dussault et al. (2006) found that NiCuMgAl-LDOs produced quality CNFs, and that LDO with 3.8 wt.% Cu resulted in a narrow size distribution of CNFs. CoFeAl-LDOs can also catalyze the formation of CNTs via a similar process where Co content in LDHs precursors is critical to CNT yield and structure, because Co readily forms spinel-like oxides (e.g. CoAl2O4, CoFe2O4 and Co3O4), e.g. the active cobalt clusters are well stabilized and dispersed in the oxide matrix (Xiang et al., 2009). Very interestingly, N-doped carbon nanotubes (NCNTs) can also be prepared over LDH derived catalysts. Cao et al. (2009) synthesized NCNTs by pyrolyzing ethylenediamine over NiMgAlLDO at 650 C. The N content and the morphology of as-formed NCNTs were related to the NiII content in LDH precursors. The higher NiII content in the catalyst resulted in NCNTs with a higher N content (up to 8.8 wt.% N) and a more graphitic-like structure. Xue et al. (2010) used Co-based catalyst derived from Co2Al-LDHs to efciently produce large-scale NCNTs from methane and acetonitrile. The typical NCNTs obtained have bamboo-like structures with a varying N content that depends on the gas ow rate and the methane/acetonitrile ratio.

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2.7. H2 production: Steam reforming Hydrogen provides a clean and environmentally friendly energy that is most desirable for sustainable development, and thus the technology for H2 production from sources such as methanol, ethanol, and methane has been exhaustedly researched in recent times. Steam reforming of these gasses over an active catalyst appears to be a most promising technology (Palo et al., 2007). The most often used catalysts are normally metals supported on single metal oxides or mixed oxides, and mixed oxides that can be readily derived from LDH precursors, and there are many publications reporting the progress of H2 production over these mixed oxide catalysts, e.g. CH4 steam reforming: CH4 H2 OCO 3H2 endothermic CO H2 OCO2 H2 exothermic: As summarized in the previous review (Braterman et al., 2004), the steam reforming reactions can be actively catalyzed with many transition metal-containing (Co, Cu, Ni etc.) oxides derived from LDH precursors. For example, Lucrdio and Assaf (2006) prepared CoMgAlLDH precursors in three different ways: co-precipitation of Co, Mg and Al nitrates; co-precipitation of Mg and Al nitrates with pre-synthesized cobalt chelate anion; and anion-exchange of MgAl-NO3 with cobalt chelate anion. They noted that anion-exchange results in a more homogeneous active phase distribution and thus a better catalytic activity for CH4 steaming reforming. Guil-Lpez et al. (2006) compared the fresh NiMgAl-LDO catalyst and regenerated one in the catalytic performance for CH4 steaming reforming. Thanks to the stabilization of MgO on Ni particles and the high removal of carboneous deposition, the regenerated catalyst showed an increasing H2 production. In another study using LDO as the support, the smaller NiO crystal size and the higher resistance to coke formation could be responsible for the higher activity and stability (Christensen et al., 2006). Ashok et al. (2008) carried out CH4 steam reforming at 600700 C over NiCuAl-LDO with varied Cu/Al ratios. They found that the catalyst with a molar ratio of 60:25:15 (Ni:Cu:Al) led to the highest hydrogen yield. The role of Cu is probably to strengthen NiII species (active couple) dispersion and thus produce more active sites. Therefore, good dispersion of metals or the active oxide on the surface seems to be highly desirable in order to obtain a satisfactory productivity and selectivity in the methane steam reforming. Recently, the Takehira group doped noble metals (Pt, Ru and Rh) into NiMgAl-oxide by rehydration and calcination (0.050.5 wt.%) to improve the activity and stability for CH4 steam reforming in a daily start-up and shut-down operation (Li et al., 2008; Takehira et al., 2007). Steam reforming of hydrocarbons (such as n-heptane and n-hexane mixture) has been reported over LDO-based catalysts (Melo and Morlanes, 2008). Steam reforming has also been extended to methanol and ethanol. Qi et al. (2005) compared the activity of NiAl-LDO and noble metal (Au, Rh or Ir)-NiAl-LDO in methanol steam reforming. Doping noble metals increases the methanol conversion, however, decreases the H2 and CO2 selectivity, especially at high temperatures. Turco et al. (2004) found that CuZnAl-LDO is a good catalyst for oxidative steam reforming of methanol with high selectivity to H2 production. Tang et al. (2009) investigated the effect of calcination temperature on the activity of CuZnAl-LDO in methanol steam reforming. They found that CuAl2O4 spinel, depending on the calcination temperature, plays a key role in isolating and stabilizing the nano-sized Cu and ZnO particles on the surface, for example, leading to the conversion of more than 96% with a H2O/CH3OH of 1.3:1 after calcination at 600 C. Similarly, He et al. (2009) used CoNiMgAl-LDO (with different Co/Ni ratio) as catalysts for H2 production via ethanol steam reforming, the best catalytic performance being obtained with the Co/Ni= 3:1. Other examples were Ni(Zn/Mg)Al-LDO and CoZnAl-LDO in catalyzing ethanol steam reforming, reported by Resini et al. (2009) and Busca et al. (2010). They

proposed that the reaction rst starts decomposition to generate methane, COx and hydrogen, followed by water gas shift and methane steam reforming. The formation of methane and water gas shift equilibrium limits H2 production yield. Qi et al. (2005) also indicated that methane was an undesirable by-product in producing H2. In steam reforming, catalyst deactivation is always a problem. For instance, the best catalyst (CoNiMgAl-LDO with Co/Ni = 3:1) was deactivated after being run for 45 h (He et al., 2009). Carbon solubility, diffusion and sintering are the factors to deactivate catalysts. Resini et al. (2009) also observed deactivation phenomena due to the formation of carbon whiskers/nanotubes and to the change of catalyst particle morphology. The deactivation seems to be sensitive to the metal composition (ratio and dispersion), and also to the catalyst preparation history (such as LDH precursor and calcinations), while doping a trace amount of noble metals (Pt, Ru and Rh in 0.05 wt.%) could signicantly enhance the catalyst stability (Li et al., 2008; Takehira et al., 2007). 2.8. VOC total decomposition Volatile organic compounds (VOCs) emitted from many industrial processes and transport vehicles signicantly contribute to atmospheric pollution, and the catalytic total combustion is one of the most effective and economically attractive treatments. Most catalysts contain noble metals, while recently transition metal mixed oxides have been examined as the cheaper alternatives that hopefully have similar activity. As multi-metal mixed oxides can be conveniently prepared from the LDH precursors, a few research groups are currently examining the catalytic performance of transition metal-containing LDH-based catalysts for the total combustion of some commonly encountered VOCs, such as toluene, methane and ethanol, as summarized below. The example reported by Dula et al. (2007) indicated that Mncontaining mixed oxide (MgAlMn-oxide) derived from Mn II incorporating MgAl-LDH was more active than that derived from MnO4-intercalated MgAl-LDH in combusting toluene in air. The higher activity of the former could be attributed to the fact that the surface Mn4+/Mn3+ species for redox are more readily accessible to the reactants on the surface of as-generated mixed oxide particles. The full replacement of Mg with Mn (and Co), as reported by Lamonier et al. (2007), led to a bit higher activity in total toluene oxidation, which is quite similar to the case over NiAl-LDH derived catalyst. The activity of the latter catalyst seems to be linearly dependent on the reducible amount of Ni in the catalyst (Mikulova et al., 2007). Recently, Jiratova et al. (2009) further reported that the best catalyst Co4MnAl-LDO found in their previous research (Mikulova et al., 2007) can be greatly improved in the activity for total catalytic oxidation of toluene through doping KNO3 (1 wt.% of K). The improvement is supposedly caused by the increase of alkalinity and reducibility of the catalyst. Similarly, total decomposition of ethanol is also dependent on incorporation of transition metal ions and their combination in the LDH structure. NiAl-LDO catalyst showed some activity (Mikulova et al., 2007), while CoMnAl-LDO has a much improved activity (Kovanda et al., 2006). For example, the temperature for 50% ethanol decomposition (T50) was about 240 C over NiAl-LDO while it was 170180 C over CoMnAl-LDO under similar conditions. A much greater improvement in ethanol decomposition has been gained again by doping KNO3, reducing T50 to 130140 C with 3 wt.% of K doped in the catalyst (Jiratova et al., 2009). Methane is a VOC which is a bit more difcult to oxidize due to its high inertness, and its complete oxidation, as examined over various LDO catalysts containing transition metals, occurs at much higher temperatures. For example, 50% methane decomposition occurred at 480490 C with 1% v/v methane in air at a GHSV of 30,000 h 1 over a Cu-containing MgAl-LDO catalyst (Tanasoi et al., 2009). It was also noted that the activity is dependent on the Cu loading, i.e. the reducible amount of Cu in the catalyst. Incorporating Co and Mn into the catalyst can improve the catalytic activity. For example, LDH-derived

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Cu1Co2Mn0.2Al0.8-LDO reduced T50 for methane oxidation to 429 C in a 1% v/v methane air stream at a GHSV of 60,000 h 1 (Cheng et al., 2008). 2.9. Photocatalytic decomposition Some metal-containing LDHs and derived LDOs are semiconductors, with the band gap normally ranging from 2.0 to 3.4 eV, and thus are potential photocatalysts using UV or solar light as the irradiation source. There are actually a number of efforts dedicated to investigating the photocatalytic properties of LDH-based catalysts and their possible applications in organic wastewater treatment. A few Zn-containing LDOs have been intensively examined for this purpose under UV light radiation. Seftel et al. (2008b) prepared four ZnAl-LDHs (Zn/Al = 1, 2, 3, and 4) that were converted to mixed ZnAl oxides after calcination at 300 and 500 C, with the band gap of ~3.2 eV. The higher Zn/Al ratio led to more ZnO being formed after calcination, and the corresponding mixed oxide absorbed more UV light and showed a higher activity for methyl orange (MO) decomposition under 365 nm UV light irradiation. In addition, the mixed oxides derived at 500 C while absorbing more UV light showed a higher degree of MO decomposition. These authors also investigated the photocatalytic decomposition of MO over ZnSn-LDO that seems to be a bit more active than ZnAl-LDO (Seftel et al., 2008a). On the other hand, Valente et al. (2009) investigated MgZnAl-LDO for photodegradation of 2,4-dichlorophenoxiacetic acid. MgZnAl-LDO with 5 wt.% of Zn showed the highest activity. The same research group prepared ZnAlFe-LDOs in the similar way, and found that the oxides have a much lower and narrower band gap (2.002.59 eV) (Mantilla et al., 2009). However, their photocatalytic activity seems similar to that of MgZnAl-LDO. In general, using LDO-based photocatalysts to remove organic compounds probably involves two consecutive processes. First, the organic compound (such as 2,4-DPA) is quickly adsorbed onto calcined MgZnAl-LDO during the LDO reconstruction; and secondly, the adsorbed organic compound is decomposed under UV light irradiation. In the rst process, reconstruction of the layer structure attracts anionic species (such as 2,4-DPA) or polar species (such as phenol), and thus facilitates adsorption, a prerequisite for its decomposition in the next step. As the solar light can be used as the energy source without any cost, so recently a number of efforts have been made to develop the solarlight driven catalysts for organic waste decomposition. An example was NiTi-mixed oxide derived from NiTi-LDH precursor after acid treatment (Shu et al., 2008). This NiTi-mixed oxide, a mixture of NiO and NiTiO3, had an activity much higher than P25 (a commercial photocatalyst product) under visible light irradiation for methylene blue decomposition. The activity is supposedly related to the content of NiTiO3 phase. Another example was ZnCr-LDH where Cr(III) moves the band gap to the visible light range, with two strong absorbance bands at 410 and 570 nm. Using AgNO3 as the sacrice electrode, this catalyst was able to decompose water and produce oxygen under visible light irradiation with a quantum yield up to 60% at 410 nm (Silva et al., 2009). Research conducted by Li et al. (2009) involved coating LDH particles onto magnetic Fe3O4 particle surface to form a core-shell structure. The calcined LDH/Fe3O4 composite particles were then immersed in W7O246 solution to load this POM during reconstruction of the LDH phase. This magnetic recoverable POM-LDH/Fe3O4 composite catalyst showed a high photocatalytic activity for hexachlorocyclohexane under the visible light emitted from high-pressure mercury lamp, and the activity was kept unchanged after cycling for 6 times. 2.10. Greenhouse gas abatement: DeNOx and DeSOx Emission of NOx (N2O, NO and NO2) and SOx (SO2 and SO3) into the atmosphere is directly responsible for various environment problems

including photochemical smog, acid rain, greenhouse gas effect and stratospheric ozone destruction that are harmful to plants, animals and the human health. Catalysis researchers and environmental scientists are endeavoring to explore efcient DeNOx and DeSOx technologies to meet the criteria of the strict emission regulations. In general, NOx can be removed from the lean-burn exhaust in three ways: (i) direct decomposition of NOx; (ii) selective catalytic reduction (SCR); and (iii) NOx storage and reduction (NSR). SOx is usually removed from the uid catalytic cracking (FCC) unit, the main individual source of SOx emissions, with the so-called SOx-transfer catalyst. Pioneering research using LDO to DeNOx and DeSOx has been reported by Corma and his colleagues (Corma et al., 1997; Palomares et al., 1999) who examined CuMgAl-LDO and CoMgAl-LDO catalysts in a simultaneous removal of NOx and SOx in the FCC unit. Direct decomposition of NOx (mainly N2O and NO) is thermodynamically favorable, occurring over various oxides and mixed oxides that can be prepared by thermal decomposition of the corresponding LDHs. As reviewed previously (Yu et al., 2009), a number of transition metal-containing LDOs were extensively investigated for this purpose. In recent years, more studies have been reported in this research area, including more types of transition metals in the system and revealing more detailed mechanisms of the relevant redox reactions. For example, the substitution of MgII or AlIII with NiII or MnII in Mg2AlLDOs, respectively, resulted in an increased catalytic activity for N2O decomposition (Obalov et al., 2006). However, catalyst Ni2Mn-LDO does not have such a high catalytic activity. While in the other research, Co4MnAl-LDO showed the highest catalytic activity, reaching 95% N2O decomposition at 450 C (Obalov et al., 2007). They ascribed this to the optimum metal composition and concentration on the catalyst surface. Doping K or Na into CoMnAl-LDO modied the acidbase function of the catalyst surface and enhanced the catalytic activity (Karskov et al., 2010; Obalov et al., 2009). However, the presence of O2, NO, NO2 or water vapor all inhibited N2O conversion (Obalov et al., 2006, 2008). Chang et al.'s (2006) work showed that the presence of CO increased the N2O destruction rate and eliminated the NO inhibition effect due to the scavenger role of CO and the direct CO involvement in the destruction of N2O. In addition, Yu et al. (2007a) found that CaCoAl-LDO and CaCoLaAl-LDO can directly decompose more than 50% of NO to N2 and O2 at 300 C. The process of selective catalytic reduction (SCR) selectively reduces NO with a reducing agent (for example, NH3 and hydrocarbons) in the presence of excess oxygen. Carja and Delahay (2004) tested the SCR of NO with NH3 over the mixed oxides derived from oxovanadate-pillared LDHs, and found that 7080% of NO was decomposed and the selectivity towards N2O was not more than 2%. The existence of Cu lowered the maximum conversion temperature from about 450 to 350 C. In other research, Carja et al. (2009) doped CeO2 onto the surface of a mixed oxide derived from Fe-LDH and improved the catalytic performance in the low temperature range. Wongkerd et al. (2008) utilized PW12O40- and SiW12O40-pillaredLDOs to reduce NO with NH3 with over 99% N2 selectivity in the test temperature range. Inclusion of Fe in LDH precursors in this case slightly enhanced the NO conversion while keeping similar N2 selectivity. On the other hand, using C3H6 and C3H8 as the reducing agent, Kumar et al. (2008) and He et al. (2008) obtained a high NO conversion over CuAl-LDO and CoAl-LDO, respectively, which is presumably ascribed to the active spinel phase (CuAl2O4 and CoAl2O4). NOx storage and reduction (NSR) is becoming a more popular catalytic technology to abate lean-burn NOx. There are a lot of alkaline-earth metal-based oxides extensively examined for this purpose, and quite a few LDOs show some promise in both storing and reducing NOx. For example, Yu et al. (2006) found that CoxMg3x/ Al-LDO with x = 2.5 stored a higher amount of NOx, and proposed that Co oxide facilitated NO oxidation to nitrites and nitrates that were then stably stored on Mg/Al oxide. In the next step, they substituted

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50% AlIII in Mg0.5Co2.5Al-LDHs with FeIII, MnIII, ZrIV, or LaIII to examine the effect of substitution on NOx NSR, and noted that LaIII enhanced both the storage and reduction of NOx (Yu et al., 2007a). In this system La2O3 is proposed to link the redox/storage region and lower the activation energies, making the whole process take place more smoothly (Yu et al., 2009). To further increase the NSR activity, they incorporated CaII instead of MgII and enhanced alkalinity of the system for nitrite and nitrate storage (Yu et al., 2007a). As a result, Ca2Co1AlLDO stored 0.43 mmol(NOx)/g (vs. MgCoAl-HT with 0.15 mmol(NOx)/ g) and Ca2Co1La0.1Al0.9-LDO 0.634 mmol(NOx)/g at 300 C (Yu et al., 2007b). The capture of SOx from the FCC unit is normally carried out through SOx transfer catalysts that are some mixed oxides, for which LDHs are the good precursors. For example, transition metal-containing MgAl-LDOs greatly enhanced the SOx storage capacity with an order of CuII N CoII N FeIII N CrIII (Polato et al., 2008). When MgII was partially substituted by MnII, SOx was found to be xed mainly as MgSO4 and MnSO4 (Polato et al., 2009). In the further research, incorporation of CeO2 into MnMgAl-LDO increased the regeneration efciency (from ~20% to 4050%), but decreased the SOx uptake efciency (from 56 to 3.5 4.5 mmol(SO2)/g) in 21 successive reactionregeneration cycles (Pereira et al., 2010). Cant et al. (2005) found that MgFe-LDO and MgAlFe-LDO were good catalysts for SO2 adsorption and reduction while incorporation of Ce did not improve the catalytic performance. In addition, CuAl-LDOs (Cu/Al=52) were able to capture a large amount of SOx (Centi and Perathoner, 2007). In general, SOx uptake probably undergoes chemisorptions, oxidation by transition metal ions and then a bulk diffusion as sulfate. In the case of CuAl-LDOs, Cu/Al ratio, Cu dispersion on the surface and the degree of sulfation all affected these processes. Similarly, the reductive efciency of sulfate (adsorbed SOx) in the catalyst is inuenced by both the nature of the transition metal and the reductive agent (such as propane and H2), as revealed in the report by Polato et al. (2008).

As schematically shown in Fig. 2, the catalytically active constituents of LDHs include hydroxide groups (weak base), metal ions (redox center), and anions in the interlayer that are all inherited in derived LDOs. Therefore, the alkalinity of hydroxide groups (Lewis base) or O groups in derived LDOs (Bronsted base) can be enhanced by incorporating the alkaline-earth metal ions, as demonstrated in DeNOx (Yu et al., 2007a). The other way to have a high alkalinity is by directly doping K2CO3, for example for C\N bond formation (Likhar et al., 2007). In addition, one can also intercalate basic anions to enhance the alkinility, such as F for C_C bond formation (Choudary et al., 2001b) and BuO for N-O bond formation (Choudary et al., 2004). Although an LDH is seemingly a weak base, intercalation of acidic anions (such as many POM anions) makes it simultaneously possess acidity, which has been well demonstrated in the epoxidation of various olens. Most interesting is the variation of transition metal ions in the brucite-like layer that enables LDHs to show a spread spectrum of catalytic activity for oxidation and reduction, which has been exemplied in the applications for total oxidation of VOCs, H2 production, DeNOx, DeSOx and CNT formation, as summarized in the corresponding sections. It is true that LDHs and LDOs are extensively explored for catalytic applications recently, with about 100 papers published each year, but most efforts have been made only in the systems with one or two active components. The synergic (coordination) interactions of two or more active components that contribute to the catalytic activity seem to lack a comprehensive understanding, which seems to be the prerequisite for the future rational design of more active LDH-based catalysts, particularly for applications in DeNOx, DeSOx, full oxidation of VOCs and steam reforming reactions for H2 production. Acknowledgement The authors wish to acknowledge the nancial support by the Australian Research Council for the discovery project (DP0879769) and from the Science and Technology Department of Zhejiang Provincial Government for the related collaborative research and development (Project no 2009C14G2020021). Dr Xu also acknowledges the support from the Australian Research Council for his Australian Research Fellowship. References
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3. Concluding remarks and perspectives As described in the previous sections, the catalytic applications of LDHs and LDOs make full use of the inherent properties of LDH materials. These properties include (1) a wide range of choice of MII and MIII (and MIV) cations; (2) an unlimited combination of MII and MIII with two or more types; (3) a free selection of anions; and (4) a nearly homogeneous distribution of cations in the brucite-like layers and anions in the interlayer spacing. Thus in principle, the catalytic activity of LDHs and LDOs can be well controlled by adjusting these properties.

Fig. 2. Functional groups in LDHs available for catalytic functions.

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