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com/locate/micromeso

**Microtextural properties of layered double hydroxides: a theoretical and structural model
**

Juan J. Bravo-Surez a

b

a,b

, Edgar A. Pez-Mozo c, S. Ted Oyama a

b,*

a Centro de Investigaciones en Catlisis, Escuela de Ingeniera Qumica, Universidad Industrial de Santander, A.A. 678, Bucaramanga, Colombia a ı ı Environmental Catalysis and Nanomaterials Laboratory, Department of Chemical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061-0211, USA c Centro de Investigaciones en Catlisis, Escuela de Qumica, Universidad Industrial de Santander, A.A. 678 Bucaramanga, Colombia a ı

Received 11 July 2003; received in revised form 14 October 2003; accepted 14 October 2003

Abstract In this paper, a theoretical method to estimate the textural properties of layered double hydroxides (LDHs) of the type [M2þ M3þ (OH)2 ][AnÀ ] is presented. The theoretical calculations are based on the structure and composition of the LDH, using 1Àx x x=n geometrical models of an LDH crystallite and the intercalating anion. Several examples of the application of this model to LDHs and pillared LDHs are shown. The estimated properties include the interpillar distances, the interlamellar and external areas, the interlamellar free volume, the fraction of external anions and the apparent and true density of the LDH. For well crystallized LDH samples, agreement between the estimated and the experimental results is found, for poorly crystalline samples, a correlation between the degree of crystallite agglomeration and the experimental areas is proposed. Ó 2003 Elsevier Inc. All rights reserved.

Keywords: Layered double hydroxides; Hydrotalcite; Textural properties; Theoretical model; Agglomeration

1. Introduction Among layered compounds, layered double hydroxides (LDHs) represent one of the most technologically promising materials because of their relative ease of preparation and broad uses as adsorbents, anion exchangers, catalysts and catalyst supports [1]. The LDHs can be described as layered compounds of brucite-like structure (Mg(OH)2 ), with positively charged layers due to a partial substitution of divalent M2þ metals by trivalent M3þ metals. Between the layers there are counter anions to balance the electrical charge and coordinating water molecules. LDHs are commonly represented by the general formula: [M2þ M3þ 1Àx x (OH)2 ]xþ (AnÀ ) Æ mH2 O, where M2þ and M3þ can be any x=n divalent and trivalent metal ions (with ionic radius similar to Mg2þ ), x is the metal ratio M3þ /(M2þ + M3þ )

Corresponding author. E-mail addresses: jbravo@vt.edu (J.J. Bravo-Surez), oyama@ a vt.edu (S. Ted Oyama). 1387-1811/$ - see front matter Ó 2003 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2003.10.003

*

and AnÀ is the interlamellar charge-compensating anion. The ﬂexibility of the LDHs to incorporate in their structure a variety of metals and anions has increased the interest in these materials. Special attention is being paid to LDHs with bulky and stable anions, i.e. polyoxometalates (POMs), since they can give rise to a wide range of microporous materials [2]. The speciﬁc surface area (SSA) of LDH compounds can range from a few m2 /g up to about 100 m2 /g. The synthesis method can have a great inﬂuence on the ﬁnal properties of the SSAs. Several factors may play a major role in determining the textural properties, such as the aging and hydrothermal treatments of LDH precipitates as well as the degasiﬁcation regimes used before measuring the adsorption–desorption isotherms [3]. Some examples of how the SSA changes with these parameters are given in Table 1 [3–6]. In general, in the case of small inorganic anions (carbonates, nitrates, chlorides, etc.) the chemical composition of the LDHs does not have a signiﬁcant eﬀect on the obtained SSAs. Although, in some cases, the use of mixtures of organic solvents and

some new structural and textural relationships can be readily obtained which are not possible with the models already published.6]. the charge of the LDH layers and the distribution of charges in the LDH [8]. none of them can be eﬃciently used to predict the textural properties of LDHs compounds by only taking into account structural and geometrical considerations. Cavalcanti et al. while pillared compounds must.15. assume spherical particles to estimate the SSAs of the LDHs [3. the models are sometimes dependent on experimental results. Although there exist in the literature several models to explain experimental ﬁndings such as the above. Recently.19 Synthesis T (K) 373 338 r. The thermal and chemical stability and the porosity are the features that distinguish a pillared compound from an intercalation compound.25 0. In this manner. Some LDHs pillared with POMs also show high SSAs [11. [14] studied the accessibility to the interlayer space of LDHs intercalated with ferri. even in these cases. an intercalation compound results from the insertion of guest species in the interlayer region of a layered solid. 338 338 Synthesis t (h) 36 18 30 30 30 0. then it is denominated a pillared compound.16]. When a layered compound is transformed into a thermally and chemically stable micro or mesoporous layered material. Some examples of calculations for several pillared LDHs are given. Bravo-Surez et al.10].5 0. Among the anions used as examples are the ferricyanate. giving rise to an increase in the basal spacing. the speciﬁc interlamellar area. In this latter study the SSA was calculated with a geometrical model based on the LDH unit cell. the speciﬁc interlamellar free volume. Other authors also related the experimental SSA results of some POM pillared LDHs with the areas estimated from the unit cell of the pillared compounds.5 SBET (m2 /g) 24 80 75 88 136 92 88 Comments Homogeneous precipitation by urea hydrolysis ±6 m2 /g after degasiﬁcation at 343.33 0. Degasiﬁcation at 353 K Drying overnight at 343 K and degasiﬁcation at 303 K for 10 h Drying overnight at 343 K and degasiﬁcation at 303 K for 10 h r. However.and ferrocyanate anions using a simple structural model based on the LDH unit cell.33 0. . Degasiﬁcation at 353 K Synthesized in H2 O/ethanol. / Microporous and Mesoporous Materials 67 (2004) 1–17 a Table 1 SSAs of several Mg1Àx Alx –CO3 LDHs [3–6] x 0. Contributions due to the edges of the brucite-like layers and due to the anions in the borders of these layers have been taken into account. Layered compounds can be classiﬁed into two types: intercalation compounds and pillared compounds. water can modify the superﬁcial texture of the ﬁnal LDH due to an aggregation eﬀect of the crystallites [3. their average particle diameter and the LDH composition. Most of these pillared LDHs have been reported in the literature [12]. High SSAs and microporous volumes have been attainable thus far only with hexacyanometal anions [9.t. These estimated theoretical properties include the speciﬁc external area.J. Keggin type POMs and the dicobaltatedecamolybdate anion. The interlayer spacings in pillared compounds should be at least one N2 diameter and the interlayer region must be accessible to molecules at least as large as N2 . According to IUPAC [7] rules. and the free interpillar distance (IPD) was estimated using data for the anionic exchange capacity of the LDHs and the experimental values of the micropore volumes. [8] made a theoretical evaluation of the microporosity present in LDHs pillared with the ferricyanate anion and Keggin type POMs.2 J. Nijs et al.12]. To overcome these limitations. and their number and distribution in the LDH layers. decavanadate. synthesized in H2 O/ethylenglycol. the micropore volume was calculated assuming pillars of cylindrical geometry. Very few examples can be found in the literature of pillared LDHs that possess relatively high micropore volumes. ¼ room temperature. Also.25 0. the present work describes a procedure for predicting several microtextural characteristics of LDH compounds based on only structural and geometrical considerations of the crystallites.t. The main advantage of this procedure is the ability to relate textural properties of samples with measurable properties of the LDH crystallites such as their average thickness (distance in the basal plane 0 0 l). and the interpillar free distance. Intercalation compounds do not necessarily possess stability and porosity.25 0. These last two characteristics depend on the pillar charge.23 0. the experimental microporous surface areas are smaller than the theoretical values expected from calculations using the layer spacing and the charge density of the anions [13]. especially when compared to the pillared compounds obtained from cationic clays. the apparent and true density. r. in some cases. are restricted to a limited range of compositions or. r. Degasiﬁcation at 353 K Heating at 373 K in air for 16 h.t.t. The porosity in the pillared LDHs can be inﬂuenced by several factors among which the most important are the dimensions of the anionic pillars. 378 or 453 K or calcination at 513 K Heating at 373 K in air for 16 h.

2 and 3 show respectively. Fig. a hexagonal geometry for the brucite-like layers is used. 5 shows the schematic arrangement of equally spaced pillars on the surface of a brucite-like layer. [Mg0:66 Al0:33 ][CO3 ] ¼ 0. as shown in p Fig. Therefore.308 nm. among others.308 nm. the thickness of a brucite-like layer (lb ) and the interlayer spacing (h). assuming a hexagonal geometry. the number of brucite-like layers (m). In the present work an average value of 0. [Zn0:75 Al0:25 ][Cl] ¼ 0. where a represents the mean distance between OH groups on the same side of the layer. the number of metallic octahedra present in a brucite-like layer (NMb ) is given by the ratio Fig. Many authors have reported values of a for several LDHs [17–19]. Expanded schematic view of the layers of an LDH crystallite. lb $ 0:48 nm. for example: [Mg0:75 Fe0:25 ][CO3 ] ¼ 0. Fig.304 nm. A model for an LDH crystallite is shown in Fig. Schematic view of equally spaced pillars on a brucite-like layer. Scanning electron micrograph of a [Mg0:66 Al0:33 ][OH] LDH.J. 2 and 3.312 nm.311 nm. 2. [Zn0:66 Cr0:33 ][Cl] ¼ 0. 2. where IPD is the mean interpillar distance and dp is the mean pillar diameter. IPD dp Fig. The top view area of each octahedron in an LDH layer (AEO ).310 nm is used for all the calculations.J. LDHs com1Àx x x=n monly form hexagonal-shaped crystals as seen in Fig. 4. can be calculated by the formula: AEO ¼ a2 3=2.48 nm. Bravo-Surez et al. 2. Therefore. . thickness of layer $0. Schematic side view of a brucite-like layer. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 3 2. Interpillar free distance The variables for an LDH crystallite include the mean diameter (dc ). Fig.1. The location of the metallic octahedra in an LDH layer can also be seen in Figs. Theoretical calculations All theoretical calculations are based on the general LDH formula: [M2þ M3þ (OH)2 ]xþ [AnÀ ]. Based on Fig. Schematic top view of a brucite-like layer. 1. for the calculations of the textural properties. Although the lattice of pillars is likely to be commensurate with the underlying hexagonal array of LDH octahedra. the layer area of an octahedral unit (AEO ) is 0. a $ 0:31 nm. [Mg0:75 Al0:25 ][CO3 ] ¼ 0. 3. the derivations provided below do not make this assumption. 5. Fig. the schematic top and side view of an LDH crystallite layer of mean diameter (dc ). 1. Figs. the thickness (lc ). 4.083 nm2 . 2.306 nm and [Mg0:80 Al0:20 ][CO3 ] ¼ 0.

AWOHÀ and AWAnÀ are the atomic weights of the M2þ . M3þ . respectively. (3). Speciﬁc areas The two pillar geometries of cubic and cylindrical shape are also used in the calculations of the speciﬁc external and interlamellar areas. dp is the equivalent pillar diameter and h is the pillar height. and m is the number of brucite-like layers in the LDH crystallite. as calculated for the cubic and cylindrical models. respectively. . which is calculated by the following formula: MWC ¼ ½ð1 À xÞAWM2þ þ ðxÞAWM3þ þ ð2ÞAWOHÀ þ ðx=nÞAWAnÀ NMb m=NAV ð5Þ where AWM2þ . where x is the metal ratio M3þ /(M2þ + M3þ ) and n is the charge of the interlayer anion. Cubic pillar model. The areas of the pillars 2 are easily calculated as 2dp þ 4dp h for a cubic pillar and 2 2p½ðdp =2Þh þ ðdp =2Þ for a cylindrical pillar. Total speciﬁc interlamellar area All of the properties calculated per unit weight need the molecular weight of the LDH crystallite (MWC). respectively. are given in Table 2.4 J. It can be easily demonstrated that the number of interlamellar pillars in the crystallite borders is given p by ð2 3dc Þ=ðdp þ IPDÞ. and the pillar diameter (dp ) needs to be obtained. Therefore. since the result is the total number of pillars per brucite-like layer. Here. 5 is a conventional cell. Cylindrical pillar model. Yb ¼ area of brucite layer area accommodating a single pillar p 2p 2p ¼ ðdc 3=2Þ=½ð1=3Þð 3ðdp þ IPDÞÞ 3=2 Fig. dp ¼ pillar diameter. the total speciﬁc interlamellar area (TIA) based on cubic pillars is given by: TIAcub ¼ ðm À 1Þ 2 2 3dc À 2Yb dp þ 4Yb dp h i. and the composition (x) and dimensions of the LDH crystallite (dc ) are known. 4. and IPD ¼ interpillar distance. a It has been assumed that the contribution to the external surface area due to the interlamellar pillars in the crystallite borders is dp h and pðdp =4Þh for cubic and cylindrical pillars. In order to calculate the IPD.48 nm). Therefore. OHÀ and AnÀ . All of the diﬀerent contributions to the total interlamellar area (TIA). 6. With respect to Fig. the number of pillars per LDH layer (Yb ). p À dp hð2 3dc Þ=ðdp þ IPDÞ MWC hp ð7Þ Table 2 Contributions of layers and pillars to the total interlamellar area in an LDH crystallite Contribution +LDH layers )Interlamellar pillars +Interlamellar pillars )Interlamellar pillars in the crystallite bordersa Cubic pillar p 2 3ðm À 1Þdc 2 2ðm À 1ÞYb dp 4ðm À 1ÞYb dp h p ðm À 1Þdp hð2 3dc Þ=ðdp þ IPDÞ Cylindrical pillar p 2 3ðm À 1Þdc 2pðm À 1ÞYb ðdp =2Þ2 2pðm À 1ÞYb ðdp =2Þh p ðm À 1Þpdp ðh=4Þð2 3dc Þ=ðdp þ IPDÞ m ¼ number of brucite-like layers in a crystallite. For this purpose the ratio between the area of a brucite-like layer and one-third the area of the hexagonal unit cell as given in Fig. 5 is used. m can be calculated by: m ¼ lc =ðlb þ hÞ ð6Þ where lc and lb are the crystallite and brucite-like layer thickness ($0.1. and the actual unit cell is a rhombohedron of one-third the hexagon area containing a single pillar. 2. 6 and 7. respectively.2. ð3Þ The factor of one-third appears because the hexagonal cell in Fig. Using Eq. NAV is Avogadro’s number.023 · 1023 . 2. 6. Yb ¼ number of pillars per layer. h ¼ pillar height.2. AWM3þ . / Microporous and Mesoporous Materials 67 (2004) 1–17 a 2p 3=2) between the area of a brucite-like layer (dc p and the layer area of an octahedral unit (AEO ¼ a2 3=2): NMb ¼ ðdc =aÞ 2 ð1Þ Assuming electroneutrality in the LDH. the number of pillars per LDH crystallite layer (Yb ) is: Yb ¼ x Á NMb =n ð2Þ Fig. the IPD can be calculated if the geometry. Bravo-Surez et al. a relationship between the IPD and the mean diameter of the LDH layer (dc ). These two models can be seen in Figs. 7. dc ¼ mean diameter of a crystallite.J. the IPD is calculated by: p IPD ¼ ðdc = Yb Þ À dp ð4Þ In the present study cubic and cylindrical geometries for the pillars are used. dimensions (dp ) and charge of the pillars (n).

/ Microporous and Mesoporous Materials 67 (2004) 1–17 a 5 And the total speciﬁc interlamellar area for cylindrical pillars is: hp 2 2 TIAcyl ¼ ðm À 1Þ 3dc À 2pYb ðdp =2Þ þ 2pYb ðdp =2Þh i.3.2. lb ¼ brucite-like layer thickness. complex anions are shown. In columns A and B two diﬀerent arrangements of the anion in the interlamellar region are illustrated. p XAE ¼ ½ð2 3dc Þ=ðdp þ IPDÞðm À 1Þ þ Yb 100=ðYb mÞ ð15Þ ADc ¼ MWC=ðlc dc 2p And the total speciﬁc external area for cylindrical pillars is: Âp 2 p TEAcyl. the apparent density (ADc ) and the true density of the LDH crystallite (TDc ).J. and dp ¼ pillar diameter.min ¼ hp p p 2 3dc þ 2 3mdc lb þ ðm À 1Þdp hð2 3dc Þ i ð10Þ =ðdp þ IPDÞ =MWC Table 4 Contributions of layers and pillars to the total interlamellar free volume in an LDH crystallite Contribution +LDH layers )Pillar Cubic pillar p 2 ðm À 1Þhdc 3=2 2 Yb ðm À 1Þhdp Cylindrical pillar p 2 ðm À 1Þhdc 3=2 pYb ðm À 1Þhðdp =2Þ2 m ¼ number of brucite-like layers in a crystallite.2.1. Finally. The structures of these anions are shown in Table 5 [20–23]. the total speciﬁc external area (TEA) minimum and maximum based on cubic pillars is: hp p 2 TEAcub. h ¼ pillar height. and the true density is the mass of the crystallite divided by its volume excluding pores. Column C shows the top view of the structure shown in column B with a calculated area. Yb ¼ number of pillars per layer. 2p 2 TIVcub ¼ ðm À 1Þhðdc 3=2 À Yb dp Þ=MWC ð13Þ And the total interlamellar free volume for cylindrical pillars is: 2 2p TIVcyl ¼ ðm À 1Þhðdc 3=2 À pYb ðdp =2Þ Þ=MWC ð14Þ Other variables of interest that can be calculated are the molar percent of anions in the external surface of the LDH crystallite (XAE ).max ¼ 3dc þ 2pYb ðdp =2Þh þ 2 3mdc lb p þ ðm À 1Þpðdp =4Þhð2 3dc Þ Ã =ðdp þ IPDÞ =MWC ð11Þ TEAcyl. are given in Table 3. dc ¼ mean diameter of a crystallite. Bravo-Surez et al. 2. p À pðdp =4Þhð2 3dc Þ=ðdp þ IPDÞ MWC ð8Þ 2. dp ¼ pillar diameter. Estimated microtextural properties of several intercalated LDH materials In this section some examples of the estimated microtextural properties of several LDHs intercalated with various large. h ¼ pillar height.min ¼ Âp p þ ðm À 1Þpðdp =4Þhð2 3dc Þ Ã =ðdp þ IPDÞ =MWC p 2 3dc þ 2 3mdc lb 3=2Þ ð16Þ ð17Þ 2p TDc ¼ MWC=ðlc dc 3=2 À TIV Á MWCÞ ð12Þ 3.2. as calculated for the cubic and cylindrical models. m ¼ number of brucite-like layers in a crystallite. and IPD ¼ interpillar distance. The total interlamellar free volume (TIV) based on cubic pillars is calculated by the following equation: Table 3 Contributions of layers and pillars to the total external area in an LDH crystallite Contribution +LDH layers )External pillar +External pillar +Layer edges +Interlamellar pillars in the crystallite borders Cubic pillar p 2 3dc 2 Yb dp 2 Yb dp þ 4Yb dp h p 2 3mdc lb p ðm À 1Þdp hð2 3dc Þ=ðdp þ IPDÞ Cylindrical pillar p 2 3dc pYb ðdp =2Þ2 pYb ðdp =2Þ2 þ 2pYb ðdp =2Þh p 2 3mdc lb p ðm À 1Þpdp ðh=4Þð2 3dc Þ=ðdp þ IPDÞ dc ¼ mean diameter of a crystallite. . All of the contributions to the total external area. Yb ¼ number of pillars per layer.max ¼ 3dc þ 4Yb dp h þ 2 3mdc lb i p þ ðm À 1Þdp hð2 3dc Þ=ðdp þ IPDÞ =MWC ð9Þ TEAcub.J. The apparent density is deﬁned as the mass of the crystallite divided by its volume including open pores. Total speciﬁc interlamellar free volume The layer and pillar contributions to the interlamellar free volume for cubic and cylindrical pillar geometries are given in Table 4. Total speciﬁc external area The calculations are similar to the ones in Section 2.

4. the calculations of the textural properties of the intercalated materials are easily obtained by applying the already described equations: the IPD with Eq.26].6 J. All of these properties are shown in Tables 6–11. the total interlamellar area (TIA) with Eqs. (4). (13) and (14). Interpillar distances An expression that relates the number of pillars per brucite-like layer (Y ). for pillars with similar geometry and dimensions but diﬀerent charges. (5). (19) reduces to: p IPD ¼ 0:310 ðn=xÞ À dp ð19Þ Eq. the molar percent of anions in the external surface of the LDH crystallite (XAE ) with Eq. (15). In the determination of the anion base for a given model. In order to convert the values of the textural properties expressed per unit weight. (4). for a cylindrical model the ferricyanate anion has the following dimensions: dp ¼ 0:729 nm and h ¼ 0:644 nm. a Based on the anion structural information given in Table 5. The experimental textural properties of some LDHs and pillared LDHs are shown in Tables 12 and 13 [12. the following conversion factor is used: MWC=ðNMb Á mÞ. Bravo-Surez et al.25. Discussion 4. For the results in Tables 6–9. the mean diameter of the LDH layer (dc ) and the pillar diameter (dp ) with the IPD has been obtained by relating the area of a hexagonalshaped brucite-like layer with a hexagonal conventional cell area. (7) and (8). the LDH composition (x) and the equivalent pillar diameter (dp ). A simpler equation is attained by substituting Eqs. This relation is given by Eq. For instance.J. (13) and (14).e. using the product TIV Æ MWC. In the case of the meixnerite-like LDH (LDH-OH) an ionic radius of 0. the total external area (TEA) with Eqs. Some examples of the textural properties per unit charge of the LDH are given in Table 6. the apparent density (AD) and true density (TD) with Eqs. / Microporous and Mesoporous Materials 67 (2004) 1–17 a Table 5 Structures of diﬀerent anions that can be pillared in LDHs [20–23] Anion Phosphotungstate i. in units of charge of the LDH. (1) and (2) into Eq. Therefore. In general.135 nm is used for the OHÀ group [24]. [PW12 O40 ]3À h ¼ 1:11 nm h ¼ 1:03 nm A $ 1:014 nm2 A B Ca Decamolybdodicobaltate [H4 Co2 Mo10 O38 ]6À h ¼ 1:07 nm h ¼ 0:80 nm A $ 1:052 nm2 Decavanadate [V10 O28 ]6À h ¼ 1:03 nm h ¼ 0:71 nm A $ 0:761 nm2 Ferricyanate [Fe(CN)6 ]3À h ¼ 0:72 nm h ¼ 0:64 nm A $ 0:417 nm2 Contributions due to the ionic radius of the terminal atoms and also of the atoms present in the borders of the anion structure have been taken into account in the calculations of the top view area. (16) and (17). Eq. the total interlamellar free volume (TIV) with Eqs. and for a cubic model the dimensions are: dp ¼ 0:646 nm and h ¼ 0:644 nm. the LDH crystallite dimension (dc Â lc ) has been estimated as 200 nm · 20 nm. (4): p IPD ¼ a ðn=xÞ À dp ð18Þ For a ¼ 0:310 nm.1. (9)–(12). it is expected . (19) is a simple relationship that shows the dependence of the IPD with variables such as the pillar charge (n). respectively. the anion height based on the arrangement in column B of Table 5 has been used. and the absolute total interlamellar free volume (TIV) of the crystallite with Eqs. the area of the anion viewed normal to the basal plane (top view) shown in column C of Table 5 is utilized.

25 0.0 67.012 11.348 12.538 2.49 0.4 84.191 0.125 0.6 67.163 [PV2 W10 O40 ]5À [PW11 Fe(H2 O)O39 ]4À [PW12 O40 ]3À [H4 Co2 Mo10 O38 ]6À [V10 O28 ]6À [Fe(CN)6 ]3À [CO3 ]2À [OH]À x ¼ M3þ =ðM2þ þ M3þ ).689 0.136 0.004 1.25 1.57 0.088 0.2 85.051 0.403 13.744 14.1 637.4 43.428 13.0 101.002 0.94 0.011 0.059 0.3 746.175 0.174 0.59 0.171 TIVc · 1016 (cm3 ) 2.150 0.426 1.210 0.463 13.7 1779.35 0.35 0.15 0.5 109.8 1530.15 0.678 1.2 49.796 12.049 )0. Bravo-Surez et al.8 37.0 98.6 91.46 0.632 2.426 1.304 0.355 9.8 66.138 0.9 842.38 0.06 0.7 87.175 0.25 0.025 2.859 2.678 0.41 0.15 0.171 0.0 86.231 0.38 TIA (nm2 /eþ ) 0.029 0.15 0.123 0.725 8.5 96.167 0. from Table 6.63 0. where the predicted order of IPDs is the following: [PW 11 O 39 ] 7À > [PV 2 W 10 O 40 ] 5À > [PW 12 O 40 ] 4À > [PW12 O40 ]3À .3 38.004 0.06 0.024 )0.7 64.002 0.077 0.7 90.138 0.231 0.8 1176.1 69. the IPD of the [Mg0:75 Al0:25 ][V10 O28 ]6À (0.730 2.9 105.066 1.145 0.015 Heading descriptions as in Table 6. and MWC ¼ molecular weight of crystallite.5 96.028 TEAmax (nm2 /eþ ) 0.152 TIVc · 1016 (cm3 ) 3.675 2.5 1090.063 0.0 98.255 0.0 87.78 0.058 0.9 TIV (cm3 /g) 0.294 1.7 46.931 12.3 113.7 930.J.25 0.15 0.38 0.888 17.8 59.29 TIA (m2 /g) 1012.313 0.4 56.46 0.2 TEAmin (m2 /g) 74.04 0.409 16.5 152. TEAmax ¼ total external area maximum.8 30.092 )0.725 1.15 0.029 0.65 0.49 0.066 2.2 1855.3 868.8 782.099 0.838 10.060 0.2 1561.26 0.294 2.849 2.4 111.673 1.9 797.047 0.65 nm) is larger than the IPD of the [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ]6À (0.38 0.221 0.0 63.097 0.12 0.024 )0.015 1.38 0. TEAmin ¼ total external area minimum. pillars with the same charge will show an inverse IPD trend. IPD ¼ interpillar distance. duly following an inverse .10 0.63 0.2 1696.049 1.8 30.6 46.15 0.23 0.3 651.038 TIV (nm3 /eþ ) 0.078 1.137 10.1 72.102 1.141 9.779 TEAmin (nm2 /eþ ) 0.9 138.J.312 17.25 0.332 1.037 0.119 0.948 18.0 1596. Table 7 Estimated textural properties per unit charge (eþ ) of a Mg0:75 Al0:25 LDH intercalated with diﬀerent anions using a cubic pillar model and crystallite dimensions of 200 nm · 20 nm Anion [PW11 O39 ]7À [PV2 W10 O40 ]5À [PW11 Fe(H2 O)O39 ]4À [PW12 O40 ]3À [H4 Co2 Mo10 O38 ]6À [V10 O28 ]6À [Fe(CN)6 ]3À [CO3 ]2À [OH]À IPD (nm) 0.284 1.678 2.049 )0.078 1.8 1737.028 21.849 1.072 TIV (cm3 /g) 0.35 0.9 91.23 0. TIVc ¼ total interlamellar volume of crystallite.059 0.180 0.864 11.075 )0.805 0.2 107.892 1.35 0.9 81.848 MWC · 1016 (g) 10.064 0.35 IPD (nm) 1.099 0.74 0. In this case.003 9. This trend can be observed in Table 6 for the intercalated anions with Keggin geometry. the larger the diameter the smaller the IPD.145 0.104 0.6 937.4 721.8 97.8 62.118 0.4 83.25 0.7 102.2 54.181 2.210 0.9 79.265 0.678 )0. TIA ¼ total interlamellar area. Another variable that aﬀects the IPDs is the equivalent pillar diameter.160 0.49 nm).745 26.25 0.35 0.15 0.773 0.118 0.073 0. For example.481 2.7 1089.43 0.15 0.542 20.7 83.045 0.794 2.138 0.16 0.35 0.25 0.43 0.32 0.793 12.329 0.173 2.4 74.7 718.3 95.5 1927. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 7 Table 6 Estimated textural properties of a Mg1Àx Alx LDH intercalated with diﬀerent anions using a cubic pillar model and crystallite dimensions of 200 nm · 20 nm Anion [PW11 O39 ]7À x 0.7 93.0 62.2 839.884 0.1 1298.0 TEAmax (m2 /g) 110.0 162.25 0.25 0. TIV ¼ total interlamellar volume.35 0.9 1772.794 1.429 11.72 0.65 0.140 0.38 0. that those with the highest anion charges will show the largest IPD values.198 26.

2 31.25 0.6 17. using an ideal structural model of the unit cell.86 2.30 1.9 797.678 0.4 728.83 2.3 102.55 9.138 0.4 721.77 5.7 1788.9 59.8 37.7 27.016 0.51 and 0.12 7.24 0. [8] reported some IPD results for [Mg1Àx Alx ][Fe(CN)6 ]3À .35 AD (g/cm3 ) 1. The results of IPDs for the [Mg1Àx Alx ][Fe(CN)6 ] LDH obtained in the present study are similar to those reported by several authors.0 83.35 and 0.1 26.49 4.16 4.321 1.45 IPD (nm) 0.49 0.00 2.002 0.15 0.9 673.5 TIV (cm3 /g) 0.78 2.415 2. TIV ¼ total interlamellar volume. TEAmax ¼ total external area maximum.2 69. TEAmin ¼ total external area minimum.143 0.01 TD (g/cm3 ) 1.58 1.0 50.8 118. The estimated IPDs using Eq.4 38.51 3. TIA ¼ total interlamellar area.2 48.0 TIV (cm3 /g) 0.48 9.426 1.59 nm for the cylindrical and cubic pillar model.13 8.3 64.6 TEAmax (m2 /g) 95.632 )0.86 6.09 3.4 991.01 2.8 1621.99 2.93 3.434 3.55 1.2 TEAmin (m2 /g) 264.86 3.6 67. It is easily deduced from Eq.41 0.7 1505.35 0.7 106.25 0.264 0. Table 10 Estimated textural properties of a [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ]6À LDH with variable crystallite thickness (lc ) using a cubic pillar model and crystallite dimensions of 200 nm · lc lc (nm) 5 10 15 20 25 30 35 40 50 100 IPD (nm) 0.2 81.851 2.50 0.3 84.49 TIA (m2 /g) 669.42 9.16 0.7 912.231 0.210 0.8 71.09 16.98 1.4 87.679 1.54 0.294 2.9 971.74 AD (g/cm3 ) 2.84 2.6 46.0 89.46 3.142 0.761 nm2 < 1. / Microporous and Mesoporous Materials 67 (2004) 1–17 a Table 8 Estimated textural properties of a Mg0:75 Al0:25 LDH intercalated with diﬀerent anions using a cylindrical pillar model and crystallite dimensions of 200 nm · 20 nm Anion [PW11 O39 ]7À [PV2 W10 O40 ]5À [PW11 Fe(H2 O)O39 ]4À [PW12 O40 ]3À [H4 Co2 Mo10 O38 ]6À [V10 O28 ]6À [Fe(CN)6 ]3À [CO3 ]2À [OH]À IPD (nm) 0.4 TEAmin (m2 /g) 63.8 TIV (cm3 /g) 0. (19) that for a given anion the smaller the value of LDH charge (x) the larger the IPD. Table 9 Estimated textural properties of a [M2þ Alx ][PV2 W10 O40 ]5À LDH using a cubic pillar model and crystallite dimensions of 200 nm · 20 nm 1Àx M2þ Mg x 0.49 0.7 83.4 966.91 9.35 TIA (m2 /g) 808.78 2.35 0.49 0.171 TIVc · 1016 (cm3 ) 2.221 0.68 9.7 77.7 40.018 10.91 9. Nijs et al.79 1.064 1.5 28. For example.10 )0.7 978.905 3.81 1.169 XAE (%) 35.87 1.098 0.80 2.849 2.45 3.7 136.134 0.16 0. as it is seen in the examples of Table 6.88 AD (g/cm3 ) 1.35 10. (19) are 0.4 741.052 nm2 ).55 9.60 3.015 TIVc · 1016 (cm3 ) 2.725 1.42 2.6 144.49 0.57 9.24 3. the eﬀect of the LDH metal ratio x ¼ M3þ =ðM2þ þ M3þ Þ on the IPDs can be analyzed.725 1.0 77.176 0.5 564.8 TEAmax (m2 /g) 105.94 1.099 0.5 84.99 3.82 2.9 84.415 XAE (%) 10.85 Heading descriptions as in Tables 6 and 8.049 )0.078 1.35 0.78 0.94 1.099 0.49 0.175 0.085 0.34 2.6 87.377 2.89 1.1 625.45 0.9 650.70 TD (g/cm3 ) 3.3 46.4 30. [14].75 6.4 36.63 5. XAE ¼ molar fraction of external anions.014 XAE (%) 10.962 5.144 0.45 nm among anions in the [Mg0:75 Al0:25 ][Fe(CN)6 ]4À LDH.88 Zn Heading descriptions as in Tables 6 and 8.6 1109.64 2.02 TIA (m2 /g) 930.678 0.2 53.32 9. the IPDs for .7 209.49 0.138 0.14 3. respectively.026 )0.71 7.15 0. Bravo-Surez et al.13 3.75 2.54 11.4 32.5 869.01 2.2 951.7 96.145 0.46 2. TIVc ¼ total interlamellar volume of crystallite.07 0.026 )0.96 1.792 1.3 33.7 93.24 5.8 91.7 TEAmax (m2 /g) 478.78 0.38 0.4 647.49 0.3 60.91 9.141 0.140 0.3 TEAmin (m2 /g) 56.9 685.8 J. For instance.11 TD (g/cm3 ) 2.8 97.49 0.632 )0.40 IPD ¼ interpillar distance.68 3.4 44. estimated minimum and maximum distances of 0. relation with the occupied anion areas (0.029 )0. Similarly.70 2.1 58. Cavalcanti et al.146 TIVc · 1016 (cm3 ) 0.54 2.64 2.23 2.83 3.49 0.36 1.77 3.83 2. and TD ¼ true density.J.793 2.24 3.127 0.38 0.0 82.4 860. AD ¼ apparent density.35 0.4 41.3 960.8 937.57 9.02 0.

20 nm.0 65.1 3.49 0.93 9.35 and 0.9 937.31 7.29 nm. the intercalated fraction (IF): Yb ¼ IF Á x Á NMb =n.6 1.3 2.160 7.2 938.64 2.138 TIVc · 1016 (cm3 ) 0. there must be other compensating anions to reach electroneutrality in the LDH.9 71. x ¼ 0:25 and 0.94 TD (g/cm3 ) 2.138 0.849 4. measured from a ﬁgure in the original reference).5 109.138 0.26] LDH-A Mg0:75 Al0:25 –CO3 Mg0:75 Al0:25 –CO3 Mg0:80 Al0:20 –CO3 Mg0:80 Al0:20 –CO3 Mg0:86 )Al0:14 –CO3 Mg0:86 )Al0:14 –CO3 Mg0:75 Al0:25 –NO3 Mg0:75 Al0:25 –NO3 Mg0:75 Al0:25 –NO3 Mg0:75 Al0:25 –NO3 Mg0:75 Al0:25 –NO3 Mg0:75 Al0:25 –NO3 Method MW MW MW MW MW MW HT HT HT US US US Treatment time (min) 0.0 11.5 TEAmin /SBET 1. respectively. Bravo-Surez et al.5 SBET a (m2 /g) 80 85 50 90 15 95 2.94 1.5 10 0.5 114.116 0. in agreement with Drezdzon’s results.49 0.2 TEAmax (m2 /g) 124. respectively (read from a graphic in the original reference).44 nm for the cubic pillar model and 0.7 162.040 1.43 and 0.138 0.8 66.49 0.50 0.J. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 9 Table 11 Estimated textural properties of a [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ]6À LDH with variable crystallite mean diameter ðdc Þ using a cubic pillar model and crystallite dimensions of dc · 20 nm dc (nm) 50 75 100 150 200 300 400 500 1000 IPD (nm) 0.0 TIV (cm3 /g) 0.65 7.16 AD (g/cm3 ) 1.3 18.5 10 10 60 600 5 30 60 lc (nm) 13.8 1. the IPD is given by: p IPD ¼ 0:310 ðn=ðIF Á xÞÞ À dp ð20Þ Eq. and if the obtained . From Table 6 or using Eq. the estimated IPD is 0.89 7.49 TIA (m2 /g) 925.64 2.2 82. The IPD values for the cylindrical model are 0. One way to facilitate this is by introducing in Eq. These mixed interlayer anions also aﬀect the textural properties by modifying the molecular weight of the crystallite. TEAmin ¼ total external area minimum.1 20.26 nm.8 10. a Samples of MgAl–NO3 were dried at 423 K for 5 h before BET analysis.9 9.J. (19).64 2.9 2.4 69. For this.2 56.3 TEAmin (m2 /g) 81. Table 12 Experimental textural properties of some LDHs [25.2 180.5 15. the anions average charge can be calculated by nave ¼ ½Rðyi =ni ÞÀ1 and dpave is lower or equal to Rðyi Á dpi Þ.6 118.94 1.5 102.94 1. for the cubic pillar model.64 2.7 71.3 1. Drezdzon [15] estimated that the IPD is large enough to accommodate water molecules ($0. although the presence of diﬀerent anions in the interlamellar region may not be thermodynamically favored [27]. (20) indicates that if the pillars are uniformly distributed along the layers of the LDH crystallite layers.32 13.35 are about 0.55 9.0 99. the IPD can be estimated by introducing a new term in Eq.51 0.3 140.64 Heading descriptions as in Tables 6 and 8.40 and 0.3 0. The IPD values estimated in this work and shown in Table 6. The analysis of IPDs of mixed interlayer anions is complex.2 97.12 8.49 0.1 134.9 9. In some cases the 100% intercalation of pillars is not possible.6 104.2 lc ¼ crystallite thickness.14 11.64 2.0 9.94 1.5 98.2 144.260 0.395 11.2 935.1 939. Using idealized models of the unit cell for a [Mg0:66 Al0:33 ][V10 O28 ]6À LDH. If yi is the molar ratio of the ith anion with charge ni .94 1. SBET ¼ area BET.8 1.8 61.94 1.7 933.50 0.4 7.5 10 0. b Assumed crystallite mean diameter (dc ) of 150 nm and cubic anion model.220 XAE (%) 16.2 7.7 55.4 9. and US ¼ ultrasound.138 0.64 2. HT ¼ hydrothermal at 363 K.138 0.555 46. are 0. For samples of MgAl–CO3 no data on the treatment before BET analysis were reported.5 939.5 930.5 940.94 1. the IPDs will be larger when the intercalated fraction is smaller.7 89.2 8.3 15.8 87. With this change. (2).5 54.5 96.6 7.1 124. (4) the concepts of anions average charge (nave ) and diameter (dpave ).7 53.5 48.138 0.9 162.33 nm for the cylindrical pillar model.6 72. it should not be forgotten that in the cases where IF < 1 for the anion of interest. In practical terms. the prediction of IPDs in the LDHs can be used to know in advance if the synthesis of a pillared material is feasible or not. MW ¼ microwave.94 1.7 TEAmin b (m2 /g) 100.8 59.138 0.138 0. respectively.18 nm. However.64 2.462 1.64 2.49 0.

3 177.28 0.30 0.25 0.39 0. Hui et al.110 0.26 0.34 0.4 82.i . h m varies between 7 and 11 (lc ¼ 7:8 À 12:3 nm).016 IPDb (nm) 0. e Degasiﬁcation at 423 K for 16 h under vacuum.5 300.008 0.3 177.9 62.35 SBET (m2 /g) 73 58 294 438 367 254 173 47 45 63 166 136 123 98 lPVc (cm3 /g) 0. On the other hand.047 0.004 0. f [Mg1Àx Alx ][Fe(CN)6 ]3À e. e.152 0. Based on merely geometrical and structural arguments. elemental analysis and powder XRD. However.3 69.03 0.2 213.0 645.090 0. the best microporosity results should be obtained at small values of x. f Assumed crystallite dimensions of 150 nm · 10 nm.33 0.2 TEAmax (m2 /g) 215. d Synthesis by anion exchange with a slurry of LDH–NO3 recently synthesized. These dimensions can vary and are mainly functions of the synthesis method and the hydrothermal treatments given to the LDH.21 0.7 77.3 600.110 0.9 180.3 308. [28] reported the synthesis of the [Zn0:68 Al0:32 ][PW12 O40 ]3À LDH.231 0.032 0. i Synthesis by anion exchange with an LDH–terephthalate (prepared by anion exchange with an LDH–NO3 ). the presence of a mixture of [PW11 O39 ]7À and [PW12 O40 ]3À can be a plausible explanation of the results.5 74.7 190.1 114. k m varies between 5 and 8 (lc ¼ 7:6 À 12:1 nm). as shown in Table 6.3 197.9 347. A typical dimension of an LDH crystallite described by several authors is 200 nm · 20 nm [12].25 0.5 618.031 0.008 )0. the IPD of this material results in a negative value ()0.048 0. j Degasiﬁcation at 393 K for 12 h under vacuum.17 TIA (m2 /g) 1045.40 0.10 0.18 0.140 0. Hence.k Heading description as in Table 6. In the case of the cubic pillar model some results are shown in Table 6. With all these conditions fulﬁlled.8 177.077 0.45 0.121 0. carbonate and hydroxyl) in LDHs have been estimated. the external and interlamellar areas of several intercalated anions (POMs.06 nm).h xi a 0.43 nm) [10].56 0.258 0.48 0. f [Zn1Àx Alx ][PV2 W10 O40 ]5À f .2 1614.1 607.29 0.159 0. small diameter) and a molecular height larger than the diameter of a N2 molecule.0 TIV (cm3 /g) 0.9 332.23 0. a x before intercalation.1 177. will have a higher probability of having microporosity.43 0.014 0.19 0. g Synthesis by anion exchange with an LDH–NO3 pre-swelled in water.j .028 0. the IPDs can be directly related to the microporous properties of pillared LDHs. since the [PW12 O40 ]3À can decompose into [PW11 O39 ]7À at the pH of the synthesis (4.7 94.6 313. those materials that show interlayer spacings and IPDs larger than the diameter of a N2 molecule ($0.2 1640. Bravo-Surez et al.20 0.40 0. As seen in Table 6 for hexagonal-shaped crystallites of dimensions 200 nm · 20 nm.36 0.38 0. e.2 177.1 1607.31 0. the interlamellar areas of the intercalated materials can potentially reach maximum values of up to 1700 m2 /g and external areas of up to 150 m2 /g.25 0.34 0. In this work.25 0.33 xf b 0.10 J.6 165. up to now only a maximum experimental value of BET area of only 438 m2 /g has been obtained [11].J. This result indicates that the synthesis of the totally exchanged and pure [PW12 O40 ]3À pillared LDH compound is not theoretically feasible.0) and the anion [PW11 O39 ]7À shows higher positive IPD values. In this particular case. This result suggests that the textural possibilities oﬀered by pillared LDHs have not .2.20 0.6 68. / Microporous and Mesoporous Materials 67 (2004) 1–17 a Table 13 Experimental textural properties of some pillared LDHs [12] LDH-A [Mg1Àx Alx ][V10 O28 ]6À d. ferricyanate.50 0.107 0.0 1659.59 0. Recently. b x after intercalation.20 0.8 156.7 656.3 193.003 0.33 0.6 185.154 0.20 0. dimensions and charge of the LDH.25 0.024 [Mg1Àx Alx ][PV2 W10 O40 ]5À d.045 0.5 586.2 1596.20 0. material could present microporous properties.39 0.37 nm).29 0.1 631. Such is the case for [Mg0:75 Al0:25 ][Fe(CN)6 ]3À LDH (h ¼ 0:64 nm and IPD ¼ 0.23 0. g.0 TEAmin (m2 /g) 126.003 0. and the composition.215 0.011 0. 4. to obtain microporous pillared LDHs the ideal pillar should possess a large relative ratio of charge to equivalent diameter (high charge.f . c Experimental micropore volume.5–5.2 that several variables can inﬂuence the calculations of the external and interlamellar speciﬁc areas of LDH materials such as the charge and geometrical model of the pillar. External areas It was seen in Section 2. In spite of satisfactory 0:11 characterizations by FTIR spectroscopy.1 995.

although the estimated IPDs are slightly smaller when using the cylindrical anion model.31] reported BET areas for the LDH Mg0:75 Al0:25 –CO3 of 120 m2 /g for a sample crystallized at 338 K for 18 h and 14 m2 /g for a sample crystallized at 473 K for 18 h. expressed in nm2 /eþ . as proposed by Yun and Pinnavaia [29]. Similarly. only a fraction of the TEAmin values can be experimentally measured by a probe molecule such as N2 . it is noted that the TEA and the TIA reach an almost constant value when dc is over 150 nm.358 · 10À12 m2 . the eﬀect of the LDH molecular weight on the textural properties for diﬀerent metals in the brucite-like layers can be observed in Table 9. The estimated textural properties of the LDH [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ]6À for crystallites with diﬀerent thickness and mean diameter dimensions are given in Tables 10 and 11. [Mg0:75 Al0:25 ][PV2 W10 O40 ]5À and [Mg0:75 Al0:25 ][PW11 Fe(H2 O)O39 ]4À are 1. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 11 been totally exploited. The crystallite TIA and TEA results for an LDH crystallite of [Zn1Àx Alx ][PV2 W10 O40 ]5À and [Mg1Àx Alx ][PV2 W10 O40 ]5À in m2 are also the same. either for the same anion or anions with the same geometry (i. [Mg1Àx Alx ][PW11 O39 ]7À LDH (x ¼ 0:15. The predictions for minimum and maximum SSAs are also shown in Table 6.25 and 0. Keggin type). For example. From the results in Table 11.35) has crystallite TIA values of 1. When the TIAs are expressed in m2 /g.J. If the same results are expressed in nm2 /eþ .123 nm2 /eþ .37 nm.207 · 10À12 . then the smaller the anion charge the smaller the TIA values due to a higher anion concentration and therefore a higher molecular weight of the LDH.37 nm. If the TIAs expressed in m2 /g are compared. Because the height of the carbonate anion (h ¼ 0:27 nm) is smaller than 0. the crystallite TIA for the LDHs: [Mg0:75 Al0:25 ][PW11 O39 ]7À . giving larger crystallite TIAs and TEAs (expressed in m2 ). the TEAmax for the LDHs [Zn0:75 Al0:25 ][PV2 W10 O40 ]5À and [Mg0:75 Al0:25 ][PV2 W10 O40 ]5À are both equal to 0. the anions present in the borders and in the exterior of the top and bottom layers. Thus. which will reduce the predicted values. 1. the crystallite diameter (dc ) also has some eﬀect on the speciﬁc areas. For the interlamellar areas. a reduction of 50% in the crystallite thickness results in an increase of almost 100% in the TEAs.2 m2 /g) may be more appropriate. so that the interlamellar area of the crystallite (TIA Æ MWC) should be larger. However. 2. These BET area results were explained using crystallite dimensions of 200 nm · 10 nm (TEAmin ¼ 125 m2 /g) and 1000 nm · 100 nm (TEAmin ¼ 13 m2 /g). [8]. Bravo-Surez et al. The maximum TEA includes all possible contributions. The textural properties expressed per unit weight of the LDH will be higher for the [Zn1Àx Alx ][PV2 W10 O40 ]5À than for the [Mg1Àx Alx ][PV2 W10 O40 ]5À because of the greater molecular weight of the Zn in comparison to the Mg. a contribution to . in many diﬀerent ways. The minimum TEA does not take into account the contribution due to the anions in the external surfaces. These results are shown in Table 6. the larger the LDH charge the higher the concentration of the anions in the interlayer region. when the TIA is expressed per unit charge of the LDH. although not as pronounced as in the case of the crystallite thickness. Reichle [30. especially on the TEA. when the h or IPDs are close to or smaller than 0. such as the external surface and edges of the LDH layers. the total speciﬁc areas of the LDH. The LDH charge can inﬂuence. The results in Table 7 show that the same trend is obtained when comparing the TIAs expressed in nm2 /eþ and this is because the pillar dimensions and the LDH charge have been kept constant. On the other hand. respectively. the larger the values of lc the smaller the values of TIA and TEA. these dimensions are somewhat large. respectively.207 · 10À12 and 1. the TEA will be near the minimum value.8 m2 /g) and 500 nm · 50 nm (TEAmin ¼ 26. It is worthwhile to note this inverse relationship of the lc ’s with the TEAs (in m2 /g).358 · 10À12 and 1. respectively. 1. According to Nijs et al. the speciﬁc areas are similar for both cubic and cylindrical anion models.e. the fraction of a p hexagon covered by a spherical probe molecule is p=ð2 3Þ. This result is expected since the textural properties expressed per unit charge do not depend on the LDH molecular weight.37 nm. the TEA may be close to the maximum value. When considering the eﬀect of the charge of similar anion geometries on the speciﬁc areas. On the other hand.490 · 10À12 m2 . the results are very similar to those observed for the charge of the LDH. a completely opposite behavior is obtained.056 · 10À12 . and from the published TEM results of these materials [30. For example. However. it is observed that the crystallite thickness (lc ) has a considerable eﬀect on the speciﬁc areas. In cases where the LDH materials have a uniform distribution of anions on the external surface and the values of h and IPD are much larger than 0. 0. In addition. The diﬀerence in molecular weight for different LDHs can be seen in the values of MWCs for diﬀerent LDH charges.31] the dimensions 100 nm · 10 nm (TEAmin ¼ 133. interlamellar pore blocking and collapse of brucite-like layers can occur during the intercalation process. Therefore the measurable TEAmin (mTEAmin ) will be given by pTEAmin = p ð2 3Þ. For example.J. From the results in Tables 6 and 8. The smaller the anion charge the higher the number of anions necessary to reach electroneutrality. the higher the charge of the LDH the smaller the TIA. With regards to Fig. From the results in Table 10. respectively. it is diﬃcult to establish a relationship with the LDH charge since in this case the TIA is a function not only of the geometry and charge of the anion and the brucite-like layers. but also of the molecular weight of the intercalated LDH. then the areas will be the same for both materials as long as LDH charges are the same. For instance.

when the LDH was synthesized with hydrothermal treatments under a microwave ﬁeld using exposure times between 0. In this way. The estimated TEAmin for a crystallite with dimensions of 2000 nm · 40 nm is 28.6–118. have not been reported. [5] reported the values of crystallite thickness for the LDHs [Mg0:77 Al0:23 ][CO3 ] (17. However. / Microporous and Mesoporous Materials 67 (2004) 1–17 a the total area due to external and interlayer anions is excluded. there are more aggregates at shorter microwave exposure times for an LDH with the same charge (½Mg0:86 Al0:14 ½CO3 À 0:5 min ¼ 9:6 > ½Mg0:86 Al0:14 ½CO3 À 10 min ¼ 1:2) and at smaller values of x for diﬀerent LDH charges (½Mg0:86 Al0:14 ½CO3 À 0:5 min ¼ 9:6 > ½Mg0:80 Al0:20 ½CO3 À 0:5 min ¼ 2:8 > ½Mg0:75 Al0:25 ½CO3 À 0:5 min ¼ 1:3). respectively. or the drying process before BET analysis. the observed BET areas are around 80–90 m2 /g. [33] observed average diameters of 2 lm. these discrepancies in BET areas can be explained by the diﬀerences in the average dimensions of the LDH crystallite. Constantino et al. Velu et al.3. the values of the average crystallite thickness (distance in the basal plane 0 0 l). This result indicates that the crystallite thickness may have a value close to 40 nm. [4] obtained a BET area of 24 m2 /g. The resulting face-to-face type aggregate from two crystallites would form a ‘‘new crystallite’’ of greater thickness. there is a lower probability of forming face-to-face aggregates.4 nm for microwave exposure times of 0. 50–90 and 15–95 m2 /g. even though they can be easily calculated from powder XRD results by means of Scherrer’s equation [32]. The measured crystallite mean diameter by the SEM method varied between 0. resulting in TEAmin /SBET values close to 1.0 nm. According to Rives [3]. The estimated mTEAmin for the MgAl–CO3 LDHs crystallized at 338 and 473 K are 121. then the estimated mTEAmin for these LDHs are 70. 30 and 60 min) the TEAmin /SBET are 3. speciﬁc areas and micropore volumes.8 m2 /g and the mTEAmin is 26. In most of the cases.3–18. Similar behavior is noted from the results of the synthesis of the LDH Mg0:75 Al0:25 –NO3 subjected to hydrothermal (363 K) and ultrasound treatments.9.2. However.1.2 and 144.J. with the exception of the LDH [Mg0:75 Al0:25 ][CO3 ] synthesized in a water/ethylene glycol medium. then the total external surface area can be decreased up to 50%. These estimated values are comparable with the experimental results. These results are in agreement with the experimental ﬁndings. Therefore.0– 11. For the rest of the LDHs in Table 1. which may be in agreement with the high crystallinity of these materials as observed in the published powder XRD patterns.3 and 23. Using similar synthetic conditions. [Mg0:80 Al0:20 ][CO3 ] and [Mg0:86 Al0:14 ][CO3 ] varied between 13. 9. the observed diﬀerences are mostly a result of the aging and hydrothermal treatments given during the synthesis.8 and 1. from the results in Table 12. If an average crystallite diameter of 150 nm is assumed. From a structural point of view. the crystallinity of the sample is higher and the values of lc are much larger.5–15. Assuming a particle diameter (dc ) of 150 nm. The results of TEAmin /SBET for the hydrothermally treated samples (t ¼ 10. The diﬀerences observed with the sample synthesized in the water/ethylene glycol media can be explained by a variation in the mean diameter and thickness of the crystallite. 140. and the BET areas were 80–85.5 and 10 min.1 m2 /g. These BET area results can be estimated using a value of crystallite diameter (dc ) close to 150 nm.2 m2 /g. Bravo-Surez et al. have been published [3].5 and 10 lm. The BET area of LDHs can show substantial diﬀerences even for the same material. Recently. respectively.3. [26] studied the eﬀect of microwave radiation and ultrasound on the synthesis of MgAl LDHs and the eﬀect that these treatments have on the textural properties of the resulting materials. If the interfacial space between these two crystallites is not accessible or very limited to N2 molecules. [25] and Seida et al.6 nm) and [Mg0:81 Al0:19 ][CO3 ] (12. Hussein et al. At elevated treatment times (HT or US).6–72.7–89.0.7 m2 /g. in the synthesis of the LDH [Mg0:75 Al0:25 ][CO3 ] by the urea method. The ﬁrst authors presented the evolution of the crystallite thickness (lc ) together with the BET area of the resulting LDHs. The experimental results are given in Table 12. respectively. respectively. and for the samples treated under ultrasound (t ¼ 5.12 J. very few of these comprise a full textural characterization with crystallite thickness and mean diameter.1. shown in the present work to have an appreciable inﬂuence in the speciﬁc areas of LDHs. A more detailed discussion of this diﬀerence is not possible since the values of dc and lc were not described in the original reference. neither of the two studies indicated values of the average crystallite thickness. The larger deviations presented by the BET areas at the shortest exposure time can be explained by the poor crystallinity of the samples and due to a crystallite aggregation of the type face-to-face or card-house [19]. 60 and 600 min) are 82. as seen in Table 1. the estimated TEAmin for these materials are 100. The observed crystallite thickness for the LDHs [Mg0:75 Al0:25 ][CO3 ]. For instance.9 nm).5 and 10 min.8 m2 /g.9 and 93. respectively. Many other examples of the synthesis and characterization of LDH compounds. the BET areas of these materials are shown in Table 1. An analysis of the ratio TEAmin / SBET shows that when large values are obtained there is a high tendency to form face-to-face aggregates with a higher number of crystallites. and a crystallite thickness (lc ) of about 15. respectively. respectively. 1. including their morphological characteristics. . 20. Oh et al. resulting in a reduction in the total external area. 92 and 88 m2 /g.3 and 2.4 and 9. which means that at these conditions the experimental values of the BET area agree with the mTEAmin .

a similar behavior is also noted.2 and 18. 0. the LDH crystallite thickness becomes greater giving as a result a reduction of the BET area. respectively. it would be erroneous to think that these N2 molecules can reach the interlamellar region since the interlayer distance for the CO2À is about 3 0. and 45 and 32 m2 /g (read from a graphic in the original reference).4 nm for a sample not treated hydrothermally. since it is very probable that the synthesized material contains other isopolyvanadates species of lower charge that would make access more diﬃcult to the interlayer region. From the results in Table 13.5 m2 /g. For these two intercalated compounds. Bravo-Surez et al. 0. 0. the resulting areas are quite small ($3 m2 /g).’s results would have to do with the poor crystallinity of the synthesized materials together with a high agglomeration of the crystallites. 0.35) the IPDs are 0. the obtained values are similar. [35] synthesized the LDHs of [Zn0:64 Al0:36 ][CO3 ] and [Zn0:63 Al0:37 ][NO3 ]. even for the [Mg1Àx Alx ][V10 O28 ] that shows an IPD of 0. then the measurable TEAmin (mTEAmin ) are 35. the N2 can supposedly diffuse more easily into the interlayer region. the values of TEAmin are almost twice the BET area for the LDH [Mg1Àx Alx ][V10 O28 ]. including direct synthesis [29]. This result may indicate that the BET area is mainly due to the external area of the LDH crystallite.46 and 0. this would explain why in some cases the obtained interlayer distances are smaller than expected. 0. anion exchange by acid elimination [15] and reconstruction of the LDH structure [40. The BET areas of these samples ranged from 55. similar trends for the textural 1Àx x x=n properties have been found in LDHs of the type [Mþ M3þ (OH)2 ]ð2xÀ1Þþ [AnÀ 1Àx x ð2xÀ1Þ=n ] [36]. The experimental results indicated that the longer the time of the hydrothermal treatment at 403 K the larger the crystallite thickness. and according to Nijs et al. Ulibarri et al. From the results in the present study and from the literature. 0. Also. the values of TEAmin estimated with the model are much closer to the BET areas. Again. relatively short precipitation times (10 min) and a subsequent treatment of the LDH slurry with microwave radiation for 5 min. For instance.25. The intercalation of POMs in LDHs has been well studied owing to the potential that these materials present as catalysts and adsorbents with shape selectivity [2]. a diﬀerence in the crystallite thickness could explain these variations. Recently.39]. respectively. direct anion exchange [38. respectively.18. which prevents N2 molecules 3 from accessing the interlayer space. 0. A more satisfactory explanation of Fetter et al. These results follow the same behavior observed for the LDH of the type [M2þ M3þ (OH)2 ][AnÀ ]. Regarding the temperature of the hydrothermal treatment. The BET area diﬀerences of the MgAl–NO3 with the MgAl–CO3 are explained by these authors in terms of the higher interlayer density of the NOÀ anions in the LDH.34) are much smaller than those of the ﬁnal intercalated material. 0. 0.27 nm. Although the IPDs for the MgAl–CO3 are larger than a N2 molecule.25. The explanation for why the BET area is smaller than the TEAmin may be that face-to-face aggregates are formed or simply a crystallite thickness larger than 10 nm is present. These values are comparable with the experimental results. [9]. Several methods of intercalation of POMs in LDHs have been described in the literature. if we compare the equivalent molecular weights of the crystallites of MgAl–NO3 and MgAl– CO3 with the same dimensions. since both anions possess a similar geometry and 3 a diﬀerent charge. with a lower anion density. For the LDH [Mg1Àx Alx ][PV2 W10 O40 ].39. In the case of the LDHs [Mg1Àx Alx ][V10 O28 ] and [Mg1Àx Alx ][PV2 W10 O40 ] the values of the TEAs and the crystallite diameter (dc ) and thickness (lc ) were not described.6 and 48. As the temperature of the hydrothermal treatment at 48 h increased.0 nm. Some of the results of this study are shown in Table 13. For the MgAl–CO3 . This may be because the initial x values of the original LDH (x ¼ 0:20. while for the [Mg1Àx Alx ][CO3 ] (x ¼ 0:15.10 and 0. In the LDH [Mg1Àx Alx ][PV2 W10 O40 ] (xf ¼ 0:34.5 M). It is true that in an LDH the NOÀ density is higher than for the 3 CO2À .6 m2 /g. Nijs et al. These faults in the lamellar structure could be used by the POMs as exchange sites.50 nm. where the larger the crystallite 1Àx x x=n thickness the smaller the TEAmin . Consequently. The crystallite thickness (lc ) and the BET areas were 25. due to a partial dissolution of the Mg from the brucite-like layers.03 nm).55–0. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 13 [Mg0:75 Al0:25 ][NO3 ] LDHs have been also synthesized by Fetter et al. but still larger. [12] studied the microporous properties of some of these intercalated compounds. If a crystallite diameter of 150 nm is assumed.32 nm.72. [34] using high concentrations of metals (2. the IPDs of this LDH [Mg1Àx Alx ][PV2 W10 O40 ] should be calculated for x values between xi and xf . . as given by the estimated IPDs for these materials.35) the IPDs are 0.11 nm. The textural properties of others LDHs of NOÀ and CO2À have been also pub3 3 lished in the literature. 0. up to 31.20 and 0.9 nm for a sample treated for 48 h. The obtained IPDs are 0. 0. After a degasiﬁcation of the LDH samples at 373 K for 2 h.41]. [37] studied the textural properties of the LDH [Liþ Al3þ (OH)2 ]0:33þ [AnÀ ] as a function of the time 0:33 0:67 0:33=n and the temperature of the hydrothermal treatment. these explanations are not completely satisfactory. respectively. Velu et al. The values of the crystallite thickness varied from 2.J. there is no formation of interlamellar microporosity.25.38.45). For calculation purposes.J. LDH crystallites with dimensions of 150 nm · 10 nm have been assumed. Although the results of the model presented in this study are applicable to LDHs of the type [M2þ M3þ (OH)2 ][AnÀ ].18. small and even close to zero values of IPDs are observed (0.5 to 5. For the [Mg1Àx Alx ][NO3 ] (x ¼ 0:15. respectively.

74 nm (twice the diameter of a N2 molecule). then only up to 11% of the TIA theoretical value is obtained. This model is schematically shown in Fig. then only 88% of the total IPDs will show values larger than 0. 4. The total number of available empty spaces for the ﬁrst type is given by NPs ðNPs À 1Þ and for the second type by ð2NPs À 1ÞðNPs À 1Þ. then the micropore areas can be calculated based on experimental data.43 nm.14 J.163 nm2 ). that is. an equilateral parallelogram geometry for a brucite-like layer with equally spaced cubic pillars is assumed.10. in agreement with the increasing IPDs. due to a lower thermal stability of the pillared materials at low x values. In all cases. the low interlamellar areas can be understood if we take into account that the IPDs and the interlayer spacing (h) for the ferricyanate anion are smaller than 0. For this reason. On the other hand. 8. Interlamellar areas Fig. aggregation of these low crystalline materials can contribute to the decrease of the total external area. the BET areas are also larger than the values of TEAmin . and 0. to estimate the fraction of the TIA that can be experimentally measured (FIAmea ) is obtained in the following manner. Thus. On the other hand. (21). This BET area increases as the value of x decreases.2 m2 /g.37 nm. Using Eq. an equation Some results of the estimated TIVs for several intercalated LDHs with crystallites dimensions (dc Â lc ) 200 nm · 20 nm are shown in Table 6. 8. the model explains adequately the experimental results for the [Mg0:77 Al0:23 ][Fe(CN)6 ]3À LDH. this result can be understood if the IPD is viewed as an average value.39–0. the decomposition of the [PV2 W10 O40 ]5À in other Keggin type POMs cannot be excluded. On the one hand. Two diﬀerent types of ‘‘empty spaces’’ can be identiﬁed: the ﬁrst type lies between pillars in the same row and the second type lies between two rows of pillars. This reduction is not in agreement with the theoretical predictions. With these dimensions the estimated textural properties are given in Table 13.4. which could be also intercalated in the LDH. Consequently. 273. 8. These results together with the micropore volume are an indicative of the presence of microporosity. the fraction of TIA that can be experimentally measured for the LDH [Mg0:77 Al0:23 ][Fe(CN)6 ]3À corresponds approximately to 17%.3. The BET areas register a maximum value at x ¼ 0:23. Model of a brucite like layer with equally spaced cubic anions. Additionally. the BET areas show an increasing trend as the x values decrease. respectively. The fraction of TIA that can be experimentally measured is given by the ratio between the area measured by N2 molecules and the theoretical area. According to Nijs [12] this reduction in the BET areas can be attributed to the loss of LDH crystallinity at the degasiﬁcation conditions of the sample. not all of the pores formed in the interlamellar region will be accessible to N2 molecules.8– 12. 4. Bravo-Surez et al. The interlamellar areas reach a maximum of up to 16% of the theoretical value. respectively.6–12. NPs is the number of pillars on one of the sides of the structure in Fig.J.3 and 7. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 0. only a fraction of the total interlamellar area (TIA) estimated theoretically can be measured experimentally.43 nm and a standard deviation of 0. the LDH [Mg0:75 Al0:25 ][Fe(CN)6 ]3À that has a BET area of 367 m2 /g and a relatively high thermal stability at the degasiﬁcation conditions has an IPD of about 0. an average value of 10 nm has been taken for both materials and a value of 150 nm has been estimated for the crystallite diameter (dc ). and below it the BET areas start decreasing. as expected.1 nm. if this material is assumed to have a normal distribution of IPDs with an average value of 0. Simplifying common terms and also for values of NPs ) 1 the following equation is obtained: p FIAmea ¼ 3AN2 =ð3 3IPD2 þ 4dp hÞ ð21Þ where AN2 is the molecular cross sectional area of a nitrogen molecule (0. If the external area of these intercalated materials is assumed to have a value close to the TEAmin . This ratio expressed as a function of NPs is: ½AN2 NPs ðNPs À 1Þ þ p AN2 ð2NPs À 1ÞðNPs À 1Þ=½IPD2 NPs ðNPs À 1Þp 3 þ 2dp hNPs ðNPs À 1Þ þ IPD2 ð2NPs À 1ÞðNPs À 1Þ 3 þ dp hð2NPs À 1ÞðNPs À 1Þ. In the case of the [Zn1Àx Alx ][PV2 W10 O40 ]. The [Mg1Àx Alx ][Fe(CN)6 ]3À LDH presents values of TEAmin smaller than the BET area. Therefore. If the micropore areas are calculated by SBET )TEAmin . respectively [9]. Similarly.37 and 0.74 nm.05 nm. Interlamellar free volumes To estimate the fraction of TIA measured experimentally. For example.03 nm. For IPD values between 0. By comparing this result with the experimental 257 m2 /g. These diﬀerences can be explained with similar arguments used for the [Mg1Àx Alx ][Fe(CN)6 ]3À materials. together with the micropore volumes it can be said that this material has microporosity.18–0. the TIV decreases when the LDH charge (x) . The LDHs [Mg1Àx Alx ][Fe(CN)6 ]3À and [Zn1Àx Alx ][PV2 W10 O40 ] have crystallite thicknesses between 7.

independent of the anion model utilized. the estimated TIVs follow the trend: [PW11 O39 ]7À > [PV2 W10 O40 ]5À > [PW11 Fe(H2 O)O39 ]4À > [PW12 O40 ]3À .145). the area occupied by the anion remains the same. For example. calculated from the liquid density of N2 at the boiling point (0. The lPV/ TIV ratio of these materials varies between 7% and 69%. Therefore. This equation takes into account contributions due to the top and bottom external crystallite layers and also the anions in the borders of the LDH crystallite layers.J. Bravo-Surez et al. then the estimated TIV remains constant. For [Mg0:77 Al0:23 ][Fe(CN)6 ]3À the maximum fraction of the TIV that can be measured is about 45%. (21) is derived to determine the fraction of TIV that can be experimentally measured (FIVmea ): ½VN2 NPs ðNPs À p 1Þ þ VN2 ð2NPs À 1ÞðNPs À 1Þ=½ð 3=2ÞIPD2 hNPs ðNPs À p 1Þ þ ð 3=2ÞIPD2 hð2NPs À 1Þ ðNPs À 1Þ.175) > [OH]À (0.210) > [PW11 O39 ]7À (0. in the case of the TIVc ’s. (15) is based on the assumption that there are enough interlamellar anions in each layer (Y ) to equilibrate the LDH charge (x).74 nm. Therefore. the XAE is a function of . In absolute terms. because when the IPDs and the interlayer spacings fall between 0. in nm3 /eþ : [PW11 O39 ]7À (0. On the other hand. as a result of a higher concentration of anions in the interlayer region. In the case of the LDH [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ] with a constant crystallite diameter (dc ). the TIVc (in cm3 ) is the same as long as the LDH charge and crystallite dimensions are the same. If two anions of similar charge are compared. the experimental value is 69%. As noted from Eq. an expression similar to Eq. the LDH [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ]6À (0.849). in nm3 /eþ or in cm3 .808 g/cm3 ). molecules reacting per active site per unit time.118) and in cm3 · 1016 : [PW11 O39 ]7À (2. the anion order of the ﬁve highest TIVs expressed in cm3 /g are: [Fe(CN)6 ]3À (0. / Microporous and Mesoporous Materials 67 (2004) 1–17 a 15 increases. Three diﬀerent strategies can be utilized to compare TIVs of intercalated LDHs with similar crystallite dimensions: using TIVs expressed in cm3 /g.37 and 0.180) > [V10 O28 ]6À (0. Simplifying terms and for NPs ) 1 the following expression is obtained: p FIVmea ¼ 2VN2 =ð 3IPD2 hÞ ð22Þ VN2 is the volume of a N2 molecule. it is not possible to experimentally measure all of the theoretical TIV. The molar fraction of the LDH external anions (XAE ) is an important variable in the pillared LDH compounds. When the eﬀect of the metals in the brucite-like layers is studied. is only function of the LDH charge and molecular weight. a constant increase of the crystallite interlamellar free volume is observed as the values of dc or lc are incremented. Similarly to the TIA. The experimental results of the micropore volumes of several pillared LDHs are shown in Table 13. with the same LDH charge.138 cm3 /g) has a lower TIV than the LDH [Mg0:66 Al0:33 ][V10 O28 ]6À (0. For example. for the LDHs Mg0:75 Al0:25À AnÀ observed in Table 7. when the crystallite thickness (lc ) increases the TIV also increases. it is more likely that the reactions will be carried out in the external surface of the LDH.5. The TORs in reactions catalyzed by LDH-POMs are typically calculated on the basis of the total POMs present in the LDH [13].231) > [V10 O28 ]6À (0.37 and 0. In this case. in many cases the reacting molecules are too big to access the interlamellar region. for the Keggin anion series shown in Table 6. (22) is valid for values of h and IPDs between 0. For this same material. Thus. reaching an almost constant value over a lc of 25 nm. For instance.119) > [Fe(CN)6 ]3À (0. Other properties Other LDH properties that can be estimated in the present study include the molar fraction of the anions present in the external surface of the crystallite and the LDH apparent and true densities. the [Zn0:75 Al0:25 ][PV2 W10 O40 ]5À and the [Mg0:75 Al0:25 ][PV2 W10 O40 ]5À have the same TIVc ¼ 1:678 Â 10À16 cm3 .078) > [OH]À (2. the catalytic activity can be expressed as turnover rates (TOR).138) > [PV2 W10 O40 ]5À (0.015) > [H4 Co2 Mo10 O38 ]6À (1. the polyoxometalate usually plays the role of active site in the catalytic process. especially when they are used as catalysts. For a given LDH compound. This result could be explained by the presence of IPDs > 0:74 nm and by a contribution to the micropore volume from the external area. Therefore. the total anions present in the top and bottom external crystallite layers are Y .125) > [H4 Co2 Mo10 O38 ]6À (0. the TIV is lower for the bulkier anion.171) > [CO3 ]2À (0. In this work. However. (15). in the POM pillared LDHs. (15) is used for the calculation of the fraction of external anions.294) > [Fe(CN)6 ]3À (2. Eq. if the crystallite thickness is kept constant and the crystallite diameter is modiﬁed. the estimated TIVs are the same since. The same result is obtained when the units of the TIVs are expressed in nm3 /eþ since the conversion factor g/eþ . The highest value is presented by the LDH [Mg0:77 Al0:23 ][Fe(CN)6 ]3À . in the calculations. This result can be explained if the method used to measure the micropore volume using N2 is taken into account. The eﬀect of the crystallite dimensions can be seen in Tables 10 and 11. 4. In catalysis.J.74 nm. a comparison of anions of similar volume within an LDH of the same charge shows that the TIVs are higher for the anions of higher charge.426) > [V10 O28 ]6À (2. However. the LDH mesoporosity or both [42]. the lower TIVs are for the LDHs that contain the heavier metals due to the molecular weight eﬀect on the TIVs expressed in cm3 /g. as shown in Tables 10 and 11. A similar result is obtained when the TIVs are expressed per unit charge of the LDH (nm3 /eþ ) because the LDH charge is the same for both materials. Eq. MWC/ (NMc Á x Á m). However. Eq. the crystallite thickness presents a more pronounced eﬀect on the TIVs than the crystallite diameter.210 cm3 /g).

such as the average crystallite diameter and thickness (spacing in the basal plane 0 0 l). Vaccari. Acknowledgements We acknowledge ﬁnancial support for this work by the Director.30 g/cm3 for the [Mg0:75 Al0:25 ][Fe(CN)6 ] up to 3. the apparent density is a function of the dimensions and molecular weight of the LDH crystallite. The results of densities for the LDH [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ] as a function of the crystallite diameter and thickness are given in Tables 10 and 11. The results also potentially assist in the synthesis of LDHs for speciﬁc applications. The results of predicted LDH densities indicate that it may be possible to obtain textural information of the LDH crystallite from the experimental measurement of the LDH apparent and true densities. However. The true density is also a function of the interlamellar free volume. Layered Double Hydroxides: Present and Future. References [1] F. / Microporous and Mesoporous Materials 67 (2004) 1–17 a the dimensions and charge of the LDH and the intercalated anion. One of the main advantages of this approach is the correlation of the LDH textural properties with LDH characteristics that can be experimentally measured. Division of Chemical and Thermal Systems of the National Science Foundation under grant CTS-0321979.A. the densities of the [Zn1Àx Alx ][PV2 W10 O40 ] are greater than for the [Mg1Àx Alx ][PV2 W10 O40 ] due to the heavier molecular weight of the Zn with respect to the Mg. Today 11 (1991) 173. On the other hand. 5. Density calculations shown in Table 8. Chem. Rives.00 g/cm3 for the [Mg0:75 Al0:25 ][PW11 Fe(H2 O)O39 ]. Ohashi. Chem. [2] V. for the LDHs Mg0:75 Al0:25 -A with crystallites of dimensions 200 nm · 20 nm. A small reduction in the values of XAE is noted when increasing the LDH charge. Chem. the LDH density can vary appreciably depending on the intercalated anion. Suzuki. The results obtained with this model are comparable with experimental results for BET areas and micropore volumes. Density is one of the properties of the LDHs that has been little studied. Inc. Conclusions Several simple equations have been presented for the calculation of the textural properties of LDH com- . showing little variation at values of lc over 30 nm and reaching an almost constant value over 50 nm. Note that XAE values decrease as the crystallite thickness increases. T. with crystallites of dimensions 200 nm · 20 nm. Although the variation of the crystallite diameter (dc ) does not aﬀect the obtained density values. Vivani. [3] V. Bravo-Surez et al. code 110205665-95. A similar trend is observed when the crystallite diameter is increased and the crystallite thickness is kept constant. As seen from Eqs. Rives (Ed. density values of 2. M. giving some correlations for their prediction. Okasaki. the results of this study contribute to a better understanding of the textural properties of the LDHs. The true density values are also larger as the crystallite thickness increases.).86 g/cm3 for the [Mg0:75 Al0:25 ][Fe(CN)6 ] up to 3.3%. For both materials the apparent and true densities are larger at higher LDH charges. In cases of poor crystallinity. are shown in Table 8. K. Catal. as shown in this study. The eﬀect of the LDH charge on the XAE can be observed in Table 9. These estimates were made by modeling the properties of an LDH crystallite and the intercalating anion. It was also demonstrated that properties such as the areas and interlamellar free volumes expressed per unit charge of the LDH give better results than when expressed per unit weight of the LDH. J. the results of XAE for the LDH [Mg0:75 Al0:25 ][H4 Co2 Mo10 O38 ]. F. A. Typically. (1998) 1439. Taking into account the results predicted by the model and the method for the experimental determination of the LDH textural properties.J. Rev. 2001. (16) and (17). The true density values vary from 1. Eur. pounds. Cavani. in the frame of the project ‘‘Synthesis. these divergences are explained in terms of the formation of agglomerates of a face-to-face type. and also that they can be useful when comparing diﬀerent LDHs.51 g/cm3 for the [Mg0:75 Al0:25 ][PW11 Fe(H2 O)O39 ]. However. which has thus far exhibited the highest BET area. are presented in Table 10. The values of XAE for the POMs can vary between 8. Marmottini. [4] U. Nocchetti. The density calculations for the [M2þ Alx ][PV2 W10 O40 ](M2þ ¼ Mg. S.6%. Inorg. F. in: V.Zn) 1Àx LDHs with crystallite dimensions of 200 nm · 20 nm are given in Table 9. but the variation is greater than that observed for the apparent density. 11 (1999) 2163. and for the ferricyanate anion it is 7. Additionally. [5] S. p.16 J. Costantino.7% and 10. The results of XAE for several intercalated Mg0:75 Al0:25 LDHs. characterization and testing of biomimetic catalysts for selective oxidation’’. indicate that the apparent density values vary from 1. In general. Coord. R. 181 (1999) 61. Tomura. Mater. with a crystallite of constant diameter (dc ) and variable thickness (lc ). we were able to explain satisfactorily the textural results of the LDH [Mg0:77 Al0:23 ][Fe(CN)6 ]3À . Nova Science Publishers.00 g/ cm3 are assumed. the apparent density is larger when the crystallite thickness (lc ) is increased. although at values of dc over 300 nm the variation of XAE is slight. Triﬁro. 229. Velu. the results of the model do not agree with the BET values. and from Universidad Industrial de Santander and COLCIENCIAS. M. Rives. New York. Osaki. Ulibarri. M. F.

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