Applied Catalysis A: General 356 (2009) 243249

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Pillared clays with AlFe and AlCeFe in concentrated medium: Synthesis and catalytic activity
N.R. Sanabria a, M.A. Centeno b, R. Molina a, S. Moreno a,*
a b

lisis Ambiental, Departamento de Qumica, Universidad Nacional de Colombia, Carrera 30 No. 45-03, Bogota Colombia , lido y Cata Estado So rico Vespucio, 41092 Sevilla, Spain Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla-CSIC, Av. Ame

A R T I C L E I N F O

A B S T R A C T

Article history: Received 2 September 2008 Received in revised form 7 January 2009 Accepted 9 January 2009 Available online 16 January 2009 Keywords: Polyhydroxocation multimetallic AlFe AlCeFe Pillared clays CWPO

This paper proposes a new methodology for the modication of clays with the mixed AlFe and AlCeFe systems, which involves the synthesis of solid polymeric precursors and their use as pillaring agents in the modication of clays. The process of intercalation of clay with Al13, Al13 + Fe and Al13 + Ce + Fe nitrate was performed using ultrasound. The pillaring agents Al13, Al13 + Fe and Al13 + Ce + Fe were characterized by XRF, XRD, SEM and 27Al NMR techniques, and pillared clays were characterized by XRF, XRD and N2 adsorption to 77 K. The catalytic properties of pillared clays were evaluated using catalytic wet peroxide oxidation of phenol in dilute aqueous medium, demonstrating activity comparable to that of solids modied by the conventional method. 2009 Elsevier B.V. All rights reserved.

1. Introduction Synthesis of pillared clays (PILC) at the laboratory level primarily entails the suspension of diluted clay (2 wt.%) within a pillaring solution (typically 0.25 M), and it involves considerable contact time and large amounts of water [13]. To expand the pillaring process to an industrial scale, there is a need for simplication of procedures and optimization of the unit operations involved, particularly to decrease the relative volume of water. From a technical and economical point of view, Vaughan [1] lays down three conditions for the synthesis of pillared clays at a commercial scale:  Minimum treatment of clay for purication.  No prior requirement of clay exchange with sodium solutions.  The use of concentrated suspensions of clay. Current research into the process of pillaring is focused on the synthesis with concentrated suspensions, both of clay and of the pillaring agent. In this regard, Aouad et al. [2] developed a procedure for pillaring clays with aluminum, which minimizes the processing time and the amount of water used, allowing its extension to an industrial scale. To simplify the preparation of AlPILC, natural clay is used without purication or chemical

* Corresponding author. Tel.: +57 1 3165000; fax: +57 1 3165220. E-mail address: smorenog@unal.edu.co (S. Moreno). 0926-860X/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2009.01.013

pretreatment, so the clay powder and solid Al13 nitrate come into contact in a dialysis membrane. The solid pillared by means of the aforementioned method has features similar to those of the solid synthesized by the conventional procedure that uses dilute suspensions [2]. In contrast, the chemical structure of the pillar can be modied through synthesis of so-called mixed pillars, which are derived from the hydrolysis of solutions containing two or more metal cations. The pillaring of clay with mixed metal complex of Al and Fe has been reported in detail by Lee et al. [4], who determined by Mossbauer spectroscopy that Fe is located preferentially on the surfaces of the pillars of alumina. Palinko et al. [5,6] analyzed by FTIR and Mossbauer spectroscopy the nature of the mixed species AlFe generated in pillared clays, as well as in pillaring agents precipitated as sulfates. They have concluded that there is no tetrahedral or octahedral isomorphous substitution of Fe in the Keggin structure of Al13, which indicates the presence of cohydrolysis and co-pillaring during the modication. The clays modied by means of mixed pillars offer great potential as catalysts in various reactions of industrial interest due to the introduction of metal cations with catalytic properties. The decomposition of hydrogen peroxide in the presence of ions Fe3+/ Fe2+ (Fenton system) is an important example, which prompted the proposal of a similar system with iron species supported in clays for oxidation reactions of organic compounds [79]. In order to improve the distribution of the active phase and increase the catalytic properties of the AlFePILC, some authors reported the addition of cerium to the mixed system [1012].

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In this article, we report the synthesis of Al13, Al13 + Fe and Al13 + Ce + Fe sulfate as precursors of Al13, Al13 + Fe and Al13 + Ce + Fe nitrate, respectively. We used a procedure similar to that developed by Furrer et al. [13] for basic aluminum sulfate and nitrate, but we included Fe and Ce as second and third cations. The intercalation of clay powder with the Al13, Al13 + Fe and Al13 + Ce + Fe nitrate was carried out using a dialysis membrane, applying ultrasound to promote diffusive processes and reduce synthesis time. 2. Experimental 2.1. Synthesis of the pillaring agent The polymeric precursor in an aqueous solution was synthesized using the methodology of Furrer et al. [13] for basic aluminum chloride [13], but adding Fe and Ce as second and third metals. From AlCl36H2O, FeCl36H2O, CeCl37H2O and NaOH, three pillaring solutions were prepared: rst, the Al solution; second, Al Fe with 5 mol% of Fe; and third, AlCeFe with 2 mol% of Ce and 5 mol% of Fe. The OH/metal hydrolysis ratio was 2.46. Once hydrolysis was completed, the solutions were aged for 4 h at 60 8C. Aqueous solutions of Al13, Al13 + Fe and Al13 + Ce + Fe chlorides were added to 0.1 M solution of Na2SO4, with a molar ratio of metal/SO4 of 1.0, while maintaining agitation at 700 rpm for 2 h. The mixture was then allowed to stand for 36 h. After this time, the precipitate was separated from the suspensions by centrifugation; successive washings with a buffer solution of citric acid/sodium citrate were made in order to dissolve the hydrolyzed iron not associated to the Keggin structure. The Al13, Al13 + Fe and Al13 + Ce + Fe sulfates were dried at 60 8C, dissolved in a solution of Ba(NO3)2, and subjected to ultrasound for 4.5 h [13]. Finally, the solution was separated from the solid (BaSO4) by centrifugation and evaporated at 60 8C in an oven until crystals of Al13, Al13 + Fe and Al13 + Ce + Fe nitrates were obtained. These nitrates were ground and sifted in a 100 mesh to then be used as pillaring agents in the modication of clays. 2.2. Synthesis of pillared clays The starting clay was a natural bentonite from Valle del Cauca, Colombia, which was segregated by particle size (fraction <2 mm) following the gravimetric sedimentation procedure [14]. The fraction of clay was homoionized with CaCl2 [15], washed with distilled water until reaching a <20 mS/cm conductivity, dried at 60 8C and nally ground and sifted in a 100 mesh. Solids were synthesized at a ratio of Al13, Al13 + Fe and Al13 + Ce + Fe nitrates to clay of 20 meq metal/g clay. This ratio produced solids with good textural properties and excellent catalytic activity in the oxidation reaction of phenol in a dilute aqueous medium [8,1012,16]. In a dialysis membrane, metal nitrate was mixed with calcium clay. The membrane was covered with distilled water and agitated for 3 h, allowing the passage of water though it. Subsequently, the container with the membrane was left in an ultrasound bath at 50 kHz for a period of 30 min. The intercalated solids were removed from the membrane, centrifugally washed until reaching a conductivity near that of distilled water, dried at 60 8C, ground and sifted in a 100 mesh. Finally, the solids were heated to 400 8C at 2 8C/min and calcined for 2 h. 2.3. Characterization of the pillaring agent Al13, Al13 + Fe and Al13 + Ce + Fe sulfates as well as Al13, Al13 + Fe and Al13 + Ce + Fe nitrates were characterized by X-ray uorescence (XRF) on a Philips Magix Pro PW2440 instrument, with

samples prepared as pearls. For the X-ray diffraction, a Shimadzu LabX XRD-6000, which operates with Cu Ka radiation (steps of 0.0182u and 2 s/step), was used. The scanning electron microscopy (SEM) was performed on a Jeol JSM-5400 equipment, using samples that were previously gold coated. The NMR spectra were taken on a Bruker DRX400 spectrometer with a magnetic eld of 9.36 T and equipped with a multinuclear probe. Powdered samples were packed in 4 mm zirconia rotors and spun at 10 kHz. 27Al NMR spectra were recorded at 104.26 MHz with a p/20 pulse width of 1.6 ms and delay time of 1 s. The chemical shift is reported in ppm from 0.1 M solutions of AlCl3. 2.4. Characterization of pillared clays The starting clay and pillared clays were characterized by X-ray uorescence (Philips Magix Pro PW2440), X-ray diffraction (Shimadzu LabX XRD-6000, with Cu Ka radiation, powder samples, steps of 0.05 82u and 2 s/step) and N2 adsorption to 77 K. Textural properties were studied by N2 adsorption measurements at liquid nitrogen temperature. The experiments were carried out in a Micromeritics ASAP 2020 equipment, where samples were degassed for 1 h at 90 8C and 3 h at 300 8C in vacuum. 2.5. Catalytic activity The catalytic activity of the solids was evaluated in the oxidation reaction of phenol in a dilute aqueous medium by the procedure reported in previous works [8,12,16]. For each test, the reactor was loaded with 100 ml of a 5 104 M phenol solution, 0.5 g of the catalyst, a 0.1 M hydrogen peroxide solution and brought to a pH of 3.7. Monitoring of the phenol conversion with time and for the appearance of subproducts in the oxidation reaction were carried out by high performance liquid chromatography (HPLC) using a Hitachi D-7000 (LaChrom) instrument equipped with a Lichrosphere 60 Select B column. The assessment for total organic carbon (TOC) was carried out by means of an AnaTOC instrument. In all tests, a relative error less than 4% was estimated in the ranges from 60 to 240 min for the phenol conversions and from 120 to 240 min for TOC conversions [12]. 3. Results and discussion 3.1. Characterization of pillaring agent Table 1 summarizes the results of chemical analysis for Al13, Al13 + Fe and Al13 + Ce + Fe sulfates and nitrates. The atomic ratio Al:Na:S 13:0.1:3.55 for basic aluminum sulfate with a crystalline monoclinic system was established by Kloprogge et al. [17] based on an ICP-AES analysis, which corresponds to the structural formula Na0.1[Al13O4(OH)24(H2O)12](SO4)3.55.xH2O. The basic aluminum sulfate with crystalline cubic system, described by Johansson [18], corresponds to the formula Na[AlO4Al12(OH)24(H2O)12](SO4)4xH2O, while the one indexed by Parker et al. [19] has the chemical formula Na[AlO4Al12(OH)24(H2O)12](SO4)410H2O. According to the values in Table 1, the atomic ratios of Al/Na and S/Na for sulfates synthesized in this work are lower than those obtained by Johansson [18] and near those of Parker et al. [19]. Differences in values may be associated with the method of analysis, since the atomic ratio in this case was obtained by X-ray uorescence with a semi-quantitative application. Taking into account the nominal amounts of Fe and Ce used in the synthesis, the incorporation of these two metals accounted for 22.3% of Fe in Al13SO4 + Fe, and, for 23.8% and 0.94% of Fe and Ce, respectively, in Al13SO4 + Ce + Fe. In Al13NO3 + Fe and Al13 NO3 + Ce + Fe, the percentage of incorporated Fe and Ce is much lower than in sulfates, given that, in the SO4/NO3 exchange process,

N.R. Sanabria et al. / Applied Catalysis A: General 356 (2009) 243249 Table 1 Chemical analysis of Al13, Al13 + Fe and Al13 + Ce + Fe sulfates and nitrates and atomic ratios of Al/Na and S/Na. Sample Al13SO4 Al13-SO4 + Fe Al13SO4 + Ce + Fe Al13NO3 Al13NO3 + Fe Al13NO3 + Ce + Fe (%): Mass percentage. Al (%) 30.59 30.83 30.49 31.52 31.62 31.59 Na (%) 2.04 2.18 2.13 2.30 2.39 2.34 S (%) 11.25 9.32 10.23 0.25 0.11 0.02 Fe (%) 0.75 0.44 0.17 0.17 Ce (%) 0.03 0.01 Al/Na (%) 12.78 12.05 12.20

245

S/Na (%) 3.95 3.07 3.44

Fig. 3. Change in the a parameter vs. concentration of Fe.

Fig. 1. XRD of Al13, Al13 + Fe and Al13 + Ce + Fe sulfates and nitrates.

BaSO4 is produced. Part of the Fe occluded among the crystals is withdrawn with the formed precipitate. The incorporation of Fe in Al13NO3 + Fe was 5.0%, and 4.8% and 0.28% for the Fe and Ce in Al13NO3 + Ce + Fe, respectively. The patterns of X-ray diffraction of Al13, Al13 + Fe and Al13 + Ce + Fe sulfates are similar (Fig. 1), though with smaller displacements of 2u signals of Al13 + Fe and Al13 + Ce + Fe sulfates

compared to the Al13 sulfate. Some of the displacements of the 2u signals can be seen in Fig. 2. The pattern of X-ray diffraction reported by Kloprogge et al. [17] and subsequently by Aouad et al. [2], for the basic aluminum sulfate with formula Na0.1[Al13O4(OH)24(H2O)12](SO4)3.55nH2O, has a Pa or P2/a space group and a monocline crystalline system. The basic aluminum sulfate, rst synthesized by Johansson [18] and then described by Parker et al. [19] and Shi et al. [20], has a Na[Al13O4(OH)24(H2O)12](SO4)4xH2O formula, space group F-43m and a cubic crystalline system. This leads to the assertion that the basic aluminum sulfate can exist in two crystalline systems: monocline and cubic. The XRD of Al13, Al13 + Fe and Al13 + Ce + Fe sulfates shown in Fig. 1 correspond to a cubic crystalline system. The (a) unit cell parameter for Na[Al13O4(OH)24(H2O)12](SO4)410H2O is 17.856 (2) A [19], and those obtained in this work are 17.993(5) A,

Fig. 2. Displacements of signals in the XRD of Al13 + Fe and Al13 + Ce + Fe sulfates compared with Al13SO4.

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Fig. 4. SEM images for (a) Al13SO4, (b) Al13SO4 + Fe and (c) Al13SO4 + Ce + Fe.

Fig. 5.

27

Al NMR spectra for Al13, Al13 + Fe and Al13 + Ce + Fe sulfates and nitrates.

17.927(4) A and 17.972(5) A for Al13SO4, Al13SO4 + Fe and Al13 SO4 + Ce + Fe, respectively. To complement the XRD analysis, Al13SO4 + Fe with 2.0 mol% and 3.5 mol% Fe was synthesized and the unit cell parameter was determined (Fig. 3). A linear change was found in the a parameter with molar percentage of Fe used in the synthesis, which agrees

Fig. 6. XRD of clays modied with Al, AlFe and AlCeFe.

with Vegards law [21]. The a parameter of the Al13SO4 + Fe samples with 2.0, 3.5 and 5.0 mol% of Fe gradually decreases in relation to Al13SO4, which might indicate a substitution of Al for Fe in the structure of Al13SO4. Relying only on the analysis of the change in the a parameter in Al13SO4 + Fe, it is not possible to establish whether the substitution of Fe occurs in Al(IV) or Al(VI) of Al13 Keggin. It is proposed that the Fe3+ should be replacing the Al(VI). This theory is based on the facts that that ionic radii of Al(IV) and Al(VI) are 0.53 and 0.68 A, respectively [22], that those of the Fe2+ and Fe3+are 0.82 and 0.67 A, respectively [23], and that, by Mossbauer analysis, it was found that Fe is in octahedral coordination (the results were not detailed in this paper). Additionally, since the ionic radio of Fe3+ (0.67 A) is lower than that of Al(VI) (0.68 A), it would be expected that the a parameter appears reduced. The DRX of Al13, Al13 + Fe and Al13 + Ce + Fe nitrates (Fig. 1) show a low crystallinity and a wide peak with spacing between 11.8 and 12.7 A, similar to that reported in literature for the complex Al13 with nitrate anions [2]. There is also presence of contamination by Ba(NO3)2 in Al13NO3 + Ce + Fe, which has been seen by Aouad et al. [2] in the basic aluminum nitrate as a result of an incomplete interchange of species. Fig. 4 shows the scanning electron microscopy of Al13, Al13 + Fe and Al13 + Ce + Fe sulfates. Different morphologies have been reported for the Al13 sulfate, forming plate-like, rectangular and tetrahedral shapes, among others. Furrer et al. [13] only reported tetrahedral shapes with a typical diameter of 0.1 nm, while images obtained by Duong et al. [24] and Johansson [18] just show tetrahedral morphology for the basic aluminum sulfate with a cubic crystalline system. The morphology of basic aluminum sulfate in all samples of Fig. 4 is eminently tetrahedral with aggregates of variable size. However, in the Al13 + Fe and Al13 + Ce + Fe sulfates, the aggregates present erosion and irregularities on the surface, likely caused by the effect of the metal (Fe and/or Ce) added to the aluminum Keggin polymer. Given the low crystallinity of Al13, Al13 + Fe and Al13 + Ce + Fe nitrates, microscopies do not allow for observation of a specic morphology or differences between compounds. 27 Al NMR spectra for Al13, Al13 + Fe and Al13 + Ce + Fe sulfates and nitrates are presented in Fig. 5. The spectra of sulfates show a peak centered around 62 ppm, which is characteristic of Al13 polycation [25]. However, there is no signal between 3.42 and 5.72 ppm reported by Kloprogge et al. [17] for the basic aluminum sulfate, nor is there a 9.8 ppm peak described by Aouad et al. [2] for the same compound with a monocline crystalline system [2]. The absence of such signals may be associated with the synthesis method and type of crystalline system obtained. Indeed, the spectrum of Al13 sulfate shown in Fig. 6 corresponds to a cubic crystalline system and is identical to that described by Allouche et al. [25] for the same crystalline system. 27 Al NMR spectra of Al13, Al13 + Fe and Al13 + Ce + Fe nitrates show two wide peaks: the rst between 2.6 and 3.9 ppm and the second at 61.5 ppm, which corresponds to aluminum in tetra-

N.R. Sanabria et al. / Applied Catalysis A: General 356 (2009) 243249 Table 2 Chemical analysis of pillared clays with Al, AlFe and AlCeFe and atomic ratios of Si/Al and Si/Fe. Sample B-nat B-Al B-AlFe B-AlCeFe Si (%) 22.87 20.47 21.57 21.59 Al (%) 9.83 15.22 13.45 14.46 Fe (%) 6.03 5.08 5.39 5.35 Mg (%) 1.49 1.19 1.26 1.27 Ca (%) 0.36 0.47 0.51 0.50 Na (%) 2.23 0.50 0.51 0.52 Ce (ppm) 42 Si/Al 2.33 1.34 1.60 1.49

247

Si/Fe 3.79 4.03 4.00 4.04

(%): Mass percentage.

Table 3 Textural characterization of natural bentonite and pillared clays. Sample B-nat [29] B-Al B-AlFe B-AlCeFe SBET (m2/g) 42.8 102.5 145.0 120.3 SLangmuir (m2/g) 43.7 118.7 161.5 133.7 STotal
BET-Remy

(m2/g)

SExternal 41.6 36.2 33.3 34.6

BET-Remy

(m2/g)

Smicropore (m2/g) 1.7 79.3 126.4 102.1

Vmicropore (cm3/g) 0.0006 0.0285 0.0447 0.0361

43.3 115.5 159.7 136.6

hedral coordination in the e-Keggin ion. The signal at 3.9 ppm (Al13NO3), 2.6 ppm (Al13NO3 + Fe) and 3.1 ppm (Al13 NO3 + Ce + Fe) corresponds to aluminum in octahedral coordination, as described by Kloprogge et al. [17] for the basic aluminum sulfate. The difference in the signal position for each polymer could be associated with differences in the chemical composition of Al(VI), caused by the effect of de added Fe and Ce. According to Parker et al. [19], the substitution of Al(IV) of Al13 and polymerization of Al13 units (to form AlP2 or higher species) causes a decrease in the signal of 63 ppm, and only analysis of the solid product (XRD, NMR) obtained by precipitation can permit a distinction between substitution (with a metal) and conversion (to AlP2 or other species). Taking into account variations in the patterns of X-ray diffraction of Al13SO4 + Fe and Al13 SO4 + Ce + Fe with respect to Al13SO4 and changes in the NMR signal of Al(VI) and sulfates and nitrates, an effective isomorphous substitution of octahedral Al3+ for Fe3+ in Keggin ion salts is proposed. 3.2. Characterizing pillared clays In general, all the clays were modied (Table 2), revealing, according to the Si/Al ratio, an increase in the Al content in the solids B-Al, B-AlFe and B-AlCeFe. The ratio of Si/Fe remained fairly constant in all modied clays, since the content of Fe in the pillaring agents Al13NO3 + Fe and Al13NO3 + Ce + Fe was only 0.17%. Regarding Ce, the content was 0.01% in the polymer Al13 NO3 + Ce + Fe and 42 ppm in the solid B-AlCeFe. The X-ray diffraction patterns of pillared clays (Fig. 6) show the effective introduction of metal polyhydroxocations and the subsequent formation of pillars in the interlaminar spacing. The shift in d001 reection for the basal spacing of 13.8 A for the starting clay of (B-nat not calcined) at 17.1 A (B-Al), 18.2 A (B-AlFe) and 18.3 A (B-AlCeFe) conrms the successful modication of the three solids via pillaring. These basal spacing are greater than those reported for the same bentonite modied with Al, AlFe (10 mol% Fe) and AlCeFe (10 mol% Ce and 10 mol% Fe) obtained by the conventional method (clay 2 wt.% and a diluted pillaring solution) whose d001 values: 16.5, 15.8 and 17.7 A, respectively [11]. To determine the surface area of natural bentonite and pillared clays, models BET [26] and BET corrected according to Remy et al. [27] and Langmuir [28] were used. External surface area and microporous volume were assessed by t curves (statistical thickness between 3.5 and 5.0 A), using the Harkins-Jura equation [28]. The values of surface area and microporous volume of the modied solids (Table 3) show an increase in surface area, corresponding to successful pillaring of the clay and consequent

formation of microporous structures. In fact, the measured surface area on the modied solids is practically given by the microporous area. The surface area (SBET) of clays pillared with Al and AlFe, using the conventional method, is 86 and 118 m2/g, and the micropore volumes are 0.0253 and 0.0372 cm3/g, respectively [11], both values are less than those obtained in this work for the same system. AlCe Fe pillared clay in a concentrated medium shows not only a surface area (SBET = 132 m2/g) but also micropore volume (0.0418 cm3/g) less than those obtained from the same pillared clay using conventional methodology. These differences could be caused by the nominal amount of Fe and Ce used in both syntheses and by the incorporation of these two metals in the pillared clays.

Fig. 7. Catalytic activity of the modied clays in the phenol oxidation reaction in dilute aqueous medium, at 25 8C.

Fig. 8. TOC elimination by the modied clays in the phenol oxidation reaction in dilute aqueous medium, at 25 8C.

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Table 4 Comparison of catalytic activity of pillared clays after 4 h reaction. Sample Conventional method [11,16] Phenol conversion (%) B-Al B-AlFe B-AlCeFe 100 100 100 TOC conversion (%) 38 50 56 Concentrated medium Phenol conversion (%) 100 100 100 TOC conversion (%) 36 48 58

Fig. 10. TOC elimination by the fresh and reused catalyst in the phenol oxidation reaction in dilute aqueous medium, at 25 8C.

Fig. 9. Catalytic activity of the fresh and reused catalyst in the phenol oxidation reaction in dilute aqueous medium, at 25 8C.

3.3. Oxidation of phenol in dilute aqueous medium The results of the catalytic evaluation of pillared clays conrm the benecial effect of the introduction of Fe and Ce species into solids, both in the conversion of phenol (Fig. 7) and in the total organic carbon, TOC (Fig. 8). The solids B-AlFe and B-AlCeFe reach 100% conversion of phenol at 2 h of reaction, while the B-Al solid reaches it after 3 h. Calcined B-nat only reached 37.8% conversion of phenol after 4 h of reaction. The three pillared clays (B-Al, B-AlFe and B-AlCeFe) show conversion values of total organic carbon much higher than those of natural calcined bentonite at 400 8C. The percentage of conversion of COT for modied solids ranges between 36% and 58%, being higher for the B-AlCeFe. When comparing the catalytic results of pillared clays (B-Al, BAlFe and B-AlCeFe) in a concentrated medium, with those of similar solids synthesized using the conventional method (2% clay and dilute pillaring solution) [11], signicant differences in the conversion of phenol and TOC are not observed (Table 4). Most of the active catalysts proposed for CWPO of phenol are solids containing either noble metals (Pt, Ru) or transition metals (Cu, Co, Mn, Fe) as the active redox phases. Typical reaction conditions allowing phenol conversion >9095% and TOC removal >8090% are T = 100200 8C and t = 13 h [30]. Therefore, the results obtained in this work are excellent, considering that the reaction was carried out at 25 8C and at atmospheric pressure. Considering that the solids synthesized in this work have smaller quantities of Fe and Ce, the amount of leachate Fe is much lower. The leachate iron in the medium, after 4 h of reaction, was 0.13 ppm for B-nat calcined, 0.16 ppm for B-Al, 0.18 ppm for B-AlFe and 0.16 ppm for B-AlCeFe. These values were lower than those reported for similar solids synthesized by the conventional method (0.20, 0.21y 0.25 ppm for a bentonite pillared with Al, AlFe y Al CeFe, respectively [10]), thus demonstrating the stability of the active phase.

To assess the stability of pillared clays, re-use tests in the oxidation reaction of phenol using the B-AlFe and B-AlCeFe solids were performed (Figs. 9 and 10). In both cases, the catalysts preserved their activity during the two re-use test. As shown in Figs. 9 and 10, none of the catalysts becomes deactivated after the re-use. On the contrary, a slight increase in the conversion of phenol and TOC with the re-use is observed, a behavior already recorded in these types of solids as a result of the cleaning of the catalysts surface, which leaves the active phase more exposed to the reaction [16]. The contents of Fe leached during re-uses were lower than 0.12 ppm, suggesting that the active phase is strongly linked to the clay and is highly stable. This fact shows that the fraction of iron leached from the catalyst is not capable to transforming the phenol, and the homogeneous part of the reaction, is of minor importance [7]. 4. Conclusions The synthesized Al13, Al13 + Fe and Al13 + Ce + Fe sulfates exhibit a cubic crystalline system. The value of a cell unit parameter linearly varies with the molar % of Fe used in the synthesis: 2.0%, 3.5% and 5.0%, following Vegards law, which may indicate a substitution of the octahedral Al3+ for Fe3+ in the structure of Al13SO4. Changes in the signal of Al(VI) in the spectra of 27Al NMR for Al13 + Fe and Al13 + Ce + Fe sulfates and nitrates alter the environment of Al(VI). The synthesis of Al13, Al13 + Fe and Al13 + Ce + Fe nitrates from the corresponding sulfates allows the use of these polyhydroxocations as pillaring agents. The synthesis of pillared clays by mixed systems AlFe and Al CeFe in a concentrated medium allows a 9095% decrease in the volume of water and a reduction in the intercalation times between 70% and 93% with respect to the conventional synthesis. The pillared clays using this new methodology show a catalytic activity and selectivity comparable to those of solids synthesized by the conventional method in a dilute medium. Additionally, the active phase is stable in the reaction medium and the leached Fe is lower than 0.18 ppm. Acknowledgements The authors are grateful for the nancial support offered by projects CSIC-COLCIENCIAS (code 2006CO0015) and DIB (code 201010010522) of Universidad Nacional de Colombia Sede Bogota.

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