Catalysis Communications 10 (2008) 227231

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Liquid phase oxidation of ethylbenzene on pure and metal doped HS-AlF3

Irmina K. Murwani a, Kerstin Scheurell b, Erhard Kemnitz b,*
a b

Jurusan Kimia FMIPA-ITS, Kampus ITS Keputih Sukolilo, Surabaya-60111, Indonesia Humboldt University of Berlin, Institute of Chemistry, BrookTaylor Street 2, Berlin D-12489, Germany

a r t i c l e

i n f o

a b s t r a c t
Pure and doped high surface aluminium uorides (HS-AlF3) with different active metal species (Fe, Mn, V, and Nb) were prepared by a solgel uorination technique. The resulting solids were characterised by MAS NMR, pyridine photoacoustic spectroscopy, NH3 TPD and O2 chemisorption. As probe reaction for the catalytic behaviour of the samples the selective liquid phase oxidation of ethylbenzene (EB) to acetophenone (AP) was used. The catalytic behaviour strongly depends on the type and strength of the surface acid sites formed and on the oxidation capacities of the active metal sites. The best results were obtained (high EB conversion and selectivity towards AP) with the vanadium and iron doped aluminium uoride, whereas the vanadium containing sample tends to leach under the reaction conditions. 2008 Elsevier B.V. All rights reserved.

Article history: Received 17 April 2008 Received in revised form 27 August 2008 Accepted 28 August 2008 Available online xxxx

1. Introduction Usually silica, zirconia and alumina are used as supports for catalytic active transition metal oxides in the selective oxidation of organic compounds with oxygen as oxidant. The performance of such catalysts strongly depends on the coordination and dispersion of the active metal oxide species as well as on the surface properties of the solid system [1,2]. By means of bulk doping methods, such as solgel techniques, a high dispersion of the active metal sites can be achieved [3]. Besides the oxidation capability of such active sites, the surface acidity of the solid surface is of particular importance for the catalytic behaviour. Earlier studies demonstrate that the presence of Brnsted acid sites leads to a lower selectivity to the desired products of partial oxidation processes, since total oxidation products are favoured [3]. Therefore, Lewis acid catalysts are required for a more selective activation of organic reactants. It has been shown that a new class of aluminium uoride based solids are applicable as catalysts for the oxidative dehydrogenation of propane to propene. In case of VOx doped aluminium uorides no mobile lattice oxygen is available, but the activity and selectivity in the ODH of propane is comparatively high [4,5]. The properties of the uoride anion host lattice combined with a high concentration of almost exclusively Lewis acid sites are responsible for the remarkable oxidation behaviour of the VOx doped aluminium uorides [5]. From the results of the catalytic studies of the VOx doped aluminium uorides the question arised, whether fully uorinated aluminium uorides with different active transition metal sites (V, Fe, Mn, and Nb) also apply as selective oxidation catalysts.

For the preparation of the doped uorides, the synthesis route to HS-AlF3 can be adapted [6]. In order to obtain fully uorinated samples, a special postuorination treatment has to be performed (see below). Such aluminium uorides are highly Lewis acidic and in combination with redox active metal sites they should be suitable for catalytic oxidation reactions. In most cases, the activation of gaseous organic reactants in oxidation reactions requires temperatures (300500 C) higher than the postuorination temperature of dry AlF-gels. For that reason in the present study the liquid phase oxidation of ethylbenzene (EB) at 60 C was used as probe reaction for the prepared oxidation catalysts. The oxidation products of EB are widely employed as intermediates in organic, steroid and resin synthesis [79]. Usually, H2O2 is used as liquid oxidant for the oxidation of organic substrates [10], but the presence of oxygen donors such as t-butylhydroperoxide (TBHP) are shown to be more and more important [1113]. Here, we report on the preparation and catalytic properties of pure and doped high surface aluminium uorides (HS-AlF3) with different active metal species (Fe, Mn, V, and Nb). Detailed MAS NMR, pyridine photoacoustic spectroscopy, NH3 TPD and O2 chemisorption studies were performed to explain the different catalytic behaviour. 2. Experimental 2.1. Catalyst preparation Following the synthesis route described in ref. [5,6,14], doped aluminium uorides with different transition metals (Fe, Mn, V, and Nb) were prepared by the solgel reaction of aluminium triisopropoxide (Aldrich, P98%), anhydrous hydrogen uoride and the metal precursors (iron(III) ethoxide, 99% ABCR; manganous acetyl-

* Corresponding author. Tel.: +49 30 2093 7555; fax: +49 30 2093 7277. E-mail address: erhard.kemnitz@chemie.hu-berlin.de (E. Kemnitz). 1566-7367/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2008.08.025

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acetonate, Aldrich; vanadium(V) oxytripropoxide, P98%, Aldrich and niobium(V) ethoxide (99.9% STREM). After removing the solvent, the dried precursors were postuorinated by a CHClF2 gas ow for several hours up to 200230 C. 2.2. Characterisation XRD measurements were performed using the FMP 7 equipment (Rich. Seiffert & Co., Freiberg) with Cu Ka1.2, (k = 1.5418 ) radiation. 19 F and 27Al MAS NMR were recorded at room temperature on a Bruker AVANCE 400 spectrometer (Lamor frequencies: m19F = 376.4 MHz; m27Al = 104.3 MHz) using a 2.5 mm magic angle spinning (MAS) probe (Bruker Biospin) and applying spinning frequencies up to 25 and 30 kHz, respectively. 19F MAS NMR spectra were recorded with a p/2 pulse duration of p1 = 2 ls and a recycle delay of 30 s. The isotropic chemical shifts diso of the 19F resonance are given below with respect of the CFCl3 standard. 27Al MAS NMR (I = 5/2) spectra were recorded with an excitation pulse duration of 1 ls. A 1 M aqueous solution of AlCl3 was used as reference for the chemical shift of 27Al. The recycle delay was chosen as 1 s and an accumulation number of 7950 was used. The solid state NMR spectra were handled using the Bruker XWIN NMR software. Lewis acid sites (LPy) and Brnsted acid sites (BPy) were analysed by FTIR photoacoustic spectroscopy after pyridine adsorption (Py-PAS). For that purpose, pyridine was adsorbed on the sample at 150 C, and the FTIR spectra of pyridine loaded and unloaded samples were recorded at room temperature between 4000 and 400 cm1 using a MTEC 200 photoacoustic cell (FTIR system: Digilab Excalibur FTS 3000-spectrometer; 2.5 kHz, 64 scans). The intensities of the bands at about 1445 cm1 (LPy), 1490 cm1 (Lpy and BPy) and 1540 cm1 (BPy) in the normalised spectra were used to determine the type of acid sites semiquantitatively. For the NH3 TPD experiments, the samples were pretreated at 250 C for 1 h. Afterwards, ammonia was adsorbed onto the surface of the samples at 120 C. Ammonia desorption was monitored during TPD (10 C/min up to 500 C) by FTIR detection (FTIR system 2000, Perkin Elmer) of the band at 930 cm1. The total amount of ammonia desorbed was determined by a reaction with an excess of sulphuric acid and back titration with sodium hydroxide solution. Oxygen uptakes were measured in a volumetric adsorption unit (Micromeritics ASAP 2020) using a standard double isotherm method [15]. For each experiment the samples (100 mg) were pretreated under vacuum at 300 C. After that, oxygen was introduced into the manifold system and was equilibrated for 10 s. Then the sample, at 300 C, was exposed to the gas. A 10 s equilibration time was used. The rate of change of pressure from the rst to the last pressure point was computed. 2.3. Catalytic experiments The liquid phase oxidation of ethylbenzene was carried out under inert conditions (Ar-ow) in a 50 ml Schlenk ask which was connected with a reux condenser. The reaction mixture (50 mg catalyst; 1.2 ml EB; 5.5 ml TBHP and 10 ml acetonitrile) was stirred at 60 C with a magnetic stirrer. After 2, 4, and 6 h the oxidation products were identied by gas chromatography (Shimadzu GC 2010) equipped with FID detector using an innowax capillary column.

AlOi(Pr)3 (iPrOH)

+ metal precursor
homogenis e

homogeneous mixture + HF (iPrOH)

wet gel
drying 70C ; vacuum

xerogel
activation; C H C l F2 200 230C

Al 0.9M0.1F3
Scheme 1.

step, gels are formed, which contain considerable amounts of residual organics. In a second step the uoride catalysts arise from these dry gels by postuorination by a CHClF2 ow at 200230 C. Under these conditions the exchange of the remaining alkoxide groups by uorine takes place. Based on elemental analysis, the resulting carbon content of the samples is lower than 1% and aluminium as well as the doped metals are almost completely uorinated. The strength of the Lewis acid sites can be estimated from the conversion of the uorination agent CHClF2 near room temperature [6]. Only strong Lewis acid sites catalyse this reaction at room temperature. Crystalline, catalytic active b-AlF3 needs temperatures of about 280 C [16]. In Table 1 the maximum temperature for almost complete conversion of CHClF2 and the conversion at 30 C is given for the different prepared aluminium uorides. It clearly shows that a CHClF2 conversion of nearly 100% (30 C) is only achieved with pure HS-AlF3 and Fe and V doped samples. The other samples are more or less inactive at 30 C. Apparently, by doping HS-AlF3 with Nb and Mn no strong Lewis acid sites were formed. 3.1. Bulk properties X-ray diffraction analysis conrmed the X-ray amorphous character of all samples, which is characteristic for many phases prepared via the solgel route described above [17]. Due to the moisture free synthesis followed by a postuorination under mild conditions solid aluminium uorides were obtained whose host lattices have a high degree of structural distortion [17,18]. The local environment of the aluminium and uorine species of selected samples has been investigated by MAS NMR spectroscopy. The 27Al MAS NMR spectra of pure HS-AlF3 and Fe and Nb doped aluminium uorides are shown in Fig. 1. The spread of the spinning side bands is very similar for all three samples. The featureless shape of the spinning side bands indicates distributions of quadrupole coupling constants (QCC) caused by highly distorted alumin-

Table 1 Maximum temperature and conversion of CHClF2 at 30 C for the postuorination reaction Samples Tmax (C) 230 220 230 230 200 X CHClF2 (%) 96 96 96 96 96 X CHClF2 at 30 C (%) 99 97 30 99 15

3. Results and discussion The synthesis route to HS-AlF3 and the metal (Fe, Mn, V and Nb) doped HS-AlF3 according to [6] is described in Scheme 1. In a rst

HS-AlF3 Al0.9Fe0.1F3d Al0.9Mn0.1F3+d Al0.9V0.1F3+d Al0.9Nb0.1F3+d

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3.2. Surface properties FTIR spectra of pyridine adsorbed on pure and metal doped high surface aluminium uoride are shown in Fig. 2. The vibration bands at 1540 and 1450 cm1 correspond to pyridinium ions formed on Brnsted acid sites (BPy) and pyridine coordinated on Lewis acid sites (LPy), respectively [23]. Pure HS-AlF3 exhibits both Lewis as well as Brnsted acid sites, the latter caused by water adsorbed during the sample preparation [24]. As can be seen from the ratio of the vibration bands at 1450 and 1490 cm1, the doping of the HS-AlF3 with the metals Mn and V leads to the formation of predominantly Lewis acid sites at the solid surfaces. In case of Fe as doping metal, only Lewis acid sites were formed. According to Resini et al. [25] who discussed the acid base properties of binary and mixed metal oxides depending on their oxidation state, cation size and MO bond nature, similar considerations also apply to the surface properties of the doped aluminium uorides. However, the distinct Lewis acid character of the doped uoride samples indicates that the metals Mn and V are not present in their highest oxidation state. The strong decrease of Lewis acid sites on the surface of the Nb doped aluminium uoride may be caused by its very high sensitivity toward hydrolysis. Probably, in spite of a preparation under moisture free conditions it was not possible to avoid an access of traces of moisture and similar to the pure HS-AlF3 where very strong Lewis acid sites are available directly after the postuorination; small amounts of water (during the sample preparation and/or storage) can easily adsorb and initiate the hydrolysis on these surface sites. In such cases less or none Lewis acid sites can be found on the solid surfaces. As can be seen from Fig. 3, the desorption prole of the ammonia band of pure HS-AlF3 is broad and structured; acid sites of different strengths (from medium strong until strong) are formed and their concentrationcalculated from the amount of ammonia desorbedis with 899 lmol/g (Table 2) relatively high. This behaviour is known for high surface aluminium uorides and a comparison with VOx

Fig. 1. 27Al MAS NMR spectra of pure and metal doped HS-AlF3 taken with 2.5 mm probe and a spinning speed of 25 kHz; the central transitions given enlarged as insert.

ium environments [19]. In the pure and metal doped aluminium uorides the aluminium atoms of the bulk are in a sixfold uorine coordination as can be seen from the position of the central line at 15 to 17 ppm [20]. It seems, during the incorporation of the metals Fe and Nb the aluminium uoride matrix is almost unchanged. However, more pronounced differences exist in the shape of the central transitions. For the Fe containing sample the signal of the central 27Al transition is much broader than the others. On one hand, inhomogeneous distributions are responsible for the observed line broadening and for the engraftment of the spinning side bands. On the other hand, this marked broadening can be a direct consequence of the paramagnetism of the Fe ions, whose unpaired electrons generate a local magnetic eld that strongly perturbs the resonance of the 27Al nuclei. These conclusions are conrmed by the 19F MAS NMR measurements of the same samples (not expl. shown here). According to Knig and Chupas et al., who developed a partial chemical shift scale for 19F depending on its environment uorine and/or oxygen, the chemical shift of dF = 167 to 169 ppm indicates the formation of mainly AlF6 units in a distorted matrix [21,22].

Fig. 3. NH3 TPD curves on pure and metal doped HS-AlF3.

Table 2 Results of the surface properties determined by BET, NH3 TPD and O2 chemisorption Samples HS-AlF3 Al0.9Fe0.1F3d Al0.9Mn0.1F3+d Al0.9V0.1F3+d Al0.9Nb0.1F3+d SBET (m2/g) 251 198 181 178 113 dp () 79 73 131 47 37 NH3
des

(lmol/g)

O2 uptake (ml STP/g) 0.15 4.57 0.50 3.57 n. d.

Fig. 2. FTIR spectra of pyridine adsorbed on pure and metal doped HS-AlF3.

899 932 141 634 1033

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doped aluminium oxyuorides and aluminium uorides shows that such high acidities can only be achieved by almost complete exclusion of moisture during the synthesis [46]. Doping of the HS-AlF3 with the metals V and Fe leads to a shift of the desorption proles to higher temperatures; i.e., the strength of the acid sites is increased. In contrast, in case of the Nb doped sample the ammonia is already completely desorbed at 400 C. Here the acid sites (Brnsted) are only medium strong, but their concentration is with 1033 lmol/g rather high. The acidity (strength as well as concentration) of the Mn containing solid, however, is very poor. The results of the dismutation (see above) and of ethylbenzene oxidation experiments (see below) clearly suggest that Nb and Mn cannot generate Lewis acid sites on the HS-AlF3 surface which are strong enough for catalytic applications. 3.3. Oxygen chemisorption From temperature dependent oxygen uptake experiments an uptake beginning at about 300 C was observed. Obviously, the chemisorption and/or oxidation properties of the aluminium uorides depend on the type of active metal species. On undoped HSAlF3 a small amount of oxygen was consumed-only by chemisorption on the strong Lewis acid sites (Table 2). Due to an additional oxidation process, the V and Fe containing solids adsorb more oxygen. Apparently, these metals exist in their lower oxidation states after the synthesis and can consume oxygen under these conditions. The Mn doped sample exhibits a totally different adsorption/ oxidation behaviour. Obviously, the very small amount of oxygen (0.5 ml STP/g) was adsorbed only by minor interactions between O2 and the solid surface. This can be explained by two reasons:

1. the total acidity (see Table 2) of the Mn doped aluminium uoride is very low and chemisorption processes are suppressed and/or, 2. manganese can not be oxidised to a higher oxidation state under the above conditions. For the Nb doped aluminium uoride it was not possible to analyse the oxidation behaviour because of the fact that the OHgroups on the solid surface promote hydrolysis to HF resulting in corrosion of the measuring equipment. 3.4. 4. Catalytic properties The oxidation of ethylbenzene (EB) with t-butylhydroperoxide (TBHP) on HS-AlF3 and the metal doped aluminium uorides has been carried out in liquid phase (acetonitrile as standard solvent) at 60 C with a feed ratio EB:TBHP of 1:3 (Table 3). In order to avoid the contact of the catalysts with water at the beginning of the catalytic reaction, an organic solution of TBHP (in decane) has been used. Using aqueous solutions of H2O2 or TBHP as oxidants, the catalytic EB oxidation usually results in the formation of three main products (acetophenone AP, benzaldehyde BZ, benzoic acid BA), whereby BA is formed due to consecutive oxidation of BZ [11,26]. As can be seen from Table 3, the same oxidation products were obtained in case of the pure and metal doped aluminium uorides in an organic solution of TBHP. In addition to the main products AP, BZ and BA, small quantities of different by-products were formed, whose total amount is given as others. Surprisingly, the EB conversion on the pure HS-AlF3 is with 42% (after 6 h) relatively high. Obviously, the activation of the educts takes place only on strong Lewis acid surface sites. Unfortunately, the selectivity towards the desired product AP is poor (16%). According to Vetrivel et al. [11] the formation of AP requires chemisorption of alkylhydroperoxide on Lewis acid sites followed by the oxidation of the secondary carbon of EB and appropriate cleavage of bonds. The direct correlation between oxygen uptake and AP yield (Fig. 5) demonstrates that in case of HS-AlF3 no additional oxidising sites are available on the catalyst surface. Hence, the oxidation of EB is suppressed and only small amounts of AP can be formed. Similar to the results of the CHClF2 dismutation experiments (see above), the doping of HS-AlF3 with the metals Mn and Nb leads to a decrease of the EB conversion (Table 3). Investigations of the surface properties (type and concentration of the acid sites) revealed that the Mn doped sample contains only a small amount of medium - weak Lewis acid sites and the Nb doped sample exhibits a very high concentration of Brnsted acid sites. Apparently, on these catalysts the educts cannot be sufciently activated. In contrast to that, the EB conversion as well as the selectivity to AP are increased by doping the HS-AlF3 with V and Fe. The best results were obtained for the sample Al0.9Fe0.1F3d (XEB = 70% and SAP = 72%). A similar AP selectivity was observed by Bhoware [26] and Radhika et al. [27] on ceria supported vanadia and cobalt containing MCM-41 respectively, but the EB conversion for these systems is lower. In case of the ceria supported vanadia under the same reaction conditions (60 C; 6 h) a highest conversion of only 21% was obtained. In contrast to that the conversion of EB at the cobalt containing MCM-41 systems was with 47% higher, but the reaction conditions (80 C; 24 h) were different from the conditions used in this work. A correlation between the catalytic results and the acid site concentration (Fig. 4) and the adsorption/oxidation behaviour (Fig. 5) of the prepared catalysts shows that a combination of a high oxidation power of the active metal sites and a sufcient quantity of Lewis acid surface sites are crucial for the catalytic reaction. Already, a high Lewis acid site concentration alone (Fig. 4; HS-AlF3) leads to

Table 3 Oxidation of ethylbenzene (EB) at 60 C Catalyst HS-AlF3 Reaction time (h) Conversion (%) Selectivity (%) AP BZ BA Others Conversion (%) Selectivity (%) AP BZ BA Others Conversion (%) Selectivity (%) AP BZ BA Others Conversion (%) Selectivity (%) AP BZ BA Others Conversion (%) Selectivity (%) AP BZ BA Others 2 2 16 33 0 51 41 65 9 <1 26 6 16 38 0 46 6 25 40 <1 35 0 0 0 0 0 4 37 15 36 0 49 53 71 8 <1 20 19 18 53 0 29 62 34 41 <1 24 7 9 25 0 66 6 42 16 36 0 48 70 72 8 <1 20 20 25 57 0 19 76 39 32 0 29 21 16 22 0 62

Al0.9Fe0.1F3-d

Al0.9Mn0.1F3+d

Al0.9V0.1F3+d

Al0.9Nb0.1F3+d

Reaction conditions: 50 mg catalyst; molar ratio EB:TBHP = 1:3; acetonitrile as solvent AP: acetophenone; BZ: benzaldehyde; BA: benzoic acid

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4. Conclusion Aluminium uorides doped with different transition metals (Mn, Nb, V, and Fe) as active species for the ethylbenzene oxidation have been synthesised using a solgel uorination technique. The catalytic results correlate well with the type and concentration of the acid sites and the oxygen chemisorption capacities of the catalysts. If only Brnsted (Al0.9Nb0.1F3+d) or small amounts of weak Lewis acid sites (Al0.9Mn0.1F3+d) are available on the solid surfaces, the EB conversion is very low. In contrast, the undoped strong Lewis acid HS-AlF3 shows a signicant conversion of EB, but the selectivity to the desired product AP is poor. The best catalytic results (high EB conversion and selectivity to AP) can be achieved by doping the aluminium uoride with vanadium or iron. In such cases the catalysts possess both, a high concentration of strong Lewis acid sites and a relatively high oxygen chemisorption capacity. Unfortunately, the vanadium containing sample tends to leach under the reaction conditions used.

Fig. 4. EB conversion and AP selectivity of pure and metal doped HS-AlF3 depending on their acid sites concentration.

Acknowledgement Irmina K. Murwani gratefully acknowledges the DAAD for nancial support. We also thank Dr. G. Scholz and DC R. Knig for performing the MAS NMR, S.Baessler for Py PAS/NH3 TPD and I. Hinz for the catalytic measurements. References
[1] I.E. Wachs, Y. Chen, J.M. Jehng, L.E. Briand, T. Tanaka, Catal. Today. 78 (2003) 13. [2] B.M. Weckhuysen, D.E. Keller, Catal. Today. 78 (2003) 25. [3] K. Scheurell, E. Hoppe, K.W. Brzezinka, E. Kemnitz, J. Mater. Chem. 14 (2004) 2560. [4] K. Scheurell, E. Kemnitz, J. Mater. Chem. 15 (2005) 4845. [5] K. Scheurell, G. Scholz, A. Pawlik, E. Kemnitz, Solid State Sci. 10 (2008) 873. [6] E. Kemnitz, U. Gross, S. Rudiger, C.S. Shekar, Angew. Chem. Int. Edit. 42 (2003) 4251. [7] N.K. Mal, V. Ramaswamy, S. Ganapathy, A.V. Ramaswamy, Appl. Catal. a-Gen. 125 (1995) 233. [8] R. Alcantara, L. Canoira, P.G. Joao, J.M. Santos, I. Vazquez, Appl. Catal. a-Gen. 203 (2000) 259. [9] G.L. Tembe, P.A. Ganeshpure, S. Satish, J. Mol. Catal. a-Chem. 121 (1997) 17. [10] J.S. Reddy, R. Kumar, P. Ratnasamy, Appl. Catal. 58 (1990) L1. [11] S. Vetrivel, A. Pandurangan, J. Mol. Catal. a-Chem. 217 (2004) 165. [12] I.W.C.E. Arends, R.A. Sheldon, Appl. Catal. a-Gen. 212 (2001) 175. [13] T.H. Bennur, D. Srinivas, S. Sivasanker, V.G. Puranik, J. Mol. Catal. a-Chem. 219 (2004) 209. [14] S. Rudiger, G. Eltanany, U. Gross, E. Kemnitz, J. SolGel Sci. Techn. 41 (2007) 299. [15] V.N. Kalevaru, B.D. Raju, V.V. Rao, A. Martin, Catal. Commun. 9 (2008) 715. [16] E. Kemnitz, D.H. Menz, Prog. Solid State Ch. 26 (1998) 97. [17] S. Ruediger, E. Kemnitz, Dalton T. (2008) 1117. [18] R. Konig, G. Scholz, E. Kemnitz, Solid State Nucl. Mag. 32 (2007) 78. [19] K. Scheurell, G. Scholz, E. Kemnitz, J. Solid State Chem. 180 (2007) 749. [20] G. Scholz, O. Korup, Solid State Sci. 8 (2006) 678. [21] R. Knig, G. Scholz, E. Kemnitz, J. Fluorine Chem. submitted (2008). [22] P.J. Chupas, D.R. Corbin, V.N.M. Rao, J.C. Hanson, C.P. Grey, J. Phys. Chem. B. 107 (2003) 8327. [23] T. Barzetti, E. Selli, D. Moscotti, L. Forni, J. Chem. Soc. Faraday T 92 (1996) 1401. [24] T. Krahl, A. Vimont, G. Eltanany, M. Daturi, E. Kemnitz, J. Phys. Chem. C. 111 (2007) 18317. [25] C. Resini, T. Montanari, G. Busca, J.M. Jehng, I.E. Wachs, Catal. Today 99 (2005) 105. [26] S.S. Bhoware, A.P. Singh, J. Mol. Catal. a-Chem. 266 (2007) 118. [27] T. Radhika, S. Sugunan, Catal. Commun. 8 (2007) 150.

Fig. 5. Correlation between AP yield and O2 uptake on pure and metal doped aluminium uorides.

a medium EB conversion (42%). But only the presence of redox active sites in addition to the Lewis acid sites (Fig. 5) increases the EB conversion as well as the AP selectivity. The role of Lewis acid sites might be speculated as follows: 1. Activation of the hydroperoxide (TBHP) on the doped metal uorides as Lewis acid and redox centre. 2. Depending on the redox power of the doped metal, the oxidation of the secondary carbon of EB by the activated oxygen yield AP as main product. In order to conrm the heterogeneity of the catalysts, a leaching study was carried out using a hot ltrate (catalysts were removed after 6 h reaction) at the same reaction conditions. Only the V containing HS-AlF3 revealed a leaching effect, all other samples did not show any further EB conversion after ltration.