Applied Catalysis A: General 223 (2002) 147160

Incorporation of iron in sodalite structures and their transformation into other iron containing zeolites Synthesis of Fe-NaA (LTA)
Pl Fejes a, , Imre Kiricsi a , Kristf Kovcs b , Kroly Lzr c , Istvn Marsi d , Albert Oszk e , Antal Rockenbauer f , Zoltn Schay c
Department of Applied and Environmental Chemistry, University of Szeged, Rerrich ter 1, 6720 Szeged, Hungary b Department of Silicate and Materials Engineering, University of Veszprm, Veszprm, Hungary c Institute of Isotope and Surface Chemistry, Chemical Research Center of the Hungarian Academy of Science, Szeged, Hungary d Juhsz Gyula Teachers Training College, Institute of Chemistry, University of Szeged, Rerrich ter 1, 6720 Szeged, Hungary e Institute of Solid State and Radiochemistry, University of Szeged, Rerrich ter 1, 6720 Szeged, Hungary f Institute of Experimental Physics, Technical University, Budapest, Hungary Received 15 May 2001; received in revised form 11 July 2001; accepted 11 July 2001
a

Abstract In the low temperature digestion of gibbsitic aluminium ores an iron content impurity phase, desilication product (DSP), will be separated from the sodium aluminate liquor. Due to its main component: (hydroxy- or carbonate-) sodalite (SOD) and amount, reaching 710% of the feedstock, the DSP is an important raw material for synthesising various zeolites. Applying the solgel technique the authors developed synthesis methods to prepare iron content (chloride-) sodalites, in order to model how they can be transformed to commercially interesting types of zeolites (e.g. to NaA (LTA)). Using diluted mineral acids (e.g. 5 wt.% sulfuric acid) in amounts equivalent (or rather in 10% excess) to the ion exchange capacity, a heat-treatment at 100 C, lasting 3 h leads to an amorphous product which can easily be recrystallised to various zeolites. Outgoing from iron containing SOD, a new kind of NaA (LTA) could be prepared possessing various amounts of iron. Mssbauer, XP, ESR and UVVIS spectroscopic investigations revealed that up to 3 wt.% total iron content, as an average, about 6062% iron is sited in framework (FW) positions, in Th co-ordination. The other part is located in the voids, in extra-framework (EFW) positions, in Oh co-ordination, as highly dispersed iron oxide. This component exhibits strong magnetic interaction which manifests itself in large linewidths when taking the ESR spectra. Mssbauer spectroscopy revealed that the FW/EFW iron ratio decreased with the total iron content. Due to the chemistry of solgel technique, in alkaline environments complete iron incorporation into zeolitic frameworks can never be attained. Applying complexing agents or other methods EFW iron can be dissolved during the acid treatment permitting the synthesis of low module zeolites with uniform Fe(III) siting. The various kinds of iron content LTA zeolites may catalyse (biomimetic) selective oxidation reactions between reactants capable to enter the pore structure. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Fe (and 57 Fe) content NaA (LTA) zeolites; Instrumental characterisation by SEM; XRD; Mssbauer; DR UVVIS; XP and ESR spectroscopy

Corresponding author. Tel.: +36-62-544-316. E-mail address: fejes@chem.u-szeged.hu (P. Fejes).

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 7 5 4 - 2

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1. Introduction An alternative extraction process for Bayers universally used aluminium manufacture is low temperature (140160 C) digestion of aluminium ores containing predominantly oxides with compositions close to the trihydrate, like gibbsite and hydrargillite (see, e.g. [1]). The removal of silica from the sodium aluminate pregnant liquor (desilication) produces an important by-product, the desilication product (DSP), in amounts reaching 710 wt.% of the gibbsitic type feedstock whose composition approximates that of (hydroxy- or carbonate-) sodalite: 3[Na2 OAl2 O3 2SiO2 (2 + k )H2 O]Na2 X (where 0 k 2, and X: 2OH , CO3 2 , SO4 2 , 2[Al(OH)4 ] or 2Cl ). As impurity phase the DSP contains sulfate sodalite (noseane) and cancrinite as well, in lower quantities. By virtue of its composition DSP can be processed further to higher added value products such as various commercialised zeolites (like NaA (LTA), NaPc (GIS) (e.g. maximum aluminium P, or simply MAP), NaX (FAU) (e.g. low silica X, or LSX), etc.) provided the thermodynamically stable sodalite phase can somehow be transformed into the metastable, thermodynamically not-preferred zeolite phases mentioned previously.

Sodalites are unbelievably stable in alkaline environments (even in caustic melts!), but cannot withstand acids: in diluted mineral acids (sulfuric acid preferred) H3 O+ ions (4 mol dibasic acid is needed per formula-weight sodalite if it contains 2 mol intercalate NaOH) exchange for Na+ ions and at the boiling temperature the sodalite structure turns amorphous within a few hours without complete disintegration of the solid. In the amorphised sodalite the structural aluminium is left practically intact and the sodium content appears dissolved as the relevant sodium salt. The acid treated solid sample can be washed out or even dried if necessary and used as such for synthesising various zeolites. These experimental observations were the key issues to a Hungarian invention providing possibility for the utilisation of amorphised alkali (earth alkali) aluminium hydrosilicates in zeolite syntheses [2]. At the onset of this research work we have got two DSP samples from Ziar nad Hronom (Slovakia). The XRD of this sample (see Fig. 1) reveals clearly that the most intense reexions are due to (hydroxy-) sodalite, indeed, thus what we want to tell about the modication of sodalites is mutatis mutandis valid for DSP samples as well. This paper tries to nd the answers to a few unresolved questions concerning acid treatment (theoreti-

Fig. 1. XRD of a desilication product from Ziar nad Hronom.

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cal and practical amounts of acid, experimental procedures for reliable removal of traces of the sodalite phase, possibility of deferration during the treatment, etc.) and attempts to open up new experimental ways to crystallise amorphised (iron containing) sodalites into NaA (LTA) or other zeolites which contain incorporated Fe(III) ions in the framework structure. It is worth appreciating that the known siting of iron in LTA structures might be advantageous in heterogeneous catalysis as well. Because the Ziar DSP samples, as far as their amounts and iron impurity levels are concerned, were not adept to the task, rst of all it was necessary to synthesise SOD (and thereafter NaA (LTA)) samples with Fe(III) contents between 03 wt.%. Their study by Mssbauer, ESR, XP and diffuse reectance UVVIS absorption spectroscopies was also an important task of this paper.

Typical Si/Fe ratios in the synthesis slurries were: 200, 100, 50 and 25. The crystallisation of slurries was preceded on all occasions by milling (non-abrasive Teon balls!) lasting at least 5 h. The synthesis containers were made of Teon placed in stainless steel casing. For syntheses in the microwave oven pressure-tight autoclaves were applied, made fully of Teon. The fairly lengthy sodalite syntheses could be shortened to 45 min (without ageing and mixing) in the microwave oven. When air thermostat was applied the milled slurry was aged overnight (1415 h) using rocking agitation followed by 5 h crystallisation at 140 C, maintaining the mixing. Iron containing NaA (LTA) specimen were synthesised both from iron silicate gels and acid treated sodalites (containing iron). The approximate composition of this raw material was: 2SiO2 1.0(Al2 O3 + Fe2 O3 )1.2H2 O. Outgoing from gels, part of the high content of water was removed (down to <80%) by soaking the gel in absolute methanol (dehydration using supercritical carbon dioxide was unsuccessful!). Optimum slurry composition was adjusted as in the SOD syntheses. Milling of the inhomogeneous slurry was important here, too. Due to the short crystallisation times in the microwave oven (about 9 min at 88 C) it was not easy to reach maximum crystallinity for NaA without commencing sodalite formation (which might also be caused by local overheating). Therefore, in most of the cases crystallisation of NaA (LTA) slurries has been implemented in air thermostat (ageing overnight at 65 C while mixing, crystallisation at 88 C for 22.5 h). The products underwent the usual post-crystallisation treatments (ltering, washing with warm distilled water (pH < 10.5), drying at 110 C), including inspection by optical microscope and XRD. In order to achieve most uniform distribution of Fe(III) ions the initial iron silicate gels as stipulated by Szostak, we developed a number of synthesis methods referred to further on by letter codes (like A, B, C, etc.), revealing at the same time the Si/Fe ratio too, in the slurry. For example, the mnemonic code Fe-SOD-A50 denotes an iron containing SOD sample,

2. Experimental 2.1. Synthesis methods to produce iron containing sodalites and NaA zeolites According to Szostak the synthesis of Fe(III) content zeolites has to be carried out at low pH of the medium in order to avoid precipitation of insoluble Fe hydroxide [3] which, if formed, cannot be incorporated in the zeolitic framework. Pursuing this principle the (Fe/Al) silicate gels for the planned sodalite and NaA (LTA) syntheses were always prepared in strongly acidic solutions (hydrochloric acid, sulfuric acid; Hammett constants around 2 to 2). Using the solidied gel as such or after careful washing the composition of the synthesis slurry was adjusted by adding the necessary amounts of sodium aluminate (standard composition in mol/100 g solution: 0.124Al2 O3 0.307Na2 O3.398H2 O), NaOH, distilled water and a crystallisation promoter (either NaCl or NaClO4 , or both). Characteristic slurry compositions (in mol) are as follows. For sodalites: 2SiO2 1.0(Al2 O3 + Fe2 O3 )4.19Na2 O98.0H2 O For NaA (LTA): 1.73SiO2 1.0(Al2 O3 + Fe2 O3 )3.58Na2 O92.0H2 O

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prepared by the method A from a slurry where the Si/Fe ratio was 50. A short description of the various methods can be found below. 2.1.1. SOD-A syntheses The Fe (and Al) containing gels were prepared from Fe(NO3 )3 9H2 O and AlCl3 6H2 O in hydrochloric acid solution and Aldrich type waterglass (standard composition in mol/100 g solution: 0.450SiO2 0.175Na2 O3.453H2 O). 2.1.2. SOD-B syntheses In the preparation of these sodalite samples carefully washed (and partly by methanol dehydrated) iron silicate gels (Si/Fe = 200, 100, 50 and 25) were used. In order to increase resonance-absorption in Mssbauer spectroscopy the Si/Fe = 200 samples were prepared with 57 Fe tracer. 2.1.3. SOD-C, acid treatments Iron containing sodalites could be made fully amorphous by treating them with 5 wt.% sulfuric acid at 100 C for 3 h. Application of a slight (10%) excess (4.4 mol sulfuric acid per 3 mol SOD) is advantageous. 2.1.3.1. Description of a typical acid treatment. To 10.0 g of sodalite stored previously under ambient conditions add 85.4 g of 5 wt.% sulfuric acid preferably in a crystallisation container with Teon lining. Close the container, place it in preheated air thermostat and let the acid react at 100 C for 3 h, applying rocking agitation. After cooling lter off the amorphised sodalite, wash it with warm water (and save the rst 200 ml of ltrate for later ICP analysis (Al and Fe)). Dry the solid at 110 C for 45 h. Determine the yield. This amorphised dry sodalite can be used as raw material for various zeolite syntheses. For its composition see the description of NaA-G syntheses. The sodium content of sodalite appears in the aqueous solution as sodium sulfate. Only 1.53% of the aluminium content can be found dissolved as an average value of several treatments. However, it can be conjectured that even this small amount stems not from the lattice, rather from rests of the initial amorphous gel (i.e. from detrital material). The fate of iron is completely different (vide infra).

2.1.4. NaA-F syntheses using gels As described previously, the sol/gel technique is very effective to prepare iron silicate gels with different Si/Fe ratios. After careful washing and (partial) dehydration with absolute methanol these gels are excellent raw materials for NaA syntheses. 2.1.5. NaA-G syntheses outgoing from amorphised sodalites The acid treatment results in an excellent SiO2 and (Al2 O3 + Fe2 O3 ) source of the approximate composition: 2SiO2 1.0(Al2 O3 + Fe2 O3 )1.2H2 O. Comparing this and the optimum slurry composition for NaA (LTA) it is felt that only the missing 3.58 mol Na2 O and (92.01.2) mol H2 O should be supplied. Actually, in order to have smooth crystallisation it is highly recommended to introduce 0.1 mol Al2 O3 in excess in form of sodium aluminate. 2.1.5.1. A representative synthesis description for recrystallisation of amorphised sodalites into NaA (LTA). Pound in a mortar 5 g dry, amorphised sodalite. Put it into a (200 ml) Teon-lined crystallisation container, wet the sample with 12 ml distilled water and make it slightly alkaline by adding a few drops of 50 wt.% NaOH solution (check the pH). Add 43.2 g 14.5 wt.% NaOH and 1.24 g standard aluminate solution (vide supra). To ensure good mixing place 23 Teon balls in the vessel and age the slurry while mixing at 65 C overnight (1214 h). The next morning rise the temperature to 88 C and crystallise the slurry at this temperature for an additional 2.5 h maintaining the agitation. Wash and dry the NaA product as usual. 2.2. Transmission and scanning electron microscopy The microstructure of tenderly powdered samples was investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) in a TESLA BS540 TEM at 120 kV and a Philips XL30 SEM using 20 kV accelerating voltage. Both TEM and SEM specimens were rst ultrasonically dispersed in isopropyl alcohol for 10 min. Drops of the uid were dried onto the Formvar coated TEM grids and polished SEM specimen holders. TEM and SEM specimens were carbon and gold coated, respectively. All TEM micrographs conrmed SEM observations, therefore

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the paper contains the visually more descriptive SEM micrographs only. 2.3. X-ray diffraction X-ray powder diffraction spectra were registered in the 2 = 343 interval using ltered Cu K radiation of the DRON-3 type X-ray diffractometer of the Department for Applied and Environmental Chemistry, Szeged University (Hungary). Both SOD and NaA (LTA) zeolites have primitive cubic crystal structure (P4 3n and Fm3c, respectively). For determining the u.c. parameters the DebyeScherrer powder spectra were registered with reduced scan rate (0.5 min1 ) and increased sensitivity. A modied version of the POWDER code [4] allowed the determination of u.c. parameters within 0.1% cumulative error (instrumental and XRD evaluation error). 2.4. Mssbauer spectroscopy The zeolitic samples were pressed into wafers of 12 mm thickness and submitted to various treatments (heat-treatment, evacuation, reduction by carbon monoxide, etc.) before taking the Mssbauer spectra. The reduction aimed at establishing the emplacement of Fe(III) ions in various (framework, FW, or extra-framework, EFW) positions. EFW Fe(III) ions can be reduced by CO more easily than those sited in (oxygen-) shielded FW positions, thereby, as isomer shifts (IS) and quadrupole splittings (QS) differ markedly for (reduced) Fe(II) and (unreduced) Fe(III) ions, their presence and approximate amounts can at least in principle be assessed by computer deconvolution of the superimposed Mssbauer signals. IS data are always referred to -iron as standard. Location of the Mssbauer signals could be determined with an accuracy of 0.03 mm/s. Description of the measuring cell and additional experimental details can be found in [5]. 2.5. ESR measurements ESR spectra were taken in quartz tubes of 4 mm inner diameter at room temperature on an upgraded JEOL JES-FE3X spectrometer with 100 kHz eld modulation, using Mn(II)-doped MgO for the

calibration of g-measurements. A Lake Shore Model 647 Magnet Power supply and a Stanford Model SR830 DSP Lock-in Amplier were applied. The eld was measured by temperature-stabilised Hall-probe with an accuracy of 105 T. The spectrometer was controlled by a Pentium 100 computer. The spectra were tted by a simulation program capable to approximate each parameter by the combination of various iterative techniques [6]. The experimental spectra were considered as an S = (1/2) (1/2) transition with an effective g-tensor possessing axial symmetry. Powder averaging was carried out in 90 points using anisotropic linewidths. 2.6. XP spectroscopy X-ray photoelectron spectra were registered on a KRATOS XSAM 800 equipment using Al K source, 50 meV step size, 300 ms dwell time, 40 eV pass energy in FAT mode and 10 sweeps for the Fe(2p) range. The VISION software of KRATOS was used for data evaluation. The samples were pressed into wafers of 2 mm thickness and measured in the as received state (including the heat-treated samples as well). The binding energies were referenced to Si(2p) at 103.3 eV. 2.7. Diffuse reectance UVVIS absorption spectroscopy (DRS) Diffuse UVVIS reectance absorption spectra were registered by Perkin-Elmer Lambda 15 type spectrometer working under computer guidance in the 200900 nm wave length domain, using MgO as reference. The spectra were taken at room temperature and ambient conditions without special precautions. 2.8. Chemical analysis After acid treatments the supernatant liquors of samples were analysed for Al and Fe contents using ICP spectrometer at the Department of Inorganic and Analytical Chemistry, Szeged University. The importance of these investigations cannot be overestimated: eventually in the possession of these analytical data could be assessed how much aluminium (or, if at all, iron) will be dissolved from the samples. Had this amount exceeded an acceptable level, this would have

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inevitably contributed to the relinquishment of this promising zeolite by-product utilisation technology.

3. Discussion of results The synthesis of sodalites containing both aluminium and iron is dealt with in the papers [79]; there are a few describing the preparation and characteristics of sodalites with iron [10,11] or aluminium [12,13] content only. All silica sodalite analogues were synthesised rst by Bibby and Dale [14]. The usual way to carry out these syntheses (see, e.g. [7,8]) is to prepare a slurry similar to those seen previously and to admix the aqueous solution of an iron salt in the last step. This is absolutely incompatible with the claims of Szostak and Thomas [3] because of the inadvertent formation of Fe(III) hydroxide in the alkaline environment. Under common synthesis conditions (NaOH concentration 13 wt.%, temperature < 150 C) the iron hydroxide is insoluble in the slurry and so it cannot be incorporated into the lattice. In light of these considerations it is unbelievable that the materials thus obtained may appear white as we can read in the respective papers (see, e.g. [11]). It remains to be seen whether under arduous conditions (temperature 180 C, and strongly

alkaline medium) some iron can be dissolved as ferrat capable to enter the zeolite lattice. The alternative synthesis methods (from A to G and still further) have been developed in order to comply with the principles stipulated by Szostak, always keeping in mind to let orthosilicic acid react with possibly mononuclear Fe(III) ions in strong acids before the slurry turns alkaline during the addition of sodium aluminate and NaOH. In Fig. 2a, Fe-SOD sample (crystallised by method SOD-B from a Si/Fe = 200 washed iron silicate gel) appears in 30,000 magnication as conglomerate of irregular polyhedra, each of about 0.4 m size, stuck closely together. According to our experience the shape of product zeolites depends both on the iron content and the method of preparation. On TEM pictures (not shown) the sonicated samples are very often cubes or parallelepipeds of 0.10.17 m size. It is a renowned view that isomorphic substitution of silicon in the framework by another element exhibiting larger ionic radius in tetrahedral co-ordination (Th ) gives rise to an increase of the u.c. constant(s) and therewith volume, and if it actually happens, this attests that isomorphic substitution occurred. Table 1 shows the most important data of sodalite samples synthesised according to methods A and B. EDX analysis proved that even when iron contents in

Fig. 2. SEM micrograph of a Fe-content SOD-B sample (produced from Si/Fe = 200 gel).

P. Fejes et al. / Applied Catalysis A: General 223 (2002) 147160 Table 1 Compositions and u.c. constants of Fe-content SOD-A and SOD-B samples Sample Product Si/Fe ratio in slurry 25 SOD-A Si/Fe Fe (wt.%) a ()a Si/Fe Fe (wt.%) a ()b 10.100 3.360 8.922 13.400 2.550 8.812 a 50 20.200 1.700 8.906 21.500 1.590 8.904 100 23.700 1.450 8.905 41.600 0.830 8.895 200 35.100 0.980 8.918 79.300 0.430 8.907

153

SOD-B

a b

a = 8.913 0.009. a = 8.880 0.045;

= 8.896 0.035.

the slurries and solid phases changed in parallel, the primitive cubic u.c. constants (designated by a) of the SOD-A and SOD-B products remained uninuenced within a standard deviation of 0.4% (this means 0.035 ). Including each sample the mean value of a: a = 8.896 0.035 is in good agreement with a = 8.893 0.002 published by Vaughan et al.

[7] for sodalites with Fe contents in the interval: 19.6 Si/Fe 50; only the standard deviations differ slightly. Just here we nd a hint about the possible formation of NaA (LTA) stating that at <100 C and low (?) Fe(III) concentrations instead of NaA the phase Fe-NaX (FAU) is produced because: . . . the rigidity of zeolite A lattice does not tolerate hetero-atom substitution. This sole sentence was the second important reason which stimulated this research work! Then we simply could not believe that while sodalites with their compact, inexible structure smoothly incorporate Fe(III) (and the proof for that is Fig. 3 in the paper cited where both XANES and EXAFS spectra show convincingly the statements validity) this is not possible for the more open structure of NaA. Nonetheless, we admit frankly that our experiments to prepare iron content NaA have proved elusive, too, at the beginning. The sole product we always arrived at was NaX (FAU), signifying the apparent validity of Vaughan et al.s previous statement. Hereinafter it turned out that the necessary amount of NaOH (in the type A syntheses) was mistakenly underestimated.

Fig. 3. XRDs of Fe-content NaA (LTA)-G samples prepared from acid treated SODs ((a) Si/Fe = 200 and (b) Si/Fe = 25, in the SOD slurries).

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P. Fejes et al. / Applied Catalysis A: General 223 (2002) 147160 Table 2 Compositions and u.c. constants of Fe-content NaA-F and NaA-G samples Sample Product Si/Fe ratio in slurry 25 LTA-F Si/Fe Fe (wt.%) a ()a Si/Fe Fe (wt.%) a ()b 17.200 2.190 24.644 12.100 3.020 24.611 a 50 36.200 1.110 24.616 20.500 1.860 24.636 100 54.100 0.730 24.638 41.200 0.930 24.657 200 71.000 0.560 24.630 71.400 0.550 24.596

When turned to methods F (washed iron silicate gel) and G (syntheses outgoing from amorphised sodalites) the products were NaA (LTA) zeolites with iron content, as expected. Fig. 3 shows two XR diffractograms: a belongs to a NaA sample prepared from SOD-B200 (with an iron content of 0.36 wt.%) after amorphisation, whereas the starting material to b was a SOD-B25 sample (containing 2.55 wt.% iron) and the method of preparation was the same. The diffractograms imply that the presence of iron hinders crystallisation and by reducing particle size contributes to the increase of linewidths. The same sample a can be seen in Fig. 4 in 30,000 magnication. The little glistening crystals under the optical microscope are actually crystal balls of 0.30.6 m size, consisting of hundreds of elementary crystals whose size is about 0.05 m. Here too, the appearance of the Fe-NaA product zeolites depends in a sensitive way on the raw material, the iron content and preparation method. TEM pictures (not shown) revealed very often Fe-NaA crystals as cubes with rounded off edges (i.e. they expose [1 1 1] type faces as well). The compositions and u.c. constants of Fe-NaA (LTA) samples are compiled in Table 2. Vaughan et al. have been absolutely right in that the structure of NaA was rigid, too. Whilst EDX analyses revealed a

LTA-G

a b

a = 24.632 0.012. a = 24.625 0.027;

= 24.629 0.020.

monotonous increase of iron content in the solid phase in conjunction with the slurry composition, this had no profound effect on the u.c. constants; they remained practically unchanged (for the whole set of samples) within a standard deviation of 0.08%, corresponding to the cumulative error of evaluation. The virtual independence of u.c. constants, on the other hand the gradual shift of sample colour from off-white over buff to rust-red with the increase of iron content gave rise to the suspicion that either no iron incorporation has taken place at all, or if had, it could have been only partial: an unknown percentage

Fig. 4. SEM micrograph of a Fe-content NaA (LTA) sample (from SOD-B200).

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was present as FW constituent, in Th co-ordination (and we know that in the absence of magnetic interactions this iron imparts a nearly invisible green hue to the crystals [15]) and another percentage was sited as EFW component in the voids and on the external surface of crystals in octahedral, Oh , co-ordination as iron oxide (-hydroxide). It is worth appreciating that only one question remained to be answered, notably the pertaining amounts of FW and EFW iron! In contrast to isomorphously substituted high silica zeolites this question cannot be answered by measuring the zeolites ion exchange capacity. The zeolitic specimen we are dealing with here are low module types where part of the aluminium was substituted by iron, thus, for the FW iron Si/(Al + Fe(FW)) 1 and is independent of the FW/EFW iron ratio and this is valid for the ion exchange capacity as well. Therefore, for estimating the FW/EFW iron ratio other experimental techniques should be used. In order to provide reliable answer, in situ Mssbauer spectra were obtained on SODB25 and SODB200 samples in calcined and CO-reduced states. Then, having the samples recrystallised to NaA form, spectra were recorded again and were compared to those of the SOD form. Fig. 5 displays the 77 K in situ spectra of Si/Fe = 25 sample. The calcined SOD sample exhibits a typical Fe(III) doublet (Fig. 5a; the respective data are compiled in Table 3). The following CO treatment provides a means to estimate the portion of iron ions located in close vicinity to each other: removal of oxygen atoms from Fe(III)OFe(III) pairs results in reduction to Fe(II) state. Thus, presence of associated EFW iron ions and Fe(FW)OFe(EFW) pairs can be conrmed. In contrast, single framework substituted Fe(III) ions cannot be reduced this way. Upon treating the SOD sample with CO at 370 C ca. 2/3 of iron remains in ferric form whereas ca. 1/3 is reduced to ferrous state (Fig. 5b). Thus, the greater portion of iron is probably located in FW position in the SOD-25 sample. The recrystallisation of SOD-25 to NaA results in a signicant increase in the amount of EFW iron available to CO molecules. The Fe(II) state is prevailing in the spectrum recorded after the respective CO treatment (Fig. 5d and Table 3), and even evidences for presence of ferromagnetic -iron carbide can be found in separate particles (with characteristic size exceed-

Fig. 5. Mssbauer spectra of Si/Fe = 25 SOD (a, b) and NaA (ce) samples recorded at 77 K and at ambient temperature (e); after calcination (a, c) and reduction by CO at 350 C (b, d, e).

ing 3 nm, e.g. the peak at 1.8 mm/s). The presence of Fe5 C2 is conrmed also in a 77 K spectrum recorded in a larger velocity range, not shown. For comparison, the corresponding 300 K spectrum is also presented (Fig. 5e): having the CO desorbed, EFW Fe(III) in octahedral co-ordination appears in a large proportion (50% relative intensity) together with carbidic and ferrous iron species located mostly in octahedral co-ordination.

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Table 3 Mssbauer parameters extracted from spectra of Figs. 5 and 6a Treatment Fe SOD Si/Fe = 25 Calculated (77 K) 620 K/CO (77 K) Comp. Fe3+ Fe3+ Fe2+ Fe2+ IS 0.42 0.39 0.81 1.18 0.44 0.45 0.08 0.52 0.95 1.36 0.33 0.34 0.81 1.00 0.36 0.33 1.13 0.47 0.45 0.97 1.10 1.13 1.22 0.45 0.85 1.15 QS 0.74 0.87 1.86 2.21 0.54 1.05 3.33 0.88 2.19 2.19 3.90 0.91 0.52 1.81 0.81 0.87 1.89 0.64 1.05 0.54 1.62 2.06 2.79 1.08 0.53 1.71 FWHM 0.62 0.90 0.95 0.69 0.54 0.49 0.45 0.60 0.57 0.69 0.26 0.56 0.29 0.60 0.80 0.75 0.76 0.36 0.59 0.36 0.56 0.33 0.39 0.57 0.25 0.76 RI 100 62 15 23 64 36 29 17 25 29 10 50 15 25 100 91 9 35 65 20 26 40 13 15 57 28

Fe-NaA Si/Fe = 25 Calculated (77 K) 620 K/CO (77 K)

Fe3+ Fe3+ Fecarbide b Fe3+ + Fe2 tetr 2 + Fe Fecarbide b Fe3+ + Fe2 tetr Fe2+ Fe3+ Fe3+ Fe2+

620 K/CO (300 K)

57 Fe

SOD Si/Fe = 200 Calculated (77 K) 640 K/CO (77 K)

57 Fe-NaA

Si/Fe = 200 Calculated (77 K) 640 K/CO (77 K)

Fe3+ Fe3+
+ Fe2 tetr 2 + Fe Fe2+ Fe2+

640 K/CO (300 K)

Fe3+ + Fe2 tetr 2 + Fe

a Spectra were recorded at temperatures shown in brackets in the left column. IS: isomer shift, related to -iron, mm/s; QS: quadrupole splitting, mm/s; FWHM: full line width at half maximum, mm/s; RI: relative spectral area, %. b The pair of lines at 1.7 and +1.6 mm/s is the central part of a magnetic sextet of -Fe C . 5 2

The proportion of the FW iron is expected to increase by decreasing considerably the amount of iron in the sample (i.e. by increasing the Si/Fe ratio to 200). Indeed, the majority of ferric iron cannot be reduced, the proportion of EFW Fe(II) is only ca. 1/10 in the spectrum of the CO treated SOD-B200 sample (Fig. 6b). The acid treatment and recrystallisation of the sample exert a dramatic effect on the distribution of ions between FW and EFW emplacements. The CO treatment at 370 C results again in a full Fe(III) Fe(II) reduction as the 77 K spectrum at-

tests (Fig. 6d). However, in contrast to the NaA-25 sample, a planar co-ordination is dominating for Fe(II) ions (IS = 0.85 mm/s, QS = 0.53 mm/s) in the spectrum recorded at room temperature (see Fig. 6e). This prevailing component may most probably be attributed to single EFW ions (cf. [16]). A minor (about 15%) portion of iron is immediately reoxidised by raising the temperature of measurement from 77 to 300 K while maintaining the CO atmosphere. This Fe(III) component is indicative of Fe(FW)OFe(EFW) pairs. In this component a slight increase in the IS value of Fe(III)

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Fig. 7. XP Fe(2p) doublet spectra of a Fe-NaA-G specimen (from SOD-B25) ((a) untreated and (b) heat-treated at 500 C for 5 h).

Fig. 6. Mssbauer spectra of Si/57 Fe = 200 SOD (a, b) and NaA (ce) samples recorded at 77 K (ad) and at ambient temperature (e); after treatments of calcination (a, c) and reduction by CO at 350 C (b, d, e).

and a simultaneous decrease of the corresponding IS of Fe(II) can be explained by Fe(II) Fe(III) inervalence charge transfer as suggested by Burns [17]. The studies by XP spectroscopy bear out the conclusions drawn from the Mssbauer spectra in every aspect. The sample studied here was a recrystallised

Fe-NaA-G specimen obtained from acid treated Fe-SOD-B25. The Fe(2p) doublet spectra are seen in Fig. 7 for the untreated a and treated b sample which was exposed to a 500 C heat-treatment for 5 h. In the last case, the binding energies of the respective core levels are shifted by 0.45 eV towards lower energies, but the 13.4 eV distance between the 2p1/2 and 2p3/2 doublets did not change. Not the slightest indication could be detected that the binding energies for FW and EFW Fe(III) ions were perceptively different, contrary to Fe-ZSM-5 samples previously studied where a slight (1.9 eV) shift in the respective peaks energies had been observed [18]. What can be seen is not more than a decrease to 2/3 value of the original line intensities caused by the heat-treatment plus an increase of linewidths revealing a change in the co-ordination of iron. The change is obviously an increase of Oh percentage manifested by deepening of the samples rusty colour as well. The diffuse reectance UVVIS absorption spectrum of a similar Fe-NaA-G sample (the raw material

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Fig. 8. Diffuse reectance UVVIS spectrum of a Fe-NaA-G sample (from Fe-SOD-B50).

for that was acid treated Fe-SOD-B50 with an iron content of 1.1 wt.%) is shown in Fig. 8. Although the spectrum is barely structured, it lends itself to further verify the simultaneous presence of FW and EFW iron co-ordination. The rst band centred at 246 nm is a strong ligand-to-metal charge transfer (CT) transition proving the presence of Fe(III) ions in tetrahedral co-ordination by electronegative (in this case O2 ) ions [19]. The four to six possible electronic transitions between states of different spin multiplicity in the 350570 nm region are actually forbidden, therefore, of low intensity. The band located at about 370 nm is of this type and characteristic of Fe(III) in tetrahedral co-ordination, too. The other possible transitions of similar origin are superimposed here by a wide diffuse band in the visible 470570 nm region (bluish-green/green) due to iron oxide/hydroxide debris in the zeolitic voids, whose complementary colour we perceive as rust-red. This colour manifests itself by strong magnetic interactions between the oxide particles which eventually leads to widening of the ESR signals (see later). In a previous publication [20] we extensively dealt with the partial incorporation of Fe(III) ions into zeolitic frameworks, attributing the failure to achieve complete substitution to various causes. In relatively dilute (20 wt.%) solutions of sulfuric (and other common) acid(s) (pH 0) the Fe(III)

ions are present as binuclear (FeOFe)4+ twins of various structures [21]. The same ions can be identied in the iron silicate gels, too. However, when these gels crystallise only one Fe(III) ion is capable to enter the lattice, the other remains outside and thereby develops an interesting heterolinkage (Th Oh link). In concentrated solutions of hard acids (like perchloric acid; Hammett constant is less than 2) the concentration of Fe(III) twins is considerably reduced. But, in the slurry ready to be crystallised into SOD, NaA and similar zeolites there is aluminate in excess and the pH is high, thus, from the iron silicate gel made at very low pH part of Fe(III) ions will inevitably be set free to form insoluble iron hydroxide increasing the rusty impurity in the voids. This is a serious obstacle which can be side-stepped only by a masterly trick we would like to deal with in the next publication. The ligand elds for FW and EFW Fe(III) ions in the very narrow and symmetric structure of sodalites and NaA (LTA) zeolites are similar, thus, the difference in the binding energies of core level electrons might be so small that it cannot be resolved by todays ESCA or XP spectrometers. This can be the reason, too, that experimental X-band ESR spectra of low (0.3 wt.%) and higher (3.0 wt.%) iron contents in SOD and NaA (LTA) zeolites do not reveal any zero-eld structure. The spectra can be interpreted as transitions between 1/2 and 1/2 magnetic levels. Both the g-value and the linewidth reveal signicant anisotropy that can be ascribed to the indirect effect of zero-eld interactions, but the impact of locally disturbed ligand eld due to the statistically distributed paramagnetic Fe(III) ions can also be important. Each spectrum can successfully be modelled by one or two centres, both exhibiting axial symmetry (i.e. in the effective spin Hamiltonian g is anisotropic and D = 0, E = 0), while the increasing spinspin interactions, as the iron content is becoming larger, produce the linewidth anisotropy. Powder averaging of the sub-spectra was carried out in 90 points taking into account the g-factor and linewidth dependence on the orientation of crystallites. It is an obvious choice to assign one of these sites to FW and the other to EFW iron types, but the strong magnetic interactions currently hinder attempts to quantify the model. Nevertheless, the gzz

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and gxx = gyy values remain for both types near to 2.0 uninuenced by the iron content, as expected, only the respective (anisotropic) linewidths experience an enormous increase (e.g. at 0.3% iron content the linewidth Wzz equals to 50 Gauss for FW sites which increases to 2200 Gauss when the iron content reaches 3.0 wt.%). Further details of the ESR spectroscopy of the samples will be published elsewhere. It is worth noting that in the incompressible lattice the solid surface tension cannot develop fully rhombic environments (see [20]), so the characteristic signal at g = 4.29 is very weak or missing. Following the acid treatment, the amorphised sodalites can be recrystallised into various other types. Having practised this technique as a routine it was recognised soon that by adding various complexing agents or applying special techniques EFW iron can be removed while that sited in the framework remains almost unimpaired. Among other indirect proofs this follows from the simple fact that while the dissolved amount of aluminium varies between 1.74 and 2.97%, that for iron reaches the fairly high EFW levels observed by spectroscopic methods, e.g. 11.1 g of a Fe-SOD-B200 sample (iron content 0.36 wt.%) contained 48 mg Fe. After treatment with 5 wt.% sulfuric acid and a reducing agent at 100 C and lasting 3 h, 15.4 mg, i.e. 38% could be identied in the supernatant liquor. This part of the research work seems to be promising: provided the low temperature digestion of gibbsitic aluminium ores supply ample amounts of the sodalite by-product, even the colour of the zeolites synthesised from this raw material can be advantageously inuenced. This technique is capable to produce zeolites (within a well dened family) with Fe(III) or even 57 Fe(III) tracer ions located exclusively in FW positions permitting unequivocal matching of the respective Mssbauer and ESR signals. It is thought that it is of great theoretical importance. Not at last, this type of Fe-content LTA zeolites (e.g. CaA) permit the preparation of tailor-made (biomimetic) selective oxidation catalysts for reactants not excluded from the pore structure by sieving effects. From the experimental results and their various evaluations the following conclusions can be drawn. Syntheses of isomorphously substituted zeolites in alkaline media (irrespective of the module, cf. [22])

result inevitably in partial incorporation whichever synthesis method is chosen. The co-ordination of the substituent is always mixed (FW and EFW); an increasing part of the substituting ion (in our case Fe(III)) appears in EFW position at the expense of FW substituent, as its amount in the synthesis slurry increases. Mssbauer spectroscopy revealed that at low (about 0.4 wt.%) Fe loading the incorporation reached about 90% and it diminished approximately to 60% at 3 wt.% iron in the slurry. Contrary to high module types where substituting ions larger than silicon always cause an increase of u.c. volume, the rigidity and high symmetry of SOD and LTA structures hampers lattice expansion. Their u.c. volumes remain strictly constant irrespective of the degree of substitution. In full agreement with this the X-ray photoelectron energies for FW and EFW species are inseparable. The difference in g-values of the respective ESR spectra for the same ions sited in ligand elds of (commencing) axial symmetry is very little; the observed linewidth anisotropy is caused by spinspin interaction of high dispersity EFW iron oxide, located in the voids. Treatment of low module natural or articial zeolites (like SOD, LTA, etc.) by diluted mineral acids in amounts corresponding to the ion exchange capacity, or 10% in excess, leads within 3 h at 100 C to complete amorphisation, while the solid habit of material so obtained will be retained. After washing (and drying, if necessary) this silicon and aluminium source may serve as raw material to synthesise other commercially interesting zeolites. The acid treatment combined with addition of complexing and/or reducing agents (a theme for the second publication) allows complete removal of EFW iron. The products exhibit white colour and are characterised by Fe(III) ions emplaced exclusively in framework position and tetrahedral co-ordination. The advantages of uniform Fe(III) ions siting from the point of view of Mssbauer and ESR spectroscopy is obvious. The possibility of inuencing Fe(III) siting in LTA structures may have importance in the preparation of selective oxidation catalysts for reactants of small kinetic diameter.

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Acknowledgements P. Fejes, I. Kiricsi, K. Lzr and A. Rockenbauer acknowledge herewith the Grant no. T 029463 from the OTKA Commission. The authors express thanks to professor Lovat V.C. Rees (University of Edinburgh) for his valuable suggestions concerning Mssbauer spectroscopy measurements. Thanks are due to I. Saj (Central Research Institute for Chemistry of Hungarian Academy of Science, Budapest) for the diffractograms, Mrs. F. Barna for the sometimes complicated synthesis work and to Mrs. Cs. Csikkel for the ICP spectral analyses. The contribution of P. Szab (Budapest Technical University) in preparing the SEM micrographs is also highly appreciated. References
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