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Microporous and Mesoporous Materials 58 (2003) 155162 www.elsevier.

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A simple route towards magnetically modied zeolites


Athanasios B. Bourlinos a, Radek Zboril b, Dimitrios Petridis
b

a,*

a Institute of Materials Science, NCSR Demokritos, Ag. Paraskevi Attikis, Athens 153 10, Greece Department of Inorganic and Physical Chemistry, Palacky University, Krizkouskeho 10, Olomouc 771 47, Czech Republic

Received 29 April 2002; received in revised form 11 November 2002; accepted 17 November 2002

Abstract A simple route for decorating the external surfaces of zeolites with maghemite nanoparticles is described. The synthesis comprises feeding of a zeolite support with dierent amounts of iron(III) by employing melt exchange reactions, exposure of the iron-containing solids to vapors of formic acid and nally calcination of the resulting derivatives in air to aord maghemite nanoparticles embedded in the zeolite host. The as-prepared magnetically modied ssbauer and magnetic measurements and SEM and TEM techniques, were found to solids, characterized by XRD, Mo retain the cation exchange capacity of the parent zeolite as well as its structural integrity. 2002 Elsevier Science Inc. All rights reserved.
Keywords: Carboxylic acid vapor treatment; Iron(III) containing zeolite Y; Maghemite; Magnetically modied zeolite Y; Melt exchange reactions

1. Introduction Zeolites, synthetic and natural, have unique structural, physical and chemical properties that make them valuable materials for many technological, agricultural and environmental applications [13]. In many applications, it would be of practical importance to coat the zeolite surfaces with a magnetic component. Magnetically modied zeolites oer the advantage of easy separation and recovery of powdered zeolites after catalytic runs or after environmental remediation by means of an applied magnetic eld. In addition, magnetic zeolites could be advantageous in technological

processes, including uidized beds of ferromagnetic particles [4,5], ferromagnetic ion exchangers [6], 1 magnetic refrigeration [7] and in biosciences [8]. There are two methods to obtain magnetically modied zeolites. The rst refers to the decoration of zeolite surfaces with magnetic metallic nanoparticles (Fe, Co, Ni). It comprises feeding of zeolites with transition metal ions via ion exchange, followed by reduction of the cations to their metallic state by either hydrogen under drastic conditions [9] or borohydride at ambient temperature [10]. The second involves the modication of natural zeolites with colloidal magnetite particles as described in a patent [6] and briey reported. 1 The use of magnetic iron oxides, magnetite (Fe3 O4 ) or maghemite (c-Fe2 O3 ), as modiers is of
1

Corresponding author. Tel.: +30-1-650-3343; fax: +30-1651-9430. E-mail address: dpetrid@ims.demokritos.gr (D. Petridis).

See Ref. [3], p. 340.

1387-1811/02/$ - see front matter 2002 Elsevier Science Inc. All rights reserved. PII: S 1 3 8 7 - 1 8 1 1 ( 0 2 ) 0 0 6 1 3 - 3

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particular value since the oxides present thermal and air stability for various applications [11]. In the frame of advancing general routes for the modication of various inorganic supports with magnetic iron oxide particles, we describe here a simple procedure for the partial coverage of zeolite surfaces with the magnetic c-Fe2 O3 . In previous reports we have demonstrated that the interaction of iron(III) centers, embedded in inorganic solids, with vapors of a carboxylic acid RCOOH (R: H, CH3 , CH2 CH3 ), followed by pyrolysis of the received solids at 300400 C in air, leads to surface decoration of the particular solids with nanophase c-Fe2 O3 magnetic particles. In this manner, iron(III) exchanged clay minerals, iron(III) impregnated silica, MCM-41 porous silica and perlite were successfully converted to multifunctional magnetic derivatives exhibiting all the characteristic properties of the particular inorganic matrices [1214]. By the same strategy magnetically modied activated carbons can be also produced [15]. In the present work, zeolite Y was chosen as the solid matrix to host c-Fe2 O3 nanoparticles. Zeolite Y is characterized by interconnected sodalite cages forming a three-dimensional open frame) [16]. work structure (opening of the window: 7 A The method for endowing the zeolite solid with magnetic properties comprises three steps: (i) iron(III) loading of the sodium form of zeolite Y via Fe(NO3 )3 9H2 O/NaNO3 melt exchange reactions [17], (ii) exposure of the iron(III) containing solid to vapors of formic acid (HCOOH), and (iii) calcination of the output solid at 400 C in air. The experimental details as well as the characterization and features of the nal magnetic solids are presented below.

exchange capacity (CEC) of the zeolite Y (4 meq g1 , determined according to Ref. [18]). The as-received powders, without any washing, were exposed to vapors of HCOOH (85%, 0.25 cm3 or 0.5 cm3 , respectively) at 80 C for 2 h in a closed vessel (volume: 70 cm3 ) and then calcined at 400 C for 1 h in air. The obtained solids were washed with water in order to remove any remaining sodium compounds, and after drying in an oven for 34 h gave the samples ZEOMAG1 (8.5 wt.% Fe) and ZEOMAG2 (16 wt.% Fe) with intense magnetic properties, as evidenced from their attraction to a permanent magnet. 2.2. Hg2 uptake curves Mercuric ions (Hg2 ) were determined by photometric analysis [19]. Briey, the magnetically modied samples were treated with aliquots of HgCl2 aqueous solutions of precise concentration (5100 ppm) to form aqueous dispersions of 0.2 g of solid per 100 cm3 of water. The mixtures were stirred for 1 h at room temperature prior to ltration of the solids. Subsequently, an excess of KSCN was added to each ltrate, the aqueous solutions were extracted with a certain volume of n-butanol and then the absorption of each Hg(II) organic solution was measured photometrically at 286 nm. Using a standard curve for mercuric ions (530 ppm), we calculated in each case the absorbed ppm Hg2 by subtracting the remaining amount from the initial. 2.3. Instrumentation X-ray powder diraction patterns were recorded on a Siemens XD-500 diractometer using CuKa radiation and a secondary graphite monochromator. The measurements were performed by using the following combination of slits: 1.0/1.0/ 1.0 as aperture diaphragms, 0.15 as detector diaphragm and 0.15 as diracted beam monochromator diaphragm. The measured 2h range was ssbauer spectra scanned in steps of 0.03 s1 . Mo were obtained with a constant acceleration spectrometer with a 50 mCi 57 Co(Rh) source moving at room temperature, while the sample (absorber) was kept in a variable temperature cryostat. The

2. Experimental 2.1. Procedure 0.4 g of commercially available zeolite NaY were ground with 0.21 g or 0.42 g Fe(NO3 )3 9H2 O (melting point: 56 C) in a mortar and placed in an oven at 80 C for 1 h. The added amounts of iron salt correspond to one and two times the cation

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parameters were obtained by a least square tting program assuming Lorentzian line shapes. Isomer shift values are given with respect to metallic iron. Magnetic measurements were carried out at room temperature with a VSM magnetometer. Optical measurements were carried out with a Shimadzu UV2100 photometer. A CM20 Phillips instrument was used for the transmission electron microscopy (TEM) study. Finally, scanning electron microscopy (SEM) images were taken on a Philips model 515 microscope operating at 25 kV.

-F e 2O 3
3 5 .6
o

c
*

Intensity

* N aN O * * * * * *

3. Results and discussion 3.1. ZEOMAG1 An iron(III) containing zeolite was prepared by the melt exchange route between the sodium ions of the zeolite and Fe(NO3 )3 9H2 O. The melt route was preferred over conventional exchange methods in solution for two reasons: First, in aqueous solutions the insertion of iron(III) centers breaks down the zeolite structure [20], and second, in nonaqueous solutions, e.g. isopropanol, although the structural integrity of the zeolite is retained after exchange, we found by XRD data (not shown) that the formation of the magnetic phase in the nal solid seriously aects the crystallinity of the zeolite host leading to a nearly amorphous solid. Fig. 1 presents the XRD patterns of the parent sodium zeolite Y (a) and of the sample received after the exchange reaction in the melt (b). Two features follow from these patterns: (i) the high crystallinity of the parent zeolite is still retained in the as-treated solid, except for a relative change in peak intensities, and (ii) we discern additional reections (denoted with asterisks) derived from crystalline NaNO3 present in the exchanged solid. Both results unveil that, at least a partial exchange between the sodium ions of the zeolite and the positively charged oligonuclear iron(III) species took place. The relative change in peak intensities after exchange may stem from a non-quantitative replacement of the sodium ions in the zeolite matrix, which, in turn, introduces structural inhomogeneities in the partially exchanged solid [21]. It is also observed that the NaNO3 reections remain

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2( )
Fig. 1. XRD patterns of zeolite NaY (a), of the sample received after the exchange procedure (b), and of the magnetically modied sample ZEOMAG1 (c).

almost unchanged in their relative intensities even after 24 h exchange reaction time. This implies that the exchange takes place mostly near the external boundaries of the zeolitic crystallites and proceeds little within the structure due to blocking of the zeolitic channels by the inserted oligonuclear iron(III) species. Sodium elemental analysis of the pristine zeolite Y and of the iron-containing sample after washing with water in order to remove any NaNO3 crystallites from its surfaces revealed that 60% of the sodium ions had been exchanged after the melt treatment. The second and third steps in the synthesis comprise the chemisorption of HCOOH vapor molecules by the iron(III) centers and pyrolysis of the resulting derivative at 400 C. The chelation of the iron(III) centers by the carboxylic acid is essential for the magnetic phase formation prior to the pyrolytic step. Omitting this treatment leads to a non-magnetic phase after calcination, usually hematite (a-Fe2 O3 ). The key role of the carboxylic acid treatment for the magnetic phase formation has been described elsewhere [1214]. Fig. 1c

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ssbauer spectra (left) and magnetization versus applied eld curve at room temperature (right) for the Fig. 2. Variable temperature Mo ZEOMAG1 sample.

shows the XRD pattern of the ZEOMAG1 sample. The solid, apart from the characteristic reections of the parent zeolite, exhibits also a broad reection at ca. 35.6 ascribed to maghemite particles. The oxide is believed to be grafted to the zeolite host through SiOFe or AlOFe bonds, derived from the aluminosilicate matrix and the iron oxide particles near their contacting surfaces [22]. It is important to note that, because anchoring of the magnetic nanoparticles is through chemical bonding, no phase separation between the zeolite and the magnetic particles is observed upon dispersing the magnetically modied zeolite in water. The average size of the magnetic particles  according to the Scherrer is estimated to 120 A equation and, therefore, these particles are mainly located at the external surfaces of the zeolite. A contribution to the magnetic phase formation probably comes from intra-zeolite iron(III) species. These species migrate to the external zeolite surfaces during the carboxylic acid treatment, as a result of their displacement by the acid protons. Under these circumstances, a high concentration of iron formate species would be expected to occur

at the external surfaces of the zeolite leading, after calcination, to large enough magnetic particles with considerable magnetization. The magnetic nature of the nanoparticles in ssbauer spectroZEOMAG1 was studied by Mo ssbauer spectra scopy. Fig. 2, left, presents the Mo of ZEOMAG1 recorded at room temperature (RT), liquid nitrogen (LN) and helium (LHe). The room temperature spectrum of the sample displays a paramagnetic doublet (77%) and a magnetic hyperne component (23%). When the temperature of measurement was lowered, the magnetic component raised from 23% at RT to 59% at LN and to 92% at LHe. These temperature-depending changes in the spectra are typical of small particles with superparamagnetic behavior [23]. A small paramagnetic doublet (8%, isomer shift: 0.37 mm s1 , quadrapole splitting: 0.55 mm s1 ) is still present in the LHe spectrum and is likely due to the incorporation of a small part of the initial trivalent iron to defect sites of the zeolite framework through chemical bonding [21,24]. The quadrupole interaction of the magnetic sextets is zero indicating a cubic geometry around the iron site. In

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addition, isomer shift and hyperne eld values for the magnetic components are typical of ferric iron and close to those of bulk c-Fe2 O3 (RT: 0.35 mm s1 , 3:26 107 A m1 , LN: 0.45 mm s1 , 4:14 107 A m1 , LHe: 0.48 mm s1 , 4:14 107 A m1 ). The magnetization versus applied eld curve for the ZEOMAG1 at room temperature is characteristic of materials possessing ferromagnetic properties, Fig. 2, right. Extrapolation to the magnetization axis shows that the saturation magnetization value for ZEOMAG1 (8.5 wt.% Fe) is 3.5 A m2 kg1 , or by a simple conversion 28.8 A m2 per kg of c-Fe2 O3 . Fig. 3 presents the SEM (upper) and TEM (lower) micrographs of ZEOMAG1. The SEM image reveals the presence of strongly aggregated zeolite particles with a mean particle size of ca. 1 lm. The aggregated state of the particles can be explained from the calcined state of the sample and from the presence of maghemite nanoparticles at the external surfaces of the host crystallites. Because these as-made maghemite particles have

the ability to strongly interact with aluminosilicate matrices through chemical bonding at the interfaces, we may conclude that the maghemite nanoparticles interconnect neighboring zeolite crystallites acting as an adhesive. On the other hand, the TEM picture locates at the external surfaces of the zeolite matrix the presence of small  in diameter) of maghemite particles (100200 A nearly spherical morphology packed in an aggregated form. The aggregated state of the magnetic particles is not surprising and must result from the small external surface area of the zeolite microcrystallites in conjunction with the melt conditions employed in the iron deposition. The ZEOMAG1 solid exhibits two characteristic features: (i) its CEC overwhelms that of the original zeolite NaY, and (ii) it is structurally stable upon an exchange reaction with transition metal ions, e.g. Fe3 . The CEC of ZEOMAG1, determined by a standard procedure [18], was 4.8 meq g1 versus 4 meq g1 for zeolite NaY. The enhanced CEC value probably arises from the

Fig. 3. SEM (upper) and TEM (lower) images of ZEOMAG1 (inset photo depicts nearly spherical maghemite particles in an aggregated form).

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-F e 2O 3

(b) Intensity
Fig. 4. Uptake curves for mercuric ions at room temperature for the parent zeolite Y and ZEOMAG1 in the region 5100 ppm.

(a)

hosted maghemite nanoparticles at the zeolite surfaces. The nano-size, high surface area and active hydroxyl groups of the hosted oxide are factors that can contribute to the increased CEC. In fact, separate experiments showed that nanosized maghemite particles embedded in silica possess excellent adsorptive capacities towards heavy metal ions. Fig. 4 presents the uptake curves of zeolite NaY and ZEOMAG1 for mercuric ions, in the region 5100 ppm. We discern that both solids are quite eective absorbents at low concentrations of mercuric ions, but at larger concentrations the straight lines diverge and the ZEOMAG1 exhibits better sorption properties. As far as the structural stability of the composite material is concerned, Fig. 5 shows the XRD patterns of the parent zeolite Y and that of ZEOMAG1, after aqueous exchange reactions with FeCl3 6H2 O. It is seen that aqueous exchange of the sodium ions of zeolite Y with trivalent iron ions leads to an amorphous, collapsed derivative in which the iron centers are buried within the aluminosilicate matrix and therefore are not accessible to molecules that interact with trivalent iron, e.g. HCOOH. The same treatment does not aect the crystallinity of the ZEOMAG1 solid or the grafted maghemite particles. However, it should be pointed out that the structural stability of the zeolite network in ZEOMAG1 upon exchange treatments could mainly result from its calcined state, which straightens the aluminosilicate matrix, rather than

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2( )
Fig. 5. XRD patterns of the parent zeolite Y (a) and of ZEOMAG1 (b), after aqueous exchange reactions with FeCl3 6H2 O.

from scaolding eects of the maghemite particles or from the incorporated structural iron(III) centers. Thus, similarly to ZEOMAG1, the network of a calcined zeolite Y (highly crystalline) does not collapse upon insertion of iron(III) species into the channels. 3.2. ZEOMAG2 Magnetically modied zeolites with more intense magnetic properties than ZEOMAG1 can be obtained by the same procedure but using an amount of Fe(NO3 )3 9H2 O twice the CEC of the zeolite Y. The XRD pattern of this sample (ZEOMAG2), as shown in Fig. 6, is composed of some weak, relative broad reections ascribed to a zeolite support of low periodicity, e.g. with partially collapsed channels, and some intense, sharp reections ascribed to large magnetic iron oxide nanoparticles formed at the external surface of the solid (denoted with asterisks). The average size of the magnetic particles is estimated to be at least

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Magnetization (A m Kg )

10 8 6 4 2 0 0.0 0.2 0.4

Finally, similarly to ZEOMAG1, ZEOMAG2 also exhibits a remarkable stability against aqueous exchange reactions.

-1

*
0.6 0.8 1.0 1.2 6 -1 1.4 1.6

4. Conclusions
* -F e 2 O 3

Intensity

Field (x10 A m )

* * * * *

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2( )

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Fig. 6. XRD pattern and magnetization versus applied eld curve at room temperature (inset photo) of the ZEOMAG2 sample.

 according to the Scherrer equation, while 160 A ssbauer data identify the presence of cthe Mo Fe2 O3 particles. On account of the higher iron content and larger size of the maghemite particles, ZEOMAG2 exhibits more intense magnetic properties [25] (Fig. 6, inset photograph). ZEOMAG2 (16 wt.% Fe) possesses a saturation magnetization of 9 A m2 kg1 or 39.5 A m2 per kg of c-Fe2 O3 (>28.8 A mm2 kg1 ). The larger size of the magnetic particles can be attributed to the higher number of iron centers per surface area of the zeolite solid which, in turn, increases their tendency to aggregate and form larger particles. In contrast to ZEOMAG1, ZEOMAG2 possesses an equal CEC and the same sorption properties as the parent zeolite NaY (4 meq g1 ). Nevertheless, it is likely that ZEOMAG2 possesses also a somehow larger CEC, but the collapsed state of a part of the zeolite channels, in conjunction with partial blocking of the pore openings by large maghemite particles, could hide some of the exchange sites of the zeolite support, thus giving rise to a rather phenomenal CEC value.

Zeolite Y, loaded with iron(III) species by a melt exchange route, chemisorbs formic acid to give a derivative that, upon pyrolysis at 400 C, leads to aggregated, nearly spherical maghemite (c-Fe2 O3 )  in size) grafted onto the nanoparticles (>100 A external surface of the zeolite microcrystallites. The size of the maghemite particles, the magnetic properties of the solids, and the crystallinity of the host zeolite are strongly inuenced by the iron content of the composite materials: the higher the iron content the larger the size of the as-formed magnetic particles, the more intense the magnetic properties, but the lower the crystallinity of the zeolite support. The maghemite-zeolite composites exhibit two characteristic features: enhanced CEC and, in contrast to the original zeolite NaY, remarkable structural stability against exchange treatments with metal ions.

Acknowledgements Financial support through a NATO Linkage Grant HTECH LG 973515 is acknowledged.

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