Microporous and Mesoporous Materials 79 (2005) 712 www.elsevier.

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Eect of the silica sources on the crystallinity of nanosized ZSM-5 zeolite

Reda M. Mohamed
a

a,*

, Hisham M. Aly b, Mohamed F. El-Shahat c, Ibrahim A. Ibrahim

Central Metallurgical R&D Institute, Department of Nanostructured Material, CMRDI, P.O. Box 87, Helwan, Cairo 11421, Egypt b Faculty of Science, Benha Branch, Zagazig University, Benha 13518, Egypt c Faculty of Science, Ain Shams University, Cairo, Abbasia 11566, Egypt Received 31 August 2004; received in revised form 20 October 2004; accepted 20 October 2004 Available online 8 December 2004

Abstract Silica sources can inuence dierent aspects of ZSM-5 crystallization and it leads to change in the properties of the nal product. The crystallinity of nanosized ZSM-5 zeolite from precursors mixtures containing dierent silica sources, e.g. tetraethylorthosilicate (TEOS), colloidal silica (Ludox LS 30), sodium metasilicate and fumed silica have been studied. The produced samples are investigated using XRD, SEM, and carbon % in the samples after calcination in air and BET surface area. The product obtained by TEOS, fumed silica and colloidal silica is ZSM-5 phase, but the product obtained by sodium metasilicate is the quartz phase. The crystallinity, and % of the nanosized ZSM-5 zeolite increased in the following order: sodium metasilicate < colloidal silica < TEOS < fumed silica. The average crystal size increased in the following order: fumed silica < TEOS < colloidal silica < sodium metasilicate. The surface area increased in the following order: sodium metasilicate < colloidal silica < TEOS < fumed silica. The template was almost completely removed from the ZSM-5 by calcination at 550 C for 8 h in air. 2004 Elsevier Inc. All rights reserved.
Keywords: Nanosized-ZSM-5; Silica sources; Crystallinity

1. Introduction ZSM-5 catalysts are important from industrial and academic point of view of their unique structure, thermal stability, acidity, shape selective property and applications in oil renery, petro-chemical industry and environmental catalysis [15]. The synthesis conditions, such as temperature, time, sources of silica and alumina inuenced the physico-chemical and catalytic properties of zeolite catalysts [69]. Some of important parameters describing the process of zeolite crystallization like the nucleation and crystallization rates depend on the dissolution of the silica precursors. The fragile silicate intermediates released during the process of the silica
*

Corresponding author. Tel.: +20 2 5010643; +20 2 5010639. E-mail address: redama123@yahoo.com (R.M. Mohamed).

dissolution, which play an important role in zeolite formation, are also inuenced by the nature of the silica used. Besides the eects on the formation of a particular zeolite, the silica source can inuence the specic features of the zeolite material [10]. The impurities introduced by the silica source in the starting system can also aect the morphology [11] and chemical properties [12,13] of the zeolite. The synthesis of zeolite crystals with equal particle radius requires homogeneous distribution of the viable nuclei in the system. Therefore, the homogeneity of the starting system and simultaneity of the events leading to the formation of precursor gel particles and their transformation into crystalline zeolitic material are of primary importance. In order to obtain such homogeneous starting systems abundant amounts of tetraalkylammonium hydroxides and water were employed [1418]. On the other hand, the content

1387-1811/$ - see front matter 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2004.10.031

R.M. Mohamed et al. / Microporous and Mesoporous Materials 79 (2005) 712

of alkaline cations is very limited. All these factors together with careful choice of the reactants allow the stabilization of clear starting mixtures where only discrete gel particles are present [1922]. Most of the investigations were devoted to the synthesis of nanosized zeolites with tetraethylorthosilicate as a silica source. A limited number of articles discuss the formation of nanosized zeolites by using other silica sources [2329]. The aim of the present study was to investigate the eect of silica sources on the crystallinity of nanosized ZSM-5.

a rate of 100 cm3/min; 5.039 mg from the synthesized zeolite was put in platinum cell. Surface areas were recorded using Nova 2000 series, Chromatech. The FTIR spectra were recorded using Jasco FT-IR-460 plus, Japan; % of carbon content in the sample after removal of the template was recorded by using Strohlein. The zeolite samples were also characterized by scanning electron microscopy using a Jeol scanning microscope model JSM5410. The amount of silica and alumina in the crystalline samples were obtained by EDAX technique.

3. Results and discussion 2. Experimental 2.1. Materials and procedure The silica sources employed were tetraethylorthosilicate (TEOS, 98%, Fluka), colloidal silica, sodium metasilicate and fumed silica (Aldrich). The alkaline source was sodium hydroxide pellets (A.R 98%) and template source employed was tetrapropylammonium hydroxide (TPAOH, 20% Fluka). The produced hydrogel was prepared by mixing the reagents in the following order: 0.212 g of NaOH was dissolved in 19.6 g of distilled water, 10 ml of 20% tetrapropylammonium hydroxide was added drop wise to the sodium hydroxide solution with stirring, the mixture was stirred for 30 min; then 13.75 g of silica was added drop wise, the resulting mixture (I) was stirred for 30 min. 0.212 g of NaOH was dissolved in the 19.6 g of distilled water, 1.1 g of sodium aluminate and 196 ml of methanol, as structure directing agent, were added to the sodium hydroxide solution with stirring for 1 h; the resulting mixture (II) was added dropwise to mixture (I) with stirring and the resulting gel was stirred for 1 h. Finally, the creamy gel was put into 500 ml parr autoclave at 230 C for 45 h, and then the autoclave was quenched immediately with cold water. The pH of slurry was about 11, the solid product was ltered and washed with distilled water until the pH is dropped to 9, and the product was dried at 110 C overnight. The unlined autoclaves were cleaned with 10% NaOH at 160 C prior to each experiment to avoid adventitious seeding. 2.2. Characterization X-ray diraction (XRD) patterns and average crystal size were collected with Bruker axs, D8 Advance. The crystallinity was determined from the peak area between 2h = 2225 using a highly crystalline ZSM-5 sample (ZSM-5 820NAA supplied by Mobil company Japan) as reference. Thermal analyses were carried out by using Shimadzu DTA-50 and Shimadzu TGA-50H. The temperature of the sample was raised at a uniform rate of 10 C/min from ambient to 1000 C in an air owing at Changing silica sources as fumed silica, TEOS, colloidal silica and sodium metasilicate under the following conditions has carried out a series of experiments: alumina source: sodium aluminate, silica/alumina mole ratio: 40, template oxide/silica mole ratio: 0.215, type of template: tetrapropylammonium hydroxide, H2O/SiO2 mole ratio: 9.5, Na2O/SiO2 mole ratio: 0.133, CH3OH/SiO2 mole ratio: 22.

The samples were crystallized at 230 C for 45 h, then washed and centrifuged until the pH of the liquid reached 9, then the solid material was dried overnight at 110 C. The obtained samples were characterized using X-ray, FT-IR, surface area, SEM, % of carbon, DTA and TGA. 3.1. X-ray diraction and surface area Fig. 1 shows the XRD patterns of samples that were crystallized by using dierent sources from silica as TEOS, fumed silica, colloidal silica and sodium metasilicate. The patterns of the product synthesized by TEOS, fumed silica and colloidal silica indicate that ZSM-5 phase existed, but the pattern of the product synthesized by sodium metasilicate shows that quartz silica existed. The pattern of the product synthesized by fumed silica indicates that it is the highest in crystallinity. This is attributed to when a monomeric silica source is used, nucleation and crystal growth occur more rapidly than when a highly condensed source of silica is used. Table 1 shows the eect of silica sources on structural parameters of the obtained samples together with those of standard sample. The results show that the structural parameters of as-synthesized ZSM-5 samples, which were prepared by using fumed silica, colloidal silica and TEOS as a source of silica are near those of standard samples. But the structural parameters of the sample, which is prepared by using sodium metasilicate as silica source, are dierent from those of standard sample

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(113.6) < sodium metasilicate (135.5). The surface area was decreased in the following order: fumed silica > TEOS > colloidal silica > sodium metasilicate due to decreasing crystallinity [30]. 3.2. FT-IR

b
Intensity

10

20

30

40

50

60

70

80

2- Theta

Fig. 1. Eect of silica sources on crystallinity of ZSM-5 formed where a = fumed silica, b = TEOS, c = colloidal silica and d = sodium metasilicate.

Fig. 2 shows IR spectra of as-synthesized samples obtained by using dierent silica sources. The results show that the bands near (1219 and 542 cm1 characteristic of the presence of double ve member ring) [31], (1080 cm1 characteristic of internal asymmetric stretching vibration of SiOT linkage), (790 cm1 characteristic of the symmetric stretching of the external linkage) and (450 cm1 characteristic of TO bending vibration of the SiO4 and AlO4 internal tetrahedral) are present for the samples, which were prepared by using TEOS, fumed silica and colloidal silica as silica sources, but bands around 542 and 450 cm1 characteristic of the ZSM-5 crystalline structure [32] are not present for the sample which was prepared by using sodium metasilicate due to formation of quartz silica. Table 3 shows the eect of silica sources on the ratio of the intensities of the peaks near (A) 542 and (B) 450 cm1, which provides an approximate estimate of the degree of crystallinity [33]. The results show that the ratio

Table 1 Eect of silica sources on structural parameters of as-synthesized samples ) Silica sources Structural parameters (A Unit cell )3 V (A a b c Standard ZSM-5 Fumed silica TEOS Colloidal silica Sodium metasilicate 20.02 19.92 19.92 20.16 4.24 19.89 19.92 19.92 19.90 3.01 13.38 13.36 13.36 13.44 5.43 5332.0249 5301.3330 5301.3330 5391.9120 69.2990

due to formation of quartz silica. Table 2 shows the effect of silica sources on surface area, crystallinity, % and average crystal size of as-synthesized ZSM-5. The average crystal size was increased in the following order: fume silica (55.8) < TEOS (90.3) < colloidal silica

Table 2 Eect of silica sources on crystallinity, surfaces area and average crystal size of as-synthesized ZSM-5 Silica sources Fumed silica TEOS Colloidal silica Sodium metasilicate Crystallinity of ZSM-5, % 97.3 77.1 46.7 Surface area, m2/g 358.21 351.16 285.00 9.17 Average crystal size, nm 55.8 90.3 113.6 135.7 Phase formed ZSM-5 ZSM-5 ZSM-5 Quartz silica

Fig. 2. IR spectra of as-synthesized ZSM-5 zeolite samples obtained by using dierent silica sources where a = colloidal silica, b = TEOS, c = fumed silica and d = sodium metasilicate.

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Table 3 Eect of silica sources on the ratio of the intensities of the peaks near (A) 542 and (B) 450 cm1 and also correlation between XRD crystallinity and relative crystallinity estimated from IR Silica sources A/B ratio Relative crystallinity estimated from IR, % 96.7 73.0 45.0 XRD crystallinity, %

similar and hence the samples are homogeneous. From the crystallinity view, the optimum conditions for silica source are fumed silica at 55.8 nm crystal size, 358.21 m2/ g surface area and 97.3% crystallinity. 3.4. Thermal analysis

Fumed silica TEOS Colloidal silica Sodium metasilicate

0.967 0.730 0.450

97.3 77.1 46.7

and consequently relative crystallinity increased in the following order: colloidal silica > TEOS > fumed silica that is in close agreement with that calculated from XRD. 3.3. SEM Fig. 3 shows SEM data for the prepared samples by using dierent silica sources as fumed silica, TEOS, colloidal silica and sodium metasilicate. The results show that the sample which was prepared by fumed silica crystallized in cubical shape crystals, the samples which were prepared by TEOS and colloidal silica crystallized in twinned and intergrown shape crystals, but the sample which was prepared by sodium metasilicate crystallized in needle shape crystals. The chemical composition of the prepared samples was measured by EDX techniques summarized in Table 4. The results show that the Si/Al atomic % at three areas is almost

The thermal analysis was carried out to determine the thermal stability of the optimum ZSM-5 zeolite and to measure water and template loss. Fig. 4 shows the TG/ DTA curves for the optimum ZSM-5. The observed exotherms (444.26 C) are due to the oxidative decomposition of the template. Endotherm (58.72 C) represents water loss. Total weight losses in the temperature range from 30 to 600 C represent water loss as well as loss of template are about 11.5%. The TG/DTA curves for the optimum ZSM-5 revealed that the temperature of the framework decomposition of zeolite is above 1000 C, which is in agreement with the published literature [33]. These data suggest that although ZSM-5 crystallization methods are dierent their framework rigidity or structural stability is almost the same. 3.5. The eect of calcination time on the % of carbon remaining To study eects of calcination time on the % of carbon remaining, the optimum as-synthesized ZSM-5 zeolite was calcined in air at 550 C for dierent times (2 8 h) and the percentage of carbon remaining in the samples was measured. The results show that the carbon

Fig. 3. SEM images of sample prepared by using dierent silica sources, where in a = fumed silica, b = colloidal silica, c = sodium metasilicate and d = TEOS.

R.M. Mohamed et al. / Microporous and Mesoporous Materials 79 (2005) 712 Table 4 Si/Al atomic % ratio of the produced samples measured by EDX Technique at three areas Silica sources Si/Al atomic % A1 Fumed silica TEOS Colloidal silica Sodium metasilicate
a

11

A2 28.78 22.33 20.08 48.93a

A3 27.9 23.70 19.98 37.77a

Average Si/Al atomic % 28.16 23.16 20.46 44.32a

27.8 23.46 21.31 46.27a

Only Si is present and no Al present.

6 0 -2 4 -4

DTA ( uV)

-6 2 -8 -10 0 DTA -14 -2 0 200 400 600 800 1000 -16 1200 TG -12

TG ( Wt. loss

Temperature, C

Fig. 5. FT-IR spectra of optimum ZSM-5 in its dierent forms: (a) assynthesized (ZUC), (b) calcined zeolite (ZC), (c) ion-exchange zeolite (ZCI) and (d) calcined after ion-exchanging (ZCIC).

Fig. 4. DTA/TG curves for as-synthesized fully crystalline ZSM-5 zeolite.

Table 5 The eect of calcination time on the % of carbon remaining Calcination time, h 0 2 4 6 8 % of carbon remaining 3.02 1.25 0.8 0.75 0.26

eect of removal of template on structural parameters. The results show that the unit cell parameters of the ZSM-5 sample are greater than that of ZSM-5-tetrapropyl sample. This is attributed to removal of template from ZSM-5 pores; this is conrmed by increasing surface area of ZSM-5 sample from 358.21 to 381 m2/g. Fig. 5 shows the XRD patterns of ZSM-5-tetrapropyl sample and ZSM-5. The results demonstrate that the crystallinity of ZSM-5-tetrapropyl sample is almost similar to that of ZSM-5, so that the removal of template has no signicant eect on the crystallinity. 3.6. The formation of H-ZSM-5 form The optimum ZSM-5 sample (ZUC) was calcined at 550 C in air for 8 h. After the rst calcination, the zeolite sample was noted as calcined (ZC). This sample was ion-exchanged to replace sodium ion for hydrogen ion present on the active sites. A 1.0 M aqueous solution of ammonium nitrate was used at 80 C for carrying out ion-exchange, the zeolite to solution ratio was 1 g to 150 cm3 and the stirring was carried out for 1 h. After ion-exchange, the zeolite was ltered, washed and dried at 120 C overnight. After ion-exchange, the zeolite was noted as (ZCI). The ZCI was calcined at 550 C for 3 h in airow to decompose the ammonium ion to produce hydrogen form (ZCIC). Fig. 6 shows the infrared spectra of zeolites (ZUC, ZC, ZCI and ZCIC). These spectra show the appearance and disappearance of dierent

remaining in the sample was decreased from 3.02% to 0.26% by increasing calcination time from 2 to 8 h, respectively, as shown in Table 5. Hence, the template was almost completely removed from the ZSM-5 by calcination of the sample, which was prepared by using fumed silica at 550 C for 8 h in air. Table 6 shows the
Table 6 Eect of removal of template on structural parameters ZSM-5 Structural parameters ) (A a Standard ZSM-5-tetrapropyl ZSM-5-tetrapropyl sample Standard ZSM-5 ZSM-5 sample 20.022 19.920 19.870 19.910 b 19.899 19.920 20.107 20.030 c 13.383 13.360 13.369 13.400 5332.0249 5301.3330 5343.6836 5343.8800 Unit cell )3 V (A

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ZSM-5 tetrapropyl

Intensity

ZSM-5

10

20

30

40 2- Theta

50

60

70

80

Fig. 6. XRD patterns of ZSM-5 tetrapropyl and ZSM-5.

absorption bands during the pretreatment procedure. The spectra of as-synthesized zeolite (ZUC) show weak CH stretching absorption bands in the region 2980 2880 cm1 due to presence of the template together with two broad bands at 3670 and 3460 cm1 assigned to tetraalkylammonium OH stretching modes. Calcination results in disappearance of absorption bands assigned to the template. Following ion-exchange with aqueous solution of ammonium nitrate, new bands appeared at 3170 and 1400 cm1 due to NH stretching and bending modes. When the ammoniated zeolite was calcined to produce the hydrogen form of the zeolite, the bands at 3170 and 1400 cm1 disappeared and the intensities of OH stretching bands increased [34].

4. Conclusions The silica sources inuenced on zeolite crystallization and lead to changes in the properties of nal product. Fumed silica, TEOS and colloidal silica give ZSM-5 phase, but sodium metasilicate gives quartz phase. The crystallinity % of ZSM-5 produced increased in the following order: colloidal silica < TEOS < fumed silica. SEM data show that the sample which was prepared by fumed silica crystallized in cubical shape crystals, the samples which were prepared by TEOS and colloidal silica crystallized in twinned and intergrown shape crystals, but the sample which was prepared by sodium metasilicate crystallized in needle shape crystals. The synthesized zeolite was found to be thermally stable up to 1000 C. Calcination of zeolites to decompose and remove templates eectively was achieved by heating the zeolite in airow for 8 h at 550 C. Calcination of zeolite has no signicant on crystallinity %. Unit cell and surface area are increased by calcination and ion-exchange zeolite material.