Accepted Manuscript

Insight into seed-assisted template free synthesis of ZSM-5 zeolites

Majid H. Nada, Sarah C. Larsen

PII: S1387-1811(16)30505-4
DOI: 10.1016/j.micromeso.2016.10.040
Reference: MICMAT 7980

To appear in: Microporous and Mesoporous Materials

Received Date: 11 September 2016

Revised Date: 21 October 2016
Accepted Date: 25 October 2016

Please cite this article as: M.H. Nada, S.C. Larsen, Insight into seed-assisted template free synthesis of
ZSM-5 zeolites, Microporous and Mesoporous Materials (2016), doi: 10.1016/j.micromeso.2016.10.040.

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 ACCEPTED MANUSCRIPT

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ZSM-5 seed crystals
Template-free ZSM-5 product

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AC = ZSM-5 Seeds
= New nuclei formed on surface

Growth of new ZSM-5 particles = Template-free ZSM-5 crystals

on the surface of the seeds Aluminosilicate gel
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Insight into Seed-Assisted Template Free Synthesis of ZSM-5 Zeolites

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Majid H. Nada, and Sarah C. Larsen*

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* Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA.
Tel.: +1 319 335 1346
E-mail: sarah-larsen@uiowa.edu
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ABSTRACT

Synthesizing nanocrystalline ZSM-5 using a templating method is considered to be time, energy,

and materials inefficient. In addition, the production of CO2 from the calcination process has a

negative impact on the environment. Therefore, finding another method to synthesize

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nanocrystalline ZSM-5 without using an organic template would be beneficial. Here,

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nanocrystalline ZSM-5 was synthesized successfully in high yield by using a seed-assisted

method and without using the organic template. In addition, the effects of synthesis temperature,

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synthesis time, pH, amount of seeds, size of seeds, aging time, and use of calcined and

uncalcined seeds were investigated. The synthesized nanocrystalline ZSM-5 materials were

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characterized by using X-ray diffraction (XRD), gas adsorption isotherm (BET/BJH), inductively
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coupled plasma optical emission spectroscopy (ICP/OES), and transmission electron microscopy

(TEM). It was found that the synthesis temperature and time have a strong influence on the
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crystallinity of the synthesized nanocrystalline ZSM-5. Under the conditions reported here, the
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ideal synthesis temperature and time to synthesize fully crystalline ZSM-5 crystals are 165 ͦ C,
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and 14-24 h, respectively. Controlling the pH and seed amount facilitated the synthesis of ZSM-

5 with high crystallinity. A basic environment with Na2O/SiO2 = 0.4, and a seed amount of 0.35
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wt. % were necessary to form fully crystalline ZSM-5 particles. In addition, ZSM-5 with high

crystallinity and yield could be obtained using calcined seeds. Finally, seeds with large complex
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aggregates showed a strong influence on the size and aggregation of the synthesized particles.
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Keywords: ZSM-5 zeolites, Synthesis, Nanocrystals, Seed-assisted method

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1. Introduction

Zeolites are crystalline aluminosilicate materials composed of silicon and aluminum that

are arranged in tetrahedral coordination and are linked by oxygen atoms [1–3]. In addition, the

structure of the zeolite contains micropores of molecular dimensions. The structure of ZSM-5 is

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three dimensional with two kinds of intersecting channels, straight channels and zigzag channels,

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that are formed by 10-ring pores with pore diameters of ∼0.55 nm [4,5]. ZSM-5 zeolites are used

in a variety of applications in industry and medicine [3,6,7]. Nanocrystalline ZSM-5 zeolites,

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with at least one dimension of 100 nm or less, have great potential in catalysis, separations,

adsorption, designing nanoscale devices, nanofilms, and membranes [3,6–9]. Because

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nanocrystalline ZSM-5 zeolites have a high surface area with different active sites, small pore
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sizes, and a short diffusion path, they can be used effectively as catalysts. For example, catalytic
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cracking reactions in petrochemical industries use nanocrystalline ZSM-5 zeolites because they

have acid sites (Bronsted acid sites) on the surface, which have catalytic activity toward
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hydrocracking reactions [10–13]. Nanocrystalline ZSM-5 can be used to catalyze a selective

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catalytic reduction (SCR) of NOx to reduce the emission of harmful pollutants such as nitrogen

oxides [14]. Nanocrystalline ZSM-5 is used as a solid catalyst to convert different types of
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biomass to chemicals such as olefins and aromatics, which can be used as fuels [15,16].

Zeolites can be found in natural or synthetic forms. Several methods can be used to
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synthesize the zeolite commercially in different sizes and structures, including various crystalline
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structures. Currently, there are about 40 types of naturally occurring zeolites and about 200

synthetic versions. The chemical composition and structural framework of the materials

determine the type and zeolite properties [1,3]. In general, zeolites are formed in a closed system

such as a Parr autoclave, where reactions lead to initial nucleation and crystal growth [2,3,7,17].

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Several studies have been published describing different methods of synthesizing nanocrystalline

ZSM-5 zeolites. Persson and coworkers first synthesized nanocrystalline ZSM-5 using a clear sol

system with a low temperature [7]. Because of the desire to produce very small particles and to

make the reaction rate very fast, several methods have been developed [5,14,18]. In all of these

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methods the synthesis of nanocrystalline ZSM-5 has been accomplished by using an organic

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structure directing agent (OSDA) such as tetrapropylammonium (TPA) as a template [7,17–20].

The challenge with conventional methods is the use of the OSDA as a template to

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facilitate the growth of the nanocrystalline ZSM-5. These organic templates are expensive and

have complex structures that have to be removed by calcination at a high temperature to form the

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pores and reveal the internal surface of nanocrystalline ZSM-5. This process consumes energy
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and produces gases that are environmentally unfriendly such as CO2. For these reasons, finding a

method to synthesize nanocrystalline ZSM-5 without using the organic template is strongly
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desired because it will be less costly and more environmentally friendly. Several studies have
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reported attempts to synthesize ZSM-5 and other zeolite types using template-free or seed-
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assisted methods. Grose and Flanigen reported the first synthesis of ZSM-5 by a template-free

and seed-assisted method in 1981 using high temperatures of 200 °C and a long heating time of
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68-72 h [21].

Since then, many studies have been conducted to synthesize ZSM-5 and other zeolites
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without using the template. One of the proposed ways to synthesize zeolites without using the
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organic template is the template-free synthesis. ZSM-5 was synthesized by using a template-free

method with structure and properties similar to those synthesized with the template [22][23].

Another study was done to synthesize ZSM-5 by using agricultural waste materials as a silica

source in the absence of the organic template [24,25]. However, these synthesis approaches

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required long synthesis and treatment times to obtain ZSM-5 with good crystallinity and yield.

Therefore, another way to synthesize ZSM-5 in the absence of the organic template was

proposed which is the seed assisted method. In this method, seed crystals of the target zeolite are

synthesized using the conventional method with an organic template, and then a small amount of

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the synthesized seeds are added to the organic template-free reactant gel to form the desired

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zeolite. The added seed crystals increase the crystallization rate, and enhance the quality of the

product zeolite by improving the crystallization [26,27]. Relatively few synthetic studies have

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been conducted to synthesize ZSM-5 by using the seed assisted method. The majority of these

studies required the use of a large amount of seed crystals with a long synthesis time to form

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pure ZSM-5 crystals with high crystallinity [26–31].
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In the study reported here, nanocrystalline ZSM-5 was synthesized with a high quality

and yield by using a small amount of seeds and a short synthesis time. Distinct from previous
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studies of seed-assisted template-free ZSM-5 synthesis methods, the effect of the seed particle size
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and aggregation of the ZMS-5 seeds on the ZSM-5 final product was studied by using seeds with different
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sizes. In addition, the effect of other synthesis conditions such as synthesis temperature,

synthesis time, pH, amount of seeds, aging time, and use of calcined and uncalcined seeds were
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also systematically investigated.

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2. Experimental Section
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Materials

Seed synthesis: Tetrapropylammonium hydroxide (TPAOH, 40 wt. % aqueous solution),

Tetraethyl orthosilicate (TEOS), Sodium hydroxide (NaOH), and Aluminum isopropoxide.

Seed- assisted synthesis: Sodium aluminate, Silica sol (30 wt. %), Sodium hydroxide (NaOH)

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2.1 Synthesis of Nanocrystalline ZSM-5 Seeds

Nanocrystalline ZSM-5 seeds were synthesized using a method developed previously in

our lab with making some modifications to the molar ratio, temperature, and synthesis time to

vary the particle size (Table S1) [20]. The synthesis procedure was as follows: a measured

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amount of aluminum isopropoxide was dissolved in distilled water with stirring, and then NaOH

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was added to the mixture followed by adding TPAOH and TEOS, respectively. The reaction

mixture was left for 2 h at room temperature with a continuous stirring. After that, the mixture

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was transferred to an autoclave equipped with a Teflon liner following by a hydrothermal

treatment at 165 ͦ C for 120 h. Then, the particles were separated by the centrifugation and

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washed with distilled water twice and once with ethanol. The obtained particles were dried at 80 ͦ
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C overnight to be used as seed crystals. Part of one sample was calcined at 550 ͦ C for 12 h to be
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used as template-free seeds.

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2.2 Seed-assisted Synthesis

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To start the synthesis, a specific amount of the synthesized seed crystals (70 ± 2 nm, 90 ±

4 nm, and 250 ± 5 nm) from the above method was measured to serve as seeds in this procedure.
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The seeds were added to 1.0 mL of ethanol to prepare a seed suspension. Then the seed

suspension was sonicated for 2-3 h. In another vessel, an aluminosilicate gel with a chemical
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composition of 6SiO2:0.3Al2O3:xNa2O:300H2O (where x = 1, 1.5, 2.5 and 3.5) was formed by

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dissolving a measured amount of sodium aluminate in distilled water following by adding the

sodium hydroxide. Next, the silica sol was added to the mixture. The reaction mixture was stirred

for 2 h at room temperature. The seed suspension was added to the reaction mixture and

transferred to an autoclave to be treated hydrothermally. Next, the synthesized nanocrystalline

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ZSM-5 particles were collected by centrifugation and washed with acidic ethanol (1.0 mL of

HCl/ 1.0 L of Ethanol), and then with distilled water two times. The collected particles were

dried at 80 ͦ C overnight. The amount and size of the seeds, temperature, amount of NaOH, and

time were varied to investigate their effect on the synthesis as listed in Table 1.

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2.3 Instruments

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The obtained materials were characterized by using a D-8 X-ray diffractometer with Cu

Kα to collect the XRD pattern between 2θ angles of 5 to 55 with a 0.04 step size. Then, the XRD

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patterns were used to estimate the relative crystallinity (RC) of the samples by integrating the
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peaks between 2θ of 22.5 to 25 and compare that with a commercially available ZSM-5
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(Zeolyst) (Figure S1). More details about calculating the relative crystallinity (RC) are explained

in the supporting information file. To get precise measurements of relative crystallinity, identical
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amounts of the sample (analyzed) and commercial ZSM-5 (reference) were used and packed in a

similar way in the sample holder of XRD.

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Surface area analysis was done by using BET method on a Nova 1200 Nitrogen
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adsorption instrument (Quantachrome). Surface area for a standard material was run several

times to find the experimental error, which was found to be RSD % = 4.07. To start the surface
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area measurement, approximately 100 mg of the obtained materials was dried over night at 120 ͦ

C under vacuum by using the outgas station on the BET instrument. Then, surface analysis of 7-
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points BET isotherm was run to measure the surface area of the materials by using pure nitrogen

gas as the adsorbate. For the seed samples, the external surface area before the calcination was

used to calculate the particle size by using this equation; particle size = 3216/ external surface

area [18,20].

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The TEM images were collected by using JEOL JEM-1230 Transmission Electron

Microscopy. The samples were prepared by dissolving a very small amount of the ZSM-5 zeolite

in ethanol following by sonicating for 20 min. A drop from the sample suspension was placed on

a carbon grid coated with copper and left to dry at room temperature before doing the TEM

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analysis. Table 1 summarizes the synthesis experiments and the characterization results for the

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samples.

Elemental analysis of the seeds and products was done by using inductively coupled

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plasma optical emission spectroscopy (Varian 720-OES) to determine Si/Al ratio. The sample

was prepared by placing 10 mg of the ZSM-5 zeolite powder in a plastic tube following by

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adding 1.6 mL of 70:30 HCl:HF solution. The obtained suspension was sonicated for 10 minutes.
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After that, 6 mL of 5 vol. % boric acid and 0.6 mL of concentrated nitric acid were added. Then,

DI water was added to adjust the total volume to be 10 mL.

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3. Results and Discussion

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During the seed-assisted synthesis process, the synthesis temperature, synthesis time,
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basic environment, amount of the seeds, aging time, size of the seeds, and use of the calcined and

uncalcined seeds were varied systematically to study the effect of these factors on the synthesis
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of nanocrystalline ZSM-5. The crystals of the products had a Si/Al ratio of approximately 24 as
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measured by ICP, and it is very close to the Si/Al ratio of the seeds (Table S1). The zeolite yield
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was calculated and represented in terms of mole of Si in zeolite nanocrystals recovered for each

batch per mole of Si in the precursor to show the utilization of the starting materials. An

overview of the synthetic results is provided in Table 1.

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3.1 Effect of the Synthesis Temperature

In order to investigate the effect of the temperature on the seed-assisted synthesis

process; three experiments (samples S1, S2, and S3-ZSM-5) were carried out at different
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temperatures (150, 165, and 180 C) for 24 h. The gel composition was

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6SiO2:0.3Al2O3:2.5Na2O:300H2O with 0.35 wt. % of the 250 nm seed crystals. The XRD

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patterns of the products show a strong effect of the synthesis temperature on the formation of

ZSM-5 nanocrystals (Figure 1).

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From the XRD patterns, it can be seen that at the low temperature 150 ͦ C, the formation

of ZSM-5 crystals is not fully completed and evidence of an amorphous material is observed in

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the XRD powder pattern in the area between 2θ = 10 ͦ - 20 ͦ. This indicates that at a low
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temperature, there is not enough energy for the complete transformation of the precursor
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aluminosilicate to ZSM-5 crystals. Therefore, at temperature 150 ͦ C during the synthesis time of

24 h, only part of the aluminosilicate gel was transformed to ZSM-5 crystals while the remaining
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amount remained as amorphous materials. Increasing the temperature was beneficial as the XRD
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of the sample with synthesis temperature of 165 ͦ C shows clear peaks for ZSM-5 nanocrystals

with no impurities. The relative crystallinity of this sample is 92%, and the surface area is 250 ±
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10 m2/g, which is typical for large ZSM-5 particles, and the yield of this sample was very high

1.7 /1 molar ratio ( mole of Si in zeolite product per mole of Si in precursor). Further increasing
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the synthesis temperature shows the formation of other zeolite impurity forms in addition to
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ZSM-5. The XRD of the sample that was synthesized at 180 ͦ C shows an additional peak at 25.8 ͦ

(indicated with an asterisk), which is assigned to a keatite zeolite phase that was formed along

with ZSM-5.

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The optimal synthesis temperature of 165 °C that was found in this study to obtain highly

crystalline, impurity-free ZSM-5 is slightly different from what was found in other studies by

using the seed-assisted method [28–30]. Valtchev and coworkers and Li and coworkers found

optimal synthesis temperatures of 170 ͦ C and 180 ͦ C, respectively, using different amounts of

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seed crystals (3.0 wt. % and 5.0 wt. %, respectively) relative to our study [28,29], which used a

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smaller amount of seed crystals of 0.35 wt. % at a slightly lower synthesis temperature of 165 ͦ C.

The formation of impurities at high temperature 180 ͦ C indicates that our synthesis is sensitive to

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the temperature, and the synthesis temperature shows a strong influence on the formation of

ZSM-5 zeolites by affecting both the nucleation and growth process.

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3.2 Effect of Synthesis Time
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It was found that the synthesis time also has a strong effect on the crystallization of the

nanocrystalline ZSM-5 formed by templated synthesis methods [5,14,18]. In order to find the
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optimal time required to synthesize ZSM-5 by the seed-assisted method, the effect of synthesis
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time was investigated by conducting four experiments (sample S4, S5, S6, and S7-ZSM-5) with

different synthesis times (10, 14, 24, 48 h, respectively). The chemical composition of the initial
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gel, and the amount of seeds were the same as in the temperature effect studies. In this set of

experiments, the optimal synthesis temperature of 165 ͦ C that was found from the S1-S3
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experiments was used with 0.35 wt. % of the 70 nm seeds. The XRD patterns of the products

show that the crystallinity of the product was strongly influenced by changing the synthesis time

(Figure 2). First, at a very short time of 10 h, the crystallinity of ZSM-5 is very low. The main
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peaks of ZSM-5 in the range of 2θ = 7-9 and 23-25 ͦ appear in the XRD, but the relative

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crystallinity of this sample is 65%. This indicates that the crystallization process of the product

was not complete and more time was required.

Increasing the synthesis time to 14 and 24 h shows a positive impact on the crystallinity

of ZSM-5 as the main peaks of ZSM-5 appear in the XRD (samples S5 and S6 in Figure 2), and

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the relative crystallinities are 98% and 94 % respectively. More characterization of these two

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samples (S5 and S6) was conducted such as BET and TEM measurements. The surface areas of

S5 and S6 are 280 ± 10 m2/g, and 250 ± 10 m2/g respectively, and the yields were 1.4 and 1.6 to

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1 ( mole of Si in zeolite product per mole of Si in precursor), respectively. The TEM images

(Figure 3) show a particle size of 260 ± 40 nm for the ZSM-5 that was synthesized at 14 h, and

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280 ± 50 nm at 24 h. It is clear that increasing the synthesis time forms large particles, as the
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growth rate will increase with increasing time during the hydrothermal treatment.

Further increasing in the synthesis time to 48 h resulted in the formation of other

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materials along with ZSM-5 nanocrystals. The two additional peaks in the XRD of the sample
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that was synthesized at 48 h (S7) correspond to quartz materials that are considered as impurities.
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Other researchers found an optimal synthesis time of 24 h to synthesize highly crystalline

ZSM-5 by the seed-assisted template free synthesis [27–30]. Valtchev and coworkers found long
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synthesis times of greater than 18 h are required to obtain highly crystalline ZSM-5 when low

amounts (0.1 wt. % ) of zeolite seed crystals were used [28]. This is similar to what is reported in
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our study except that we were able to use a slightly lower synthesis temperature of 165 ͦ C and
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shorter time. It should also be noted that Valtchev and coworkers used silicalite seed crystals

(purely siliceous form of ZSM-5) in their study and ZSM-5 seed crystals were used in our study.

Yu and coworkers found that ~ 30 h is required to get high crystalline ZSM-5 at 170 ͦ C using

ZSM-5 seeds [30] whereas we found that increasing the synthesis time to 24 h resulted in

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impurities in addition to the ZSM-5 crystals under the synthesis conditions specific to our study.

Yu and coworkers were primarily interested in varying the Si/Al ratio of the product ZSM-5 and

therefore did not vary other synthesis parameters such as synthesis temperature and time. From

the above experiments and observations, increasing the synthesis time has both advantages and

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disadvantages. Long synthesis time (~ 14 – 24 h) are required to form fully crystalline materials,

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but excessive synthesis time will promote the formation of other undesired materials along with

nanocrystalline ZSM-5. Generally these results are comparable to previous reports with the

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caveat that ZSM-5 seed crystals of different sizes were also explored in this study as will be

discussed in section 3.6.

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3.3 Effect of the Basic Environment

It was proposed that a basic environment is needed if a seed-assisted method is used to

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synthesize zeolite crystals [27,30]. When the seed particles are introduced to a gel mixture, the
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external surface of the seed particles will be gel-wrapped. Therefore, the basic environment will
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partially dissolve the gel-wrapped surface and expose the surface of the seed particles as

potential nucleation sites. In another study, it was found that the Na+ cation has a strong effect on
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the formation of zeolite crystals in the absence of both organic templates and seeds [32].

Therefore, to study the effect of the basic environment in the seed-assisted synthesis of
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nanocrystalline ZSM-5, four experiments were run using different amounts of NaOH (sample S6,
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S8, S9, and S10-ZSM-5 with pH = 11.5, 8.5, 9, 12, respectively). The synthesis temperature and

time were kept at 165 ͦ C for 24 h, and the amount of the seeds was 0.35 wt. % with an average

size of 70 nm. The study was conducted in terms of Na2O/SiO2 ratio. The NaOH is the source of

Na2O in the mixture, so increasing the amount of NaOH will increase Na2O/SiO2 ratio. The

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collected XRD patterns of the four are represented in Figure 4. The results show that with a very

low amount of NaOH (Na2O/SiO2 = 0.16, pH = 8.5) the crystallinity of ZSM-5 is very poor, and

this is clear from the presence of amorphous materials in the area between 2θ of 10 ͦ – 20 ͦ.

Increasing the amount of NaOH (Na2O/SiO2 = 0.25, pH = 9) enhances the crystallinity to 73 %,

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but the amorphous materials are still present with the ZSM-5 crystals. In addition to the low

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surface area of that sample which is 150 ± 6 m2/g, the TEM image of the sample clearly shows

the presence of amorphous materials (Figure 5A). The fully crystalline ZSM-5 materials were

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obtained at Na2O/SiO2 = 0.40, pH = 11.5 with relative crystallinity of 94 % and surface area of

250 ± 10 m2/g. On the other hand, using a very high amount of NaOH (Na2O/SiO2 = 0.60, pH =

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12) shows a negative impact by the formation of a keatite zeolite phase.
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These results confirm what has been found about the effect of the basic environment on

the crystallinity of ZSM-5 synthesized by template free methods [30,32]. Cheng and coworkers
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studied the effect of basicity on the crystallinity of the synthesized ZSM-5 in the absence of both
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organic template and seeds, and they found at very low basic environment, amorphous materials
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were formed, and at very high basicity, impurities were formed [32]. Our results in this study are

in agreement with what has been found about the effect of the basic environment by Cheng and
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coworkers. However, the observation from this study is different from what has been reported

recently by Yu and coworkers in which they observed that a severely strong basic environment
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was required to facilitate the nucleation, the growth and to get high crystalline ZSM-5 by the
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seed-assisted method [30]. In contrast, we observed that a very strong basic environment (pH =

12) resulted in the formation of impurities with the targeted materials (ZSM-5) under the

synthesis conditions reported here. Consequently, a strongly basic environment is required to

improve the formation and the crystallinity of nanocrystalline ZSM-5 by enhancing the

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nucleation process on the surface of the seed crystals; however the strongest basicity resulted in

the formation of impurities along with ZSM-5 crystals.

3.4 Effect of Seed Amount

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In order to achieve optimal crystallization of nanocrystalline ZSM-5, the effect of the

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seed amount was investigated by conducting two different experiments (sample S11 and S6-

ZSM-5) using different amounts of seeds (0.2 wt. % and 0.35 wt. %). The initial gel composition

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was prepared with the optimum amount of NaOH found from the experiments described in

sections 3.2 and 3.3. The temperature and synthesis time were maintained at 165 ͦ C and 24 h,

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respectively. From the XRD patterns (Figure 6), calculated relative crystallinities, and TEM
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images, we can observe that using a small amount of seeds 0.2 wt. % will give ZSM-5

nanocrystals with some amorphous materials, and this is demonstrated by the low relative
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crystallinity of 80 %, low surface area of 190 ± 8 m2/g, and by the TEM image that shows a clear
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presence of amorphous materials with ZSM-5 nanocrystals (Figure 5B). On the other hand, using
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the larger amount of seeds 0.35 wt. % shows a great enhancement of the ZSM-5 crystallinity

(relative crystallinity of 94 % and surface area of 250 ± 10 m2/g). In addition, the TEM image
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shows fully crystalline ZSM-5 nanocrystals (Figure 7A).

As a result, the amount of the seeds has a strong affect on the crystallinity of the ZSM-5.
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Using an optimal amount of seeds tends to be beneficial by increasing the crystallinity, but the
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lower amount results in nanocrystalline ZSM-5 with a lower crystallinity. In a similar study by

Valtchev and coworkers, the seed amount of silicalite seeds was varied from 0.1 to 3.0 wt. %.

They determined that the amount of seeds impacted the crystallinity and the aggregation state of

the product more than the size of the product. In their study, the ZSM-5 materials with the

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greatest crystallinity were obtained with seed amounts of 3.0 wt. % [28]. Other studies showed

that seed amounts of ~5 - 10 wt % are required to synthesize ZSM-5 by the seed assisted method

[27,29,30]. Generally, our study indicates that highly crystalline ZSM-5 can be obtained in a

seed assisted template free synthesis using a relatively low amount of seeds (0.35 wt. %) at lower

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temperature and shorter synthesis time compared to previous studies.

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3.5 Effect of Aging Time

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Because it was found that aging the reaction mixture for a period of time before the

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hydrothermal treatment tends to be useful by enhancing the nucleation process in the template-
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free synthesis,[32] the effect of aging time in the seed-assisted method of nanocrystalline ZSM-5

was explored in this study. Two experiments (sample S13 and S2-ZSM-5) were conducted: one
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with aging the reaction mixture for 24 hours before the hydrothermal treatment, and another

without aging. The initial gel was prepared according to the ideal amounts and conditions found
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from the above studies. The XRD of these two samples are represented in Figure 8. The typical
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peaks of nanocrystalline ZSM-5 appear in the XRD pattern when the sample was synthesized

without aging the mixture. However, the XRD of the sample synthesized with aging the mixture
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for 24 h shows additional peaks along with the main peaks of nanocrystalline ZSM-5. The

additional peaks are due to mordenite and keatite zeolite phases, which are considered as
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impurities.

Therefore, aging the mixture for a period of time was not beneficial to be implemented

with the conditions used in our study of the seed-assisted synthesis of nanocrystalline ZSM-5.

Recently, two studies reported synthesizing ZSM-5 by the template free and seed-assisted

synthesis where they showed that aging the mixture for 24 - 48 h before the hydrothermal

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treatment was beneficial to get high crystalline ZSM-5 without any impurities [30,32]. However,

our study showed that, under the conditions reported here, aging the mixture for 24 h facilitated

the formation of impurity phases along with ZSM-5 materials.

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3.6 Effect of Seed Particle Size

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Three different seed crystal particle sizes were used to study the relationship between the

size of the seeds and the size of the product. The average sizes of the seeds are 70 ± 2 nm, 90 ± 4

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nm, and 250 ± 5 nm as determined by surface area measurements [5]. The optimized gel

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composition and conditions were used as discussed in previous sections. The collected XRD
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patterns of the three samples (samples S6, S12, and S2-ZSM-5) show the main peaks of

nanocrystalline ZSM-5 without any impurities (Figure 9). The relative crystallinities are 94 %,
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95%, and 92% respectively. The size of the synthesized particles was larger than the size of the

seeds. The TEM images show that the 70 nm seeds resulted in particles with an average size of
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280 ± 50 nm, the 90 nm seeds resulted in particles with an average size of 710 ± 70 nm, and the
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250 nm seeds resulted in particles with an average size of 310 ± 50 nm ( Figure 7). The surface

areas of these three samples are 250 ± 10 m2/g, 240 ± 10 m2/g and 250 ± 10 m2/g respectively
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(see Table 1). By looking at the TEM images of the seeds, we can make an observation about

why the small seeds give particles with sizes bigger than the larger seed crystals. The TEM
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images of both the 70 nm and 90 nm seed crystals show that these particles are forming large

complex aggregates that are formed by very small particles (Figure 7. A and B left images). On

the other hand, the TEM image of the 250 nm seeds shows monodispersed isolated particles

without little aggregation. These particles are large enough to be relatively stable (Figure 7.C left

image).

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Therefore, the nucleation and growth process in the seed-assisted synthesis were strongly

affected by the way in the aggregation state of the seeds in the mixture. In the first sample with

70 nm seeds, the TEM image of the seeds shows some discrete small particles and some large

aggregates. Therefore, the nucleation and the growth of new ZSM-5 particles during the seed-

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assisted synthesis were promoted by both isolated and aggregated particles. However, the TEM

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image of 90 nm seeds shows relatively big complex aggregates with size more than 200 nm.

These complex aggregates contain small particles, and the growth of new particles in the seed-

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assisted synthesis occurs on the surface of these aggregates. In contrast, the TEM image of 250

nm seeds shows discrete isolated particles, and the growth of new particles occur directly on the

external surface of the seed particles.

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From the above explanation, we can observe that there are two types of growth systems

in the seed-assisted synthesis: one by using large complex aggregates of seeds, and another by
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using isolated seed particles. In the former one, the growth will occur on the surface of the seed
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particles, which are close to each other in an aggregated system, and this will lead to form a very
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large particles. This is what happens when using the 90 nm seeds. Because of the large

aggregates in these seeds, the synthesized ZSM-5 particles are very big (710 ± 70 nm) (Figure
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7.B). As the system has low aggregated complexes with some isolated seeds, the size of the

product will be relatively small as the 70 nm seeds with less aggregated particles forms particles
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with 280 ± 50 nm (Figure 7.A). The good control over the size of the product shows with using
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the 250 nm seeds. Because these seeds are fully isolated and no aggregates are present, the

growth is controlled by discrete, isolated particles rather than aggregated complexes, and this

gives a good control over the size of the product (310 ± 50 nm) (Figure 7.C).

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Previous studies of template-free seed assisted synthesis of ZSM-5 have not directly

investigated the effect of seed particle size on the product particle size. However, Valtchev and

coworkers provided insight into the role of seed aggregation in the ZSM-5 synthesis process.

They used seeds that remained dispersed in solution prior to use in the seed assisted synthesis

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compared to seeds that had been dried and calcined thus increasing aggregation. In this study,

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they found that the aggregation of seeds impacted the product aggregation state [28] which is in

agreement with our observations from this study related to the effect of the size and aggregation

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of the seeds on the product. As a result, having fully isolated monodispersed particles will allow

for a greater control over the particle size of the product. Having a system with discrete and

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small particles will facilitate the nucleation and the growth of the new particles with size
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relatively close to the size of the seeds.
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3.7 Effect of Using Calcined and Uncalcined Seeds

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In the seed-assisted method seeds are generally used that have been synthesized using an
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organic template. In order to make the synthesis completely template free, we calcined a portion

of the 70 nm seed crystals and investigated the use of calcined seeds versus uncalcined seeds
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under otherwise identical synthesis conditions. An additional experiment was conducted with the

same gel composition and conditions as in sample S6-ZSM-5 with the use of calcined 70 nm
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seeds. The XRD of this sample shows the main peaks of nanocrystalline ZSM-5 without any
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impurities (Figure 9). The relative crystallinity of the product is 95% with surface area 270 ± 10

m2/g, and high yield of 1.8 /1 (mole of Si in zeolite product per mole of Si in precursor).

Valtchev and coworkers found that using calcined or freeze-dried silicalite seeds resulted

in low crystallinity of the targeted material (ZSM-5) [28] compared to uncalcined silicalite seeds

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at 150 °C with 1 wt% seeds. They attributed this observation to the increased aggregation of the

silicalite seed crystals for both the freeze-dried and the calcined samples relative to the seeds that

had been stored as a colloidal suspension. In our study, we found that using calcined ZSM-5

seeds and the synthesis conditions used in this study (165 °C, 0.3 wt% seeds, 24 h) resulted in

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little change in the observed product which remained highly crystalline and impurity-free. The

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difference can be explained by the differences in the observed aggregation of the ZSM-5 seed

crystals used in our study relative to the silicalite seed crystals used in their study. The calcined

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and uncalcined ZSM-5 seed crystals used in our study are both highly aggregated and therefore,

as expected the resulting product under similar reaction conditions are also similar with respect

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to relative crystallinity and phase. Therefore, our study suggests that calcined seeds can be used
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instead of the uncalcined seeds, in cases where the seed aggregation state has not changed

dramatically during calcination, to synthesize nanocrystalline ZSM-5 zeolites with a high yield
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and crystallinity.
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4. Conclusion

Nanocrystalline ZSM-5 zeolites were synthesized by using the seed-assisted template-

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free method with the following molar ratio 6SiO2:0.3Al2O3:2.5Na2O:300H2O. The temperature

and the time of synthesis had a strong affect on the crystallinity of the product ZSM-5. The
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optimal conditions of temperature and time required to obtain ZSM-5 product with high relative
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crystallinity and yield were determined to be 165 ͦ C and approximately 14-24 h, respectively. A

basic environment with pH = 9 – 11.5 was necessary during the synthesis process to facilitate the

nucleation step, and a mixture with a pH of 11.5 was ideal to obtain ZSM-5 with high

crystallinity. However, using a very strong basic environment (pH = 12) resulted in the formation

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of impurities along with ZSM-5 particles. Controlling the size of the synthesized particles by

using different sizes of the seeds was a unique variable explored in this study. Using seeds that

have monodispersed, isolated particles in the synthesis system helps control the size of the

synthesized nanocrystalline ZSM-5. However, the seeds that have large complex aggregates will

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form very large particles compared to the size of the seeds. Moreover, the amount of the seeds in

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the mixture plays a crucial role in controlling the crystallinity and the yield of the product.

Having an appreciable amount of the seeds (0.35 wt. %) will provide enough nucleation and

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growth sites that form crystalline ZSM-5 particles. Using calcined seeds without any organic

template in their structures to synthesize nanocrsytalline ZSM-5 in this study resulted in very

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similar product crystallinity and yield when 70 nm seeds were employed. The results were
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generally in agreement with the previous literature in which various aspects of the seed-assisted

template-free synthesis have been investigated. In addition to varying the size of the seed
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crystals, another distinctive aspect of this study was the comprehensive and systematic approach
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to varying the reaction conditions including, temperature, time, basicity, seed size, amount and
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calcination, and aging time in a single comprehensive study.

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Acknowledgments

The research described in this article has been funded by a scholarship from the Higher

Committee of Educational Development in Iraq (HCED). Chemistry Department at University of

Iowa and Larsen research group members are acknowledged for their support and help

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throughout this project.

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[19] S.C. Larsen, J. Phys. Chem. C.phs. Chem 111 (2007) 18464–18474.

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[20] W. Song, R.E. Justice, C. a Jones, V.H. Grassian, S.C. Larsen, Langmuir 20 (2004) 8301–
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sample Molar ratio Size of seed wt. % Temp. S.Time (h) Size of Crystallinity Surface Type of
(nm) a of seed ( ͦC ) (A.time (h))b particle % area impurity
(nm) c m2/g

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S1-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 250 0.35 150 24 ----- ---- Amorphous

S2-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 250 0.35 165 24 310 92 250 -----

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S3-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 250 0.35 180 24 ---- ---- ---- Keatite

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S4-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 70 0.35 165 10 ---- 65 ---- -----

S5-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 70 0.35 165 14 260 98 280 -----

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S6-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 70 0.35 165 24 280 94 250 ------

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S7-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 70 0.35 165 48 ---- ---- ---- Quartz

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S8-ZSM-5 6SiO2:0.3Al2O3:1Na2O:300H2O 70 0.35 165 24 ---- ---- ---- Amorphous

S9-ZSM-5 6SiO2:0.3Al2O3:1.5Na2O:300H2O 70 0.35 165 24 ---- 73 150 Amorphous

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S10-ZSM-5 6SiO2:0.3Al2O3:3.5Na2O:300H2O 70 0.35 165 24 ---- ---- ---- Keatite

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S11-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 70 0.20 165 24 ---- 80 190 Amorphous
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S12-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 90 0.35 165 24 710 95 240 ------

S13-ZSM-5 6SiO2:0.3Al2O3:2.5Na2O:300H2O 250 0.35 165 24 ---- ---- ---- Mordenite

(24) and Keatite
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Table 1 Summary of synthesis and characterization of nanocrystalline ZSM-5 by the seed-assisted method.
a
: the particle size was calculated by the following equation: particle size (nm) = 3216/BET surface area of as-synthesized ZSM-5 samples [20].
b
: S.Time = synthesis time, A.time = Aging time
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: the particle size was calculated from the TEM images

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Figures:

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Figure 1. XRD of three samples (S1, S2, and S3-ZSM-5) that were synthesized at
different temperatures (150, 165, and 180 ͦ C) for 24h and by using 0.35 wt. % of the 250
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nm seeds
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Figure 2. XRD of four samples (S4, S5, S6, and S7-ZSM-5) that were synthesized by
using different synthesis time (10, 14, 24, and 48 h) at 165 C and by using 0.35 wt. % of
the 70 nm seeds.

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Figure 3. TEM images of the sample S5-ZSM-5 (280m2/g) that was synthesized at

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14 h (left image), and the sample S6-ZSM-5 (250 m2/g) that was synthesized at 24 h
(right image).
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Figure 4. XRD of four samples (S8, S9, S6, and S10-ZSM-5) that were synthesized by
using different amount of NaOH at 165 C for 24h and by using 0.35 wt. % of the 70 nm
seeds, and x = Na2O/SiO2 molar ratio

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Figure 5. TEM images that show nanocrystalline ZSM-5 with amorphous material present

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(indicated by the arrow) for the sample S9-ZSM-5 that was synthesized with N2O/SiO2=
0.25 (A), and the sample S11-ZSM-5 that was synthesized by using 0.2 wt. % of the seeds
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(B) with a scale bar of 200 nm.
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Figure 6. XRD of two samples (S11, and S6-ZSM-5) that were synthesized by using
different amount of seeds (seed wt. % listed)

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Figure 7. TEM images of the seeds (left images), and the synthesized nanocrystalline ZSM-5
by using the seeds on the left (right images). In group (A), the 70 nm seeds (left), and the
sample S6-ZSM-5 (250 m2/g) (right). In group (B), the 90 nm seeds (left), and the sample
S12-ZSM-5 (240 m2/g) (right). In group (C), the 250 nm seeds (left), and the sample S2-ZSM-
5 (250 m2/g) (right).

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Figure 8. XRD of the two samples (S13, and S2-ZSM-5) that were synthesized with
aging time of 24 h (A), and without aging (B).
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Figure 9. XRD of synthesized nanocrystalline ZSM-5 by using seeds with different sizes
70 nm, 90 nm, and 250 nm (sample S6, S12, and S2-ZSM-5 respectively), and by using
the 70 nm calcined seeds.

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Highlights  
 
• Calcined  seed  crystals  are  effective  in  the  template-­‐free  synthesis  of  ZSM-­‐5.  

• Size  and  aggregation  of  seed  crystals  impacts  product  size  and  shape  

• High  yields  and  crystallinity  were  obtained  with  relatively  low  cocentration  

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of  seeds.  

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