Microporous and Mesoporous Materials 303 (2020) 110247

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Microporous and Mesoporous Materials

journal homepage: http://www.elsevier.com/locate/micromeso

Green synthesis and characterization of zeolite silicalite-1 from recycled

mother liquor
Jun Yang a, Ya-Xi Huang a, Yuanming Pan b, Jin-Xiao Mi a, *
a
Fujian Provincial Key Laboratory of Advanced Materials (Xiamen University), Department of Materials Science and Engineering, College of Materials, Xiamen
University, Xiamen, 361005, Fujian Province, People’s Republic of China
b
Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK, S7N 5E2, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Researches on zeolite silicalite-1 have focused mainly on improving its performance, with little attention paid on
Green synthesis green and economic synthesis. Herein, a novel route for green synthesis of pure silicalite-1 from the recycled
Zeolite mother liquor has been developed. This route starts from the hydrothermal reaction of natural quartz with NaOH
Silicalite-1
to form a sodium silicate solution, which is then transformed into a silicic acid (H2SiO3) gel by hydrochloric acid
Organic template
Recycled mother liquor
titration. Then the solid silicic acid (H2SiO3) gel and fumed silica (SiO2) are mixed with water under stirring to
form a highly active slurry, which can be hydrothermally “dissolved” in a dilute NaOH aqueous solution. Using
this slurry with a high SiO2/Na2O molar ratio of 5 : 1 as the silica source as well as tetrapropylammonium
bromide (TPABr) as the organic template, MFI-type pure silicalite-1 has been successfully synthesized. After each
synthesis, the mother liquor of centrifuged supernatant was recovered and recycled. The silica source and organic
template were added to the recycled mother liquors for the synthesis of pure silicalite-1. The minimum TPABr/
SiO2 molar ratio needed to synthesize pure silicalite-1 in the initial run is 0.04 : 1. In comparison, only half the
amount of the organic template is needed in subsequent runs with the recovered mother liquors. Through
recycling, all reactants in the mother liquors were ultimately utilized without any waste, leading to not only
effectively reducing the cost of silicalite-1 synthesis but also minimizing its environmental impact.

1. Introduction
Zeolites commonly refer to a class of aluminosilicate molecular
sieves with rich three-dimensional channels, and are widely used in
catalysis [1,2], adsorption [3,4], separation [5,6] and ion exchange [7,
8]. An aluminum-free zeolite, which has an extremely simple chemical
composition of silica (SiO2), high thermal and chemical stability and
unique shape selectivity, is known as silicalite [9]. Among the known
polymorphs of pure silica zeolites, the aluminum-free end members of
the MFI-type zeolite ZSM-5 and the MEL-type zeolite ZSM-11 have been
named as silicalite-1 and silicalite-2, respectively [10]. Notable appli­
cations of silicalite-1 have been in the areas of sensors [11,12],
bio-medicine [13,14] and miscellaneous aspects [15].
In the past decade, researches on silicalite-1 have focused largely on
its crystallization mechanism as well as tunable crystal morphology and
particle size, which exert significant controls on the properties and
performances of zeolites. For example, Feng et al. demonstrated that the
crystallization processes of zeolites could be accelerated by hydroxyl
free radicals under hydrothermal conditions [16]. Lupulescu and Rimer
proposed a two-stage synthesis mechanism of silicalite-1 with an early
growth governed by a classical model and followed by silica precursor
covered on crystal surfaces for concomitant structural rearrangement
and three-dimensional growth in a nonclassical way [17]. Mintova et al.
studied the effects of different silicon sources on the size of silicalite-1
nanocrystals [18]. Zhang et al. introduced a facile strategy to prepare
high-quality single-crystalline MFI-type nanozeolites (10–55 nm) [19].
Bonilla et al. employed structure-directing agents to control the three
axial crystal growth rate and crystal morphologies of silicalite-1 [20].
Dai et al. reported a simple strategy for the preparation of hollow
nanocubes and three-dimensionally macroporous monoliths of
silicalite-1 [21].
However, industrial applications of zeolites not only require excel­
lent performances but also need economical and green production pro­
cesses. At present, there are various ways to reduce the costs of zeolites
synthesis: (1) Developing new synthesis methods or conditions. Xiao’s
group reported a sustainable and environmentally friendly technique for

* Corresponding author.
E-mail address: jxmi@xmu.edu.cn (J.-X. Mi).

https://doi.org/10.1016/j.micromeso.2020.110247
Received 17 February 2020; Received in revised form 4 April 2020; Accepted 7 April 2020
Available online 18 April 2020
1387-1811/© 2020 Elsevier Inc. All rights reserved.
J. Yang et al.
synthesizing zeolites Beta and ZSM-5 without using any organic tem­
plates and solvents [22]. Ng and co-workers reported an effective
method for synthesizing large-pore EMT zeolite nanocrystals (6–15 nm)
from template-free colloidal precursors at low temperature (30 � C) with
high yield [23]. (2) Using cheap substitutes for organic templates. Chen
et al. introduced an economical way for SSZ-13 zeolite preparation with
the inexpensive choline chloride as template instead of more expensive
and toxic ones [24]. (3) Synthesizing zeolites with recycled organic
templates. Liu et al. reported a green and efficient preparation of hollow
titanium silicalite-1 (TS-1) by using recycled mother liquor [25].
Moreover, completely different from the methods as described above,
Davis and colleagues developed a new synthetic strategy for micropo­
rous crystalline molecular sieves that organic structure-directing agents
inside the zeolite can be disassembled in solution without high tem­
perature combustion treatment and reassembled for recycling [26].
ZSM-5 zeolites can be prepared by template-free methods [27], but
template is usually needed to synthesize silicalite-1. Synthesis of
silicalite-1 requires at least a source of silica and a template of tetra­
propyl ammonium (TPA) salts. For example, quaternary ammonium
salts, such as TPABr (tetrapropylammonium bromide) or TPAOH (tet­
rapropylammonium hydroxide), are commonly used to promote the
nucleation and crystallization of silicalite-1. Therefore, the organic
template as a structure directing agent is indispensable in the prepara­
tion of silicalite-1. Nevertheless, organic templates are very expensive
and toxic [28]. Reducing the amount of organic template used in the
synthesis of silicalite-1 can not only lower the production cost, but also
minimize environmental pollution. Because the size of the template
molecule is larger than the pore size of silicalite-1 [9], it is difficult to
recover the template embedded in zeolite. This part of the template can
be removed only by chemical or thermal decomposition (ex. calcination)
[9,29]. A notable feature for most synthesis processes is that the soluble
starting materials always partially remain in the mother liquor, which
means that the organic template is not completely consumed in the
synthesis process, but wasted in significant amounts in the mother liquor
discarding process. Therefore, the recovery and reuse of the remaining
template from the mother liquor are an effective method to reduce the
consumption of organic templates in the synthesis of silicalite-1.
Silica is the essential source for the synthesis of silicalite-1. Several
silicon sources such as tetraethylorthosilicate (TEOS) [21,30–32],
colloidal silica [33] and fumed silica [2] have been used in the literature
[18,34]. Obviously, for large-scale industrial production, silicic acid,
which was first proposed by Kalipcilar and Culfaz [35], is by far the most
cost-effective silicon source. Silica is soluble in alkali (NaOH) or hy­
drofluoric acid (HF), so many synthesis methods of zeolites generally
included the presence of NaOH or HF (or fluoride) [34–37]. In com­
parison, the synthesis of zeolites with HF (or fluoride) has various ad­
vantages, such as incorporation of heteroatoms (e.g. Si substitution by Al
and B), crystallization at low pH values, and formation of high crystal­
linity products [34,36]. On the other hand, notable disadvantages of the
fluorine-containing routes are high toxicity of fluorine and higher cost of
HF than NaOH. Major advantages of NaOH for the synthesis of zeolites
are that high alkalinity promotes nucleation and reduces particle size
[37], in addition to its cost and safety advantages over HF. One obvious
disadvantage of the NaOH routes is that high alkalinity often reduces the
yield [35]. In addition, wastewaters generated from the NaOH routes
have to be neutralized with acids to minimize adverse environmental
impacts. Therefore, improvement of the NaOH routes by recycling the
wastewaters (or the mother liquor hereafter) to increase the yields and
minimize environmental impacts has both economic and environmental
benefits.
To the best of our knowledge, there has been no report of recycling
the mother liquor used for the synthesis of silicalite-1, although various
methods of this type are available for the synthesis of other zeolites [25].
In this work, we report a new strategy for the preparation of pure
silicalite-1 using natural quartz and fumed silica as the silicon source,
and using TPABr as the organic template. In particular, the TPABr
2
Microporous and Mesoporous Materials 303 (2020) 110247
template left in the mother liquor after each synthesis run were recycled
and reused for subsequent syntheses. Also, the effect of the amount of
template on the crystallization of silicalite-1 has been studied in detail.
Interestingly, with the template agent being recovered from the mother
liquor, other unreacted reactants are recovered simultaneously. There­
fore, with the continuous recycling of the mother liquor, all reactants
will be ultimately utilized without any waste. Meng and Xiao pointed
out that the concept of “green chemistry” involves the designing and
development of chemistry and chemical processes to reduce or eliminate
negative environmental impacts, including reduction of waste and
improvement of efficiency [28]. Therefore, we emphasize that this
efficient utilization of TPABr as well as other materials can effectively
reduce the synthesis cost of silicalite-1 and minimize adverse environ­
mental impact by avoiding any discharge of waste water with toxic
organic agents.
2. Experimental section
2.1. Starting materials
As-received natural quartz (SiO2, �99 wt%) was supplied by Xiamen
Xinyisheng Advanced Technology Co. Ltd; sodium hydroxide (NaOH, �
96 wt%) and hydrochloric acid (HCl, 36–38 wt%) were purchased from
Xilong Chemical Co. Ltd; tetrapropylammonium bromide (TPABr,
(CH3CH2CH2)4N(Br), 98 wt%, formula weight (FW) 266.26, was pur­
chased from Aladdin Corporation; fumed silica (SiO2, 99.8 wt%) was
purchased from Evonik Degussa Corporation. All starting materials were
used without further purification, except that natural quartz composed
of millimeter or submillimeter-sized single crystals was refined by first
manual selection under a binocular optical microscope and then
washing with hydrochloric acid (HCl) to remove surface impurities.
2.2. Preparation of silica sol
Dozens of parallel experiments with the same starting materials in
the same proportion were carried out simultaneously. In each experi­
ment, a mixture of quartz (1.818 g, 0.03 mol) and 6 M NaOH (10.00 mL,
0.06 mol) aqueous solution with a molar ratio of SiO2: NaOH ¼ 1 : 2 was
first put into a 25 mL Teflon-lined stainless steel autoclave. All auto­
claves were then placed in an oven and heated at 463 K for 24 h. After
hydrothermal treatment [38,39], quartz was completely dissolved in the
NaOH solution to form a sodium silicate (Na2SiO3) solution at about
10.80 mL in volume in each autoclave. The sodium silicate solutions
from these autoclaves were then divided into two groups for different
purposes: one for forming a solid H2SiO3 gel and the other for preparing
dilute sodium silicate solutions.
The sodium silicate solutions from the first group of autoclaves were
dropwise added with 3 M hydrochloric acid (HCl) to form a gel (i.e.,
H2SiO3) until the pH value at 1.0. The resulting H2SiO3 gel was centri­
fuged and washed with distilled water three times, and subsequently
dried at 348 K for 36 h (Fig. 1).
The sodium silicate solution from each autoclave of the other group
was divided into five parts. One fifth of the divided sodium silicate so­
lution (about 2.16 mL, 0.006 mol) from each autoclave was diluted by
adding 25 mL water. Each diluted sodium silicate solution (~27.16 mL,
0.006 mol of Na2SiO3) was added with 1.170 g solid silicic acid gel
(0.015 mol) to make a slurry by stirring. After being stirred for 3 h, each
set of the slurry was transferred to a 100 mL Teflon-lined stainless steel
autoclave. Several 100 mL autoclaves with the same composition were
prepared, and heated to and kept at 338 K overnight, resulting in a
transparent silica sol (~28 mL) with a nominal molar ratio of SiO2:
Na2O ¼ 3.5 : 1.
Table 1 shows that the maximum SiO2/Na2O molar ratio of the clear
silica sol that can be prepared with the procedure described above is 3.5.
Increasing the solution alkalinity can dissolve more silica. However, the
yield of silicalite-1 decreases with increasing the solution alkalinity
J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247

Fig. 1. Schematic illustration of the synthesis route of silicalite-1 (left for the initial synthesis route; right for the recycling route; R.T. abbreviated for room
temperature).

centrifuged and separated into two parts: supernatant and solid pre­
Table 1
cipitate. The supernatant (mother liquor hereafter) was recovered for
Dissolution of silicic acid and Na2SiO3 in water (at 338 K).
reusing in subsequent synthesis experiments. The solid precipitate was
Na2SiO3 (mol) H2O (mol) H2SiO3 (mol) Product washed with distilled water three times, dried overnight at 348 K, and
1 0.006 (2.16 mL) 1.39 (25.00 mL) 0.009 (0.702 g) Clear solution then calcined at 823 K for 6 h to remove the template embedded in
2 0.006 (2.16 mL) 1.39 (25.00 mL) 0.012 (0.936 g) Clear solution products. The calcined products were weighted to calculate the yield of
3 0.006 (2.16 mL) 1.39 (25.00 mL) 0.015 (1.170 g) Clear solution silicalite-1 and the silica deficiency in the recycled mother liquor.
4 0.006 (2.16 mL) 1.39 (25.00 mL) 0.018 (1.404 g) Solid residual

[35]. Moreover, our experiments show that neutralization of excessive 2.4. Recycling mother liquor for synthesis of silicalite-1
alkali in the solution with sulfuric acid leads to the formation of impure
silicalite-1 with tridymite-O and quartz as the impurity phases. In order The experimental conditions with the lowest TPABr dosage for the
to increase the molar ratio of SiO2: Na2O to 5 required in the following preparation of pure silicalite-1 in the previous step were selected as the
crystallization step, highly active nano-sized fumed silica (0.541 g, optimal initial synthesis conditions (OISC) for the subsequent experi­
0.009 mol) was added as an additional silica source. Note that experi­ ments. Four samples under the same OISC as described above (i.e. Na2O
ments with the use of the silicic acid gel as the only silica source (i.e., 0.006 mol, SiO2 0.030 mol and H2O 1.50 mol, at 423 K for 24 h) and
without any fumed silica) yielded impure silicalite-1. Under the initial TPABr ¼ 0.04 � SiO2 (i.e., x ¼ 0.04) were prepared (Table 2). Then four
synthesis conditions, three different silica sources, sodium silicate groups of mother liquors were obtained after centrifugation. The yield
(Na2SiO3), solid silicic acid (H2SiO3) and fumed silica, were used. The based on SiO2 after calcination was about 64%. Correspondingly, the
first two were made from natural quartz (collectively as Q-silica). Our samples were named as G1-0.04-R0, G2-0.04-R0, G3-0.04-R0 and G4-0.04-
synthesis experiments show that the optimal ratio of Q-silica to fumed R0, respectively.
silica for the synthesis of high purity silicalite-1 is 7 : 3.
The slurry was stirred at room temperature for 3 h, and then trans­ Table 2
ferred to a Teflon-lined stainless steel autoclave. The autoclave was kept Summary of ingredients used for the hydrothermal synthesis of silicalite-1 at
at 338 K overnight. 423 K for a duration of 24 h.
Runs (Rn) Na2SiO3 H2SiO3 Fumed H2O NaOH TPABr
(mol) (g) SiO2 (mol)
2.3. Optimization of TPABr quantity (G0)
OISC R0 0.006 1.170 0.541 g 25 mL – 0.04
1st – m1i 0.541 g to 28 to 0.012 yi
The effect of the organic template - tetrapropylammonium bromide recycle mLa
(TPABr) content on the crystallization of silicalite-1 has been studied. In R1
each round of experiments, four samples (denoted as G0) with different 2nd – m2i 0.541 g to 28 to 0.012 yi
amounts of TPABr (0, 0.163, 0.326, 0.489 g) were prepared. Each recycle mL
R2
sample was composed of the TPABr mixed with above as-synthesized 28
3rd – m3i 0.541 g to 28 to 0.012 yi
mL silica sol and 0.541 g fumed silica (0.009 mol). The mixture com­ recycle mL
positions for crystallization were prepared according to the molar ratios R3
of SiO2: Na2O: H2O: TPABr ¼ 1 : 0.2: 50: x, where x varies from 0 to 0.06 a
The amounts of water and NaOH added in the recycling runs were to keep
with a 0.02 step (x ¼ 0, 0.02, 0.04, 0.06). After being stirred and aged at the total solution volume at 28 mL and NaOH at 0.012 mol before the template
room temperature for 13 h, homogeneous mixtures were transferred and fumed silica added. OISC abbreviated for optimal initial synthesis condi­
into 100 mL Teflon-lined stainless steel autoclaves and crystallized at tions. Rn denoted for recycle runs; mni for the addition amount of H2SiO3; yi for y
423 K for 24 h (Fig. 1). ¼ TPABr/SiO2 (molar ratio). The values of mni and yi in each run (n) and group (i)
After hydrothermal reaction, the as-synthesized products were are given in Table 3.

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J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247

The recycled mother liquors obtained from the above procedure
contain unreacted TPABr, SiO2, NaOH and H2O, and are reused for the
next three rounds of synthesis experiments. During each cycle, the
mother liquors of the previous round were used for the next round, and
the silica deficiency in the recycled mother liquors was compensated for
by adding appropriate amounts of solid silicic acid (H2SiO3) and fumed
silica (SiO2) to match OISC.
The additional amounts of TPABr required in the runs with the
recovered mother liquors have been investigated. In each recycle round,
four samples were prepared using supplements of TPABr in quantity
with molar ratios of SiO2: Na2O: H2O: TPABr ¼ 1 : 0.2: 50: y, where y ¼
0, 0.01, 0.015 and 0.02 (Table 3). The supplemental silica in the each
cycle consisted of the fumed silica and solid silicic acid besides the
unreacted SiO2 remaining in the recovered mother liquors. In each cycle,
the additional amount of fumed silica was 0.541 g (0.009 mol) but the
amount of the solid silicic acid gel (H2SiO3) was controlled by the yield
of the previous round (Tables 2 and 3). The mass weight (mni) of the solid
silicic acid gel (H2SiO3) was calculated from (M(n-1)i 0.541)/60 � 78,
where M(n-1)i was the weight of the calcined solid product from the
previous round (Table 3). Thus the total amount of the added fumed
silica, the solid silicic acid gel as well as the unreacted SiO2 from the
mother liquors summed up to 0.030 mol of SiO2, equal to that in the
OISC. Finally, water and 6 M NaOH were added to reach a total volume
of ~28 mL, containing 0.012 mol of NaOH before the template and
fumed silica added (Fig. 1, Tables 2 and 3).
All ingredients were added in the order shown in Fig. 1. Repeat the
steps of aging, crystallization, centrifugation and calcination as in the
previous procedure. Repeat the above steps of recycling the mother li­
quor and the subsequent operation twice.
The obtained samples are named as Gi-yi-Rn, where Gi means the
group names; yi represents the molar ratio of the added amount of TPABr
to the total amount of SiO2 in gel (yi ¼ 0 denotes no added TPABr), Rn
represents the recycled runs of the mother liquor (R0 indicates the initial
synthesis) (Table 3).
The 13C liquid NMR spectra were recorded on a Bruker Advance 500
spectrometer with a 5 mm QXI probe equipped with a Z gradient coil.
3. Results and discussion
3.1. Determination of optimal initial synthesis condition (OISC)
Fig. 2 shows the PXRD patterns of the products (G0) as a function of
the parameter of x – the amount of TPABr used to synthesize pure
silicalite-1 with the ingredient compositions of SiO2: Na2O: H2O: TPABr
¼ 1 : 0.2: 50: x (molar ratio) at a constant crystallization temperature of
423 K and a constant duration of 24 h. When x ¼ 0, no apparent peak but
broad background was observed, demonstrating an amorphous product.
This result confirms that silicalite-1 can not be synthesized without the
template of TPABr. When x ¼ 0.02, the PXRD pattern shows the distinct
peaks at 7.97� , 8.87� , 23.17� , 24.02� , and 24.46� (2θ), which fit well to
the five characteristic peaks of the MFI-type zeolite structure (PDF No.
44–0696) [31,32]. But some additional peaks such as those at 21.75�
that do not belong to MFI zeolite are also observed, and attributed to
tridymite-O (PDF No. 42–1401). This suggests that silicalite-1 can form
under this condition but contains significant impurities. For both x ¼
0.04 and 0.06, all the diffraction peaks in the PXRD patterns belong to
the MFI-type structure, indicative of pure silicalite-1. The slight differ­
ence in intensity of the observed diffraction peaks between different
samples (x ¼ 0.04 and 0.06) most likely arises from the crystal size and
crystallinity of the samples analyzed. Note that all samples reported
herein had been calcined in air at 823 K for 6 h before PXRD analyses.
Scanning electron microscopy (SEM) was used to further evaluate

2.5. Characterization

The powder X-ray diffraction (PXRD) patterns were collected on a

Bruker D8 Advance powder X-ray diffractometer with Cu Kα (λ ¼
1.54056 Å) radiation, operated at 40 kV and 40 mA. The crystal
morphology and the elemental composition were characterized using a
SU-70 field emission scanning electron microscope (Oxford Instruments)
equipped with an energy-dispersive X-ray (EDX) spectrometer, operated
at 20 kV. The Fourier transform infrared (FT-IR) spectra were generated
on a Thermo Scientific Nicolet iS10 FT-IR Spectrometer over the range of
400–4000 cm 1. Ar adsorption isotherms were measured using a
Micromeritics ASAP 2020 surface analyzer at 87 K. All samples were
degassed under vacuum at 623 K for 10 h before the adsorption mea­ Fig. 2. Comparison of PXRD patterns of the samples (G0) synthesized with
surement. Total surface area (SBET) was calculated by the BET method. adding different TPABr amounts (x ¼ 0, 0.02, 0.04 and 0.06). The Bragg po­
sitions of silicalite-1 (PDF No. 44–0696) are marked by the vertical bars below
Total pore volume (Vtol) was estimated from the amount adsorbed at P/
the observed patterns. Star (*) represented for impurities of tridymite-O (PDF
P0 ¼ 0.97. Micropore surface area (Smicro), external surface area (Sext)
No. 42–1401).
and micropore volume (Vmicro) were calculated using the t-plot method.

Table 3
The amounts of TPABr and H2SiO3 used in each group of the recycling runs and the weight of products.
G1 G2 G3 G4

y1 mn1 (g) Mn1 (g) y2 mn2 (g) Mn2 (g) y3 mn3 (g) Mn3 (g) y4 mn4 (g) Mn4 (g) Yield (%)

R0 0.04 1.170 1.172 0.04 1.170 1.166 0.04 1.170 1.161 0.04 1.170 1.156 64.22
R1 0 0.820 0.889 0.01 0.813 1.037 0.015 0.806 1.107 0.02 0.800 1.122 77.06
R2 0 0.452 0.983 0.01 0.645 1.015 0.015 0.736 1.043 0.02 0.755 1.101 82.86
R3 0 0.575 0.935 0.01 0.616 1.073 0.015 0.653 1.112 0.02 0.728 1.024 85.02

*Mni denoted for the weight of products, where subscripts of n and i represent runs in row and groups in column, respectively; mni for the additional amount of H2SiO3.
mni is calculated from (M(n-1)i 0.541)/60 (formula weight of SiO2) � 78 (formula weight of H2SiO3), where M(n-1)i is the weight of the calcined solid product in the
previous cycle (i.e. in (n-1)th run). Samples named as Gi-yi-Rn, where Gi: denoted for the group name; yi for y ¼ TPABr/SiO2 (molar ratio); Rn for recycle runs (n). Only
the yields of pure silicalite-1 in group 4 are listed and calculated based on the cumulative amounts of synthetic products/silica used.

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J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247

the synthesis products. No apparent crystalline materials but powder

aggregates were observed for the sample at x ¼ 0 (absence of TPABr
template) (Fig. 3a). In contrast, well-developed crystal morphologies
were observed for the samples at x ¼ 0.02–0.06 (Fig. 3b–d). Interest­
ingly, for both x ¼ 0.04 and 0.06, all the crystals, identified to be pure
silicalite-1, have a single morphology with obvious reentrant angles,
which indicate penetration twins formed from the mutual penetration of
cylindrical and square prismatic individuals. For the case of x ¼ 0.02,
multilevel laminated crystal forms in addition to penetration twins are
observed, further supporting that this sample contains impurities (of
tridymite-O, PDF No. 42–1401). It is obvious that the crystal sizes of
silicalite-1 decrease from x ¼ 0.02 and 0.04 to x ¼ 0.06 (Fig. 3). The
mechanism responsible for this variation in crystal size may be as fol­
lows: increasing TPABr leads to an increased number of silicalite-1
nuclei in the solution, resulting in reduced crystal sizes [33].
From the above analysis, the minimum amount of TPABr for the
crystallization of pure silicalite-1 at 423 K is x ¼ 0.04. Therefore, the
optimal initial synthesis conditions (OISC) are the molar ratio of SiO2:
Fig. 4. Comparison of PXRD patterns of the samples synthesized under the
Na2O: H2O: TPABr ¼ 1 : 0.2: 50: 0.04, the crystallization temperature at initial synthesis condition (G1-0.04-R0) and those from three recycle rounds
423 K, and the duration of 24 h. without adding any TPABr to the mother liquors. The Bragg positions of
silicalite-1 (PDF No. 44–0696) are marked by the vertical bars below the
observed patterns. Star (*) represented for quartz (PDF No. 46–1045).
3.2. The effect of TPABr amount (y) on recycled mother liquor
40,41] besides minor porous spheres. In contrast, the morphologies in
For the case of y ¼ 0 (without adding any TPABr to the recycled the 2nd and 3rd recycle rounds consist of dominantly porous spheres.
mother liquor), the PXRD patterns and SEM images of the products These results confirm that the TPABr does exist in the mother liquor
(denoted as G1) obtained from using the recycled mother liquor for three recycled from the initial synthesis process and can be used for the
rounds, are shown in Figs. 4 and 5, respectively. In the first recycle of the crystallization of silicalite-1, but its content is not sufficient to crystallize
mother liquor, most of the sample G1-0-R1 was still the phase of pure silicalite-1. The recycled mother liquors from the 1st and 2nd
silicalite-1 identified by PXRD. However, only several broad and weak rounds, on the other hand, do not have any TPABr for the crystallization
peaks ascribed to quartz (SiO2, PDF No. 46–1045) were found in the of silicalite-1. Note that the crystals of the sample G1-0-R1 from the 1st
second and third recycle rounds. Correspondingly, the crystal mor­ recycle round have a coffin shape, which has been suggested to arise
phologies in the 1st recycle round consist of mainly a characteristic from intergrowth twinning as observed in ZSM-5 zeolites [41,42].
coffin shape of ZSM-5, similar to those observed in previous reports [15,

Fig. 3. Comparison of SEM images for the same samples (G0): a, b, c, d for x ¼ 0, 0.02, 0.04 and 0.06, respectively.

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J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247

Fig. 5. Comparison of SEM images for the same samples (G1) as used in Fig. 4.

For the cases of y ¼ 0.01 and 0.015, in which TPABrs were added
with the molar ratio of y � SiO2 to the recycled mother liquor in different
groups (Tables 2 and 3), all the resulting samples (denoted as G2 and G3)
contain silicalite-1 (Figs. S1–4). Within the same group, the sample
purity decreases with the increasing rounds of the recycled mother li­
quors. This may be attributed to the fact that the amount of TPABr added
was not sufficient for the crystallization of pure silicalite-1, resulting in
decreased TPABr in each of the subsequent recycle rounds. In Figs. S2
and S4, the crystal sizes of G2-0.01-R2 and G3-0.015-R2 were abnormally
reduced relative to those of G2-0.01-R1 and G3-0.015-R1, respectively.
This is not consistent with the results mentioned above that the crystal
sizes decrease with the increasing amount of TPABr, but may be
explained by excessive addition of NaOH that leads to high alkalinities
promoting nucleation [37].
For the case of y ¼ 0.02 (Tables 2 and 3), both PXRD patterns and
SEM images suggest that all the products (denoted as G4) synthesized
from using the recycled mother liquors are pure silicalite-1 crystals.
Figs. 6 and 7 show that all the observed diffraction peaks belong to
silicalite-1 (PDF No. 44–0696) and all samples (i.e., G4-0.04-R0, G4-0.02- Fig. 6. Comparison of PXRD patterns of the samples (G4) synthesized under the
R1, G4-0.02-R2 and G4-0.02-R3) show well-developed penetration twins. optimal initial synthesis conditions (OISC) and using recycled mother liquor
The main difference among them is that the crystal sizes became larger three runs with the supplemented amount of TPABr ¼ 0.02 � SiO2
with increased recycling rounds (Fig. 7). It should be pointed out that (molar ratio).
under the initial synthesis conditions, pure silicalite-1 can not be syn­
thesized by using TPABr in a molar fraction of 0.02 � SiO2. Therefore, existence of pure silicalite-1 (Fig. 8). The vibration band at 446 cm 1 is
the TPABr addition of only 0.02 � SiO2 for the synthesis of pure assigned to the typical Si–O–Si bending [30,43,44]. The band at 800
silicalite-1 further confirms the presence of unreacted TPABr in the cm 1 is attributed to the Si–O–Si symmetric stretching (outer SiO4 tet­
recycled mother liquors. rahedron), while the band at 1106 cm 1 arises from the Si–O–Si asym­
The elemental compositions of the silicalite-1 products have been metric stretching (inter SiO4 tetrahedron) [30,43,45]. The peak at 1233
confirmed by EDX analysis (Fig. S5). The EDX spectrum shows almost cm 1 is assigned to Si–O–Si asymmetric stretching (outer SiO4 tetrahe­
pure SiO2, without any detectable Al but a minor peak of Na Kα (Fig. S5), dron) [30,43,44]. The peak at 550 cm 1 is attributable to the vibration
which may arise from adsorption of the unreacted Na2SiO3 on the sur­ of the double-five ring, which is a characteristic band of the MFI-type
faces of silicalite-1. The FT-IR spectra of three samples at y ¼ 0.02 and structure [45]. Moreover, the intensity of the characteristic peak at
one sample at OISC are also very similar and further confirm the 550 cm 1 is useful for evaluating the stability and crystallinity of the

6
J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247

Fig. 7. Comparison of SEM images for the same samples (G4) as used in Fig. 6.

Table 4
Parameters representing pore characters obtained from Ar adsorption.
Sample SBET (m2 Smicro (m2 Sext (m2 Vtot (cm3 Vmicro (cm3
g 1) g 1) g 1) g 1) g 1)

G4-0.04- 290 271 20 0.130 0.112

R0
G4-0.02- 299 274 26 0.139 0.113
R1
G4-0.02- 299 274 24 0.138 0.114
R2
G4-0.02- 282 266 16 0.128 0.111
R3

* SBET denoted for specific surface area (m2 g¡1); Smicro for micropore surface
area (m2 g¡1); Sext for external surface area (m2 g 1); Vtot for total pore volume
(cm3 g¡1); and Vmicro for micropore volume (cm3 g¡1).

data demonstrate that all prepared samples have similar crystallinity

Fig. 8. Comparison of FT-IR spectra for the same samples (G4) as used in Fig. 6.
obtained samples [45]. The intensities of the peak at 550 cm 1 in Fig. 8
are similar, suggesting that the obtained samples are similar in structure,
stability and crystallinity.
Fig. S6 shows the comparison of the Ar adsorption isotherms for the
three G4 samples at y ¼ 0.02 and one sample at OISC. An abrupt increase
in the isotherms at the low P/P0 pressure region between 0 and 0.01 is a
typical feature of microporous materials. These adsorption isotherms are
classified as type I of the International Union of Pure and Applied
Chemistry (IUPAC) [34]. Detailed surface areas and pore volumes data
of these samples are given in Table 4. It can be seen that the samples
synthesized from the recycled mother liquors (i.e., G4-0.02-R1,
G4-0.02-R2 and G4-0.02-R3) have similar specific surface area (SBET),
micropore surface area (Smicro), pore volume (Vtot), and micropore vol­
ume (Vmicro) with that synthesized under the OISC (G4-0.04-R0). These
and structure. Moreover, the external surface areas of all samples are
small (Table 4). This is mainly related to the choice of the experiments
that were carried out under the condition of a low template dosage. As
mentioned earlier, increasing the template amount will reduce the final
crystal size. Conversely, a low amount of template tends to produce
micron-sized rather than nano-sized silicalite-1 crystals, resulting in a
relatively small external surface area.
3.3. NMR measurement of the mother liquor
The pure silicalite-1 can be successfully synthesized by using the
recycled mother liquor with the addition of small amounts of TPABr. The
existence of unreacted TPABr in the recycled mother liquor has been
further evaluated by 13C liquid NMR analysis (Fig. 9). The three peaks at
chemical shifts of 10.86, 15.88, and 60.72 ppm in the 13C liquid NMR
spectrum are the characteristic chemical shifts of the TPAþ

7
J. Yang et al.
13
Fig. 9. C liquid NMR spectrum of the recycled mother liquor.
(tetrapropylammonium) cation, confirming that the recycled mother
liquor contains unreacted TPABr [46]. The fourth peak at the chemical
shift of 77.21 ppm is from deuterated chloroform (CDCl3, chloroform-d)
as the internal standard for the chemical shifts.
3.4. Discussion
Attempts to use the hydrothermally prepared silica gel from natural
quartz as the only silica source (i.e. without adding fumed silica) for
synthesizing pure silicalite-1 had been made but were not successful.
The samples (denoted as Ga) were synthesized under the same condi­
tions as the samples G4 except for using silica gel partially instead of
fumed silica. The PXRD patterns and SEM images of the samples (Ga)
using the recycled mother liquor and additional TPABr at y ¼ 0.02 are
shown in Fig. S7 and Fig. S8, respectively. It can be seen that the samples
synthesized by the second and third rounds of the recycled mother liquor
contain impurities such as tridymite-O and quartz. The reason why the
recycled mother liquor can not be used directly may be due to the
limited contents of silicic acid that can be dissolved in the alkaline so­
lution. The maximum ratio of SiO2 to Na2O in the silica sol is about 3.5
(Table 1). In order to meet the requirements of SiO2/Na2O ¼ 5 for the
synthesis of silicalite-1, various acids such as sulfuric acid and hydro­
chloric acid were used to neutralize excessive Na2O to reduce alkalinity.
With the continuous recycling of the mother liquor, NaOH should be
added continuously to dissolve silicic acid, and then sulfuric acid should
be added accordingly to neutralize the excessive Na2O, resulting in the
accumulation of Na2SO4. However, the accumulation of Na2SO4 will
accelerate the polymerization of sol, impeding crystallization, and
finally leads to the recycling process unable to continue [27].
To the best of our knowledge, there have been no reports of the
synthesis of pure silicalite-1 from recycled mother liquor, except for
other zeolites [25,27]. The main obstacle arises from the fact that silica
(SiO2) is not dissolved in water but is soluble in alkaline solutions.
Synthesis of silicalite-1 from recycled mother liquor leads to the increase
of Na2O in solutions. In order to reduce the concentration of Na2O,
sulfuric acid is added to balance the pH value, but it will lead to the
accumulation of Na2SO4, and then lead to the appearance of an impurity
phase. Interestingly, mixing solid silicic acid (H2SiO3) gel and fumed
silica (SiO2) with water under starring can form a highly active slurry,
which can be hydrothermally “dissolved” in a dilute NaOH aqueous
solution. This method can not only enhance the SiO2/Na2O ratio, but
also overcome the accumulation of Na2SO4 in solutions, making it
possible to use the recycled mother liquor for the synthesis of pure
silicalite-1. Our experimental results show that it is possible to synthe­
size pure silicalite-1 by adding small amounts of TPABr along with silicic
acid and fumed silica to compensate for the consumed silica source in
the recycled mother liquor. This process achieves the goals of more
8
Microporous and Mesoporous Materials 303 (2020) 110247
efficient usages of both TPABr and raw materials as well as minimization
of waste products, consequently making the silicalite-1 synthesis process
green and economic.
4. Conclusion
We have developed a new route for the synthesis of pure zeolite
silicalite-1 from recycled mother liquors. First, natural quartz was used
as the silica source and hydrothermally transformed into a silicic acid
(H2SiO3) gel. Using the solid silicic acid gel and fumed silica as the
common silicon source, pure silicalite-1 can be synthesized. In contrast,
the use of the solid silicic acid gel as the only silica source results in the
formation of impure silicalite-1. Specifically, adding both solid silicic
acid (H2SiO3) gel and fumed silica (SiO2) as the silica source in the so­
dium silicate solution can not only enhance the SiO2/Na2O ratio, but
also overcome the problem of accumulating Na2SO4 in the recycled
mother liquors. The effects of the amounts of TPABr on the synthesis of
silicalite-1 from the recycled mother liquor have been studied in detail.
Our results show that under the initial synthesis conditions, the mini­
mum TPABr/SiO2 molar ratio needed to synthesize pure silicalite-1 is
0.04 : 1. In comparison, only half the amount of the organic template
TPABr is needed in subsequent runs with the recovered mother liquors.
The approximately half the amount of the organic template imbedded in
silicalite-1, which cannot be recovered at the present time, is also sup­
ported by the calcination experiments. Through recycling, all reactants
such as the organic template, NaOH and water remaining in the mother
liquors were ultimately utilized without any waste. Therefore, this novel
route for the synthesis of pure silicalite-1 achieves the goals of efficient
usage of both TPABr and raw materials, forming a green and economic
process. Moreover, this route may be extended to the synthesis of
silicalite-1 nanocrystals as well as other zeolites at larger scales, for
which economic and environmental benefits would be more obvious.
Declaration of competing interest
All authors declare no conflict of interest.
CRediT authorship contribution statement
Jun Yang: Methodology, Investigation, Formal analysis, Writing -
original draft. Ya-Xi Huang: Data curation, Software, Validation,
Writing - original draft. Yuanming Pan: Validation, Visualization,
Writing - review & editing. Jin-Xiao Mi: Conceptualization, Resources,
Supervision, Validation, Writing - review & editing.
Acknowledgements
This work is supported by the National Key Research Program of
China (No. 2016YFB0901502), funds from Xiamen Construction Bureau
(No. XJK2019-1-12), Xiamen Science and Technology Bureau (No.
3502Z20193008), and Natural Science and Engineering Research
Council of Canada for financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2020.110247.
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