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Síntesis y Caracterización Verde de Zeolita Silicalita-1 A Partir de Materiales Reciclados. Licor Madre
Síntesis y Caracterización Verde de Zeolita Silicalita-1 A Partir de Materiales Reciclados. Licor Madre
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 free radicals under hydrothermal conditions [16]. Lupulescu and Rimer
proposed a two-stage synthesis mechanism of silicalite-1 with an early
Zeolites commonly refer to a class of aluminosilicate molecular growth governed by a classical model and followed by silica precursor
sieves with rich three-dimensional channels, and are widely used in covered on crystal surfaces for concomitant structural rearrangement
catalysis [1,2], adsorption [3,4], separation [5,6] and ion exchange [7, and three-dimensional growth in a nonclassical way [17]. Mintova et al.
8]. An aluminum-free zeolite, which has an extremely simple chemical studied the effects of different silicon sources on the size of silicalite-1
composition of silica (SiO2), high thermal and chemical stability and nanocrystals [18]. Zhang et al. introduced a facile strategy to prepare
unique shape selectivity, is known as silicalite [9]. Among the known high-quality single-crystalline MFI-type nanozeolites (10–55 nm) [19].
polymorphs of pure silica zeolites, the aluminum-free end members of Bonilla et al. employed structure-directing agents to control the three
the MFI-type zeolite ZSM-5 and the MEL-type zeolite ZSM-11 have been axial crystal growth rate and crystal morphologies of silicalite-1 [20].
named as silicalite-1 and silicalite-2, respectively [10]. Notable appli Dai et al. reported a simple strategy for the preparation of hollow
cations of silicalite-1 have been in the areas of sensors [11,12], nanocubes and three-dimensionally macroporous monoliths of
bio-medicine [13,14] and miscellaneous aspects [15]. silicalite-1 [21].
In the past decade, researches on silicalite-1 have focused largely on However, industrial applications of zeolites not only require excel
its crystallization mechanism as well as tunable crystal morphology and lent performances but also need economical and green production pro
particle size, which exert significant controls on the properties and cesses. At present, there are various ways to reduce the costs of zeolites
performances of zeolites. For example, Feng et al. demonstrated that the synthesis: (1) Developing new synthesis methods or conditions. Xiao’s
crystallization processes of zeolites could be accelerated by hydroxyl 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. Microporous and Mesoporous Materials 303 (2020) 110247
synthesizing zeolites Beta and ZSM-5 without using any organic tem template left in the mother liquor after each synthesis run were recycled
plates and solvents [22]. Ng and co-workers reported an effective and reused for subsequent syntheses. Also, the effect of the amount of
method for synthesizing large-pore EMT zeolite nanocrystals (6–15 nm) template on the crystallization of silicalite-1 has been studied in detail.
from template-free colloidal precursors at low temperature (30 � C) with Interestingly, with the template agent being recovered from the mother
high yield [23]. (2) Using cheap substitutes for organic templates. Chen liquor, other unreacted reactants are recovered simultaneously. There
et al. introduced an economical way for SSZ-13 zeolite preparation with fore, with the continuous recycling of the mother liquor, all reactants
the inexpensive choline chloride as template instead of more expensive will be ultimately utilized without any waste. Meng and Xiao pointed
and toxic ones [24]. (3) Synthesizing zeolites with recycled organic out that the concept of “green chemistry” involves the designing and
templates. Liu et al. reported a green and efficient preparation of hollow development of chemistry and chemical processes to reduce or eliminate
titanium silicalite-1 (TS-1) by using recycled mother liquor [25]. negative environmental impacts, including reduction of waste and
Moreover, completely different from the methods as described above, improvement of efficiency [28]. Therefore, we emphasize that this
Davis and colleagues developed a new synthetic strategy for micropo efficient utilization of TPABr as well as other materials can effectively
rous crystalline molecular sieves that organic structure-directing agents reduce the synthesis cost of silicalite-1 and minimize adverse environ
inside the zeolite can be disassembled in solution without high tem mental impact by avoiding any discharge of waste water with toxic
perature combustion treatment and reassembled for recycling [26]. organic agents.
ZSM-5 zeolites can be prepared by template-free methods [27], but
template is usually needed to synthesize silicalite-1. Synthesis of 2. Experimental section
silicalite-1 requires at least a source of silica and a template of tetra
propyl ammonium (TPA) salts. For example, quaternary ammonium 2.1. Starting materials
salts, such as TPABr (tetrapropylammonium bromide) or TPAOH (tet
rapropylammonium hydroxide), are commonly used to promote the As-received natural quartz (SiO2, �99 wt%) was supplied by Xiamen
nucleation and crystallization of silicalite-1. Therefore, the organic Xinyisheng Advanced Technology Co. Ltd; sodium hydroxide (NaOH, �
template as a structure directing agent is indispensable in the prepara 96 wt%) and hydrochloric acid (HCl, 36–38 wt%) were purchased from
tion of silicalite-1. Nevertheless, organic templates are very expensive Xilong Chemical Co. Ltd; tetrapropylammonium bromide (TPABr,
and toxic [28]. Reducing the amount of organic template used in the (CH3CH2CH2)4N(Br), 98 wt%, formula weight (FW) 266.26, was pur
synthesis of silicalite-1 can not only lower the production cost, but also chased from Aladdin Corporation; fumed silica (SiO2, 99.8 wt%) was
minimize environmental pollution. Because the size of the template purchased from Evonik Degussa Corporation. All starting materials were
molecule is larger than the pore size of silicalite-1 [9], it is difficult to used without further purification, except that natural quartz composed
recover the template embedded in zeolite. This part of the template can of millimeter or submillimeter-sized single crystals was refined by first
be removed only by chemical or thermal decomposition (ex. calcination) manual selection under a binocular optical microscope and then
[9,29]. A notable feature for most synthesis processes is that the soluble washing with hydrochloric acid (HCl) to remove surface impurities.
starting materials always partially remain in the mother liquor, which
means that the organic template is not completely consumed in the 2.2. Preparation of silica sol
synthesis process, but wasted in significant amounts in the mother liquor
discarding process. Therefore, the recovery and reuse of the remaining Dozens of parallel experiments with the same starting materials in
template from the mother liquor are an effective method to reduce the the same proportion were carried out simultaneously. In each experi
consumption of organic templates in the synthesis of silicalite-1. ment, a mixture of quartz (1.818 g, 0.03 mol) and 6 M NaOH (10.00 mL,
Silica is the essential source for the synthesis of silicalite-1. Several 0.06 mol) aqueous solution with a molar ratio of SiO2: NaOH ¼ 1 : 2 was
silicon sources such as tetraethylorthosilicate (TEOS) [21,30–32], first put into a 25 mL Teflon-lined stainless steel autoclave. All auto
colloidal silica [33] and fumed silica [2] have been used in the literature claves were then placed in an oven and heated at 463 K for 24 h. After
[18,34]. Obviously, for large-scale industrial production, silicic acid, hydrothermal treatment [38,39], quartz was completely dissolved in the
which was first proposed by Kalipcilar and Culfaz [35], is by far the most NaOH solution to form a sodium silicate (Na2SiO3) solution at about
cost-effective silicon source. Silica is soluble in alkali (NaOH) or hy 10.80 mL in volume in each autoclave. The sodium silicate solutions
drofluoric acid (HF), so many synthesis methods of zeolites generally from these autoclaves were then divided into two groups for different
included the presence of NaOH or HF (or fluoride) [34–37]. In com purposes: one for forming a solid H2SiO3 gel and the other for preparing
parison, the synthesis of zeolites with HF (or fluoride) has various ad dilute sodium silicate solutions.
vantages, such as incorporation of heteroatoms (e.g. Si substitution by Al The sodium silicate solutions from the first group of autoclaves were
and B), crystallization at low pH values, and formation of high crystal dropwise added with 3 M hydrochloric acid (HCl) to form a gel (i.e.,
linity products [34,36]. On the other hand, notable disadvantages of the H2SiO3) until the pH value at 1.0. The resulting H2SiO3 gel was centri
fluorine-containing routes are high toxicity of fluorine and higher cost of fuged and washed with distilled water three times, and subsequently
HF than NaOH. Major advantages of NaOH for the synthesis of zeolites dried at 348 K for 36 h (Fig. 1).
are that high alkalinity promotes nucleation and reduces particle size The sodium silicate solution from each autoclave of the other group
[37], in addition to its cost and safety advantages over HF. One obvious was divided into five parts. One fifth of the divided sodium silicate so
disadvantage of the NaOH routes is that high alkalinity often reduces the lution (about 2.16 mL, 0.006 mol) from each autoclave was diluted by
yield [35]. In addition, wastewaters generated from the NaOH routes adding 25 mL water. Each diluted sodium silicate solution (~27.16 mL,
have to be neutralized with acids to minimize adverse environmental 0.006 mol of Na2SiO3) was added with 1.170 g solid silicic acid gel
impacts. Therefore, improvement of the NaOH routes by recycling the (0.015 mol) to make a slurry by stirring. After being stirred for 3 h, each
wastewaters (or the mother liquor hereafter) to increase the yields and set of the slurry was transferred to a 100 mL Teflon-lined stainless steel
minimize environmental impacts has both economic and environmental autoclave. Several 100 mL autoclaves with the same composition were
benefits. prepared, and heated to and kept at 338 K overnight, resulting in a
To the best of our knowledge, there has been no report of recycling transparent silica sol (~28 mL) with a nominal molar ratio of SiO2:
the mother liquor used for the synthesis of silicalite-1, although various Na2O ¼ 3.5 : 1.
methods of this type are available for the synthesis of other zeolites [25]. Table 1 shows that the maximum SiO2/Na2O molar ratio of the clear
In this work, we report a new strategy for the preparation of pure silica sol that can be prepared with the procedure described above is 3.5.
silicalite-1 using natural quartz and fumed silica as the silicon source, Increasing the solution alkalinity can dissolve more silica. However, the
and using TPABr as the organic template. In particular, the TPABr yield of silicalite-1 decreases with increasing the solution alkalinity
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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 The 13C liquid NMR spectra were recorded on a Bruker Advance 500
contain unreacted TPABr, SiO2, NaOH and H2O, and are reused for the spectrometer with a 5 mm QXI probe equipped with a Z gradient coil.
next three rounds of synthesis experiments. During each cycle, the
mother liquors of the previous round were used for the next round, and 3. Results and discussion
the silica deficiency in the recycled mother liquors was compensated for
by adding appropriate amounts of solid silicic acid (H2SiO3) and fumed 3.1. Determination of optimal initial synthesis condition (OISC)
silica (SiO2) to match OISC.
The additional amounts of TPABr required in the runs with the Fig. 2 shows the PXRD patterns of the products (G0) as a function of
recovered mother liquors have been investigated. In each recycle round, the parameter of x – the amount of TPABr used to synthesize pure
four samples were prepared using supplements of TPABr in quantity silicalite-1 with the ingredient compositions of SiO2: Na2O: H2O: TPABr
with molar ratios of SiO2: Na2O: H2O: TPABr ¼ 1 : 0.2: 50: y, where y ¼ ¼ 1 : 0.2: 50: x (molar ratio) at a constant crystallization temperature of
0, 0.01, 0.015 and 0.02 (Table 3). The supplemental silica in the each 423 K and a constant duration of 24 h. When x ¼ 0, no apparent peak but
cycle consisted of the fumed silica and solid silicic acid besides the broad background was observed, demonstrating an amorphous product.
unreacted SiO2 remaining in the recovered mother liquors. In each cycle, This result confirms that silicalite-1 can not be synthesized without the
the additional amount of fumed silica was 0.541 g (0.009 mol) but the template of TPABr. When x ¼ 0.02, the PXRD pattern shows the distinct
amount of the solid silicic acid gel (H2SiO3) was controlled by the yield peaks at 7.97� , 8.87� , 23.17� , 24.02� , and 24.46� (2θ), which fit well to
of the previous round (Tables 2 and 3). The mass weight (mni) of the solid the five characteristic peaks of the MFI-type zeolite structure (PDF No.
silicic acid gel (H2SiO3) was calculated from (M(n-1)i 0.541)/60 � 78, 44–0696) [31,32]. But some additional peaks such as those at 21.75�
where M(n-1)i was the weight of the calcined solid product from the that do not belong to MFI zeolite are also observed, and attributed to
previous round (Table 3). Thus the total amount of the added fumed tridymite-O (PDF No. 42–1401). This suggests that silicalite-1 can form
silica, the solid silicic acid gel as well as the unreacted SiO2 from the under this condition but contains significant impurities. For both x ¼
mother liquors summed up to 0.030 mol of SiO2, equal to that in the 0.04 and 0.06, all the diffraction peaks in the PXRD patterns belong to
OISC. Finally, water and 6 M NaOH were added to reach a total volume the MFI-type structure, indicative of pure silicalite-1. The slight differ
of ~28 mL, containing 0.012 mol of NaOH before the template and ence in intensity of the observed diffraction peaks between different
fumed silica added (Fig. 1, Tables 2 and 3). samples (x ¼ 0.04 and 0.06) most likely arises from the crystal size and
All ingredients were added in the order shown in Fig. 1. Repeat the crystallinity of the samples analyzed. Note that all samples reported
steps of aging, crystallization, centrifugation and calcination as in the herein had been calcined in air at 823 K for 6 h before PXRD analyses.
previous procedure. Repeat the above steps of recycling the mother li Scanning electron microscopy (SEM) was used to further evaluate
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).
2.5. Characterization
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
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
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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)
* 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).
7
J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247
4. Conclusion
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J. Yang et al. Microporous and Mesoporous Materials 303 (2020) 110247
[4] P. Gomez-Alvarez, E.G. Noya, E. Lomba, S. Valencia, J. Pires, Langmuir 34 (2018) [25] M. Liu, H.J. Wei, B.J. Li, L.Y. Song, S.Z. Zhao, C.C. Niu, C.F. Jia, X.Y. Wang, Y.
12739–12750, https://doi.org/10.1021/acs.langmuir.8b02326. Q. Wen, Chem. Eng. J. 331 (2018) 194–202, https://doi.org/10.1016/j.
[5] Q. Wen, J.C. Di, L. Jiang, J.H. Yu, R.R. Xu, Chem. Sci. 4 (2013) 591–595, https:// cej.2017.08.082.
doi.org/10.1039/c2sc21772d. [26] H. Lee, S.I. Zones, M.E. Davis, Nature 425 (2003) 385–388, https://doi.org/
[6] S.R. Venna, M.A. Carreon, J. Am. Chem. Soc. 132 (2010) 76–78, https://doi.org/ 10.1038/nature01980.
10.1021/ja909263x. [27] N.Y. Kang, B.S. Song, C.W. Lee, W.C. Choi, K.B. Yoon, Y.K. Park, Microporous
[7] M. Iwamoto, H. Yahiro, N. Mizuno, W.X. Zhang, Y. Mine, H. Furukawa, S. Kagawa, Mesoporous Mater. 118 (2009) 361–372, https://doi.org/10.1016/j.
J. Phys. Chem. 96 (1992) 9360–9366, https://doi.org/10.1021/j100202a055. micromeso.2008.09.016.
[8] M. Iwamoto, H. Yahiro, K. Tanda, N. Mizuno, Y. Mine, S. Kagawa, J. Phys. Chem. [28] X.J. Meng, F.S. Xiao, Chem. Rev. 114 (2014) 1521–1543, https://doi.org/10.1021/
95 (1991) 3727–3730, https://doi.org/10.1021/j100162a053. cr4001513.
[9] E.M. Flanigen, J.M. Bennett, R.W. Grose, J.P. Cohen, R.L. Patton, R.M. Kirchner, J. [29] L. Lang, S.H. Zhao, J.F. Jiang, W.S. Yang, X.L. Yin, Microporous Mesoporous Mater.
V. Smith, Nature 271 (1978) 512–516, https://doi.org/10.1038/271512a0. 235 (2016) 143–150, https://doi.org/10.1016/j.micromeso.2016.07.044.
[10] D.M. Bibby, N.B. Milestone, L.P. Aldridge, Nature 280 (1979) 664–665, https:// [30] J. Qi, T.B. Zhao, X. Xu, F.Y. Li, G.D. Sun, J. Porous Mater. 18 (2011) 509–515,
doi.org/10.1038/280664a0. https://doi.org/10.1007/s10934-010-9404-2.
[11] S.N. Talapaneni, J. Grand, S. Thomas, H.A. Ahmad, S. Mintova, Mater. Des. 99 [31] S. Barot, M. Nawab, R. Bandyopadhyay, J. Porous Mater. 23 (2016) 1197–1205,
(2016) 574–580, https://doi.org/10.1016/j.matdes.2016.03.035. https://doi.org/10.1007/s10934-016-0178-z.
[12] D. Jadsadapattarakul, C. Thanachayanont, J. Nukeaw, T. Sooknoi, Sensor. [32] Y.Q. Deng, S.F. Yin, C.T. Au, Ind. Eng. Chem. Res. 51 (2012) 9492–9499, https://
Actuator. B Chem. 144 (2010) 73–80, https://doi.org/10.1016/j.snb.2009.10.035. doi.org/10.1021/ie3001277.
[13] T. Kihara, Y.H. Zhang, Y.Y. Hu, Q.F. Iviao, Y. Tang, J. Miyake, J. Biosci. Bioeng. [33] B. Soydas, P.Z. Culfaz, H. Kalipcilar, A. Culfaz, Cryst. Res. Technol. 44 (2009)
111 (2011) 725–730, https://doi.org/10.1016/j.jbiosc.2011.01.017. 800–806, https://doi.org/10.1002/crat.200900113.
[14] K. Bhattacharya, P.C. Naha, I. Naydenova, S. Mintova, H.J. Byrne, Toxicol. Lett. [34] K. Jiao, X.Y. Xu, Z. Lv, J.Q. Song, M.Y. He, H. Gies, Microporous Mesoporous
215 (2012) 151–160, https://doi.org/10.1016/j.toxlet.2012.10.007. Mater. 225 (2016) 98–104, https://doi.org/10.1016/j.micromeso.2015.11.043.
[15] P. Nian, M.H. Su, T. Yu, Z. Wang, B.X. Zhang, X.L. Shao, X.Y. Jin, N.Z. Jiang, S. Li, [35] H. Kalipcilar, A. Culfaz, Cryst. Res. Technol. 35 (2000) 933–942, https://doi.org/
Q. Ma, J. Mater. Sci. 51 (2016) 3257–3270, https://doi.org/10.1007/s10853-015- 10.1002/1521-4079(200008)35:8.
9638-0. [36] J.L. Guth, H. Kessler, J.M. Higel, J.M. Lamblin, J. Patarin, A. Seive, J.M. Chezeau,
[16] G.D. Feng, P. Cheng, W.F. Yan, M. Boronat, X. Li, J.H. Su, J.Y. Wang, Y. Li, R. Wey, ACS Symp. Ser. 398 (1989) 176–195, https://doi.org/10.1021/bk-1989-
A. Corma, R.R. Xu, J.H. Yu, Science 351 (2016) 1188–1191, https://doi.org/ 0398.ch013.
10.1126/science.aaf1559. [37] A.E. Persson, B.J. Schoeman, J. Sterte, J.E. Ottesstedt, Zeolites 14 (1994) 557–567,
[17] A.I. Lupulescu, J.D. Rimer, Science 344 (2014) 729–732, https://doi.org/10.1126/ https://doi.org/10.1016/0144-2449(94)90191-0.
science.1250984. [38] J.Q. Wang, Y.X. Huang, Y.M. Pan, J.X. Mi, Microporous Mesoporous Mater. 199
[18] S. Mintova, V. Valtchev, Microporous Mesoporous Mater. 55 (2002) 171–179, (2014) 50–56, https://doi.org/10.1016/j.micromeso.2014.08.002.
https://doi.org/10.1016/s1387-1811(02)00401-8. [39] J.Q. Wang, Y.X. Huang, Y.M. Pan, J.X. Mi, Microporous Mesoporous Mater. 232
[19] Q. Zhang, G.R. Chen, Y.Y. Wang, M.Y. Chen, G.Q. Guo, J. Shi, J. Luo, J.H. Yu, (2016) 77–85, https://doi.org/10.1016/j.micromeso.2016.06.010.
Chem. Mater. 30 (2018) 2750–2758, https://doi.org/10.1021/acs. [40] X.X. Chen, W.F. Yan, X.J. Cao, J.H. Yu, R.R. Xu, Microporous Mesoporous Mater.
chemmater.8b00527. 119 (2009) 217–222, https://doi.org/10.1016/j.micromeso.2008.10.015.
[20] G. Bonilla, I. Diaz, M. Tsapatsis, H.K. Jeong, Y. Lee, D.G. Vlachos, Chem. Mater. 16 [41] L. Karwacki, M.H.F. Kox, D.A.M. de Winter, M.R. Drury, J.D. Meeldijk, E. Stavitski,
(2004) 5697–5705, https://doi.org/10.1021/cm048854w. W. Schmidt, M. Mertens, P. Cubillas, N. John, A. Chan, N. Kahn, S.R. Bare,
[21] C.Y. Dai, A.F. Zhang, L.L. Li, K.K. Hou, F.S. Ding, J. Li, D.Y. Mu, C.S. Song, M. Liu, M. Anderson, J. Kornatowski, B.M. Weckhuysen, Nat. Mater. 8 (2009) 959–965,
X.W. Guo, Chem. Mater. 25 (2013) 4197–4205, https://doi.org/10.1021/ https://doi.org/10.1038/nmat2530.
cm401739e. [42] C. Weidenthaler, R.X. Fischer, R.D. Shannon, O. Medenbach, J. Phys. Chem. 98
[22] Q.M. Wu, X. Wang, G.D. Qi, Q. Guo, S.X. Pan, X.J. Meng, J. Xu, F. Deng, F.T. Fan, Z. (1994) 12687–12694, https://doi.org/10.1021/j100099a036.
C. Feng, C. Li, S. Maurer, U. Muller, F.S. Xiao, J. Am. Chem. Soc. 136 (2014) [43] X.B. Yang, J. Chen, H.X. Lai, J.P. Hu, M. Fang, X.T. Luo, RSC Adv. 7 (2017)
4019–4025, https://doi.org/10.1021/ja500098j. 38519–38525, https://doi.org/10.1039/c7ra05863b.
[23] E.P. Ng, D. Chateigner, T. Bein, V. Valtchev, S. Mintova, Science 335 (2012) 70–73, [44] M. Nawab, S. Barot, R. Bandyopadhyay, J. Chem. Sci. 131 (2019) 2, https://doi.
https://doi.org/10.1126/science.1214798. org/10.1007/s12039-018-1579-0.
[24] B.H. Chen, R.N. Xu, R.D. Zhang, N. Liu, Environ. Sci. Technol. 48 (2014) [45] Y.F. Yeong, A.Z. Abdullah, A.L. Ahmad, S. Bhatia, Microporous Mesoporous Mater.
13909–13916, https://doi.org/10.1021/es503707c. 123 (2009) 129–139, https://doi.org/10.1016/j.micromeso.2009.03.038.
[46] A. Tuel, Zeolites 16 (1996) 108–117, https://doi.org/10.1016/0144-2449(95)
00109-3.