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Continuous flow synthesis of ZSM-5 zeolite on the

order of seconds
Zhendong Liua, Kotatsu Okabea, Chokkalingam Ananda, Yasuo Yonezawaa, Jie Zhua, Hiroki Yamadaa, Akira Endob,
Yutaka Yanabac, Takeshi Yoshikawac, Koji Oharad, Tatsuya Okuboa, and Toru Wakiharaa,1
a
Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan; bNational Institute of Advanced
Industrial Science and Technology, Ibaraki 305-8565, Japan; cInstitute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo,
153-8505, Japan; and dJapan Synchrotron Radiation Research Institute/SPring-8, Kouto 1-1-1, Sayo-gun, Hyogo 679-5198, Japan

Edited by Mark E. Davis, California Institute of Technology, Pasadena, CA, and approved November 8, 2016 (received for review September 23, 2016)

The hydrothermal synthesis of zeolites carried out in batch reactors established (1113). The ultrafast route on the order of minutes
takes a time so long (typically, on the order of days) that the not only enabled the continuous flow synthesis but also demon-
crystallization of zeolites has long been believed to be very slow strated that the crystallization of zeolites can proceed much faster
in nature. We herein present a synthetic process for ZSM-5, an than generally observed.
industrially important zeolite, on the order of seconds in a contin- Owing to specific physical and chemical properties, supercritical
uous flow reactor using pressurized hot water as a heating medium. water or pressurized water with extremely high temperatures
Direct mixing of a well-tuned precursor (90 C) with the pressurized (usually near or above 300 C) offers several potential advantages
water preheated to extremely high temperature (370 C) in the mil- for hydrothermal processing (14). Continuous flow hydrothermal
limeter-sized continuous flow reactor resulted in immediate heating synthesis of functional nanostructured materials in those mediums
to high temperatures (240300 C); consequently, the crystallization has been extensively exploited in recent years, and the associated
of ZSM-5 in a seed-free system proceeded to completion within tens merits, such as rapid formation of crystalline materials and facile

ENGINEERING
of or even several seconds. These results indicate that the crystalli- tuning of the properties, have been demonstrated (15, 16). The
zation of zeolites can complete in a period on the order of seconds. hydrothermal synthesis of zeolites using supercritical water or
The subtle design combining a continuous flow reactor with pres- pressurized water with extremely high temperatures, however,
surized hot water can greatly facilitate the mass production of zeo- has rarely been reported. The challenge arises from the intrinsic
lites in the future.
complexity of zeolite formation. Zeolites are formed as a metastable
phase compared with their dense-phase counterparts, which implies
crystal growth | continuous flow synthesis | zeolites | ultrafast synthesis | that overly high temperatures may only lead to the formation of
ZSM-5
nonporous materials (17, 18). Meanwhile, the complicated assembly
of inorganicorganic species leading to the formation of zeolites
Z eolites have typically been synthesized via hydrothermal
treatment, a process designed to artificially mimic the geo-
logical formation conditions of natural zeolites (1, 2). Depending
may not be favored under the less hydrophilic conditions of water
with too high temperatures (19). Finally, the organic structure-
directing agent (OSDA) tends to decompose at high temperatures,
on the targeted framework and composition, several hours to days which imposes further restrictions (20). To realize a synthesis in
(or even several weeks) are required to complete the synthesis of a such environments, it is of paramount importance that the crystal-
crystalline product (3). As a great improvement over the hundreds lization of the target phase should be completed before the for-
or thousands of years required for the formation of natural zeolites, mation of a dense phase as well as the complete decomposition
artificial synthesis on the order of days allows us more opportu- of OSDA.
nities to obtain zeolites with tunable properties (4, 5). Nevertheless,
the hydrothermal synthesis of zeolites has remained a time-con-
Significance
suming process. Long periods of hydrothermal treatment, for one
thing, cause a burden on both energy efficiency and operational
costs. Furthermore, pressure-tight vessels used for the hydrother- Zeolites have greatly contributed to modern industries. Con-
sumption of zeolites is expected to increase with the emergence
mal treatment as well as harsh conditions therein make mechanistic
of newly commercialized applications. Typical synthesis of zeo-
studies using in situ techniques difficult to perform (6, 7). The
lites relies on batchwise hydrothermal synthesis, which usually
complexity of crystallization, in turn, hinders the attempts at short-
takes tens of hours or even several days to complete. People have
ening the synthesis period. This dilemma explains to some extent the
thus long believed that the crystallization of zeolites is very slow
reason behind the long-held belief that crystallization of zeolites is
in nature. We herein demonstrate the continuous flow synthesis
extremely slow in nature.
of ZSM-5, an industrially important zeolite, on the order of sec-
The other major hurdle for the widespread application of zeolites
onds. Crystallization from amorphous state to full crystallinity
is the difficulty in mass production. Batchwise synthesis using au-
could be completed in tens of or even several seconds. The syn-
toclaves is convenient for basic laboratory investigations but poses thesis on the order of seconds provides a great potential to fa-
several challengesin terms of economic efficiency, quality control, cilitate the mass production as well as to deepen the fundamental
and operation flexibilitywhen large-scale manufacturing is con- understanding of zeolite crystallization.
sidered (8). In contrast, continuous flow process has proved to be
beneficial in the production of various chemicals (9, 10). Due to the Author contributions: T.W. designed research; Z.L., K. Okabe, C.A., Y. Yonezawa, and J.Z.
time-consuming hydrothermal treatment used for the synthesis of performed research; A.E., Y. Yanaba, T.Y., and K. Ohara contributed new reagents/analytic
zeolites, however, making a direct switch from batchwise synthesis tools; Z.L., H.Y., T.O., and T.W. analyzed data; and Z.L., T.O., and T.W. wrote the paper.

to continuous flow manufacturing is not easy. To realize continuous The authors declare no conflict of interest.
flow production, shortening the synthesis period is therefore an This article is a PNAS Direct Submission.
issue of the highest priority. Recently, we have developed an Freely available online through the PNAS open access option.
ultrafast route to synthesize industrially important zeolitic materials 1
To whom correspondence should be addressed. Email: wakihara@chemsys.t.u-tokyo.ac.jp.
on the order of minutes (e.g., 10 min for aluminosilicate SSZ-13), This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.
based on which the continuous flow synthesis was successfully 1073/pnas.1615872113/-/DCSupplemental.

www.pnas.org/cgi/doi/10.1073/pnas.1615872113 PNAS Early Edition | 1 of 5


detailed explanation of the HEXTS results, see Fig. S3). The Si/Al
ratio of the product, analyzed by inductively coupled plasma
atomic emission spectrometer (ICP-AES), was 105, which is sim-
ilar to that of the reference ZSM-5 (with a Si/Al ratio of 108). The
micropore volumes for both products were also comparable (0.128
and 0.124 cm3/g for the product synthesized in 6 s and the refer-
ence ZSM-5, respectively; Fig. 3B).
A stable hydrodynamic condition was maintained in the con-
tinuous flow synthesis, as indicated by the temperature and pres-
sure profiles (Fig. S1). Hydrodynamic failure is one of the main
Fig. 1. Flowchart for the continuous flow synthesis of ZSM-5 on the order
obstacles for the continuous flow synthesis involving solid reactants
of seconds.
and/or products. Continuous production having a high solid con-
tent is susceptible to hydrodynamic failure caused by constriction,
We present herein a continuous flow method for the synthesis bridging, and random detachment of solid particles (23). In our
of ZSM-5 using pressurized hot water with extremely high tem- case, the solid content in the synthesis mixture was significantly
perature (370 C) as the heating medium. ZSM-5 is an alumi- high even in the presence of pressurized hot water. Despite a high
nosilicate zeolite with intensive industrial applications (21, 22), solid content, the compressed-air-driven vibrator, as sketched in
yet typically its synthesis consumes tens of hours. In this work, we Fig. 1, proved to be a powerful technique, which can be easily
demonstrate that the direct mixing of synthesis precursor and the incorporated, to minimize precipitation or blockage problems.
pressurized hot water in a millimeter-sized continuous flow reactor The ultrashort synthesis period required for complete crystalli-
could result in immediate heating up to high temperatures (Fig. 1; zation also helped prevent hydrodynamic failure. The yields for
for details of the continuous flow reactor see Fig. S1); conse- the continuous flow synthesis are shown in Fig. S4, which dem-
quently, the crystallization of ZSM-5, from amorphous state to full onstrates that high yields comparable to those in batch syntheses
crystallinity, proceeded to completion at a remarkably fast rate in a could be achieved.
system without the addition of any seed. The well-tuned synthesis Instantaneous temperature increase generated by the direct
precursor, obtained by aging the initial aluminosilicate gel at 90 C mixing of the synthesis precursor with the pressurized water at
for a certain period, triggered the nucleation and ensured the extremely high temperature is one of the key factors responsible
formation of ZSM-5 without any byproduct at extremely high for shortening the synthesis time within the order of seconds. In
temperatures. Consequently, the crystallization rate surpassed the our previous studies, we introduced a tubular reactor that helps
decomposition rate of OSDA because of the creation of a favor- achieve fast heating in a preheated oil bath so as to minimize the
able environment for ultrafast crystallization. This design enabled thermal lag that usually exists in a conventional autoclave, and
the synthesis of ZSM-5 within tens of or even several seconds, consequently achieved complete synthesis on the order of minutes
depending on the aging conditions. Due to the complex nature (1113). Further shortening the synthesis period in the tubular
of zeolite crystallization, it is not possible to realize a synthesis reactor is hindered because it still takes almost 1 min for heat
on the order of seconds using conventional methods carried out transfer from the external heating medium to the synthesis pre-
in conventional autoclaves. The continuous flow reactor to- cursor inside the tubular reactor. Direct mixing with the heating
gether with pressurized hot water as a heating medium com- medium would be an ideal approach to prompt the heat transfer,
prises a feasible technique to explore the time limit of zeolite and hence reduce the synthesis period further. In this study, direct
crystallization. Further novel findings, such as the discovery of mixing of the synthesis precursor with water at extremely high
new structures and in situ tuning of the properties of zeolites, temperature (370 C) remarkably facilitated a faster heating; as a
will be expected using this synthetic platform. Moreover, with a result, the crystallization of ZSM-5 could proceed immediately
remarkably short synthesis period, the continuous flow syn- after the synthesis precursor was fed. With this strategy, the
thesis would be particularly advantageous for the mass pro- thermal lag could almost be eliminated, which is very important to
duction of industrially important zeolites. realize an ultrafast synthesis, because the crystallization can be
The initial synthesis mixture had a composition of 50 NaOH: induced and completed before the complete decomposition of
Al2O3:300 SiO2:20 TPAOH:2,300 H2O (where TPAOH is tetra- OSDA under strongly basic, high-temperature conditions. The
propylammonium hydroxide). Using this composition, conven- synthesis of ZSM-5 using the tubular reactor, heated in an
tional synthesis of ZSM-5 was carried out in a Teflon-lined
autoclave at 170 C for 24 h. The synthesized product was con-
firmed to be completely crystalline ZSM-5 and was chosen as a
reference sample hereafter. Fig. 2A shows the X-ray diffraction
(XRD) patterns of the products obtained from the continuous flow
reactor after different residence times at 260 C. Before the high-
temperature synthesis, the synthesis mixture was aged at 90 C for
16 h. After aging, the collected solid phase was still amorphous.
When this aged gel was subjected to high-temperature synthesis,
apparent peaks due to the MFI (a three letter structure code
assigned by the International Zeolite Association Structure Com-
mission) structure could be observed after a synthesis time of only
1 s, demonstrating that considerable crystal growth had occurred.
After a synthesis time of 6 s, fully crystalline ZSM-5 was obtained.
Fig. 2B shows the SEM image of the ZSM-5 synthesized after 6 s,
which had a smaller particle size compared with the reference Fig. 2. Continuous flow synthesis of ZSM-5 on the order of seconds. (A) XRD
ZSM-5 (Fig. 2C). The atomic-level local structure of the ZSM-5 patterns for the products synthesized over different periods at 260 C (the
products was analyzed using high-energy X-ray total scattering reference ZSM-5 was synthesized in a conventional autoclave at 170 C for
(HEXTS) and 29Si solid-state magic-angle spinning NMR (29Si 24 h). (B and C) SEM images for the ZSM-5 product synthesized in 6 s at
MAS NMR), as shown in Fig. 3A and Fig. S2, respectively (for 260 C and the reference ZSM-5, respectively.

2 of 5 | www.pnas.org/cgi/doi/10.1073/pnas.1615872113 Liu et al.


tetrapropylammonium-containing silicates (21). Meanwhile, it is
worth noting that the particle size of the solid intermediates be-
came larger with the aging period, which is consistent with pre-
vious reports (25, 26). These results indicate that the short-range
order might have started to form during the aging stage, which
creates an environment favorable for the immediate crystal growth
under high temperatures, resulting in the synthesis on the order
of seconds.
We further studied the effect of the synthesis temperature on
the crystallization rate of ZSM-5. Fig. 5 AD shows the 27Al MAS
NMR spectra of the products synthesized at 240, 260, 280, and
300 C, respectively. The 27Al MAS NMR spectrum can serve as
an accurate indicator of crystallinity because aluminum hydroxide
with a gibbsite structure, whose peak appears at around 0 ppm,
totally dissolves and is consumed only on complete crystallization
(14). Clearly, the fastest crystallization rate was observed at a
synthesis temperature of 260 C. The crystallization rate became
slower when the synthesis was performed at 240 C. Interestingly,
Fig. 3. Confirmation of the properties of the ZSM-5 product synthesized in synthesis temperatures higher than 260 C did not further prompt
6 s. (A) Comparison of pair distribution function, G(r), of the product syn-
thesized in 6 s and the reference ZSM-5 (for detailed explanation, see Fig.
the crystallization, and on the contrary, slower crystallization rates
S3). (B), Comparison of N2 adsorptiondesorption isotherms and micropore were observed. A higher temperature indeed prompted the rate of
volumes of the product synthesized in 6 s and the reference ZSM-5. crystal growth during the initial stage, according to the NMR
spectra for the samples with a short synthesis period (2 s, for ex-
ample). In contrast, the enhancement of crystallization rate with

ENGINEERING
aluminum block and operated in batch, was also attempted. The temperature was not sustained, as seen from the NMR spectra for
results show that it took around 5 min to obtain a fully crystalline the longer synthesis periods. One possible reason for this obser-
ZSM-5 product as opposed to 6 s in the continuous flow synthesis vation is the low stability of OSDA at high temperatures, that
(Fig. S5). Measurement of the decomposition of TPAOH, the is, higher temperatures cause faster decomposition of OSDA,
OSDA used in this study, was also carried out using the aluminum resulting in a slower crystal growth rate during the later stages of
block as a heating medium (Fig. S6). The result clearly shows that crystallization. Overly high temperatures are not good for zeolite
considerable amount of oil phase (mainly comprising tripropyl- crystallization as a dense phase might be formed due to the de-
amine, one of the products of the TPAOH decomposition) was composition of OSDA. Although the formation of a dense phase
generated after a heating period of 3 min at 260 C, indicating that was not observed in this study, the results obtained from the batch
apparent decomposition took place even within a short period experiments clearly prove that adverse effects, including slower
of heating. crystallization rates, were observed at 300 C (Fig. S5) primarily
The duration of aging played an important role in determining because of the enhanced decomposition of OSDA.
the crystallization rate. Fig. 4A shows the crystallinity curves (on the Although it is considered that zeolites are susceptible to hot water
basis of XRD peaks, shown in Fig. S7) for the syntheses using the owing to the accelerated hydrolysis of silanol groups at high tem-
aluminosilicate gels with different aging periods at 90 C. Clearly, peratures (27, 28), they can withstand the hot water environment
extremely fast synthesis within 16 s could also be achieved even
when gels with an aging period as short as 2 h were used. Syn-
thesis of zeolites starts from the mixing of raw materials, which is
usually followed by an aging period, performed either at room
temperature or at an elevated temperature. During the aging
process, not only physical mixing occurs but also several impor-
tant chemical reactions toward the formation of precursors are
also triggered, leading to the formation of species that can ini-
tiate the nucleation and significantly influence the crystallization
rate as well as the properties of the resultant crystals (24). The
XRD patterns in Fig. 4B show that peaks due to aluminum
source [gibbsite Al(OH)3] rather than MFI structure are ob-
served, indicating that samples collected after aging were largely
amorphous. The 29Si MAS NMR spectra in Fig. 4C demonstrate
the formation of aluminosilicates and silicates [Q4(2Al) and Q3 spe-
cies, as represented by the broad peak centered around 101 ppm].
No long-range order could be detected, which is further con-
firmed by the results obtained from HEXTS (shown in Fig. S8).
The high-resolution transmission electron microscopy (HRTEM)
images shown in Fig. 4 DF demonstrate that long-range order
has not yet formed, as no lattice can be found. However, thermal
gravimetric analysis (TGA) results show that the weight loss for
the samples collected after certain aging periods became higher
Fig. 4. Effect of aging. (A) Crystallinity curves for the syntheses using the
compared with the one separated from the initial gel, implying a
synthesis mixture aged for different periods at 90 C (synthesis temperature,
stronger interaction between inorganic and organic species along 260 C). (B) XRD patterns of the solids collected after different aging periods
with the aging period (Fig. S9). Because the gibbsite Al(OH)3 [the circles denote the peaks due to gibbsite Al(OH)3]. (C) The 29Si MAS NMR
remained partially undissolved (Fig. 4B and Fig. S9) after aging, spectra of the solids collected after different aging periods. (DF) HRTEM
the inorganicorganic species may mainly come from the images for the samples aged for 2, 6, and 16 h, respectively.

Liu et al. PNAS Early Edition | 3 of 5


technique applied here can greatly facilitate the mass production
and will be extended to the continuous flow synthesis of other
zeolites (and related materials) in the future. Compared with the
extremely short hydrothermal synthesis time, the precursor tuning
through aging takes time. We next aim to deeply understand the
nature of aging by combining chemistry and engineering per-
spectives and hope to further shorten the overall production time
in the future.

Materials and Methods


Materials. The following materials were used as provided: colloidal silica
(LUDOX AS-40, 40 wt % suspension in H2O), TPAOH (40% aqueous solution,
Merck), aluminum hydroxide (with gibbsite structure, 100%, Wako), and
sodium hydroxide (particulate, Wako).

Preparation of Synthesis Mixture for ZSM-5. The synthesis mixture had a


composition of 50 NaOH:Al2O3:300 SiO2:20 TPAOH:2,300 H2O, which was
prepared as follows: TPAOH solution, NaOH aqueous solution (20 wt %), and
aluminum hydroxide were mixed and stirred for 5 min, and thereafter col-
loidal silica was added and stirred for an additional 30 min. Before high-
temperature synthesis, this mixture was aged at 90 C in a plastic bottle that
was rotated in an oven with a speed of 20 rpm.

Detailed Description of the Continuous Flow Synthesis. The continuous flow


apparatus contains the following key components: HPLC pumps, electronic
heaters and temperature controller (MTCS, Misumi), pressure gauges (PGI-63B-
MG10-LAQX, Swagelok), compressed-air-driven vibrator, back-pressure regu-
lator (TESCOM 261700, Emerson, US) and an in-house-assembled computer
control system. The continuous flow reactors and necessary connecting units
were all made from stainless steel standard parts (purchased from Swagelok).
A detailed illustration of the system can be found in Fig. S1. In a typical op-
eration, the system was gradually preheated to target temperatures using
water as a circulating medium, and accordingly, the system pressure was ad-
justed to 23 MPa using the back-pressure regulator. After the temperature
and pressure conditions became steady, the synthesis gel was fed to replace
the circulating water and the continuous flow synthesis started. The flow rates
for the synthesis gel and the hot water were maintained at 1 mL/min and
1.6 mL/min, respectively, which resulted in a synthesis temperature of 260 C.
Considering the density of water at 260 C (780 kg/m3), the actual velocity in
the continuous flow reactor (1/8-inch standard tube, with an inner diameter of
2.18 mm) was 0.015 m/s, which means that the length of the continuous flow
reactor required for a residence time of 6 s was 0.09 m. At the outlet of the
Fig. 5. Effect of synthesis temperature. (AD) The 27Al solid NMR spectra continuous flow reactor, cooling water was fed to cool down the slurry at a flow
for the products synthesized at 240, 260, 280, and 300 C, respectively. rate of 10 mL/min. To minimize the precipitation of the solids, the compressed-
(tetra and octa denote tetrahedral and octahedral coordination, air-driven vibrator kept shaking the continuous flow reactor at a frequency of
respectively.) 100 Hz (under a pressure of 0.1 MPa). The slurry flowing out of the continuous
flow reactor was centrifuged, washed, and dried to obtain the final ZSM-5
crystals. Considering the gel flow rate (1 mL/min) used in the typical operation
if the residence time is short. We demonstrate herein the con- conditions, a production rate of 260 g ZSM-5 per day could be achieved. Because
tinuous flow synthesis of ZSM-5, where direct mixing of a well- the actual reactor volume was quite small (15.6 mL), the continuous flow process
tuned precursor with pressurized hot water at high temperature generated a very high spacetime yield [7,000 kg/(m3h)].
was used to quicken the crystallization rate, resulting in the syn-
thesis on the order of seconds. These unexpectedly fast crystalli- ACKNOWLEDGMENTS. This work is partly supported by the New Energy and
Industrial Technology Development Organization. The high-energy X-ray
zation rates in a continuous flow apparatus help us to approach total scattering experiments at SPring-8 were approved by the Japan Syn-
the limit of the zeolite crystallization and provide a unique op- chrotron Radiation Research Institute under Proposals 2015B0115, 2016A0115,
portunity for carrying out mechanistic studies. Furthermore, the and 2016B0115.

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