One-step synthesis, characterization and catalytic performance of hierarchical Zn-ZSM-11 via facile ZnO routes

Article abstract of DOI:10.1039/c4ra14375b

Hierarchical Zn-ZSM-11 zeolite with an olive-shaped intergrowth morphology was synthesized via a novel and facile one-step hydrothermal method by using tetrabutylammonium bromide (TBABr) and zinc oxide (ZnO) as a difunctional template and zinc source, respectively. Structural characterizations (XRD, IR, TG-DTA, SEM, and N₂ adsorption-desorption) were conducted to analyze the textural properties of Zn-ZSM-11 samples. Compared with the Zn containing ZSM-11 samples prepared by other methods (ZnSO₄ method, ZnO-impregnated-seed method and impregnation method), the Zn-ZSM-11 prepared by ZnO method exhibited enriched mesopores as well as good catalytic activity in methanol conversion. TEM images showed that Zn species were well incorporated into the zeolite framework, while the different morphology of Zn-ZSM-11 from ZSM-11 further verified that the Zn species had been involved in the formation of the ZSM-11 framework. ²⁷Al and ²⁹Si MAS NMR spectra revealed that Zn species in the zeolite framework significantly impacted the coordination of Si. The XRD pattern variation of the ZnO containing gel was also tracked to illustrate the crystallization process. It was found that the ZnO would be gradually dissolved under the severely alkaline environment and subsequently incorporated into the ZSM-11 framework in the crystallization process. This facile new synthesis strategy can also be extended to prepare other Zn containing zeolites and is potentially important for practical utilization.

Full text of DOI:10.1039/c4ra14375b

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ARTICLE TYPE
One-step synthesis, characterization and catalytic performance of
hierarchical Zn-ZSM-11 via facile ZnO routes
a,b
*b
a
a
Qingjun Yu , Chunyi Li , Xiaolong Tang and Honghong Yi
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
Hierarchical ZnꢀZSMꢀ11 zeolite with an oliveꢀshaped intergrowth morphology was synthesized via a
novel and facile oneꢀstep hydrothermal method by using tetrabutylammonium bromide (TBABr) and zinc
oxide (ZnO) as a difunctional template and zinc source, respectively. Structural characterizations (XRD,
IR, TGꢀDTA, SEM, and N adsorptionꢀdesorption) were conducted to analyze the textural properties of
2
1
1
2
0
5
0
ZnꢀZSMꢀ11 samples. Compared with the Zn containing ZSMꢀ11 samples prepared by other methods
(
ZnSO method, ZnOꢀimpregnatedꢀseed method and impregnation method), the ZnꢀZSMꢀ11 prepared by
4
ZnO method exhibited enriched mesopores as well as good catalytic activity in methanol conversion.
TEM images showed that Zn species were well incorporated into the zeolite framework, while the
different morphology of ZnꢀZSMꢀ11 from ZSMꢀ11 further verified that the Zn species had been involved
2
7
29
in the formation of ZSMꢀ11 framework. Al and Si MAS NMR spectra revealed that Zn species in
zeolite framework significantly impacted the coordination of Si. The XRD patterns variation of the ZnO
containing gel were also tracked to illustrate the crystallization process. It was found that the ZnO would
be gradually dissolved under the severely alkaline environment and subsequently incorporated into the
ZSMꢀ11 framework in the crystallization process. This facile new synthesis strategy can also be extended
to prepare other Zn containing zeolites and is potentially important for practical utilization.
some chemical factors must be considered. For example, the
1
. Introduction
metal ion species should be able to undergo an easy mobilization
in the gel phase, generally achieved through solubilization in
Over the last few decades, transition metal ions modified zeolites,
particularly, the metalꢀmodified pentasil zeolites have gained a
great deal of attention since the incorporation of transition metals
endows zeolites many special catalytic properties.
them, Zn or Ga modified ZSMꢀ5 or ZSMꢀ11 have been known as
the active catalysts for aromatization of light paraffins; the
ZSMꢀ5 and ZSMꢀ11 zeolites containing Co or Cu display
excellent activity in selective NO reduction with methane or NO
and N O decomposition,
with Fe and Mn confers to the materials a good selective
ꢀ
ꢀ
basic (OH ) or neutral (or acidic) (F ) media. Then they also must
be ready to condense further under the subsequent hydrothermal
5
5
6
6
7
0
5
0
5
0
17
3+
2+
conditions. However, most of the metal ions, like Fe (Fe ),
1
ꢀ3
2
3
3
4
4
5
0
5
0
5
Among
2+
Cu , etc., form more readily insoluble or sparingly soluble
hydroxides or oxides that are hardly depolymerized and
mobilized into the useful metallosilicate anionic species able to
condense further viably to form zeolite framework. Thus, some
specific synthetic conditions and a restricted selection of reactants
are required to promote the incorporation of metals into zeolite
framework. A few suitable mineralizing agents that can form
metal complexes sufficiently stable as to prevent their progressive
hydrolysis and their stepwise dissociation with the release of the
metallic ionic species before their involvement in the zeolite
crystallization process have been developed. Gabelica and
Valange, in their review, have proposed that the shortꢀchain
alkylamine, as mobilizingꢀcomplexing agents, can effectively
4
ꢀ6
7
ꢀ11
the modification of ZSMꢀ5 zeolites
2
1
2, 13
oxidation performance.
incorporated into the zeolite phase by postꢀtreatment methods of
ionꢀexchange or impregnation.
Generally, these metal species can be
4, 14, 15
However, impregnation
method often causes the aggregation of metal species, which
might block the channels of zeolite. By contrast, the incorporated
metal species via ionꢀexchange method have better dispersion in
zeolite phase. Nevertheless, the postꢀtreatment procedures make
it complicated to obtain metalꢀzeolites materials and thus limit
their industrial applications.
In view of this, the direct synthesis method of incorporating
metal ions into the zeolite phase during the crystallization process
seems to be a preferable way for its simplification to obtain wellꢀ
2+
3+
3+
2+
incorporate several metallic species (Zn , Ga , Fe , Cu , etc.)
17
into the framework of ZSMꢀ5. Some other metallic precursors,
12
2+
such
as
manganese(III)ꢀacetylacetonate,
were also prepared as one kind of reactant instead of
[Zn(NH ) ]
3 4
1, 16
complex,
being introduced in the form of metal salt. In addition, some
researchers proposed that the metallic species could be introduced
into the silica source. Then, the prepared metalꢀcontaining silica
materials were mixed with the other materials of Al source,
1, 12, 16
dispersed and stable metal species in the zeolite framework.
In order to incorporate heteratoms into the zeolitic frameworks,
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NaOH and template. By this way, FeꢀZSMꢀ5 with the
morphology of nanorodꢀaggregation and polyꢀnanocrystallites
has been obtained by Zhao and Wang, respectively.
2.3 Synthesis of Zn-ZSM-11
1
3
18
ZnꢀZSMꢀ11 zeolites were obtained from the hierarchical ZSMꢀ11
seeded gel mixture containing Zinc compounds via various
synthesis methods.
5
6
6
7
7
5
0
5
0
5
In this paper, a very facile route was developed for the
synthesis of ZnZSMꢀ11 with a microporeꢀmesopore hierarchical
structure by introducing ZnO directly into the silicaꢀaluminum
gel mixture with a pH of 12ꢀ13. It was found that the ZnO would
be gradually dissolved and incorporated into the ZSMꢀ11
framework with crystallization time under the severely alkaline
environment. To the best of our knowledge, this is the first time
that a highly Zn loaded ZSMꢀ11 with hierarchical structure has
been synthesized via a very facile route by adding ZnO into the
reaction gel. For comparison, Zn was also introduced into the gel
in the form of ZnSO4 or ZnOꢀimpregnatedꢀseed. Besides, Zn
containing ZSMꢀ11 was also obtained by impregnation method to
clarify the dispersion of Zn species in the zeolite crystals. In our
previous study, it has been found that the hierarchical ZSMꢀ11
with intergrowth morphology exhibit superior high selectivity to
propylene as well as high gasoline yield in the methanol
5
0
5
0
(1) Seed-ZnSO4 method. ZnꢀZSMꢀ11 zeolite synthesized by
using zinc sulfate as zinc source was designated as Z11ꢀZn[S],
which was prepared as follows: aluminum sulfate and sodium
hydroxide were dissolved in deionized water, followed by
addition of the mixture of silica sol and template (TBABr)
1
1
2
(mixture I). Then, the aqueous solution of zinc sulfate was added
dropwise into the former mixture I under strong stirring (mixture
II). Finally, some amount of ZSMꢀ11 seed crystals (5 wt%
relative to the total solid content of the initial gel) was introduced
to accelerate the crystallization process. After vigorous stirring
for a period, the wellꢀmixed gel was transferred to stainlessꢀsteel
autoclaves, followed by a hydrothermal reaction at 170 C for a
period. After filtering, washing and drying at 100 C, the obtained
solid was calcined in air at 550 C for 2 h to remove the template.
(2) Seed-ZnO method. The synthesis procedure as well as the
reactant composition of sample Z11ꢀZn[O] was almost the same
as that of Z11ꢀZn[S] except for the use of ZnO as zinc source.
Instead of introducing the solution of ZnSO , the ZnO powder
was added into the mixture II directly at a very slow rate.
o
o
o
1
9
conversion reaction. Here, the Zn containing ZSMꢀ11 samples
prepared by ZnO method were also applied in the methanol
conversion and also present a good catalytic performance.
4
2
. Experimental section
(3) ZnO-Impregnated seed method. The extraneous seed was
2
.1 Materials
pretreated by the impregnation of zinc nitrate followed by the
calcination to become the ZnO loaded form. For the synthesis of
sample Z11ꢀZn[PreO], the Zn species was introduced into
25
30
35
The synthesis was performed with colloidal silica (40 wt% SiO2,
6
sulfate (Al (SO ) ·18H O, Sinopharm Chemical Reagent Co.,
Ltd.), sodium hydroxide (96.0 wt%, Sinopharm Chemical
Reagent Co., Ltd.) as silica source, aluminum source and alkali
source, respectively. Zinc oxide (ZnO, 99.7 wt%, Qingdao
0 wt% H O, Qingdao Haiyang Chemical Co., Ltd.), aluminum 80 mixture II just in the form of ZnO loaded ZSMꢀ11 seed.
2
All the initial gel mixture made by the three methods above
have the same molar composition of 9.0 Na O: 1.0 Al O : 4.0
2
4 3
2
2
2
3
ZnO: 65 SiO : 1.0 (TBA) O: 1300 H O and the crystallization
2
2
2
process were performed from 12 h to 36 h to get wellꢀcrystallized
NakasenZinc& Technology Co., Ltd.), zinc sulfate 85 products. For comparison, all the products were obtained after
ZnSO ·7H O, 98.5 wt%, Sinopharm Chemical Reagent Co.,
crystallizing for 36 h.
4) Impregnation method. For comparison, Znꢀimpregnated
ZSMꢀ11 sample was also prepared by the postꢀtreatment method
(
4
2
(
Ltd.) and zinc nitrate (Zn(NO ) ·6H O, 99 wt%, Sinopharm
Chemical Reagent Co., Ltd.) were used as the Zinc source.
Tetrabutylammonium bromide was used as the template to induce
3
2
2
of impregnating an aqueous solution of Zn(NO ) ·6H O into the
3 2
o
2
the structure of ZSMꢀ11. All chemicals were used as received 90 Z11 sample, followed by a calcination at 550 C for 2 h. The
without further purification. Besides, hierarchical ZSMꢀ11 with
intergrowth morphology was chosen as seed crystals, which was
prepared according to the literature.
resultant sample was designated as Z11ꢀZn[Pre].
2
0
2.4 Characterization
All samples were characterized by Xꢀray diffraction (XRD) on
the X’Pert PRO MPD (PANalytical Co.) diffractometer at 40 kV
4
0
2.2 Synthesis of ZSM-11
o
95
and 40 mA with Cu Kα radiation at a scanning rate of 2 /min in
The ZSMꢀ11 without Zn species (Z11) was prepared as described
o
21
the 2 θ range from 4.5 to 65 . The relative crystallinity was
as elsewhere. In a typical synthesis, aluminum sulfate and
sodium hydroxide were dissolved in deionized water, followed by
addition of the mixture of silica sol and template (TBABr)
(mixture I). Then, some amount of ZSMꢀ11 seed crystals (5 wt%
relative to the total solid content of the initial gel) were
introduced. After vigorous stirring for a period, the wellꢀmixed
gel with the molar composition of 9.0 Na O: 1.0 Al O : 4ZnO: 65
calculated based on the integration of the XRD characteristic
o
o
o
o
peaks at 2 θ of 7.9 , 8.7 , 23.0 and 23.9 compared with that of
2
0
the hierarchical ZSMꢀ11 seed prepared according to literature.
00 The characteristic vibration bands of the zeolite particles were
confirmed by FTIR on Nexus Model Infrared
45
1
a
Spectrophotometer (Nicolet Co, USA). Thermogravimetry (TG)
and differential thermal analysis (DTA) were performed on a
NETZSCH Proteus STA449C in an air stream at a programming
2
2
3
SiO : 1.0 (TBA) O: 1300 H O was transferred to stainlessꢀsteel
2
2
2
o
50
autoclaves, followed by a hydrothermal reaction at 170 C for 12
h. After filtering, washing and drying at 100 C, the obtained
solid was calcined in air at 550 C for 2 h to remove the template.
o
o
1
05 rate of 10 C/min from room temperature to 700 C. Particle size
and crystal morphology of the samples were examined with a
scanning electron microscopy (SEM), S4800, equipped with an
Energy dispersive Xꢀray spectroscopy (EDX) probe for the semiꢀ
o
o
2
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o
quantitative direct analysis of the elements. Nitrogen adsorptionꢀ
desorption experiments at 77 K were conducted in an Autosorb
instrument (Quantachrome).The total surface (SBET
calculated according to the (BrunauerꢀEmmetꢀTeller) BET
isothermal equation, and the total volume (Vtotal) was determined
550 C for 2 h. Then the Hꢀform samples were used as an active
component to be mixed intimately with silica sol and kaolin clay,
)
was 30 which served as a binder and inert support for the zeolite,
respectively. After stirring for 2 h, the formed slurry was dried at
o
o
5
0
5
0
100 C for 3 h, followed by calcination at 700 C for another 2 h.
Then the catalyst bulks were crushed and sieved for later use.
The methanolꢀtoꢀolefin (MTO) reaction was conducted to
from the nitrogen adsorbed volume at P/P =0.990. Both the
0
micropore surface area (Smicro) and the micropore volume (Vmicro
)
were calculated by application of the tꢀplot method. The external 35 evaluate the catalytic performance of the ZnꢀZSMꢀ11 catalysts.
surface area (S ) and mesopore volume (Vmeso) were obtained by
For each test, 2 g catalyst with particle size of 0.250ꢀ0.425 mm
was loaded between two layers of quartz wool in the reactor.
After temperature got stable at 450 C, the feed of pure methanol
ext
1
1
2
the calculated total data minus the corresponding micropore data.
Mesopore size distributions were obtained by using a method
based on nonlocal density functional theory (NLDFT). The acid
o
solution was introduced by a HPLC infusion pump at a fixed rate
properties of samples were measured by pyridine adsorption on a 40 of 0.164 mL/min, accompanied with N gas through a mass flow
2
Nexus Model Infrared Spectrophotometer (Nicolet Co, USA). Xꢀ
ray fluorescence spectroscopy (XRF) conducted with an Axios
Advanced Xꢀray Spectrometer was used to analyze the chemical
compositions of samples. The transmission electron microscopy
controller at a rate of 21 mL/min. The weight hourly space
ꢀ
1
velocity (WHSV) for methanol was 5.53 h . Effluent gas from
the reactor was collected and analyzed by a Bruker 450ꢀGC gas
chromatography (GC) equipped with a TCD detector and a FID
(TEM) images were recorded using
a
JEMꢀ2100UHR 45 detector column. The corresponding liquid products were
transmission electron microscopy. UVꢀvisible absorption spectra
were measured on a JASCO Vꢀ550 UVꢀVis spectrometer at room
temperature. A Bruker AVꢀ400 nuclear magnetic resonance
analyzed on Agilent 6820 gas chromatograph with an HPꢀ
INNOWAX capillarycolumn (30m×0.32mm×0.25ꢁm) and a
flame ionization detector (FID) using ethanol as internal standard.
The coking amount was calculated from a TGꢀDTA curve
50 measured on a NETZSCH Proteus STA449C in air at a heating
2
7
29
(NMR) spectrometer was used to collect Al and Si MAS
NMR spectra.
o
o
rate of 10 C/min from room temperature to 800 C.
2
.5 Catalytic performance
3. Results
2
5
All the zeolites were transformed into the Hꢀform by ionꢀ
o
exchanging Naꢀform with 1.0 M NH NO solution at 80 C for 2
4
3
h (three times), followed by washing, drying and calcination at
Table 1 Textural properties of ZSMꢀ11 and ZnꢀZSMꢀ11 samples prepared by various methods
R.C., %
c
2
d
2
e
3
f
3
g
Particle size (ꢁm)
Smicro (m /g)
Sext (m /g)
Vmicro (cm /g)
Vmeso (cm /g)
a
b
XRD
IR (I550/I450)
Z11
111.07
64.78
69.45
76.11
87.09
0.87
0.84
0.84
0.82
0.86
2.0ꢀ2.5
Aggregation
(1.5ꢀ1.7)*2.3
(1.2ꢀ1.4)*1.7
ꢀ
340.7
220.4
250.0
242.5
304.0
72.3
24.3
60.3
50.2
0.14
0.09
0.10
0.10
0.13
0.10
0.04
0.12
0.09
0.08
Z11ꢀZn[S]
Z11ꢀZn[O]
Z11ꢀZn[PreO]
Z11ꢀZn[Pre]
47.4
a
o
o
o
o
5
6
6
5
0
5
The relative crystallinity was calculated based on the integration of the XRD characteristic peaks at 2
θ
of 7.9 , 8.7 , 23.0 and 23.9 compared with that of the
hierarchical ZSM-11 seed.
b
-1
-1
The relative crystallinity estimated by the ratio of intensity of the band at 550 cm and 450 cm in the FTIR (fourier transform infrared spectroscopy) of samples.
c
The particle size measured according to the SEM images of samples.
d,f
Both the micropore surface area (Smicro) and the micropore volume (Vmicro) were calculated by application of the t-plot method.
e,g
Both the external surface area (Sext) and mesopore volume (Vmeso) were obtained by the calculated total data minus the corresponding micropore data, while the
total surface (SBET) was calculated according to the (Brunauer-Emmet-Teller) BET isothermal equation and the total volume (Vtotal) was determined from the
0
nitrogen adsorbed volume at P/P =0.990.
XRD patterns
introduced either via synthesis or impregnation methods.
75 Notably, the ZnꢀZSMꢀ11 samples obtained from the direct
synthesis of zinc contained gel mixtures also display an extra
XRD was carried out to investigate the structure change of
zeolite samples after zinc species were introduced via different
methods. As shown in Figure 1(A), the diffraction patterns of the
zinc containing samples are very similar with that of the blank
sample Z11, all of which are belonged to the typical MEL
topology. Besides, no diffraction peaks of ZnO crystallites are
observed in the ZnꢀZSMꢀ11 samples, indicating that the zinc
species are well dispersed in the zeolite crystals after they are
o
diffraction peak at about 2 θ of 5.96 , which can be ascribed to
carbonaceous organic species and can be removed by calcination
in air flow (Figure 1A, inset).These results suggest that the
existence of zinc species in the initial gel can react with the
template to form organic species during the crystallization
process, which might have an influence on the properties of final
product zeolites.
8
0
7
0
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Crystallinity, as assessed by both XRD and FTIR
TG-DTA analysis
techniques, were listed in Table 1. When zinc species are
introduced into the initial gel, the obtained ZnꢀZSMꢀ11 samples
show evident decreased peak intensities than the Z11 sample,
The TGꢀDTA analysis was carried out to determine the
thermal stability of the synthesized ZSMꢀ11 samples with or
5
0
5
0
resulting in the very poor XRD crystilinity of Znꢀcontained 30 without Zn and to measure the weight loss of both water and
ꢀ
1
samples. However, the ratios of optical densities of the 550 cm
band and 450 cm band (I550/I450), which also can give an
templates. Thermograms of the samples were illustrated in Figure
2. Under air atmosphere, the main loss of weight for all the ZSMꢀ
ꢀ
1
o
approximate estimation of the crystallinity for ZSMꢀ11 or ZSMꢀ5
11 samples with and without zinc occurs below 200 C and in the
4, 22
o
zeolites,
show no obvious difference among these ZnꢀZSMꢀ11
range of 400ꢀ500 C, which are caused by the loss of physically
1
1
2
and ZSMꢀ11 samples. As listed in Table 1, all the samples have 35 adsorbed water and the oxidative decomposition of the template
2
4
the I550/I450 ratio larger than 0.7, indicating that the crystallinity is
present in zeolite channels, respectively. It should be noted that
all the Zn containing samples present an additional exothermic
2
2, 23
approximate 100 %.
These results indicate that the
o
incorporation of Zn species has no obvious influence on the
crystallization degree of zeolite structures but has an effect on the
peak at 300ꢀ400 C (Figure 2(bꢀd)), which cannot be observed in
the ZSMꢀ11 sample (Figure 2a). Considering the XRD peak at 2
Xꢀray diffraction peak intensities of samples. It is well known 40 θ of 5.96 , it can be confirmed that the weight loss at 300ꢀ400 C
o
o
that the XRD peak intensity can reflect the relative content of
some phase in the whole samples. Therefore, it can be deduced
that the decrease of peak intensity of ZnꢀZSMꢀ11 samples are
probably due to the dilution of ZSMꢀ11 phase by incorporating
Zn species.
was due to the decomposition of carbonaceous organic species
formed during the crystallization of zincꢀcontaining gel mixture.
In addition to the weight loss described above, there is no
substantial weight loss above 500 C in both Zn containing and
45 blank ZSMꢀ11 samples, indicating the Znꢀcontaining ZSMꢀ11 is
as stable as the ZSMꢀ11 material.
o
Fig.2 TGꢀDTA curves of ZSMꢀ11and various ZnꢀZSMꢀ11 zeolites: (a)
Z11; (b) Z11ꢀZn[S]; (c) Z11ꢀZn[O]; (d) Z11ꢀZn[PreO]
50
SEM images
SEM was used to understand the effect of zinc species on
the morphology and crystal size distribution of ZSMꢀ11 zeolites.
Figure 3 shows SEM images of ZSMꢀ11 and ZnꢀZSMꢀ11
synthesized by different methods. Intergrowth microsphere
morphology of seedꢀassisted synthesized ZSMꢀ11 is clearly
observed and the particle size is about 2ꢀ3 ꢁm (Figure 3b), much
smaller than the extraneous hierarchical ZSMꢀ11 microspheres
55
Fig.1 XRD patterns (A) and FTIR spectra (B) of ZnꢀZSMꢀ11 prepared by
different methods: (a) Z11; (b) Z11ꢀZn[S]; (c) Z11ꢀZn[O]; (d) Z11ꢀ
Zn[PreO]; (e) Z11ꢀZn[Pre]. The inset in Figure 1A is the enlarged 2θ
60 (6ꢀ7 ꢁm, Figure 3a). This distinction in particle size distribution
of seed and product zeolites is mainly attributed to the surface
nucleation behavior occurring on the seeds. After zinc was
25
o
25
region in 4ꢀ10 of XRD patterns of calcined samples (b), (c) and (d)
4
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introduced into the initial gel, the prepared zinc containing
with the synthesis methods. For instance, the sample Z11ꢀZn[S]
products also exhibit the similar intergrowth morphology to Alꢀ
ZSMꢀ11 (Figure S1), which is mainly due to the scaffold of
prepared by seedꢀZnSO method have an irregular shape (Figure
3c), while the samples synthesized via SeedꢀZnO and ZnOꢀ
Impregnated seed methods give uniform olivary (Figure 3d) and
4
2
0, 26
TBABr for directing the mesoꢀstructure.
Meanwhile, the size
5
of individual particles for all the ZnꢀZSMꢀ11 samples is smaller 15 ellipsoidal shape (Figure 3e). The variation in shape of different
than the seed’s particle size, demonstrating that the incorporation
of zinc species has no obvious effect on the behavior of seeds.
Nevertheless, different from the microspherical nanorods
aggregates of the pure ZSMꢀ11, the zinc containing ZnꢀZSMꢀ11
samples display completely different particle shape, which vary
zinc containing samples suggest that the existence of zinc species
participate in the crystallization of MEL structure, irrespective of
their various forms of ZnO or ZnꢀAlꢀSi species in the alkaline
environment.
1
0
2
0
Fig.3 SEM images of ZSMꢀ11and various ZnꢀZSMꢀ11 zeolites: (a) ZSMꢀ11 seed; (b) Z11; (c) Z11ꢀZn[S]; (d) Z11ꢀZn[O]; (e) Z11ꢀZn[PreO] . (c1), (d1)
and (e1) are the TEM images of an individual particle of sample Z11ꢀZn[S], Z11ꢀZn[O] and Z11ꢀZn[PreO]
N isotherms
2
2
5
Fig.4 N
properties (C) of ZSMꢀ11 and various ZnꢀZSMꢀ11 zeolites (r
a) Z11; (b) Z11ꢀZn[S]; (c) Z11ꢀZn[O]; (d) Z11ꢀZn[PreO]; (e) Z11ꢀZn[Pre]
2
adsorptionꢀdesorption isotherms (A), the corresponding mesopore size distribution (DFT) (B) and the ratios of mesopore properties to micropore
27
s v
=external surface area/micropore surface area; r =mesopore volume/micropore volume) :
(
The porosity properties of ZnꢀZSMꢀ11 samples were tested
by nitrogen sorption experiments. Figure 4 (A) illustrates the N2
adsorptionꢀdesorption isotherms of ZSMꢀ11 and ZnꢀAlꢀZSMꢀ11 35 10 and a hysteresis loop at P/P = 0.4ꢀ0.8, attributed to the filling
show the similar isotherms to the blank sample Z11, which
ꢀ
7
3
0
possess a steep increase at a low relative pressure of 10 < P/P <
0
ꢀ
2
0
obtained by various methods. All the zinc containing materials
of micropores and the capillary condensation of N in mesopores,
2
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respectively. What’s more, a somewhat overlapping increase is
incorporates Zn species in the form of ZnO, exhibits the largest
also observed above P/P = 0.8 in some samples and this is due to 60 mesopore properties, then followed by the sample Z11ꢀZn[PreO]
0
2
8, 29
N condensation in the larger voids between nanocrystals.
prepared by the ZnOꢀimpregnatedꢀseed method. The sample Z11ꢀ
Zn[Pre] prepared via the impregnation method presents a slightly
decreased mesopore properties compared with the ZSMꢀ11
zeolite (Z11), while the sample Z11ꢀZn[S] shows both the
2
The corresponding mesopore size distribution curves of various
samples were depicted as Figure 4 (B). Compared with the blank
ZSMꢀ11 sample which mainly possesses the mesopore size
5
0
5
0
5
0
5
0
5
0
5
distribution concentrated below 10 nm, the Zn containing 65 smallest rs and rv ratios, in accordance with its aggregation
samples show a wider size distribution ranging from 3 to 100 nm.
Particularly, the sample Z11ꢀZn[O] prepared via the ZnO method
shows an evident larger amount of pores with large size (> 50
nm) than the other samples (Figure 4B(c)), which is in good
morphology. All these results above indicate that when Zn was
introduced in the form of ZnO, these species can be well
incorporated into the zeolite phase without affecting the
formation of intercrystalline mesopores.
1
1
2
2
3
3
4
4
5
5
agreement with its larger N adsorption amount in the higher
70
2
pressure of P/P > 0.8 (Figure 4A(c)). By contrast, the sample
Acidity analysis
0
Z11ꢀZn[S] prepared by SeedꢀZnSO method shows the smallest
4
mesoporsity, which is well agreement with the unconspicuous
hysteresis loop of its isotherm. Considering the similar nanorods
The FTIR spectra of pyridine adsorbed on ZSMꢀ11 and ZnꢀZSMꢀ
11 samples are shown in Figure 5. A serious of bands are
intergrowth morphology but different mesoporosity of these Zn 75 observed over the blank ZSMꢀ11 sample. According to the
22, 31, 32
ꢀ1
containing samples, it is reasonable to deduce that the intergrowth
or stacking state of the nanrod crystals in different samples varies
with the preparation methods. Therefore, the voids that contribute
greatly to the mesopore properties show great difference among
literature,
the bands at 1635 and 1540 cm can be ascribed
to the interaction of pyridine with Brønsted acid sites, while the
ꢀ
1
bands at 1600 and 1450 cm are due to the interaction of pyridine
ꢀ
1
with Lewis acid sites. The band at 1490 cm refers to the
different samples. TEM images were collected to illustrate the 80 vibration of pyridine absorbed over Brønsted and Lewis acid
intergrowth of stacking state of nanoroods in various samples. As
shown in Figure 3(d1, e1), dotted bright parts could be clearly
observed among the intercrossed nanorod crystals of samples
Z11ꢀZn[O] and Z11ꢀZn[PreO], demonstrating that the nanorods
sites. Notably, as zinc species are incorporated into the zeolite
phase, the amount of Brönsted acid sites displays a significant
decrease and the amount of Lewis acid sites increases. What’s
ꢀ
1
more, an additional intense signal at 1616 cm is observed in all
intergrowth or stack with each other in a relatively loose way. By 85 the ZnZSMꢀ11 samples, representing the new Lewis acid sites
33
contrast, the TEM image of sample Z11ꢀZn[S] present an almost
whole dark microsphere (Figure 3c1), indicating that all the
nanorod crystals intercrossed with each other in a close state.
Correspondingly, the mesopore volume depended upon the voids
generated by zinc incorporation. Correspondingly, the band at
ꢀ
1
1450 cm also splits into two bands after for the ZnꢀZSMꢀ11
samples. The position of the band at higher wavenumbers (1455
ꢀ
1
cm ) can be considered as the Lewis sites caused by Al species,
ꢀ
1
existing among the aggregated nanorod crystals becomes the 90 while the band at lower wavenumbers (1440 cm ) can be
smallest in sample Z11ꢀZn[S].
assigned to the newlyꢀformed Lewis sites. These results suggest
the incorporation of Zn species can form more Lewis acid sites at
the expense of consuming Brønsted sites. That is, the
incorporated Zn species combine with the Brønsted acid sites and
Table 1 gives the detailed BET surface area and pore volume
of the ZSMꢀ11 materials with and without zinc species. When Zn
species are introduced by impregnation method, a slight decrease
is observed in both the micropore micropore surface and 95 form the new [AlꢀOꢀZnꢀOꢀZnꢀOꢀAl] or [AlꢀOꢀZnꢀOꢀAl] species,
34, 35
micropore volume due to the dilution effect. By contrast, the
external surface area and mesopore volume show a greater
decrease. The results reveal that the ZnO nanoparticles are mainly
dispersed on the outer surface of the ZSMꢀ11 crystals via
impregnation followed by calcination. Compared with the sample
Z11ꢀZn[Pre] obtained by impregnating Z11 with Zn(NO ) ·6H O
which act as the Lewis acid sites.
3
2
2
followed by the calcination procedure, the samples synthesized
directly from the zinc containing gel present obviously smaller
2
micropore surface area (220ꢀ250 m /g) and volume (0.09ꢀ0.10
3
cm /g). Nevertheless, the Zn containing samples Z11ꢀZn[O] and
Z11ꢀZn[PreO] show mesopore properties comparative to the Z11
sample. These results indicate that the Zn species are mainly
incorporated into the micropore structures of samples through the
direct synthesis method.
Generally, the existence of mesopore in microporous zeolite
materials does a great contribution to improve the catalytic
20, 30
activity of materials due to the efficient mass transport.
Here,
the external to micropore surface area ratios (r ) and the mesopore
s
to micropore volume ratios (r ) are used as practical parameters to
v
characterize the mesoporosity of the samples. As shown in Figure
Fig.5 PyꢀIR spectra of ZSMꢀ11 and ZnꢀZSMꢀ11 prepared by various
methods: (a) Z11; (b) Z11ꢀZn[S]; (c) Z11ꢀZn[O]; (d) Z11ꢀZn[PreO]; (e)
Z11ꢀZn[Pre]
4
(C), it is evident to observe that the sample Z11ꢀZn[O], which
100
6
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16
Catalytic activity
. Therefore, the Zn containing sample Z11ꢀZn[O], which
possesses both largest rs and rv values, exhibits the longest
catalytic lifetime, while the sample Z11ꢀZn[S] prepared by using
ZnSO method presents the lowest r and r values, resulting in its
The catalytic conversion of methanol was investigated over all
the ZSMꢀ11 catalysts with and without Zn species. As shown in
4
s
v
5
0
5
0
5
Figure 6, these catalysts exhibit quite different catalytic activities. 30 lowest catalytic activity.
Compared with sample Z11, the Zn containing samples shows a
relatively faster deactivation rate, which might be ascribed to the
enhanced Lewis acid amount aroused by Zn species introduction.
Among these ZnꢀZSMꢀ11 samples, when Zn species are
It has been well documented that the Zn containing zeolites
will yield more liquid products but less gaseous products than the
16, 31
H form zeolites.
In this work, the gasoline yield variation
with time on stream over different materials is depicted in Figure
1
1
2
2
introduced in the form of ZnSO , the obtained sample Z11ꢀZn[S] 35 6b. It is clearly observed that the Zn containing ZSMꢀ11 samples
4
shows a rapid deactivation rate at the beginning of reaction. By
contrast, the samples with the Zn species incorporated in the form
of ZnO demonstrate a much slower deactivation rate and the
deactivation rate decreases in the sequence of Z11ꢀZn[Pre] >
show higher gasoline yield but a lower propylene selectivity than
the Z11 sample after the reaction time of 90 min. Comparing the
difference in acidity among these samples, it is rational to
conclude that as the Zn species are incorporated into the ZSMꢀ11
Z11ꢀZn[PreO] > Z11ꢀZn[O]. Taking into account of the similar 40 crystals, the decrease of Brønsted acid sites leads to the weaker
acidity but different textural properties among these ZnꢀZSMꢀ11
samples, it can be postulated that catalytic activity of various Znꢀ
ZSMꢀ11 samples greatly depends on their mesoporous properties.
According to the report of Ryoo and coworkers, it was found that
propylene selectivity, while the increase of Lewis acid sites
results in the increase of gasoline yield. In addition to the acidity,
the textural properties of samples also play a vital role in the
product selectivity. Obviously, the samples prepared via ZnOꢀ
the coke was deposited on the external surfaces more than it was 45 seed methods still exhibit evident higher propylene selectivity
3
6
inside the micropores of ZSMꢀ5 zeolites . In this work, the
intercrystalline voids among the nanorods of the ZnꢀZSMꢀ11
samples may act in a manner similar to the intracrystalline
mesopores discussed by Ryoo and provide enough space to stock
cokes and prevent the entrance of the micropore from blocking up
than that prepared by impregnation method, following the order
of Z11ꢀZn[O] Z11ꢀZn[PreO] Z11ꢀZn[Pre], which is
corresponding to their different mesoporous properties (Figure
>
>
37
4C)
.
50
Fig.6 Catalytic performance in MTO over catalysts as a function of time on stream ( Z11;
Z11ꢀZn[Pre];
Z11ꢀZn[O];
Z11ꢀZn[PreO];
Z11ꢀ
Zn[S]).
4. Discussions
5
5
Table 2 Chemical composition of ZSMꢀ11 and ZnꢀZSMꢀ11 prepared by different methods
Si/Al
Si/Zn
EDX
Sample
Initial mixture
32.5
EDX
14.0
13.0
13.1
13.0
XRF
25.4
26.4
ꢀ
Initial mixture
16.25
XRF
Z11
ꢀ
ꢀ
Z11ꢀZn[PreO]
Z11ꢀZn[O]
Z11ꢀZn[S]
32.5
16.25
7.9
6.6
5.9
25.3
32.5
16.25
32.5
ꢀ
16.25
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As described above, the incorporation ways of Zn species have a
vital influence on the morphology and textural properties of the
product samples, which finally affect their catalytic activity. The
gives the crystallization curves in different synthesis systems.
Notably, when Zn is added into the gel mixture in the form of
ZnSO , about 30 h is needed to get well crystallized product
4
spherical intergrowth morphology is well retained when Zn 40 zeolites. For comparison, when Zn was introduced in the form of
5
0
5
0
5
0
5
species are introduced by impregnation method. No obvious ZnO
clusters are observed in this sample, indicating that the Zn species
are well dispersed in the crystals. In comparison, the ZnꢀZSMꢀ11
samples directly synthesized from the Zn containing gels show
ZnO, the time necessary to complete the crystallization is much
shorter. Particularly, in the system containing ZnO impregnated
seed, the crystallization rate is as fast as that in the Znꢀfree
system and only 6 h is needed to complete the crystallization
more or less different morphologies, revealing that Zn species 45 process. Combining with the Si/Zn ratio of the three different
1
1
2
2
3
3
have participated in the formation of ZSMꢀ11 framework. In
order to have a better comprehension on the behavior of Zn
species in the synthesis process, the Si/Al and Si/Zn ratios were
detected by both XRF and EDX. According to the surface
analysis, the EDX is mainly used to carry out outer rim analysis,
samples, it is clear to find that the incorporation of Zn species
also has a relationship with the crystallization duration. That is,
more amount of Zn species will be incorporated into the zeolite
phase after a longer crystallization period.
4
, 38
while the XRF can give the bulky composition.
For the sample ZSMꢀ11, the aluminum near the surface
Si/Al=14.0 by EDX) is much higher than that in the whole
(
crystal (Si/Al=25.4 by XRF). These results suggest that in the
beginning of crystallization, siliconꢀrich nuclei are formed, while
the aluminum species are primarily incorporated into the zeolite
3
8ꢀ40
framework during the crystal growth process.
The similar
case also appears when Zn species are introduced into the initial
reaction gel. As listed in Table 2, the Zn containing sample Z11ꢀ
Zn[PreO] shows a bulky Si/Zn ratio of 25.3, much larger than the
outer rim Si/Zn ratio of 7.9, indicating that the Zn species are also
incorporated in the crystal growth stage. It is noteworthy that all
the three Zn containing samples present the similar Si/Al ratio
(EDX) but different Si/Zn ratio. Considering their preparation
methods, it can be reasonable to deduce that more amount of Zn
species are incorporated into the framework when they are added
2+
in the form of Zn than ZnO.
50
In the previous work, it has been found that the
Fig.7 Crystallization curves of systems with and without Zn species by
different methods
crystallization duration has
a significant effect on the
4
0
incorporation of aluminum species. The longer period is needed
for the completion of crystal growth, the more aluminum species
will be incorporated into the framework and vice versa. Figure 7
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Fig.8 XRD peaks evolution of Z11ꢀZn[PreO] samples with crystallization time
It should be mentioned that in spite of the shortest time is
the zeolite phase in the subsequent recrystallization process.
needed to get well crystalline ZSMꢀ11 phase when using ZnO
impregnated seeds, the characteristic peaks designating ZnO
clusters are also detected in the final products. As shown in
Figure 8, the sample from the ZnOꢀimpregnatedꢀseed assisted
system presents evident ZnO characteristic peaks even the
crystallization time is prolonged to 12 h. As the hydrothermal
crystallization time increases, the peak intensity representing the
Zn content in the sample decreases and finally disappears at the
crystallization time of 36 h. In the meantime, the diffraction peak
5
0
5
0
5
0
1
1
2
2
3
o
at about 2 θ of 5.96 , which designates the carbonaceous organic
species appears. These results indicate the ZnO cluster can be
dissolved in the alkaline environment at high temperature,
irrespective of in a relatively long period. These soluble zinc
species then will gradually participate in the crystallization of
zeolite, which can be referred as the “recrystallization process”.
The formation of carbonaceous organic species verifies this
recrystallization process.
Compared with the system containing ZnOꢀimpregnatedꢀseed, in
the system where ZnO and seed are added into the system
simutaneously, about twice time than the former (12 h) is needed
to complete the crystallization process (Figure 9). But different
from the former system, the ZnO peaks have disappeared after 10
h, at which time the ZSMꢀ11 crystals are yet well crystallized.
These results suggest that when Zn species are impregnated into
the extraneous seed crystals before being added into the reactant
gels, some interaction occurs between the ZnO clusters and seed
crystal. Thus, the ZnO clusters cannot be easily dissolved in the
presence of seeds and the Zn species are mainly incorporated into
Fig.9 XRD peaks evolution of Z11ꢀZn[O] samples with crystallization
35
time
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4
5
5
5
0
5
another two evident signals are also observed below –100 ppm
centered at ꢀ99 and ꢀ96 ppm, which can be attributed to Si(2Al)
43
and Si(3Al) sites. In contrary, the samples prepared by ZnOꢀ
impregnatedꢀseed method only shows a very weak signal at ꢀ96
ppm, while the sample with Zn species introduced by
impregnation method presents almost the same signals with the
blank sample. These results further proved the postulation
proposed above. That is, the Zn species can be well incorporated
into the zeolitic framework to substitute the Si or Al sites through
direct synthesis procedure. For the ZnOꢀImpregnated seed
method, there will be two behaviors of Zn species in the crystals,
some of them will be incorporated into the framework and the
others will disperse in the crystals, which is similar to the
2
7
impregnation method. What’s more, from the difference of Al
29
and Si NMR spectra among these samples with and without Zn,
Fig.10 TEM images of ZnꢀZSMꢀ11 prepared by various methods: (a)
60 it is reasonable to believe that the incorporation of Zn species into
zeolite framework has a close relationship with the Si species and
thereby impact the coordination of Si species.
Z11ꢀZn[Pre]; (b) Z11ꢀZn[S] (c) Z11ꢀZn[O] (d) Z11ꢀZn[PreO]
Theoretically, as the Zn species are incorporated as a counter
ion, two Al are required in a nearly geometrical neighborhood to
5
0
5
0
5
0
5
0
2
+ 4
interact with one Zn . As a result, the theoretical Zn/Al value is
about 0.5. In this paper, the product samples show the Zn/Al
ratios of 1.6ꢀ2.2, much larger than the theoretical value (0.5). So
it can be postulated that except for the Zn species incorporated
into the zeolitic structures, there are still some Zn species existing
in the ZSMꢀ11 phase by dispersion or other forms. Figure 10
illustrates the state of Zn species in the ZSMꢀ11 phase. From
Figure 10a, obvious ZnO nanoparticles are observed in the zeolite
crystals of sample obtained by impregnation method. By
contrast, when Zn species are directly introduced as the reactant
1
1
2
2
3
3
4
2+
materials, no matter in the form of ZnO or Zn , the
crystallization product presents only zeolite phase, with no
evident ZnO particles. From these results, it can be thought that
the Zn species are well incorporated into the framework or well
dispersed in the crystals through the direct synthesis method.
Notably, if Zn species are impregnated into the seed crystal, the
ZnO cannot be well involved in the formation of ZSMꢀ11
frameworks. As shown in Figure 10d, evident ZnO particles can
be observed in the crystal of sample Z11ꢀZn[PreO], however, in a
much smaller amount than the impregnated sample Z11ꢀZn[Pre].
This result reveals that there are still some Zn species
incorporated into the zeolitic structure during the crystallization
process, which might mainly occur in the recrystallization stage.
27
29
Al and Si MAS NMR have been viewed as a powerful
characterization method to detect the coordination situation of Al
and Si species in zeolite crystals, which can also reflect the state
27
of Zn species in zeolite framework. Figure 11 shows the Al and
2
9
Si NMR spectra of ZSMꢀ11 and ZnꢀZSMꢀ11 samples prepared
by various methods. All the samples exhibit one intense signal
centered at around 54 ppm associated to tetrahedrally coordinated
4
1
Alꢀatom in the framework, indicating the introduction of Zn
species has little effect on the incorporation of Al species into the
frameworks. Nevertheless, the samples Z11ꢀZn[O] and Z11ꢀ
2
7
29
Fig.11 Al MAS NMR and Si MAS NMR spectra of AlꢀZSMꢀ11 and
ZnꢀAlꢀZSMꢀ11 samples prepared by different methods. (a) Z11; (b) Z11ꢀ
Zn[S]; (c) Z11ꢀZn[O]; (d) Z11ꢀZn[PreO]; (e) Z11ꢀZn[Pre]
65
Zn[S] prepared by adding ZnO or ZnSO into the reaction gel
4
2
9
display distinctively different Si NMR spectra from the blank
sample Z11. In addition to the four peaks in the range of ꢀ116~ꢀ
Conclusions
1
03 ppm, which are assigned to the inequivalent framework T
42
In summary, we have developed a facile, oneꢀstep synthesis
method to obtain hierarchical ZnꢀZSMꢀ11 with oliveꢀshaped
sites corresponding to Si(0Al) groupings (ꢀ112 and ꢀ116 ppm)
41, 43, 44
and Si(1Al) groupings (ꢀ107 and ꢀ103ppm), respectively,
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intergrowth morphology and superior catalytic properties from
the ZnOꢀcontaining gel mixture. For comparison, Zn containing
3. H. Chen, Y. Yan, Y. Shao and H. Zhang, RSC Adv., 2014, 4, 55202ꢀ
55209.
ZSMꢀ11 samples were also prepared by direct synthesis method 60 4. O. A. Anunziata, J. Cussa and A. R. Beltramone, Catal. Today, 2011,
of using ZnSO4 or ZnOꢀimpregnatedꢀseed as zinc source and
impregnation method. The XRD patterns and IR spectra shows
that all the Zn containing samples possess pure ZSMꢀ11 phase
and high crystallinity. Besides, all the samples obtained from the
direct synthesis method exhibit the similar intergrowth
morphology to the extraneous seeds, which can be ascribed to the
scaffold effect of TBABr. Nevertheless, the samples Z11ꢀZn[O],
Z11ꢀZn[S] and Z11ꢀZn[PreO] exhibit obvious distinctive particle
shape from the ZSMꢀ11, indicating Zn species have been
incorporated into the zeolite framework in the crystallization
process and the incorporation amount follows the order of Z11ꢀ
171, 36ꢀ42.
5
0
5
0
5
0
5
5
6
7
.
.
.
A. Hagen and F. Roessner, Catal. Rev., 2000, 42, 403ꢀ437.
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8. M. Shelef, Chem. Rev., 1995, 95, 209ꢀ225.
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.
M. Y. Kustova, A. Kustov, S. E. Christiansen, K. T. Leth, S. B.
1
1
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Rasmussen and C. H. Christensen, Catal. Commun., 2006, 7, 705ꢀ
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08.
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0. M. Y. Kustova, S. B. Rasmussen, A. Kustov and C. H. Christensen,
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29
11. P. Xie, Z. Ma, H. Zhou, C. Huang, Y. Yue, W. Shen, H. Xu, W. Hua
Zn[S] > Z11ꢀZn[O] > Z11ꢀZn[PreO]. The TEM images and Si
MAS NMR spectra further verify the fact that Zn species can be
well incorporated into the ZSMꢀ11 framework by ZnO and
and Z. Gao, Microporous Mesoporous Mater., 2014, 191, 112ꢀ117.
1
1
2. Y. Meng, H. C. Genuino, C.ꢀH. Kuo, H. Huang, S.ꢀY. Chen, L.
Zhang, A. Rossi and S. L. Suib, J. Am. Chem. Soc., 2013, 135, 8594ꢀ
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ZnSO method, while only a small amount of Zn species can be
4
incorporated into zeolitc framework by ZnOꢀimpregnated seed
2
9
3. B. Li, B. Sun, X. Qian, W. Li, Z. Wu, Z. Sun, M. Qiao, M. Duke and
D. Zhao, J. Am. Chem. Soc., 2013, 135, 1181ꢀ1184.
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that Zn species in the zeolite framework has an important impact
the coordination of Si species. The textural properties determined
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by N adsorptionꢀdesorption experiment shows that the sample
2
Z11ꢀZn[O] prepared by ZnO method possesses both micropores 80 15. L. Yu, S. Huang, S. Zhang, Z. Liu, W. Xin, S. Xie and L. Xu, ACS
and mesopores, further resulting in its good methanol converse
activity. By tracking the crystallization process, it is found that
the ZnO could be gradually dissolved under the severely alkaline
environment and subsequently incorporated into the ZSMꢀ11
framework during the crystallization process. However, in the
ZnOꢀimpregnated seeded system, the ZnO cannot be well
incorporated in zeolite framework as a result of its interaction
with seeds. This work provides a very simple route to synthesize
ZnꢀZSMꢀ11 with good catalytic performance and this strategy
can also be extended to prepare other Zn containing zeolites for
reactions needing the Zn active sites and zeolite pore structures
simultaneously.
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Acknowledgements
2
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Graphic abstract for
One-step synthesis, characterization and catalytic performance of
hierarchical Zn-ZSM-11 via facile ZnO routes
a,b
b
a
a
Qingjun Yu , Chunyi Li* , Xiaolong Tang* and Honghong Yi
a
Department of Environmental Engineering, Civil and Environmental Engineering
School, University of Science and Technology Beijing, Beijing 100083,China;
b
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East
China), Qingdao 266555, China
Corresponding author Fax: +86 532 86981787; Tel: +86 532 86981862; E-mail:
chyli_upc@126.com; txiaolong@126.com
Hierarchical Zn-ZSM-11 with an olive-shaped intergrowth morphology was
synthesized via a novel and facile one-step hydrothermal method.