Solvent-free syntheses of hierarchically porous aluminophosphate-based zeolites with AEL and AFI structures

Article abstract of DOI:10.1002/chem.201403890

Development of sustainable routes for synthesizing aluminophosphate-based zeolites are very important because of their wide applications. As a typical sustainable route, solvent-free synthesis of zeolites not only decreases polluted wastes but also increa

Full text of DOI:10.1002/chem.201403890

DOI: 10.1002/chem.201403890
Full Paper
&
Zeolite Synthesis
Solvent-Free Syntheses of Hierarchically Porous
Aluminophosphate-Based Zeolites with AEL and AFI Structures
Yinying Jin,[a, b] Xian Chen,[a] Qi Sun,[a] Na Sheng,[a] Yan Liu,[a] Chaoqun Bian,[a] Fang Chen,[a]
Xiangju Meng,*[a] and Feng-Shou Xiao*[a]
Abstract: Development of sustainable routes for synthesiz-
ing aluminophosphate-based zeolites are very important be-
cause of their wide applications. As a typical sustainable
route, solvent-free synthesis of zeolites not only decreases
polluted wastes but also increases product yields. Systematic
solvent-free syntheses of hierarchically porous aluminophos-
phate-based zeolites with AEL and AFI structures is present-
ed. XRD patterns and SEM images show that these samples
have high crystallinity. N2 sorption isotherm tests show that
these samples are hierarchically porous, and their surface
areas are comparable with those of corresponding zeolites
from hydrothermal route. Chosen as an example, catalytic
oxidation of ethylbenzene with O2 shows that cobalt substi-
tuted APO-11 from the solvent-free route (S-CoAPO-11) is
more active than conventional CoAPO-11 from hydrothermal
route owing to the sample hierarchical porosity.
Introduction
Notably, the syntheses of aluminophophate-based zeolites
usually require the presence of solvents such as water and al-
cohols.[1–8] The use of these solvents normally produces wastes,
reduces synthesis efficiency, and generates high pressure.[3a] To
solve these problems, great efforts have been devoted. For ex-
ample, Bandyopadhyay et al. reported the synthesis of APO-11
and APO-5 aluminophosphate zeolites from dry gel conversion
(DGC),[8] which could greatly increase the synthesis efficiency,
but the process was time-consuming and energy-intensive.
Morris et al. developed an ionothermal route for the synthesis
of aluminophosphate zeolites such as APO-11, and later, Tian
et al. reported the synthesis of APO-5 in the same way.[9] This
route could effectively eliminate the high pressure, but its rela-
tively high cost and slight solubility of silicon limit this method
for wide applications.
Since the discovery of a new family of microporous crystalline
aluminophosphate-based zeolites in the early of 1980s,[1] they
have been paid much attention owing to the variety of struc-
ture types and framework composition as well as their applica-
tions in catalysis, adsorption, and separation.[2] As a typical ex-
ample of this family, APO-11 with AEL-type structure, having
one-dimensional 10 membered rings (10MR) of approximately
0.65ꢀ0.40 nm, has been extensively studied not only because
of its advantages such as excellent hydrothermal and thermal
stabilities, but also of its easy substitution of tetrahedral frame-
work with a wide range of non-metal and metal ions.[3] The in-
corporation of silicon into the framework of APO-11 results in
the formation of SAPO-11, which is an industrial catalyst for hy-
droisomerization of long-chain alkanes owing to the weakly
acidic strength and suitable pore size.[4] The incorporation of
metals into the frameworks results in the formation of MAPO-
11s, which has been used as effective catalysts for selective oxi-
dations.[5] APO-5 zeolite with AFI-type structure, having one-di-
mensional 12 MR channels and its heteroatom-substituted
structures, also exhibit good properties in catalysis and
adsorption.[6,7]
Recently, Xiao et al. reported a solvent-free synthesis with
advantages of reducing the waste production and increasing
zeolite yield as well as eliminating high pressure.[10] More re-
cently, we briefly showed a preliminary work of silicoalumino-
phosphate SAPO-34 zeolite from the solvent-free route. We re-
ported the details for synthesizing aluminophosphates with
AEL and AFI structures and their frameworks substituted with
heteroatoms of Si, Co, and Mg under solvent-free conditions.[11]
The samples obtained exhibit comparable properties to those
of the samples obtained from conventional hydrothermal
route. Particularly, these aluminophosphate-based zeolites syn-
thesized from the solvent-free route are hierarchically porous,
which is very favorable for improving catalytic properties.
[a] Y. Jin, X. Chen, Q. Sun, N. Sheng, Dr. Y. Liu, C. Bian, F. Chen, Dr. X. Meng,
Prof. F.-S. Xiao
Department of Chemistry, Zhejiang University
Hangzhou 310028 (P. R. China)
E-mail: mengxj@zju.edu.cn
fsxiao@zju.edu.cn
[b] Y. Jin
Department of Analytical Chemistry, Shaoxing University
Shaoxing 312000 (P. R. China)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201403890.
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Results and Discussion
Aluminophosphate zeolite with AEL structure (APO-11)
As a typical example of aluminophosphate zeolites, the sol-
vent-free synthesis of APO-11 was performed by grinding at
room temperature and heating at 2008C for solid compounds
of di-n-propylamine phosphate (DPA·H3PO4) and boehmite.
This sample was designated as S-APO-11. Figure 1 shows the
sample XRD pattern, N2 sorption isotherms, SEM and TEM
image. The sample XRD pattern exhibits well-resolved peaks in
the range of 5–408 (Figure 1A), which is in good agreement
with those of the AEL zeolite structure.[12] After calcined at
6008C for 4 h, the sample N2 sorption isotherms exhibit
a steep increase in the curve at a relative pressure of 10ꢀ6 <P/
P0 <0.01, which is due to the filling of micropores.[3a] Mean-
while, at a relative pressure of 0.45–0.95, a hysteresis loop can
be observed, suggesting the presence of mesoporosity and
macroporosity in the sample.[13] Accordingly, BET surface area,
pore volume, and BJH pore size distribution are estimated at
212 m2 gꢀ1, 0.16 cm3 gꢀ1, and about 5 nm, respectively (Table 1).
Table 1. Composition and textural parameters for AEL zeolites synthe-
sized in the absence of solvent.
Samples
Al/P/M
(M=Si,Co,Mn)[a]
BET surface area
[m2gꢀ1
Pore volume
[cm3gꢀ1
]
]
S-APO-11
49.9/50.1/—
46.0/45.4/8.6
43.8/52.6/3.6
44.9/51.7/3.4
212
198
175
168
0.16
0.18
0.14
0.16
S-SAPO-11
S-CoAPO-11
S-MnAPO-11
[a] determined by ICP.
SEM microscopy shows that the sample with particle sizes at
1–3 mm aggregated with small particles (200-800 nm, Fig-
ure 1C), which could contribute to the formation of macro-
porosity in the sample. Furthermore, the sample TEM image
clearly shows the presence of mesoporosity and macroporosity
(Figure 1D). These results are consistent with those in the N2
sorption isotherm test (Figure 1B).
Figure 2 shows XRD patterns of S-APO-11 samples during
the crystallization at 2008C. Before the crystallization, the
sample gives five peaks (7.958, 13.808, 21.198, 24.018, and
24.228; Figure 2a) associated with the solid compound of
DPA·H3PO4. After treatment at 2008C for 3 h, the peaks of
DPA·H3PO4 become weak (Figure 2b), at the same time a peak
at 6.658 appears, which is related to the interaction between
the DPA·H3PO4 with Al species. Heating at 2008C over 6 h, typi-
cal peaks assigned to AEL structure appear (Figure 2c,d). With
decreasing of the peak at 6.658, the peaks of AEL structure sig-
nificantly increase. A further increase in crystallization time to
12 h, the peak at 6.658 completely disappears (Figure 2 f).
These results suggest that the AEL structure might be trans-
formed from the intermediate at 6.658. The structure of this in-
termediate is under investigation. When the crystallization
time is over 24 h, there is no obvious change in the XRD pat-
Figure 1. A) XRD pattern, B) N2 sorption isotherms, C) SEM image, and
D) TEM image of an S-APO-11 sample. Inset in (C): Enlargement.
terns (Figure 2 h,i), indicates that the crystallization of S-APO-
11 is almost finished at the crystallization time of 24 h.
In the solvent-free synthesis of S-APO-11, the ratio of
DPA·H3PO4 to Al2O3 plays an important role. XRD patterns of S-
APO-11 samples crystallized at various ratios of DPA·H3PO4 to
Al2O3 are shown in the Supporting Information, Figure S1.
When the ratios are lower than 1.4, there is amorphous phase;
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Figure 2. XRD patterns of S-APO-11 samples crystallized at a) 0, b) 3, c) 6,
d) 7, e) 9, f) 12, g) 15, h) 24, and i) 36 h.
when the ratios are higher than 1.8, there are impurities such
as APO-T; when the ratio reaches to 2.2, it is obtained a pure
phase of APO-T. The suitable DPA·H3PO4/Al2O3 ratio should be
about 1.6. In this case, pure AEL structure with high crystallini-
ty is obtained.
It is worth mentioning that the use of DPA·H3PO4 is very im-
portant for the solvent-free synthesis of aluminophosphate-
based zeolites. The DPA·H3PO4 offers both organic templates
and phosphorus source as well as avoidance of amine volatili-
zation in the synthesis.
Heteroatom-substituted APO-11 zeolites
Figure 3. A) XRD pattern, B) N2 sorption isotherms, and C) SEM image of an
S-SAPO-11 sample. Inset: Enlargement.
Solvent-free synthesis of silicon-substituted APO-11 was per-
formed by grinding at room temperature and heating at
2008C for 24 h. This sample was designated as S-SAPO-11.
Figure 3 shows an XRD pattern, N2 sorption isotherms, and
SEM image of S-SAPO-11 zeolite. The XRD pattern shows that
as-synthesized sample has good crystallization with AEL struc-
ture. After calcination at 6008C for 4 h, the N2 sorption iso-
therms of calcined S-SAPO-11 samples exhibits a steep increase
in the curve at a relative pressure of 10ꢀ6 <P/P0 <0.01 and
a hysteresis loop at a relative pressure of 0.85–1.0. The pres-
ence of this loop might be related to the macroporosity
formed between intercrystals.[12] The sample BET surface area
Figure 4 shows 27Al, 31P, and 29Si MAS NMR spectra of as-syn-
thesized and calcined S-SAPO-11 samples. The 27Al MAS NMR
spectrum of as-synthesized S-SAPO-11 (Figure 4A, top) exhibits
two peaks at 48.3 and 18.5 ppm. The peak at 48.3 ppm is as-
signed to four-coordinate Al species in the zeolite frame-
work,[14] and the peak at 18.5 ppm might be attributed to five-
coordinate Al species resulted from the coordination of tetra-
hedral Al sites with organic templates.[15] After calcination, the
peak at 51.3 ppm is dominant with a shoulder peak at 41.6,
both assigned to four-coordinate Al species. The new peak at
ꢀ5.4 ppm that is due to six-coordinate Al species appears,
which is associated with the interaction between the four-co-
ordinate Al species and water molecules (Figure 4A, bottom).
This phenomenon is interpreted by that the sample calcination
eliminates the coordination of tetrahedral Al species with or-
ganic templates, allowing the interaction between the Al spe-
cies with water to occur. Notably, as-synthesized S-SAPO-11
has much stronger 18.5 ppm peak intensity than conventional
SAPO-11 synthesized from hydrothermal route,[16] suggesting
that the interaction of Al species with organic templates in S-
and pore volume are estimated at 198 m2 gꢀ1 and 0.18 cm3 gꢀ1
,
respectively (Table 1). The sample SEM image shows that the
particles are in the range of 1–10 mm, which are formed by ag-
gregation of smaller crystals of 0.1–0.5 mm.
In the solvent-free synthesis of S-SAPO-11, the ratios of both
DPA·H3PO4/Al2O3 and SiO2/Al2O3 strongly influence the sample
crystallinity. When DPA·H3PO4/Al2O3 ratios are 1.4–1.6 (Support-
ing Information, Figure S2) and SiO2/Al2O3 ratios lower than 0.2
(Supporting Information, Figure S3), the samples give pure AEL
structure with high crystallinity.
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Figure 4. A) 27Al, B) 31P, and C) 29Si NMR spectra of (top) as-synthesized and
(bottom) calcined S-SAPO-11 samples (? sideband).
Figure 5. A) XRD patterns, B) N2 sorption isotherms, C),D) SEM images of
a) S-CoAPO-11 and b) S-MnAPO-11 samples (The isotherms for sample b are
offset vertically by 100 cm3gꢀ1). Inset: Enlargement.
SAPO-11 is much stronger than that in conventional SAPO-11,
which may be favorable for filling organic templates in the
zeolite framework.
31P NMR spectrum of as-synthesized S-SAPO-11 (Figure 4B, 11 and S-MnAPO-11).The XRD patterns indicate that these sam-
top) exhibits two strong peaks at ꢀ31.6 ppm and ꢀ27.6 ppm, ples have high crystallinity with pure phase. Figure 5B shows
which are assigned to four-coordinate P species in the zeolite N2 sorption isotherms of calcined S-CoAPO-11 and S-MnAPO-11
framework.[17] After calcination, the sample gives peaks at samples, and their textural parameters are presented in
ꢀ29.5 ppm and ꢀ24.1 ppm. The peaks are obviously shifted to Table 1. Notably, both S-CoAPO-11 and S-MnAPO-11 samples
lower, which is explained by the interaction between the four- show a steep increase occurring in the curve at a relative pres-
coordinate
bottom).[17,18]
P
species and water molecules (Figure 4B, sure less than 0.01, which is due to the filling of micropores.
Furthermore, at a relative pressure of 0.50–0.95, they appear as
The 29Si MAS NMR spectrum of as-synthesized S-SAPO-11 hysteresis loops, suggesting their hierarchical porosity in the
(Figure 4C, top) shows a major peak at ꢀ95.8 ppm attributed samples (Figure 5B). Their BET surface areas (175 and
to Si(3Al) species.[19] After calcination, the calcined sample 168 m2gꢀ1) are a little lower than that of S-APO-11, which is
shows obvious peak at 90.1 ppm associated with Si(4Al) spe- due to the substitution of the heavy heteroatom in the frame-
cies.[19] These results suggest that Si species mainly substitute work of AEL structure. Figure 5C,D shows SEM images of S-
P atoms in the framework of the sample.[20]
CoAPO-11 and S-MnAPO-11. Both samples are aggregated with
Figure 5A shows XRD patterns of cobalt- and manganese- smaller crystals (0.5-2 mm for S-CoAPO-11 and 0.2-3 mm for S-
substituted AEL zeolites from solvent-free synthesis (S-CoAPO- MnAPO-11).
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Table 2. Catalytic properties for S-CoAPO-11 and C-CoAPO-11 samples in
ethylbenzene oxidation.
Catalyst[a]
Conversion
[%]
Selectivity
[%]
aceto-
phenone
phenyl-
ethanol
benz-
aldehyde
S-CoAPO-11
C-CoAPO-11
14.8
8.3
77.9
48.6
9.7
16.8
12.4
34.6
[a] 2.00 g of ethylbenzene, 0.05 g of catalyst, 0.05 g of tert-butyl hydro-
peroxide solution, 3.0 MPa, 1408C, 4 h.
Aluminophosphate zeolite with AFI structure (APO-5)
The solvent-free synthesis of APO-5 was performed by grinding
at room temperature and heating at 2008C for solid com-
pounds of di-n-propylamine phosphate (DPA·H3PO4), tetraethy-
lammonium bromide (TEABr), and boehmite. Figure 7 shows
an XRD pattern, N2 sorption isotherms, and SEM image of S-
Figure 6. UV/Vis spectra of A) Co- and B) Mn-substituted a) as-synthesized
and b) calcined S-MAPO-11 samples (M=Co or Mn).
Figure 6 shows UV/Vis spectra of S-MAPO-11 samples (M=
Co and Mn). The absorption bands for as-synthesized S-
CoAPO-11 are typical for a perfect tetrahedron [CoO4] with one
triplet centered at 580 nm (Figure 6A,a), which demonstrates
the incorporation of Co2+ in the framework.[21] After calcina-
tion, a fraction of the Co species in the framework is oxidized
to high-spin tetrahedral Co3+ with its characteristic and very
intense O!Co3+ charge transfer transitions at around 320 nm
and 400 nm (Figure 6A,b).[21,22] This transformation is also sup-
ported by low-temperature ESR spectra (Supporting Informa-
tion, Figure S4). After oxidation of ethylbenzene with molecular
oxygen, the sample has almost no change in the band, indicat-
ing a good stability of the cobalt species in the zeolite frame-
work (Supporting Information, Figure S5). As-synthesized S-
MnAPO-11 shows a strong band at 260 nm (Figure 6B,a) asso-
ciated with four-coordinate Mn2+ [23]
After calcination, a new
.
shoulder adsorption at 216 nm appears, which is due to the
presence of Mn3+ (Figure 6B,b).[24] These results suggest that
both as-synthesized and calcined samples have four-coordinate
heteroatoms.
It is well-known that transition metals such as Co species are
catalytically active for oxidation of hydrocarbons with molecu-
lar oxygen. Table 2 presents catalytic data in a model oxidation
of ethylbenzene with molecular oxygen over S-CoAPO-11 and
C-CoAPO-11 from the hydrothermal route (Supporting Infor-
mation, Figure S6), where both samples have similar cobalt
contents. The C-CoAPO-11 gives the conversion at 8.3% with
product selectivity for acetophenone at 48.6%. In contrast, the
S-CoAPO-11 exhibits the conversion at 14.8% with acetophe-
none selectivity at 77.9%. Obviously, the S-CoAPO-11 is more
active and selective than the C-CoAPO-11, which might relate
to the unique hierarchical porosity in the S-CoAPO-11. More
importantly, there is almost no cobalt leaching in the oxidation
(Supporting Information, Table S2). These results indicate that
the S-CoAPO-11 has excellent recyclability.
Figure 7. A) XRD pattern, B) N2 sorption isotherms, and C) SEM image of S-
APO-5 sample. Inset: enlargement.
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APO-5 zeolite. The sample XRD pattern indicates its good crys-
tallinity with high purity; the sample N2 sorption isotherms in-
dicate the hierarchical porosity in the S-APO-5; the sample
SEM image indicates the aggregative crystals. The BET surface
area, pore volume, and BJH pore size distribution are
217 m2 gꢀ1, 0.18 cm3 gꢀ1, and 10 nm, respectively.
ratios of DPA·H3PO4/Al2O3 are 1.4–1.8, the ratios of TEABr/Al2O3
are 0.1–0.4, and the ratios of SiO2/Al2O3 are 0.4–1.0, pure S-
SAPO-5 with high crystallinity was finally obtained.
Figure 9 shows XRD patterns and SEM images of S-SAPO-5
samples crystallized at various times. After heating at 2008C
for 1 h, the sample becomes amorphous because of disappear-
ance of the XRD peaks (Figure 9A,b). Heating at 2008C for
1.5 h results in appearance of a series of weak peaks associated
It is notable that two templates including both DPA·H3PO4
and TEABr have been used in the synthesis of S-APO-5. If there
is only one template in the synthesis, we cannot obtain the S-
APO-5. Clearly, the templation of S-APO-5 require a synergistic
effect of DPA·H3PO4 and TEABr. The details are under
investigation.
Heteroatom-substituted APO-5 zeolite
Figure 8 shows XRD pattern, N2 sorption isotherms, and SEM
image of S-SAPO-5. The sample XRD pattern shows strong
peaks related to the AFI structure; the sample N2 sorption iso-
therms indicate the hierarchical porosity; the sample SEM
image gives spherical crystals at 3-5 mm. The sample BET sur-
face area and pore volume are 250 m2 gꢀ1 and 0.17 cm3 gꢀ1
.
As presented in the Supporting Information, Table S1, the
ratios of DPA·H3PO4/Al2O3, TEABr/Al2O3, and SiO2/Al2O3 are
strongly dependent on the crystallinity and purity. When the
Figure 9. A) XRD patterns and B) SEM images of the samples: a) uncrystal-
lized, b)–g) crystallized at b) 1, c) 1.5, d) 2, e) 3, f) 12, and g) 24 h for synthe-
sizing the S-SAPO-5 sample.
with AFI structure. At the same time, crystals are observed in
the sample (Figure 9B,c). These results indicate that a small
amount of SAPO-5 crystals have been formed already. Increas-
ing the crystallization time to 3 h, the sample peak intensities
increase significantly (Figure 9A,e). A further increase of crystal-
lization time to 12 h, results in disappearance of amorphous
phase (Figure 9B,f), indicating full crystallization of the sample
(Figure 9A,f). When the crystallization time is over after 12 h,
there is no obvious change in the XRD pattern (Figure 9A,g),
indicating that the crystallization of S-SAPO-5 is almost finished
and that the crystallization of S-SAPO-5 zeolite results from the
solid phase transformation.
Figure 10 shows XRD patterns and SEM images of cobalt-
and manganese-substituted AFI zeolites (S-CoAPO-5 and S-
MnAPO-5). The XRD patterns indicate that they have high crys-
tallinity and purity (Figure 10A), and the SEM images show
Figure 8. A) XRD pattern, B) N2 sorption isotherms, and C) SEM image of S-
SAPO-5 sample. Inset: enlargement.
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thesis. More interestingly, the sample hierarchical porosity is
formed in the absence of any mesoscale organic templates.
Normally, the formation of the hierarchical porosity in the sam-
ples should be created by the mesoscale templates, as report-
ed recently.[25] The combination of simple process, high yields,
and hierarchical porosity in the solvent-free synthesis, would
offer a good opportunity for synthesizing various zeolites in
the future.
Acknowledgements
We thank the Steady High Magnetic Field Facility (SHMFF), one
of the large-scale scientific facilities in Hefei for ESR measure-
ment. This work is supported by the Natural National Science
Foundation of China (21422306, 21333009, and 21203165), Na-
tional High-Tech Research and Development program of China
(2013AA065301), Science and Technology Innovative Team of
Zhejiang Province (No. 2012R10014-02), and Fundamental Re-
search Funds for the Central Universities (2013XZZX001).
Keywords: AEL structure · aluminophosphate zeolites · APO-
11 · heteroatom substitution · solvent-free synthesis
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their irregular morphology of the crystals (Figure 10B,C). UV/
Vis spectra of S-CoAPO-5 and S-MnAPO-5 (Supporting Informa-
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Conclusion
Aluminophosphate zeolites with AEL and AFI structures and
their heteroatom-substituted analogues (Si, Co, and Mn) have
been successfully synthesized from the solvent-free route
through mechanically mixing of solid raw materials, followed
by heating in the closed vessel. Compared with the zeolites
synthesized from hydrothermal routes, they exhibit similar
crystallinity and textural parameters, but their syntheses are
simple and product yields are very high. In particular, the sol-
vent-free route results in the formation of hierarchical porosity
in the samples, which might be related to relatively fast crystal-
lization and slow diffusion of the solid materials. The formation
of the hierarchical porosity is very favorable for mass transfer
in catalysis, leading to a significant enhance of catalytic per-
formance. As expected, catalytic tests in oxidation of ethylben-
zene with molecular oxygen show that the hierarchically
porous S-CoAPO-11 is more active and selective than the con-
ventional CoAPO-11 synthesized from the hydrothermal syn-
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Received: June 10, 2014
Revised: August 13, 2014
Published online on && &&, 0000
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ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
FULL PAPER
Hierachically porous aluminophos-
phate-based zeolites with AEL and AFI
structures have been successfully syn-
thesized by a solvent-free route. Cataly-
sis tests in the oxidation of ethylben-
zene with molecular oxygen show that
S-CoAPO-11 is more active than conven-
tional CoAPO-11 from the hydrothermal
route.
&
Zeolite Synthesis
Y. Jin, X. Chen, Q. Sun, N. Sheng, Y. Liu,
C. Bian, F. Chen, X. Meng,* F.-S. Xiao*
&& – &&
Solvent-Free Syntheses of
Hierarchically Porous
Aluminophosphate-Based Zeolites
with AEL and AFI Structures
Chem. Eur. J. 2014, 20, 1 – 9
www.chemeurj.org
9
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ