Synthesis of aluminophosphate molecular sieve AlPO

4
-11
nanocrystals
Guangshan Zhu
a
, Shilun Qiu
a,
*
, Feifei Gao
a
, Gang Wu
a
, Runwei Wang
a
,
Binsong Li
a
, Qianrong Fang
a
, Yafeng Li
a
, Bo Gao
a
, Xianzhu Xu
a
,
Osamu Terasaki
b,
*
a
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, China
b
Department of Physics, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
Received 5 May 2000; received in revised form 12 August 2001; accepted 12 August 2001
Abstract
AlPO
4
-11 nanocrystals, 0:05 0:08 lm in size, were synthesized by optimizing the following chemical parameters:
the crystallization temperature and time, the H
2
O content, the molar ratio of phosphorus to organic template (P
2
O
5
/R),
and the HF content. The products were characterized by powder X-ray diraction and scanning electron microscope.
AlPO
4
-11 nanocrystals could not be obtained by optimizing only the crystallization temperature, time and the water
content, but obtained by optimizing the molar ratio of P
2
O
5
/R, the organic template, and the HF content. 2001
Elsevier Science B.V. All rights reserved.
Keywords: AlPO
4
-11; Nanocrystal; Synthesis; Aluminophosphate; Molecular sieve
1. Introduction
Due to the dierent diusion-path lengths, the
size of molecular sieve crystals can aect their
performance when used as catalysts, adsorbents,
ion exchangers and containers for guest molecule.
As a consequence, controlling the size of molecular
sieve crystals is desirable. Currently, there is an
increasing interest in using nanocrystalline-sized
molecular sieves for their catalytic applications
and potential as the precursors in the production
of the thin lms [1]. Using traditional hydrother-
mal crystallization techniques, only a few zeolite
nanocrystalline products have been synthesized
so far, viz. SOD [2], LTA, FAU [3,4], MFI [5],
LTL [6] and BEA [7], and there has been little
information on the synthesis of aluminophosphate
molecular sieves with nanocrystalline-sized dimen-
sions in the literature.
Currently, aluminum phosphate molecular
sieves are of growing importance. AlPO
4
-11 has
10-membered ring channels, 6:3 3:9

AA [8] in size,
and similar to those of medium pore zeolites. In
the AlPO
4
-11 framework, the substitution of sili-
con (SAPO-11) [9] and a number of divalent metal
Microporous and Mesoporous Materials 50 (2001) 129135
www.elsevier.com/locate/micromeso
*
Corresponding authors. Tel.: +81-22-217-6472; fax: +81-
22-217-6475 (O. Terasaki); Tel.: +86-431-516-6328; fax: +86-
431-567-1974 (S. Qiu).
E-mail addresses: sqiu@mail.jlu.edu.cn (S. Qiu), tera-
saki@msp.phys.tohoku.ac.jp (O. Terasaki).
1387-1811/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S1387- 1811( 01) 00431- 0
ions (MAPO-11) for phosphorus and aluminum,
respectively, produces acidic AlPO
4
-11 [10]. The
presence of these acid sites makes substituted
AlPO
4
-11 a good catalyst for aromatic reactions
such as the alkylation and disproportionation of
toluene, and the isomerization and dispropor-
tionation of styrenes, etc. [1012]. The present
paper reports the synthesis of nanocrystalline-sized
aluminophosphate molecular sieve (AlPO
4
-11),
and the inuence of various synthetic chemical
parameters on the crystal size and the character-
ization of the products.
2. Experimental
2.1. Synthesis
In the synthesis of AlPO
4
-11, pseudoboehmite
or aluminum tri-isopropoxide [Al(
i
PrO)
3
] and
phosphoric acid (H
3
PO
4
, 85 wt.%) were used as
aluminum and phosphorus sources, respectively.
Ammonia (25 wt.%), sodium hydroxide (99 wt.%)
and hydrochloric acid (36 wt.%) were used to ad-
just the pH value. Di-isopropylamine, di-propyl-
amine and di-butylamine were used as the organic
templates and, when necessary, aqueous hydrogen
uoride was added. The typical synthesis proce-
dure is as follows: (1) aluminum and phosphorus
sources were dissolved separately in distilled water;
(2) a phosphoric acid solution was added dropwise
to the aluminum solution, and the mixture was
allowed to age for 30 min at 90 C; (3) after so-
lution (2) was cooled to room temperature, it be-
came a viscous aluminophosphate gel, to which
the organic template was added; (4) ammonia,
sodium hydroxide solution or a hydrogen uoride
solution was slowly added, dropwise, to the ho-
mogeneous slurry to adjust the nal pH of the
reaction mixture; (5) having been stirred for
30 min, the nal reaction mixture was sealed in
Teon-lined autoclaves and heated at 160200 C
under autogenous pressure for 12 days. Any
solids, larger than 1 lm, were recovered by lter-
ing, washing and drying. With centrifugation at
20,000 rpm crystalline products less than 1 lm
were obtained. The solid samples were repeatedly
centrifuged for 1530 min, then dispersed in dis-
tilled water using ultrasonic to remove the re-
maining mother liquid, the procedure was repeated
until the pH of the dispersion was near 7. The
nanocrystalline products were obtained after they
were dried at 80 C for 4 h.
2.2. Characterization
Phases were identied on a Rigaku D/MAX
IIIA X-ray powder diractometer (XRD) with a
rotating target and Ni-ltered CuKa (k 1:5418

AA) radiation at room temperature. The crystal size

and morphology were investigated by a Hitachi
X-650B scanning electron microscope (SEM).
3. Results
3.1. Synthesis
3.1.1. Eect of the crystallization temperature and
time
The inuence of the crystallization temperature
and time on the average size of AlPO
4
-11 crys-
tal was investigated in the system 1.6i-Pr
2
NH:
1.3P
2
O
5
:1.1Al
2
O
3
:70H
2
O. In the synthesis of alu-
minophosphate molecular sieves AlPO
4
-n, the
molar ratio P
2
O
5
/Al
2
O
3
is usually 1 [13]. Accord-
ing to the experimental results of this work, it
is easy to obtain products with high crystallinity
if the molar ratio is higher than 1. As shown in
Table 1 (runs 1a1e), the range of the crystalliza-
tion temperature is from 160 to 200 C, and within
this range, low crystallization temperatures fa-
vor the formation of larger AlPO
4
-11 crystals. In
run 1b, at a crystallization temperature of 160 C,
15 20 lm AlPO
4
-11 crystals were obtained, but
in run 1d, at 200 C, 0:5 2 lm crystals were
obtained. When the crystallization temperature
was increased to over 200 C (run 1e), a dense
phase was precipitated. In the same system and at
200 C, the results obtained in runs 1f1j indicate
that average sizes of AlPO
4
-11 crystals did not
change much as the crystallization time was de-
creased. When the crystallization time was less
than 24 h, the reaction mixture remained a slurry
without crystallizing. It seems, therefore, that the
130 G. Zhu et al. / Microporous and Mesoporous Materials 50 (2001) 129135
crystallization time has little eect on the AlPO
4
-
11 crystal size.
3.1.2. Eect of the molar H
2
O content
Table 2 shows the inuence of the molar H
2
O
content on the AlPO
4
-11 crystal size. As shown in
runs 2a2c, when the reaction mixtures with the
composition 1.6i-Pr
2
NH:1.3P
2
O
5
:1.1Al
2
O
3
:xH
2
O
were crystallized at 200 C for 40 h, the average
crystal size increased from 0:2 0:7 to 0:3 2 lm
when the value of x(H
2
O) was changed from 35 to
70. When x was further increased to 175 and 200
(runs 2d, 2e), AlPO
4
-11 crystals were precipitated
with larger average crystal sizes of 1 4 and
2 9 lm, respectively. When x was 175 and 200
(runs 2f, 2g), at a crystallization temperature of
180 C, AlPO
4
-11 products were obtained with
average crystal sizes of 2 5 and 3 10 lm, re-
spectively.
3.1.3. Eect of the molar ratio of P
2
O
5
/R
The molar P
2
O
5
/R ratio aects the pH value of
the nal reaction mixture (Table 3). The range
of pH suitable for the crystallization was from
5 to 9, and for values higher than 9 or lower than
5,no AlPO
4
-11 crystals were obtained. At a pH
6.5 (run 3a), the size of the produced crystals was
0:3 1 lm. When the pH of the nal reaction
mixture was increased to 8 by adding ammonia or
sodium hydroxide solution (run 3a
0
), or reduced
to 5.5 by adding hydrochloric acid (run 3a
00
),
the size of the produced crystals was 0:3 1 and
0:5 1:2 lm, respectively. When the pH of the
nal reaction mixture was increased to 7.5 and 8.0
by reducing the P
2
O
5
/R molar ratio (runs 3c, 3b),
the precipitated crystals were 1 5 and 10
15 lm in size, respectively. When the pH of the
nal reaction mixture was reduced to 5.5 by in-
creasing the P
2
O
5
/R molar ratio (runs 3d3f), the
size of the product crystals was reduced to
0:05 0:08 lm. When di-butylamine (runs 3g, 3h)
or di-propylamine (runs 3i, 3j) was used instead of
di-isopropylamine as the organic template, under
the same synthesis conditions as those of 3f and 3c,
the size of the produced crystals was 0:5 1:2 and
0:05 0:08, and 0:3 0:8 and 0:5 1:2 lm, re-
spectively.
Table 1
The eects of the crystallization temperature and time on the
average size of AlPO
4
-11 crystals
No. Tempera-
ture (C)
Time
(h)
Average crys-
tal size (lm)
Phase
1a 140 40 Gel
1b 160 40 15 20 AlPO
4
-11
1c 180 40 0:8 5 AlPO
4
-11
1d 200 40 0:5 2 AlPO
4
-11
1e 240 27 Dense
phase
1f 200 48 0:5 3 AlPO
4
-11
1g 200 40 0:5 2 AlPO
4
-11
1h 200 35 0:3 2 AlPO
4
-11
1i 200 30 0:3 2 AlPO
4
-11
1j 200 27 0:3 1 AlPO
4
-11
Table 2
The eect of the H
2
O content on the average size of AlPO
4
-11
crystals with the gel composition 1.6i-Pr
2
NH:1.3P
2
O
5
:1.1Al
2
O
3
:
xH
2
O
No. x(H
2
O) Tempera-
ture (C)
Time (h) Average crys-
tal size (lm)
2a 35 200 40 0:2 0:7
2b 60 200 40 0:4 1
2c 70 200 40 0:3 2
2d 175 200 40 1 4
2e 200 200 40 3 9
2f 175 180 40 2 5
2g 200 180 40 3 10
Table 3
The eects of molar P
2
O
5
/R ratio and the templates on the
average size of AlPO
4
-11 crystals with the gel composition
xP
2
O
5
:yR:1.1Al
2
O
3
:70H
2
O at 200 C
No. x(P
2
O
5
) y(R) pH Average crystal
size (lm)
3a 1.3 1.6
a
6.5 0:3 1
3a
0
1.3 1.6
a
8.0 0:3 1
3a
00
1.3 1.6
a
5.5 0:5 1:2
3b 1.14 2.2
a
8.0 10 15
3c 1.3 2.0
a
7.5 1 5
3d 1.3 1.2
a
6.0 0:8 4
3e 1.5 1.6
a
6.0 0:1 0:5
3f 1.73 1.6
a
5.5 0:05 0:08
3g 1.73 1.6
b
5.5 0:5 1:2
3h 1.3 2.0
b
7.5 0:05 0:08
3i 1.73 1.6
c
5.5 0:3 0:8
3j 1.3 2.0
c
7.5 0:5 1:2
a
R i-Pr
2
NH.
b
R Bu
2
NH.
c
Pr
2
NH.
G. Zhu et al. / Microporous and Mesoporous Materials 50 (2001) 129135 131
3.1.4. Eect of the HF content
In the reaction mixture with the composi-
tion 1.6i-Pr
2
NH:1.3P
2
O
5
:1.1Al
2
O
3
:70H
2
O:xHF (see
Table 4), the average crystal size was increased
from 0:3 0:8 to 2 10 lm at 200 C when the
molar ratio of HF x increased from 0.1 to 0.5
(runs 4a4c). However, when x was further in-
creased to 0.8 and 1.2 (runs 4d, 4e), the size was
reduced to 0:1 0:5 lm. When the amount of HF
was increased to 3, only an aluminophosphate
dense phase was precipitated. Under the same
synthesis conditions as run 4d and at the crystal-
lization temperature of 160 C (4d
0
), nanocrystals,
0:05 0:08 lm in size, were precipitated.
3.1.5. Characterization
Fig. 1 shows the XRD patterns of the as-syn-
thesized AlPO
4
-11 samples from runs 1b (a) and
4d
0
(b). Both patterns show a pure AlPO
4
-11 phase
though some peak broadening was observed for
pattern (b).
Fig. 2 shows the SEM micrographs of the as-
synthesized AlPO
4
-11 samples with average crystal
sizes of 15 20 (a), 10 15 (b), 3 10 (c), 2 5
(d), 0:3 1 (e) and 0:05 0:08 lm (f), obtained
from runs 1b, 3b, 2g, 2f, 3a and 4d
0
, respectively,
which indicates a reduction in size from 20 to 0.08
lm in the length with all the crystals having a
single uniform morphology and narrow particle
size distribution.
4. Discussion
An ecient procedure for the synthesis of na-
nometer-sized crystals of AlPO
4
-11 was found by
studying, systematically, the factors aecting the
crystallization process, including synthesis tem-
perature and time, the molar ratios of H
2
O, P
2
O
5
/
R, HF and the nature of the templates. Before the
crystallization, the aging of the initial reaction
mixture for 30 min at 90 C is necessary, otherwise
a broad size distribution and other phases appear
because organic templates like di-propylamine can
be used to synthesize other aluminophosphate
molecular sieves [13,14]. Aging the reaction mix-
ture to become homogeneous, which is benecial
to narrow the particle size distribution [6,15,16].
In order to obtain small and uniform AlPO
4
-11
crystals, the water content is minimized (run 2a),
which causes the higher supersaturation and pro-
motes the nucleation rate and competition for the
available chemical nutrients. The reaction tem-
perature is maximized (run 1d) as this promotes
the rapid formation of nuclei and consumption
of chemical nutrients. However, it should be em-
phasized that nanometer-sized AlPO
4
-11 crystals
cannot be obtained only by optimizing the water
content and the reaction temperature. Optimizing
Table 4
The inuence of the presence of HF on the average size of
AlPO
4
-11 crystals with the gel composition of 1.6i-Pr
2
NH:
1.3P
2
O
5
:1.1Al
2
O
3
:70H
2
O:xHF
No. x(HF) Tempera-
ture (C)
Time (h) Average crys-
tal size (lm)
4a 0.1 200 24 0:3 0:8
4b 0.3 200 24 0:5 1:2
4c 0.5 200 24 2 10
4d 0.8 200 24 0:8 2
4d
0
0.8 160 24 0:05 0:8
4e 1.2 200 24 0:1 0:5
4f 3.0 200 24 Dense phase
Fig. 1. XRD patterns of as-synthesized AlPO
4
-11 in (a) run 1b
and (b) run 4d
0
.
132 G. Zhu et al. / Microporous and Mesoporous Materials 50 (2001) 129135
the molar ratio of P
2
O
5
/R, selecting a proper or-
ganic template, and adding a proper amount of
HF also play crucial roles in the formation of
nanometer-sized AlPO
4
-11 crystals.
The proper pH range for synthesizing pure
AlPO
4
-11 is 59, which can be adjusted by adding
ammonia or sodium hydroxide solution, or hy-
drochloric acid, however, the average size of the
product crystals changes slightly (run 3a3a
00
).
Changing the molar ratio of P
2
O
5
/R in the nal
reaction mixture can also make the pH value
varied. For example, when the molar ratio of
P
2
O
5
/R was increased from 0.52 to 1.08 (runs 3b
3f), the pH changed from 8 to 5.5. At the same
time, the sizes of the crystals were decreased from
10 15 to 0:05 0:08 lm. Accordingly, the molar
ratio of P
2
O
5
/R (R: di-isopropylamine) in the re-
action mixture is one of the key roles which aect
the average size of the nal products.
When di-butylamine was used instead of di-
isopropylamine as the organic template, under the
high P
2
O
5
/R molar ratio (run 3g) and the same
conditions as those of run 3f, which results in the
formation of nanocrystalline products, crystals
with 0:5 1:2 lm in size were precipitated. With a
low P
2
O
5
/R molar ratio (run 3h) and the same
conditions as those of run 3c, which are the con-
ditions forming the products 1 5 lm in size,
nanocrystalline products, 0:05 0:08 lm in size,
were precipitated. When di-propylamine was used
as the organic template, the average crystal size did
not change with high or low P
2
O
5
/R molar ratios
(runs 3i, 3j). This suggests that the nature of the
organic templates aects the average crystal size
in dierent ways, even under the same synthesis
conditions. In order to obtain nanocrystals, the
P
2
O
5
/R molar ratio must be optimized for one
kind of organic template.
Fig. 2. SEM photographs of as-synthesized AlPO
4
-11 with average crystal sizes of 15 20 (a), 10 15 (b), 3 10 (c), 2 5 (d), 0:3 1
(e) and 0:05 0:08 lm (f), obtained in runs 1b, 3b, 2g, 2f, 3a and 4d
0
, respectively.
G. Zhu et al. / Microporous and Mesoporous Materials 50 (2001) 129135 133
The synthesis of molecular sieves in the pres-
ence of HF, rst reported by Guth et al. [14], was
developed by Qiu et al. [17] for the preparation
of single crystals. It is believed that the reaction
species form a uoride complex, during the initial
stage of crystallization, which is then slowly hy-
drolyzed to form other less uorinated species
which slowly and continuously supply the chemi-
cal nutrients for the growth of single crystals.
For synthesizing AlPO
4
-11 (runs 4a4c), when the
molar ratio of HF in the reaction mixture was
below 0.5, the uoride ions formed the uoride
complexes AlF
3
6
and PF

6
with aluminate and
phosphate species present before crystallization.
Those complexes hydrolyzed to form less uori-
nated aluminate and phosphate species, supplying
chemical nutrients to promote the crystal growth.
Thus the nal AlPO
4
-11 crystal size increased with
increasing HF content. However, when a larger
amount of HF added (run 4d), the uoride com-
plexes were dicult to hydrolyze, which inhibited
further crystal growth and adding an excess of HF,
gave aluminophosphate dense phase (run 4f). By
changing only the molar ratio of HF in the reac-
tion mixture, the products with the maximum
and minimum average sizes of 2 10 and 0:1
0:5 lm were precipitated (runs 4c, 4e), respec-
tively, from the reaction mixture composition 1.6i-
Pr
2
NH:1.3P
2
O
5
:1.1Al
2
O
3
:70H
2
O:xHF at 200 C.
When another factor, crystallization tempera-
ture, was changed to 160 C (run 4d
0
), nanocrys-
tals as smaller as 0:05 0:08 lm were obtained in
the gel.
5. Conclusions
(1) Supersaturation in liquid reaction systems is
aected by some synthetic chemical parameters,
such as crystallization temperature and time, H
2
O
content, the molar ratio of P
2
O
5
/R and the nature
of organic template. Since the size of microporous
crystals appears to be controlled by the supersat-
uration of the liquid reaction system, crystals with
dierent average size can be synthesized by opti-
mizing synthetic parameters. AlPO
4
-11 crystals
with dierent average sizes from 0.05 to 20 lm
have been synthesized by changing the synthetic
parameters. It also notes that both the P
2
O
5
/R
ratio and the nature of the templates play key roles
in the synthesis of AlPO
4
-11 nanocrystalline par-
ticles.
(2) The presence of HF aects the average size
of AlPO
4
-11 nanocrystals. The crystals with the
average size from 0.5 to 10 lm can be obtained by
adjusting the HF content in the reaction mixture.
By optimizing other synthetic parameters, such as
crystallization temperature and the HF content,
nanocrystals, 0:05 0:08 lm in size, have been
obtained.
Acknowledgements
This work was supported by the National
Natural Science Foundation of China, the State
Basic Research Project (G2000077507), and
CREST, Japan Science and Technology Corpo-
ration (JST). We thank Dr. Frank Lincoln, Uni-
versity of Western Australia for critical reading
of the manuscript and for his helpful suggestions.
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