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Microporous and Mesoporous Materials 115 (2008) 332–337

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Synthesis of SAPO-34 with only Si(4Al) species: Effect of Si

contents on Si incorporation mechanism and Si coordination
environment of SAPO-34
Lei Xu a,b, Aiping Du a, Yingxu Wei a, Yingli Wang a,b, Zhengxi Yu a,b, Yanli He a,
Xinzhi Zhang a, Zhongmin Liu a,*
a
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, China

Received 12 December 2007; received in revised form 30 January 2008; accepted 2 February 2008
Available online 10 February 2008

Abstract

SAPO-34 molecular sieves with different Si coordination environment were synthesized by adjusting SiO2/Al2O3 molar ratio in start-
ing gel. The crystal structure, element composition and Si coordination environment of the as-synthesized samples were characterized by
XRD, SEM, XRF and NMR. SAPO-34 molecular sieve could be obtained when the SiO2/Al2O3 molar ratio of the starting gel was
higher than 0.075. The content and modeling of Si incorporated into SAPO-34 framework varied with the SiO2/Al2O3 molar ratios
in the starting gel and different Si chemical environments were formed correspondingly. SAPO-34 with only Si(4Al) coordination struc-
ture could be prepared when the SiO2/Al2O3 molar ratio of the starting gel was in range of 0.075–0.15.
Ó 2008 Elsevier Inc. All rights reserved.

Keywords: SAPO-34; Si incorporation mechanism; Si coordination environment

1. Introduction The acidity of SAPO molecular sieve is generated by the

surface bridge hydroxyl group, which originates from the
SAPO-34 molecular sieves, with 8-ring pore opening and protons for compensating the unbalanced electric charges
medium-strong acidity, showed excellent performance in due to Si incorporation into the neutral framework of
catalytic conversion of methanol to light olefins (MTO) AlPOs molecular sieve. Many researchers have studied
[1–3]. This provided a potential way for developing a com- the mechanism of Si incorporation into AlPOs framework
mercial MTO process to produce light olefins from coal or and the Si substitution mechanism is generally recognized
natural gas, as an alternative to the conventional oil route. in the crystallization process of SAPO molecular sieve
In the past two decades, MTO reaction over SAPO-34 [5,7–9]. First, AlPOs structure was formed, then Si atoms
catalyst has been an important topic in academic and was incorporated into the AlPOs framework by isomor-
industrial fields. The structure, acidity and catalytic perfor- phous substitution. It is a general rule that the linkage of
mance of SAPO-34 directly depend on the number and dis- the type Si–O–P is avoided. Thus, Si was incorporated into
tribution of Si in the framework [4–6], which is related AlPOs framework by two different substitution mecha-
closely to Si incorporation mechanism and coordination nisms: (1) SM2 substitution mechanism, the replacement
environment. of phosphorus by silicon; (2) SM3 substitution mechanism,
the double substitution of neighboring aluminum and
*
Corresponding author. Tel.: +86 411 84685510; fax: +86 411
phosphorus by two Si atoms [4]. Prakash proposed that
84379289. Si incorporation by the first mechanism formed Si(4Al)
E-mail address: liuzm@dicp.ac.cn (Z. Liu). structures when the SiO2/Al2O3 molar ratio was low in

1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.02.001
 L. Xu et al. / Microporous and Mesoporous Materials 115 (2008) 332–337 333

starting gel, while for a starting gel with increasing SiO2/ denoted as SP-0.025, SP-0.075, SP-0.10, SP-0.15, SP-0.20
Al2O3 molar ratio, Si(3Al), Si(2Al), Si(1Al) and Si(0Al) and SP-0.60, respectively.
structures were formed simultaneously by the second mech- X-ray power diffraction (XRD) patterns were recorded
anism [9]. It is recognized that the Si coordination struc- on a RIGAKU D/max-rb Diffractometer using Cu Ka
tures has significant effect on the acid intensity of SAPO radiation with nickel filter. SEM photographs were
molecular sieve, which was enhanced in the order of obtained on a KYKY-AMRAY-1000B scanning electron
Si(0Al) < Si(4Al) < Si(3Al) < Si(2Al) < Si(1Al) [10]. In our microscopy. X-ray fluorescence analysis (XRF) was per-
previous work [11], The results showed that Si atoms were formed on a Philips Magix-601 X-Ray Fluorescence Spec-
incorporated into the framework of as-synthesized SAPO- trometer. All NMR spectra were recorded at room
34 with higher Si content (SiO2/Al2O3 = 0.6) by two mech- temperature on a Bruker DRX-400 spectrometer with
anisms in different crystallization stages. In the earlier stage BBO MAS probehead using 4 mm ZrO2 rotors. The 31P
of the crystallization, Si, P and Al formed crystal nucleuses MAS NMR spectra with high-power proton decoupling
by the crystallization mechanism of direct participation, were performed at 161.9 MHz, using a 2.0 ls pulse, a 2 s
and only Si(4Al) species are found in the framework struc- repetition time, and 4096 scans. Spinning speed was
ture. In the growth period of the crystal grains, the remain- 8 kHz and chemical shift was referenced to 85% phosphoric
ing small amount of Si in the gel is incorporated into the acid which has a chemical shift of 0 ppm from TMS. The
29
framework to form Si-rich species by SM2 and SM3 substi- Si MAS NMR spectra with high power proton decou-
tution mechanisms and the amount of Si(4Al) increases pling were obtained at 79.49 MHz using a 0.8 ls pulse, a
slightly and Si(3Al), Si(2Al), Si(1Al) and Si(0Al) are 4 s repetition time, and 2000 scans. Spinning speed was
formed. This indicated that during the SAPO-34 crystalli- 4 kHz and chemical shift was referenced to 4,4-dimethyl-
zation, SM2 and SM3 substitutions take place simulta- 4-silapentane sulfonate sodium (DDS) which has a chemi-
neously until Si contents of SAPO-34 framework were up cal shift of 0 ppm from TMS.
to a threshold value.
These observations interested us to investigate the mech-
anism of Si incorporation into SAPO-34 as-synthesized 3. Results and discussion
with various Si content in the starting gel with a long crys-
tallization period. These investigations provide the possi- 3.1. Crystalline structure analysis
bility to adjust Si coordination structure by controlling Si
content in the starting gel. In the present work, SAPO-34 Fig. 1 presents XRD patterns of as-synthesized samples
molecular sieves with different Si coordination environ- of SP-0.025, SP-0.075, SP-0.10, SP-0.15, SP-0.20 and SP-
ments were synthesized by adjusting SiO2/Al2O3 molar 0.60, in which the sample codes correspond to the SiO2/
ratios of the starting gels. The mechanism of Si incorpora- Al2O3 molar ratios in the starting gel. It was found that
tion for forming different Si coordination environments SAPO-18 molecular sieve with AEI topological structure
was discussed. was formed when the SiO2/Al2O3 molar ratio of the start-
ing gel was the lowest (0.025) [12–16]. SAPO-34 molecular

2. Experimental

SAPO-34 was synthesized by a hydrothermal method

from a gel molar composition of 3.0R:1.0Al2O3:xSiO2:1.0-
P2O5:50H2O, where R is a templating agent and x is equal
to 0.025, 0.075, 0.10, 0.15, 0.20 and 0.60. Pseudoboehmite SP- 0.60
(72 wt% Al2O3), orthophosphoric acid (85 wt% H3PO4)
and silica sol (25 wt% SiO2) were used as the starting mate- SP- 0.20
rials to get aluminum, phosphorus and silicon, respectively.
The templating agent was triethylamine (TEA). Pseud- SP- 0.15
oboehmite was dissolved in deionized water to form alu-
mina sol, and then silica sol was added to the prepared SP- 0.10
alumina sol under stirring. Orthophosphoric acid was then
added slowly under continual stirring for 10 min. After SP- 0.075
that, triethylamine was added to the prepared mixture,
SP- 0.025
and stirred for 20 min until attaining a homogeneous gel
mixture. The gel mixture was sealed in 200 ml Teflon-lined
stainless steel pressure vessels and heated in an oven at 0 10 20 30 40 50
200 °C under autogenic pressure for 24 h. After crystalliza- 2 Theta
tion, as-synthesized samples were obtained after centrifugal Fig. 1. XRD patterns of the as-synthesized products from the starting gel
separation, washing, and drying at 120 °C, which were with different SiO2/Al2O3 ratios.
334 L. Xu et al. / Microporous and Mesoporous Materials 115 (2008) 332–337

sieves with CHA topological structure could be obtained molecular sieves exhibited two resonance peaks at 29
when the SiO2/Al2O3 molar ratio was higher than 0.075. and 12 ppm. The former one comes from the overlapping
The topological structure figures of AEI and CHA are peaks of P1 and P2 species with the P(4Al) structures. The
depicted in Fig. 2 [17]. Both structures have the same peri- latter one comes from P3 species [16,18]. As for SAPO-34
odic building units of double six ring (D6 R) layers molecular sieves, only one resonance peak was shown at
(Fig. 2a), which are interconnected forming different 8-ring 29 ppm. It could be concluded that only one kind of P
opening. The AEI and CHA topological structure are chemical environment existed in SAPO-34 molecular
formed because of the different connection mode through sieves. However, a weakened resonance peak at 12 ppm
the oxygen bridges, dissymmetry mode for CHA (Fig. 2b) could be observed in the 31P MAS NMR spectra of SP-
or mirror symmetry for AEI (Fig. 2c). Although the same 0.075 and SP-0.10. This implies that the as-synthesized
primary building units existed in the framework of SAPO-34 is mixed with some SAPO-18 crystal or CHA-
SAPO-34 and SAPO-18 molecular sieves, the connection AEI intergrowths occurs when the SiO2/Al2O3 molar ratios
mode through the oxygen bridges can be changed by are 0.075 and 0.1 in the starting gel [19].
adjusting the SiO2/Al2O3 molar ratios of the starting gel. The SEM photograph of SAPO-18 with AEI topological
Apparently, the AEI topological structure was formed eas- structure is presented in Fig. 4a. The slice-like morphology
ily when the SiO2/Al2O3 molar ratio is low. With the can be observed. The SEM photograph of SAPO-34 as-
increase of the SiO2/Al2O3 molar ratio, SAPO-34 with synthesized with SiO2/Al2O3 = 0.6 is given in Fig. 4c. It
the CHA topological structure is obtained. is seen clearly that the uniform cubic-like crystals are
Fig. 3 presents the 31P MAS NMR spectra of the as-syn- obtained. In the Fig. 4b, for SP-0.075, some slices SAPO-
thesized samples with different SiO2/Al2O3 molar ratios in 18 crystals or CHA-AEI intergrowths are observed among
the starting gel. In 31P MAS NMR spectra, SAPO-18 the cubic SAPO-34 crystals.

Fig. 2. Building scheme for CHA and AEI (a) periodic building unit (b) connection mode for CHA (c) connection mode for AEI.

-2 9

-1 2

SP-0.025
* *
SP-0.075
* *
SP-0.10
* *
SP-0.15
* *
SP-0.20
* *
SP-0.60
* *
40 20 0 -20 -40 -60 -80 -100
Chemical shift (ppm)
31
Fig. 3. P NMR spectra of the as-synthesized products from the starting gel with different SiO2/Al2O3 ratios. () indicates spinning sidebands.
 L. Xu et al. / Microporous and Mesoporous Materials 115 (2008) 332–337 335

Fig. 4. SEM images of the as-synthesized products (a) SP-0.025 (b) SP-0.075 (c) SP-0.60.

3.2. Element composition analysis Si(4Al)

It is known that the (Si + P)/Al ratio is equal to 1 when

Si is incorporated into the AlPO structure by the Si directly
participating in the crystallization or by the SM2 substitu-
tion mechanism with the formation of Si(4Al) species. The
(Si + P)/Al ratio is more than 1 when the Si is incorporated
into the AlPOs structure by the SM3 substitution mecha-
nism with the formation of Si(nAl) (n = 3–0) coordination
structures. Table 1 presents molar composition of the start- Si(3Al)
ing gel and the as-synthesized products. In the starting gel, Si(2Al)
the molar fraction of phosphorus is equal to that of alumi-
Si(1Al) Si(0Al)
num, and the SiO2/Al2O3 molar ratios are 0.025, 0.075, SP-0.60
0.10, 0.15, 0.20 and 0.60. It was seen that the Si contents
of the products increased with the increase of the SiO2/
Al2O3 molar ratios in the starting gel. The framework SP-0.20
(Si + P)/Al ratio of the products is equal to 1 when the
SiO2/Al2O3 molar ratios of the starting gel is in the ranges SP-0.15
of 0.075 to 0.20, which indicates that Si atoms are incorpo-
rated into the SAPO-34 framework by the Si direct partic-
SP-0.075
ipation mechanism and the SM2 substitution mode during
the crystallization of SAPO-34. When SiO2/Al2O3 molar
ratios of the starting gel was up to 0.60, the framework -80 -85 -90 -95 -100 -105 -110 -115 -120
(Si + P)/Al ratio is more than 1, impling that Si incorpora- Chemical shift (ppm)
tion with SM3 substitution mechanisms takes place during
Fig. 5. 29Si MAS NMR spectra of the as-synthesized products from
the crystallization.
starting gel with different Si/Al ratios.

3.3. Si coordination structure

as-synthesized SAPO-34 with different SiO2/Al2O3 molar
29
Si MAS NMR experiments have been successfully ratios in the starting gel. In the 29Si MAS NMR spectra,
used to determine the silicon distribution in SAPO struc- only one resonance peak at 93 ppm is observed when
tures [20]. Fig. 5 presents 29Si MAS NMR spectra of the the SiO2/Al2O3 molar ratios is less than 0.15, which comes

Table 1
Molar composition of the initial gel and as-synthesized products
Sample Starting gel composition Product composition
Molar composition Si/(Si + P + Al) Molar composition (Si + P)/Al Si/(Si + P + Al)
SP-0.025 1.0P2O5:1.0Al2O3:0.025SiO2 0.006 Al0.506P0.487Si0.007O2 0.976 0.007
SP-0.075 1.0P2O5:1.0Al2O3:0.075SiO2 0.018 Al0.500P0.470Si0.030O2 1.000 0.030
SP-0.10 1.0P2O5:1.0Al2O3:0.10SiO2 0.024 Al0.500P0.464Si0.036O2 1.000 0.036
SP-0.15 1.0P2O5:1.0Al2O3:0.15SiO2 0.036 Al0.500P0.447Si0.053O2 1.000 0.053
SP-0.20 1.0P2O5:1.0Al2O3:0.20SiO2 0.048 Al0.500P0.440Si0.060O2 1.000 0.060
SP-0.60 1.0P2O5:1.0Al2O3:0.60SiO2 0.130 Al0.493P0.413Si0.094O2 1.028 0.094
336 L. Xu et al. / Microporous and Mesoporous Materials 115 (2008) 332–337

from the contribution of the Si(4Al) coordination. This When the SiO2/Al2O3 ratio is up to 0.6, Si content in the
also confirms that the Si directly participating in the crys- framework of SAPO-34 is largely less than that in the start-
tallization or the SM2 substitution mechanism is predomi- ing gel. Meanwhile, it may be deduced that Si content of
nant for forming Si(4Al) structure by Si–O–Al linkage. the as-synthesized SAPO-34 should be equal to that in
When the SiO2/Al2O3 molar ratios increase to 0.20, a weak the starting gel at point C.
shoulder peak appears at 97 ppm in SP-0.2 sample, which In Fig. 6, it was seen that the slope of AB segment is
corresponds to Si(3Al) coordination environment. This higher than that of BC segment. This illustrates that the
shows that Si incorporation by SM3 substitution mecha- increase of Si content is more predominant in the AB seg-
nism takes place when the SiO2/Al2O3 molar ratio is ment, and the increase trend is weakened in the BC seg-
0.20. With the increase of the SiO2/Al2O3 molar ratio to ment. This also shows that the ability of Si incorporation
0.60, the 29Si MAS NMR spectrum of as-synthesized SP- into the framework is different between AB and BC. 29Si
0.6 shows more resonance peaks at 101, 106, and MAS NMR results indicated that only Si(4Al) was found
111 ppm, which are attributed to Si(2Al), Si(1Al) and in the structure of SP-0.075 and SP-0.10. Thus, when Si
Si(0Al) species, respectively [7,9,21]. Furthermore the content in the starting gel is lower than the corresponding
shoulder peak at 97 ppm from the Si(3Al) species is inten- x-coordinate value of point B, all the Si atoms would take
sified. This shows that Si incorporation by SM3 substitu- part in the SAPO-34 crystal nucleuses by the mechanism of
tion mechanism increased during the crystallization of Si directly incorporated into the framework. The frame-
SP-0.6. work Si content of the as-synthesized sample is largely
higher than that in the starting gel. But the content of Si
3.4. Si incorporation mechanism atoms incorporated by direct participation of the crystalli-
zation mechanism has a threshold, which is the corre-
Fig. 6 lists the interrelation curve of Si content [Si/ sponding y-coordinate value at point B. When Si content
(Si + P + Al)] in the products and the starting gel. The in the starting gel is higher than the corresponding x-coor-
curve can be divided into three segments, such as AB, BC dinate value of point B, the increased rate of framework Si
and CD, respectively. Point A is the beginning of the curve, content is reduced. In the 29Si MAS NMR spectra, the
B is the intersection point of two tangents with different Si(3Al) structure is found in SP-0.20 sample, and SM3
slope, and C is the intersection point between the curve and SM2 substitution mechanisms took place for samples
and line y = x, in which Si content in the as-synthesized with a Si/Al-ratio in the range of the line BC. In other
product would be equal to that in the starting gel. When words, when the Si content in the starting gel is more than
the SiO2/Al2O3 molar ratio is 0.025 in the starting gel, the corresponding x-coordinate value of B point, part of Si
SAPO-18 molecular sieve with AEI topological structure atoms took part in the SAPO-34 crystal nucleation by the
is synthesized, and Si content in the framework is slightly mechanism of Si directly incorporated into framework,
higher than that in the starting gel. When the SiO2/Al2O3 when the framework Si content is up to the corresponding
molar ratios were in the range of 0.075 to 0.2, CHA-AEI y-coordinate value of B point, the residual Si atoms in the
structure intergrowths or SAPO-34 with CHA structure gel are incorporated into SAPO-34 framework by SM2 and
are formed, and Si content in the framework is largely SM3 substitution mechanism. When Si content in the start-
more than that in the starting gel (AB and BC segments). ing gel continues to increase (CD segment), the framework
Si content in the as-synthesized product is smaller than that
in the starting gel. This could be explained by an increase in
the proportion of SM3 substitution mechanism, and
0.18 Si(3Al), Si(2Al), Si(1Al) and Si(0Al) coordination environ-
0.16 a ments were formed.
In summary, the modeling of Si incorporation
Si/(Si+P+Al) in the products

0.14
into SAPO-34 framework varies with Si content in the
0.12 starting gel. When Si content in the starting gel is less than
0.10 D the abscissa value of point B [Si/(Al + P + Si) = 0.031], Si,
P and Al directly form the SAPO-34 framework with
0.08
C Si(4Al) coordination environment. When Si content in
0.06 B the gel is higher than the abscissa value of point B, some
0.04
Si atoms are incorporated into the SAPO-34 framework
by direct participation of the crystallization with the for-
0.02 A mation of isolated and well-distributed Si(4Al) species,
0.00 with the amount of Si atoms in the framework increasing
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 to the threshold [Si/(Al + P + Si) = 0.052], the remain-
Si/(Si+P+Al) in the starting gel ing Si atoms entered the framework by combined SM2
Fig. 6. Changes of Si/(Si + P + Al) in the products with Si/(Si + P + Al) and SM3 substitution mechanisms to form Si(nAl)
in the starting gel. species.
 L. Xu et al. / Microporous and Mesoporous Materials 115 (2008) 332–337 337

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