Journal of Physics and Chemistry of Solids 68 (2007) 16921699

Porosity of microporous zeolites A, X and ZSM-5 studied by

small angle X-ray scattering and nitrogen adsorption
Xiaoming Du, Erdong Wu

Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
Received 5 January 2007; received in revised form 4 April 2007; accepted 11 April 2007
Abstract
Small-angle X-ray scattering (SAXS) using synchrotron radiation and nitrogen adsorption have been applied to characterizations of
porosities and microporous structures for the zeolites of NaA, KA, CaA, NaX and ZSM-5. Besides the information on the external
morphology of the particles of the zeolites, the complementation of the two techniques has revealed rich and consistent structural and
surface information on the molecular scale crystalline pores of these zeolites. Analyses of the data suggest that the determined sizes of the
micropores imply the pore spaces occupied by the probe molecules of water in the SAXS and nitrogen in adsorption techniques,
respectively. The microporous information of NaA and KA are difcult to obtain from nitrogen adsorption, due to the blocking of
nitrogen by their narrow channels, but have been satisfactorily measured by SAXS. The factors causing variations of the measured values
of the parameters in different analysis methods have been discussed.
r 2007 Published by Elsevier Ltd.
Keywords: A. Microporous materials; C. X-ray diffraction; D. Microstructure; D. Surface properties
1. Introduction
Zeolites are a large class of highly crystalline alumino-
silicate materials, dened by a topological network of
uniformly linked cavities and pores of molecular dimen-
sions that gives rise to their molecular sieving properties [1].
Accordingly, zeolites have been used in a wide range of
industrial processes, such as gas storage, catalysis and ion-
exchange [2,3]. Owing to the richness of the pore structures
of these molecular sieving materials, various methods have
been applied to characterize the pore structures of the
zeolites, in particular, the pore size distribution and surface
area. The carbon dioxide, argon or nitrogen adsorption
and Hg-porosimetry methods are commonly used to
quantify the relevant parameters. Results for any particular
zeolite, however, vary depending upon the uid probe
used, which reects the specicity of sorption phenomena.
Other techniques used to characterize porosity and pore
size distribution include scanning electron microscope
(SEM), transmission electron microscope (TEM), small-
angle scattering of X-rays (SAXS) and neutrons (SANS).
Among these techniques, SAXS is often more easily
available and can provide the average topological informa-
tion of porous materials on a scale covering a range from a
few A

to about 2000 A

. SAXS probes the uctuations of

the electronic density, which reects the chemical hetero-
geneity and density variations within a medium, for
example, there exists a high contrast between pore space
and matrix in zeolites for scattered X-rays. The theory and
practice of SAXS can be found in an extensive literature
[48].
The previous work has shown that SAXS technique is
suitable for pore structure characterization of activated
carbon [911], carbon aerogels [12], mesoporous silicas [13]
and MCM-41 type of zeolites [14,15]. However, there are
few SAXS measurements on the porosity and surface
characteristics of microporous zeolites (such as A, X-type
and ZSM-5) so far [16]. In a SAXS study on zeolites A, X
and Y, the gyration radius of the pores was reported.
However, other porous characteristics available from
SAXS measurements, such as specic surface areas, fractal
ARTICLE IN PRESS
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0022-3697/$ - see front matter r 2007 Published by Elsevier Ltd.
doi:10.1016/j.jpcs.2007.04.013

Corresponding author. Tel.: +86 24 23971952; fax: +86 24 23971952.

E-mail address: ewu@imr.ac.cn (E. Wu).
dimensions and pore size distribution, have not been
reported.
In the present paper, we investigated the porosity of
some microporous zeolites, i.e. NaX, ion-exchange A-type
(KA, NaA and CaA) and ZSM-5 by SAXS and nitrogen
adsorption at 77 K. The SAXS data have been explained in
terms of fractal dimension from power law, mean pore
diameter from Guiniers law, specic surface area and pore
size distribution of the samples. In comparison, these
parameters were also obtained from nitrogen adsorption
using various methods including BET equation, t-plot or
a
S
-plot and HorvathKawazoe methods. It needs to be
noted that both SAXS and gas adsorption are, to a certain
extent, insufcient for characterization of the microporous
structures. The combination of the two techniques provides
a much clearer view of the microporosity and surface
characteristics of the materials.
2. Experimental
Five samples of three types of microporous zeolites have
been selected for the studies, which are NaA (LTA
structure type) and two of its ion-exchanged forms of
KA and CaA, NaX (FAU structure type) and H-ZSM-5
(MFI structure type). The zeolites were commercial
products obtained from Shanghai MLC Molecular Sieve
Co., Ltd. (A, X) and Shanghai Changfeng Chemical
Industrial Factory (H-ZSM-5).
The SAXS measurements were performed using syn-
chrotron radiation as X-ray source with a long slit
collimation system at the Beijing Synchrotron Radiation
Laboratory. The incident X-ray wavelength l was 1.54 A

,
the distance between sample and detector is 1495 mm and
the region of the scattering vector q 4p sin y/lo0.25 A

1
,
that corresponding to the scattering angle 2y of approxi-
mately 03.51. The scattered X-ray intensity I(q) is
recorded using the image plate technology. The absorp-
tion of the samples and background scattering were
corrected. In order to evaluate the effect of scattering
intensity of SAXS at large scattering angle (2y33.51),
XRD measurements were also carried out for all the
samples on a Rigaku D/max-rA diffractometer with CuKa
radiation.
For the porous texture analysis of the samples, nitrogen
adsorption measurements were carried out on an ASAP
2010 volumetric adsorption analyzer from Micromeritics
at liquid nitrogen temperature (77.4 K) in a relative
pressure range from about 10
6
to 0.99. Before measure-
ments, the samples were outgassed for 2 h at the
temperature of 473 K under a residual pressure lower than
6.6 10
4
Pa in the degas port of the adsorption appara-
tus. In this case, the water and impurity gas molecules
adsorbed in the pores of zeolites can be removed, but the
structural water molecules still exist. Therefore, the water
contents in the samples were also determined by using a
Perkin-Elmer Thermogravity Analyzer (TGA-7) at the
temperatures up to 700 K.
3. Results and discussion
3.1. SAXS data analysis
Fig. 1 displays the small-angle scattering for ve samples
of three types of zeolites in log I(q) vs. log q plots. From the
gure, it follows that these scattering curves have a
common character, i.e., each curve has roughly two linear
portions jointed with a characteristic bend. This indicates
that the scattering intensities are caused by different size
scales of structure and regimes of constant mass/size
scaling. It is possible to t these regimes separately using
different power-law functions and exponential functions.
Based on the power law of I(q) I
0
q
a
, where I
0
is a
constant [1719], the mass fractal (D
m
) and surface fractal
(D
s
) dimensions of scattering objects in porous materials
can be calculated from the value of the power-law exponent
a. For mass fractals, 1oao3, D
m
a, whereas for surface
fractals, 3oao4, D
s
6a. As shown in Fig. 1, examina-
tions of the linear portions of the scattering curves suggest
that the slopes of the curves between that in the low q
regions (qo0.01 A

1
) and that in the middle q
(0.01 A

1
oqo0.05 A

1
) regions are slightly different, and
can be least square tted to different straight lines,
respectively, and agreement factor is in the range of 0.97
0.99. Accordingly, the calculated D
m
and D
s
in the low- and
mid-q regions have been exhibited in Table 1. For the high-
q regions after the bends, a attening of the scattering
curves has been observed. The values of a for the attened
regions are signicantly smaller than 1, which cannot be
explained by the mass- or surface-fractal scattering laws,
but will be discussed with respect to the results of the
exponential function ts later.
The SAXS data, along with the tted lines, for all of
zeolite samples show a slight transition between two
different power-law scattering regimes. The low-q power
law is owing to mass fractal aggregates, and the mid-q
ARTICLE IN PRESS
1E-6
1E-5
1E-4
1E-3
0.01
I

(
q
)
q/
NaX
CaA
NaA
KA
ZSM-5
0.01 0.1
A
-1
Fig. 1. SAXS data for the zeolite molecular sieves NaX, CaA, NaA, KA
and ZSM-5 plotted as I(q) vs. q on loglog scales. The solid lines are ts to
a power-law equation.
X. Du, E. Wu / Journal of Physics and Chemistry of Solids 68 (2007) 16921699 1693
power law is due to surface scattering from the primary
particles. The transition region occurs relative to the size
scale of the primary particles (see Fig. 1). As shown in
Table 1, the values of surface fractal dimension of all
zeolites NaX, CaA, KA, NaA and ZSM-5 are larger than
2, and approximately the same at around 2.87. This implies
that the primary particles of the samples have a rough
poresolid interface and micropores inside [20]. The mass-
fractal dimensions of all samples have the similar trends in
the low-q regions (see Table 1), indicating the similar length
scales of the primary particles for the samples.
The bend in Fig. 1 reects a change of exponential
decay in scattered intensity that corresponds to different
average structural sizes for heterogeneities according to
Guiniers law in exponential form. Structural sizes were
determined by the method of tangents on the base of the
Guiniers law for the dilute and monodispersed system:
I(q) I(0)exp(R
g
2
q
2
/3), where I(0) is the extrapolated
value to q 0 of the scattering intensity, and R
g
is the
radius of gyration of for heterogeneities [4]. Before using
radius of gyration in analysis of the structural sizes in the
samples, it is essential to consider the applicability of the
Guinier equation to estimating the structural sizes of
different scales. The Guinier equation is applicable, strictly
speaking, only to monodisperse systems, for it holds good
for values qR
g
p3 [21]. In the case of a polydisperse system,
its use is complicated by the fact that the head portion of
the curves for the scattering of smaller particles falls within
the scattering region of larger particles. In this work, the
inequality criteria could be fullled for the whole q regions
of the measurements.
As shown in Fig. 2(a), the slopes of Guinier plots of for
all the zeolites are in continuous changes at low q regions
(qo0.1 A

1
). Therefore, as shown in Table 1, the values of
the sizes for heterogeneities calculated from the radius of
gyration in separated q regions are spread in a range from 4
to 44 nm. This range has been beyond the lattice dimen-
sions of about 2 nm for the samples in the present work.
Accordingly, these heterogeneities should be the size
distributions of the primary particles or primary particle
aggregates in the samples. Moreover, the particle sizes
calculated from Scherrer equation by using FWHM of the
XRD data are 43, 37, 44, 46, 44 nm for zeolites NaX,
ZSM-5, CaA, NaA, KA, respectively. These results are
consistent with the primary particle sizes obtained from
SAXS in a low-q region of qo0.021 A

1
(see Table 1).
However, in the high q range of q40.1 A

1
, the slopes of
Guinier plots of all zeolites remain unchanged (see
Fig. 2(b)). This indicated that the values of the radius of
gyration for the zeolites are constant in this section of the
curves. As exhibited in Table 1, the calculated radius of
gyration are 3.984.50 A

and the corresponding sizes of the

heterogeneities are 10.511.8 A

for zeolites A and X based

on the spherical objects, 2.81 and 4.5 A

for ZSM-5 based

on the cylinder object with an assumed height to diameter
ratio of 1.8 from the crystallographic information of
ZSM-5 [22], respectively. The values of the radius of
gyration for the zeolites A are in good agreement with that
of the hydrated samples determined by Howell [16].
Moreover, the distributions of the sizes of heterogeneities
(volume vs. diameter) corresponding to the same q regions
calculated using the Glatter and Vonk methods [23,24] are
ARTICLE IN PRESS
Table 1
Summary of SAXS parameters of zeolites A, X and ZSM-5
q-range (A

1
) NaX ZSM-5 CaA NaA KA
D
s
0.010.06 2.92 2.88 2.87 2.88 2.82
D
m
o0.01 2.54 2.86 2.34 2.38 2.37
R
g
(A

) 0.10.25 4.2 2.8 4.0 4.1 4.5

d (A

) 0.10.25 11.2 4.5 10.5 10.6 11.8

d
particle
a
(nm) o0.021 44 35 43 43 43
0.0210.044 17 11 17 18 18
0.0440.08 6.4 4.0 8.7 7.7 7.6
S
p
(m
2
/g) 598 490 471 458 388
a
d
particle
stand for the diameter of primary particles or particle
aggregates. The standard deviation is unity in the last decimal of a
parameter.
-14
-12
-10
-8
-6
-4
l
n

(
I

(
q
)
)
KA
NaX
NaA
ZSM-5
CaA
0.01
-13.6
-13.4
-13.2
-13.0
-12.8
l
n

(
I

(
q
)
)
CaA
NaA
ZSM-5
NaX
KA
linear fit
q
2
/
-2
0.000 0.002 0.004 0.006 0.008 0.010
q
2
/
-2
0.00 0.02 0.03 0.04 0.05 0.06 0.07
Fig. 2. Guinier law plots for zeolite molecular sieves NaX, CaA, NaA,
KA, ZSM-5, (a) q range from 0.1 to 0.25 A

1
, (b) q less than 0.1 A

1
.
X. Du, E. Wu / Journal of Physics and Chemistry of Solids 68 (2007) 16921699 1694
presented in Fig. 3. It is shown that the local maximum of
size distribution curves of zeolites A and X occurs at nearly
same diameter (about 11 A

), whereas that of zeolites

ZSM-5 occurs at the diameter of around 5 A

. Based on
the crystal structures of the zeolites, the primary crystalline
spherical cavities of a-cages in zeolite A and supercages in
zeolite X are 11.4 and 12.6 A

, respectively. Whereas the

dimension of the micropores in ZSM-5 is 5.15.6 A

[25].
These results indicate that the sizes of the heterogeneities
derived from SAXS are approaching to the primary
crystalline micropores of the relevant zeolites, and would
plausibly be attributed to the scattering of the micropores
[21]. It should be addressed that although the pore size in a
crystallized zeolite could be obtained from the crystal-
lographic measurement, e.g. by XRD in [26], the accurate
volumetric capacity of the pore is difcult to determine due
to the uncertainties in the effective volumes of the
constituent atoms of the pore [27]. It would be demon-
strated that the SAXS and the aftermentioned N
2
adsorption techniques determine the pore size just from
this aspect.
The pore sizes derived in SAXS have been ascribed to the
cations or the cations and water molecules, rather than the
micropores themselves in the zeolites, as the long-range
ordered cages in the zeolite crystals would not scatter in
this q region [16]. As zeolite ZSM-5 does not contain
alkaline or alkaline earth cations, but only H
+
, the water
molecules in the micropores are the more likely scatterers
in our study. It is known that the scatterers following the
well-resolved Guinier plots in Fig. 2(b) have to be
randomly distributed dilute objects in a uniform matrix,
and it appears that the sizes of the detected objects (say
water molecules) have reected the size scales of the textual
micropores of the zeolites. The water concentrations in the
samples of zeolites NaX, ZSM-5, CaA, NaA and KA
obtained from TGA are 7.9, 7.15, 13.7, 14 and 10.7 wt%,
respectively, which correspond to 65, 25, 124, 127 and 91
water molecules per unit cell. In these zeolites, only zeolites
A can contain some ordered water molecules [28,29], which
account for a minority proportion of the total water
molecules. Based on the relative sizes of the water
molecules and the primary cavities of the zeolites, the
evenly distributed nonordered water would only occupy a
small proportion of a cavity. For example of zeolite NaX,
the evenly distributed water molecules would take 28%
volume with a sphere size of 7.7 A

in each supercage,
whereas the randomly distributed water molecules could ll
some cavities and form larger aggregations, which would
take 12% of the total volume of the zeolite, and meet the
dilute distribution limit (12%) required by Guinier
equation [30]. Therefore, the information suggest that the
water molecules in the zeolites intend to aggregate into
randomly distributed clusters and appear to ll the whole
primary cavities, and the sizes of the micropores imply the
spaces seen by the water probes, which are associated with
the SAXS intensities at the region of q40.1 A

1
. Radlinski
et al. [8] analyzed the SAXS and SANS data of coals in the
large-q region (q40.1 A

1
) in which the scattering curves
have also become attening. They believed that the
appearance of the phenomenon is due to the micropores
in coals, and the scattering contrast in the region is caused
by nearly molecular-size particles of inorganic matter in the
clogged micropores. Our argument appears to be consistent
with their explanation.
There may still be some concerns in using Guinier
equation in such high-q region (q40.1 A

1
). First, the
values of R
g
obtained from the Guinier plots correspond to
a size dimension of close to or even less than 10 A

, which
has reached the distinguishable limit of SAXS, and could
be interfered by the low angle reections. Second, the
power-law exponents derived in the region are meaningless.
The ttings of the XRD patterns of the zeolite samples by
Lorentzian prole have conrmed that the effects of the
tails of the rst XRD reections at 2y671 on the SAXS
intensities in qo0.25 A

1
(2y3.51) region are neglectable.
On the other hand, in the SAXS study of zeolites A by
Howell [16], similar high-q regions corresponding to
meaningless power-law exponents have also been used to
obtain R
g
as small as 4 A

. Very small particle sizes of

below 10 A

obtained in the high-q regions have also been

reported for the SAXS studies of polymers [31] and
zirconia aerogels [20]. Therefore, the pore sizes obtained
at the high-q region appear to be reasonable. The mean-
ingless exponent reects a fact that although the molecular-
scale structure can be revealed by SAXS, the interface
morphology described by the exponent has become
ambiguous for an object at such a scale, and has to be
redened.
Based on the ttings of the SAXS data, the surface areas
of the samples can be determined by the tting parameters
of an equation (S
p
1.62(C
mi
/R
4
g
), where C
mi
is a tting
constant) proposed by Kalliat et al. [32] and Sousa et al.
[33]. The derived specic surface areas, S
p
, of the
micropores have been shown in Table 1 for comparison
with the values derived from the aftermentioned N
2
ARTICLE IN PRESS
0 2 4 6 8 10 12 14 16 18
0.0
0.1
0.2
0.3
0.4
0.5
P
o
r
e

v
o
l
u
m
e

(
r
e
l
a
t
i
v
e
)
KA
NaA
CaA
NaX
ZSM-5
Pore diameter /
Fig. 3. Pore size distribution calculated from SAXS data.
X. Du, E. Wu / Journal of Physics and Chemistry of Solids 68 (2007) 16921699 1695
adsorption. The S
p
of the macro and mesopores can also be
calculated from Kalliat et al.s equation. However, the
macro and mesopores values are negligible fractions, and
thus providing further evidences for the formation of the
nanosize primary particles or primary particle aggregates
rather than nanosize cavities in the zeolite samples.
3.2. N
2
adsorption data analysis
Fig. 4 exhibits the N
2
adsorption and desorption
isotherms at 77 K for zeolites NaX, CaA and ZSM-5.
The features of the isotherms indicate only volume lling of
micropores and no presence of mesopores. The kinetics of
the N
2
adsorption for zeolites NaA and KA are too slow to
reach equilibriums at each point of the isotherms at 77 K.
Therefore, no regular isotherms, but only specic areas
data are obtained for these two samples from the N
2
adsorption measurements. The causes of the phenomenon
will be discussed later.
The pore sizes and pore size distributions based on the
N
2
adsorption isotherms can be derived from several
methods, such as non-local density function theory
(NLDFT) method [34], DubininAstakhov (DA) equation
based on micropore lling theory [35], and Horvath
Kawazoe (HK) method based on the interaction potential
between adsorbate and adsorbent [36]. Among them, the
HK method is a simple and popular method proposed by
Horvath and Kawazoe [36] for evaluating pore size
distribution of microporous materials. The original HK
models discussed slit-shape pores only [36]. Subsequently,
the models for spherical pores [37,38] and cylindrical pores
[39] have been proposed. This technique has been success-
fully used for the determination of pore size distribution in
many microporous adsorbents such as activated carbons
and zeolites over the last decade. In this study, the
HK models corrected by Yang [38] and Saito [39] have
been used to reveal the pore size distributions of the
microporous zeolites based on the N
2
adsorption isotherms
at 77 K.
The micropore sizes and size distributions obtained from
the HK method are shown in Table 2 and Fig. 5, respec-
tively. A single sharp peak on each of the pore size
distribution curves for the samples under study (see Fig. 5)
indicates that the zeolites have mono-disperse pores, with
diameters of 14, 12 and 5.7 A

for NaX, CaA and ZSM-5

(Table 2), respectively. Therefore, the measured micropore
sizes reect the primary cavity sizes mentioned above for
these zeolites. Rege and Yang [38] have reported the pore
sizes of 13, 9.8 and 5.7 A

for the three types of zeolites,

respectively, using HK models based on Ar adsorption at
87 K. The pore sizes determined in our study are
slightly larger than their reported values except for that
of ZSM-5. The difference may be attributed to the
variation of interaction potential between adsorbate and
adsorbent in the system. Due to a large quadrupole
moment of nitrogen molecule, the interactions between
the polar adsorbate of nitrogen and the polar adsorbents of
NaX and CaA are stronger than that between nitrogen and
the non-polar or weakly polar adsobent of ZSM-5.
However, for the non-polar adsorbate of Ar, the differ-
ences of interactions between polar and non-polar adsor-
bate would be less.
In comparison with SAXS data in previous section
(Table 1 and Fig. 3), the pore diameters calculated from
HK models are slightly larger (Table 2). Moreover,
the pore size distributions are considerably narrower
(Fig. 5). As mentioned above, the sizes of the micropores
ARTICLE IN PRESS
0
50
100
150
200
250
ZSM-5
CaA
NaX
A
d
s
o
r
p
t
i
o
n

a
m
o
u
n
t

/
c
m
3

S
T
P
/
g
0.0 0.2
P/P
0
0.4 0.6 0.8 1.0
Fig. 4. Nitrogen adsorption isotherms of zeolite molecular sieves NaX,
CaA, and ZSM-5 at 77 K, closed symbol: adsorption, open symbol:
desorption.
Table 2
N
2
adsorption characteristics of the zeolites A, X and ZSM-5
D (A

) V
m
(cm
3
/g) S
ex
(m
2
/g) S
BET
(m
2
/g)
HK Eq. DR Eq. t-method a
S
-method t-method a
S
-method Our work [Ref]
NaX 14 0.27 0.25 0.26 28 28 565 662 [48]
ZSM-5 5.7 0.22 0.21 0.20 24 26 445 431 [49]
CaA 12 0.21 0.18 0.18 47 44 428 565 [48]
NaA 32
KA 32
The standard deviation is unity in the last decimal of a parameter.
X. Du, E. Wu / Journal of Physics and Chemistry of Solids 68 (2007) 16921699 1696
determined from the two techniques may be illustrated as
the pore spaces occupied by the particular probes of water
in the SAXS and nitrogen in adsorption techniques,
respectively. Since water molecular has a larger polarity
but a smaller size than that of nitrogen, a plausible
explanation for the above phenomena would be that the
sizes of the water clusters in the cavities are spread, whereas
some smaller pores or cavities, such as the sodalite cages in
zeolites X and A, could be accessible to water, but not to
nitrogen, leading to broader volume distributions and
averaged smaller pore sizes detected in SAXS.
The micropore volumes, V
m
, described as the total
volume of the micropore per unit mass of the samples, were
initially determined by N
2
adsorption using the Dubinin
Radushkevich (DR) equation [40]: log V log V
m

Dlog
2
(p
0
/p), where V is the volume of liquid adsorbate in
the range of experimental equilibrium relative pressures
and D is the constant. The V
m
(see Table 2) are obtained
from the intercept at log
2
(p
0
/p) 0 in linear tting of log V
vs. log
2
(p
0
/p) for NaX, CaA and ZSM-5 in Fig. 6.
However, to compare the V
m
derived from different
methods, and obtain external surface areas, S
ex
, of the
samples, the isotherms are also analyzed by the t-plot
(the statistical lm thickness of adsorbates, t, as a function
of the adsorbed amount expressed as liquid volume) and
a
S
-plot (the amount adsorbed on a sample as a function of
that on a suitable reference adsorbent, i.e. non-porous
silica [41] in this work) methods [40], which are most
commonly used to determine V
m
and S
ex
of a microporous
material. The slopes of the linear parts of both plots
(t43.55 A

for t-plot and a41 for a

S
-plot) can be used to
calculate S
ex
, whereas V
m
are assessed by the intercept with
the vertical axes of the plots (Figs. 7(a) and (b)). The
specic areas, S
BET
, of the samples were determined by
BET equation in the region of relative pressure of 0.060.2
of the adsorption isotherms. All derived data are listed
in Table 2.
ARTICLE IN PRESS
0 5 10 15 20 25 30 35 40 45 50
0.00
0.05
0.10
0.15
0.20
0.25
D
i
f
f
e
r
e
n
t
i
a
l

P
S
D

/
c
m
3
/

(

.
g
)
NaX
ZSM-5
CaA
Pore diameter /
Fig. 5. Pore size distributions for NaX, CaA and ZSM-5 calculated using
the HorvathKawazoe method.
0 5 10 15 20 25 30 35
-1.0
-0.9
-0.8
-0.7
-0.6
-0.5
l
o
g

V
log
2
(P
0
/P)
ZSM-5
NaX
CaA
DR fit
Fig. 6. DR plots for nitrogen adsorption of zeolite molecular sieves NaX,
CaA, and ZSM-5 at 77 K.
0 1 2 3 4 5 6 7 8
0.00
0.04
0.08
0.12
0.16
0.20
0.24
0.28

A
d
s
o
r
p
t
i
o
n

a
m
m
o
u
n
t

(
c
m
3
/
g
)
ZSM-5
CaA
NaX
0.8 1.0 1.2 1.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
S
a
m
p
l
e
s

ZSM-5
CaA
NaX
t ()
Reference
0.2 0.4 0.6
Fig. 7. (a) t-plots for NaX, CaA and ZSM-5 with nonporous silicas as a
reference. (b) a
S
-plot for NaX, CaA and ZSM-5 with non-porous silicas as
a reference.
X. Du, E. Wu / Journal of Physics and Chemistry of Solids 68 (2007) 16921699 1697
It is shown that the V
m
by DR equation are, for all the
samples, slightly higher than that by t-plot and a
S
-plot
methods. Remy et al. [42] have suggested that DR equation
overestimated the V
m
of solids with important external
surface. Our results appear to agree with Remy et al.s
suggestion. The V
m
reported in the literatures for zeolite
ZSM-5 were diverse, between 0.126 and 0.185 cm
3
/g by
Voogd [43] and Pavol et al. [25], between 0.163 and
0.18 cm
3
/g by Remy et al. [42] and 0.20 cm
3
/g by Ding et al.
[44], whereas for NaX, the values of 0.287 and 0.304 cm
3
/g
were reported by Ding et al. [44] and Maurin et al. [45],
respectively. It can be seen that our values of V
m
for NaX
and ZSM-5 are very close to that by Ding et al. [44]. For
the S
ex
of these zeolites, only the values of 3562.5 m
2
/g by
Remy [42] for ZSM-5 are available, which are somewhat
larger than the values obtained in this work. The
differences may be attributed to the variations in prepara-
tion processes of the producers. In our measurements, in
comparison with the S
ex
for NaX and ZSM-5, the values
for CaA are considerably larger, whereas the S
BET
for CaA
are similar or even smaller than that for NaX and ZSM-5
(see Table 2). Consequently, the value of S
ex
/S
BET
0.1 for
CaA is about twice of that for NaX and ZSM-5, which will
reduce the adsorbed amount of nitrogen in the micropores
of CaA.
As shown in Table 2, NaA and KA have shown
unexpectedly low S
BET
. The kinetic diameter of nitrogen
molecule (3.64 A

) is comparable to the effective channel

diameter of NaA (about 4 A

), so the block of the channels

would occur for nitrogen in NaA, with the low S
BET
as a
direct consequence [46]. Such judgment could also apply to
KA with even narrower channels. Due to the mentioned
difculties, there were few reported values of specic
surface areas for the two zeolites [47]. However, the specic
surface areas of 458 and 388 m
2
/g for NaA and KA,
respectively, have also been obtained by SAXS in this
work, and appear to be reasonable (see Table 1). These
examples demonstrate how the complementation of the
two techniques provide a much clearer view to the
microporosity and surface characteristics of the zeolite
materials. For NaX, ZSM-5 and CaA, the S
BET
obtained
from the isotherms are about 515% smaller than that
from the SAXS (see Table 1). This phenomenon may also
be explained by the effect caused by different probe
molecules in the two techniques. On the other hand, the
values of S
BET
for the three zeolites in this work, obtained
by either SAXS or nitrogen adsorption, are all slightly
lower than that reported in Ref. [48]. Although the exact
causes are not clear, the variation in hydration states of the
samples is the most likely explanation.
4. Conclusions
SAXS measurements of the zeolites in the low- and mid-
q regions indicate primary particles or primary particle
aggregates with spread size distributions. The primary
particle sizes obtained in the low-q region are consistent
with that calculated from the XRD data. These primary
particles or primary particle aggregates have a rough pore
solid interface and micropores inside.
SAXS scattering curves in the large-q region become
attening, correspond to constant sizes approaching to the
primary crystalline micropores of the zeolites, which are
the results of the scattering contrast between matrix and
water molecules in the micropores.
The micropores sizes and specic surface areas for all
zeolites are satisfactorily measured by SAXS, where the
former are relatively smaller and the later are relatively
larger than that from the nitrogen adsorption, respectively.
The phenomenon is explained by the different probe
molecules in the two techniques.
The nitrogen adsorption isotherms indicate volume
lling of micropores and no presence of mesopores. The
pore size distribution curves indicate mono-disperse
micropores. The measured micropore sizes reect the
primary cavity sizes for the zeolites.
The differences in pore sizes determined by HK method
reect the interaction potential variations between different
adsorbates and adsorbents. The micropore volumes
measured by DR equation are slightly higher than that
by t-plot and a
S
-plot methods, indicating that DR equation
overestimates the micropore volumes. The NaA and KA
have shown unexpectedly low-specic areas. The phenom-
enon is attributed to the blocking of the channels of the
zeolites by nitrogen.
Acknowledgments
The authors acknowledge the facility supports of BSRF
at Institute of High Energy Physics, Chinese Academy of
Sciences, and the assistances in the SXAS measurements by
the staffs of BSRF, Z.H. Wu, Z.J. Chen, Z.H.Li and B.Z.
Dong, and the nitrogen adsorption measurement by F. Li
of IMR. The funding support from the Innovation
Program of Chinese Academy of Science is appreciated.
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