Microporous and Mesoporous Materials 236 (2016) 63e70

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Determination of micropore volume and external surface of zeolites

Christoph Buttersack*, Jens Mo
€ llmer, Jo
€ rg Hofmann, Roger Gla
€ser
Institute for Non-classical Chemistry at the University of Leipzig, Permoser Str. 15, 04318, Leipzig, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Original and thermally degraded FAU type zeolites were characterized by nitrogen adsorption at 77 K and
Received 30 September 2015 compared with isotherms for amorphous silica from literature. The isotherms were evaluated by the
Received in revised form method of Remy and Poncelet which is an additive composition of the Dubinin-Radushkevich and the
28 December 2015
BET equation. Nonlinear fits typically generate two optimal values. One is attributed to very low, the
Accepted 19 August 2016
other to very high values of the C-constants of the BET part. The conversion of the DR-isotherm to a set of
Available online 21 August 2016
Langmuir isotherms with different affinities shows that the low value is correct. For comparison all data
were compared with those obtained by the t-plot method. The t-plot generally yields a less good fit with
Keywords:
Nitrogen adsorption
the experimental data, lower micropore volumes and deviating external surfaces, especially in the case of
BET equation thermally degraded zeolites with an enhanced degree of mesopores. The entire isotherms from p/
C-term po ¼ 0.5 to 0.98 are covered by an additive combination of the Dubinin-Radushkevich equation and the
t-plot general Aranovich equation. That equation, however, fails for the determination of the external surface.
Micropore © 2016 Elsevier Inc. All rights reserved.
External surface

1. Introduction
A lot of classical procedures exist to evaluate the data of N2
adsorption isotherms at 77K. They range from methods claming to
be universal [1] or with a sophisticated view to the adsorbent
surface on the molecular level [2]. The aim of this contribution is
the evaluation of a method of data analysis for materials with mi-
cropores and an external surface, especially for zeolites.
Although adsorption data analysis based on molecular simula-
tion of adsorbate-adsorbent interaction, such as NLDFT [3], has
found a growing scientific and commercial interest, the application
of classical methods prevails. The calculation of micropore volumes
and external surfaces of zeolites is mostly done by the t-plot
method originally developed by de Boer [4]. Sing has evidenced the
strong influence of the chemical composition of the surface on the
evolution of the statistical thickness t [5]. It was recommended to
choose a non-porous material of the same chemical composition
[6] or characterized by the same C-value of the BET-plot [7]. But
such a look to a reference material is effortful. Mostly the universal
t-plot accounting for the average surface property of a lot of
different materials is used [8].
In addition to the question which type of t-plot is appropriate,
the extrapolation procedure generally depends on the arbitrarily
* Corresponding author.
E-mail address: buttersack@inc.uni-leipzig.de (C. Buttersack).
used pressure range [9]. Furthermore, Galarneau et al. have also
shown that this type of extrapolation has principally to be ques-
tioned [2], and in addition, the thickness t calculated according to
de Boer is only correct in case of ideally flat surfaces. In reality, the
surface curvature has an effect which cannot be neglected [2]. The
incorporation of that effect into the t-plot method requires data
which are not available in the most cases of routine characteriza-
tions of porous materials. Therefore a simple mathematical tool for
the reliable determination of the micropore volume and the
external surface is requested.
For the practical use the method should especially focus on the
course of the isotherm describing the transition between micro and
mesopores. Remy and Poncelet defined that region as an additive
superposition of the Dubinin-Radushkevich (DR) equation for
micropore adsorption [10] and a BET term [11] for the behaviour on
the external surface (DR-BET method [12]). The authors have
compared their results with the external surface obtained by the t-
plot (2 types of reference systems) and by the usual BET method.
Great discrepancies were found. The question remains if the
method of Remy and Poncelet [12] is sound enough to replace
commonly used methods. Based on the DR term in combination
with BET one has to address the weakness of both equations alone.
The clearness of the BET theory is based on ideal prerequisites
which are the homogeneous solid surface, neglected “horizontal”
interactions in the same adsorbed layer, and identical forces be-
tween each layers from the first up to infinite [13,14]. But in reality
these conditions are only partly fulfilled. As a consequence it was

http://dx.doi.org/10.1016/j.micromeso.2016.08.018
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64 C. Buttersack et al. / Microporous and Mesoporous Materials 236 (2016) 63e70

emphasized that the C-parameter should not be considered as a (  2 )

constant [1], and in the practice the usual BET method is only V1 E
¼ exp  (3)
applied for pressures not larger then p/po ¼ 0.3 [13]. The DR Vmicro Eo
equation is based on the arbitrary assumption that the fraction of
filled micropore volume is proportional to a Gaussian energy dis- where V1 is the micropore volume filled by nitrogen, Vmicro the total
tribution. Furthermore the isotherm does not obey the Henry law at micropore volume, Eo the characteristic energy1 and E is given by
the limit p ¼ 0 [15]. It is therefore more of empirical than theoretical the Polanyi equation [28].
nature.
Up to now, the application of the DR-BET method is rare. Remy E ¼ RT lnðp=po Þ (4)
and Poncelet transferred their method to the characterization of
further zeolites [16,17] and pillared clays [18]. Two publications The adsorption on the external surface is described by the common
deal with the comparison of different methods including the DR- BET equation [11].
BET-method for zeolites [19,20]. Quite other porous materials
x
were also characterized [21]. For the characterization of super- V2 ¼ Vext C (5)
ð1  xÞ ð1 þ ðC  1Þ xÞ
microporous materials the DR-BET method was extended by a
limited number of BET layers [22,23]. Another group extended the
with V2 being the volume filled by multilayer adsorption on the
method by an additional Henry term [24].
external surface, Vext is the volume of a monolayer, and C is the
At last, the description of the full isotherm by a modification
adsorption constant, while x is the partial pressure
with up to 3 additional parameters has to be mentioned [25]. It is
obvious that the increase of adjustable parameters generates a x ¼ p=po (6)
higher statistical degree of freedom during the non-linear fitting
process. In addition, the physical meaning of some parameters may With respect to the molecular mass of nitrogen MN2, its density at
be unclear or of less importance. Therefore, this contribution has 77 K (r77K ¼ 0.808 g cm3), and its cross-sectional area
the focus on the evaluation if the number of parameters can be (s ¼ 0.162 nm2) the external surface is given by
reduced to the essential ones.
Sext ¼ Vext r77K NA s=MN2 ¼ sv Vext (7)
2. Material and methods The total volume filled with nitrogen at a certain value of x is then
defined by the sum of V1 and V2 and the equation of the isotherm is
The industrial FAU type zeolites CBV500, CBV760, CBV 780 were
obtained from Zeolyst, Y307, Y411, Y 756 and Y100 came from o Sext sv C x
Albemarle, HSZ390 from Tosoh, DAY from the former Degussa V ¼ Vmicro expf k ðlnð1=xÞÞ2 þ
ð1  xÞ ð1 þ ðC  1Þ xÞ
company, and a 13X zeolite (Ko € strolith 13XBF) in the form of
(8)
binder-free pellets from CWK Bad Ko €stritz in Germany. The zeolites
covered a Si/Al ratio between 1.3 and 400. Some zeolites were with
dealuminated by contact for 20 h in 1N HCl at room temperature.
Others were treated for up to 20 days in pure boiling water, some of  2
RT
these treatment liquids additionally contained NaCl or HCl. All k¼ (9)
Eo
samples were analyzed by nitrogen adsorption at 77 K with the
equipment of BELSORP max (BEL Japan Inc.). Prior to the mea- The latter equations are the basis for the concept of Remy and
surement the samples were heated up to 400  C with a heating rate Poncelet called hereafter the DR-BET method [12]. 4 parameters
of 3 K min1 up and hold there for 16 h. The final pressure was p < 5 have to be fitted with the experimental isotherm, namely Vmicro,
102 Pa. The isotherms were analyzed by non-linear regression via Vext, k, and C. By this way only the lower part of the experimental
SigmaPlot (Systat Software Inc.) based on the algorithm of Leven- isotherm is captured.
berg and Marquardt [26]. The analysis via the method of Remy and According to Marcilla et al. [25] in a lot of cases the full isotherm
Poncelet [12] was performed with different boundary conditions. can be described by
For comparison, all data were analyzed by the t-plot method using
o Sext sv C x
the universal curve [7]
V ¼ Vmicro expf k ðlnð1=xÞÞ2 þ
ð1  xÞm ð1 þ ðC  1Þ xÞ
t 2 ¼ 13; 99=ðlogð1=xÞ þ 0; 034Þ (1) (10)
with x ¼ p/po and po being the atmospheric pressure. Most samples The additional parameter m is 1 for BET and 1/2 for the theoretical
showed a linear curve for 0.4 < t < 1 nm, and the micropore volume derived equation of Aranovich [29,30]. Characteristic values of m
was obtained by extrapolation to t ¼ 0 while the external surface depending on the adsorbent were also proposed by Aranovich [31]
was taken from the slope and the physical meaning of m between 0 and 1 was interpreted in
a density change of the adsorbed layer according to the Ono-Kondo
Sext ¼ DV=Dt (2) lattice model. Equation (10) is called hereafter the DR-Aranovich
isotherm.
Respective results for industrial zeolites and an amorphous silica
An alternative version of the combined capture of micropores
are compiled in Table 1.
and external surface simply replaces the Dubinin-Radushkevich
term by a constant and yields an equation with only 3 parame-
3. Theory ters [32].

According to Dubinin and Radushkevich [10,27] the isotherm for

the filling of micropores with adsorbed condensed nitrogen is 1
more common in the literature is the substitution of Eo by b E* where b is a
assumed to obey a Gaussian distribution scaling factor.
 C. Buttersack et al. / Microporous and Mesoporous Materials 236 (2016) 63e70 65

Table 1
Characteristic parameters of industrial zeolites and amorphous silica (LiChrospher 1000, data from literature [35]). Total volume Vtot at x ¼ 0.95, Stot by the I-point method [1], t-
plot (0.4 > t > 1 nm) by Equation (1) with the correlation coefficient r. Si/Al and particle size taken from the producer.

t-plot

Type Si/ Size Ionic Vtot Stot Vmicro Sext r

Al /mm form /cm3g1 /m2g1 /cm3g1 /m2g1

HSZ390 385 6 Hþ 0.52 913 0.320 84.7 0.99956

DAY 128 6 Hþ 0.35 823 0.301 40.1 0.99695
Y100 59 8.0 Hþ 0.46 840 0.323 66.8 0.99766
Y756 28 7.4 Hþ 0.42 823 0.299 56.3 0.99293
Y530 15 8.3 Hþ 0.41 833 0.303 55.9 0.99717
Y411 6.0 7.8 Hþ 0.40 840 0.305 48.4 0.99703
Y307 3.8 5.7 Hþ 0.36 806 0.296 33.9 0.99560
CBV780 40 6.8 Hþ 0.51 900 0.339 97.7 0.99930
CBV760 30 5.7 Hþ 0.52 926 0.341 99.0 0.99651
CBV500 2.6 Hþ 0.37 825 0.294 49.9 0.99768
13X 1.3 2000 Naþ 0.33 874 0.326 5.6 0.97557
LiChrospher ∞ 0.032 25 0.0032 19.0 0.99830

4. Results and discussion
4.1. Analysis of the DR-BET method
Fig. 1 shows the nitrogen isotherm measured with a X-zeolite.
The non-linear fitting procedure due to the DR method was
generally restricted to partial pressures lower than 0.45. This is also
advised by the reason that capillary condensation between the
powdered samples can occur [33]. In most cases the lowest partial
pressure used for the evaluation was not lower than 0.005. This is a
consequence of a limited time available for attaining the adsorption
equilibrium within the experimental procedure. The fitting due to
DR-BET performed with the boundary conditions
0 < Vext < 0.01
0 < k < 0.1
and
0<C
results in very great optimal values of C > 10000 and leads to the
blue curve. However, when the additional condition C < 10 was
used, the optimal value for C was small (C ¼ 6.4) leading to the
green curve. These 2 optima were found for all samples. The ob-
tained characteristic parameters were shown in Table 2 for 11
Fig. 1. Nitrogen adsorption (77K) on a 13X zeolite. Fitting according to the DR-BET
isotherm (8) (0.0005 < x < 0.4) and the DR-Aranovich Equation (10)
(0.0005 < x < 0.98).
industrial FAU type zeolites. The values of Vmicro and Sext for the CBV
zeolites were similar to those reported by Remy and Poncelet [12].
In total 165 samples were evaluated with these methods. In all
cases, the high C-values were situated above C > 104 (Fig. S1).
Therefore, as shown in Fig. 2, a change of C in the range of 104e108
has practically no influence on the regression coefficient and the
optimal values of Vmicro. In that case the BET term is a rectangular
function and only a constant value of Sext is superposed to the DR
term. The region of 2 < C < 20 is instable and no optimal values
were found. The instability is also due to the applied algorithm
(Levenberg and Marquardt [26]) for the non-linear regression. In
contrast, some sensitivity is found for the low C-values (Fig. 2)
which means that the BET term is a slow increasing function su-
perposed to the DR-term. Analogous results were found for the
parameters Sext and Eo (Fig. S2). For all 165 samples the regression
coefficient r2 of the second optimum is only marginally greater than
that of the first optimum. The mean ratio is r2/
r1 ¼ 1.00032 ± 0.00092.
The high C-values correspond to the mathematical property of
the BET Equation (5). For very large C-values, C 1 approaches C,
and the BET-Equation (5) is reduced to
V2 ¼ Vext =ð1  xÞ (11)
At this point no dependence on C is possible. Exactly that limit
value of the BET equation, where C approaches infinity, was called
“point of inversion” and proposed as a reference point for the
calculation of the total specific surface area [34].
Fig. 3 shows the data of Fig. 1 within a half-logarithmic plot. The
measured data clearly obey the DR term within a large pressure
range with values of p/po down to 106, as expected independent
on the C-term. The underlying experimental data was obtained
with extremely long times of equilibration for each measuring
point within the low pressure region. All other zeolite samples
were measured with lower effort, and only the data above x ¼ 0.005
were used for the regression analysis.
In order to get information for the external surface of the zeo-
lites, a set of data from amorphous silica [35] is presented here. It
stems from the literature and was originally measured for the
purpose of having a reliable reference for the so-called as-plot [36].
Both regression types of the DR-BET-isotherm can be applied for
the pressure range from x ¼ 106 to 0.4 but as shown in Fig. 4, the
fitting with low C-values is significantly better than that with high
values. The C-values of 12000 and 12.6 resp. are in the same order
than those found for the zeolites. Although the material was
claimed to have a total amorphous character, the application of the
DR-BET method yields a fraction of micropores (Table 2) which
66 C. Buttersack et al. / Microporous and Mesoporous Materials 236 (2016) 63e70

Table 2
Characteristic parameters of industrial zeolites obtained by the DR-BET Equation (8) for 0.004 < x < 0.4 with the correlation coefficients r1 and r2. In addition the DR-BET results
of an amorphous silica (LiChrospher 1000, data from literature [35]) for 106 < x < 0.5 are listed.

Type DR-BET 1, high optimum DR-BET 2, low optimum

Vmicro/cm3g1 Sext/m2g1 Eo/kJ mol1 C r1 Vmicro/cm3g1 Sext/m2g1 Eo/kJ mol1 C r2

HSZ390 0.333 62.9 2.19 399986 0.99953 0.353 47.1 2.26 2.72 0.99978
DAY 0.316 16.9 2.37 471985 0.99909 0.321 20.7 2.40 0.97 0.99961
Y100 0.338 43.8 2.22 319684 0.99974 0.352 32.9 2.27 2.58 0.99988
Y756 0.316 29.5 2.26 1720670 0.99978 0.325 24.1 2.30 2.30 0.99988
Y530 0.314 38.8 2.25 196720 0.99900 0.327 30.9 2.29 1.94 0.99916
Y411 0.314 34.7 2.39 711570 0.99934 0.323 25.3 2.48 5.45 0.99985
Y307 0.302 26.0 2.47 713633 0.99943 0.308 18.9 2.55 6.28 0.99989
CBV780 0.285 182.0 1.95 1611450 0.99904 0.345 122.1 2.20 6.96 0.99988
CBV760 0.307 179.0 2.02 1286929 0.99911 0.357 102.0 2.23 6.99 0.99987
CBV500 0.308 25.5 2.51 572890 0.99981 0.316 20.6 2.55 2.38 0.99993
13X 0.320 15.6 3.07 394415 0.99990 0.325 8.5 3.10 6.41 0.99995
LiChrospher 0.0075 11.5 1.26 11774 0.99980 0.0081 12.6 1.81 6.35 0.99995

Fig. 2. Calculated micropore volume and correlation coefficients depending on fixed

values of the C-terms. Experimental data for Y756, 0.0005 < x < 0.4.
Fig. 4. Nitrogen adsorption (77K) on amorphous silica (LiChrospher 1000). Fitting with
DR-BET (upper and lower optimum) (106 < x < 0.5) and by usual BET (0.005 < x < 0.5).
Experimental data from the literature [35].

Fig. 3. Nitrogen adsorption (77K) on the 13X zeolite. Fitting according to the DR-BET
isotherm (8) (low optimum) (106 < x < 0.4).
even so amounts to 23% of the total volume and is significantly
greater than that obtained by the t-plot (Table 1). For comparison,
the usual BET-plot using the data between x ¼ 0.005 and 0.4 is also
shown in Fig. 4. The C-value is 250 and similar to those reported in
the literature [34,37], but due to the model used here the value of
12.6 is correct. The external surface of the dealuminated zeolites
and the silica are similar with respect to the chemical nature. The
zeolite surface should be characterized by an imperfect crystal
structure and contain silanol groups such as the amorphous
counterpart. However, the principal difference of the zeolite surface
is established by the presence of the pore entries. The respective
surface fraction is the region where micropores and external sur-
face are overlapping. The larger surface area of the amorphous
material is therefore reasonable but the result has to be supported
by the comparison with further materials.
To evaluate the correctness of the C-value one can also compare
the DR-term with the BET-term of the same experimental data. The
C-value expresses the affinity of the monolayer formation as a
Langmuir process. It is shown here that it is mathematically
possible to express the DR-equation as a sum of Langmuir
isotherms
Vmicro X
n
ki x
V ¼ Vmicro expf  kðlnð1=xÞÞ2 g ¼ (12)
n i¼1 1 þ ki x
where ki can be found by nonlinear regression. By that way the DR
isotherm calculated for a typical dealuminated Y zeolite was con-
verted to a series of expansion with 10 or 12 terms (Fig. S3,
Table S1). As shown in Fig. 5 the first molecules were adsorbed with
ki ¼ 109 while the last ones are adsorbed with a constant of about
25. The values of ki can directly be compared with the C-values.
 C. Buttersack et al. / Microporous and Mesoporous Materials 236 (2016) 63e70 67

300

-1
C = 3.6 ) / m g
2
250

200

150

Sext (lower optimum,

100

50

0
0 50 100 150 200 250 300
S ext (lower optimum) / m2 g-1

Fig. 6. Correlation of the 3 parameter with the 4-parameter optimization.

Fig. 5. Representation of the DR-equation by a sum of Langmuir isotherms according

to Equation (12). Experimental data for nitrogen adsorption on Y756.

Principally the adsorption in the micropore must be more stronger

than that on the external surface. The low C-values must therefore
be the correct ones. As a result one can also conclude that the
adsorption on the external surface starts to proceed when both the
adsorption energies in the micropore and on the surface are equal.
If the DR-isotherm is considered as a sum of Langmuir isotherms, a
general isotherm would exist of which the BET equation would be a
special case where the infinite number of Langmuir isotherms is
reduced to only one.
Due to the scientific background of Equation (12) a remark has
to be added. Dubinin et al. found that the pore filling is funda-
mentally different compared to the layer-by-layer formation of
surface adsorption [38e40]. Therefore it seems to be forbidden to
apply the Langmuir concept to pore filling. However, in the case of
infinite Langmuir isotherms, each of which is attributed to an Fig. 7. Correlation of the 3 parameter with the 4-parameter optimization.
infinite small (homogeneous) surface fraction, the aforementioned
difference is only artificial. In addition, it has to be mentioned that,
in contrast to the current opinion, the volume filling of micropores the assumption of a constant C-value seems to be the method of
was theoretically described by Langmuir type isotherms [41]. choice. By reducing the number of free parameters from 4 to 3 all
The dependence of ki on i, as shown in Fig. 5, is nearly but not information concerning the external surface is then redirected to
actually linear. The respective underlying function is worth to be Sext.
established as an analytical (and theoretically founded) function in An analogue further reduction of the parameters is possible
the future. with respect to the characteristic energy which is scattering around
In contrast to the work of Pomonis et al. [34] the model pre- 2.3 kJ mol1 for all 165 samples (Fig. S5).
sented here, is defined by a definite C-value and not by those
extremely high resp. infinite C-values of the inversion point (“I-
point”). Some surface values obtained by that method are listed in 4.3. DR-Aranovich isotherm
Table 1 and are situated between 800 and 900 m2 g1. They obvi-
ously include the inner surface of the micropores which is beyond Fig. 1 also contains the curve fitting where the BET-term is
the term of external surface. replaced by the general Aranovich-term (Equation (10)). Here, the
full experimental isotherm is covered. That procedure also works
with data of other zeolites. The fitting was excellent in every case,
4.2. Practical aspects of the DR-BET method but for the additional parameter m different values were obtained
(Table 3). The values of m between 0 and 1 mean that less nitrogen
The C-values of the lower optimum of all 165 zeolite samples are is adsorbed on the zeolite surface than predicted by the BET
situated in a range from 0.2 to 6 and are clustering mainly around isotherm (m ¼ 1). At a first glance power functions seem to be of
3.6 (Fig. S4). Although each value represents the optimal value, the empirical nature also in this case, but nevertheless the question
question arises, if the different values are really characteristic for arises how to construe the power of m.
the external surface. As the main interesting parameter is the sur- Aranovich has tried to explain it by surface compression. That
face Sext, the fitting process was also performed with an arbitrarily means that the density of the surface adsorbed nitrogen is not a
fixed parameter of C ¼ 3.6. As shown in Fig. 6, the values of Sext constant but enhanced with increasing filling-up of the multilayers.
depend somehow on the C-values, especially for those C-values Increasing lateral interactions will then lead to a more flat isotherm
originally situated below 1. The respective dependence of Vmicro can [42]. In addition the flattening of the BET-curve may be explained
be neglected (Fig. 7). For the comparison of similar porous solids by the surface roughness.[2, 43e45] The effect is then caused by the
68 C. Buttersack et al. / Microporous and Mesoporous Materials 236 (2016) 63e70

Table 3
Characteristic parameters of industrial zeolites obtained by the t-plot and by the DR-Aranovich Equation (10) and the simplified Equation (14) with m ¼ 0.36. In addition the
DR-BET results of an amorphous silica (LiChrospher 1000) for 106 < x < 0.5 are listed.

Type DR-Ara (1) x ¼ 0.0005 …. 0.99 DR-Ara (2) m ¼ 0.36, x ¼ 0.0005 …. 0.40

Vmicro/cm3g1 Sext/m2g1 Eo/kJ mol1 C m r Vmicro/cm3g1 Sext/m2g1 Eo/kJ mol1 C r

HSZ390 0.360 819.5 2.50 0.050 0.025 0.99787 0.353 88.3 2.26 1.290 0.99986
DAY 0.320 42.9 2.42 0.916 0.316 0.99922 0.321 54.0 2.40 0.391 0.99960
Y100 0.355 90.5 2.23 0.369 0.434 0.99944 0.352 63.3 2.27 1.179 0.99989
Y756 0.327 177.0 2.27 0.122 0.246 0.99974 0.325 63.8 2.30 0.694 0.99991
Y530 0.328 62.3 2.27 0.631 0.460 0.99917 0.327 71.9 2.29 0.773 0.99921
Y411 0.328 376.4 2.39 0.066 0.000 0.99943 0.323 46.5 2.47 2.064 0.99994
Y307 0.311 43.3 2.49 0.617 0.395 0.99945 0.309 33.9 2.54 2.377 0.99997
CBV780 0.342 173.4 2.24 5.123 0.326 0.99988 0.347 172.2 2.19 3.893 0.99995
CBV760 0.353 145.3 2.27 5.239 0.373 0.99863 0.358 143.4 2.22 3.978 0.99993
CBV500 0.316 197.3 2.56 0.191 0.000 0.99993 0.316 44.9 2.55 0.872 0.99992
13X 0.325 11.6 3.11 6.089 0.307 0.99984 0.325 12.7 3.10 3.705 0.99996
LiChrospher 4.76 105 28.2 1.77 1.41 0.292 0.99986

progressive smoothing of the liquid-covered surface during the
multilayer filling process.
The overall effect of the surface compression can be comprised
in a correction function f (x) which connects the Aranovich function
with the BET term according to
1 f ðxÞ
¼ (13)
ð1  xÞm ð1  xÞ
The correcting function f (x) principally must have an impact on the
fitting procedure similar to the findings presented in Fig. 2, also in
case of a limitation to small values of x. To illustrate that effect the
exponential term is expressed by a Taylor series of expansion
a constant or simply m ¼ 1. The application of the DR-Aranovich
isotherm is therefore regarded as an interesting empirical tool,
but according to the present knowledge it has no relevance for the
characterization of porous systemsin practice.
The full adsorption isotherm of the silica up to x ¼ 0.97 again can
be described by the combination of the DR-isotherm with the
Aranovich equation (Equation (10)). According to the low value of
m ¼ 0.29 the C-value of 28 is greater than that obtained with DR-
BET (Table 3, Fig. S6).
4.4. Comparison of the DR-BET-method with the t-plot
Fig. 8 shows the striking disadvantage of the t-plot compared

1 ðm  1Þm 2 ðm  1Þmðm þ 1Þ 3
f ðxÞ ¼ ¼ 1 þ ðm  1Þx þ x þ x þ/
ð1  xÞm1 2! 3! (14)
; m>0

After truncation of the series (14) behind the second term Equation with the DR-BET isotherm. The t-plot is the linear extrapolation of
(10) can now be modified to the linear part of the plot of V versus t. The linear part of t (see
Equation (1)) was found to exist between 0.4 and 1 nm for most
Sext sv Cxð1 þ ðm  1Þx Þ
V ¼ Vmicro expf  kðlnð1=xÞÞ2 g þ (15)
ð1  xÞð1 þ ðC  1Þx Þ
As shown in Table 3, the values of m obtained by fitting with
Equation (10) over the full pressure range of 0.005 < x < 0.98 were
found to spread from 0 to 0.5 for 11 different FAU type zeolites. It
seems to be improbable to assign those differring m-values to
multilayer compression alone. Especially at high partial pressure
capillary condensation in the void between aggregated zeolite
particles may influence the isotherm [33] and thus allow an influ-
ence by the sample preparation. Nevertheless, the validity of the
DR-Aranovich isotherm (Equation (10)) is remarkable. The value of
m has no essential influence on the evaluation of the micropore
volume, but a strong influence on the external surface and the C-
term exists. To evaluate that effect, Equation (15) is applied in the
same lower pressure region used for the DR-BET-method
(0.005 < x < 0.4) and a constant value of m ¼ 0.36, being the
average of those belonging to all zeolite samples with m > 0.1, was
inserted as well. Compared with the DR-BET method, the regres-
sion coefficients are similar, but the external surface is doubled,
while the C-terms are halved (Table 3). To compare the surface data Fig. 8. Comparison of the DR-BET isotherm (low optimum, 0.0004 < x < 0.60) with the
of similar zeolites with each other, it is therefore essential that m is t-plot (0.4 < t < 10 nm) based on the experimental data for zeolite Y756.

Fig. 9. Comparison of the micropore volume obtained by the DR-BET method (low
optimum) with that of the t-plot.
500
-1
external surface Sext (t -plot) / m g
450
2
400
350
300
250
200
150
100
50
0 [6] G.D. Parfitt, K.S.W. Sing, D. Urwin, J. Coll. Interf. Sci. 53 (1975) 187e193.
0 50 100
external surface S ext (DR-BET low optimum) / m g
Fig. 10. Comparison of the external surface obtained by the DR-BET method (low
optimum) with that of the t-plot.
zeolite samples. That region corresponds to a pressure range of
0.15 < x < 0.75. The extrapolated micropore volume lays outside
that region. In contrast, the DR-BET plot of most zeolite samples is
based on the region of 0.0005 < x < 0.5 covering the transition
between micropore filling and external adsorption. The calculated
micropore volume is located inside that region. In Fig. 8 an example
is given for both procedures.
Fig. 9 shows the comparison of the micropore volume evaluated
with DR-BET and the t-plot of all 165 zeolite samples. The t-plot
values are about 8% lower. Thermally degraded zeolites with low
micropore volume show the greatest discrepancy. The external
surfaces are extremely different. Here, a split was observed. Some
results of the t-plot were greater, most of them smaller than those
obtained by DR-BET (Fig. 10).
5. Conclusion
Based on the nitrogen adsorption data of 165 FAU-type zeolites
with different Si/Al and different strong exposure to thermal stress
the DR-BET method is superior to the t-plot. The method yields 4
characteristic parameters, which are Vmicro, Eo, Sext, and C. The curve
fitting principally yields two optima, that with the low C-value
being the correct one. By the conversion of the DR-term to a sum of
Langmuir equations it is possible to compare the affinity of the
adsorption in the micropores with that on the external surface.
Some interdependence of the optimal external surfaces and the
optimal C-values exists. For the comparison of similar samples the
optimization with constant C-values is recommended.
C. Buttersack et al. / Microporous and Mesoporous Materials 236 (2016) 63e70 69
While the DR-BET method uses the pressure range of
0.0005 < x < 0.4 … 0.6, the DR-Aranovich method covers the
pressure range up to 0.98. Vmicro and Eo may be found, but the values
obtained for Sext and C have to be questioned, as they depend on the
additional parameter m, the nature of which remains unclear.
Analogous results are presented for the nitrogen adsorption on
amorphous silica where the RD-BET method yields a very small
fraction of micropores. The method may be therefore also of in-
terest for other non-zeolite materials.
Acknowledgement
Financial support of the Bundesministerium für Wirtschaft und
Energie for the Project: ZIM-KF 2067505ZG1 is gratefully
acknowledged.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.micromeso.2016.08.018.
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