You are on page 1of 8

Microporous and Mesoporous Materials 151 (2012) 126–133

Contents lists available at SciVerse ScienceDirect

Microporous and Mesoporous Materials


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

The BET equation, the inflection points of N2 adsorption isotherms


and the estimation of specific surface area of porous solids
A.K. Ladavos a,⇑, A.P. Katsoulidis b, A. Iosifidis c, K.S. Triantafyllidis d, T.J. Pinnavaia e, P.J. Pomonis c
a
University of Western Greece, G. Seferi 2, Agrinio 30100, Greece
b
Department of Chemistry, Northwestern University, Evaston, IL 60208, USA
c
Department of Chemistry, University of Ioannina, Ioannina 45110, Greece
d
Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece
e
Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA

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

Article history: The N2-adsorption isotherms of porous solids are received in the form V = f(P/Po). If such data are depicted
Received 7 August 2011 in the form V(1  P/Po) = f(P/Po) or V(1  P/Po)/(P/Po) = f(V(1  P/Po)), they show an identical inversion
Received in revised form 12 October 2011 point (I-point, Inversion or Inflection point), which corresponds exactly to the monolayer volume Vm.
Accepted 3 November 2011
As a result the value of specific surface area S is determined with unique precision via the trivial relation-
Available online 11 November 2011
ship S (m2 g1) = 4.356Vm (cm3 g1) without any use of the classic BET treatment. The derivates dV/d[(P/
Po)] vs. (P/Po) and d(V[1  (P/Po)])/d[(P/Po)] vs. (P/Po) exhibit maxima exactly at the same pressure (P/Po),
Keywords:
while the second order derivative d2V/d[(P/Po)]2 vs. (P/Po) exhibits a minimum exactly at the same pres-
Nitrogen adsorption isotherm
BET isotherm
sure (P/Po) with the I-point. As a consequence the specific surface area of solids can be determined just
Specific surface area from experimental raw (P/Po), V data without any use, neither of linear BET treatment nor the Inversion or
Inflection type graphs. For some MCM-41 type mesoporous materials, the I-plots show not one but two
Inversion points/I-points. The first inversion/inflection point at lower (P/Po) values, ‘‘ILP-point’’, corresponds
to the completion of the adsorption procedure on the bare surface and the formation of monolayer and is
useful for the determination of specific surface area S. The second inversion/inflection point at higher (P/
Po) values, ‘‘IHP-point’’, corresponds to the completion of the pore filling via condensation and may be use-
ful for the determination of mesopore volume.
Ó 2011 Elsevier Inc. All rights reserved.

1. Introduction Eq. (1) is not linear and for the determination of Vm it is used in
its linear form (2):
The determination of specific surface areas – ssa S (m2 g1) of
various adsorbents and catalysts is practically nowadays based
ðP=Po Þ=½Vð1  ðP=P o Þ ¼ 1=CV m þ ðC  1ÞðP=P o Þ=CV m ð2Þ
on the BET equation (1) proposed in 1938 by Brunauer, Emmett Then plots in the form (P/Po)/[V(1  (P/Po)] = f(P/Po) provide straight
and Teller [1]: lines at low pressure range, usually 0.05 < (P/Po) < 0.25, depending
on the sample. From such linear plots, with slope s = (C  1)/CVm
V=V m ¼ CðP=Po Þ=½1 þ ðC  1ÞðP=Po Þ½1  ðP=P o Þ ð1Þ
and intercept t = 1/CVm, two unique values of C and Vm can be
In Eq. (1) the symbols have their customary meaning and details estimated.
about its derivation and properties can be found in some standard Nevertheless those unique C and Vm values may be influenced
text books on this subject [2–4]. by the pressure range used in drawing the linear plots, which influ-
The BET equation (1) is considered classical in the original ences in turn the estimation of surface area in a quantitative way
meaning of this word, i.e. every possible proposed improvement up to 25–30%. But the estimation of a single value for the C-param-
of methodology, or calculations, in the determination of ssa will eter conveys the qualitative wrong impression that this is a con-
use BET as a stick of comparison. The determination of ssa takes stant which is not. To be more precise the explicit relationship
place via estimation of the volume of the adsorbed monolayer Vm for C is given by Eq. (3) [2–4]:
and if N2 is used as adsorptive, which is usually the case, then S C ¼ ½a1 m2 =a2 m1  exp½ðq1  qL Þ=RT ð3Þ
(m2 g1) = 4.356Vm (cm3 g1).
where a1 and a2 are the condensation coefficients for the first and
⇑ Corresponding author. Tel.: +30 2641074126; fax: +30 2641074179. the second layers, m1 and m2 are the frequencies of oscillation of
E-mail address: alantavo@cc.uoi.gr (A.K. Ladavos). the molecules in the first and the second layers normal to the

1387-1811/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2011.11.005
A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133 127

surface, q1 is the heat of adsorption in the first layer on the bare sur- Consequently in 2006, this methodology applied successfully for
face and finally qL is the heat of condensation which is equal for all the determination of specific surface areas of various mesoporous
of the layers except the first. materials like MCM-41, MCM-48, SBA-15 and SBA-16 containing
The term [a1m2/a2m1] = m is often considered equal to unity microporosity [10] as well in studying the properties characterizing
although it has been suggested by Kembal and Schreiner [5] that the complexity of silicas by adsorption of nitrogen and methanol
it can varies as much as 106 orders (!) of magnitude in the whole [11].
range of adsorption 0 < (P/Po) < 1. So the C-constant found in the In 2007 Rouquerol, Llewellyn and Rouquerol in order to define
traditional BET-treatment is given by: precisely the linear region of the BET equation used graphs of the
form given by Eq. (7).
C ¼ expðq1  qL Þ=RT ð4Þ
V½1  ðP=Po Þ v s: ðP=Po Þ ð7Þ
and corresponds approximately to the value of the C-parameter at
Based on such graphs they proposed the following two consistency
the point where the adsorbed monolayer is formed. The determina-
criteria [12]: (i) the pressure range selected should have values of
tion of C-parameter in the whole range of adsorption is unattainable
V(Po  P) increasing with (P/Po), and (ii) the y intercept of the linear
in the traditional treatment.
region must be positive to yield a meaningful value for the
The high values of C during the first stages of adsorption reflect the
high values of the condensation coefficient a1 in the first layer com- C-parameter, which should be greater than zero. Those consistency
criteria are related to the original observation made by members of
pared to the values of a2, as well as the high values of q1 compared to
qL. As the adsorption proceeds, the case where a1 = a2 is eventually the same group in 1964 [6].
The next few years 2008–2010 these consistency criteria, and
reached. For m1  m2, which is a realistic approximation as the pressure
and the surface coverage increase, V tends to Vm. At this limit, Eq. (4) graphs similar to Eq. (7) were applied extensively by the Snurr’s
group in order to study the Inflections and steps in carbon dioxide
applies. To cite an example at 77 K, RT = 0.6 kJ mol1. Then for
(q1  qL) = 4.2 kJ mol1, C  1100, whereas for (q1  qL) = 2.0 kJ mol1, adsorption isotherms in metal–organic frameworks [13,14] and for
evaluating the BET method for determining surface areas of MOFs
C  20.
So as far as q1 is larger than qL even by 1–2 kJ mol1, there and zeolites that contain ultra-micropores [15]. These studies
showed beyond any doubt that the consistency criteria [12] are in-
should be a positive value of C. But the difficulty of choosing the
deed a very useful guide for choosing the pressure range used in
pressure range for drawing the classical BET-plots leads sometimes
the fitting of adsorption data and obtaining correct results via
to negative values of C-parameter, and consequently erroneous
the BET treatment, at least for the microporous materials treated
values of Vm.
in Refs. [13,14].
Aware of such problems, Rouquerol et al. (1964) [6] made the
The same year 2007 where the consistency criteria were pro-
very penetrating observation that the corrected choice of pressure
posed, it was also observed that for some mesoporous materials
range, providing the corrected values of S, is that where the term
of MCM-41 type exhibiting morphogenesis [16] as well of MSU
[V(1  (P/Po)] of the BET equation increases with the increase of
type solids [17], the I-plots show not one but two (2) Inversion
pressure (P/Po). Beyond that limit negative values of C are obtained.
points/I-points. This was attributed to the existence of different, dis-
In essence this is the first precise definition of a singular Inflection
creet and distinct domains of microporosity and mesoporosity in the
point of the BET equation, termed as the B-point in the various
solids. If the porosity is random such effects are masked. The first
handbooks [2–4] and used for the determination of S. But the po-
inversion/inflection point at lower (P/Po), V values, termed ‘‘low
tential of this observation was not appreciated for a long time by
pressure ILP-point’’, corresponds to the completion of the adsorption
the researchers in the field.
procedure on the bare surface and the formation of monolayer and
Then in 2004–2005 the I-point method was proposed by Pomo-
is useful for the determination of specific surface area S. The second
nis’ group [7–9]. The method was realized by rearranging the stan-
inversion/inflection point at higher (P/Po), V values, termed ‘‘high
dard BET equation (1) in a non-linear BET/Scatchard-type plot as
pressure IHP-point’’, corresponds to the completion of the pore fill-
follows:
ing via condensation and may be useful for the determination of
½Vð1  ðP=Po ÞÞ=ðP=Po Þ ¼ CV m  ðC  1Þ½Vð1  ðP=Po ÞÞ ð5Þ mesopore volume. This last point has not fully explored yet.
In 2010 the group of Collins undertook the task of evaluation of
Then plots of the right hand part V[1  (P/Po)]/(P/Po) vs.
the BET, I-Point, and as-plot procedures for the routine determina-
V[1  (P/Po)] provide lines, which have the shape of an inclined V
tion of external specific surface areas of highly dispersed and por-
i.e. >. Such lines exhibit one Inversion point termed I-point and have
ous silicas [18]. After comparison of the nitrogen adsorption
two very interesting features: First, their slope, corresponding to
isotherms of four candidate reference materials by means of shape
(C  1), is not constant but varies from 106 at low (P/Po) to about
ratio, certain silica was chosen to be the reference material. Then
zero at high (P/Po) as suggested indeed by Kembal and Schreiner
twenty-two (22) solids were evaluated for the effects of micropo-
[5]. Therefore the values of C can be determined in the whole range
rosity on the determination of their specific surface areas. The sam-
of adsorption independently of the Vm parameter. On the same token
ple isotherms were then adjusted to minimize micropore
the C-value at the point where the formation of monolayer is com-
adsorption and the BET plot and I-point procedures were applied
pleted can be also defined and corresponds more or less to its sin-
to give the external specific areas from all three procedures. The
gle value estimated during the linear BET treatment.
authors conclude that the I-point procedure, as proposed by Pomo-
Second, the I-point where the slope of the inclined V line
nis and co-workers [7–9] or the modified approach described by
changes from negative (upper part) to positive (lower part), pro-
Rouquerol’s and co-workers [6,12] presents the advantage, for
jected on the horizontal V[1  (P/Po)] axis, (x-axis), corresponds ex-
the many cases where the contribution of micropores to the spe-
actly to the volume of monolayer Vm. So at the I-point we have
cific surface area is unimportant, that it does not require prior defi-
V m ¼ ½V I ð1  ðP=Po ÞI  ð6Þ nition of the (P/Po) range in order to obtain the total specific surface
area. However, when it is important to determine the external (i.e.,
where VI and PI is the volume and the pressure at the I-point. As a non-micropore) specific surface area, the as-plot procedure has a
result the value of S is determined without any knowledge of C significant advantage over the other procedures as no independent
parameter with unique precision via the trivial relationship S determination of the micropore capacity is required: both the
(m2 g1) = 4.356Vm (cm3 g1). micropore capacity and the external specific surface area are
128 A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133

Table 1
Samples studied and some features of their porosity and specific surface areas.

No. Sample Kind of porosity and porosimeter useda Sp/BET (m2/g) Sp/ILP-point (m2/g)b Sp/IHP-point (m2/g)c Ref.
1 OMSi–Ce–Co/1:9/A Worm-like mesoporosity with some microporosity (S) 1261 1234 – [16]
2 OMSi–Ce–Co/1:9/B Worm-like mesoporosity with some microporosity (S) 989 1041 – [16]
3 OMSi–Ce–Co/1:9/C Worm-like mesoporosity with some microporosity (S) 782 786 – [16]
4 OMSi–Ce–Co/1:3/A Worm-like mesoporosity with some microporosity (S) 980 1012 – [16]
5 OMSi–Ce–Co/1:3/B Worm-like mesoporosity with some microporosity (S) 896 816 997 [16]
6 OMSi–Ce–Co/1:3/C Worm-like mesoporosity with some microporosity (S) 869 819 966 [16]
7 OMSi–Ce–Co/1:1/A Worm-like mesoporosity with some microporosity (S) 767 743 875 [16]
8 OMSi–Ce–Co/1:1/B Worm-like mesoporosity with some microporosity (S) 725 701 847 [16]
9 OMSi–Ce–Co/1:1/C Worm-like mesoporosity with some microporosity (S) 682 652 769 [16]
10 2% Al-MSU-S/W(BEA) Ordered mesoporosity with some microporosity (Q) 895 845 1066 [17]
11 2% Al-MSU-S/W(BEA) Ordered mesoporosity with some microporosity (M) 928 884 1025 [17]
12 Zeolite beta Microporous (Q) 599 598 – [17]
13 Al-MCM-41 Ordered mesoporosity with some microporosity (Q) 875 869 1132 [17]
14 5% beta + 95% Al-MCM-41 Mixed mesoporosity and microporosity (Q) 840 835 1082 [17]
15 15% beta + 85% Al-MCM-41 Mixed mesoporosity and microporosity (Q) 815 808 1020 [17]
16 30% beta + 70% Al-MCM-41 Mixed mesoporosity and microporosity (Q) 763 746 928 [17]
17 50% beta + 50% Al-MCM-41 Mixed mesoporosity and microporosity (Q) 706 688 793 [17]
18 75% beta + 25% Al-MCM-41 Mixed mesoporosity and microporosity (Q) 669 659 660 [17]
a
The designations (Q), (M) and (S) correspond to the porosimeters Quantachrome, Micromeritics and Sorptomatic employed.
b
Corresponds to the Sp estimated by the I-point at lower pressure (LP).
c
Corresponds to the Sp estimated by the I-point at higher pressure (HP).

obtained from the same plot. For this, however, an appropriate ref- – The second aim is to clarify the meaning and usefulness of the
erence isotherm, without micropore capacity must be available: ‘‘low pressure ILP-point’’ and the ‘‘high pressure IHP-point’’ in the
I-point diagrams V[1  (P/Po)]/(P/Po) vs. V[1  (P/Po)] or/and
– The first aim of this work is to draw attention to the fact that the Inflection point diagrams V[1  (P/Po)] vs. (P/Po) in the esti-
Inversion point of the I- point method [7–9] tallies exactly to mation of specific surface area.
the Inflection point observed in the application of consistency – The third point is to show that those identical Inversion or
criteria [6–12]. Inflection points can be estimated very precisely from experi-
mental adsorption (P/Po), V data without resorting to any kind

Fig. 1. Graphs for OMSi–Ce–Co/1:9/A sample: (a) the N2 adsorption–desorption isotherms as well as the I-point plot are shown in the form (V[1  (P/Po)]/(P/Po) vs. V[1  (P/
Po)]. The I-point is indicated by a star (w), (b) plot of the form (V[1  (P/Po)]) vs. (P/Po). The N2 adsorption–desorption isotherms V = f(P/Po) are shown for comparison, (c) plots
in the form dV/d[(P/Po)] vs. (P/Po) and d(V[1  (P/Po)])/d[(P/Po)] vs. (P/Po), (d) plot in the form d2V/d[(P/Po)]2 vs. (P/Po). The star (w) in (b–d) corresponds the I-point from (a).
A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133 129

Fig. 2. Graphs for OMSi–Ce–Co/1:1/B sample: (a) the N2 adsorption–desorption isotherms as well as the I-point plot are shown in the form (V[1  (P/Po)]/(P/Po) vs. V[1  (P/
Po)]. ILP-point and the IHP-point are indicated by a star (w), (b) plot of the form (V[1  (P/Po)]) vs. (P/Po). The N2 adsorption–desorption isotherms V = f(P/Po) are shown for
comparison, (c) plots in the form dV/d[(P/Po)] vs. (P/Po) and d(V[1  (P/Po)])/d[(P/Po)] vs. (P/Po), (d) plot in the form d2V/d[(P/Po)]2 vs. (P/Po). The stars (w) in (b–d) correspond to
the I-points from (a).

of (V[1  (P/Po)]/(P/Po) vs. V[1  (P/Po)] or/and V[1  (P/Po)] vs. been discussed previously in Refs. [16,17] and are cited in Table
(P/Po) graphs and as a consequence of this last point, to show 1 which also contains some features of their porosities and the
that the specific surface area of solids can be determined just determined specific surface areas.
from experimental raw (P/Po), V data without any use, neither To be more precise the eighteen (18) isotherms correspond to
of linear BET treatment nor the Inversion or Inflection type the following samples:
graphs.
(i) Nine (9) isotherms (No. 1–9 in Table 1) correspond to orga-
Attention should be drawn to the fact that the values of the nized mesoporous silicate materials containing Co and Ce
‘‘specific surface area – ssa’’, referred to in the present article, heteroatoms. They will be designated in the next as OMSi–
may be different from the ‘‘geometrical surface area – gsa’’ in spe- Ce–Co/x:z/A–B–C where x:z is the nominal ratio of cations
cial cases of slit-like pores with openings less than 1.5 nm as ex- in the original synthesis bath and A–B–C corresponds to
plained clearly by Do et al. in a recent article [19]. But this is not the pH value 5.5–7.5–9.5 at which the particular sample
the case in the present article and the ssa meant here is the one was isolated. For details of preparation please see Ref. [16].
determined via N2 adsorption experiments. This corresponds to (ii) Two (2) isotherms (No. 10,11 in Table 1) correspond to one
the surface accessible to the probing molecules and is considered (1) nanostructured mesoporous aluminosilicate 2% Al-
to be the ‘‘correct’’ results, useful for all practical purposes, for MSU-S/W(BEA) solid and were obtained using different
example use in surface reaction rate equations expressed as porosimeters (see next). The sample was synthesized using
mole/s/m2. zeolite beta seeds and tripropylene tetraamine as the meso-
porous structure-directing agent resulting in a wormhole-
2. Experimental like pore structure with a pore diameter of 3.6 nm. The
zeolite beta (BEA) seeds were prepared using tetraethylam-
2.1. Samples and methods of preparation monium ions, as BEA-structure directors, and tetraethyl
orthosilicate (TEOS) and aluminum tri-sec-butoxide as sili-
In this study eighteen (18) N2 adsorption–desorption isotherms con and aluminium sources, respectively. For details of prep-
were employed. The samples were chosen intentionally as to cover aration see Ref. [17].
different kinds of porosity: Some of them possessed only ordered (iii) Seven (7) isotherms (No. 12–18 in Table 1) correspond to
microporosity, some others solely ordered mesoporosity, a third mechanical mixtures of a mesoporous Al-MCM-41 sample
group disordered mesoporosity with various amounts of micropo- with a microporous commercial zeolite Beta (provided by
rosity, and a fourth group was mechanical mixtures of purely Zeolyst) with 0, 5, 15, 30, 50, 75 and 100 wt.% level of Beta
microporous plus purely mesoporous materials. All of them have addition in the mixture. For details see Ref. [17].
130 A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133

Fig. 3. Graphs for 2% Al-MSU-S/W(BEA) sample: (a) the N2 adsorption–desorption isotherms as well as the I-point plot are shown in the form (V[1  (P/Po)]/(P/Po) vs. V[1  (P/
Po)]. ILP-point and the IHP-point are indicated by a star (w), (b) plot of the form (V[1  (P/Po)]) vs. (P/Po). The N2 adsorption–desorption isotherms V = f(P/Po) are shown for
comparison, (c) plots in the form dV/d[(P/Po)] vs. (P/Po) and d(V[1  (P/Po)])/d[(P/Po)] vs. (P/Po), (d) plot in the form d2V/d[(P/Po)]2 vs. (P/Po). The stars (w) in (b–d) correspond to
the I-points from (a).

referred to samples 10–18 of the same table. To be more precise


2.2. Nitrogen porosimetry all the results in those SI figures are organized as follows:

The samples were tested for their porosity characteristics by N2  In Fig. S-1a and b the isotherms V = f(P/Po) as well as the
adsorption–desorption porosimetry at 77 K. Before each measure- I-point plots, in the form (V[1  (P/Po)]/(P/Po) vs. V[1  (P/Po)],
ment the samples were degassed overnight at different tempera- are shown for the two groups of samples. The I-point, or the
tures and vacuum depending on the type of the solid and the ILP-point and the IHP-point, when two such points coexist, are
porosimeter used. The measurements were conducted on three dif- indicated by arrows.
ferent porosimeters for comparison of the experimental data and re-  In Fig. S-2a and b, apart from the isotherms V = f(P/Po), the
sults. These were: (a) an automatic volumetric sorption analyzer graphs for the consistency criteria are shown in the form
(Autosorb-1, Quantachrome) where the samples were degassed at V[1  (P/Po)] vs. (P/Po) according to the proposal by Rouquerol
1.0  103 mbar vacuum, (b) a Micromeritics Tristar 3000 Sorptom- et al. [12]. The star(s) (w) at the Inflection points in those figures
eter where the samples were degassed at 1.33  106 mbar vacuum, are not their own maxima but the I-point(s) from Fig. S-1a and b
and (c) a Sorptomatic 1990 Fisons porosimeter which operated at respectively.
1.0  103 mbar vacuum. The zeolitic, the OSiCoCe and the mechan-  In Fig. S-3a and b plots of the first derivatives in the form dV/
ical mixtures of zeolite + MCM-41 samples, were degassed at 700 K d[(P/Po)] vs. (P/Po) and d(V[1  (P/Po)])/d[(P/Po)] vs. (P/Po) for all
prior to measurements. The Al-MSU-S/W(BEA) samples were mea- samples are shown. The maxima of the two derivatives appear
sured after degassing both at 420 K and 700 K in order to detect pos- exactly at the same pressure (P/Po) indicated by the vertical line.
sible differentiations. In Table 1 the porosimeters employed in each The star(s) (w) correspond to the I-point(s) from Fig. S-1a and b.
measurement is indicated by (Q), (M) ad (S) for Quantachrome, The isotherms V = f(P/Po) are also shown for comparison.
Micromeritics and Sorptomatic, respectively.  Finally in Fig. S-4a and b plots of second derivatives of the iso-
therms V = f(P/Po) in the form d2V/d[P/Po)]2 vs. (P/Po) for the two
group of samples in Table 1 are shown. The minimum of those
3. Results
second derivatives appears exactly at the same pressure (P/Po) of
the I-point indicated by the star (w). The isotherms V = f(P/Po)
All the original adsorption data for the 18 samples of Table 1 are
are also repeated for comparison.
provided as Supplementary Information (SI) in Figs. S-1–S-4 in the
form V = f(P/Po). The presentation of those isotherms in all the SI
Figs. (S-1–S-4) is made for comparison with the different kind of 4. Discussion
plots drawn in the same figures. Each of those four SI figures con-
tain two parts: The S-1a, S-2a, S-3a and S-4a parts are referred to Since the data for all 18 samples are rather numerous, the fol-
samples 1–9 of Table 1. The S-1b, S-2b, S-3b and S-4b parts are lowing discussion will be based on four typical, representative
A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133 131

Fig. 4. Graphs for 30% beta + 70% Al-MCM-41 sample: (a) the N2 adsorption–desorption isotherms as well as the I-point plot are shown in the form (V[1  (P/Po)]/(P/Po) vs.
V[1  (P/Po)]. ILP-point and the IHP-point are indicated by a star (w), (b) plot of the form (V[1  (P/Po)]) vs. (P/Po). The N2 adsorption–desorption isotherms V = f(P/Po) are shown
for comparison, (c) plots in the form dV/d[(P/Po)] vs. (P/Po) and d(V[1  (P/Po)])/d[(P/Po)] vs. (P/Po), (d) plot in the form d2V/d[(P/Po)]2 vs. (P/Po). The stars (w) in (b–d) correspond
to the I-points from (a).

samples, the OMSi–Ce–Co/1:9/A, OMSi–Ce–Co/1:1/B, 2% Al (iii) From comparison of Figs. 1–4(a) and Figs. 1–4(b), and also
-MSU-S/W(BEA) and 30% beta + 70% Al-MCM-41. The treatment the corresponding SI data for the rest of the samples, a third
of data for those materials is shown in Figs. 1–4, respectively. important point becomes apparent: if two (2) Inversion
The following important observations can be made from the points exists (see (i)), then those points are apparent only
data shown in those figures, as well as the data shown in the SI. in the I-plots of the form (V[1  (P/Po)]/(P/Po) vs. V[1  (P/
Po)] but maybe difficult or impossible to distinguish them
(i) In Figs. 1–4(a) the N2 adsorption–desorption isotherms V = f(P/ in the consistency criteria plots of the form (V[1  (P/Po)])
Po) as well as the I-point plots are shown in the form (V[1  (P/ vs. (P/Po).
Po)]/(P/Po) vs. V[1  (P/Po)]. The I-point, or the ILP-point and the (iv) A forth important point from Figs. 1–4(a) and Figs. 1–4(b),
IHP-point, when two such points do exist, are indicated by a and the SI data, is the following: if two (2) Inversion points
star (w). Careful examination of these data, as well as of the are apparent in the I-plots of the form (V[1  (P/Po)]/(P/Po)
data shown in SI, reveal the following fact: A second I-point vs. V[1  (P/Po)], then the Inflection point seen in the
at higher pressure (IHP-point), appears only in cases where consistency criteria plots (V[1  (P/Po)]) vs. (P/Po) corre-
the material exhibits well organized mesoporosity as testify sponds to the higher pressure IHP-point (not the lower pres-
by the appearance of distinct adsorption knee in the V = f(P/ sure ILP-point). In that case, care must be taken in order to
Po) plots. Otherwise a single I-point appears. define the linear part of the BET treatment according to
(ii) In Figs. 1–4(b) plots of the form (V[1  (P/Po)]) vs. (P/Po) are the consistency criteria.
shown, which may be used to define the linear part of the (v) In Figs. 1–4(c) the derivatives of the adsorption isotherms
BET treatment according to the consistency criteria proposed in the form dV/d(P/Po) vs. (P/Po) as well as the derivative
by Rouquerol et al. [12]. The N2 adsorption–desorption iso- of the consistency criteria plots in the form d(V[1  (P/
therms V = f(P/Po) are also shown for comparison. The star(s) Po)])/d(P/Po) vs. (P/Po) are shown. Now a fifth important
(w) at the Inflection point(s) of the plots (V[1  (P/Po)]) vs. point is observed: the maxima of the derivatives of adsorp-
(P/Po) is(are) not their own but they are the I-point(s) from tion isotherms, as well as of the consistency criteria plots,
Figs. 1–4(a). From these figures, as well as from the SI data, appear exactly at the same pressure (P/Po). This is true
it is observed beyond any ambiguity a second fact: The Inflec- not only for the data in Figs. 1–4(c) but also for all samples
tion points of the plots (V[1  (P/Po)]) vs. (P/Po) correspond in SI figures where the pressure (P/Po) of the common max-
exactly and precisely to the Inversion Points of the plots imum is indicated by a vertical line. The star(s) (w) in Figs.
(V[1  (P/Po)]/(P/Po) vs. V[1  (P/Po)] when and only when a 1–4(c) correspond to the I-point(s) from Figs. 1–4(a). The
single such point exists. same is true for the corresponding figures in the SI.
132 A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133

either from the single I-point, or from the second derivative


of the adsorption isotherms, or from both, the ILP-point and
the IHP-point, when two such inflection/Inversion points
exist. The numerical data are from Table 1. It is observe that
the ssa (BET) tallies to the ssa (I-point) or the ssa (ILP-point).
On the contrary it does not matches to the ssa (IHP-point).
Therefore if two Inversion points coexists, then the low pres-
sure ILP-point is suitable for the estimation of the ssa accord-
ing the BET narrative.
(x) A final point of interest is what may be the meaning of dif-
ference between and IHP-point and the ILP-point? This differ-
ence corresponds to a difference of volume of adsorbed N2
and probably defines the limits (start–end) of the adsor-
bant’s condensation phenomena in the mesopores. Let us
be more precise: as discussed above, in some mesoporous
materials, the I-plots exhibits two Inversion points/I-points
and this was attributed [17] to the existence of different, dis-
creet and distinct domains of microporosity and mesoporos-
Fig. 5. Specific surface area obtained by I-point method vs. ssa from classic BET
ity in the solids. If micro- and meso-porosity is mixed-up
method. Open symbols correspond to ssa values estimated using ILP-point (open
square) or the single I-point (open triangle) while dark symbols correspond to ssa and random, then such effects (e.g. the distinction of two
values estimated using IHP-point. I-points) are masked. The first inversion/inflection point at
lower (P/Po), V values, ‘‘ILP-point’’, corresponds to the com-
pletion of the adsorption procedure on the bare surface
(vi) The mathematical proof for the above observation at point (v) and the formation of monolayer. Then from this point, as
is as follows: the derivative d(V[1  (P/Po)])/d[(P/Po)] equals the pressure increases, multilayer condensation phenomena
d(V)/d(P/Po)[1  (P/Po)]  V. Therefore if dV/d[(P/Po)] = A and start into the pores. The second inversion/inflection point at
d(V[1  (P/Po)])/d[(P/Po)] = B, then B = A[1  (P/Po)]  V. For higher (P/Po), V values, ‘‘IHP-point’’, corresponds to the com-
(P/Po), V small, then B?A and the two lines almost coincide. pletion of the pore filling via condensation and may be use-
For (P/Po), V large, then B?A  A[1  (P/Po)]  V and the line ful for the determination of the core volume of the discreet
corresponding to B exhibits values smaller by an amount and distinct mesopores. This hypothesis is elaborated in
equal to A[1  (P/Po)]  V compared to the original derivative Fig. 6 where the difference {IHP-point minus ILP-point} = DV
A. This abstraction does not affect the position of maxima of (pore core) is shown as a function of % content of the purely
the A and B lines along the (P/Po) axis. Those calculations show mesoporous sample Al-MCM-41 in mechanical mixtures
that the similarities between the derivates A and B are not with purely microporous zeolite beta. The relevant data
artifacts but mathematically justified and expected. They also are in Table 1 and shown in Fig. S-4b.
provide a hint that the mathematical information about the
Inversion or Inflection points, (very useful parameters indeed As seen there, the difference {IHP-point minus ILP-point} is di-
for the estimation of specific surface area!), may be common rectly related to the % Al-MCM-41 content in the mechanical mix-
in A and B lines and can be revealed via the suitable treatment. tures with zeolite via the relationship:
In line B this treatment corresponds to its integration, leading
of course to the consistency plots. In line A, which contains the fIHP -point minus ILP -pointg ¼ 79ð% of Al-MCM-41Þ  17:2
original experimental data, this treatment corresponds to its
derivation as shown next at point (vii) where the difference {IHP-point minus ILP-point} is expressed in vol-
(vii) In Figs. 1–4(d) plots of the second derivatives of the adsorp- ume units (cm3) of adsorbed gaseous N2. This relationship conveys
tion isotherms in the form d2V/d[(P/Po)]2 vs. (P/Po) are the fact that the difference {IHP-point minus ILP-point} depends
shown. It is observed (see also the corresponding figures in
SI) that the minimum of the second derivative appears
exactly at the same pressure (P/Po) of the single I-point,
which is indicated by the star (w). Therefore in this case
the ssa can be estimated without any knowledge, or use,
or treatment of BET equation. In other words the minimum
in the second derivative corresponds exactly to the comple-
tion of monolayer.
(viii) If two I-points exists in the I-point plots, then the minimum
of the second derivative d2V/d[(P/Po)]2 vs. (P/Po) corresponds
to the higher pressure IHP-point. In this case the observed
minimum does not correspond to the completion of mono-
layer during adsorption. As mentioned above, two I-points
are observed in porous materials with distinct mesoporous.
In such cases the higher pressure IHP-point, and the mini-
mum of the second derivative, correspond to the completion
of N2 condensation in the mesopores.
(ix) In order to make clear the difference between the two inver-
sion/inflection points, the one at low pressure (ILP-point) and
the one at high pressure (IHP-point), we compare in Fig. 5 the Fig. 6. The difference (IHP-point minus ILP-point) as a function of % Al-MCM-41
classical BET ssa with the corresponding values estimated content in (zeolite beta/Al-MCM-41) mixtures.
A.K. Ladavos et al. / Microporous and Mesoporous Materials 151 (2012) 126–133 133

linearly on the content of mesopores in the mixture as only Al-MCM- (G) The second I-point at higher pressure (IHP-point) corresponds
41 contributes mesopores in the mixtures with zeolite. Furthermore, to the pore filling via N2 condensation in the mesopores.
for the mechanical mixture (20% of Al-MCM-41 + 80% zeolite beta),
then {IHP-point minus ILP-point}  zero (cm3) which means that, at
least for the present materials and instrumentation, the distinction Appendix A. Supplementary data
of organized mesoporous domains is not attainable in adsorption
isotherms when the specific pore volume of those organized do- Supplementary data associated with this article can be found, in
mains is less than about 20% of the rest not-organized volume. the online version, at doi:10.1016/j.micromeso.2011.11.005.

5. Conclusions References

(A) The adsorption isotherms, at least those treated in the pres- [1] S. Brunauer, P.H. Emmett, E. Teller, J. Am. Chem. Soc. 60 (1938) 309.
[2] J.S. Gregg, K.S.W. Sing, Adsorption, Surface Area and Porosity, second ed.,
ent article, are distinguished in two groups. The 1st contains Academic Press, 1982.
samples with a single I-point, or Inflection point, and the 2nd [3] F. Rouquerol, J. Rouquerol, K.S.W. Sing, Adsorption by Powders and Porous
group samples with two I-points/Inflection points. Adsorp- Solids: Principles, Methodology and Applications, Academic Press, London,
1999.
tion isotherms with more than two I-points (let us say three [4] S. Lowell, Introduction to Powder Surface Area, John Wiley and Sons, 1979.
I-points) may exist in special cases, like the type VI isotherm [5] C. Kembal, G.D.L. Schreiner, J. Am. Chem. Soc. 72 (1950) 5605–5607.
according to the standard IUPAC classification. [6] F. Rouquerol, J. Rouquerol, B. Imelik, Bull. Soc. Chim. Fr. (1964) 635–639.
[7] P.J. Pomonis, D.E. Petrakis, A.K. Ladavos, K.M. Kolonia, G.S. Armatas, S.D. Sklari,
(B) The existence of a single or two inversion/inflection points in P.C. Dragani, A. Zarlaha, V.N. Stathopoulos, A.T. Sdoukos, Micropor. Mesopor.
the adsorption isotherms are better distinguished in the I- Mater. 69 (2004) 97–107.
plots (V[1  (P/Po)]/(P/Po) vs. V[1  (P/Po)] but may be masked [8] P.J. Pomonis, D.E. Petrakis, A.K. Ladavos, K.M. Kolonia, C.C. Pantazis, A.E.
Giannakas, A.A. Leontiou, Catal. Commun. 6 (2005) 93–96.
in the consistency plots (V[1  (P/Po)]) vs. (P/Po).
[9] G.S. Armatas, D.E. Petrakis, P.J. Pomonis, Micropor. Mesopor. Mater. 83 (2005)
(C) The Inversion points seen in the I-plots (V[1  (P/Po)]/(P/Po) 251–261.
vs. V[1  (P/Po)] and the Inflection points observed in the con- [10] J.K. Knowles, G.S. Armatas, M.J. Hudson, P.J. Pomonis, Langmuir 22 (2006) 410–
sistency criteria plots (V[1  (P/Po)]) vs. (P/Po) are identical. 418.
[11] R. Denoyel, J.M. Meneses, G.S. Armatas, J. Rouquerol, K.K. Unger, P.J. Pomonis,
(D) If a single I-point exists, then this inversion/inflection point Langmuir 22 (2006) 5350–5357.
can be used safely for the determination of the ssa. Such treat- [12] J. Rouquerol, P. Llewellyn, F. Rouquerol, Stud. Surf. Sci. Catal. 160 (2007) 49–56.
ment still necessitates some knowledge of the BET equation. [13] K.S. Walton, A.R. Millward, D. Dubbeldam, H. Frost, J.J. Low, O.M. Yaghi, R.Q.
Snurr, J. Am. Chem. Soc. 130 (2008) 406–407.
(E) If a single I-point exists, then the second derivative d2V/d[(P/ [14] A.O. Yazaydin, R.Q. Snurr, T.-H. Park, K. Koh, J. Liu, M.D. LeVan, A.I. Benin, P.
Po)]2 of the adsorption isotherm shows a minimum which Jakubczak, M. Lanuza, D.B. Galloway, J.J. Low, R.R. Willis, J. Am. Chem. Soc. 131
corresponds to the completion of monolayer during adsorp- (2009) 18198–18199.
[15] Y.-S. Bae, A.O. Yazaydin, R.Q. Snurr, Langmuir 26 (2010) 5475–5483.
tion and can be used for the determination of ssa without [16] A.P. Katsoulidis, D.E. Petrakis, G.S. Armatas, P.J. Pomonis, J. Mater. Chem. 17
any knowledge of BET equation. (2007) 1518–1528.
(F) If two I-points appear, this is due to of different, discreet and [17] K.S. Triantafyllidis, T.J. Pinnavaia, A. Iosifidis, P.J. Pomonis, J. Mater. Chem. 17
(2007) 3630–3638.
distinct domains of microporosity and mesoporosity in the [18] K.E. Collins, C.H. Collins, C.M. Maroneze, V. Cappovila, R. Custodio, Langmuir.
solids. Then the first I-point at low pressure (ILP-point) corre- 27 (2011) 187–195, doi:10.1021/la103640z.
sponds to the completion of monolayer and may be [19] D.D. Do, L. Herrera, Chunyan Fan, A. Wongkoblap, D. Nicholson, Adsorption 16
(2010) 3–15, doi:10.1007/s10450-009-9203-8.
employed for the determination of ssa.

You might also like