Physisorption

Methods and Techniques
Quantachrome
I N S T R U M E N T S
Pore Size by
Gas Sorption
Micro and Mesopore Size
Determination by Gas Sorption
First: Quantitative estimation of
micropore volume and area…
T-plot and DR methods.
Multilayer adsorption
Type II, IV
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

After the knee,
micropores cease to
contribute to the
adsorption process.
Low slope region in middle of
isotherm indicates first few
multilayers, on external surface
including meso and macropores…
before the onset of capillary
condensation
Estimation of Micropores...
the t-plot method
This method uses a mathematical representation of
multi-layer adsorption. The thickness, t, of an
adsorbate layer increases with increasing pressure.
The t-curve so produced is very similar in
appearance to a type II isotherm. For every value of
P/Po, the volume adsorbed is plotted against the
corresponding value of “t”.
If the model describes the experimental data a
straight line is produced on the t-plot...
The t-plot
Resembles a type II
Relative Pressure (P/Po)
S
t
a
t
i
s
t
i
c
a
l

t
h
i
c
k
n
e
s
s

A statistical monolayer
A statistical multilayer
t-plot Method
(mesoporous only)
1 2 3 4 5 6 7
t ()
Slope = V/t = A
t-plot Method
showing a “knee”
Slope A - slope B = area contribution by micropores size C
1 2 3 4 5 6 7
t ()
X
X
X
X
X
X
X
C
A
B
A
C
B
What is an o
s
plot?
o
s
(for Ken Sing) is a comparison
plot like the t-plot but its slope
does not give area directly.
A
?
?
?
?
?
?
?
Quiz
Estimation of Micropores
Dubinin-Radushkevich (DR) Theory
(
(
¸
(

¸

|
.
|

\
|
|
|
.
|

\
|
÷ =
P
P
log
T
B exp W W
0
2
2
0
|
W = volume of the liquid adsorbate
W
0
= total volume of the micropores
B = adsorbent constant
| = adsorbate constant
A linear relationship should be found between log(W) and log
2
(Po/P)...
Log
2
(Po/P)
L
o
g

(
W
)

Extrapolation
yields Wo
Estimation of Micropores
Dubinin-Radushkevich (DR) Plot
0
Pore Size Determination
Requires a recognition and
understanding of different basic
isotherm types.
t-plot Method
(in the presence of micropores)
1 2 3 4 5 6 7
t ()
Intercept = micropore volume
Types of Isotherms
Type I
Type II
Type III
Type IV
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Type V
Types of Isotherms
Type I or
pseudo-“Langmuir”
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Steep initial region due to very strong
adsorption, for example in micropores.
Limiting value (plateau) due to filled
pores and essentially zero external area.
Why pseudo Langmuir?
Langmuir applies to monolayer
limit, not volume filling limit.
A
?
?
?
?
?
?
?
Quiz
Types of Isotherms
Type II
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Rounded knee
indicates approximate
location of monolayer
formation.
Absence of hysteresis indicates adsorption
on and desorption from a non-porous
surface..
Low slope region in middle of
isotherm indicates first few
multilayers
Types of Isotherms
Type III
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Lack of knee represents extremely
weak adsorbate-adsorbent interaction
BET is not applicable
Example: krypton on polymethylmethacrylate
Types of Isotherms
Type IV
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Rounded knee
indicates approximate
location of monolayer
formation.
Low slope region in middle of
isotherm indicates first few
multilayers
Hysteresis indicates capillary
condensation in meso and
macropores.
Closure at P/Po~0.4 indicates
presence of small mesopores
(hysteresis would stay open
longer but for the tensile-
strength-failure of the nitrogen
meniscus.
Types of Isotherms
Type V
Relative Pressure (P/Po)
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Lack of knee represents extremely
weak adsorbate-adsorbent interaction
BET is not applicable
Example: water on carbon black
Types of Hysteresis
Large pores/voids
Gel
Mesopores
MCM
V
o
l
u
m
e

a
d
s
o
r
b
e
d

Relative Pressure (P/Po)
MesoPore Size
by Gas
Sorption
(BJH)
Analyzer measures volume of pores:
Yes or No?
NO! It measures what leaves
supernatent gas phase
A
?
?
?
?
?
?
?
Quiz
Pore Size Distribution
Hysteresis is indicative of the presence of
mesopores and the pore size distribution can be
calculated from the sorption isotherm.
Whilst it is possible to do so from the adsorption
branch, it is more normal to do so from the
desorption branch...
Mesopore (Greek meso = middle): 2nm - 50 nm diameter
Macropore (Greek macro = large): >50 nm diameter
Micropore (Greek micro = small): 0 nm - 2 nm diameter
Adsorption / Desorption
Adsorption =
multilayer formation
Desorption =
meniscus development
Kelvin* Equation
) P / P log(
.
) A ( r
k
0
15 4
* Lord Kelvin a.k.a. W.T. Thomson
u
¸
= cos
2
ln
0
rRT
V
P
P
Pore Size
t r r
k p
r
p
= actual radius of the pore
r
k
= Kelvin radius of the pore
t = thickness of the adsorbed film
Statistical Thickness, t
• Halsey equation
• Generalized Halsey
• deBoer equation
• Carbon Black STSA
BJH Method
(Barrett-Joyner-Halenda)
t r r
Kelvin pore
Pore volume requires assumption
of liquid density!
Pore Size Distribution
40 Pore Diameter (angstrom)
d
V
/
d
l
o
g
D

Artifact
Relative Pressure (P/Po)
A
m
o
u
n
t

a
d
s
o
r
b
e
d

~ 0.42
Pore Size Data
• Volume and size of pores can be expressed from
either adsorption and/or desorption data.
• The total pore volume, V, is taken from the
maximum amount of gas adsorbed at the “top” of the
isotherm and conversion of gas volume into liquid
volume.
• The mean pore diameter is calculated from simple
cylindrical geometry:
A
V
d
4
=
where A is the BET
surface area.
Pore size analysis of MCM 41
(Templated silica) by N
2
sorption
at 77 K
0 0.2 0.4 0.6 0.8 1
P/P
0
100
200
300
400
500
600
V
o
l
u
m
e

[
c
c
/
g
]
Exp. Nitrogen sorption at 77 K in MCM 41 Exp. Nitrogen sorption at 77 K in MCM 41
DFT- Isotherm DFT- Isotherm
Pore size analysis of MCM 41:
Calculations compared
15 23 31 39 47 55
Pore Diameter [Å]
0
0.05
0.1
0.15
0.2
0.25
0.3
D
v
(
d
)

[
c
c
/
Å
/
g
]
BJH-Pore size distribution BJH-Pore size distribution
DFT-Pore size distribution DFT-Pore size distribution
Calculation
Models
Comparisons
• Gas Sorption Calculation Methods

P/Po range Mechanism Calculation model
1x10-7 to 0.02 micropore filling DFT, GCMC, HK, SF, DA, DR
0.01 to 0.1 sub-monolayer formation DR
0.05 to 0.3 monolayer complete BET, Langmuir
> 0.1 multilayer formation t-plot (de-Boer,FHH),
> 0.35 capillary condensation BJH, DH
0.1 to 0.5 capillary filling DFT, BJH
in M41S-type materials
Different Theories of
Physisorption
Surface area Pore volume Pore size
BET Total pore vol DR ave
Langmuir
t-plot (
µ
pore vol)
BJH
DR
DR (
µ
pore vol)
DH
MP and t-plot DA DFT
o
s
plot
BJH HK
(BJH) (DFT) SF
(DH) (DH)
(DFT)
HK & SF
Horvath-Kawazoe & Saito-Foley
• HK
• Direct mathematical relationship between relative
pressure (P/Po) and pore size. Relationship calculated
from modified Young-Laplace equation, and takes into
account parameters such as magnetic susceptibility.
Based on slit-shape pore geometry (e.g. activated
carbons). Calculation restricted to micropore region (s
2nm width).

• SF
• Similar mathematics to HK method, but based on
cylindrical pore geometry (e.g. zeolites). Calculation
restricted to micropore region (s 2 nm diameter).
DA & DR
Dubinin-Astakov and Dubinin-Radushkevic
• DA
• Closely related to DR calculation based on pore filling mechanism.
Equation fits calculated data to experimental isotherm by varying two
parameters, E and n. E is average adsorption energy that is directly
related to average pore diameter, and n is an exponent that controls
the width of the resulting pore size distribution. The calculated pore
size distribution always has a skewed, monomodal appearance
(Weibull distribution).

• DR
• Simple log(V) vs log
2
(Po/P)

relationship which linearizes the isotherm
based on micropore filling principles. “Best fit” is extrapolated to
log
2
(Po/P)

(i.e. where P/Po = 1) to find micropore volume.
BET
• The most famous gas sorption model. Extends Langmuir
model of gas sorption to multi-layer. BET equation
linearizes that part of the isotherm that contains the
“knee” , i.e. that which brackets the monolayer value.
Normally solved by graphical means, by plotting
1/(V[(Po/P)]-1) versus P/Po. Monolayer volume (Vm) is
equal to 1/(s+i) where s is the slope and i is the y-intercept.
Usually BET theory is also applied to obtain the specific
surface area of microporous materials, although from a
scientific point of view the assumptions made in the BET
theory do not take into account micropore filling. Please
note, that for such samples the linear “BET” range is
found usually at relative pressures< 0.1, in contrast to the
classical BET range, which extends over relative
pressures between 0.05 – 0.3.
Langmuir
• Adsorption model limited to the formation of a
monolayer that does not describe most real
cases. Sometimes can be successfully applied
to type I isotherms (pure micropore material) but
the reason for limiting value (plateau) is not
monolayer limit, but due to micropore filling.
Therefore type I physisorption isotherm would
be better called “pseudo-Langmuir” isotherm.
t-plot
Statistical Thickness
• Multi-layer formation is modeled mathematically to calculate
a layer “thickness, t” as a function of increasing relative
pressure (P/Po). The resulting t-curve is compared with the
experimental isotherm in the form of a t-plot. That is,
experimental volume adsorbed is plotted versus statistical
thickness for each experimental P/Po value. The linear
range lies between monolayer and capillary condensation.
The slope of the t-plot (V/t) is equal to the “external area”,
i.e. the area of those pores which are NOT micropores.
Mesopores, macropores and the outside surface is able to
form a multiplayer, whereas micropores which have already
been filled cannot contribute further to the adsorption
process.
• It is recommended to initially select P/Po range 0.2 – 0.5,
and subsequently adjust it to find the best linear plot.
BJH & DH
Barrett, Joyner, Halenda and Dollimore-Heal
• BJH
• Modified Kelvin equation. Kelvin equation predicts
pressure at which adsorptive will spontaneously condense
(and evaporate) in a cylindrical pore of a given size.
Condensation occurs in pores that already have some
multilayers on the walls. Therefore, the pore size is
calculated from the Kelvin equation and the selected
statistical thickness (t-curve) equation.

• DH
• Extremely similar calculation to BJH, which gives very
similar results. Essentially differs only in minor
mathematical details.

Other Methods
• FRACTAL DIMENSION
• The geometric topography of the surface
structure of many solids can be characterized by
the fractal dimension D, which is a kind of
roughness exponent. A “flat” surface is
considered D is 2, however for an irregular (real)
surface D may vary between 2 and 3 and
expresses so the degree of roughness of the
surface and/or porous structure. The
determination of the surface roughness can be
investigated by means of the modified Frenkel-
Halsey Hill method, which is applied in the
range of multilayer adsorption.
Example Data : Microporous Carbon
BET : Not strictly applicable
Example Data : Microporous Carbon
• Tag all adsorption
points
• Analyze behavior
• Note knee – transition
from micropore filling
to limited
multilayering
(plateau).
Example Data : Microporous Carbon
• Use Langmuir
(Monolayer model) /
DR for Surface Area,
Micropore Volume
• Usue Langmuir in
range of 0.05 -> 0.2
(monolayer)
Example Data : Microporous Carbon
• Langmuir Surface Area
Example Data : Microporous Carbon
• DR Method for
surface area,
micropore volume
• Choose low relative
pressure points (up
to P/P0 = 0.2)
Example Data : Microporous Carbon
• Reports micropore
surface area, and
micropore volume.
• Note Langmuir, DR
surface areas very
close (1430 m
2
/g vs.
1424 m
2
/g)
Example Data : Macroporous Sample
Little or no “knee”,
isotherm closes at
0.95
Example Data : Macroporous Sample
• BET Plot = OK
• Surface area ca. 8m
2
/g (low)
• Note hysteresis above P/P0 = 0.95 Pores > 35 nm
Example Data : Macroporous Sample
Intercept = (-),
no micropore
volume.
Example Data : Macroporous Sample
BJH Shows pores
> 20nm, to over
200 nm
Example Data : Mesoporous Silica
Hysteresis => mesopores
Also micropores ?? Test using t-
method

Example Data : Mesoporous Silica
BET Surface area = 112m
2
/g
Classic mesoporous silica !
Example Data : Mesoporous Silica
Statistical Thickness => Use de Boer for oxidic surfaces = silicas
Intercept ~ 0
Look at tabular data
MP SA = 8m
2
/g (total SA = 112)
Example Data : Mesoporous Silica
Use BJH – shows narrow pore size distribution in 14-17nm range (mesopores)
MicroPore Size
by Gas
Sorption
Available
Calculation
Models
Pore filling pressures for nitrogen in
cylindrical pores at 77 K,
(Gubbins et al. 1997)
Pore filling pressures for nitrogen in
cylindrical silica pores at 77 K
(Neimark et al., 1998)
Pore size analysis of MCM 41
by silica by N
2
sorption at 77 K
0 0.2 0.4 0.6 0.8 1
P/P
0
100
200
300
400
500
600
V
o
l
u
m
e

[
c
c
/
g
]
Exp. Nitrogen sorption at 77 K in MCM 41 Exp. Nitrogen sorption at 77 K in MCM 41
DFT- Isotherm DFT- Isotherm
15 23 31 39 47 55
Pore Diameter [Å]
0
0.05
0.1
0.15
0.2
0.25
0.3
D
v
(
d
)

[
c
c
/
Å
/
g
]
BJH-Pore size distribution BJH-Pore size distribution
DFT-Pore size distribution DFT-Pore size distribution
Gas- and liquid density profiles
in a slit pore by GCMC
(Walton and Quirke,1989)
NLDFT / GCMC (Monte
Carlo) Kernel File
Applicable Pore
Diameter Range
Examples
NLDFT– N2 - carbon kernel at 77 K
based on a slit-pore model
0.35nm-30 nm
Carbons with slit-like pores, such as
activated carbons and others.
NLDFT– N2 – silica equilibrium
transition kernel at 77 K, based on a
cylindrical pore model
0.35nm- 100nm
Siliceous materials such as some silica
gels, porous glasses, MCM-41, SBA-
15, MCM-48 and other adsorbents
which show type H1 sorption
hysteresis.
NLDFT– N2 - silica adsorption branch
kernel at 77 K, based on a cylindrical
pore model
0.35nm-100nm
Siliceous materials such as some
controlled pore glasses, MCM-41,
SBA-15, MCM-48, and others. Allows
to obtain an accurate pore size
distribution even in case of type H2
sorption hysteresis
NLDFT– Ar zeolite/silica equilibrium
transition kernel at 87 K based on a
cylindrical pore model
0.35nm -100nm
Zeolites with cylindrical pore channels
such as ZSM5, Mordenite, and
mesoporous siliceous
materials (e.g., MCM-41, SBA-15,
MCM-48, some porous glasses
and silica gels which show type H1
sorption hysteresis).
NLDFT / GCMC (Monte
Carlo) Kernel File
Applicable Pore
Diameter Range
Examples
NLDFT – Ar-zeolite/silica adsorption
branch kernel at 87 K based on a
cylindrical pore model
0.35nm-100nm
Zeolites with cylindrical pore channels
such as ZSM5, Mordenite etc., and
mesoporous siliceous materials such as
MCM-41, SBA-15, MCM-48, porous
glasses some silica gels etc). Allows to
obtain an accurate pore size distribution
even in case of H2 sorption hysteresis.
NLDFT – Ar-zeolite / silica
equilibrium transition kernel based on a
spherical pore model (pore diameter < 2
nm) and cylindrical pore model (pore
diameter > 2 nm)
0.35nm-100nm
Zeolites with cage-like structures such
as Faujasite, 13X etc. , and mesoporous
silica materials (e.g., MCM-41, SBA-
15, porous glasses, some silica gels
which show H1 sorption hysteresis).
NLDFT – Ar-zeolite / silica adsorption
branch kernel at 87 K based on a
spherical pore model (pore diameter < 2
nm) and cylindrical pore model (pore
diameter > 2 nm)
0.35nm-100nm
Zeolites with cage-like structures such
as Faujasite, 13X, and mesoporous
silica materials (e.g., MCM-41, SBA-
15, controlled-pore glasses and others).
Allows to obtain an accurate pore size
distribution even in case of H2 sorption
hysteresis.
NLDFT / GCMC (Monte
Carlo) Kernel File
Applicable Pore
Diameter Range
Examples
NLDFT – Ar - carbon kernel at
77 K based on a slit-pore model
0.35 nm - 7 nm Carbons with slit-like pores,
such as activated carbons etc.
NLDFT - CO2 - carbon kernel at
273 K based on a slit-pore model
0.35nm-1.5 nm Carbons with slit-like pores,
such as activated carbons etc.
GCMC – CO2 - carbon kernel at
273 K based on a slit-pore model
0.35nm-1.5 nm Carbons with slit-like pores,
such as activated carbons etc.
RECENT ADVANCES IN THE
PORE SIZE ANALYSIS OF
MICRO- AND MESOPOROUS
MOLECULAR SIEVES BY ARGON
GAS ADSORPTION
Micropore Size Characterization
• Physical adsorption in micropores, e.g.
zeolites occurs at relative pressures
substantially lower than in case of
adsorption in mesopores.
• Adsorption measurements using nitrogen at
77.4 K is difficult, because the filling of
0.5 - 1 nm pores occurs at P/Po of 10
-7
to
10
-5
,

where

the rate of diffusion and
adsorption equilibration is very slow.
Advantages of Using Argon
• Advantage to analyze such narrow
micropores by using argon at liquid argon
temperature (87.3 K).
• Argon fills these micropores (0.5 – 1nm) at
much higher relative pressures (i.e., at
relative pressures 10
-5
to 10
-3
) compared to
nitrogen.
Advantages of Higher
Temperature & Pressure
• Accelerated diffusion.
• Accelerated equilibration processes.
• Reduction in analysis time.
Argon Adsorption at 87.3 K versus
Nitrogen Adsorption at 77.4 K
10
-6
5 10
-5
5 10
-4
5 10
-3
5 10
-2
5 10
-1
5 10
0
P/P
0
0
70
140
210
280
350
V
o
l
u
m
e

[
c
m
3
]
N2/77K N2/77K
Ar/87 K Ar/87 K
ZEOLITE | 10.5.2001
The different pore filling ranges for argon adsorption at 87.3K and nitrogen
adsorption at 77.4K in faujasite-type zeolite are illustrated above.
Micropore Size Calculation
• Difficulties are associated with regard to the analysis of
micropore adsorption data.
• Classical, macroscopic, theories
[1]
like DR and
semiempirical treatments such those of HK and SF do
not give a realistic description of micropore filling
• This leads to an underestimation of pore sizes for
micropores and even smaller mesopores
[2].

[1] F. Rouquerol, J. Rouquerol & K. Sing, Adsorption by Powders & Porous Solids, Academic Press, 1999
[ 2 ] P. I Ravikovitch, G.L. Haller, A.V. Neimark, Advcances in Colloid and Interface Science 76-77 , 203 (1998)
New Calculation
• To overcome the above mentioned problems we
introduce a new method for micropore analysis
based on a Non-local Density Functional Theory
(NLDFT) model by Neimark and Co-workers
[3-5]
.

• The new DFT-method is designed for micro-
mesopore size characterization of zeolitic
materials ranging in size from 0.44 to 20 nm using
high-resolution low-pressure argon adsorption
isotherms at 87.3 K.
[3] P.I. Ravikovitch, G.L. Haller, A.V. Neimark, Advances in Colloid and Interface Science, 76 – 77 (1998), 203 -207
[4] A.V. Neimark, P.I Ravikovitch, M. Gruen, F. Schueth, and K.K. Unger, J. Coll. Interface Sci., 207, (1998) 159
[5] A.V. Neimark, P.I. Ravikovitch, Microporous and Mesoporous Materials (2001) 44-45, 697
Systematic, Experimental Study
• To evaluate the application of argon sorption for
micro- and mesopore size analysis of zeolites and
mesoporous silica materials including novel
mesoporous molecular sieves of type MCM-41
and MCM-48.
• The sorption isotherms were determined using a
static volumetric technique
• Samples were outgassed for 12 h under vacuum
(turbomolecular pump) at elevated temperatures
(573 K for the zeolites and 393 K for MCM-
41/MCM-48).
Results
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
P/Po
A
d
s
o
r
p
t
i
o
n
,

[
m
m
o
l
/
g
]

MCM-41
ZSM-5
50-50
Argon adsorption
isotherms at 87 K
on MCM-41,
ZSM-5 and their
50-50 mixture.
Results
0
5
10
15
20
25
0.000001 0.00001 0.0001 0.001 0.01 0.1 1
P/Po
A
d
s
o
r
p
t
i
o
n
,

[
m
m
o
l
/
g
]

MCM-41
ZSM-5
50-50
0
0.02
0.04
0.06
0.08
0.1
0.12
1 10 100 1000
D, [Å]
d
V
/
d
D

[
c
m
3
/
g

-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
V
c
u
m
,

[
c
m
3
/
g
]


histogram
integral
ZSM
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
1 10 100 1000
D, [Å]
d
V
/
d
D

[
c
m
3
/
g
]

/
g
]


0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
V
c
u
m
,

[
c
m
3
/
g
]


histogram
integral
MCM
Evaluation of DFT Algorithm
0
2
4
6
8
10
12
14
16
18
20
0.000001 0.00001 0.0001 0.001 0.01 0.1 1
P/Po
A
d
s
o
r
p
t
i
o
n
,

[
m
m
o
l
/
g
]
experimental
NLDFT fit
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
1 10 100 1000
D, [Å]
d
V
/
d
D

[
c
m
3
/
g
]

0
0.1
0.2
0.3
0.4
0.5
0.6
V
c
u
m

[
c
m
3
/
g
]


histogram
integral
Pore Size Distribution
Discussion
• Argon sorption at 77 K is limited to pore
diameters smaller than 12 nm.
i.e. no pore filling/pore condensation can be observed at this
temperature for silica materials containing larger pores.

• This lack of argon condensation for pores
larger than ca. 12 nm is associated with the
fact, that 77 K is ca. 6.8 K below the bulk
triple point
[4,5]
.

[4] M. Thommes, R. Koehn and M. Froeba, J. Phys. Chem. B (2000), 104, 7932
[5] M. Thommes, R. Koehn and M. Froeba, Stud. Surf. Sci. Catal., (2001), 135 17
Discussion
• These limitation do not exist for argon
sorption at its’ boiling temperature,
i.e. ca. 87 K.
• Pore filling and pore condensation can be
observed over the complete micro- and
mesopore size range .
Discussion
• Results of classical, and semi-empirical
methods (e.g., BJH, SF etc) indicate that
these methods underestimate the pore
size considerably.
• Deviations from the DFT-results are
often in a range of ca. 20 % for pore
diameters < 10 nm.
Summary
• Our results indicate that argon sorption
data at 87 K combined with the new
NLDFT-methods provides a convenient
way to achieve an accurate and
comprehensive pore size analysis over
the complete micro-and mesopore size
range for zeolites, catalysts, and
mesoporous silica materials.
Acknowledgements
• Special thanks go to Alex Neimark and
Peter Ravikovitch at TRI Princeton, New
Jersey, USA.
References
to research work of nitrogen, argon and krypton
in MCM-48/MCM-41 materials

(1) M. Thommes, R. Koehn and M. Froeba, “ Systematic Sorption studies on surface and pore size
characteristics of different MCM-48 silica materials”, Studies in Surface Science and
Catalysis 128, 259 (2000)
(2) M. Thommes, R. Koehn and M. Froeba, “Sorption and pore condensation behavior of nitrogen,
argon and krypton in mesoporous MCM-48 silica materials” J. Phys. Chem. B 104, 7932
(2000)
(3)M. Thommes, R. Koehn and M. Froeba, “Sorption and pore condensation behavior of pure fluids
in mesoporous MCM-48 silica, MCM-41 silica and controlled pore glass, Studies in Surface
Science and Catalysis, 135, 17 (2001)
(4)M. Thommes, R. Koehn and M. Froeba, “Characterization of porous solids: Sorption and pore
condensation behavior of nitrogen, argon and krypton in ordered and disordered mesoporous
silica materials (MCM-41, MCM-48, SBA-15, controlled pore glass, silica gel) at temperatures
above and below the bulk triple point”, Proceedings of the first topical conference on
nanometer scale science and engineering” (G.U. Lee, Ed) AIChE Annual Meeting, Reno,
Nevada, November 4-9, 2001
(5)M. Thommes, R. Koehn and M. Froeba, “Sorption and pore condensation behavior of pure fluids
in mesoporous MCM-48 silica, MCM-41 silica and controlled pore glass at temperatures
above and below the bulk triple point”, submitted to Applied Surface Science, (2001)
Rapid Micropore Size
Analysis by CO
2

Adsorption

CO
2
Adsorption at 0
o
C
on Carbon
RAPID MICROPORE ANALYSIS
• The advantages of micropore analysis with
Quantachrome’s Density Functional Theory
(DFT) and CO2 include:
• Speed of analysis; with the higher diffusion
rate at 273.15K, analysis times are reduced
as much as 90%.
• Carbon dioxide at 273.15K permits probing
pores from about 2 angstroms (0.2 nm).
DFT ADVANTAGE
DFT has recently been applied to describe the
behavior of fluids that are confined in small
pores. The current popular gas sorption
models, e.g. BJH, HK, SF, DA, etc., assume
that the density of the adsorbed phase
remains constant, regardless of the size of
the pores that are being filled. Packing
considerations suggest that these models are
less than satisfactory for analyses of pores
less than 2 nm.
DFT “Fitting”
• For a given adsorbate-adsorbent
system, DFT calculates the most likely
summation of "ideal isotherms“
calculated from "ideal pores" of fixed
sizes needed to match the experimental
results.
CO2 for Speed!
• Typically, micropore analyses with nitrogen as adsorbate
will require 24 hours or more to run.
• Using carbon dioxide as adsorbate provides several
advantages.
– Carbon dioxide molecules are slightly thinner than
nitrogen molecules (2.8 angstroms radius vs. 3.0
angstroms) and will fill smaller pores than nitrogen.
– The use of carbon dioxide allows the measurements
to be made at 273.15K, typically with an ice/water
bath.
– There is no longer any need to provide and maintain or
replenish a level of liquid nitrogen during the analysis.
CO2 Benefits
• At this temperature, the diffusion rate of
molecules moving through small and tortuous
micropores is much higher than at 77.35K. This
so-called "activated adsorption" effect led to the
popularization of the use of carbon dioxide to
characterize carbonaceous material since the
early 1960s.
CO2 Benefits
• This higher diffusion rate is responsible for
reducing the analysis time to a few hours for a
complete adsorption experiment. The faster rate
also provides for the possibility of using larger
samples than with nitrogen adsorption, thus
reducing sample weighing errors.
• Pore size distributions thus obtained are
comparable to those from a 24-hour
nitrogen/77.35K analysis.
N2 Adsorption @ 77K: 40 hours
CO2 adsorption at 273K: 2.75 hours
CO
2
Adsorption at 0
o
C
Density Functional Theory Micropore Distribution
CO
2
Adsorption at 0
o
C
Monte Carlo Simulation Micropore Distribution
How to do it?
• Hardware requirements for this new method are
minimal:
– a wide- mouth dewar and
– a water-level sensor.

• The proprietary Quantachrome Autosorb®
software provides the DFT data reduction
capabilities to do the rest. Pore size
distributions from about 2 angstroms can be
determined from the data taken at 273.15K.

• Currently, calculation parameters are optimized for
studies on carbon surfaces.
BIBLIOGRAPHY for Rapid Micropore Size Analysis by
CO
2
Adsorption
1. J. Garrido, A. Linares-Solano, J.M. Martin-Martinez, M. Molina-Sabio, F. Rodriguez-Reinoso, R.
Torregosa Langmuir, 3, 76, (1987)
2. F. Carrasco-Martin, M.V. López-Ramón, C. Moreno-Castilla. Langmuir, 9, 2758 (1993)
3. P. Tarazona. Phys.Rev.A 31, 2672 (1985)
4. N.A. Seaton, J.P.R.B. Walton, N. Quirke. Carbon, 27, 853 (1989)
5. C. Lastoskie, K.E. Gubbins, N. Quirke. J.Phys.Chem., 97, 4786 (1993)
6. J.J. Olivier. Porous Materials 2, 9 (1995)
7. P.I. Ravikovitch, S.C. Ó Domhnaill, A.V. Neimark, F. Schüth, K.K. Unger. Langmuir, 11, 4765 (1995)
8. A.V. Neimark, P.I. Ravikovitch, M. Grün, F. Schüth, K.K. Unger. COPS-IV, 1997 (in press)
9. P.I. Ravikovitch P.I., D. Wei, W.T. Chuen, G.L. Haller,A.V. Neimark. J.Phys.Chem., May 1997
10. E.J. Bottani, V. Bakaev, W.A. Steele. Chem.Eng.Sci. 49, 293 (1994)
11. M.M. Dubinin. Carbon 27, 457 (1989)

Pore Size by Gas Sorption

Micro and Mesopore Size Determination by Gas Sorption
First: Quantitative estimation of micropore volume and area… T-plot and DR methods.

Multilayer adsorption
Type II, IV
Low slope region in middle of isotherm indicates first few multilayers, on external surface including meso and macropores… before the onset of capillary condensation

Volume adsorbed

After the knee, micropores cease to contribute to the adsorption process.

Relative Pressure (P/Po)

Estimation of Micropores... the t-plot method
This method uses a mathematical representation of multi-layer adsorption. The thickness, t, of an adsorbate layer increases with increasing pressure. The t-curve so produced is very similar in appearance to a type II isotherm. For every value of P/Po, the volume adsorbed is plotted against the corresponding value of “t”.
If the model describes the experimental data a straight line is produced on the t-plot...

The t-plot
Resembles a type II Statistical thickness

A statistical multilayer

A statistical monolayer
Relative Pressure (P/Po)

t-plot Method (mesoporous only) Slope = V/t = A 1 2 3 4 5 6 7 t () .

t-plot Method showing a “knee” C C X X X X B X X X A B A 1 2 3 4 5 6 7 t () Slope A .slope B = area contribution by micropores size C .

? ? Quiz ? ? ? ? ? What is an s plot? s (for Ken Sing) is a comparison A plot like the t-plot but its slope does not give area directly. .

.Estimation of Micropores Dubinin-Radushkevich (DR) Theory   T 2  P0  2 W  W0 exp B  log     P       W = volume of the liquid adsorbate W0 = total volume of the micropores B = adsorbent constant  = adsorbate constant A linear relationship should be found between log(W) and log2(Po/P).. .

Estimation of Micropores Dubinin-Radushkevich (DR) Plot Log (W) Extrapolation yields Wo 0 Log2(Po/P) .

.Pore Size Determination Requires a recognition and understanding of different basic isotherm types.

t-plot Method (in the presence of micropores) Intercept = micropore volume 1 2 3 4 5 6 7 t () .

Types of Isotherms Type II Type I Volume adsorbed Type V Type IV Type III Relative Pressure (P/Po) .

Relative Pressure (P/Po) .Types of Isotherms Volume adsorbed Limiting value (plateau) due to filled pores and essentially zero external area. for example in micropores. Type I or pseudo-“Langmuir” Steep initial region due to very strong adsorption.

.? ? Quiz ? ? ? ? ? Why pseudo Langmuir? A Langmuir applies to monolayer limit. not volume filling limit.

Relative Pressure (P/Po) . Volume adsorbed Type II Low slope region in middle of isotherm indicates first few multilayers Rounded knee indicates approximate location of monolayer formation.Types of Isotherms Absence of hysteresis indicates adsorption on and desorption from a non-porous surface..

Types of Isotherms Example: krypton on polymethylmethacrylate Volume adsorbed Type III Lack of knee represents extremely weak adsorbate-adsorbent interaction BET is not applicable Relative Pressure (P/Po) .

Hysteresis indicates capillary condensation in meso and macropores.Types of Isotherms Type IV Closure at P/Po~0. Volume adsorbed Low slope region in middle of isotherm indicates first few multilayers Relative Pressure (P/Po) .4 indicates presence of small mesopores (hysteresis would stay open longer but for the tensilestrength-failure of the nitrogen meniscus. Rounded knee indicates approximate location of monolayer formation.

Types of Isotherms Example: water on carbon black Volume adsorbed Type V Lack of knee represents extremely weak adsorbate-adsorbent interaction BET is not applicable Relative Pressure (P/Po) .

Types of Hysteresis Large pores/voids Volume adsorbed Gel Mesopores MCM Relative Pressure (P/Po) .

MesoPore Size by Gas Sorption (BJH) .

? ? Quiz ? ? ? ? ? Analyzer measures volume of pores: Yes or No? A NO! It measures what leaves supernatent gas phase .

50 nm diameter Macropore (Greek macro = large): >50 nm diameter . it is more normal to do so from the desorption branch. Micropore (Greek micro = small): 0 nm .. Whilst it is possible to do so from the adsorption branch.2 nm diameter Mesopore (Greek meso = middle): 2nm .Pore Size Distribution Hysteresis is indicative of the presence of mesopores and the pore size distribution can be calculated from the sorption isotherm..

Adsorption / Desorption Adsorption = multilayer formation Desorption = meniscus development .

15 rk ( A )  log( P / P0 ) * Lord Kelvin a.a. W. Thomson .k.T.Kelvin* Equation P 2 V ln  cos  P0 rRT 4.

Pore Size rp  rk  t rp = actual radius of the pore rk = Kelvin radius of the pore t = thickness of the adsorbed film .

Statistical Thickness. t • Halsey equation • Generalized Halsey • deBoer equation • Carbon Black STSA .

BJH Method (Barrett-Joyner-Halenda) rpore  rKelvin  t Pore volume requires assumption of liquid density! .

Pore Size Distribution Artifact dV/dlogD 40 Pore Diameter (angstrom) .

~ 0.42 Amount adsorbed Relative Pressure (P/Po) .

Pore Size Data • Volume and size of pores can be expressed from either adsorption and/or desorption data. . V. • The mean pore diameter is calculated from simple cylindrical geometry: 4V d A where A is the BET surface area. is taken from the maximum amount of gas adsorbed at the “top” of the isotherm and conversion of gas volume into liquid volume. • The total pore volume.

Nitrogen sorption at 77 K in MCM 41 DFT.6 0.2 0.4 0.8 1 P/P0 .Pore size analysis of MCM 41 (Templated silica) by N2 sorption at 77 K 600 Exp.Isotherm 500 Volume [cc/g] 400 300 200 100 0 0.

05 0 15 23 31 39 47 55 Pore Diameter [Å] .1 0.Pore size analysis of MCM 41: Calculations compared 0.3 0.25 BJH-Pore size distribution DFT-Pore size distribution Dv(d) [cc/Å/g] 0.15 0.2 0.

Calculation Models .

GCMC. DA.1 > 0. DH DFT. DR DR BET. HK. BJH. SF.35 0.3 > 0.1 to 0.02 0. Langmuir t-plot (de-Boer.5 Gas Sorption Calculation Methods Calculation model DFT.FHH).Comparisons • P/Po range 1x10-7 to 0.1 0. BJH Mechanism micropore filling sub-monolayer formation monolayer complete multilayer formation capillary condensation capillary filling in M41S-type materials .01 to 0.05 to 0.

Different Theories of Physisorption Surface area Pore volume Pore size BET Total pore vol DR ave Langmuir BJH t-plot (pore vol) DR DH DR (pore vol) MP and t-plot DA DFT BJH HK s plot (BJH) (DFT) SF (DH) (DH) (DFT) .

but based on cylindrical pore geometry (e.HK & SF Horvath-Kawazoe & Saito-Foley • HK • Direct mathematical relationship between relative pressure (P/Po) and pore size.g. Relationship calculated from modified Young-Laplace equation. and takes into account parameters such as magnetic susceptibility. Based on slit-shape pore geometry (e. activated carbons).g. . • SF • Similar mathematics to HK method. zeolites). Calculation restricted to micropore region ( 2 nm diameter). Calculation restricted to micropore region ( 2nm width).

E is average adsorption energy that is directly related to average pore diameter. “Best fit” is extrapolated to log2(Po/P) (i. E and n. The calculated pore size distribution always has a skewed. where P/Po = 1) to find micropore volume. and n is an exponent that controls the width of the resulting pore size distribution. Equation fits calculated data to experimental isotherm by varying two parameters.DA & DR Dubinin-Astakov and Dubinin-Radushkevic • DA • Closely related to DR calculation based on pore filling mechanism.e. monomodal appearance (Weibull distribution). . • DR • Simple log(V) vs log2(Po/P) relationship which linearizes the isotherm based on micropore filling principles.

that for such samples the linear “BET” range is found usually at relative pressures< 0. i. Please note. that which brackets the monolayer value. Normally solved by graphical means.BET • The most famous gas sorption model. in contrast to the classical BET range. which extends over relative pressures between 0. although from a scientific point of view the assumptions made in the BET theory do not take into account micropore filling. .1. by plotting 1/(V[(Po/P)]-1) versus P/Po. Monolayer volume (Vm) is equal to 1/(s+i) where s is the slope and i is the y-intercept. Extends Langmuir model of gas sorption to multi-layer. Usually BET theory is also applied to obtain the specific surface area of microporous materials.05 – 0.3.e. BET equation linearizes that part of the isotherm that contains the “knee” .

but due to micropore filling. Therefore type I physisorption isotherm would be better called “pseudo-Langmuir” isotherm. Sometimes can be successfully applied to type I isotherms (pure micropore material) but the reason for limiting value (plateau) is not monolayer limit.Langmuir • Adsorption model limited to the formation of a monolayer that does not describe most real cases. .

The linear range lies between monolayer and capillary condensation. i. That is.2 – 0. The resulting t-curve is compared with the experimental isotherm in the form of a t-plot. whereas micropores which have already been filled cannot contribute further to the adsorption process. The slope of the t-plot (V/t) is equal to the “external area”. and subsequently adjust it to find the best linear plot.5. the area of those pores which are NOT micropores. t” as a function of increasing relative pressure (P/Po). macropores and the outside surface is able to form a multiplayer. Mesopores. experimental volume adsorbed is plotted versus statistical thickness for each experimental P/Po value.e.t-plot Statistical Thickness • Multi-layer formation is modeled mathematically to calculate a layer “thickness. • It is recommended to initially select P/Po range 0. .

Therefore. Kelvin equation predicts pressure at which adsorptive will spontaneously condense (and evaporate) in a cylindrical pore of a given size. .BJH & DH Barrett. Condensation occurs in pores that already have some multilayers on the walls. which gives very similar results. • DH • Extremely similar calculation to BJH. the pore size is calculated from the Kelvin equation and the selected statistical thickness (t-curve) equation. Halenda and Dollimore-Heal • BJH • Modified Kelvin equation. Essentially differs only in minor mathematical details. Joyner.

which is applied in the range of multilayer adsorption. A “flat” surface is considered D is 2. however for an irregular (real) surface D may vary between 2 and 3 and expresses so the degree of roughness of the surface and/or porous structure. .Other Methods • FRACTAL DIMENSION • The geometric topography of the surface structure of many solids can be characterized by the fractal dimension D. which is a kind of roughness exponent. The determination of the surface roughness can be investigated by means of the modified FrenkelHalsey Hill method.

Example Data : Microporous Carbon .

BET : Not strictly applicable .

Example Data : Microporous Carbon • Tag all adsorption points • Analyze behavior • Note knee – transition from micropore filling to limited multilayering (plateau). .

Example Data : Microporous Carbon • Use Langmuir (Monolayer model) / DR for Surface Area. Micropore Volume • Usue Langmuir in range of 0.2 (monolayer) .05 -> 0.

Example Data : Microporous Carbon • Langmuir Surface Area .

micropore volume • Choose low relative pressure points (up to P/P0 = 0.Example Data : Microporous Carbon • DR Method for surface area.2) .

1424 m2/g) . DR surface areas very close (1430 m2/g vs. and micropore volume. • Note Langmuir.Example Data : Microporous Carbon • Reports micropore surface area.

isotherm closes at 0.Example Data : Macroporous Sample Little or no “knee”.95 .

8m2/g (low) • Note hysteresis above P/P0 = 0.Example Data : Macroporous Sample • BET Plot = OK • Surface area ca.95 Pores > 35 nm .

.Example Data : Macroporous Sample Intercept = (-). no micropore volume.

Example Data : Macroporous Sample BJH Shows pores > 20nm. to over 200 nm .

Example Data : Mesoporous Silica Hysteresis => mesopores Also micropores ?? Test using tmethod .

Example Data : Mesoporous Silica BET Surface area = 112m2/g Classic mesoporous silica ! .

Example Data : Mesoporous Silica Intercept ~ 0 Look at tabular data MP SA = 8m2/g (total SA = 112) Statistical Thickness => Use de Boer for oxidic surfaces = silicas .

Example Data : Mesoporous Silica Use BJH – shows narrow pore size distribution in 14-17nm range (mesopores) .

MicroPore Size by Gas Sorption .

Available Calculation Models .

Pore filling pressures for nitrogen in cylindrical pores at 77 K. (Gubbins et al. 1997) .

1998) ..Pore filling pressures for nitrogen in cylindrical silica pores at 77 K (Neimark et al.

3 Exp.25 BJH-Pore size distribution DFT-Pore size distribution 400 Dv(d) [cc/Å/g] Volume [cc/g] 0.8 1 P/P0 0 15 23 31 39 47 55 Pore Diameter [Å] . Nitrogen sorption at 77 K in MCM 41 DFT.05 100 0 0.6 0.Isotherm 500 0.1 200 0.15 300 0.2 0.4 0.Pore size analysis of MCM 41 by silica by N2 sorption at 77 K 600 0.2 0.

Gas.1989) .and liquid density profiles in a slit pore by GCMC (Walton and Quirke.

Siliceous materials such as some silica gels. porous glasses.NLDFT / GCMC (Monte Carlo) Kernel File NLDFT– N2 .g..silica adsorption branch kernel at 77 K. some porous glasses and silica gels which show type H1 sorption hysteresis). SBA-15. MCM-48. based on a cylindrical pore model Applicable Pore Diameter Range 0. such as activated carbons and others. and others. SBA15. Allows to obtain an accurate pore size distribution even in case of type H2 sorption hysteresis Zeolites with cylindrical pore channels such as ZSM5. 0. Mordenite. and mesoporous siliceous materials (e. MCM-41.35nm-30 nm 0.35nm-100nm NLDFT– Ar zeolite/silica equilibrium transition kernel at 87 K based on a cylindrical pore model 0. based on a cylindrical pore model NLDFT– N2 .100nm Examples Carbons with slit-like pores. Siliceous materials such as some controlled pore glasses. MCM-41. SBA-15.35nm. MCM-48.carbon kernel at 77 K based on a slit-pore model NLDFT– N2 – silica equilibrium transition kernel at 77 K. MCM-48 and other adsorbents which show type H1 sorption hysteresis.35nm -100nm . MCM-41.

Allows to obtain an accurate pore size distribution even in case of H2 sorption hysteresis. MCM-41. MCM-41. porous glasses some silica gels etc). porous glasses.. SBA15. and mesoporous silica materials (e. 13X. Zeolites with cage-like structures such as Faujasite.g. some silica gels which show H1 sorption hysteresis). Mordenite etc.. . SBA15. MCM-48. Allows to obtain an accurate pore size distribution even in case of H2 sorption hysteresis. controlled-pore glasses and others).35nm-100nm 0. and mesoporous siliceous materials such as MCM-41.NLDFT / GCMC (Monte Carlo) Kernel File NLDFT – Ar-zeolite/silica adsorption branch kernel at 87 K based on a cylindrical pore model Applicable Pore Diameter Range 0. NLDFT – Ar-zeolite / silica equilibrium transition kernel based on a spherical pore model (pore diameter < 2 nm) and cylindrical pore model (pore diameter > 2 nm) NLDFT – Ar-zeolite / silica adsorption branch kernel at 87 K based on a spherical pore model (pore diameter < 2 nm) and cylindrical pore model (pore diameter > 2 nm) 0. SBA-15.35nm-100nm .35nm-100nm Examples Zeolites with cylindrical pore channels such as ZSM5.g. Zeolites with cage-like structures such as Faujasite. 13X etc. and mesoporous silica materials (e..

carbon kernel at 273 K based on a slit-pore model 0. such as activated carbons etc. .35nm-1.5 nm Carbons with slit-like pores. GCMC – CO2 .NLDFT / GCMC (Monte Applicable Pore Carlo) Kernel File Diameter Range Examples NLDFT – Ar .35nm-1.7 nm Carbons with slit-like pores.5 nm Carbons with slit-like pores. such as activated carbons etc. such as activated carbons etc.carbon kernel at 273 K based on a slit-pore model 0.carbon kernel at 77 K based on a slit-pore model 0.CO2 . NLDFT .35 nm .

RECENT ADVANCES IN THE PORE SIZE ANALYSIS OF MICRO.AND MESOPOROUS MOLECULAR SIEVES BY ARGON GAS ADSORPTION .

4 K is difficult.g.5 . . e.1 nm pores occurs at P/Po of 10-7 to 10-5. where the rate of diffusion and adsorption equilibration is very slow. because the filling of 0. zeolites occurs at relative pressures substantially lower than in case of adsorption in mesopores. • Adsorption measurements using nitrogen at 77.Micropore Size Characterization • Physical adsorption in micropores.

Advantages of Using Argon • Advantage to analyze such narrow micropores by using argon at liquid argon temperature (87.. . • Argon fills these micropores (0.5 – 1nm) at much higher relative pressures (i. at relative pressures 10-5 to 10-3) compared to nitrogen.3 K).e.

• Accelerated equilibration processes.Advantages of Higher Temperature & Pressure • Accelerated diffusion. . • Reduction in analysis time.

5.Argon Adsorption at 87.4K in faujasite-type zeolite are illustrated above.2001 P/P0 The different pore filling ranges for argon adsorption at 87.3 K versus Nitrogen Adsorption at 77.3K and nitrogen adsorption at 77.4 K 350 N2/77K Ar/87 K 280 Volume [cm3] 210 140 70 0 10-6 5 10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100 ZEOLITE | 10. .

Academic Press.V. Neimark. 1999 [ 2 ] P. Haller. G. A. • Classical. theories [1] like DR and semiempirical treatments such those of HK and SF do not give a realistic description of micropore filling • This leads to an underestimation of pore sizes for micropores and even smaller mesopores [2]. 203 (1998) .L. Rouquerol & K. Adsorption by Powders & Porous Solids. macroscopic. I Ravikovitch. Rouquerol. Sing. Advcances in Colloid and Interface Science 76-77 .Micropore Size Calculation • Difficulties are associated with regard to the analysis of micropore adsorption data. [1] F. J.

Schueth. Neimark.44 to 20 nm using high-resolution low-pressure argon adsorption isotherms at 87.I. P. Advances in Colloid and Interface Science.V. Neimark. A. J. Microporous and Mesoporous Materials (2001) 44-45.I Ravikovitch.New Calculation • To overcome the above mentioned problems we introduce a new method for micropore analysis based on a Non-local Density Functional Theory (NLDFT) model by Neimark and Co-workers [3-5]. F. 203 -207 [4] A. [3] P. Gruen.V. Coll. Haller. Unger..I. Neimark. (1998) 159 [5] A. 697 . G. Ravikovitch. and K. M. 76 – 77 (1998). P.K.L.V.3 K. • The new DFT-method is designed for micromesopore size characterization of zeolitic materials ranging in size from 0. Interface Sci. 207. Ravikovitch.

and mesopore size analysis of zeolites and mesoporous silica materials including novel mesoporous molecular sieves of type MCM-41 and MCM-48. • The sorption isotherms were determined using a static volumetric technique • Samples were outgassed for 12 h under vacuum (turbomolecular pump) at elevated temperatures (573 K for the zeolites and 393 K for MCM41/MCM-48).Systematic. . Experimental Study • To evaluate the application of argon sorption for micro.

4 P/Po 0. 15 10 MCM-41 5 ZSM-5 50-50 0 0 0. [mmol/g] Argon adsorption isotherms at 87 K on MCM-41.6 0. ZSM-5 and their 50-50 mixture.2 0.Results 25 20 Adsorption.8 1 .

Results 25 20 Adsorption.0001 0.00001 0.000001 0. [mmol/g] 15 10 MCM-41 ZSM-5 5 50-50 0 0.001 P/Po 0.01 0.1 1 .

35 0.08 0.4 0.04 0.ZSM 0.05 0.1 0.25 0.1 integral 0.3 0. [Å] Vcum.06 dV/dD [cm3/g histogram 0. [cm3/g] .12 0.05 D.2 0.02 0 0 1 10 100 1000 -0.15 0.

3 0.2 0.18 0. [Å] Vcum.12 0.16 0.02 0 1 10 100 1000 0 D.6 0.7 0.1 0.04 histogram integral 0.4 .1 0.MCM 0.08 0.2 0.06 0.5 0. [cm3/g] 0.14 dV/dD [cm3/g] /g] 0.

Evaluation of DFT Algorithm 20 18 16 Adsorption. [mmol/g] 14 12 10 8 6 4 2 0 0.01 0.1 1 .0001 0.000001 experimental NLDFT fit 0.00001 0.001 P/Po 0.

Pore Size Distribution
0.1 0.09 0.08 0.07 0.06 dV/dD [cm3/g] 0.05 0.04 0.03 0.02 0.3 0.5 0.6

0.4 Vcum [cm3/g]

histogram
0.2

integral
0.1

0.01
0 1 10 100 1000 0

D, [Å]

Discussion
• Argon sorption at 77 K is limited to pore diameters smaller than 12 nm.
i.e. no pore filling/pore condensation can be observed at this temperature for silica materials containing larger pores.

• This lack of argon condensation for pores larger than ca. 12 nm is associated with the fact, that 77 K is ca. 6.8 K below the bulk triple point [4,5] .
[4] M. Thommes, R. Koehn and M. Froeba, J. Phys. Chem. B (2000), 104, 7932 [5] M. Thommes, R. Koehn and M. Froeba, Stud. Surf. Sci. Catal., (2001), 135 17

Discussion
• These limitation do not exist for argon sorption at its’ boiling temperature, i.e. ca. 87 K. • Pore filling and pore condensation can be observed over the complete micro- and mesopore size range .

Discussion • Results of classical. BJH. SF etc) indicate that these methods underestimate the pore size considerably.. 20 % for pore diameters < 10 nm. • Deviations from the DFT-results are often in a range of ca.g. . and semi-empirical methods (e.

. and mesoporous silica materials.Summary • Our results indicate that argon sorption data at 87 K combined with the new NLDFT-methods provides a convenient way to achieve an accurate and comprehensive pore size analysis over the complete micro-and mesopore size range for zeolites. catalysts.

. New Jersey. USA.Acknowledgements • Special thanks go to Alex Neimark and Peter Ravikovitch at TRI Princeton.

argon and krypton in ordered and disordered mesoporous silica materials (MCM-41. Thommes. Froeba. Thommes. Ed) AIChE Annual Meeting. MCM-48. Koehn and M. R. Studies in Surface Science and Catalysis 128. Thommes. “ Systematic Sorption studies on surface and pore size characteristics of different MCM-48 silica materials”. Koehn and M. (2001) References . submitted to Applied Surface Science. Thommes. 17 (2001) (4)M. R. “Sorption and pore condensation behavior of pure fluids in mesoporous MCM-48 silica. Froeba. Phys. 7932 (2000) (3)M. silica gel) at temperatures above and below the bulk triple point”. Froeba. Chem. “Characterization of porous solids: Sorption and pore condensation behavior of nitrogen. controlled pore glass. Lee.U. B 104. R. argon and krypton in MCM-48/MCM-41 materials (1) M. Proceedings of the first topical conference on nanometer scale science and engineering” (G. Thommes. argon and krypton in mesoporous MCM-48 silica materials” J. Froeba. Koehn and M.to research work of nitrogen. Nevada. 259 (2000) (2) M. Koehn and M. R. MCM-41 silica and controlled pore glass at temperatures above and below the bulk triple point”. “Sorption and pore condensation behavior of pure fluids in mesoporous MCM-48 silica. 2001 (5)M. Studies in Surface Science and Catalysis. Koehn and M. Froeba. November 4-9. SBA-15. 135. Reno. R. MCM-41 silica and controlled pore glass. “Sorption and pore condensation behavior of nitrogen.

Rapid Micropore Size Analysis by CO2 Adsorption  .

CO2 Adsorption at 0 C on Carbon o .

analysis times are reduced as much as 90%.15K.2 nm).15K permits probing pores from about 2 angstroms (0. • Carbon dioxide at 273. .RAPID MICROPORE ANALYSIS • The advantages of micropore analysis with Quantachrome’s Density Functional Theory (DFT) and CO2 include: • Speed of analysis. with the higher diffusion rate at 273.

g.. DA. The current popular gas sorption models. . BJH. etc.DFT ADVANTAGE DFT has recently been applied to describe the behavior of fluids that are confined in small pores. assume that the density of the adsorbed phase remains constant. Packing considerations suggest that these models are less than satisfactory for analyses of pores less than 2 nm. HK. SF. e. regardless of the size of the pores that are being filled.

DFT calculates the most likely summation of "ideal isotherms“ calculated from "ideal pores" of fixed sizes needed to match the experimental results. .DFT “Fitting” • For a given adsorbate-adsorbent system.

• Using carbon dioxide as adsorbate provides several advantages. typically with an ice/water bath. micropore analyses with nitrogen as adsorbate will require 24 hours or more to run. . – Carbon dioxide molecules are slightly thinner than nitrogen molecules (2.CO2 for Speed! • Typically.0 angstroms) and will fill smaller pores than nitrogen.8 angstroms radius vs.15K. 3. – There is no longer any need to provide and maintain or replenish a level of liquid nitrogen during the analysis. – The use of carbon dioxide allows the measurements to be made at 273.

CO2 Benefits • At this temperature. . This so-called "activated adsorption" effect led to the popularization of the use of carbon dioxide to characterize carbonaceous material since the early 1960s.35K. the diffusion rate of molecules moving through small and tortuous micropores is much higher than at 77.

CO2 Benefits • This higher diffusion rate is responsible for reducing the analysis time to a few hours for a complete adsorption experiment. . thus reducing sample weighing errors.35K analysis. The faster rate also provides for the possibility of using larger samples than with nitrogen adsorption. • Pore size distributions thus obtained are comparable to those from a 24-hour nitrogen/77.

N2 Adsorption @ 77K: 40 hours .

CO2 adsorption at 273K: 2.75 hours .

CO2 Adsorption at 0 C o Density Functional Theory Micropore Distribution .

CO2 Adsorption at 0 C o Monte Carlo Simulation Micropore Distribution .

. calculation parameters are optimized for studies on carbon surfaces. • Currently. • The proprietary Quantachrome Autosorb® software provides the DFT data reduction capabilities to do the rest.15K.mouth dewar and – a water-level sensor.How to do it? • Hardware requirements for this new method are minimal: – a wide. Pore size distributions from about 2 angstroms can be determined from the data taken at 273.

Phys. Gubbins. 97. Schüth. Ravikovitch.V. N.I.Phys. P. K. 4786 (1993) 6. C.Eng. Langmuir. R. Lastoskie. Quirke. Quirke.Sci. Moreno-Castilla. Unger. Bottani.I. Chuen. 49. Carbon 27. 1997 (in press) 9. 9. Wei.. A.K. J. Rodriguez-Reinoso.B. Haller. M. 27. J. Linares-Solano.V. Steele. P.A. 3.P. J. 4765 (1995) 8. Porous Materials 2. N. 76. A. D.R. C. M. Chem. N. K. (1987) 2. Neimark. 2672 (1985) 4.I. P.Rev.A 31. J.V.I.Chem. W. Bakaev. Dubinin. Carbon. E.Chem.K.M. Phys.C. V. P. 11.A. F. Molina-Sabio.L. M. S. K. Martin-Martinez. López-Ramón.. 853 (1989) 5. Tarazona. 2758 (1993) 3. Schüth. F. Seaton. F. 293 (1994) 11. J..M. Grün. Unger.J. Carrasco-Martin.J. Ravikovitch. Langmuir. Ó Domhnaill.A.BIBLIOGRAPHY for Rapid Micropore Size Analysis by CO2 Adsorption 1. 9 (1995) 7. F.V. Torregosa Langmuir. May 1997 10.E. Ravikovitch P. 457 (1989) . Walton. Neimark. Neimark. J. W.T. Garrido. COPS-IV. A. G. M. Olivier.