Bet

Quantachrome
INSTRUMENTS
Micropore Size
Calculations
© 2004-2006 Quantachrome
QuantachromeInstruments
Instruments
Multilayer adsorption
Types II, IV
Volume adsorbed
Types II+I, IV+I
Low slope region in middle of

isotherm indicates first few
multilayers, on external surface
After the knee, including meso and macropores…
micropores cease to before the onset of capillary
contribute to the condensation
adsorption process.
Relative Pressure (P/Po)

© 2004-2006 Quantachrome Instruments
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.
t-plot
isotherm

The t-plot
Resembles a type II isotherm
Statistical thickness
A statistical multilayer
A statistical monolayer

The t-plot method
Not Only Multilayer Correction to
the Kelvin Equation,
But Also Estimation of Micropores...
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...

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

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

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

Micropore Size Determination
by Gas Sorption
Limiting value (plateau) due to filled

pores and essentially zero external area.
Volume adsorbed
Type I or
pseudo-“Langmuir”
Steep initial region due to very strong
adsorption, for example in micropores.

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

DR & DA
Dubinin-Radushkevic and Dubinin-Astakov
• DR
Simple log(V) vs log2(Po/P) relationship which linearizes the
isotherm based on micropore filling principles. “Best fit” is
extrapolated to log2(Po/P) (i.e. where P/Po = 1) to find micropore
volume.
• 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).
Estimation of Micropores
Dubinin-Radushkevich (DR) Theory
  T 2  P  
2
W  W0 exp   B  log  0  
     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 log 2(Po/P)...

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

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 ( 2nm width).
• SF
Similar mathematics to HK method, but based on cylindrical
pore geometry (e.g. zeolites). Calculation restricted to
micropore region ( 2 nm diameter).

DFT
Density Functional Theory
a) Provides a microscopic treatment .
b) Complex mathematical modelling of fluid
interactions plus geometrical considerations
(pore geometry).
c) Fluid interactions are “calibrated”.
d) “Kernel” consists of up to 100 theoretical,
individual pore isotherms.

Gas- and Liquid Density Profiles
in a Slit Pore by GCMC
(Walton and Quirke,1989)

Pore Filling Pressures for Nitrogen
in Cylindrical Silica Pores at 77 K
(Neimark et al, 1998)

Pore Size Analysis of MCM 41
(Templated Silica)
by N2 Sorption at 77 K
600
Exp. Nitrogen sorption at 77 K in MCM 41

DFT- Isotherm
500
Volume [cc/g]
400
300
200
100
0 0.2 0.4 0.6 0.8 1
P/P0

Pore Size Analysis of MCM 41:
Calculations Compared
0.3
BJH-Pore size distribution

0.25 DFT-Pore size distribution
0.2
Dv(d) [cc/Å/g]
0.15
0.1
0.05
0
15 23 31 39 47 55
Pore Diameter [Å]

Quantachrome
I N S T R U M E N T
S
Recent Advances in
Pore Size Characterization by
Physical Adsorption
Author: Dr. Matthias Thommes

Director of Applied Science, Quantachrome Instruments
Boynton Beach, Florida, USA
Presented by Dr. Martin A. Thomas

Director of Business Development and Applied Technology
Quantachrome Instruments
Boynton Beach, Florida, USA

Adsorption Potentials : Planar Surface,
Meso- and Micropores
Planar Surface Mesopores (2-50 nm) Micropore (<2 nm)

IUPAC’s Classification of
Sorption Isotherms

Adsorption in
Micro- and Mesopores
Micropores (pore size < 2 nm):
 Micropore filling (continuous process)
at very low relative pressures P/P0 < 0.15
Type I isotherm (IUPAC Classification)
Mesopores (pore size 2 - 50 nm):

 Multilayer adsorption, pore condensation
and hysteresis (pore condensation
reflects as 1st order phase transition,
i.e., discontinuous process)
in relative pressure (P/P0) range from 0.15 – 1
Type IV, and V isotherm (IUPAC Classification)

Quantachrome
I N S T R U M E N T
S
Recent Advances in
Micropore (< 2 nm) Analysis

Commonly Used Adsorptives for Surface Area
and Pore size Analysis
Nitrogen: at 77.35 K (liquid nitrogen temperature, T/Tc = 0.61)
 pore size analysis of micro-,meso and macropores
 surface area analysis
Argon: at 77.35 K (T – Tr = - 6.5 K; Tr : bulk triple point

temperature; T/Tc = 0.50)
at 87.27 K (liquid argon temperature, T/Tc = 0.57 )
 pore size analysis of micro- , meso- and macropores
 surface area analysis
CO2 : at 195 K (T/Tc = 0.63)

at 273 K (T/Tc = 0.89)  pore size analysis of micropores
of widths < 1.5 nm (particularly for microporous carbons)
Krypton : at 77.35 K (T – Tr = - 38.5 K)  measurement of very low

surface areas
at 87.27 K (T – Tr = - 28.5 K)  pore size analysis of thin
micro/mesoporous films (M. Thommes et al, 2005)

Argon Adsorbate

Adsorption of Nitrogen (77.35 K) and
Argon (87.27 K) on some Zeolites
350
N2/77K
Ar/87 K
280
Faujasite: Ar and N2 Adsorption

Volume [cm3]
210
.
140 N2/77.35 K
70 Ar/87.27 K
0
10-6 5 10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100
ZEOLITE | 10.5.2001 P/P0
Adsorption of Nitrogen (77.35 K) and Argon
(87.27 K) on some Zeolites
360
13X
300 NaX
MCM-58 Argon/87.27 K
H-Mordenite
240 Linde 5A
Volume [cc/g]
180
MCM-58
120
60 H-Mord. 1 3X
NaX
5A
0
5 10-6 5 10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100
P/P0

Argon Adsorption at 87.27 K
• Due to weaker attractive fluid-wall interactions

(and the lack of a quadrupole moment), argon fills
micropores of dimensions 0.4 nm – 0.8 nm at
much higher relative pressures, (.i.e., at least 1.5
decades higher in relative pressures) as compared
to nitrogen.
 High resolution adsorption isotherm of high
accuracy can be measured over the complete
micro-mesopore range, in less time.

Carbon Dioxide Adsorbate

CO2 Micropore Analysis of Porous
Carbons at 273.15 K
 At elevated temperatures and higher absolute pressure (P0

= 26200 Torr) CO2 can access micropores, which are not
accessible for nitrogen at 77 K.
 Fast analysis: due to higher diffusion rate equilibrium is
achieved faster as compared to nitrogen adsorption at 77 K
 dramatic decrease in analysis time i.e., 3-5 h for CO2
versus 30-50 h N2.
 No need for high vacuum system with turbomolecular
pump; 10-3 torr vacuum is sufficient.
 No need for a low-pressure transducer; 1000 Torr
transducer is sufficient.

N2 , Ar (at 77.35 K) vs. CO2 (273.15 K) Adsorption
on Activated Carbon Fiber (ACF-10) and
NLDFT-PSD Histograms
400 0.07
N2 (77 K)
0.06 CO 2
Ar (77 K)
Amount Adsorbed, cc(STP)/g
300 N2
CO2 (273 K) 0.05
N2/77.35 K Analysis Time:
Pore Volume, cc/g

0.04
200
N2 0.03 CO2 = 3 h
CO2,
100 N2 = 40 h
Ar 0.02
CO2/273.15 K 0.01
0
1E-06 1E-05 0.0001 0.001 0.01 0.1 1 0
4 6 8 10 12 14 16 18 20
Relative Pressure Pore Size Å
Quantachrome’s Powder Technote 35

Water Adsorbate

Microporous Carbons:
the Standard way
700
A5 Nitrogen, 77.35 K
600 A10
A15
500
Volume [cc/g] STP
400
300
200
100
0
0 2.10-1 4.10-1 6.10-1 8.10-1 100
P/P0
Nitrogen (77.35 K and Water Sorption (298.4K) in Activated Carbon Fibers (ACF),
(M. Thommes, et al., FOA 8, 2004)
Featureless Isotherms
Nitrogen, 77.35 K
600
A5
A10
480 A15
Volume [cc/g] STP
360
240
120
0
5 10-6 5 10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100
P/P0
(M. Thommes, et al., FOA 8, 2004
State of the Art Cryogenic
Differentiation
0.8
A5 NLDFT A 15
A10
0.64 A15
NLDFT Pore Volume [cc/g]
0.48 A 10
0.32
A5
0.16
0
6 8 10 20 40 60 80 100
Pore Diameter [Å]
The Special Behavior of Water
Water, 25 C A15
A10
A5
Hydrogen Adsorbate

Hydrogen adsorption at 77K and 273 K
for Ultramicropore Characterization
Including H2 isotherms in the PSD analysis allows extending

the lower limit of the analysis to pore sizes of about 3 Å. This
pore size range may be useful for hydrogen storage
applications.
J. Jagiello, M. Thommes, Carbon 42 (2004) 1227

H2, CO2 and N2 Adsorption and NLDFT Analysis
in ACF Activated Carbon Fibers
400
N2 (77 K)
300
Ar (77 K)
CO2 (273 K) H2,77 K
200
N2
100 Ar CO2
0
1E-06 1E-05 0.0001 0.001 0.01 0.1 1
Relative Pressure

H2, CO2 and N2 Adsorption and NLDFT Analysis
in ACF Activated Carbon Fibers
400
N2 (77 K)
Ar (77 K)
300 CO2 (273 K)
0.25
200
N2 H2 ACF10(OG)-N2
100 Ar CO2 0.2
ACF10(OG)-CO2
0 ACF10(OG)-H2
PSD, cc/(g Å)
0.15
1E-06 1E-05 0.0001 0.001 0.01 0.1 1
Relative Pressure N2
0.1 NLDFT-PSD
H2,77 K
0.05 CO2
0
2 4 6 8 10 12 14 16
Pore Width, Å

Pore Shape & Size Influence

Pore Size Analysis by Gas Adsorption
Macroscopic, thermodynamic methods
Micropores (< 2 mn): e.g., Dubinin-Radushkevitch

or more advanced methods such as Horvath-Kawazoe
(HK) and Saito-Foley (SF) , t-method, alpha-s method
Meso/Macropores (2-100 nm): e.g., Kelvin equation based methods such
as BJH (Barrett,Joyner, Halenda)
Modern, microscopic methods, based on statistical mechanics

describe configuration of adsorbed molecules on a molecular
level : e.g., Density Functional Theory (DFT), Molecular Simulation
these methods are applicable for pore size analysis of both the
micro- and mesopore size range
 An accurate pore size analysis over the complete pore size range can
be performed by a single method.

Pore Filling Pressures for Nitrogen in
Cylindrical Micropores at 77 K
C. Lastoskie and K.E.Gubbins, J. Phys. Chem 77, 9786 (1997)

Pore Size Analysis of Zeolites with Novel NLDFT Kernels
based on argon adsorption at 87.27 K
(M.Thommes et al., presented at the International Zeolite Conference, Cape Town,
2004)
300 0.7
H-Mordenite MCM-41 (NLDFT_Silica_cylindrical pore model)

13X Zeolite X_type (NLDFT_Zeolite spherical pore model)
240 NLDFT_Zeolite Fit_(spherical pore model) 0.56 Mordenite-type (NLDFT_Zeolite_cylindrical pore model)
NLDFT-Zeolite Fit (cylindrical pore model)
Volume [cc/g]
180 0.42
dV[cc/Å/g]
120 0.28
60 0.14
0 0
10-6 5 10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100 4 12 20 28 36 44
P/P0 Pore Diameter Å
X-Zeolite structure 300
Zeolite X- type
DFT-Fitting : cylindrical pore model
240 DFT-Fitting : spherical pore model
Volume [cc/g]
180
120
60
0
Mordenite structure 10-5 5 10-4 5 10-3
P/P0
5 10-2 5 10-1 5 100

Quantachrome
INSTRUMENTS
Mesopore Size
Calculations
© 2004
2004-2006
–2006Quantachrome
QuantachromeInstruments
Instruments
Pore Size Determination
Requires a recognition and
understanding of different basic
isotherm types.

Types of Isotherms
Limiting value (plateau) due to filled

pores and essentially zero external area.
Volume adsorbed
Type I or
pseudo-“Langmuir”
Steep initial region due to very strong
adsorption, for example in micropores.

Types of Isotherms
Absence of hysteresis indicates adsorption
on and desorption from a non-porous
surface..
Type II
Volume adsorbed

isotherm indicates first few
multilayers
Rounded knee
indicates approximate
location of monolayer
formation.

Types of Isotherms
Example: krypton on polymethylmethacrylate
Volume adsorbed
Type III
Lack of knee represents extremely

weak adsorbate-adsorbent interaction
BET is not applicable

Types of Isotherms
Type IV Hysteresis indicates capillary
condensation in meso and
Closure at P/Po~0.4 indicates macropores.
presence of small mesopores
Volume adsorbed
(hysteresis would stay open

longer but for the tensile-
strength-failure of the nitrogen
meniscus.
Rounded knee isotherm indicates first few
indicates approximate multilayers
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

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

Meso/Macropore Size
Determination by Gas Sorption
Type IV Hysteresis indicates capillary
condensation in meso and
Closure at P/Po~0.4 indicates macropores.
presence of small mesopores
Volume adsorbed
(hysteresis would stay open

longer but for the tensile-
strength-failure of the nitrogen
meniscus.
Rounded knee isotherm indicates first few
indicates approximate multilayers
formation.

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...
Micropore (Greek micro = small): 0 nm - 2 nm diameter

Mesopore (Greek meso = middle): 2nm - 50 nm diameter
Macropore (Greek macro = large): >50 nm diameter

Adsorption / Desorption
(macroscopic description)
Adsorption = Desorption =
multilayer formation, meniscus “control”
then…

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.

Kelvin* Equation
P 2 V
ln  cos 
P0 rRT
4.15
rk ( A) 
log( P0 / P)
* Lord Kelvin a.k.a. W.T. Thomson
BJH Pore Size
rp  rk  t
rp = actual radius of the pore
rk = Kelvin radius of the pore

t = thickness of the adsorbed film
Pore volume requires assumption of liquid density!

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

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

in Cylindrical Pores at 77 K
(Gubbins et al, 1997)

in Cylindrical Silica Pores at 77 K
(Neimark et al, 1998)

DFT & Phase Transitions
equilibrium transition
0.05 spinodal evaporation
0.04
0.03
Adsorption,
mmol/m2
spinodal condensation
0.02
Experimental (des)
0.01
Experimental (ads)
NLDFT in 4.8nm pore

0
0 0.2 0.4 0.6 0.8 1

Relative pressure, P/P0
NLDFT adsorption isotherm of argon at 87K in a cylindrical pore of diameter 4.8 nm in comparison with the appropriate
experimental sorption isotherm on MCM-41. It can be clearly seen that the experimental desorption branch is associated
with the equilibrium gas-liquid phase transition, whereas the condensation step corresponds to the spinodal spontaneous
transition. (a)Neimark A.V., Ravikovitch P.I. and Vishnyakov A. (2000) Phys. Rev. E 62, R1493; (b)Neimark A.V. and Ravikovitch P.I. (2001) Microporous and
© 2004-2006
Mesoporous Quantachrome
Materials Instruments
44-56, 697.
Where Does Cavitation
Occur?
Adsorptive Temperature ~p/po
Nitrogen 77K 0.42
Argon 87K 0.38
Argon 77K 0.23

Quantachrome
I N S T R U M E N T
S
Recent Advances in
Mesopore (2 – 50 nm) Analysis

Mesopore Analysis
Significant progress in the pore size analysis of porous
materials was recently achieved, mainly because of the
following reasons:
• (i) The discovery of novel ordered mesoporous molecular

sieves which were used as model adsorbents to test theories of gas
adsorption
• (ii) The development of microscopic methods, such as the

Non-Local-Density Functional Theory (NLDFT) or computer simulation methods
(e.g. Monte-Carlo – and Molecular-Dynamic simulations), which allow to
describe the configuration of adsorbed molecules in pores on a molecular level;
• (iii) Carefully performed adsorption experiments

TEM of MCM-41 Silica

Sorption, Pore Condensation and Hysteresis Behavior of a
Fluid in a Single Cylindrical Mesopore
From: M Thommes, “ Physical adsorption characterization of ordered and amorphous mesoporous materials”,
Nanoporous Materials- Science and Engineering” (edited by Max Lu, X.S Zhao), Imperial College Press, Chapter 11,
317-364 (2004)
Pore Size Analysis of Mesoporous Solids:
The Modified Kelvin Equation
ln(P/P0) = -2cos /RT(rp – tc)

rp: pore radius
tc : adsorbed multilayer film prior to condensation
 : surface tension
: densities of the coexistent liquid (l ) and gas (g) ( =
l - g)
 : contact angle of the liquid meniscus against the pore wall

SEM- of Mesoporous TiO2

Nitrogen Sorption at 77 K into
Mesoporous TiO2
150
Sachtopore 60
Sachtopore 100 6 nm
Sachtopore 300
120 Sachtopore 1000 10 nm
Sachtopore 2000
Volume STP [cc/g]
90
30 nm
60
30
100 nm
0
0 0.2 0.4 0.6 0.8 1
P/P0
H. Kueppers, B. Hirthe, M.Thommes, G.I.T, 3 (2001) 110
Pore Size Analysis of
Mesoporous Materials
(I) Methods based on (modified) Kelvin Equation
• e.g., - Barett-Joyner-Halenda (BJH) (1951)

- Dollimore-Heal (DH) (1964)
- Broeckhoff de Boer (BdB) (1967/68)
- Kruk-Jaroniec-Sayari (KJS)) (1997)
- Bhatia et al (mod. BdB) (1998/2004)
- D.D.Do & Ustinov (mod. BdB) (2004/2005)

Results of Sorption Studies on Ordered Mesoporous Materials in Combination With
Advanced Theoretical and Molecular Simulation Approaches :
Problem: Conventional, macroscopic, thermodynamic methods (e.g, methods

based on the Kelvin equation such as BJH, BdB) assume bulk-fluid like
behavior for pore fluid and neglect details of the fluid-wall interactions
 Errors of 25 % and more in pore size analysis!!
Solutions:
• (1) Correction,and/or proper
(e.g, KJS method):
calibration of classical methods
Disadvantage: only valid over limited pore size range
• (2) Application of microscopic methods based on statistical mechanics

(e.g., NLDFT, GCMC) which describe the configuration of the adsorbed
phase on a molecular level 
Accurate pore size analysis over complete
micro/mesopore size range

Phase Diagrams of Pure Fluids
Confined to Porous Glasses
CO2/Vycor
SF6/CPG
H. Fretwell et al, J. Phys. Condens. Matter

M. Thommes and G.H. Findenegg,
Langmuir 10 (1994), 4270 7 (1995) L717
Effect of Confinement on Sorption
and Phase Behavior
• Pore size and temperature are complimentary variables

with regard to the occurrence of hysteresis
• The shape of sorption isotherms is affected by both, the

texture of the material but also by the difference in
thermodynamic states of pore and bulk fluid phases
 In contrast to classical, macroscopic approaches modern

microcopic theories based on statistical mechanics (e.g
Density-Functional Theory and Molecular Simulation)
take these phenomena into account

Pore Size Analysis by Microscopic Methods based
on Statistical Mechanics
(a) Density Functional Theory :

e.g.- Evans and Tarazona (1985/86)
- Seaton (1989),
- Lastoskie and Gubbins (1993)
- Sombathley and Olivier (1994)
- Neimark and Ravikovitch (1995 ……)
b) Monte Carlo (MC) and Moleculardyn. (MD),
e.g. - Gubbins et. al. (1986…. )
- Walton and Quirke (1989…)
- Gelb (1999- ….)
- Neimark and Ravikovitch (1995….)

Theoretical Predictions Of The Pore Size
Dependence Of The Relative Pressure Of The
Equilibrium Condensation/Evaporation Transition
N2/77 K in cylindrical
silica pores
. Neimark AV, Ravikovitch P.I., Grün M., Schüth F., Unger K.K, (1998)
J. Coll. Interface Sci. 207,159
Nitrogen sorption (77 K) in MCM-41 and
Pore Size Analysis by BJH and NLDFT
560 0.3
N2 (77 K): ads BJH-Pore size distribution

N2 (77 K): des 0.25 DFT-Pore size distribution
490
DFT-Fitting
BJH NLDFT
0.2
Volume [10-6 m3/g]
420
Dv(d) [cc/Å/g]
350 0.15
280 0.1
210 0.05
140 0
0 0.2 0.4 0.6 0.8 1 15 23 31 39 47 55
RELATIVE PRESSURE p/p0 Pore Diameter [Å]
NLDFT method: N2/77K cylindrical-silica pore model

Nitrogen Adsorption and Pore Size
Analysis in CMK 3 Mesoporous
Carbon
1000 0.12
N2 (77.35 K) NLDFT-N2(77.4 K)
900
NLDFT- FIT 0.1 BJH-N2 (77.4 K)
800 BJH (3.5 nm)
Volume [cm3 g-1] STP
0.08
700
D(v)[cm3/Å/g]
NLDFT (5.1 nm)
600 0.06
500
0.04
400
0.02
300
200 0
0 0.2 0.4 0.6 0.8 1 20 40 60 80 100
Pressure P/P0 Pore Diameter [Å]
NLDFT Methods: N2/77K cylindrical carbon pore model
M.Thommes, H. Huwe, M. Froeba et al, to be published (2005)

Other Factors
The influence of
 Pore Geometry
 Connectivity
 Disorder (geometrical and surface heterogeneity )
on Adsorption, Pore Condensation, Hysteresis, and thus

the shape of the sorption isotherm remains under
investigation

Nitrogen Sorption at 77 K into
various Mesoporous Silica Materials
700
Vycor
600 SBA-15
Controlled-Pore Glass (CPG)
500 SE3030
VOLUME (STP) [cc/g]
400
300
200
100
0
0 0.2 0.4 0.6 0.8 1
RELATIVE PRESSURE P/P0

IUPAC Classification of Hysteresis
Cylindr.Pores
Cylindr.&Spherical
Pores
Disordered.
lamellar pore
structures, slit &
wedge, shape
pores
Micro/Mesoporous
adsorbents

Origin of Capillary
Condensation Hysteresis
Single Pore Model : Hysteresis occurs in a single pore and

reflects a intrinsic property of phase transition in a pore.
Hysteresis is due due to metastable pore fluid  H1
Hysteresis
-
Network Model: Pore blocking, percolation effects, on
desorption branch  H2 Hysteresis
Disordered Porous Materials Model:

Combination of kinetic and thermodynamic effects;
phenomena are spanning the complete disordered pore
system  H1 and H2 Hysteresis

Ar (87 K) and N2 (77 K) sorption
in MCM 48 and NLDFT-Pore size analysis by
using the NLDFT-equilibrium method (kernel)
1000
0.30 N2: ads
Des(Ar/87 K)
900 Ar(87K): Hysteresis N2: des
Ar/ 87 K
800 N2(77K): Reversible 0.25
Ar: ads
m /nm/g]
m /g]
700 Ar: des Ads(Ar/87 K)

0.20
3
N2/77K
600
3
-6
-5
0.15
VOLUME [10
500
Dv(d) [10
400 0.10
300 ads des
N2 (77 K) 0.05
200 Ar (87 K)
100 0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3.0 3.5 4.0 4.5 5.0 5.5 6.0
RELATIVE PRESSURE p/p0 PORE DIAMETER [nm]
(M. Thommes et al, Applied Surface Science, 196 (2002) 239-249)

Network Model: Pore blocking and
percolation effects in interconnected pore
systems
Type H2
Hysteresis
Problem for Pore Size Analysis:

Adsorption Branch: metastable pore fluid  delayed pore
condensation
Desorption Branch: pore blocking,percolation  delayed
evaporation
How to tackle:
 Application of approaches based on percolation theory
 Application of novel NLDFT approaches
Mesopore-Analysis by NLDFT
NLDFT-method for Pore Size Distribution

Calculation from Adsorption and Desorption
Desorption Branch:: Equilibrium liquid-gas phase
transition (evaporation)
 NLDFT-Kernel of Equilibrium Isotherms
Adsorption Branch: NLDFT-spinodal- gas-liquid phase
transition (condensation)
 NLDFT- Kernel of (Metastable) Adsorption
Isotherms
By P. Ravikovitch, A.V. Neimark, Colloids and Surfaces A: Physicochem Eng. Aspects 187-188 (2001) 11

Nitrogen adsorption/desorption at 77.35 K in SBA-15 and
pore size distributions from adsorption- (NLDFT spinodal
condensation kernel ) and desorption (NLDFT equilibrium
transition kernel)
700 0.22
600
0.2 Ads (NLDFT-spinodal condensation)
Des (NLDFT- equilibrium transition)
0.18
500 0.16
Volume STP [cc/g]
0.14
Dv(d) [cc/Å/g]
400
0.12
300 0.1
0.08
200
0.06
100 0.04
0.02
0
0 0.2 0.4 0.6 0.8 1 0
Relative Pressure P/P0 25 45 65 85 105 125
Pore Diameter [Å]
M. Thommes, in Nanoporous Materials- Science and Engineering” (edited by Max Lu), Imperial College Press, Chapter 11 p. 317 -
364 (2004)
Nitrogen sorption at 77 K in porous CPG and Vycor Glasses and
pore size distributions from adsorption- (NLDFT spinodal
condensation kernel) and desorption (NLDFT equilibrium transition
kernel)
420 0.026
Ads (NLDFT-spinodal condensation)

350 Des (NLDFT- equilibrium transition)
CPG
Volume STP [cc/g]
280
Dv(d) [cc/Å/g]
210 0.013
140
H1 Hysteresis
70
0 0
0 0.2 0.4 0.6 0.8 1 40 90 140 190 240
Relative Pressure P/P0 Pore Diameter [Å]
0.04
150
Ads (NLDFT- spinodal condensation)
Des (NLDFT- equilibrium transition)
120 Vycor 0.032
Volume STP [cm3/g]
Dv(d) [cc/Å/g]
0.024
90
H2 Hysteresis
0.016
60
0.008
30
0
0 25 50 75 100 125 150
0 0.2 0.4 0.6 0.8 1
VYCOR(PSD) | 12.11.2002 Pore Diameter [Å]
Relative Pressure p/p0
M. Thommes, in Nanoporous Materials- Science and Engineering” (edited by Max Lu), Imperial College
Press, Chapter 11 p. 317 - 364 (2004)
Conclusion: H1 Hysteresis
• Mechanism of hysteresis in single mesopores

(e.g. MCM-41, SBA-15) and in materials
consisting of ordered pore networks (e.g., MCM-
48 , CPG) seems to be similar. In both cases H1
hysteresis is observed.
 In case of H1 hysteresis methods based on the
independent pore model are in principle applicable
for pore size analysis

H2/H3 Hysteresis
 In case of type H2 hysteresis, pore blocking, percolation,

and cavitation effects play an important role. The position
of the desorption branch does not reflect the equilibrium
liquid-gas transition. Hence, a method for pore size
analysis based on the equilibrium phase transition can here
not be applied
 NLDFT-spinodal condensation method can be applied to the
adsorption branch (in case of cylindrical-like pores and silica
materials – pore size range up to 80 nm!)
 Application of a calibrated correlation between the position of
capillary condensation step and pore size.

H2/H3/H4 Hysteresis: Lower Limit of
Hysteresis Loop –Tensile Strength
Effect ??
 Hysteresis loop for N2 (77.35 K) always closes at relative pressures

> 0.42 and for argon at 87.27 K at relative pressures > 0.38.
 The lower closure point of hysteresis is believed (in the classical

picture) to be determined by the tensile strength of the capillary
condensed liquid, i.e., there exists a mechanical stability limit below
which a macroscopic meniscus cannot exist anymore and which leads
to a spontaneous evaporation of the pore liquid.
 This forced closure of the hysteresis leads to an artifical step in the

desorption isotherm  Pore size distribution artifact at ca. 4 nm
 Adsorption Branch should be selected for Pore-Size Analysis

H3 Hysteresis: Lower limit of Hysteresis
Loop –Tensile Strength Effect?
240 1
Adsorption Adsorption
210 Desorption Desorption
0.8
180 BJH-PSD
Volume STP [cc/g]
N2/77K sorption on Artifact
Dv(log d) [cc/g]
150 0.6
disordered alumina
120 catalyst
0.4
90
0.2
60
30 0
0 0.2 0.4 0.6 0.8 1 10 50 100 500 1000
Relative Pressure P/P0 Pore Diameter [Å]
M. Thommes, In Nanoporous Materials Science and Engineering, (Max Lu and X Zhao, eds.), World
Scientific, in press (2004)

H4 Hysteresis: Nitrogen adsorption at
77.4 K in activated carbon
-Tensile Strength effect?
500
Nitrogen (77 K)
400
Volume STP [cc/g]
300
200
100
0
0 0.2 0.4 0.6 0.8 1
P/P0

Pore Condensation/Evaporation in Ink-bottle Pores:
Pore Blocking and Cavitation Phenomena.
M. Thommes, B. Smarsly, P.I. Ravokovitch, A.V. Neimark et al.. Langmuir, 22, 765 (2006)

N2 and Ar adsorption on micro-mesoporous silica (SE3030)
and pore size analysis by the NLDFT- method
Pore size distribution from 0.8
metastable adsorption branch 0.7

Nitrogen (77.35 K)
Argon (87.27 K)
Cumulative Pore Volume [cc/g]

0,025
9.4 nm 0.6
1 nm 0.5 Cumulative
0,020
0.4 pore volume
Dv (cc/(Angstr. g))
0,015 0.3
0.2
0,010 0.1
0
0,005 10 50 100 500 1000
Pore Diameter [Å]
0,000 M. Thommes, B. Smarsly, P.I. Ravokovitch, A.V. Neimark et al..

Langmuir, 22, 765 (2006)
10 100
Pore size (Angström)
Mesopore Size
Micropore Volume
N2/77K sorption (NLDFT) : 9.4 nm
N2/77K: 0.12 ml/g
Ar/87K sorption (NLDFT) : 9.1 nm
SANS: 0.1 ml/g
SANS (CLD) : 9.5 nm Excellent agreement
TEM : ca. 9.5 nm
between NLDFT
Micropore Size and SANS/SAXS
N2/77K sorption (NLDFT) : ca. 1.1 nm
Nitrogen sorption of “KLE silica“ at 77K and NLDFT analysis
N2 sorption isotherm Pore size distribution
360 0.015
RUN 1 (Ads) KLE-Silica NLDFT-PSD(spherical pore model)
300 RUN1 (Des)
0.012
RUN 2( Des)
RUN 2 (Ads)
240
0.009
13.9 nm
Volume [cc/g]
dv(cc/Å/g)
1.3 nm
180
0.006
120
0.003
60
0
0 60 120 180 240 300 360
0 Pore diameter (Angström)
Pore Diameter [Å]
0 0.2 0.4 0.6 0.8 1
Relative Pressure P/P0 NLDFT analysis (spherical mesopores,
cylindrical micropores)
Mesopore Size:
N2-sorption: 13.9 nm
Excellent agreement
between SAXS and
TEM: Ca. 13 nm
new NLDFT approach!
SAXS: 13.8 nm
M. Thommes, B. Smarsly, M. Groenewolt, P. Ravikovitch, and A. Neimark, Langmuir, 22,756 (2006)

Pore Blocking/Percolation and
Cavitation
Pore Blocking/Percolation:
“Pore size” distribution determined from desorption
branch should be independent of the choice of the
adsorptive or temperature
Cavitation :
Artificial “Pore” size distribution determined from
desorption branch of hysteresis loop should depend on
the choice of the adsorptive and temperature

Poreblocking/Percolation As Dominant Evaporation
Mechanism: Nitrogen And Argon Sorption In Vycor
0.008
200 Nitrogen /77 K- NLDFT(Adsorption-Branch-Kernel)

Argon/87 K - NLDFT (Adsorption-Branch-Kernel)
Nitrogen 77 K 0.006
160 Argon 87 K
Analysis of N2 and
D(v) [cc/Å/g]
0.004
Volume [cc/g] STP
120
Ar adsorp. branches
0.002
 “Pore Size”
80
0
20 50 80 110 140 170 200 230 260 290 320
Pore Diameter [Å]
40 0.035
Nitrogen/77 K NLDFT (Desorption-Branch Kernel)

0.03 Argon/87 K NLDFT- (Desorption -Branch-Kernel)
0
0 0.2 0.4 0.6 0.8 1 0.025
P/P0 D(v) [cc/Å/g] Analysis of N2 and
0.02
Ar desorp. branches
M. Thommes, B. Smarsly, P.I. 0.015
Ravokovitch, A.V. Neimark et al.. 0.01  “Neck Size”

Langmuir, 22, 765 (2006 0.005
0
0 40 80 120 160 200 240 280 320
© 2004-2006 Quantachrome Instruments Pore Diameter [Å]
Cavitation as dominant mechanism for pore
evaporation: N2 and Ar sorption in SE3030
micro/mesoporous silica
600 NLDFT-PSD (from Adsorption Branch)
0.025
Nitrogen 77 K Argon (87 K), Ads
Argon 87 K
500
0.02
Nitrogen (77K),Ads
9.4 nm
Volume [cc/g] [STP]
400 0.015
NLDFT pore
[cm3/Å/g]
300
0.44 0.01 size from
0.47 adsorption
200 0.005
100 0
30 42 54 66 78 90 102 114 126 138 150
SE3030(PSD) | 17.2.2003 Pore Diameter [Å]
NLDFT PSD from Desorption
0 0.48
0 0.2 0.4 0.6 0.8 1
Argon 87 K
P/P0 Nitrogen 77 K
0.4
0.32
No pore size info
D(v)[cc/Å/g]
from desorption!
0.24
M. Thommes, B. Smarsly, P.I. Ravokovitch, A.V.
Neimark et al.. Langmuir, 22, 765 (2006) 0.16
0.08
0
30 40 50 60 70 80 90 100 110 120 130
© 2004-2006 Quantachrome Instruments Pore Diameter [Å]
Summary : Sorption Hysteresis in
Micro/Mesoporous Pore networks
• Sorption experiments using different adsorptives (e.g. Argon, Nitrogen) allow to
identify pore blocking/percolation and cavitation mechanisms :
Pore Blocking controlled desorption (e.g. porous Vycor glass): Neck Size from
analysis of desorption branch; Pore (Cavity) size from adsorption branch
Cavitation controlled desorption: No pore size info from analysis of desorption

branch ; pore (cavity) size from adsorption branch
• Cavitation controlled desorption is observed in SE3030, KLE and KLE/IL,SLN-326 silica,
which consist of of micro/mesoporous networks of ink-bottle like pores.
- The rel. pressure where cavitation occurs does not depend on the actual neck size as long as
Wneck < W neck,(critical), and Wneck(critical) is found to be larger than 5 nm!
- If Wneck > W neck,(critical) then pore blocking can be observed
• We confirm the validity of novel N2/silica and Ar/silica NLDFT methods,

applicable to the adsorption branch of a hysteretic isotherm. The pore size data
obtained with this method for SE3030, KLE-silica are in excellent agreement with
independently obtained results from novel SANS/SAXS techniques.
Conclusions &Recommendations:
Hysteresis and Pore Size Analysis
• H1 Hysteresis: Independent pore model applies. Pore size can in

principle be determined from both desorption branch and adsorption
branch if proper methods are available
• H2 Hysteresis: caused by pore blocking/percolation or cavitation

phenomena in mesoporous and micro/mesoporous pore networks
Pore blocking:  Pore (cavity) size from adsorption branch; Neck size
from desorption branch,
Cavitation:  Pore (Cavity Size) from adsorption branch; No pore size
information from desorption branch
• H3/H4 Hysteresis: observed in very disordered micro/mesoporous pore

networks and caused by a combination of various phenomena (incl.
cavitation, pore blocking)  Pore (Cavity Size) from adsorption
branch

Conclusions
The use of different probe molecules allows not only to
check for consistency in the pore size and surface area
analysis, but allows also to obtain a much more accurate
micro- and mesopore analysis.
The shape of sorption isotherms is affected by, surface
chemistry and the texture of the adsorbent but also by the
difference in thermodynamik states of pore and bulk fluid
phases. This has to be taken into account in order to obtain
a correct and comprehensive pore size analysis.
 Microscopic methods (e.g, NLDFT, Molecular simulation)
allow to obtain an more accurate and comprehenisve pore
size analysis compared to macroscopic, thermodynamic
methods (e.g., BJH, HK, SF, DR).

Some Selected References
(1) M Thommes, “ Physical adsorption characterization of ordered and amorphous

mesoporous materials”, Nanoporous Materials- Science and Engineering”
(edited by Max Lu, X.S Zhao), Imperial College Press, Chapter 11, 317-364
(2004)
(2) S. Lowell, J.E. Shields, M.A. Thomas and M. Thommes, Characterization of
porous solids and powders: surface area, pore size and density, Kluwer
Academic Publisher, 2004
(3) M. Thommes, B. Smarsly, P.I. Ravokovitch, A.V. Neimark et al.. Langmuir, 22,
765 (2006)
(4) B. Smarsly, M. Thommes, P.I Ravikovitch, A.V. Neimark, Adsorption 11 (2004),
653, (2005)
(5) J. Jagiello, M. Thommes, Carbon 42 (2004) 1227
(6) M. Thommes, R. Koehn and M. Froeba, Applied Surface Science 196 (2002) 239
(7) M. Thommes, R. Koehn and M. Froeba, J. Phys. Chem. B 104, 7932 (2000)

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Quantachrome

Types II+I, IV+I

Low slope region in middle of

Relative Pressure (P/Po)

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Relative Pressure (P/Po)

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For every value of P/Po, the volume adsorbed is

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Intercept = micropore volume

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Limiting value (plateau) due to filled

Relative Pressure (P/Po)

P/Po range Mechanism Calculation model

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A linear relationship should be found between log(W) and log 2(Po/P)...

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Exp. Nitrogen sorption at 77 K in MCM 41

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BJH-Pore size distribution

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Author: Dr. Matthias Thommes

Presented by Dr. Martin A. Thomas

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Planar Surface Mesopores (2-50 nm) Micropore (<2 nm)

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Type I isotherm (IUPAC Classification)

Mesopores (pore size 2 - 50 nm):

Type IV, and V isotherm (IUPAC Classification)

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Argon: at 77.35 K (T – Tr = - 6.5 K; Tr : bulk triple point

CO2 : at 195 K (T/Tc = 0.63)

Krypton : at 77.35 K (T – Tr = - 38.5 K)  measurement of very low

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Faujasite: Ar and N2 Adsorption

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• Due to weaker attractive fluid-wall interactions

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 At elevated temperatures and higher absolute pressure (P0

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Pore Volume, cc/g

Quantachrome’s Powder Technote 35

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Including H2 isotherms in the PSD analysis allows extending

J. Jagiello, M. Thommes, Carbon 42 (2004) 1227

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Micropores (< 2 mn): e.g., Dubinin-Radushkevitch

Modern, microscopic methods, based on statistical mechanics

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