Académique Documents
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• Temperature dependent
Adsorption/Desorption
• Desorption is the removal of gas molecules
from the surface of a solid… all available
surfaces including that surface inside open
pores.
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
Basic Operation
Pressure transducer(s)
Sample cell
A More Realistic Representation
Sample Temperature Control
• As the coolant evaporates,
the level sensor signals the
dewar drive to compensate cabinet
for the change in level,
level sensor
thereby maintaining a
constant and small cold sample cell
zone.
90 hr dewar
drive shaft
Level sensor
Coolant level controlled
here creates a small cold zone.
Quantachrome’s instruments
Working Equation
PV = nRT
nads = ndosed - nvoid
Equilibrium pressure
What Is The Result?
The values on the y-axis are calculated
from pressure measurements (and
temperature values)
Amount adsorbed
Equilibrium pressure
What Is The Result?
Desorption curve may overlay on, or
appear to left of, the adsorption curve
Amount adsorbed
Relative pressure
Very Low Pressure Behavior
(micropore filling)
Amount Adsorbed
The “knee”
400 0.07
Amount Adsorbed, cc(STP)/g
N2 (77 K)
0.06 CO 2
Ar (77 K)
300 N2
CO2 (273 K) 0.05
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
Nitrogen (77.35 K and Water Sorption (298.4K) in Activated Carbon Fibers (ACF),
(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]
Nitrogen (77.35 K and Water Sorption (298.4K) in Activated Carbon Fibers (ACF),
(M. Thommes, et al., FOA 8, 2004
The Special Behavior of Water
800
Water, 25 C
A15
700 A5 25C
A10 25C
600 A15 25C
500 A10
400
A5
300
200
100
0
0 0.2 0.4 0.6 0.8 1
Nitrogen (77.35 K and Water Sorption (298.4K) in Activated Carbon Fibers (ACF),
(M. Thommes, et al., FOA 8, 2004
Zeolites
– Micropores are part of their crystal structure:
• Most are synthetic
• Alumino-silicates
• Silicalite = no aluminum
• Cation can be H+, Na+, Ca2+, NH4+, etc
• Pore shape needs to be incorporated into pore
size calculation for accurate results
• Some adsorbates are better than others
Adsorption of Nitrogen (77.35 K) and Argon
(87.27 K) on a Zeolite
350
N2/77K
Ar/87 K
280
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
Different Sized Pores Fill at Different P/Po
Pore Shape is Important for
Accurate Pore Size Analysis of Zeolites
(M.Thommes et al., presented at the International Zeolite Conference, Cape Town,
2004)
300 0.7
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
300
Zeolite X- type
X-Zeolite structure DFT-Fitting : cylindrical pore model
240 DFT-Fitting : spherical pore model
(spherical pores)
Volume [cc/g]
180
120
Mordenite structure
(cylindrical pores) 60
0
10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100
P/P0
Metal Organic Frameworks
MOFs
– Synthetic materials
– Also called coordination polymers
– Similar materials without metals are called
COFs… covalent coordination polymers
– Still a very active research area
Metal Organic Frameworks
MOFs
correct
Applications II
– Mesoporous/nonporous materials
• Carbon black
• Ceramics
Pigments
• Alumina
• Silica
• Metal powders
• Pharmaceuticals
– Instrument selection for these materials
– Specific features of benefit to analyzing meso-
/nonporous materials
Applications II
– Mesoporous/nonporous materials
• Carbon black
– Essential for tires and other rubber applications. BET (NSA) and t-plot
(STSA) are important.
• Ceramics
– Particle size affects surface area, surface area remains after particle size is
history. Pore size affects wicking of liquids.
• Pigments
– Surface area and porosity “immobilize” liquids and alter rheology.
• Alumina
– Surface area and pore size are the dominant quality control parameter.
Often used as a catalyst support.
• Silica
– Surface area and pore size are the dominant quality control parameter.
• Metal powders
– Surface area supports particle size data especially fines.
• Pharmaceuticals
– Surface area is lost during tabletting (however pore size affects wicking of
liquids) but after ingestion (and dissolution of excipient) s.s.a. of active
controls release rate.
Carbon Black
Aluminas
Aluminas
Mesoporous Templated Carbons
Mesoporous Templated Carbons
Mesoporous Oxides
Mesoporous Oxides
(Calcination Temperature)
Applications II
– Mesoporous/nonporous materials
• Materials Research
– Templated silicas
» MCM41 is the most famous example. Pore size
by gas adsorption is an essential part of
characterization.
– Templated carbons
– Thin films
» For low-k (dielectric) applications. Difficulty is
associated with very small amount of porous
material.
Mesopore Analysis
Significant progress in the pore size analysis of
porous materials made in the last few years,
mainly because of the following reasons:
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 Can Also be
Controlled by Granulation
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
Different Sized Pores Fill at Different P/Po
600 3.6 nm
400
MCM-41
300
ads des
MCM-41A 3.3nm
200
MCM-41B 3.6 nm
MCM-41C 4.2 nm
100
0.0 0.2 0.4 0.6 0.8 1.0
RELATIVE PRESSURE p/p0
In : S. Lowell, J. Shields, M. Thomas, M. Thommes, Characterization of porous solids and Powders: Surface Area, Pore Size and Density, Kluwer
Academic Publ, 2004,
Different Temperatures Cause Same Sized
Pores to Fill at Different P/Po
70 Ar / 77 K and 87 K
60
77 K
50
volume [10 m /g]
87 K
3
40
-6
30 ads des
77 K
20 87 K
M. Thommes,, R. Koehn and M. Froeba et al. J. Phys. Chem B 104, (2000), 7933
Some History of Pore Size
Analysis of Mesoporous Materials
(a) Methods based on (modified) Kelvin Equation
N2 / 77K in cylindrical
silica pores
X X
. Neimark AV, Ravikovitch P.I., Grün M., Schüth F., Unger K.K, (1998) J. Coll. Interface Sci. 207,159
BJH and NLDFT Compared
560 0.3
420
Dv(d) [cc/Å/g]
350 0.15 X
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]
0.09
0.5
20 0.08
0.07
Adsorption, [mmol/g]
0.4
3
MCM-41
3
0.05 0.3
10 MCM-41
0.04 ZSM-5 histogram
ZSM-5 0.2
0.03 integral
5
50-50
0.02
0.1
0.01
0
0.000001 0.00001 0.0001 0.001 0.01 0.1 1
0 0
P/Po
1 10 100 1000
D, [Å]
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
Studying Pore Geometry, Connectivity
and Disorder
Nitrogen Sorption at 77 K into various Mesoporous Silica Materials
700
Vycor
600 SBA-15
Controlled-Pore Glass (CPG)
SE3030
VOLUME (STP) [cc/g]
500
400
300
200
100
0
0 0.2 0.4 0.6 0.8 1
RELATIVE PRESSURE P/P0
IUPAC Classification of Hysteresis
Due to intrinsic fluid property
Cylindrical
Pores Due to pore blocking /
cavitation (wide bodies,
narrow necks)
Cylindrical &
Spherical Pores
Disordered;
lamellar pore
structures, slit &
wedge, shape
pores
Micro/Mesoporous
adsorbents
Why Does Type H1 Exist?
NLDFT adsorption isotherm of argon at 87K in a cylindrical
equilibrium transition
0.05 spinodal evaporation
pore of diameter 4.8 nm in comparison with the
0.04
0.03
Adsorption,
mmol/m2
spinodal condensation
0.02
Experimental (des)
0.01
Experimental (ads)
(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 Mesoporous Materials 44-56, 697.
Pore Size from H1 Can be Calculated from Ads
and/or Des using NLDFT (but not BJH)
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)
Pore Size from H1 Can be Calculated from Ads
and/or Des using NLDFT (but not BJH)
280
Dv(d) [cc/Å/g]
210
0.013
140
70
0
0 0.2 0.4 0.6 0.8 1 0
Relative Pressure P/P0 40 90 140 190 240
Pore Diameter [Å]
M. Thommes, in Nanoporous Materials- Science and Engineering” (edited by Max Lu), Imperial College Press, Chapter 11 p. 317 - 364 (2004)
Why Does Type H2 Exist?
Type H2
Hysteresis
Nitrogen sorption at 77 K in porous Vycor Glass and pore size distributions from adsorption- (NLDFT spinodal
condensation kernel) and desorption (NLDFT equilibrium transition kernel)
150 0.04
Ads (NLDFT- spinodal condensation)
Des (NLDFT- equilibrium transition)
120 0.032
Volume STP [cm3/g]
Dv(d) [cc/Å/g]
90 0.024
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)
H3 Hysteresis
Dv(log d) [cc/g]
0.6 Artifact
150
120
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
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
H2 versus “H2”/H3/H4
NO size information
Neck size
NO size information;
Cavitation is a property
of the liquid
M. Thommes, B. Smarsly, P.I. Ravokovitch, A.V. Neimark et al.. Langmuir, 22, 765 (2006)
Product Selection
• Mesopore analysis needs:
– Regular vacuum
– 1000 torr pressure range
– 24 hour dewar
– Po station (usually)
Stations 1 1 1+1
Po ports 0 1 (1)
Full ads y y y
Full des y y y
Degas stn 2 2 2
(vac / (vacuum) (vac /
flow) flow)
Xducer (s) 0.11% 0.11% 0.11%
specification f.s. f.s. f.s.
Product Selector 2-3
TWO-THREE Quantachrome Quantachrome
SAMPLES
Full ads y y y y y y
Full des y y y y y y
Degas stn 2 - 2 4 - 4
(vac / (vacuum) (vac / (vac /
flow) flow) flow)
Xducer (s) 0.11% 0.11% 0.11% f.s. 0.11% 0.11% 0.11%
specification f.s. f.s. f.s. f.s. f.s.
Product Selector 4+
FOUR or MORE Quantachrome Q’chrome
SAMPLES
Stations 3+1 4 6
Po ports (1) 4 6
Full ads y y y
Full des y y y
Degas stn 4 - -
(vac/flow)
Xducer (s) 0.11% f.s. 0.11% f.s. 0.11% f..s.
specification
Workshop topics