BET Notes

Surface Area
and
Porosity
1
Outline
Background
Techniques
Surface area
Total - physical adsorption
External
Porosity
meso
micro
2
Tuesday, December 4, 12
Length
1 nm
10
100
1 m
10
100
1 mm
macro
meso
micro
10-10m
C-C
bond
metal
crystallite
10-9m
10-8m
Carbon
nanotube
cell
membrane
10-7m
10-6m
10-5m
red blood
cell
Transistor
gate
10-4m
human
hair
10-3m
red
ant
Techniques
Mercury intrusion
Adsorption
Physical
Chemical
Temperature Programmed Methods
4
Physical Adsorption
5
Characterization via
Adsorption
Material Characterization
Physical properties
Differentiate
Gas Adsorption
Quantity adsorbed on a surface as a function of pressure,

volume, and temperature
Modeled properties
Surface area
Pore structure
Non-destructuve
6
Static Adsorption
P
V
Adsorption
Quantity adsorbed - always normalized for mass cm3/g or moles/g
Relative pressure - equilibrium pressure divided by
saturation pressure - p/po
Equilibrium pressure - vapor pressure above the

sample - corrected for temperature (thermal
transpiration)
Saturation pressure - vapor pressure above a liquid
Surface energy - solid/fluid interaction, strength, and

heterogeneity
8
Sample Preparation
Clean the surface
Remove volatiles
Water
CO2
Solvents
Controlled environment!
Inert purge or vacuum

Temperature control
Avoid Phase Changes
Physical Adsorption
Molecules from the gas phase strike the surface.
At equilibrium the molecule adsorbs, lose the heat
of adsorption, and subsequently desorb from
surface.
At equilibrium the rate of condensation = the rate of
desorption
Constant surface coverage at equilibrium.
Surface features change the adsorption potential.

Surface area models neglect the effects of localized
phenomenon.
Curve surfaces or roughness provide enhanced
adsorption potential.
10
Physical Adsorption
Not activated (no barrier)
60
Rapid
40
Potential Energy, kJ/mol
Weak (< 38 kJ/mol)

Atomic/Molecular
Reversible
Non-specific
May form multilayers
20
0
20
40
60
80
van der Waals/dipole interactions
100
Distance from Surface,
Often measured near the

condensation temperature
11
Chemical Adsorption
May be activated
60
Covalent, metallic, ionic
Potential Energy, kJ/mol
40
20
Strong (> 35 kJ/mol)
May be dissociative
20
40
Often irreversible
60
Specific - surface symmetry
80
100
3
4
Distance from Surface,
Limited to a monolayer
Wide temperature range
12
Isotherm Types
nads
II
III
IV
VI
Constant temperature
Quantity adsorbed as a
function of pressure
Six classifications
Quantity is normalized for
sample mass
Vacuum to atmospheric
13
Classical View of
Adsorption
As the system pressure is
increased the formation of a
monolayer may be observed.
qads
IV
p/po
14
Adsorbed Layer Density
The first layer begins to form

below 1x10-4 p/po
The density continues to increase

with pressure/adsorption
The monolayer is completed

below 0.1 p/po
15
Classical View of
Adsorption
As the system pressure is increased
(gas concentration also increases)
multiple layers sorb to the surface.
qads
IV
B
A
p/po
16
The monolayer is completed below

0.1 p/po
The second layer continues to

form as pressure is increased
The third layer appears at < 0.5 p/

po
17
Classical View of
Adsorption
As pressure is further increased
we may observe capillary
condensation in mesopores.
B-C
qads
IV
C
B
A
p/po
18
Layer formation continues

as p/po increases
As p/po approaches 1, the

density becomes constant
or nearly liquid-like
19
Classical View of
Adsorption
As pressure approaches the saturation
pressure, the pores are filled and we
may estimate total pore volume.
qads
IV
B-C
C
B
A
p/po
20
Adsorptives
Nitrogen
Argon
Krypton
21
Nitrogen
Broad usage
Limitations
Strong interactions
t-plot
Pore size
distributions
Reduced precision
for materials with <
1m2/g (10mol/g
monolayer)
Surface area
BJH - bulk fluid

properties
NLDFT - excess
density
Slow diffusion < 0.5

nm pores
22
250
ZSM-5
Faujasite
Vads, cm3/g
200
150
100
50
0
1e-08
1e-07
1e-06
1e-05
0.0001
0.001
0.01
0.1
p/po
Confinement
23
Argon
Pore size distributions
H-K calculations
NLDFT - excess
density
Benefits
Reduced interaction
compared to N2
Molecular size < N2

and faster diffusion due
to size and T (87K)
Limitations
Ar molecular area not

a generally accepted
value
Statistical t-curves
based upon N2
Not used for BJH bulk fluid methods
24
Faujasite (H+)
250
Nitrogen
Argon
Vads, cm3/g
200
150
100
50
0
1e-07
1e-06
1e-05
0.0001
0.001
0.01
0.1
p/po
Y zeolite, Ar Adsorption
25
ZSM-5 (LN2)
200
180
Nitrogen
Argon
160
Vads, cm3/g
140
120
100
80
60
40
20
0
1e-08
1e-07
1e-06
1e-05
0.0001
0.001
0.01
0.1
p/po
ZSM-5, Ar Adsorption
26
140
Adsorption
Desorption
120
Vads, cm /g
100
80
60
40
20
0
1e-07
1e-06
1e-05
0.0001
0.001
0.01
0.1
p/po
ZSM-5 Low P Desorption

27
Krypton
Surface area estimates BET
Low specific surface

area (< 1m2/g)
Low absolute area limited sample

quantity
Benefits
High precision, low

pressure analysis
Limitations
Pressure range
limited to < 1 torr at
77 K (<0.3 p/po)
General agreement
with N2
Cost
Limited to surface
area applications
28
Error analysis
Gas Law calculations
Error
Typical values
Relative error
29
Error Reduction
Probe
Temperature, K Reference
P ratio
Relative
Error
Ar
77
N2
200/760
0.26
Kr
77
N2
2.4/760
0.003
Kr
87
Ar
50/760
0.07
30
Surface Area
31
Surface Area
Area from adsorption
nm - monolayer
NA - Avogadros number
Total area - physical adsorption
area of adsorbed molecule - nitrogen or

krypton
Active area - chemical adsorption
area of a surface site - metal atom

Stoichiometry
32
Type I Isotherm Langmuir Isotherm

Mono-layer adsorption
Chemical Adsorption
nads
Micropore filling
Finely divided surface

Limiting amount
adsorbed as p/po
approaches 1
33
Langmuir
Reduces to the familiar form of the
Langmuir equation for associative
adsorption
At low coverage, the Langmuir equation

converges with Henrys Law
34
Nitrogen adsorption on
Graphitized Carbon
1
Henrys Law
Adsorption
Desorption
CarboPack F
nads, (mmoles/m2)/g
0.1
0.01
Sterling FT
0.001
0.0001
1e-05
6 m2/g
0.0001
0.001
0.01
0.1
10 m2/g
P
0.1
Henrys law constant
Henrys Law - Sterling FT

Carbopack F - MIC
Carbopack F - Kruk
Sterling FT - MIC
nads, (mmoles/m2)/g
0.01
0.001
19 (mmols/m2) / atm
0.0001
1e-05
1e-06
1e-05
0.0001
P
0.001
0.01
35
X Zeolite, 0.8nm pores

250
Adsorption
200
Quantity Adsorbed, cm3/g
Langmuir
Estimate of nm
150
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/p
Langmuir Transformation, 13x Zeolite
13X
13X
0.007
0.005
p/Q, mmHg/(cm /g STP)
0.006
620 m2/g
0.004
0.003
0.002
0.001
0
0.2
0.4
0.6
Pressure, mmHg
0.8
36
Type II Isotherm
Non-porous
Macro-porous
Flat Surfaces
Uniform surface energy
II
nads
Multilayer adsorption
Infinite adsorption as
pressure approaches
saturation
37
BET Surface Area

Estimate monolayer capacity
Multi-layer adsorption
Non-porous, Uniform surface
Heat of adsorption for the first layer is higher than
successive layers.
Heat of adsorption for second and successive
layers equals the heat of liquefaction
Lateral interactions of adsorbed molecules are
ignored
38
NLDFT estimate for the

density of the adsorbed layers
p = 0.9900
p = 0.9000
p = 0.7000
p = 0.5000
p = 0.2000
p = 0.1000
p = 0.0100
p = 0.0010
p = 0.0002
p = 0.0001
0
The density varies with distance from the surface.

This is contrast to BET assumptions
However, at 0.5 p/po there are only 3 layers
39
BET Equation
Similar to Langmuir - a mass
balance for each layer is used
The first layer is unique and
subsequent layers are common
E is the heat of liquefaction
An infinite series is formed
The sum of surface fractions is 1
The total quantity adsorbed is a function
of the monolayer and the surface fractions
The multilayer may approach infinite
thickness as pressure approaches
saturation
40
BET Equation
Linear form of
BET
41
BET surface area
42
Silica, 100nm pores

40
Adsorption
Desorption
35
BET
estimate of nm
30
25
20
15
10
5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
Linear BET, Lichrosphere 1000
0.045
100 nm SiO2
Lic 1000
0.04
0.035
25.7 m2/g
1/Q(p /p-1)
0.03
0.025
0.02
0.015
0.01
0.005
0
0.05
0.1
0.15
0.2
0.25
0.3
Relative Pressure, p/po
43
Type IV Isotherm
IV
Multilayer adsorption
nads
Meso-porous
Capillary condensation
P
44
Amorphous Silica Alumina, 11nm pores

450
Adsorption
Desorption
400
Quantity adsorbed, cm3/g
Amorphous
Silica-Alumina
350
300
250
200
150
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
0.007
BET Surface Area = 215.5 m /g
0.006
11 nm pores
1/(qads(po/p - 1))
0.005
0.004
0.003
0.002
215.5 m2/g
0.001
0
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
p/po
45
Silica, 4 nm pores
600
500
MCM-41
Adsorption
Desorption
400
300
200
100
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
0.0016
BET Surface Area = 926.8
0.0014
4 nm pores
1/(qads(po/p - 1))
0.0012
0.001
0.0008
0.0006
0.0004
926.8
m2/g
0.0002
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
p/po
46
SiO2-Al2O3 MCM-41
SiO2
100 nm pores
11 nm pores
25.7 m2/g
215.5 m2/g
Silica, 100nm pores

40
Silica, 4 nm pores
600
Adsorption
Desorption
400
Adsorption
Desorption
500
25
20
15
10
350
30
926.8 m2/g

450
Adsorption
Desorption
35
4 nm pores
300
250
200
150
400
300
200
100
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.1
0.2
p/po
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0
1
0.1
0.2
0.3
0.4
p/po
0.5
0.6
0.7
0.8
0.9
p/po
47
Fluid Cracking Catalyst, 0.8nm pores

100
90
80
FCC catalyst
Adsorption
Desorption
70
60
50
40
30
20
10
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/p
0.004
BET Surface Area = 173.5 m2/g
0.0035
Y & binder
1/(qads(po/p - 1))
173.5 m2/g
0.003
0.0025
0.002
0.0015
0.001
BET range reduced

to 0.16 p/po maximum
0.0005
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
p/po
48
FCC
49
FCC - Rouquerol
50
BET surface area summary

Nitrogen or Krypton
Krypton for low surface area or small sample quantity
Isotherm
LP to 0.3 p/p
Adjust range used to fit BET parameters for -porous
materials - Rouquerol transform
C must be +
Physical constraint
Linearity
51
External Surface Area

52
t-Plot
Standard Isotherms
Monolayer region is sensitive to isotherm shape
Multilayer region is not sensitive to isotherm shape
Multilayer region is less dependent on the
adsorbent structure
qads
IV
C
B
A
p/po
53
nads
t-Plot
Standard Isotherms
thickness,
thickness,
Slope of a linear region corresponds to area

Intercept from a linear region is a pore volume
Based on BET surface area
54
t-Plot
Standard Isotherms
nads
External Area
Flat Surface
Pore Vol
thickness,
thickness,
Slope corresponds to external (matrix) area

Intercept is the micro pore volume
t-curve is critical
Statistical curves give comparative results

Reference curves are preferred
55
t-Plot
Standard Isotherms
nads
External Area
External Area
Meso Pore Vol

Flat Surface
Flat Surface
Pore Area
Pore Vol
thickness,
thickness,
Low t slope is area

Intercept is meso pore volume
High t slope is external area
56
Statistical
t-curves
20
15
Thickness, angstroms
Halsey
BJH
Harkins-Jura
Halsey
Harkins and Jura
Jaroniec et. al.
Broekhoff de Boer
t-plot
10
Jaroniec et. al.

0
Silica
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
Broehkhoff de Boer
difficult to use near saturation
57
t-Plot
58
Silica, 100nm pores

40
Adsorption
Desorption
35
Surface
Modifications
30
25
20
15
10
5
0
The reference
surface may be
modified to be similar
to the porous material
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.9
p/po
35
DFT
ODMS
30
25
20
15
10
Hydrophilic vs.
hydrophobic
5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
p/po
59
t-Plot for 13X
X Zeolite, 0.8nm pores

250
Adsorption
200
150
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/p
160
140
0 intercept
Reference curve
External area
120
100
80
60
Micropore filling
40
20
0
0
0.5
1
1.5
2.5
60

450
Adsorption
Desorption
400
Amorphous
Silica-Alumina
350
300
250
200
150
100
50
0
Negligible micropore volume
0.1
0.2
0.3
0.4
0.5
0.6
0.7
6
8
10
0.8
0.9
p/po
350
Capillary
condensation at
large t values
0
400
300
250
200
150
100
50
0
0
12
14
61
MCM-41
Silica, 4 nm pores
600
Adsorption
Desorption
500
400
300
200
100
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
6
8
10
0.8
0.9
p/po
700
Area, pore volume,

and external area
600
Ideal t-plot sample
500
400
300
200
Pore area
100
0
0
12
14
62
t-Plot summary
Area
Pore area
External area (matrix)
Pore volume
Isotherm
LP to 0.7 p/p
Positive or 0 intercept
t-curve
Reference curve is preferred
Statistical curve is convenient
63
Meso-porosity
Capillary
condensation
Fluid has bulk
behavior
BJH or DH models
Adsorbed layer
Liquid core
64
Meso-porosity
BJH models
Thickness curve to
estimate the
adsorbed layer
Kelvin equation to
estimate the radius

of the liquid core
65
Model Isotherms Kelvin Condensation
V =
Ad
4
66
Adsorption
Desorption
400
350
300
250
200
150
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
0.7
2
1.8
0.6
1.6
1.4
1.2
0.4
1
0.3
0.8
0.6
0.2
0.5
dV/d(log(D)), (cm /g)/
BJH
First V is assumed to be
from pore emptying
Subsequent V are a
combination of pore
emptying and thinning of
the adsorbed layer

450
pore volume, cm3/g
Amorphous
Silica-alumina
0.4
0.1
0
0.2
10
100
width,
67
350
300
250
200
150
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
300
250
200
dSA/dD
BJH
From pore volume and calculated
diameter, we can estimate surface
area for a cylinder
Common to observe the BJH
estimate of area is greater than the
BET estimate
Adsorption
Desorption
400
Cumulative Pore Area, m2/g
Amorphous
Silica-alumina

450
150
100
50
0
10
100
D, angstroms
1000
68

Adsorption
Desorption
400
Amorphous
Silica-alumina
450
350
300
250
200
150
100
50
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
p/po
0.7
4.5
4
0.6
3
0.4
2.5
0.3
2
1.5
0.2
dV/d(log(D)), (cm3/g)/
3.5
0.5
pore volume, cm3/g
BJH
Desorption data has been
used - historically
Best to use both Adsorption
and Desorption - they should
share common features
1
0.1
0.5
0
10
100
width,
69
BJH - PVD
Pt/Al2O3
70
Pore Area vs BET Area

Hg Pore Area
Based upon a work function
Gas Adsorption Pore Area
Geometric area of a cylinder
BET Area
Based upon the area occupied by adsorbed
nitrogen (krypton)
71
Thank-you
72

BET Notes

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BET Notes

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Surface Area

Total - physical adsorption

Quantity adsorbed on a surface as a function of pressure,

Equilibrium pressure - vapor pressure above the

Saturation pressure - vapor pressure above a liquid

Surface energy - solid/fluid interaction, strength, and

Inert purge or vacuum

Avoid Phase Changes

Surface features change the adsorption potential.

Potential Energy, kJ/mol

Weak (< 38 kJ/mol)

van der Waals/dipole interactions

Distance from Surface,

Often measured near the

Covalent, metallic, ionic

Potential Energy, kJ/mol

Strong (> 35 kJ/mol)

Specific - surface symmetry

Adsorbed Layer Density

The first layer begins to form

The density continues to increase

The monolayer is completed

Adsorbed Layer Density

The monolayer is completed below

The second layer continues to

The third layer appears at < 0.5 p/

Adsorbed Layer Density

Layer formation continues

As p/po approaches 1, the

BJH - bulk fluid

Slow diffusion < 0.5

Molecular size < N2

Ar molecular area not

Not used for BJH bulk fluid methods

ZSM-5 Low P Desorption

Low specific surface

Low absolute area limited sample

High precision, low

Area from adsorption

Total area - physical adsorption

area of adsorbed molecule - nitrogen or

Active area - chemical adsorption

area of a surface site - metal atom

Type I Isotherm Langmuir Isotherm

Finely divided surface

At low coverage, the Langmuir equation

Henrys law constant

Henrys Law - Sterling FT

X Zeolite, 0.8nm pores

Quantity Adsorbed, cm3/g

Langmuir Transformation, 13x Zeolite

p/Q, mmHg/(cm /g STP)

Uniform surface energy

BET Surface Area

NLDFT estimate for the

The density varies with distance from the surface.

BET surface area

Silica, 100nm pores

Quantity Adsorbed, cm3/g

Relative Pressure, p/po

Amorphous Silica Alumina, 11nm pores

Quantity adsorbed, cm3/g

BET Surface Area = 215.5 m /g

Quantity adsorbed, cm3/g