Surface Area

and
Porosity

Outline
• Background
✦ Techniques

• Surface area
✦ Total - physical adsorption
✦ External
✦ Porosity
✦ meso
✦ micro
2
Tuesday, December 4, 12
 Length
1Å 1 nm 10 100 1 µm 10 100 1 mm

macro
meso
micro
metal
crystallite

10-10m 10-9m 10-8m 10-7m 10-6m 10-5m 10-4m 10-3m

C-C Carbon cell red blood human red

bond nanotube membrane cell hair ant

Transistor
gate
3

Techniques
Mercury intrusion
• Adsorption
Physical
Chemical
Temperature Programmed Methods

4
Tuesday, December 4, 12
 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
Tuesday, December 4, 12
 Static Adsorption
P
V X X G
X

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
Tuesday, December 4, 12
 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
Tuesday, December 4, 12
 Physical Adsorption
Not activated (no barrier)
60
Rapid
40

Weak (< 38 kJ/mol) 20

Potential Energy, kJ/mol

Atomic/Molecular 0

−20
Reversible
−40
Non-specific
−60

May form multilayers −80

van der Waals/dipole interactions −100

0 1 2 3 4 5 6 7
Distance from Surface, Å
Often measured near the
condensation temperature

11

Chemical Adsorption
May be activated
60

40 Covalent, metallic, ionic

20
Potential Energy, kJ/mol

Strong (> 35 kJ/mol)

0

−20 May be dissociative

−40
Often irreversible
−60

−80 Specific - surface symmetry

−100
0 1 2 3 4 5 6 7 Limited to a monolayer
Distance from Surface, Å

Wide temperature range

12
Tuesday, December 4, 12
 Isotherm Types
I II III
nads

IV V VI

• Constant temperature • Six classifications

• Quantity adsorbed as a • Quantity is normalized for

function of pressure sample mass

• Vacuum to atmospheric

13

Classical View of
Adsorption
As the system pressure is
increased the formation of a
monolayer may be observed.
A

IV
qads

p/po

14
Tuesday, December 4, 12
 Adsorbed Layer Density

• The first layer begins to form

below 1x10-4 p/po
• The monolayer is completed
below 0.1 p/po
• The density continues to increase
with pressure/adsorption
15

Classical View of
Adsorption
As the system pressure is increased
(gas concentration also increases) B
multiple layers sorb to the surface. A

IV
qads

B
A

p/po

16
Tuesday, December 4, 12
 Adsorbed Layer Density

• The monolayer is completed below

0.1 p/po
• The third layer appears at < 0.5 p/
po
• The second layer continues to
form as pressure is increased
17

Classical View of
Adsorption
As pressure is further increased
we may observe capillary
condensation in mesopores. B-C
A

IV
qads

C
B
A

p/po

18
Tuesday, December 4, 12
 Adsorbed Layer Density

• Layer formation continues • As p/po approaches 1, the

density becomes constant
as p/po increases
or nearly liquid-like
19

Classical View of
Adsorption
As pressure approaches the saturation D
pressure, the pores are filled and we B-C
may estimate total pore volume. A

IV D
qads

C
B
A

p/po

20
Tuesday, December 4, 12
 Adsorptives

Nitrogen
Argon
Krypton

21

Nitrogen
Broad usage Limitations
• Surface area • Strong interactions
• t-plot • Slow diffusion < 0.5
nm pores
• Pore size
distributions • Reduced precision
for materials with <
• BJH - bulk fluid
1m2/g (10µmol/g
properties
monolayer)
• NLDFT - excess
density

22
Tuesday, December 4, 12
 250
ZSM-5
Faujasite

200

150
Vads, cm3/g

100

50

0
1e-08 1e-07 1e-06 1e-05 0.0001 0.001 0.01 0.1 1
p/po

Confinement
23

Argon
Pore size distributions Limitations
• H-K calculations • Ar molecular area not
a generally accepted
• NLDFT - excess
value
density
Benefits • Statistical t-curves
based upon N2
• Reduced interaction
• Not used for BJH -
compared to N2
bulk fluid methods
• Molecular size < N2
and faster diffusion due
to size and T (87K)

24
Tuesday, December 4, 12
 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 1
p/po

Y zeolite, Ar Adsorption
25

ZSM-5 (LN2)
200
Nitrogen
180 Argon

160

140
Vads, cm3/g

120

100

80

60

40

20

0
1e-08 1e-07 1e-06 1e-05 0.0001 0.001 0.01 0.1 1
p/po

ZSM-5, Ar Adsorption
26
Tuesday, December 4, 12
 140
Adsorption
Desorption
120

100
Vads, cm /g

80
3

60

40

20

0
1e-07 1e-06 1e-05 0.0001 0.001 0.01 0.1 1
p/po

ZSM-5 Low P Desorption

27

Krypton
Surface area estimates - Limitations
BET
• Pressure range
• Low specific surface limited to < 1 torr at
area (< 1m2/g) 77 K (<0.3 p/po)
• Low absolute area - • General agreement
limited sample with N2
quantity
• Cost
Benefits
• Limited to surface
• High precision, low area applications
pressure analysis

28
Tuesday, December 4, 12
 Error analysis
Gas Law calculations

Error

Typical values

Relative error

29

Error Reduction
Relative
Probe Temperature, K Reference P ratio
Error

Ar 77 N2 200/760 0.26

Kr 77 N2 2.4/760 0.003

Kr 87 Ar 50/760 0.07

30
Tuesday, December 4, 12
 Surface Area
31

Surface Area
• Area from adsorption
• nm - monolayer
• NA - Avogadro’s 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
Tuesday, December 4, 12
 Type I Isotherm -
Langmuir Isotherm
Mono-layer adsorption

• Chemical Adsorption I

Micropore filling

nads
Finely divided surface

Limiting amount
adsorbed as p/po P

approaches 1

33

Langmuir

Reduces to the familiar form of the

Langmuir equation for associative
adsorption

At low coverage, the Langmuir equation

converges with Henry’s Law

34
Tuesday, December 4, 12
 Nitrogen adsorption on
Graphitized Carbon
1
Henry’s Law
Adsorption
Desorption CarboPack F
0.1

•
nads, (mmoles/m2)/g

0.01
6 m2/g
0.001
Sterling FT
0.0001
1e-05 0.0001 0.001
P
0.01 0.1 1 • 10 m2/g
0.1

Henry’s law constant

Henry’s Law - Sterling FT
Carbopack F - MIC
Carbopack F - Kruk
Sterling FT - MIC

0.01

• 19 (mmols/m2) / atm
nads, (mmoles/m2)/g

0.001

0.0001

1e-05
1e-06 1e-05 0.0001 0.001 0.01
P

35

Langmuir 250
Adsorption
X Zeolite, 0.8nm pores

Estimate of nm 200
Quantity Adsorbed, cm3/g

150

100

50

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
o
p/p

Langmuir Transformation, 13x Zeolite

13X

13X 0.007

0.006
p/Q, mmHg/(cm /g STP)

0.005
3

620 m2/g 0.004

0.003

0.002

0.001

0
0 0.2 0.4 0.6 0.8 1
Pressure, mmHg

36
Tuesday, December 4, 12
 Type II Isotherm

Non-porous

• Macro-porous II

• Flat Surfaces

nads
Uniform surface energy

Multilayer adsorption

Infinite adsorption as
P
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
Tuesday, December 4, 12
 NLDFT estimate for the
density of the adsorbed layers
p = 0.9900
p = 0.9000
p = 0.7000
p = 0.5000
ρ

p = 0.2000
p = 0.1000
p = 0.0100
p = 0.0010
p = 0.0002
p = 0.0001

0 1 2 3 4 5 6 7 8
σ

• 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
Tuesday, December 4, 12
 BET Equation

• Linear form of
BET

41

BET surface area

42
Tuesday, December 4, 12
 BET 40
Silica, 100nm pores

estimate of nm
Adsorption
Desorption
35

30

Quantity Adsorbed, cm3/g

25

20

15

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po

Linear BET, Lichrosphere 1000

0.045
Lic 1000

100 nm SiO2 0.04

0.035

0.03

1/Q(p /p-1)
0.025

25.7 m2/g
o
0.02

0.015

0.01

0.005

0
0 0.05 0.1 0.15 0.2 0.25 0.3
Relative Pressure, p/po

43

Type IV Isotherm

IV

Meso-porous
nads

Multilayer adsorption

Capillary condensation

44
Tuesday, December 4, 12
 Amorphous 450
Adsorption
Amorphous Silica Alumina, 11nm pores

Desorption

Silica-Alumina
400

350

Quantity adsorbed, cm3/g

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 1
p/po
0.007 2
BET Surface Area = 215.5 m /g

0.006

0.005

1/(qads(po/p - 1))
11 nm pores 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
Adsorption
Desorption

MCM-41
500
Quantity adsorbed, cm3/g

400

300

200

100

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po
0.0016
BET Surface Area = 926.8

0.0014

0.0012
1/(qads(po/p - 1))

0.001

4 nm pores 0.0008

0.0006

0.0004

926.8 m2/g 0.0002

0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
p/po

46
Tuesday, December 4, 12
 SiO2 SiO2-Al2O3 MCM-41
100 nm pores 11 nm pores 4 nm pores

25.7 m2/g 215.5 m2/g 926.8 m2/g

Silica, 100nm pores Amorphous Silica Alumina, 11nm pores Silica, 4 nm pores
40 450 600
Adsorption Adsorption Adsorption
Desorption Desorption Desorption
35 400
500
350
30
Quantity Adsorbed, cm3/g

Quantity adsorbed, cm3/g

Quantity adsorbed, cm3/g

300 400
25
250
20 300
200
15
150 200
10
100
100
5 50

0 0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po p/po p/po

47

Fluid Cracking Catalyst, 0.8nm pores

100
Adsorption
90 Desorption

FCC catalyst 80
Quantity Adsorbed, cm3/g

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 1
o
p/p

0.004
BET Surface Area = 173.5 m2/g

0.0035

Y & binder 0.003

1/(qads(po/p - 1))

0.0025

0.002

173.5 m2/g 0.0015

0.001

0.0005

BET range reduced 0

0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
p/po
to 0.16 p/po maximum

48
Tuesday, December 4, 12
 FCC

49

FCC - Rouquerol

50
Tuesday, December 4, 12
 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 µ-porous
materials - Rouquerol transform
“C” must be “+”
Physical constraint
Linearity

51

External Surface Area

52
Tuesday, December 4, 12
 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
IV

qads
C
B
A

p/po

53

t-Plot
Standard Isotherms
nads

thickness, Å thickness, Å

Slope of a linear region corresponds to area

Intercept from a linear region is a pore volume
Based on BET surface area

54
Tuesday, December 4, 12
 t-Plot
Standard Isotherms
External Area
nads

Flat Surface

µ Pore Vol

thickness, Å thickness, Å

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
External Area External Area
nads

Meso Pore Vol

Flat Surface Flat Surface

Pore Area
µ Pore Vol

thickness, Å thickness, Å

Low ”t” slope is area

Intercept is meso pore volume
High ”t” slope is external area
56
Tuesday, December 4, 12
 Statistical
t-curves
20
Halsey
Harkins and Jura
Jaroniec et. al.
Broekhoff de Boer

15
Halsey

Thickness, angstroms
• BJH 10

Harkins-Jura
• t-plot 5

Jaroniec et. al.

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
• Silica p/po

Broehkhoff de Boer
• difficult to use near saturation

57

t-Plot

58
Tuesday, December 4, 12
 Surface 40
Silica, 100nm pores

Adsorption

Modifications
Desorption
35

30

Quantity Adsorbed, cm3/g

25

20

15

10

The reference
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po

35

surface may be
DFT
ODMS
30

modified to be similar 25

Thickness, angstroms
20

to the porous material 15

10

Hydrophilic vs. 5

hydrophobic 0 0.1 0.2 0.3 0.4 0.5

p/po
0.6 0.7 0.8 0.9 1

59

t-Plot for 13X 250

200
Adsorption
X Zeolite, 0.8nm pores
Quantity Adsorbed, cm3/g

150

100

50

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
o
p/p

160

140
External area

Reference curve 120

Quantity Adsorbed, cm3/g

100

80

“0” intercept 60

40
Micropore filling

20

0
0 0.5 1 1.5 2 2.5
Thickness, angstroms

60
Tuesday, December 4, 12
 Amorphous Amorphous Silica Alumina, 11nm pores

Silica-Alumina
450
Adsorption
Desorption
400

350

Quantity adsorbed, cm3/g

300

250

200

150

100

50

Negligible micro-
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po
400

pore volume 350

300

Quantity Adsorbed, cm3/g

250

Capillary 200

150

condensation at 100

50

large “t” values 0

0 2 4 6 8
Thickness, angstroms
10 12 14

61

MCM-41 600

500
Adsorption
Desorption
Silica, 4 nm pores
Quantity adsorbed, cm3/g

400

300

200

100

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po

700

Ideal t-plot sample 600

Quantity Adsorbed, cm3/g

500

400

Area, pore volume, 300

and external area 200

100
Pore area

0
0 2 4 6 8 10 12 14
Thickness, angstroms

62
Tuesday, December 4, 12
 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
Tuesday, December 4, 12
 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

Ad
V =
4

66
Tuesday, December 4, 12
 Amorphous 450
Adsorption
Amorphous Silica Alumina, 11nm pores

Desorption

Silica-alumina
400

350

Quantity adsorbed, cm3/g

300

250

200

150

BJH 100

50

First ∆V is assumed to be 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po

from pore emptying 0.7 2

1.8

Subsequent ∆V are a
0.6
1.6
0.5

dV/d(log(D)), (cm /g)/Å

1.4

pore volume, cm3/g

combination of pore

3
1.2
0.4
1

emptying and thinning of 0.3

0.8

0.6
0.2

the adsorbed layer 0.1

0.4

0.2

0 0
10 100
width, Å

67

Amorphous Silica Alumina, 11nm pores

Amorphous 450

400

350
Adsorption
Desorption
Quantity adsorbed, cm3/g

Silica-alumina
300

250

200

150

BJH 100

50

From ∆pore volume and calculated 0

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po
diameter, we can estimate surface 300

area for a cylinder 250

Common to observe the BJH

Cumulative Pore Area, m2/g

200

estimate of area is greater than the

dSA/dD

150
BET estimate
100

50

0
10 100 1000
D, angstroms

68
Tuesday, December 4, 12
 Amorphous Silica Alumina, 11nm pores

Amorphous
450
Adsorption
Desorption
400

350

Quantity adsorbed, cm3/g

300

Silica-alumina 250

200

150

100

50

BJH
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/po
0.7 4.5

Desorption data has been 0.6

4

3.5

used - historically 0.5

dV/d(log(D)), (cm3/g)/Å
3

pore volume, cm3/g

0.4 2.5

Best to use both Adsorption 0.3 2

and Desorption - they should

1.5
0.2
1

share common features

0.1
0.5

0 0
10 100
width, Å

69

BJH - PVD
Pt/Al2O3

70
Tuesday, December 4, 12
 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
Tuesday, December 4, 12