Pore Structure Analysis

by Physisorption

The slide was adapted from Quantachrome and other sources

only for educational purposes
Example of equipment

Autosorb Quadrasorb NOVA

Quantachrome
INSTRUMENTS
 Pores of Porous Solids

Porada et al., Progress in Materials Science 58 (2013) 1388–1442

 Pores of Porous Solids
• Pore size distribution
– Typical curves to characterise pore size:
• Cumulative curve
• Frequency curve
– Uniform size distribution (a) &
non-uniform size distribution (b)

wt dw
dd
Dwt a
b a b

Dd d d
Cumulative curve Frequency curve
 Adsorption – physisorption - chemisorption

Adsorption is the process in which matter is extracted from one

phase and concentrated at the surface of a second phase (Interface
accumulation)

Property Physisorption Chemisorption

Forces van der Waals Chemical bonding

DHads
(kJ mol-1) < 40 50-200
Ea
(kJ mol-1) Rare 60–100

Isothermal
Complete Slow or none
Reversibility

Extent Multilayers Monolayer

Wang and Guo, Chemosphere, 258, 2020, 127279

 Physisorption
The monolayer of adsorbed
molecules; typically, 15 - 20%
OT fig1.3 saturation

The multilayer capillary

condensation stage approximately
70% saturation

Total pore volume filling;

approximately 100% saturation
ADSORPTION ISOTHERM
• amount of N2 adsorbed versus relative pressure at constant temperature

• temperature: 77 K: boiling/condensation point of N2 at patm=p°

• Amount adsorbed
per unit adsorbent mass:

n mol/g
Vads, STP ml/g = cm3/g

• STP = 0 °C, 1 bar

 N , STP
V ads,liq= 2
Vads, STP
 N ,liq
2

= 0.001544  Vads, STP

how is an adsorption isotherm recorded?

• Total volume of system determined:

gas vacuum - “manifold” volume known

manifold • System is evacuated

• Start of adsorption:
P - amount of gas dosed in manifold
- p measured → quantity known
- gas expanded into sample volume
sample - equilibrium p measured; compared to calculated p
- difference → amount adsorbed at p

• p° measured to account for temp changes in liq. N2

Liq. N2 Lower p/p° limit: determined by

pump and pressure measurement
 Adsorption on Solid Surface
• Six types of physisorption isotherms are found over all solids

Thommes et al, IUPAC

Technical Report, 2015
Pure Appl. Chem. 2015; 87(9-
10): 1051–1069
 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.

Relative Pressure (P/Po)

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

Low slope region in middle of

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

Relative Pressure (P/Po)

 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)

 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.
Low slope region in middle of
Rounded knee isotherm indicates first few
indicates approximate multilayers
location of monolayer
formation.

Relative Pressure (P/Po)

 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)

Volume adsorbed
Types of Isotherms

Type VI

Stepwise multilayer
adsorption on a uniform
non-porous surface

Relative Pressure (P/Po)

 Types of Hysteresis
• H1: a narrow range of
uniform mesopores (e.g.
MCM 41, MCM 48)
• H2: complex pore structures
(e.g. pore blocking)
• H3: typical for plate-like
particles or pore network
consists of macropores
• H4: typical micro-mesopores
• H5: unusual, typically open
and partially blocked
mesopores
Thommes et al, IUPAC Technical Report, 2015
 The BET isotherm
• Theoretical development based on
several assumptions:
– multimolecular adsorption
– 1st layer with fixed heat of
OT fig1.3 adsorption H1
– following layers with heat of
adsorption constant (= latent heat
of condensation)
– constant surface (i.e. no capillary
condensation) gives
p 1 C −1 p
= + 
v a (p 0 − p ) v m  C v m  C p 0

or
p p
= I+ s
v a (p 0 − p ) p0
 The BET isotherm, cont.
• Plot of left side vs. p/p0 should give
straight line with slope s and intercept
I
p p
= I+ s
OT fig1.5 (
va p0 − p ) p0

• Reorganizing gives
1 I+s
vm = and C =
s+I I

• Knowledge of S0 (specific area for a

volume of gas then allows the
calculation of the specific surface area
Sg:
v S
Sg = m 0
mp
where mp is the mass of the sample
 Example SSA calculation

Determine the specific surface area of activated carbon,

which an N2-isotherm curve at 77 K as shown in the figure!
Standard range for BET model: P/P0: 0.05 – 0.30

P/Po Volume of adsorbate V 1/(Va(Po/P-1))

(cm3/g), at STP
p p
0,0715 264,6179 0,00029101 = I+ s
0,0953 279,7367 0,00037656 v a (p 0 − p ) p0
0,1493 307,5930 0,00057057
0,2013 332,7449 0,00075744
0,2452 354,9241 0,00091528
0,2976 383,9286 0,00110357
0,2996 385,1396 0,00111065
Standard range for BET model: P/P0: 0.05 – 0.30

p p
= I+ s
v a (p 0 − p ) p0

Specific surface area then can be calculated:

1 I+s
vm = and C =
s+I I

v m  S0
Sg =
mp
 Adsorbates
• An adsorbate molecule covers an area , calculated assuming dense
packing of the molecules in the multilayer. The corresponding area per
volume gas is S0:

Gas Temp. σ S0
[K] [Å2/molecule] [m2/cm3 gas (STP)]
N2 77,5 16,2 4,36
Kr 77,5 19,5 5,24
Ar 77,5 14,6 3,92
H2 O 298 10,8 2,90
C2H6 90 22,5 6,05
CO2 195 19,5 5,24
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
Example Data : Microporous Carbon
BET : Not strictly applicable

P/Po
 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 m2/g vs.
1424 m2/g)
Example Data : Macroporous Sample

Little or no “knee”,
isotherm closes at
0.95
Example Data : Macroporous Sample

• BET Plot = OK
• Surface area ca. 8m2/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 = 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)
Thank you