The slides are based on:

“Principles and practice of Heterogenous Catalysis”

J.M. Thomas, W.J. Thomas, VCH Publishers, 1997
Chapter 4: The significance of pore structure and
surface area in heterogenous catalysis

“Chemical Engineering Kinetics” J.M. Smith, Third

Edition, McGraw Hill Int. Editions, 1981
Chapter 8: Solid catalysts
 Adsorption

Chemical adsorption
Physical adsorption
https://www.jove.com/science-education/10383/porosimetry-of-a-sili
ca-alumina-powder
Adsorption

3
 PHYSICAL ADSORPTION

Texture and morphology

– Pore size.
– Pore shape.
– Pore-size distribution (same size or various sizes?)
- Pore volume.
– Specific surface area of solids

4
 PORE DIAMETERS, SHAPES

Pore diameters:
– micropores (< 2 nm)
Experimental techniques:
– mesopores (2 - 50 nm)
– Microscopy
– macropores (> 50 nm)
- Capillary condensation
– Hg intrusion

Shapes:
– Cylinder, slit, ink-bottle, wedge, ...

5
 PORE SHAPES

SILT Wedge
Cylindrical
Ink_bottle
Other forms…

Figure 1 . Common sizes of pores and others forms.

[LEOFANTI G., PADOVAN M., TOZZOLA G., VENTURELLI B. (1998). “Surface area and pore texture of catalysts”.]
6
 INTERNAL DIFUSION

Types of diffusion
– Molecular
– Knudsen
– Surface (also called “configurational diffusion)”

Knudsen number: Kn = λ/l

λ = molecular free path length
l = characteristic pore diameter
Kn << 1 bulk diffusion
Kn >> 1 Knudsen diffusion
7
 PORE SIZE AND DIFFUSION REGIMENS

MOLECULAR

KNUDSEN

INTRACRYSTALLINE

Figure 1. (Diffusivity and size of pore radius. Regions of molecular, Knudsen and configurational diffusion. Conditions:
373K, 1 bar. [Froment, G., Bischoff B., Chemical Reactor and Analysis design, Pag 173.]

8
SHAPE SELECTIVITY

CH3OH

44% 33% 13%

2
+

+ CH3OH
99.5%
ZSM-5
 SHAPE SELECTIVITY
Reactant selectivity
+

Product selectivity

CH3OH +

Restricted transition-state selectivity

Figure 3. Shape selectivity of the catalysts

[James T. Richardson “Principles of catalyst develpment” 1989] 10
 PORE DIAMETERS AND MEASUREMENT TECHNIQUES

Hg porosimetry

Nitrogen capillary condensation

Micro Meso Macro

2 50

Figure 2. Types of pores according the size

12
 PROPERTIES OF ADSORBATES FOR PHYSISORPTION
MEASUREMENTS

Table 1. Properties of adsorbates for physisorption measurements.

Adsorbate Boiling Point (K) Am (nm2/molecule)

N2 77.3 0.162

Ar 87.4 0.142

CO2 194.5 0.17

Kr 120.8 0.152

[Brown T., LeMay Jr., Bursten B., Chemistry: The Central Science 13

 ADSORPTION ISOTHERMS

I II III
nad

nad
nad
B
p/p0 p/p0 p/p0

IV V VI
nad

nad

nad
B
p/p0 p/p0 p/p0

Figure 2. The six IUPAC standar adsoprtion isotherms.

[ROUQUEROL F., ROUQUEROL J., SING K. Adsorption by Powders and Porous Solid.] 14
 ADSORPTION ISOTERM (TYPE I - LANGMUIR)

𝑛𝑎𝑑𝑠 =𝑛𝑚 =𝑛 𝑚

𝐾𝐴
𝑝( )
𝑝
𝑜
n ad

1+ 𝐾 𝐴
( )
𝑝
𝑝
𝑜

p /p 0

Assumptions:
• Homogeneous surface (all adsorption sites energetically identical)
• Monolayer adsorption (so no multilayer adsorption)
• No interaction between adsorbed molecules
 ADSORPTION ISOTHERMS

Figure 3. Adsorption process on micropores solids surfaces.

 TYPE II AND IV ISOTHERMS

II
Multilayer adsorption (starting at B)
nad

Common for pore-free materials

B
0

IV

same with pore condensation at high p

nad

B
p/p0
 ADSORPTION ISOTHERMS

Figure 4. Adsorption process on nonporous surfaces.

 HYSTERESIS

Figure 5. Adsorption process on mesoporous surfaces

 ADSORPTION AT PORE WALL

Adsorbed layer
Cylindrical pore
 SURFACE AREA AND MONOLAYER CAPACITY

Langmuir model: SLangmuir

specific surface Avogadro’s number

area (m2/g) (molecules/mol)

S = nmAmN

monolayer area occupied by one

capacity (mol/g) molecule
(m2/molecule)
t model: St BET model: SBET

Surface area and monolayer capacity.

 BET (BRUNAUER, EMMETT, TELLER) METHOD
Considerations:

• Based on Langmuir isotherm

• Monolayer and multilayer adsorption
• Layers of adsorbed molecules divided in:
– First layer with heat of adsorption Had,1
– Second and subsequent layers with Had,2 = Hcond

BET isotherm:

•BET equation does not fit entire adsorption isotherm

– different mechanisms play a role at low and at high p
 ADSORPTION ISOTHERMS
¿Langmuir Adsorption?

No:
• At low p strong adsorption
due to condensation in
micropores.
• At higher p saturation due to
finite (micro)pore volume

Figure 6. Adsorption-desorption isotherm of N 2 on 9%(w/w) NiO on Al2O3, determined at 77K by

the volumetric adsorption method.

Thomas J.M.; Thomas W.J., “Principles and Practice of Heterogeneous Catalysis”. Pag. 269
BET (BRUNAUER, EMMETT, TELLER) METHOD
9%(w/w) NiO on Al2O3
 SHAPES OF t–PLOTS

Adsorption isotherm

nad
nad
t  0.354 nm
nm

p
t = f(p)
Micro- and
Non-porous Microporous mesoporous

nad nad nad

Smesopores

St

t t t
 t-CURVES

1.4
Thickness of adsorbed layer (nm)

1.2

0.8

0.6

0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p/p0

Figure 7. Thickness of adsorbed layer t vs. relative pressure. Ref. [W.D Harkins and G. Jura , (1946)” An Absolute Method
for the Determination of the Area of a Finely Divided” Am. Chemical Society, (66)]
 t-plot method

𝑛 𝑎𝑑
𝑡= .0 .354 𝑛𝑚 𝑆𝑡 =𝑛𝑚 . 𝐴 𝑚 . 𝑁 𝐴
𝑛𝑚

𝑛 𝑎𝑑 𝑛 𝑎𝑑
𝑛𝑚 = .0 .354 𝑛𝑚 𝑆𝑡 = . 𝐴𝑚 . 𝑁 𝐴 . 0.354
𝑡 𝑡

Note:
nad
nad (Vad) is experimental result

Slope proportional to St t is calculated from

correlation t vs p (slope)

Intercept proportional to micropores volume

External Surface (t- plot) of 9%(w/w) NiO on Al2O3

Figure 8. Thickness of adsorbed layer vs. Volume adsorbed per catalyst gram.
Monolayer thickness is calculated by Harkins- Jura de Boer
 HYSTERESIS

Figure 10. Boer’s five types of hysteresis.

[Lowell, S., Shields, J. Powder Surface Area and Porosity, Types of Hysteresis, Pag. 57.]
 HYSTERESIS

Figure 11a. Types of hysteresis cycles.

[Thomas J.M.; Thomas W.J., “Principles and Practice of Heterogeneous Catalysis”. Pag. 278-279]
 HYSTERESIS

Figure 11b. Types of hysteresis cycles.

Thomas J.M.; Thomas W.J., “Principles and Practice of Heterogeneous Catalysis”. Pag. 280-281]
 HYSTERESIS

Figure 11c. Types of hysteresis cycles.

[Thomas J.M.; Thomas W.J., “Principles and Practice of Heterogeneous Catalysis”. Pag. 282]
 BJH (BARRET, JOYNER, HALENDA) METHOD
Pore size distribution of 9%(w/w) NiO on Al2O3

400

350
DVpl/Drp (104cm3g-1A-1)

300

250

200

150

100

50

0
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0
rp [A]

Figure 12. Pore size distribution.

[Thomas J.M.; Thomas W.J., “Principles and Practice of Heterogeneous Catalysis”. Pag 270]
 BJH (BARRET, JOYNER, HALENDA) METHOD
Accumulative distribution of pore volumen
of 9%(w/w) NiO on Al2O3

100

80
% Volumen

60

40

20

0
0 20 40 60 80 100 120 140
rp [A]

Figure 13. Accumulative distribution of pore volume.

[Thomas J.M.; Thomas W.J., “Principles and Practice of Heterogeneous Catalysis”. Pag 270]
 Please read:

“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 5: Diffusion

“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 5: Diffusion