Adsorption and Catalysis

Dr. King Lun Yeung Department of Chemical Engineering Hong Kong University of Science and Technology

CENG 511 Lecture 3

Adsorption versus Absorption

H H H H H H H H H

H2 adsorption on palladium
Adsorption Surface process Absorption bulk process
H H H H H H H H H

H H HH H H H H H H H H H H H H H H

H2 absorption palladium hydride

Nomenclature
Substrate or adsorbent: surface onto which adsorption can occur. example: catalyst surface, activated carbon, alumina Adsorbate: molecules or atoms that adsorb onto the substrate. example: nitrogen, hydrogen, carbon monoxide, water Adsorption: the process by which a molecule or atom adsorb onto a surface of substrate. Coverage: a measure of the extent of adsorption of a specie onto a surface Exposure: a measure of the amount of gas the surface had been exposed to ( 1 Langmuir = 10-6 torr s) coverage = fraction of surface sites occupied
H H H H H

H H H H H H H H

adsorbate adsorbent

Types of Adsorption Modes

Physical adsorption or physisorption

Bonding between molecules and surface is by weak van der Waals forces.

Chemical bond is formed between molecules and surface.

Chemical adsorption or chemisorption

Characteristics of Chemi- and Physisorptions

Properties Chemisorption Physisorption
near or below Tbp of adsorbate (Xe < 100 K, CO2 < 200 K)

Adsorption temperature virtually unlimited range

Adsorption enthalpy

wide range (40-800 kJmol-1) heat of liquifaction (5-40 kJmol-1) marked difference for between crystal planes often dissociative and irreversible in many cases limited to a monolayer activated process independent of surface geometry non-dissociative and reversible multilayer occurs often fast, non-activated process

Crystallographic specificity Nature of adsorption

Saturation Adsorption kinetic

Analytical Methods for Establishing Surface Bonds

Infrared Spectroscopy
Atoms vibrates in the I.R. range chemical analysis (molecular fingerprinting) structural information electronic information (optical conductivity)

IR units: wavenumbers (cm-1), 10 micron wavelength = 1000 cm-1 Near-IR: 4000 14000 cm-1 Mid-IR: 500 4000 cm-1 Far-IR: 5 500 cm-1

http://infrared.als.lbl.gov/FTIRinfo.html

I.R. Measurement

I.R. Spectrum of CO2

O C O Symmetric Stretch

Assymmetric Stretch

A dipole moment = charge imbalance in the molecule Bending mode

I.R. Spectrum of NO on Pt

Adsorption decreases
Temperature increases

Molecular conformation changes

I.R. Spectrum of HCN on Pt

H- C N

0.15 L HCN, 100 K weak chemisorption

1.5 L HCN, 100 K physisorption

H- C N
Pt

H- C N
Pt

CN
Pt 30 L HCN, 200 K dissociative chemisorption
(HCN) 2(HCN) (CN) (H-CN)

(a)

(b)

(c)

Adsorption Rate

Rads = k C x
x - kinetic order k - rate constant C - gas phase concentration

Rads = k P x
x - kinetic order k - rate constant P - partial pressure of molecule

Rads = A C x exp (-Ea/RT)

Frequency factor Activation energy

Temperature dependency of adsorption processes

Adsorption Rate
Molecular level event

Rads = S F = f() P/(2mkT)0.5 exp(-Ea/RT)

(molecules m-2 s-1) Sticking coefficient S = f() exp(-Ea/RT)
where 0 < S < 1

Flux (Hertz-Knudsen) F = P/(2mkT)0.5

where P = gas pressure (N m-2) m = mass of one molecule (Kg) T = temperature (K)

Note: f() is a function of surface coverage special case of Langmuir adsorption f() = 1- E(), the activation energy is also affected by surface coverage

Sticking Coefficient S = f() exp(-Ea/RT)

where 0 < S < 1
Tungsten

S also depends on
crystal planes and may be influenced by surface reconstruction.

Sticking Coefficient

Sticking Coefficient
Steering Effects

Surface Coverage ()
Estimation based on gas exposure

Rads = dNads/dt = S F Nads S F t

Molecules adsorbed per unit surface area Nearly independent of coverage for most situations Exposure time

Adsorption Energetics
Potential energy (E) for adsorption is only dependent on distance between molecule and surface

adsorbate

surface

P.E. is assumed to be independent of: angular orientation of molecule changes in internal bond angles and lengths position of the molecule along the surface

Adsorption Energetics
Physisorption versus chemisorption
repulsive force

E(ads)

E(ads) < Physisorption

E(ads) Chemisorption

small minima large minima weak Van der Waal formation of surface attraction force chemical bonds
Chemisorption

surface

attractive forces

Physical Adsorption
Applications: surface area measurement pore size and volume determination pore size distribution

0.3 nm

E(d)

Van der Waal forces

nitrogen Note: there is no activation barrier for physisorption fast process

metal surface

The Brunauer-Emmett-Teller Isotherm

BET isotherm

where: n is the amount of gas adsorbed at P nm is the amount of gas in a monolayer P0 is the saturation pressure n at P = P0 C is a constant defined as:

H1 and HL are the adsorption enthalpy of first and subsequent layers

BET Isotherm

Assumptions
adsorption takes place on the lattice and molecules stay put, first monolayer is adsorbed onto the solid surface and each layers can start before another is finished, except for the first layer, a molecule can be adsorbed on a given site in a layer (n) if the same site also exists in (n-1) layer, at saturation pressure (P0), the number of adsorbed layers is infinite (i.e., condensation), except for the first layer, the adsorption enthalpy (HL) is identical for each layers.

Activated Carbon

Surface area ~ 1000 m2/g

Surface Area Determination

BET surface area by N2 physisorption

- adsorption - desorption c = 69.25 nm = 4.2 x 10-3 mol Area = 511 m2/g

Plot P/n(P0-P) versus P/P0

calculate c and nm from the slope (c-1/ nmc) and intercept (1/nmc) of the isotherm measurements usually obtained for P/P0 < 0.2

c = 87.09 nm = 3.9 x 10-3 mol Area = 480 m2/g

Chemical Adsorption re = equilibrium bond distance

E(d)
Ea(ads) = 0

Applications: active surface area measurements surface site energetics catalytic site determination

Ea(des) = - H(ads) = strength of surface bonding = H(ads)

CO

Pt surface

Note: there is no activation barrier for adsorption fast process, there us an activation barrier for desorption slow process.

Chemical Adsorption Processes

Physisorption + molecular chemisorption
CO

E(d) d

physisorption chemisorption

Chemical Adsorption Processes

Physisorption + dissociative chemisorption
H2 2 H

H2 dissociation chemisorption

E(d)

physisorption atomic chemisorption

Note: this is an energy prohibitive process

Chemical Adsorption Processes

Physisorption + molecular chemisorption
CO

E(d)

physisorption/ desorption chemisorption

physisorption atomic chemisorption

Chemical Adsorption Processes

Physisorption + molecular chemisorption
CO

E(d)
direct chemisorption

physisorption atomic chemisorption

Chemical Adsorption Processes

Energy barrier

Ea(ads) ~ 0

Ea(ads) > 0

Chemical Adsorption Processes

Energy barrier
Chemical Adsorption is usually an energy activated process.

- Eades = -E(ads)

~ -H(ads)

Formation of Ordered Adlayer

Ea(surface diffusion) < kT
activated carbon

CH4

Krypton

Formation of Ordered Adlayer

Chlorine on chromium surface

Adsorbate Geometries on Metals

Hydrogen and halogens
Hydrogen H-H 2-D atomic gas H-H HH X-X Halogens high electronegativity dissociative chemisorption X-X ionic bonding compound XX XX

1-H atom per 1-metal atom

Halogen atom tend to occupy high co-ordination sites:

(111)

(100)

Adsorbate Geometries on Metals

Oxygen and Nitrogen
Oxygen O=O OO Nitrogen NN

O=O

NN

both molecular and dissociative chemisorption occurs. molecular chemisorption -donor or -acceptor interactions. dissociative chemisorption occupy highest co-ordinated surface sites, also causes surface distorsion.

molecular chemisorption -donor or -acceptor interactions.

(111)

(100)

Adsorbate Geometries on Metals

Carbon monoxide
Carbon monoxide CO CO
Terminal (Linear) all surface

CC metal carbide

Bridging (2f site) all surface

forms metal carbides with metals located at the left-hand side of the periodic table. molecular chemisorption occurs on d-block metals (e.g., Cu, Ag) and transition metals

Bridging (3f hollow) (111) surface

Adsorbate Geometries on Metals

Ammonia and unsaturated hydrocarbons
Ammonia NH3

NH2 (ads) + H (ads) NH (ads) + 2 H (ads) N (ads) + 3 H (ads)

Ethene
2HC=CH2

Active Surface Area Measurement

ost common chemisorption gases: hydrogen, oxygen and carbon monoxide

furnace

catalyst
Pulse H2, O2 or CO gases

thermal conductivity cell (TCD)

exhaust

carrier gas helium or argon

Catalyst Surface Area and Dispersion Calculation

furnace

100 l (STP)

1 g 0.10 wt. % Pt/-Al2O3 T = 423 K, P = 1 bar 3.75 peaks (H2) 4.50 peaks (O2)

Pulse H2 then titrate with O2

thermal conductivity cell (TCD)

exhaust

carrier gas helium or argon

Avogrados number: 6.022 x 1023 Pt lattice constant: a = 3.92 (FCC)

Calculate surface area of Pt and its dispersion.

Isotherms
Langmuir isotherm

S - * + A(g) S-A
Adsorbed molecules surface sites H(ads) is independent of the process is reversible and is at equilibrium

K=

[S-M] [S - *] [A]

[S-M] is proportional to , [S-*] is proportional to 1-, [A] is proportional to partial pressure of A

Isotherms
Langmuir isotherm Molecular chemisorption

b=

(1-) P

bP 1+ bP

Where b depends only on the temperature

Dissociative chemisorption

(bP)0.5 1+ (bP)0.5

Where b depends only on the temperature

Variation of as function of T and P

bP at low pressure 1 at high pressure b when T b when H(ads)

0.8 0.6

0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8

0.4 0.2 0

P1

0.2

0.4

0.6

0.8

P1

Determination of H(ads)

( InP ) 1/T

1 0.8 0.6 0.4 0.2 0 0 0.2 0.4

=const

(ads) R

InP

(P1, T1)

(P2, T2)

0.6

0.8

P1

1/T

Adsorption Isotherms

Henrys Adsorption Isotherm

Special case of Langmuir isotherm

bP << 1 = bP V = kP

where k = bV

The Freundlich Isotherm

Adsorption sites are distributed exponentially with H(ads)

bi P = =

i (1-i) i N i Ni R InP + B A kP1/n

H(ads)

In = =

Valid for low partial pressure most frequently used for describing pollutant adsorption on activated carbons

The Temkin Isotherm

H(ads) decreases with

= A InBP

H(ads)

Valid at low to medium coverage gas chemisorption on clean metal surfaces

Thermal Desorption Spectroscopy

0.2 - 50 L

Thermal desorption spectra of CO on Pd(100) after successive exposure to CO gases

Chemical Adsorption re = equilibrium bond distance

E(d)
Ea(ads) = 0

Applications: active surface area measurements surface site energetics catalytic site determination

Ea(des) = - H(ads) = strength of surface bonding = H(ads)

CO

Pt surface

Note: there is no activation barrier for adsorption fast process, there us an activation barrier for desorption slow process.

Thermal Desorption Spectroscopy

d -dNa dT dT -dNa dT

[ ]
0.2 - 50 L

Desorption Rate -dNa dT { } dT dt

= Na

k exp (

-Ed ) RT

Linear heating rate T = T0 + t dT = dt Assuming k and Ed are independent of coverage and m = 1 (i.e., first order desorption)

Thermal desorption spectra of CO on Pd(100) after successive exposure to CO gases

Ed RTp2

k exp -Ed ( RT )

Thermal Desorption Spectroscopy

Ed RTp2

k exp -Ed ( RT )

slope, m Ea

TPD provides important information on adsorption/desorption energetics and adsorbate-surface interactions.

Determination of Edes using different heating rates ()

Thermal Desorption Spectroscopy

d -dNa dT dT -dNa dT

[ ]
0.2 - 50 L

Second order desorption

Assuming k and Ed are independent of coverage and m = 2 (i.e., first order desorption) Ed RTp2

= 2(Na)p

k exp -Ed ( RT )

Characterized by a shift in the peak maxima toward lower temperature as the coverage increases

Thermal desorption spectra of CO on Ni(100) after successive exposure to CO gases

Activation Energies for CO Desorption

Influence of Surface Overlayer

Catalyst poison, strong adsorbates and coke CO desorption
Clean catalyst

Sulfur-treated catalyst

Ordered Adsorbate layer H2/Rh(110) O2/Rh(110)

Thermal Desorption Spectroscopy

2 TPD from Rh(110)

Ordered Adsorbate layer benzene/ZnO(1010)

Kelvin Probe
Measures the change in work function ()
Typical Kelvin probe for adsorption studies

Scanning Kelvin probe for surface work function (i.e., elemental and compositional) imaging also known as scanning electrical field microscopy

Kelvin Probe
Basic principle

Vibrating capacitor measures

is the least amount of energy needed for an electron to escape from metal to vacuum. is sensitive optical, electrical and mechanical properties of materials

The Freundlich Isotherm

Adsorption sites are distributed exponentially with H(ads)

bi P = =

i (1-i) i N i Ni R InP + B A kP1/n

H(ads)

In = =

Valid for low partial pressure most frequently used for describing pollutant adsorption on activated carbons

The Temkin Isotherm

H(ads) decreases with

= A InBP

H(ads)

Valid at low to medium coverage gas chemisorption on clean metal surfaces

Thermal Desorption Spectroscopy

0.2 - 50 L

Thermal desorption spectra of CO on Pd(100) after successive exposure to CO gases

Chemical Adsorption re = equilibrium bond distance

E(d)
Ea(ads) = 0

Applications: active surface area measurements surface site energetics catalytic site determination

Ea(des) = - H(ads) = strength of surface bonding = H(ads)

CO

Pt surface

Note: there is no activation barrier for adsorption fast process, there us an activation barrier for desorption slow process.

Thermal Desorption Spectroscopy

d -dNa dT dT -dNa dT

[ ]
0.2 - 50 L

Desorption Rate -dNa dT { } dT dt

= Na

k exp (

-Ed ) RT

Linear heating rate T = T0 + t dT = dt Assuming k and Ed are independent of coverage and m = 1 (i.e., first order desorption)

Thermal desorption spectra of CO on Pd(100) after successive exposure to CO gases

Ed RTp2

k exp -Ed ( RT )

Thermal Desorption Spectroscopy

Ed RTp2

k exp -Ed ( RT )

slope, m Ea

TPD provides important information on adsorption/desorption energetics and adsorbate-surface interactions.

Determination of Edes using different heating rates ()

Thermal Desorption Spectroscopy

d -dNa dT dT -dNa dT

[ ]
0.2 - 50 L

Second order desorption

Assuming k and Ed are independent of coverage and m = 2 (i.e., first order desorption) Ed RTp2

= 2(Na)p

k exp -Ed ( RT )

Characterized by a shift in the peak maxima toward lower temperature as the coverage increases

Thermal desorption spectra of CO on Ni(100) after successive exposure to CO gases

Activation Energies for CO Desorption

Influence of Surface Overlayer

Catalyst poison, strong adsorbates and coke CO desorption
Clean catalyst

Sulfur-treated catalyst

Ordered Adsorbate layer H2/Rh(110) O2/Rh(110)

Thermal Desorption Spectroscopy

2 TPD from Rh(110)

Ordered Adsorbate layer benzene/ZnO(1010)

Kelvin Probe
Measures the change in work function ()
Typical Kelvin probe for adsorption studies

Scanning Kelvin probe for surface work function (i.e., elemental and compositional) imaging also known as scanning electrical field microscopy

Kelvin Probe
Basic principle

Vibrating capacitor measures

is the least amount of energy needed for an electron to escape from metal to vacuum. is sensitive optical, electrical and mechanical properties of materials