Вы находитесь на странице: 1из 82

1

Gene and Linda Voiland School of Chemical Engineering and Bioengineering

Catalysis From
Fundamentals to
Applications
Professor Norbert Kruse

Prerequisites: Undergraduate courses of chemical reaction kinetics and


engineering

CHE 481/581: Catalysis (Spring 2015)

Prof. Norbert Kruse


Office: Wegner 155A
Email: Norbert.Kruse@wsu.edu
Office Phone: (509) 335 6601
Office Hours: Fridays 11:00 am 1 pm, with an appointment
Tanya Stewart, Secretary Senior
Office: Wegner 155C
Email: Tanya.Stewart@wsu.edu
Office Phone: (509) 335 1256
Course:
a) Aim: get acquainted with the fundamentals of (heterogeneous) catalysis. Think in terms of
kinetics and mechanisms and use the surface science approach for doing so. Get an overview
on the major large-scale applications of catalysis.
b) Textbooks: there is no unique textbook treating all the topics covered by the course. A
copy of the slides will be provided.
for Surface Chemistry: Gary Attard and Colin Barnes, Surfaces, Oxford Chemistry Primers
for Spectroscopy: J. W. Niemantsverdriet, Spectroscopy in Catalysis an Introduction ,
Wiley-VC
for Theory in Surface Chemistry: Roald Hoffman, Solids and Surfaces: A Chemists View of
Bonding in Extended Structures , VCH
c) Schedule: Terrell Lib. 24. Tu and Th 12pm to 1:15pm until May 1st. No classes on January
23rd, March 25th and 27th.
d) Methodology: Avoid a monologue, but rather try to engage a discussion when appropriate.
Slides provide a scaffold. They are to be completed by the students according to the
individual needs. Instructor jumps back to the basics when necessary. More detailed

considerations will be either developed at the blackboard or defined as homework. Try to


avoid lengthy mathematical derivation of formulas homework

Grading:
Oral (30 to 40 min each student): 70%. Project presentation: 30%
Projects will be assigned according to a list of subjects provided until end of March. A
subject may range from a hot topic in catalysis to the presentation of a large-scale catalytic
process not subject to the course. Every student has to present his/her project in PPT format
during 12 min., followed by questions during 6 min. Presentations take place on 22nd, 24th,
30th April and 1st May. Room TBD.
Homework will be defined occasionally and is intended to digest and deepen certain
aspects of a subject. No written homework is required, however, there is expectation of
background knowledge to support the new knowledge provided. The oral exam may include
questions on such homework issues.
Oral exams will take in my office at Wegner 155. Oral exam and PPT presentation will be
weighted as defined as above.
Grading Scale:
90-100%

77-79%

B-

87-89%

A-

73-76%

C+

83-86%

B+

70-72%

80-82%

0-69%

Course Website
The contents of this course will be available online on Angel: http://lms.wsu.edu or via email.

Students with Disabilities


Reasonable accommodations are available for students with a documented disability. If you
have a disability and need accommodations to fully participate in this class, please either visit
or call the Access Center (Washington Bldg 217; 509-335-3417) to schedule an appointment
with an Access Advisor. All accommodations MUST be approved through the Access
Center.

Academic Integrity
I encourage you to work with classmates on assignments. However, each student must turn in
original work. No copying will be accepted. Students who violate WSUs Standards of
Conduct for Students will receive an F as a final grade in this course, will not have the option
to withdraw from the course and will be reported to the Office of Student Standards and
Accountability. Cheating is defined in the Standards for Student Conduct WAC 50-26010(3). It is strongly suggested that you read and understand these definitions:
http://apps.leg.wa.gov/wac/default.aspx?cite=504-26-010

Safety
Washington State University is committed to maintaining a safe environment for its faculty,
staff, and students. Safety is the responsibility of every member of the campus community
and individuals should know the appropriate actions to take when an emergency arises. In
support of our commitment to the safety of the campus community the University has
developed a Campus Safety Plan, http://safetyplan.wsu.edu/. It is highly recommended that
you visit this web site as well as the University Emergency Management web site at
http://oem.wsu.edu/ to become familiar with information provided.

Caveat
The schedule and procedures outlined in this syllabus are subject to change in the event of
circumstances beyond the instructors control or in response to ongoing assessment of
learning.

Catalysis quo vadis? (Spring 2015)


Agatha Christie (1891 1976) wrote in 1930 (The Mysterious Mr. Quinn): Do
you happen to know anything about catalysis? The young man stared at him.
Never heard of it. What is it? Mr. Satterthwaite quoted gravely: A chemical
reaction depending for its success on the presence of a certain substance which
itself remains unchanged.
To appreciate Agatha Christies approach to catalysis we start this course by
reviewing the fundamentals of heterogeneous catalysis from the kinetic point of
view: adsorption, diffusion, reaction and desorption on model catalysts:

We continue by applying these concepts to real-world catalysis. Some major


industrial processes (homogeneous as well as heterogeneous) will be visited
before new lines of catalysis research to produce sustainable chemical feedstock
will be presented.

Catalysis Kinetic Phenomenon


Some early definitions:
A catalyst increases the rate of a reaction without being consumed by a reaction
Wilhelm Ostwald (1853-1932)
A chemical reaction has to be thermodynamically feasible in order to be
accelerated Alfred Mittasch (1869-1953) *
A catalyst doesnt appear in the stoichometric equation.
However: Catalysts undergo structural or chemical changes during the catalytic
reaction (mainly in heterogeneous reactions).
The catalyst is formed by the catalytic reaction.
Agatha Christie (1891-1976)
(The Mysterious Mr. Quinn, 1930): Do you happen to know anything about
catalysis? The young man stared at him. Never heard of it. What is it? Mr.
Satterthwaite quoted gravely, A chemical reaction depending for its success on
the presence of a certain substance which itself remains unchanged.
(Curtain, Poirots last case, 1940): So we get the curious result that we have here
a case of catalysis a reaction between two substances that takes place only in
the presence of a third substance, apparently taking no part in the reaction and
remaining unchanged. That is the position. It means that where X was present,
crimes took place but X did not actively take part in these crimes.
_____________________________________________________________________________________________

non-catalytic

catalytic

Some general comments on the importance of catalysis:


About 80% of the industrial production is based on the application of the catalytic
process at least in one intermediate stage.
High economic importance
About 90% of all catalytic processes are heterogeneous in nature.

Incidental remark:

homogeneous -heterogeneous catalysis

Reactants and catalyst in the same phase

not in the same phase

However: there is no general theory of catalysis Black Magic


Two examples for the importance of empirical research:
Ammonia synthesis:

N2 + 3H2 2NH3

About 20,000 different catalysts were tested

Fischer-Tropsch Reaction:

CO +H2

2O

About 15,000 different catalysts were tested

Eq. not equilibrated!

In both cases, metals are used to catalyze the reaction (mainly nano-sized
particles on an oxidic support.)

A historical example
Formation of water:

2H2 + O2 2H2O

Dbereiner (1822)

First construction of a lighter:

The lever e allows contacting a piece of zinc with


sulfuric acid in a glass vessel: Zn + 2H+ Zn2+ + H2
H2 is produced and mounts in the jack so as to mix up with O2. Sponge-like Pt
is placed inside the nozzle f and allows ignition of the reaction.

More basic kinetics:


AB

Reaction:

(ex: isomerization)
Thermodynamically feasible,

GR < O

Arrhenius:

Decrease of the reaction barrier (activation energy) by adding a catalyst

Potential Energy

a) Heterogeneous Catalysis:

AB*

EA

A
A ad
B
B ad

Reaction Advancement

The desorption process causes a separation from the catalyst.

Catalytic Cycle:
1) Adsorption
2) Reaction
3) Desorption

10

For a catalyst with a pore structure (texture) diffusion processes into the pores
and out of them have to be added.
b) Homogeneous Catalysis:

Potential Energy

Catalytic Cycle :

Reaction Advancement

A physical separation (unit operations like distillation, extraction, etc.) is


necessary in order to obtain the pure product.

Two examples involving multiple intermediate steps:


Ammonia Synthesis (heterogeneous catalysis):
All intermediate steps were clarified in a Nobel Prize winning work by G. Ertl
(Nobel Prize 2007)

11

Dissociation little activated

NH
+H ad
NH2,ad
2,ad + Had

Molecular adsorption
Dissociative adsorption
(Nad) + 3Had)
(N + 3H
ad

ad

Activation barriers for the ammonia synthesis were obtained from


experimental work with Fe model catalysts (monocrystals of (111)
orientation at low coverages: numerical values are in kJ/mol.
Hydroformylation or Oxo-process (homogeneous catalysis)
Note: The dissociation of molecularly bound nitrogen is only slightly
activated!

12

Hydroformylation (Homogeneous catalysis)

Catalysts are coordination compounds of Rh and Co

Note that the catalytic cycle above includes changes in the number of metal
valence electrons between 18 and 16, back and forth.

13

Kinetic compensation reality or fiction?

Isokinetic temperature

We can always find a temperature for which k0 has the same


numerical value, no matter which catalyst for a given
reaction is considered.

14

Example: methanation
CO + 3 H2

CH4 + H2O

ln k0

Ru

20

10

Fe
.
Pd.

. . .Co
. Ni
Rh

Pt

..Ir

60

80

100

120
EA kJ/mol

Compensation effect for the methanation of CO for a number of metals, both base
and noble.

15

Basic Kinetic Notions in Catalysis


Activity Selectivity

reaction rate in a homogeneous phase (gas or liquid):

for constant volume

for A B

since

reaction rate in heterogeneous catalysis:


intrinsic activity

S = surface area of the catalyst

we need to determine the surface area of the catalyst (method according to


Brunauer, Emmett, and Teller, BET).
Frequently also:
since m ~ S as long as the surface doesnt change

16

Best solution:
N number of active sites

since N ~ S

However: the nature of the active site may get redistributed during the reaction,
so they are subject to dynamic changes and should not be considered as fixed in
number. For example, the number of atoms defining an active site remains
unknown in most cases. Moreover, there may be similar active sites coexisting.
frequently in heterogeneous catalysis
Selectivity:

P
A

Reactions in parallel

APQ

Consecutive reactions

Define the conversion for the wanted product.

Example:
O

OH

OH

Butyraldehyde yield:

17

Conversion of crotonicaldehyde:

Butyraldehyde selectivity:

Note the distinction between:

TON is frequently used in homogeneous catalysis:

Processes start to become economic when TON > 20,000

18

Some statistical thermodynamics


Comparing reaction rates of heterogeneous catalysis with those of non-catalytic
reactions according to the Transition State Theory (TST)
Consider a bimolecular reaction (non-catalytic)

AB is the activated complex in homogeneous phase.


The same bimolecular reaction under catalytic conditions reads:

AB*2 is the activated complex bound to the surface of the catalyst.


The reaction rate according to TST then is:

19

in general:

k: Boltzmann constant
h: Planck constant
: Partition function of component i
Eo : Difference in energy of initial energy T=0 K

20

Hypothesis:

a)

b)

c)

d)

21

Heterogeneous Catalysis occurs at the surface of a solid

10nm

Transmission Electron Microscopy (TME) of metal


particles on a support (Ag/Al2O3).
Metal particles are well separated from each other
and the pore structure of the catalyst becomes visible
(texture).
Image blurring indicates carbon deposition

High Resolution Transmission


Electron Microscopy (HRTEM)
revealing the morphology of Rh
nanosized particles on a TiO2
support.

22

Ball model of a single metal grain to visualize the different sites exposed.
In white are: low coordination atoms have empty valence orbitals which are
supposed to be preferred binding sides for adsorbing atoms and molecules
(gasses or liquid molecules).

Field Ion Microscopy (FIM)


of a single Rh particle, in top
view, atom by atom. Not all atoms are
seen; only those in low coordination.
Miller indexes of individual surface
facets are also given.

23

Metal particles on a support should be nanosized so as to create as large a


surface area as possible.

r~N

Number of atoms located along the particle radius.

Ns = 2 N2

Number of atoms at the surface

Nt = 2/3 N3

Total number of atoms in the particle

Surface fraction is a function of


radius for a hemispherical particle
on a flat support.

24

Some comments on the nature of catalysts and their supports


Supports should provide high surface area so as to optimize the dispersion of the
catalytically active phase. For metal-based catalysts, frequently the following
supports are used.

Al2O3, SiO2, TiO2, ZnO, MgO, C

Some of these materials can be prepared with specific surface areas as large as
1,000 m2/g (equivalent to the size of a football field).

The catalytically active metal phase is frequently supplied by impregnation using


an aqueous solution of a suitable precursor compound such as Me-nitrate.
Impregnation can be performed wet using immersion techniques or by incipient
wetness. In the latter case, the volume of the aqueous precursor solution matches
the volume of the support pores so the solid doesnt appear wet. The preparation
in water enables solvated metal cations to bind to surface hydroxyl of the support.
The details of the binding mechanism depend on the pH conditions and the point
of zero charge (PZC) of the support.

25

pH > PZC cationic adsorption

pH < PZC anionic adsorption


A different type of catalyst are zeolites whose primary construction units are
tetrahedric [SiO4]4- and [AlO4]5- . These materials are highly crystalline with
specific surface areas sometimes exceeding 1,000 m2/g. They have acidic
properties and may or may not contain metallic cations.

[SiO4]4- and [AlO4]5- units share oxygen atoms so as to form Si-O-Al bridges.
Starting from a 3D SiO2 network the replacement of Si by Al creates localized

26

charges that have to be compensated in order to maintain electroneutrality (per


Al- either one H+ or one Me+ is needed).
General formula:

x [ (Me+, Me2+) AlO2] . y SiO2 . z H2O


The occurrence of protons causes Brnsted acidity which allows hydrocarbon
cracking in petrochemical industry.

Lewis Center

Heating

Heat treatment allows Brnsted acidity to turn into Lewis acidity.

Similar to the construction of secondary building blocks in silica highly


symmetric polyhedral units can be formed to build zeolites.

27

The number of basic zeolites can be constructed from sodalite units in which
for reasons of simplicity, the bent Si-O-Al bridges are considered as straight
lines. Corners contain either Si or Al.
Sodalite unit

Sodalite unit

Sodalite unit

Large cavity

a) Sodalite
b) Zeolite A
c) Faujasite (zeolites X and Y)
Windows vary between 2.6 in sodalite and 7.4 in faujasite.

28

More recent developments aim at synthesizing ordered silicas so as to create


mesopores molecular sieves.
Template-directed
Template
removal

Condensation

Inorganic Template
precursor

Template-oxide

Mesoporous

1992 - Scientists of Mobil Oil Corporation (USA) applied self-assembled


template (micelles of CTAB surfactant) and synthesized a family of ordered
mesoporous silicas named MCM (Mobil Composition of Matters) 41 and 48*
+
N(CH3)3 Br-

The CTAB molecule (cetyltrimethylammoniumbromide) consists of a long


(cetyl) hydrocarbon skeleton causing hydrophobic properties (tail) and a terminal
ionic group causing hydrophilic properties (head).

CTAB micelle

Silicate self-assembling around the micelle

*Kresge C.T., Leonowicz M.E., Roth W.J., Vartuli J.C., Beck J.S., Nature, 1992, 359, 710
712

29

MCM-41 is characterized by a unique pore size distribution. Pores usually have


diameters between 2-5 nm with hexagonal structure. The total specific surface
area may range from 900-1,500 m2/g.

TEM image and model of MCM-41


V. Meynen et al. / Microporous and Mesoporous Materials 125 (2009) 170223

g = V/al
g packing parameter
V volume of the hydrophobic part of
surfactant
(including solubilized compounds)
a effective area of the hydrophilic head
(depends also on counter-ions)

Micelles can be shaped by use of proper surfactants.

30

Micelle shape and type versus g


More recent developments have lead to new silicates like SBA-15 or KIT-6

KIT-6 pore size vs HTT temperature

Model of KIT-6 double


gyroid Mesostructure

Y. Doi et al, Chem. Commun., 2010, 46, 63656367

31

Physisorption and Chemisorption

Forces

Physisorption

Chemisorption

dispersion

valence or electrostatic forces


create covalent and/or ionic
bonds

van der Waals

a) E Keesom

b) E Debye

c) E London

Hphys Hcond ~5-20 kJ/mol

Hchem 5 4
kJ/mol

32

Coverage

multilayers

monolayer limit

Reactants

all gasses below


the critical temperature

reactive gasses

Reversibility

yes

yes, in many cases,


but also irreversible.

Dependence on decreases with increasing


temperature
temperature

maybe complicated in
case of an activated
process

33

Potential diagrams

Chem

Edif

The above diagram applies to the case of physisorption on top of a chemisorbed


layer. The turnover from the physisorbed state to the chemisorbed state is nonactivated for the observer but can only occur as long as empty chemisorption sites
are available. A diffusion process in the physisorbed state is possible and occurs
with activation energy of Edif.

34

H chem

*Chemisorption site

H chem

The above potential diagram applies to the case of H2 adsorption on a Cu surface.


H chem

= 34 kJ/mol

EA

= 21 kJ/mol

E (*Cu - H) = 233 kJ/mol

Generally:

H chem = 2E (M - H) - E(H - H) = 34 kJ/mol


which is low for metals with a closed d-shell.

35

The turnover from the physisorbed state into the chemisorbed state is activated
for H2/Cu. In other cases, like CO on open d-shell metals the dissociation is nonactivated and leads to the deposition of carbon and oxygen. H chem can be
considerably larger in this case (between 100-160 kJ/mol). On the other hand, CO
chemisorption on Cu occurs without dissociation and is weak.

36

Dynamics of adsorption
Calculation of the surface residence time of molecules before thermoadsorption
For kinetic for order process:

surface residence time (lifetime)

6 . 1012 s-1 at 300K


Homework:
Calculate the surface lifetimes at 300K and 600K for the activation energies Ed =
4, 20, 40, 80, 160 kJ/mol.

Calculation of the concentration (surface coverage) of adsorbed species:


For physisorption:

phys = J . . wphys

wphys

probability of physisorption

For chemisorption:

chem = J . . s

impingement rate

[ L-2 . T-1]
s

sticking probability

37

calculation of the impingement rate:


<=

mean velocity (m s-1)


n number of molecules per m3
m molecular mass in kg per molecule

with:

and

J = 2.64 . 1024 p / (M . T) ( m-2 . s-1)

molecular mass in
atomic mass units

Homework:
Calculate the impingement rate per surface site for nitrogen molecules at 1 bar
and 273K. Assume the surface site to have a size of 10 2. Calculate the number
of multiple layers assuming Ed = 40 kJ/mol and a probability of physisorption
wphys = 1.

Calculation of the rate of chemisorption:


For a non-activated process:

Ra = J . s

This allows the sticking probability to be defined as:

S = Ra / J

> tM

38

tM = characteristic time of the measurement (molecules must be on the surface to


be measured)
S0 Sticking probability at zero coverage. It can be anticipated that values of
S0 are influenced by the surface structure and the temperature.

Example : N2/Fe

S0 7 . 10-8 for the (110) surface (densely packed)


S0 4 . 10-6 for the (111) surface (open structure)
It is interesting to see that the sticking probabilities for N2 chemisorption on Fe
vary in the same manner as the reaction rate of the ammonia synthesis

N2 + 3H2 2NH3
For comparison, the sticking probability S0 of the CO molecule on transition
metal surfaces varies between 1 and 0.1.

The Langmuir Isotherm:

(NA) . Ed = Hchem

with

(Hchem / RT)

39

at constant temperature:

n .p

Model assumptions made by Langmuir


1. all surface sites are treated in the same manner: no difference is
made between terrace sites, steps or kinks
2. adsorbed species do not interact laterally
3. incoming molecules hitting an occupied site are being reflected
without energy loss
The last argument leads to the following functional dependence of s vs.
coverage :

Assuming every incoming molecule hitting an empty site will get adsorbed,
s0 = 1, we will then receive:

with

For application purposes:


V / Vs

Vs

gas volume giving rise to


monolayer formation

40

linearization leads to:

The experiment consists of introducing a known volume of gas from a calibrated


reservoir into a reactor containing the catalyst sample and measuring the volume
consumed due to adsorption.
tg = 1/ Vs . kL

1/V

1/Vs

1/p

An equivalent derivation of the Langmuir equation would be to consider a


dynamic equilibrium between adsorption and thermal desorption.

) [ ] = kd .

[]

[ ] concentration of sites per


unit surfaca area

41

= ka /kd adsorption coefficient (equilibrium constant of adsorptiondesorption), will be denoted later as KA

1
T3

T2
T1

T3 < T2 < T1

42

Evaluation of the isosteric heat of adsorption:

T1
V / Vs

T2
T3

p1 p2

dln p / dT

=const

ln p = f (T)

p3

= - Hchem / RT2
analog:Clausius Clapeyron

Hchem

isosters

qst Hchem

isosteric heat of adsorption


(only equilibrium states are
considered)

43

Homework: How does the relative sticking probability s/s0 depend on the

coverage in case physisorption on top of a chemisorbed layer is taken into


account?

Langmuir Model for the co-adsorption of two species (competitive


adsorption for the same surface sites):
Adsorption and desorption rates for A species:

Ra = ka . pA (1 Rd = kd .

). [ ]

Dynamic equilibrium:

Ra = Rd = >
Analog for B:

Homework: Calculate the coverage ratio A/ B assuming both species have the
same pressure pA = pB for adsorption at room temperature. Species A is
considered to adsorb by 40kJ/mol stronger than B:
HA HB = 40 kJ/mol. Recall that the adsorption enthalpy is given by the
difference of the activation energies for adsorption and desorption.

44

Chemisorption of atoms and molecules on metal surfaces: simple


theoretical concepts
Formation of electron bands in solids:

45

Adsorption of an atom on the surface of a metal

Free atom

46

Moving the free atom to the surface would cause a broadening of the originally
sharp electron levels due to a resonance effect. Filled states above the Fermi level
may lose charge towards the metal.

Donation effect

Acceptor effect

Example: Alkalines adsorption

on transition metal

Halogens adsorption

47

back donation

48

Consideration of the d-band effect:

1s

jellium

back donation

d-bands are less broad than s-bands. Therefore, the interaction with d bands gives
rise to localized bonding. For the chemisorption of a hydrogen molecule, both the
occupied bonding molecular orbital of H2 and the unoccupied molecular orbital
have to be correlated with the metal d-band. The partial occupation of the
antibonding MO by charge transfer from the metal to the H2 gives rise to
weakening of the H-H bond.

49

Appropriate orbitals:

dz, dyz, dxz

To dissociate the CO molecule the relative position of the Fermi level is


important. Charge transfer into antibonding MO of the CO molecule causes bond
weakening which is the first step to dissociation. As a consequence the CO
molecule will tilt to allow its oxygen atom to contact the metal surface. This
process will finally lead to bond breaking with oxygen and carbon atoms being
deposited into next nearest neighbor sites of the catalyst surface.

50

CO molecular orbitals
Metallic Orbitals

dxz
dyz

dz2

5-dz2
dxzdyz-2 *

provides bonding
provides bonding

51

Symmetry of metallic surface planes: Miller indices

52

Basic planes of the cubic face-centered system:

Plane (323)

53

The direction in a crystal is defined by brackets: [uvw], expressed by the smallest


set of integers of a collinear vector of the indicated direction, such that hu+kv+lw
=0

Ordered overlayer structures

a) E.A. Wood
J. Appl. Phys. 35 (1964) 1306
Elementary vectors of the surface a1, a2
Elementary vectors of the adsorbate b1, b2
(|b1| / |a1| x |b2| / |a2|) + angle
b) R.L. Park, H.H. Madden
Surface Sci. 11 (1968) 188
b1 = m11 a1 + m12 a2
b2 = m21 a1 + m22 a2

M=(

fcc (100), (110), (111) M = (

)
)

54

Some examples:

55

Area of the elementary unit cell

General classification of overlayer structures:


1. mij are integers simple structure (M integer)
Adsorbed species are in well-defined local positions.
2. relation between (a1 a2) and (b1 b2) given by rational numbers (M fractional
number)
two periodic lattices with 3b1 = 4a1 or b1 = 4/3a1 (incommensurate)

|b1|

3. incoherent structure: irrational numbers between a and b (M irrational number)

56

Experimental evidence for ordered overlayer structures


Low Energy Electron Diffraction (LEED)
What means low?

Electron wave length :


acceleration of electrons by
application of a potential difference
e: elementary charge

( 5 4 )

for U = 100 V

electron microscope: U = 10 V

57

k = (2/) s

s = unit vector in the same


direction as k

58

Electron diffraction at a one-dimensional grating of atoms


electron gun
Spherical screen

Constructive interference is obtained for wavelets propagating along the surface


of the cones. Diffraction only occurs for certain angles which define the order
of diffraction. For a surface, a second series of cones has to be constructed. For a
rectangular lattice, constructive interference is obtained where the two sets of
cones intersect. The screen therefore contains a periodic arrangement of spots.

a1

a2 Bragg condition

59

r: radius of screen curvature in the center of which the sample is placed.

Since distances between spots on the screen are proportional to the reciprocal
of distances in real space, the reciprocal lattice can be designed as follows:

ai aj* = ij (i, j = 1,2)

60

Construction of the reciprocal lattice and the respective lattice vector:

Nodes of the reciprocal lattice

a1a2* = 0
a2a1* = 0
a1a1* = 1
a2a2* = 1
a1* = 1/ a1 sin
a2* = 1/ a2 sin

a 1 a2 *

a1 * a 2

angle between vectors

61

Periodic surface structures and ordered overlayers in real and reciprocal space:

*
aa
2 2

It can be shown using matrix calculates that:


(M* is the matrix of M inversely transposed,

62

An example:
reciprocal lattice

real space lattice

63

Kinetic parameters for elementary reaction steps: desorption energy


for thermal desorption

Evaluation of the data is based on the Polanyi-Wigner equation:

n - is order of the desorption


process

64

, Ed and n can all be evaluated from data


The experiment consists in heating the sample according to a temperature
program, which in most cases, is linear.
T = T0 + t

Determination of the temperature for which the pressure in the reaction chamber
reaches a maximum (the chamber is continuously evacuated)

)}

Hypothesis:

{n

for the maximum

)}

65

Substitution :

1st order kinetics:

2nd order kinetics:

Tm

Result:

f ()

for the 1st order process and


a constant activation energy

Tm if for a 2nd order process with


constant activation energy: or
for a 1st order process with
coverage dependence of the
activation energy
{Ed = g ()}

n(

66

for a 1st order process, the desorption trace is


asymmetric around the maximum
for a 2nd order process, we receive a symmetric curve
around Tm

lineshape analysis:

determination of Ed:
1st order:

a) hypothesis
b) variation of

Differentiation >

2nd order:

(symmetrical peak)

n(

verification of the kinetic order:

(
n

n n

problem: Ed and

extrapolation

n
frequently depend on
0 for increasing temperature T

Best data treatment: simulation of the thermal desorption spectrum by fitting with
the Polanyi-Wigner equation

67

Some examples for Temperature Programmed Desorption experiments:

area
H2/ Ni (100)

Coverage (atoms/cm2)
(a) 4.6 x 1013
(b) 8.8 x 1013
(c) 1.0 x 1014
(d) 1.7 x 1014

68

(II)

(I)

multiple states appear not


always resolved separately but
overlapping, so a deconvolution
has to be made. The appearance
of different states may depend
on the coverage.
CO/ Ni (100)

Desorption spectra of carbon monoxide from clean Ni(100) following


adsorption at 137 K. Coverages were 7.0 x 1013 molecules/cm2 (I) and 2.6
x 1014 molecules /cm 2 (II)

69

Back to real catalysis: determining the specific surface area of


materials
Adsorption in multiple layers

4
3

layer 33
couche

couche
layer 22

1 0

couche
layer 11

surface

i is the fraction of the surface covered with i layers. is then the fraction of the
surface remaining empty. Similar to the Langmuir model, the surface is
considered homogeneous.

i = i0

0 = =

i i

i 1

0 = 1 -
i
i1
Under dynamic equilibrium conditions i values remain constant

i= i0

is

i0 = Ji wi

i = Ji wi

70

i = i 1 heat of physisorption remains constant in all layers following the


first one (molecules in direct contact with the surface are assumed to have a
different heat of physisorption and therefore, a different mean lifetime).
With:

Wi = i-1

Ji 1i-1 = i 0
) i-2 =

i = (
i = (

) 0
)

i = i-1 = i-2 = 1

1 0
we can now express the overall coverage of the surface as:

with:

c i x

x = J1 / 0 and c = 0 / 1
1-

= 1 c

71

The above formula makes use of the following series expansion:

= (1 + x + x2

i) -1=

xi = x(1+2x +3x2

i-1)

using:
and

with:
=

we obtain:

V/Vs

if pq (condensation on the surface)

then we can identify q p0 as the saturation vapor pressure

literature: S. Brunauer, P.H. Emmett, E. Teller, J. Amer.Chem.Soc. 60 (1938) 309

72

one of the advantages of the BET equation is that it can be linearized:

p/V(p 0-p)

range of application:
0.05 p/p0 0.35

p/p0

determination of the constant c:

Hphys is usually larger than Hcond since the molecules interact more strongly
with the surface than with themselves in the multilayer. The larger the difference,
the steeper the slope in the above figure.

73

if c >> 1 we receive:

Vs = V (1 - p/ p0)
For pressures far below the saturation pressure, that is p/p0 << 1 we receive

which is formally identical to the Langmuir equation.

The BET equation as derived above allows determining the specific surface area
of the entire catalytic material since physisorption is non-specific and does not
distinguish between metallic particle surfaces and support.

A(

6.023 1023 10-20 As (2)

To determine the specific surface area, we need information about the mean
surface associated with the probing molecule which in many cases, is nitrogen.

As = f (M/ Na) 2/3

temperature C
mean surface 2

N2

Ar

CO

H2O

-196
16.2

-183
13.8

-183
16.8

0
10.6

In case of small specific surface areas (< 1m2/g) it is recommended to use a gas
whose vapor pressure is smaller than that of nitrogen at -196C
Ar, Kr, CH4

74

Some examples of BET measurements:

Similar to Langmuir:
indicates a microporous
material

p/p0

The catalyst surface is hydrophobic


and the formation of the first layer is
not visible.

2O/graphite
HH2O/graphite
Br2/SiO
2/SiO
2
Br
2

p/p0

75

Some criticism as to the BET equation:


Surfaces are energetically uniform.
Lateral interactions between physisorbed molecules do not exist.
Condensed molecules are treated identically to the liquid phase of these
molecules.

76

Catalytic reaction kinetics


For reasons of simplicity, we shall consider a sequence of steps involving
adsorption, reaction, and desorption. Each of these steps will follow first order
kinetics. The scheme therefore reads:

k1
k -1

Aad

k2
k -2

Bad

k3

k -3

It is assumed that the concentration of active sites is much smaller than the
concentration of reactants and products. The steady state kinetics of the reaction
will then be determined by the surface reaction step (the concentration of active
sites being the bottle-neck of the overall speed).

quasi-equilibrium
rate determining for the
overall reaction

quasi-equilibrium

R = Ri R-i = R2 R-2 = R3 R-3 = (k2 A k-2 . B) [ ]


using:

77

At the beginning of the reaction, with little product formation:


(1)

pA + pB = p

78

Five different case studies:


1) weak adsorption (A + B)
R = k2 KA PA [ ]

facilitates equation (1)

1st order kinetics with regard to A

Bad

Attention: HA is negative!

2) strong adsorption (A)

KB pB << 1
R = k2 . [ ]

KA pA >> 1
zero kinetic order with regard to A and B

79

1/T

3) strong adsorption (B)

KB pB >> KA pA

positive 1st order kinetics with regard to A, negative 1st order kinetics for B
the apparent activation energy is now larger than in case 1 (the desorption energy
is positive and equal to the adsorpton enthalpy).
4) adsorption determines the reaction rate

R = k1.pA. [ ]

surface coverage is low

5) desorption determines the reaction rate

R = k3 . B . [ ]

KB . pB >> 1

80

What changes for bimolecular reactions?


D
Assuming that the surface reaction is the slowest step (C and D are weakly
adsorbed) we receive:

both HA and HB are negative!

z is the number of next-nearest neighbor sites

for strong adsorption of A we receive:


;

reaction follows 1st order kinetics in A and negative 1st order kinetics in B ; the
overall reaction order is zero.

81

Mechanistic alternative for reactions on the surface of oxidic


catalysts:
example: SO2 + O2 SO3 catalyst:

V2O5

redox mechanism:
CatO + A

Cat- + AO

reduction
\
of catalyst

/
oxidation

Cat + O2 CatO
_____________________________
A + O2

Rred

AO

= R oxyd

kr . pA (1-) . [ ] = ko . pO2 . . [ ]

a) if kr pA >> k0pO2

sum reaction

for steady state conditions

fraction of the reduced surface

is close to 1 oxidation is
limiting
zero reaction order for A

82

is very small compared to


1 zero order reaction kinetics
for oxygen

b) if

R = kr . pA
The difference with respect to the Langmuir-Hinshelwood type mechanism on
metals is that according to the above Mars-Krevelen mechanism is a fully
reversible chemical alteration of the catalyst surface takes place while for L-H
this does not occur at all.

Examples with industrial application:


a. oxidation of hydrocarbons on mixed oxides of V, Mo
b. oxidation of ortho-xylene to phtalic anhydride on V2O5/SiC