Professional Documents
Culture Documents
Catalysis From
Fundamentals to
Applications
Professor Norbert Kruse
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.
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.
non-catalytic
catalytic
Incidental remark:
N2 + 3H2 2NH3
Fischer-Tropsch Reaction:
CO +H2
2O
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)
Reaction:
(ex: isomerization)
Thermodynamically feasible,
GR < O
Arrhenius:
Potential Energy
a) Heterogeneous Catalysis:
AB*
EA
A
A ad
B
B ad
Reaction Advancement
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
11
NH
+H ad
NH2,ad
2,ad + Had
Molecular adsorption
Dissociative adsorption
(Nad) + 3Had)
(N + 3H
ad
ad
12
Note that the catalytic cycle above includes changes in the number of metal
valence electrons between 18 and 16, back and forth.
13
Isokinetic temperature
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
for A B
since
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
Example:
O
OH
OH
Butyraldehyde yield:
17
Conversion of crotonicaldehyde:
Butyraldehyde selectivity:
18
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
10nm
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).
23
r~N
Ns = 2 N2
Nt = 2/3 N3
24
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).
25
[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
Lewis Center
Heating
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
Condensation
Inorganic Template
precursor
Template-oxide
Mesoporous
CTAB micelle
*Kresge C.T., Leonowicz M.E., Roth W.J., Vartuli J.C., Beck J.S., Nature, 1992, 359, 710
712
29
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)
30
31
Forces
Physisorption
Chemisorption
dispersion
a) E Keesom
b) E Debye
c) E London
Hchem 5 4
kJ/mol
32
Coverage
multilayers
monolayer limit
Reactants
reactive gasses
Reversibility
yes
maybe complicated in
case of an activated
process
33
Potential diagrams
Chem
Edif
34
H chem
*Chemisorption site
H chem
= 34 kJ/mol
EA
= 21 kJ/mol
Generally:
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:
phys = J . . wphys
wphys
probability of physisorption
For chemisorption:
chem = J . . s
impingement rate
[ L-2 . T-1]
s
sticking probability
37
with:
and
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.
Ra = J . s
S = Ra / J
> tM
38
Example : N2/Fe
N2 + 3H2 2NH3
For comparison, the sticking probability S0 of the CO molecule on transition
metal surfaces varies between 1 and 0.1.
(NA) . Ed = Hchem
with
(Hchem / RT)
39
at constant temperature:
n .p
Assuming every incoming molecule hitting an empty site will get adsorbed,
s0 = 1, we will then receive:
with
Vs
40
1/V
1/Vs
1/p
) [ ] = kd .
[]
41
1
T3
T2
T1
T3 < T2 < T1
42
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
43
Homework: How does the relative sticking probability s/s0 depend on the
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
45
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
on transition metal
Halogens adsorption
47
back donation
48
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:
50
CO molecular orbitals
Metallic Orbitals
dxz
dyz
dz2
5-dz2
dxzdyz-2 *
provides bonding
provides bonding
51
52
Plane (323)
53
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=(
)
)
54
Some examples:
55
|b1|
56
( 5 4 )
for U = 100 V
electron microscope: U = 10 V
57
k = (2/) s
58
a1
a2 Bragg condition
59
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:
60
a1a2* = 0
a2a1* = 0
a1a1* = 1
a2a2* = 1
a1* = 1/ a1 sin
a2* = 1/ a2 sin
a 1 a2 *
a1 * a 2
61
Periodic surface structures and ordered overlayers in real and reciprocal space:
*
aa
2 2
62
An example:
reciprocal lattice
63
64
Determination of the temperature for which the pressure in the reaction chamber
reaches a maximum (the chamber is continuously evacuated)
)}
Hypothesis:
{n
)}
65
Substitution :
Tm
Result:
f ()
n(
66
lineshape analysis:
determination of Ed:
1st order:
a) hypothesis
b) variation of
Differentiation >
2nd order:
(symmetrical peak)
n(
(
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
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)
69
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
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
= (1 + x + x2
i) -1=
xi = x(1+2x +3x2
i-1)
using:
and
with:
=
we obtain:
V/Vs
72
p/V(p 0-p)
range of application:
0.05 p/p0 0.35
p/p0
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
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(
To determine the specific surface area, we need information about the mean
surface associated with the probing molecule which in many cases, is nitrogen.
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
Similar to Langmuir:
indicates a microporous
material
p/p0
2O/graphite
HH2O/graphite
Br2/SiO
2/SiO
2
Br
2
p/p0
75
76
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
77
pA + pB = p
78
Bad
Attention: HA is negative!
KB pB << 1
R = k2 . [ ]
KA pA >> 1
zero kinetic order with regard to A and B
79
1/T
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. [ ]
R = k3 . B . [ ]
KB . pB >> 1
80
reaction follows 1st order kinetics in A and negative 1st order kinetics in B ; the
overall reaction order is zero.
81
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
is close to 1 oxidation is
limiting
zero reaction order for A
82
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.