temperature-programmed methods 1 - · pdf filetemperature-programmed methods 2 2 ......
TRANSCRIPT
111TemperatureTemperature--programmed methods programmed methods
222TemperatureTemperature--programmed methods programmed methods
Temperature-programmed Methods in Catalysis Research
Procedures and pitfalls of a very commonly used tool
333TemperatureTemperature--programmed methods programmed methods
Definitions
• TPD: temperature-programmed desorption• TPR: temperature-programmed reduction or
– temperature programmed reaction• TPO: temperature-programmed oxidation• TPRS: temperature-programmed reaction
spectroscopy
444TemperatureTemperature--programmed methods programmed methods
Methods
• TPD: a solid is first exposed to an adsorbate gas under well-defined conditions (wide range of pressure and temperature) and then heated underinert conditions with a temperature program:– parental method: Flash desorption from metal wires in
UHV : G. Ehrlich, Adv. Catal., 1963• All other methods keep solid and reactants in
contact during temperatre-programmed processing• TPD – TPRS most suitable designations
555TemperatureTemperature--programmed methods programmed methods
Atmospheres, Reactors and Detectors
666TemperatureTemperature--programmed methods programmed methods
Atmospheres, Reactors and Detectors
777TemperatureTemperature--programmed methods programmed methods
Atmospheres, Reactors and Detectors
888TemperatureTemperature--programmed methods programmed methods
Experiment
R.N. Rogers, Anal. Chem., 32, 672, (1960)
High-pressure variantwith inert carrier G1 and reactant G2
999TemperatureTemperature--programmed methods programmed methods
Filament
z-transfer rot
Line of sight mass spectrometer nozzle Electric contacts
Metal clips
FHI-AC variable pressure TDS-reactor set-up
101010TemperatureTemperature--programmed methods programmed methods
Influence of Vacuum TreatmentInfluence of Vacuum Treatment
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Strong influence of vacuum treatment both for water and oxygendesorption traces Solid state dynamics!
Strong influence of vacuum treatment both for water and oxygendesorption traces Solid state dynamics!
0 100 200 300 400 500 600Temperature / °C
0
1∗10-9
2∗10-9
3∗10-9
4∗10-9
MS-
Res
pons
e (I.
C.) m/e=18m/e=18
“as is”
0 100 200 300 400 500 600Temperature / °C
0
5∗10-11
1∗10-10
MS-
Res
pons
e (I.
C.) m/e=32m/e=32
after 12h of vacuum
“as is”
Sample K47
111111TemperatureTemperature--programmed methods programmed methods
AssignmentAssignment ofof relevant MS relevant MS tracestraces
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Reaction study of sample “Partie 5010” (hemihydrate) after TDS treatment:
Molecule m/z fragmentsButane 43, 27, 42, 41, 39
Butene 41, 39, 55, 27, 26
Butadiene 39, 54, 27
2,5-dihydro-Furan 41, 70, 39, 42, 27
Furan 68, 39
MSA 26, 54, 98
121212TemperatureTemperature--programmed methods programmed methods
Aqueous Aqueous vsvs Alcoholic preparationAlcoholic preparation
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Hemihydrate:
0 100 200 300 400 500 600
Temperature /°C
0
1∗10-9
2∗10-9
3∗10-9
MS-
Res
pons
e (n
orm
. u.) m/e=18m/e=18
alcoholic
aqueous
131313TemperatureTemperature--programmed methods programmed methods
Aqueous Aqueous vsvs Alcoholic preparationAlcoholic preparation
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Hemihydrate:
0 100 200 300 400 500 600
Temperature /°C
2∗10-11
4∗10-11
6∗10-11
8∗10-11
1∗10-10
MS-
Res
pons
e (n
orm
. u.) m/e=32m/e=32alcoholic
aqueous
141414TemperatureTemperature--programmed methods programmed methods
Aqueous Aqueous vsvs Alcoholic preparationAlcoholic preparation
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Hemihydrate:
0 100 200 300 400 500 600
Temperature /°C
0
5∗10-11
1∗10-10
1.5∗10-10
2∗10-10
2.5∗10-10
MS-
Res
pons
e (n
orm
. u.) m/e=44m/e=44
alcoholic(“Partie 5010”)
aqueous
151515TemperatureTemperature--programmed methods programmed methods
Reactor StudyReactor Study
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Reaction study of sample K 50/16 (fresh VPO) after 2 times TDS treatment:
0 10 20 30 40 50
Time / min
0.8
0.9
1
1.1
1.2
1.3
1.4
MS
-resp
onse
(nor
m. u
.)
MSAMSA
n-butane conversion: 18%n-butane conversion: 18%
m/e=18m/e=18m/e=44m/e=44m/e=26m/e=26
m/e=43m/e=43
m/e=32 (x10)m/e=32 (x10)
m/e=54m/e=54? (MSA?)? (MSA?)
m/e=41, 39m/e=41, 39
•flow of 0.7vol% n-C4H10 / 20vol% O2 / 79.3vol% He•25 ml/min @ 1bar•T=400 °C•30 mg pellet
heating up to 400 °C
161616TemperatureTemperature--programmed methods programmed methods
Comparison sample F8 “fresh” Comparison sample F8 “fresh” vsvs equilibratedequilibrated
M. Hävecker, Electronic Structure, Dept. Inorganic Chemistry, Fritz-Haber-Institut (MPG), Berlin, Germany
Desorption peak around 300 °C typical for non- conditioned VPO(compare to previous investigations); organics from synthesis
Desorption peak around 300 °C typical for non- conditioned VPO(compare to previous investigations); organics from synthesis
0 100 200 300 400 500Temperature / °C
3∗10-13
4∗10-13
5∗10-13
6∗10-13
MS-
resp
onse
(I. C
.)
0 100 200 300 400 500Temperature / °C
2.5∗10-13
3∗10-13
3.5∗10-13
4∗10-13
4.5∗10-13
MS-
resp
onse
(I. C
.)m/z: 54 m/z: 68fresh
equilibrated
171717TemperatureTemperature--programmed methods programmed methods
Desorption of organic fragments stemming not from synthesis after reaction (m/e=26: MSA?)
Desorption of organic fragments stemming not from synthesis after reaction (m/e=26: MSA?)
100 200 300 400 500
Temperature / °C
1∗10-12
1.2∗10-12
1.4∗10-12
1.6∗10-12
1.8∗10-12
2∗10-12
MS-
resp
onse
(I. C
.)
m/e=26m/e=26
after reaction
after 1st TDS
181818TemperatureTemperature--programmed methods programmed methods
m/e=26m/e=26
m/e=39m/e=39
m/e=41m/e=41
m/e=43m/e=43
m/e=55m/e=55
m/e=68m/e=68100 200 300 400 500
Temperature / °C
4∗10-13
6∗10-13
8∗10-13
1∗10-12
1.2∗10-12
1.4∗10-12
1.6∗10-12
1.8∗10-12
2∗10-12
MS-
resp
onse
(I. C
.)
100 200 300 400 500Temperature / °C
5∗10-11
1∗10-10
1.5∗10-10
2∗10-10
2.5∗10-10
3∗10-10
MS-
resp
onse
(I. C
.)
m/e=18
m/e=32
m/e=44
2 types of organic species: product, intermediate(s),no catalyst organics
191919TemperatureTemperature--programmed methods programmed methods
gaps
• temperature-programmed methods are a prototype area for the existence of gapsbetween surface science and catalysischaracterisation.
• often same methodology and datainterpretation.
• but fundamental differences in boundaryconditions.
202020TemperatureTemperature--programmed methods programmed methods
TPD: a complex process
• The net rate of TPD is considered as the rationbetween adsorption and desorption
• in static condition: equilibrium• in TPD: disturbance by pumping or gas flow• boundary cases:
– re-adsortion possible (thermodynamic control– re-adsortion suppresed (kinetic control) case of UHV
TDS analysis
212121TemperatureTemperature--programmed methods programmed methods
TPD and TDS: relation between surfacescience and catalysis charaterisation
• TDS low pressure (probe situation)• TDS: kinetic control, no re-adsorption, usually
(tacitly) first order• no clear distinction between sorptiopn and reaction• TPD high pressure, reaction situation• TPD: transition from kinetic to thermodynamic
regime explicitely studied• changeover in reaction process from sorption to
reaction common
222222TemperatureTemperature--programmed methods programmed methods
TDS: The method
• A pre-adsorbed species is removed from a well-defined surface by rapid heating (10 K/s) in a well-pumped UHV environment (no equilibration and re-adsorption) (caveat TMP!). (Langmuir unit!)
• Care must be taken to see only desorption from the surface!
Feulner and Menzel, J. Vac. Sci. Technol., 17, (1980), 662
232323TemperatureTemperature--programmed methods programmed methods
242424TemperatureTemperature--programmed methods programmed methods
Surface compositionduring reaction:
kinetics
252525TemperatureTemperature--programmed methods programmed methods
TDS: The observation
• rate of desorption:
r = ν (Θ) Θn exp [-Edes (Θ)/RT]
r = desorption raten = desorption orderΘ= coverage in monolayersν = pre-exponential factor
ν can vary between 1013 and 1018 accordingto transition state
262626TemperatureTemperature--programmed methods programmed methods
TDS: Complete analysis
Integration to chosenlow desorption
Conventional analysisfor activation energy
272727TemperatureTemperature--programmed methods programmed methods
TDS: The cheap analysis
282828TemperatureTemperature--programmed methods programmed methods
TDS: The “elaborate analysis”
Use width and peak desorption temperatures astwo parameters for finding activation energy and pre-factor
292929TemperatureTemperature--programmed methods programmed methods
TDS: Quality of analysis
303030TemperatureTemperature--programmed methods programmed methods
The basis of TPD• Simplest case: A solid with adsorption sites S*
gets in contact with a gas G of concentration C and populates in a first order process the vacantadsorption sites.
• Langmuir boundary conditions:– fixed number N of sites S* (F/cm²)– constant adsorption enthalpy dHa (and desorption
enthalpy)– all parmetres are temperature-independent and
coverage-independent
313131TemperatureTemperature--programmed methods programmed methods
The basis of TPDdN/dT = p k na (N*-N) – knd N
Langmuir model assuming the balance between competitiveadsortion and desorption kinetics
as net effect: the ratio of the two kinetic constants and theadsorbate partial pressure p are the parameters.
k = σ (2πMRT)1/2
The kinetic constant relate to the nature of the adsorbed species bythe molecular mass M (g/mol),
the specific molecular surface area (cm-²), and the gas constant (J/Kmol)
323232TemperatureTemperature--programmed methods programmed methods
The basis of TPDp = C R T
The partial pressure relates to the gas concentration.
The TPD experiment requires the temperature dependencies of thesorption process: it is assumed that the process is thermally activated(not spontaneously occuring); only a fraction na will be adsorbed:
na = Aa exp (-Ea/RT)
kd = Ad exp (-Ea/RT) desorption process
333333TemperatureTemperature--programmed methods programmed methods
The basis of TPD
The experiment produces a signal proportional to the change in gas concentration C with temperature
C = -S/F dN/dTS denotes surface area in (cm²/g), F the flow rate (cm³(STP)/sg)
The experiment is time-programmed; one obtains C as function of time t as initial observation data:
343434TemperatureTemperature--programmed methods programmed methods
The basis of TPD
F + σ (RT/2πM)1/2 na (N*-N)
S N kdC(t) =
It is important to run the experiment strictly linear in temperature:
T = T0 + βT with β being the heating rate in (K/s)
na is the fraction of adsorbing molecules from thestream of species A and Θ is the site occupancy: Θ = N/N*
353535TemperatureTemperature--programmed methods programmed methods
Reaction rate: first order S + N* Θ Ad exp(-E
d/RT)
F + S N* (1- Θ) σ (RT/2πM)1/2 Aa exp (Ea/RT)
C(T) =
dΘ/dT = -F
S β N*C(T)
One observes the concentration of the adsorbate CT as function of sample temperature
and can relate this to the physically relevant change in surface coveragewith temperature dΘ/dT