TPX

Temperature Programmed
Techniques

Dr. Davide Ferri

Paul Scherrer Institut
056 310 27 81
davide.ferri@psi.ch
 Definitions

Temperature programmed desorption (TPD), or

thermal desorption spectroscopy (TDS)

uptake, desorption rate…

Temperature programmed reduction (TPR)

temeprature
Temperature programmed reaction (TPR)

Temperature programmed oxidation (TPO)

time

Temperature programmed reaction spectroscopy (TPRS)

 Definitions

TPD

A solid is first exposed to an adsorbate gas under well-defined conditions

(temperature and pressure) and then heated under inert conditions with a
temperature program

TPX but TPD

Solid and reactants in contact during temperature programmed experiment

 Information

desorption rate…
Tred, Tdes, Tox, Treact
Adsorption site strength, quality and quantity

uptake,
Bond strength, solid-adsorbate
Surface coverage
Quantification of desorption temperature

Adsorption enthalpy + pre-exponential factor for desorption

Advantages
Experimentally simple
Inexpensive
Access to powders and single crystals

Disadvantages
Complex determination of activation energies and pre-exponential
factors
 Temperature programmed techniques
Equipment
(A)

Thermal conductivity

gas λ 10-3 [W/(cmK)]

air 0.277
NH3 0.270
Ar 0.190 (B)
CO2 0.183
CO 0.267
He 1.574
H2 1.972
CH4 0.374
N2 0.275
O2 0.285
H2O 0.195

consumption
uptake

Reactant and carrier gases

TPR: 5 vol.% H2/Ar (or He)
TPO: 5 vol.% O2/He temperature temperature

J.W. Niemantsverdriet, Spectroscopy in catalysis, VCH, Weinheim, 2007

 Temperature programmed reduction
Reduction of a bulk metal oxide

MOn + nH2 → M + nH2O

From thermodynamics:

∆G = ∆G0 + nRT ln(pH2O/pH2) < 0

If H2 is the reducing agent,

∆G = nRT ln[(pH2O/pH2)/(pH2O/pH2)eq]

then ∆G <0, if

pH2O/pH2 < (pH2O/pH2)eq

 Temperature programmed reduction
Reduction of a bulk metal oxide
T (K) thermodynamic data for reduction (400°C)
1000 500 200
metal oxide (pH2O/pH2)eq
Fe2O3
105
10 Ti TiO2 4 10-16
TiO 2 10-9
V V2O5 6 10-4
FeO Fe3O4
VO 2 10-11
0 100 Cr Cr2O3 3 10-9
Mn MnO2 10
lnpH2O/pH2

MnO 2 10-10

pH2O/pH2
-10 Fe Fe2O3 0.7
10-5 FeO 0.1
Fe/FeO
Co CoO 50
Ni NiO 500
-20 Fe Fe/Fe3O4 Cu CuO 2 108
10-10 Cu2O 2 106
Mo MoO3 40
MoO2 0.02
-30 Ru RuO2 1012
FeO/Fe3O4 Rh RhO 1013
0 1 2 3 4 5 Pd PdO 1014
1/T 103 (K-1) Ag Ag2O 3 1017
Ir IrO2 1013
BUT!
reduction of a supported MOx can produce
completely different TPR patterns
 Temperature programmed reduction
Reduction mechanisms

Rate of reduction of MOn + nH2 → M + nH2O

- d[MOn]/dt = kred[H2]p f([MOn])

kred, rate constant of reduction reaction

p, reaction order in H2
t, time

If α is the degree of reduction, if p=0 (excess H2), if linear T-ramp (dT = β dt) and using Arrhenius
equation

dα/dT = ν/β e-Ered/RT f(1-α)

ν, pre-exponential factor
β, heating rate
Ered, activation energy of reduction reaction
Temperature programmed reduction
Reduction mechanisms

metal oxide
1.0 1.0
degree of reduction, α

f(α)

f(α)
0.5 0.5

0.0 0.0
0.0 0.5 1.0
time degree of reduction, α

shrinking core f(α) = 3 (1-α)1/3

nucleation and growth f(α) = (1-α)[-ln(1-α)]2/3

 Temperature programmed reduction
Activation energy of reduction

ln(β/T2max) = -Ered/RTmax + ln(νR/Ered) + K

if f(1-α) and α(Tmax) independent of β.

-14
Tmax Fe2O3
dry H2
111 kJ/mol

lnβ/T2max
-16
H2 uptake

wet H2 -18
wet H2
172 kJ/mol
-20
temperature (K)
1.2 1.4 1.6 1.8
dry H2
1000/T

500 550 600 650 700 750

temperature (K)
 Temperature programmed reduction
Reduction of a bulk metal oxide
…a somewhat different phase diagram

three-steps mechanism
two-steps mechanism

one-step mechanism?
Fe2O3 → Fe

J. Zielinski et al., Appl. Catal. A: General 381 (2010) 191

 Temperature programmed reduction
Effect of exp. conditions

TPR profile dependent on exp. Conditions

sample amount, H2 conc., H2O, T ramp…
Effect of fed water on pH2O/pH2?

J. Zielinski et al., Appl. Catal. A: General 381 (2010) 191

 Temperature programmed reduction
Evidence of mechanism from XRD

β2

β1

Effect of fed water on pH2O/pH2

High ratio, three step mechanism
Low ratio, two step mechanism

J. Zielinski et al., Appl. Catal. A: General 381 (2010) 191

 Temperature programmed reduction
Evidence of mechanism from XRD
low pH2O/pH2 very low pH2O/pH2

1 h-Fe2O3
2 c-Fe3O4
4 c-Fe

two-steps mech. one-step mech.

J. Zielinski et al., Appl. Catal. A: General 381 (2010) 191

Temperature programmed reduction
Supported oxides and bimetallic catalysts

Rh/SiO2 Fe/SiO2 FeRh/SiO2

Fe:Rh 1:1
Rh–O

Fe2O3→Fe3O4 as prepared
H2 uptake (molH2/molmetal)

Rh–Cl Fe3O4→Fe Rh3+→Rh

H2→2H*
Fe3+(Rh)→Fe(Rh)

after oxidation
Rh3+→Rh

0 100 200 300 400 0 100 200 300 400 0 100 200 300 400

temperature (°C) temperature (°C) temperature (°C)

 Temperature programmed reduction
Reduction mechanisms, PrCoO3

Co3++1e- Co2+
Co2++2e- Co

slow

fast

1. shrinking core Co3++1e- Co2+

2. nucleation Co2++2e- Co

Fierro et al., J. Mater. Sci. 23 (1988) 1018

 Temperature programmed reduction
Reduction of 0.5 wt.% Pd/LaCoO3: H2-TPR XRD

La2O3+Co
Co
* 700°C 0 LaCoO3
+ +
+ * + 550°C
-2

weight loss / %
+ 500°C
-4
La2Co2O5 300°C
*
-6
La3Co3O8 x 200°C Pd/LaCoO3
CoO -8
150°C
TGA
LaCoO3 ♦ 25°C -10 DTG
25 30 35 40 45 50 55 60 65 0 100 200 300 400 500 600 700
2θ temperature (°C)
Co3O4

No information on Pd

Chiarello et al., J. Catal. 252 (2007) 127 + 252 (2007) 137

 Temperature programmed reduction
Reduction of 0.5 wt.% Pd/LaCoO3: H2-TPR XANES

1.2
Pd K-edge 1.0 0
1.0
absorption / a.u.

0.8 -2

weight loss / %
fraction of Pd2+
TPR
0.8
r.t. Pd/LaCoO3 -4
0.6
50°C
0.6
100°C -6
0.4
140°C Pd2+→Pd
0.4 210°C
320°C 0.2 -8
0.2 600°C
0.0 -10
LCA
0.0
24.32 24.36 24.40 24.44 24.48 0 50 100 150 200 250 300 350 400
energy (keV) T (°C)

Chiarello et al., J. Catal. 252 (2007) 127 + 252 (2007) 137

 Temperature programmed reduction
Reduction of Pd-containing perovskites

2 wt.% Pd/LaFeO3 LaFe0.95Pd0.05O3

1.2 1.2

1.0 1.0
absorption (a.u.)

0.8 0.8
29°C (He)
29°C
0.6 28°C
0.6 35°C
29°C(He) 66°C
28°C 0.4 95°C
0.4 29°C 123°C
49°C 150°C
76°C 0.2 196°C
0.2 107°C 427°C
550°C 479°C
565°C
0.0 0.0

24.3 24.35 24.4 24.45 24.3 24.35 24.4 24.45

energy (keV) energy (keV)

10 vol.% H2/He, 10°C/min, 50 ml/min

Eyssler et al., J. Phys. Chem. C 114 (2010) 4584
 Temperature programmed reduction
Reduction of Pd-containing perovskites

2 wt.% Pd/LaFeO3 LaFe0.95Pd0.05O3

1.2 1.2

1.0 1.0
absorption (a.u.)

0.8 0.8
29°C (He)
29°C
0.6 28°C
0.6 35°C
29°C(He) 66°C
28°C 0.4 95°C
0.4 29°C 123°C
49°C 150°C
76°C 0.2 196°C
0.2 107°C 427°C
550°C 479°C
565°C
0.0 0.0

24.3 24.35 24.4 24.45 24.3 24.35 24.4 24.45

energy (keV) energy (keV)

10 vol.% H2/He, 10°C/min, 50 ml/min

Eyssler et al., J. Phys. Chem. C 114 (2010) 4584
 Temperature programmed reduction
Reduction of CeO2-based catalysts
Rh/CexZr1-xO2

CeO2
H2 consumption

x, molar content CeO2

Rh/CeO2

0 200 400 600 800 1000

temperature (°C)

Red. conditions: CeO2 → Ce2O3

Ox. conditions: Ce2O3 → CeO2

CexZr1-xO2 + δH2 → CexZr1-xO2-δ + δH2O + V0

Boaro et al., Catal. Today 77 (2003) 407

Temperature programmed desorption
Oxygen mobility in perovskite-type oxides – O2-TPD
surface oxygen (α): suprafacial catalysis
lattice oxygen (β): intrafacial catalysis

LaMnO3±δ La0.9Ce0.1MnO3±δ

β
α
 Temperature programmed desorption
Distribution of acid sites – NH3-TPD
which sites are present?
how strong are the sites?
which sites are catalytic relevant?
site structure?
4NO + 4NH3 + O2 4N2 + 6H2O
100
NH3 ads. at given T
NH3 desorption upon heating
75

NOX conversion (%)

desorption rate (a.u.)

50

25

0
300 400 500 600 700 800
temperature (K)

Greenhalg et al., J. Mol. Catal. A 333 (2010) 121