Thermal methods

Dr. Sharon Mitchell and Prof. Javier Prez-Ramrez

Institute for Chemical and Bioengineering, ETH Zurich, Switzerland E-mail: jpr@chem.ethz.ch http://www.perez-ramirez.ethz.ch

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Outline
Introduction to thermal analysis Thermal gravimetric analysis Temperature programmed desorption Temperature programmed reduction and oxidation Advanced techniques (TEOM) Concluding remarks

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Introduction to thermal analysis

Thermal analysis is a group of techniques that study the relationship between a sample property and its temperature
International confederation for thermal analysis and calorimetry, 2004.

Group? Study? Relationship?

Diverse range of techniques encompassed Time integral to experiment, includes interpretation and discussion of measured data Property measured as function of temperature or vice versa

Temperature? Controlled by user, or by a sample property

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Introduction to thermal analysis

Property?

Composition (purity, stoichiometry of surface species) Thermal stability (melting point, vaporization, sublimation, desorption, decomposition, dehydration) Chemical stability (oxidation, reduction, pyrolysis) Physical (specific heat capacity, enthalpy changes)
Thermal methods

Characterization of catalysts and surfaces, 529-0611-00L

Radiation thermometer

Introduction to thermal analysis

Temperature All physical and chemical processes temperature dependent Measure of kinetic energy of molecules, atoms or ions Measurement based on comparison with internationally defined scale

1400 K Melting point 1300 K 1200 K 1100 K

of Au 1337.33 K (1064.18C)

1000C 900C 800C 700C 600C 500C 400C 300C 200C 100C 0C

Melting point (660.323C)

1000 K of Al 933.473 K 900 K 800 K 700 K 600 K 500 K 400 K 300 K 200 K

Platinum resistance thermometer

Melting point of In 429.7485 K (156.5985C) Triple point of water 273.16 K (0.01C)

Helium based thermometers

100 K 0K

Controlled temperature program

Celcius (C)

Kelvin (K)

Linear dynamic

Isothermal

Combined

Complex

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Introduction to thermal analysis

Physical limitations of the heating process?
Gaseous exchange

Convection through surrounding atmosphere

Radiation from furnace wall

Indication of sample temperature

Conduction through sample pan

Instrumental Sample

Heating rate, atmosphere and flow rate, holder/furnace geometry, holder composition Mass, particle size, packing, thermal conductivity, history/pre-treatment
Thermal methods

Characterization of catalysts and surfaces, 529-0611-00L

Introduction to thermal analysis

Measurement atmosphere Inert Reactive Corrosive No reaction with the sample or crucible. (e.g. N2, Ar, He). Chemical reaction with sample expected (e.g. air, O2, CO2, diluted H2,NH3). Chemical reaction with sample expected, risk or reaction with crucible/cell (e.g. HCl).

Operando? Majority of studies report ex situ analysis with linear heating rates at atmospheric pressure With advances in techniques and measurement precision possible to undertake complex operando experiments

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Introduction to thermal analysis

Thermal gravimetric analysis (TGA) Differential thermal analysis (DTA) Evolved gas analysis (EGA) Thermochemiluminescence (TCL) Differential scanning calorimetry (DSC)

Principal techniques?

Thermooptical analysis (TOA) Thermal mechanical analysis (TMA)

Temperature programmed methods (TPX)

Desorption (TPD)

Reduction (TPR)

Oxidation (TPO)

Sulfidation (TPS)
Thermal methods

Characterization of catalysts and surfaces, 529-0611-00L

Introduction to thermal analysis

TG TEOM

TPX

IGA

Routinely used
Characterization of catalysts and surfaces, 529-0611-00L

Advanced studies
Thermal methods

Thermogravimetric analysis (TGA)

Measures the amount and rate of change in mass of a sample as a function of T or t in a controlled atmosphere. TGA curve (profile) in which mass is plotted against T or t.

Balance configurations

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Thermogravimetric analysis (TGA)

Weight changes?
Process
Ad- or absorption Desorption Dehydration/ desolvation Sublimation Vaporization Decomposition Solid-solid reactions Solid-gas reactions

Weight gain

Weight loss

1. 2. 3.

No change Desorption/drying Single stage decomposition Multi- stage decomposition As 4 but no intermediates or heating rate too fast Atmospheric reaction As 6 but product decomposes at higher T

Weight

4.

5.

6. 7.

T
Characterization of catalysts and surfaces, 529-0611-00L Thermal methods

Thermogravimetric analysis (TGA)

Case study: Thermal decomposition of hydrotalcite Mg4Al2(OH)6CO3.nH2O Layered structure composed of edgesharing metal hydroxide octahedra Exchangeable charge balancing anions between layers Variable amounts of interlayer water Precursor for Mg4Al2O6, a base catalyst obtained by thermal activation How is the active phase formed?
Characterization of catalysts and surfaces, 529-0611-00L Thermal methods

Thermogravimetric analysis (TGA)

Case study: Thermal decomposition of hydrotalcite
DTG

Multiple steps observed in TG profile Steps not clearly defined

TG

Differential thermogravimetric (DTG) curve shows rate of mass changes with respect to T or t Peak positions used to identify T of mass loss processes Evolved gas analysis e.g. by mass spectrometry/FTIR/TCD H2O (m/z= 18) and CO2 (m/z=44) evolved during decomposition
Thermal methods

Characterization of catalysts and surfaces, 529-0611-00L

Thermogravimetric analysis (TGA)

Case study: Thermal decomposition of hydrotalcite
i ii

Multi-step decomposition:
iii iv

i Dehydration removal of physisorbed water ii Dehydration removal of interlayer water iii Removal of weakly bound carbonate and water iv Removal of strongly bound carbonate and dehydroxylation Exact losses can be quantified from TG curve

Characterization of catalysts and surfaces, 529-0611-00L

Thermal methods

Differential methods
Compare behavior of sample (S) and reference (R) during a controlled temperature program. Differential thermal analysis (DTA) Measures difference in temperature between S and R Differential scanning calorimetry (DSC) Measures difference in heat flow into S and R. DSC is a calorimetric method Identification of endothermic and exothermic effects Direct measurement of transition and reaction enthalpies Determination of specific heat capacity

Characterization of catalysts and surfaces, 529-0611-00

Thermal methods

Temperature programmed methods (TPX)

Measure the consumption/evolution of reactive gases during a controlled temperature program Characterize chemical interactions between reactants and solid substances.
Sample

Reactive gases (+ inert carriers)

Thermal conductivity detector(TCD)?

Detects variation in thermal conductivity of exhaust gas with respect to reference flow
Thermal methods

Characterization of catalysts and surfaces, 529-0611-00

Temperature programmed methods (TPX)

Experimental protocol Pre-treatment Drying removal of volatiles Purging removal of gases Saturation introduction of adsorbate(s)

Measurement Temperature program typically dynamic but isothermal useful for kinetic studies Controlled atmosphere Evolved gas analysis TCD, MS, FTIR, GC

Characterization of catalysts and surfaces, 529-0611-00

Thermal methods

Temperature programmed desorption (TPD)

Monitors molecules desorbed from a surface (e.g. H2, CO, NH3, NO)

Some possible adsorption sites on idealized substrate surfaces and differing modes of adsorbate interaction

Heterogeneity of sorption interactions and difference in binding strengths

Thermal methods

Characterization of catalysts and surfaces, 529-0611-00

Temperature programmed desorption (TPD)

Case study: Characterization of zeolite acidity
TPD of NH3 most frequently used method. Heat of ammonia adsorption Strength and heterogeneity of acid sites Amount of adsorbed ammonia related to total acidity Two broad desorption peaks visible Low temperature peak attributed to NH4+ cation weakly adsorbed on Brnsted site or to NH3 adsorbed to weak Lewis sites (e.g. Na+) High temperature peak shows NH3 adsorbed on acid sites

TPD profiles observed on Mordenite, ZSM-5, and Beta zeolites

M. Niwa et al., in Characterization and design of zeolite catalysts, Springer-Verlag, Berlin, (2010), ch. 2, p. 9.
Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed desorption (TPD)

Case study: Characterization of zeolite acidity
Lower acidity greater overlap in desorption peaks
H+ O Si Al-

Remove weakly adsorbed NH4+ in presence of H2O

Brnsted acidity arising from isomorphous substitutions in zeolite framework

Difficult to quantify proportion of Lewis and Brnsted acidity

Complementary studies (e.g. pyridine adsorption) undertaken in parallel

TPD profiles observed on Mordenite (left) and Y zeolite (right) in the absence (a) or presence (b, c, d) of water M. Niwa et al., in Characterization and design of zeolite catalysts, Springer-Verlag, Berlin, (2010), ch. 2, p. 9.
Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed reduction (TPR)

Oxidized catalyst/ catalyst precursor
Reducing gas (e.g. H2) Temperature program

Oxidation state(s) of surface metal species Influence of support/promoters on reducibility Integration of hydrogen consumption: Amount of reducible species Degree of reduction Commonly used to find most efficient reduction conditions of oxidic catalyst precursors

B. Bridier, N. Lopez, J. Prez-Ramrez, J. Catal. 269 (2010), 80

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed reduction (TPR)

Case study: Activation of Ni catalysts derived from layered precursors

Active Ni catalyst, Ni(Al)Ox, prepared from hydrotalcite-like precursor

Calcine (C) Reduce (R) (423/623/773 K)

(623/773/1173 K)

TPR

How do conditions of precursor activation influence Ni reducibility?

S. Abell, D. Verboekend, B. Bridier, J. Prez-Ramrez, J. Catal. 259 (2008), 85
Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed reduction (TPR)

Case study: Activation of Ni catalysts derived from layered precursors
673 K TCD signal / a.u.

T/K

Reduction of pure NiO

Reduction of Ni occurs between 600-1050 K Reducibility of Ni hindered by aluminium Method of catalyst activation strongly influences TPR profile
S. Abell, D. Verboekend, B. Bridier, J. Prez-Ramrez, J. Catal. 259 (2008), 85

Characterization of catalysts and surfaces, 529-0611-00

Thermal methods

Temperature programmed reduction (TPR)

Case study: Activation of Ni catalysts derived from layered precursors
Comparison of integrated peak areas

permits determination of the fraction of metallic Ni. Pre-reduction increases amount of metallic Ni Higher calcination T requires higher reduction T to reach equivalent amounts of metallic Ni.

S. Abell, D. Verboekend, B. Bridier, J. Prez-Ramrez, J. Catal. 259 (2008), 85

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed reduction (TPR)

Case study: Quantitative analysis and calculation of activation energy
Reduction of MoO2 and MoO3 Industrial relevance? Selective oxidations (bulk MoO3) Hydrogenation, alkene metathesis, hydrosulfurization (Al2O3/SiO2 supported Mo)

P. Arnoldy, J. C.M. de Jonge, J.A. Moulijn, J. Phys. Chem. 89 (1985), 4517

Thermal methods

Temperature programmed reduction (TPR)

Case study: Quantitative analysis and calculation of activation energy
Reduction of MoO2
Influence of heating rate (K min-1). Sample size x heating rate = 1.7 (mg K min-1) H2/Ar
10

MoO2 Mo + 2H2O
TPR profiles (2 K of mass and gas composition min-1): Influence

25 mg H2O/H2/Ar

Single sharp reduction peak Shifts to higher temperature with higher heating rate

28 mg H2/Ar

0.5

0.2 1.0 mg H2/Ar

P. Arnoldy, J. C.M. de Jonge, J.A. Moulijn, J. Phys. Chem. 89 (1985), 4517

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed reduction (TPR)

Case study: Quantitative analysis and calculation of activation energy
Reduction of MoO3
Influence of heating rate(K min-1). Sample size x heating rate = 52 mg K min-1 H2O/H2/Ar H2/Ar

100

51

4 reduction peaks identified Reduced to two peaks in the presence of H2O

10

10

25

13

Peaks i, ii, and iii attributed to: MoO3 MoO2 + H2O

i iii ii iv

5 2

1 3.9

1.2

Peaks iv attributed to: MoO2 Mo + 2H2O

1 0.5 0.5

0.2

0.2

TPR profiles (2 K min-1) in H2/Ar: Influence of sample size (mg)

P. Arnoldy, J. C.M. de Jonge, J.A. Moulijn, J. Phys. Chem. 89 (1985), 4517

Thermal methods

Characterization of catalysts and surfaces, 529-0611-00

Temperature programmed reduction (TPR)

Case study: Calculating the activation energy of reduction

Arrhenius plot of data from peaks i, ii, and iii.

E determined from slope Relate to reduction mechanism

P. Arnoldy, J. C.M. de Jonge, J.A. Moulijn, J. Phys. Chem. 89 (1985), 4517

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Temperature programmed Oxidation (TPO)

Reverse of TPR.

Catalyst/ catalyst precursor

Oxidizing gas (e.g. O2) Temperature program

Directly monitor consumption of Oxygen. Complimentary technique to TPR to study redox cycles Commonly used to find optimal regeneration conditions for catalysts deactivated by coking

Characterization of catalysts and surfaces, 529-0611-00

Thermal methods

Advanced methods
TEOM (tapered element oscillating microbalance)
Reaction gas Thermocouple Purge gas

Well-defined flow profile Eliminates possible diffusion or buoyancy effects Extremely fast response time (0.1 s) Real time measurements High mass resolution (1 g) Accurate mass changes during gas solid-reactions Relevant (Operando) conditions (T, P) Suitable for adsorption, diffusion, reaction, and deactivation
Thermal methods

Furnace

Optics

Catalyst Thermocouple

Gasanalysis

Characterization of catalysts and surfaces, 529-0611-00

Advanced methods
Case study: Oxidative dehydrogenation of propane with N2O over FeZSM-5

Propylene Key building block in petrochemical industry Growing demand

FeZSM-5 High initial activity Rapid deactivation due to coking Activity recovered by oxidative catalyst regeneration

TEOM used to evaluate catalytic performance, deactivation, and regeneration

A. Gallardo-Llamas, C. Mirodatos, J. Prez-Ramrez, Ind. Eng. Chem. Rev. 44 (2005), 455

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Advanced methods
Case study: Oxidative dehydrogenation of propane with N2O over FeZSM-5
Coke content C3H6 yield

Catalytic testing

Catalyst efficiency increases with reaction temperature higher degree of coking Sharp catalyst deactivation at low reaction temperatures Good correlation between increasing coke content and decreasing propene yield

C3H8 conversion

N2O conversion

A. Gallardo-Llamas, C. Mirodatos, J. Prez-Ramrez, Ind. Eng. Chem. Rev. 44 (2005), 455

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Advanced methods
Case study: Oxidative dehydrogenation of propane with N2O over FeZSM-5
TG profile used catalyst

Catalyst regeneration

TG studies show that coke oxidation occurs in the range 650-900 K Derivative weight loss shows peak at 795 K Kinetic study of coke removal by isothermal TPO measurements Rapid regeneration at 823 K (total coke conversion in ca. 2 min

Coke conversion on regeneration

A. Gallardo-Llamas, C. Mirodatos, J. Prez-Ramrez, Ind. Eng. Chem. Rev. 44 (2005), 455

Characterization of catalysts and surfaces, 529-0611-00 Thermal methods

Concluding remarks
Thermal analyses are extremely useful in studying catalyst preparation and/or application, and for the characterization of surface species. Typically more than one method used in combination Further reading: P. Haines, Principles of Thermal Analysis and Calorimetry, Royal Society of Chemistry, 2002. L. Damjanovic, A. Auroux, Heterogeneous Catalysis on Solids in Handbook of Thermal Analysis and Calorimetry Vol.5, Elsevier, 2008, ch.11, p.387. Handbook of Heterogeneous Catalysis Vol. 8, 2nd Edition, Wiley, 2008.

Characterization of catalysts and surfaces, 529-0611-00

Thermal methods