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Water-Gas Shift Reaction: Dimitris I. Kondarides
Water-Gas Shift Reaction: Dimitris I. Kondarides
Dimitris I. Kondarides
Laboratory of Heterogeneous Catalysis Department of Chemical Engineering University of Patras GR 26504 Patras, GREECE
RESTOENE Workshop 8-10 June 2011 Residencia la Cristalera, Miraflores de la Sierra, Madrid, Spain
Outline
1. Introduction 2. Industrial WGS catalysts and reactors
Thermodynamics Industrial catalysts and reactors HTS catalysts LTS catalysts Reaction mechanism and kinetics
4. Conclusions
Introduction
Water-Gas is a synthesis gas containing H2 and CO, originally made by passing steam over red-hot coke or coal. Heat supply for this endothermic reaction was usually provided by alternating the steam with an air stream.
C + H2O CO + H2
H = 131.2 kJ/mol
C + O2 CO2
H = 393.5 kJ/mol
2C + O2 2CO
H = 221 kJ/mol
Water gas apparatus
http://chestofbooks.com/crafts/scientific-american/sup4/Apparatus-For-TheProduction-Of-Water-Gas.html
Introduction
Today, water gas (synthesis gas) can be manufactured by the reaction of a carbonaceous material (e.g., coal, coke, natural gas, naphtha, etc.) with steam, oxygen, or CO2.
H2 /CO ratio
H (kJ/mol)
131.2
3
2 1
206.3
35.6
CH4 + CO2 2 CO + 2 H2
247.4
With the exception of partial oxidation, reactions are generally endothermic. The molar ratio of H2 to CO varies depending on the source of carbon/oxygen. Steam reforming reactions are mostly used when the ultimate objective is generation of pure hydrogen.
CO + H2O CO2 + H2
= 41.1 kJ/mol
The reaction was catalyzed by oxides of iron and chromium (BASF) at 400-500 C.
Ammonia plant
Industrial applications
The water gas is used extensively in the industry for the manufacture of Ammonia Methanol Hydrocarbons (Fischer-Tropsch process) Metals (reduction of the oxide ore)
Hydrogen Hydrotreating Hydrocracking of petroleum fractions Hydrogenations in the petroleum refining and petrochemical industry
H2 production process
CO + H2O CO2 + H2
= 41.1 kJ/mol
10 8 6
ln Kp
KP
Thermodynamically, the efficiency of the WGS reaction is maximized at low temperature, high water and low hydrogen concentration.
Temperature ( C)
Variation of the equilibrium constant of the WGS reaction with temperature
ln( K eq ) =
CO + H2O CO2 + H2
= 41.1 kJ/mol
3%CO + 10%H2O
100
Conversion of CO (%)
+ 6%CO2 + 20%H2
3% CO-10% H2O 3% CO-10% H2O-6% CO2 3% CO-10% H2O-20% H2 3% CO-10% H2O-20% H2-6% CO2
+ 6%CO2 + 20%H2
500
500
Temperature ( C)
CO levels typically achieved at the exit of the HTS and LTS reactors
Temparature ( C)
CO + H2O CO2 + H2
= 41.1 kJ/mol
4 3 2
LT shift
HT shift
500
HT CO shift LT CO shift
Temperature ( C)
CO levels typically achieved at the exit of the HTS and LTS reactors
WGS reactors
CO + H2O CO2 + H2
= 41.1 kJ/mol
Water gas
WGS reactors
CO + H2O CO2 + H2
= 41.1 kJ/mol
Water gas
HT CO shift
LT CO shift
WGS reactors
The commercially available catalysts are applied in the form of pellets, containing 8-12% Cr2O3, and small amounts of CuO (~2%) as an activity and selectivity enhancer.
Effects of promotion of Fe-Cr oxide catalyst on CH4 formation and C2+ hydrocarbon production
Ratnasamy and Wagner, Chem. Rev. 51 (2009) 325-440
The commercially available catalysts are applied in the form of pellets, containing 8-12% Cr2O3, and small amounts of CuO (~2%) as an activity and selectivity enhancer. The catalyst is usually unsupported and available commercially in tablet or ring form. Major drawbacks (a) Toxicity of the water-soluble Cr6+ ions (b) Low volumetric catalytic activity (GHSV= 10000-15000 h-1), especially at low temperatures where CO conversion is favored thermodynamically.
Special care should be taken to avoid further reduction of the active phase (Fe3O4) toward lower oxides, carbides or metallic Fe. Metallic Fe catalyzes the unwanted methanation and Fischer-Tropsch reactions
= 206.2 kJ/mol
R=
When R < 1.2, there are usually no problems related to reduction of magnetite. The opposite is true for R > 1.6. The activated Fe3O4 catalyst is pyrophoric. Upon exposure to air, the catalyst must be re-reduced and stabilized by surface oxidation using an inert gas with low concentration of oxygen. Fe2O3-Cr2O3 catalysts have a lifetime of 3-5 years depending, mainly, on the temperature of operation.
CuO-ZnO-Al2O3
WGS reactors
HT CO shift
LT CO shift
WGS reactors
Cu/Cu+ 2 + Red CO + Ox
CO2 + 2
Metal/metal oxide
steam
steam
8-10% CO
3-5% CO
0.3-1% CO 0.3-
CO+H2O
CO2+H2
CO+H2O
CO2+H2
T= 350 - 400OC
T= 190 - 240OC
air
Electricity
PEM
Heat
Preferential oxidation of CO
CO + 1/22
CO2
T=120-150OC
Advantages of noble metal catalysts High activity at a wider temperature range No need for activation prior to use No degradation on exposure to air or temperature cycles Availability of wash-coating technologies, which may result in - reduced size and weight - improved ruggedness
Identification of the key parameters which determine catalytic activity of supported noble metal catalysts
Effect of the nature of the support Effect of the nature of the dispersed metallic phase Effect of addition of alkali promoters Effect of metal loading and crystallite size Effect of primary crystallite size of the support
To develop active, selective and stable LT-WGS catalysts suitable for Fuel Cell applications
Catalysts
All catalysts were prepared with the wet impregnation method, followed by reduction with H2 at 300oC.
x% Me/MOx
Commercial oxide powders used as supports Metal precursors (NH3)2Pt(NO2)2 Ru(NO)(NO3)3 (NH3)2Pd(NO2)2 Rh(NO3)3 Reducible oxides CeO2 (3.3 m2/g) TiO2 (50 m2/g) MnO (0.4 m2/g) YSZ (12 m2/g) La2O3 (7.0 m2/g) Irreducible oxides Al2O3 (83 m2/g) MgO (22 m2/g) SiO2(144 m2/g)
Conversion of CO (%)
80
60
40
The catalytic performance of Pt is improved significantly when supported on reducible rather than on irreducible metal oxides.
20
Experimental conditions
Temperature range: 150 550oC Mass of catalyst: 100 mg Particle size: 0.18 < dp < 0.25 mm Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O (balance He)
500
Temperature ( C)
WGS activity of Pt catalysts supported on commercial oxide supports.
0.5%Pt/MOx
MnO
1
SiO2 MgO
TOF (s )
The TOF of Pt supported on TiO2, CeO2 and La2O3 is 1-2 orders of magnitude higher than that of Pt supported on irreducible oxides. For example, at 250oC, TOF of Pt/TiO2 is:
La2O3
-1
0.1
Al2O3
TiO2 CeO2
~ 90 times higher than that of Pt/SiO2 ~ 22 times higher than that of Pt/Al2O3.
YSZ
1.8
2.0
-1
2.2
2.4
1000/T (K )
Turnover frequencies (TOF) of Pt catalyst dispersed on the indicated metal oxides
0.5%Pt/MOx
MnO
Ea
(kcal/mol)
Dispersion %
1
SiO2 MgO
TOF (s )
-1
18 24 49 54 62 66 86 100
0.1
Al2O3
TiO2 CeO2
YSZ
1.8
2.0
-1
2.2
2.4
1000/T (K )
Turnover frequencies (TOF) of Pt catalyst dispersed on the indicated metal oxides
0.5%Ru/MOx
100
1
TiO2 CeO2 YSZ Al2O3
Conversion of CO (%)
80
-1
60
TOF (s )
0.1
40
TiO2
20
YSZ
500
1.6
1.7
1.8
1.9
-1
2.0
2.1
Temperature ( C)
Catalytic performance of Ru supported on selected commercial oxides.
1000/T (K )
Arrhenius plot of TOFs of Ru dispersed on the indicated oxides
0.5%M/TiO2
100
0.5%M/TiO2
Conversion of CO (%)
80 60
Rh
TOF (s )
Ru Pd
0.1
Pt
40 20
Pd Ru
-1
Pt
0.01
Rh
1.4 1.6 1.8 2.0
-1
500
2.2
2.4
Temperature ( C)
Effect of reaction temperature on the conversion of CO over Pt, Rh, Ru and Ru catalysts supported on TiO2.
1000/T (K )
Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on TiO2
0.5%M/TiO2
Ru Pd
0.1
Pt
0.01 1.4 1.6 1.8 2.0
-1
Rh
2.2 2.4
1000/T (K )
Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on TiO2
0.5%M/CeO2
Ea= 24 kcal/mol
1
0.5%M/TiO2
Pd
TOF ( s )
TOF (s )
-1
-1
Rh Pt
Ru Pd
0.1
0.1
Pt
0.01 1.4 1.6 1.8
Ru
2.0
-1
0.01
2.2 2.4
Rh
1.4 1.6 1.8 2.0
-1
2.2
2.4
1000/T (K )
Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on CeO2
1000/T (K )
Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on TiO2
Conversion of CO (%)
-1
1E-5
-1
500
1.6
1.8
2.0
-1
2.2
2.4
Temperature ( C)
1000/T (K )
Conversion of CO at a given temperature increases significantly with increasing Pt loading in the range of 0.1 5.0%. The activation energy of the reaction does not practically change.
<16.2 (nm)
Reaction rate does not depend on Pt loading and crystallite size but only on the amount of exposed surface metal atoms. The rates of transfer of catalytically active species to or from the support are fast, compared to the overall reaction rate.
TOF (s )
-1
0.1
0.01 1.4
1.6
1.8
2.0
-1
2.2
2.4
1000/T (K )
TOFs of CO conversion obtained over Pt/TiO2 catalysts of variable metal loading and crystallite size
Pt/CeO2
TOF (s )
TOF (s )
0.1
1
-1
-1
0.1
0.01
2.4
1.4
1.6
1.8
2.0
2.2
-1
2.4
1000/T (K )
1000/T (K )
TOF does not depend on the structural and morphological characteristics of the dispersed metal, including loading, dispersion and mean crystallite size.
UV
(204) (215)
(301)
PC
100 9 159
P25 AT
75 23 41 100 30 8
Intensity
(213)
(116) (220)
100 9 238
AT
(110)
(101) (111)
P25 UV PC
20
30
40
50
60
70
80
UV: Hombikat UV100, Sachtleben Chemie PC: PC-500, Millenium Chemicals P25: P-25, Degussa AT: AT-1, Millenium Chemicals
Conversion of CO (%)
80
60
40
20
The catalytic performance of Pt is improved when supported on TiO2 with small primary crystallite size (high surface area).
0 500
Temperature ( C)
Effect of the type of the TiO2 support on the catalytic performance of dispersed Pt.
16 nm
25 TOF (s )
1
-1
18
UV
16
35
14
PC
12
P25
0
2.2 2.4
10 15 20 25 30 35
1000/T (K )
Reaction rate per surface Pt atom increases by more than two orders of magnitude (a factor of 120 at 250C) by decreasing the primary crystallite size of the TiO2 carrier from 35 to 16 nm. This is accompanied by a decrease of the apparent activation energy of the reaction from 16.9 to 11.9 kcal/mol.
18
TOF at 250 C (s )
-1
Why ?
Redox mechanism The strong dependence of TOF on the type of TiO2 support employed may be related to the effect of TiO2 crystallite size on its reducibility. It has been reported that reducibility of small oxide clusters depends on its size (at least for CeO2 and La2O3)
R.J. Gorte and coworkers
J. Phys. Chem. 100 (1996) 18128 J. Phys. Chem. 100 (1996) 785 Appl. Catal. B 17 (1998) 101
Associative mechanism Structural characteristics of TiO2 may influence the type, number, density and reactivity of surface hydroxyl groups, which play a key role in the formation of formate-type intermediates. Hydroxyl concentration on TiO2 surface decreases with increasing crystallite size.
PtOx TiO2
Pt TiO2-x
Ti3+ + OH-
H2 consumption
UV
P25 AT
Temperature ( C)
H2-TPR over preoxidized Pt/TiO2 catalysts
Oxidizing atmosphere
Peak (cm-1) 485 398 516 640 Assignment
AT
(e)
(*)
(*)
P25 P25 PC PC
SiO2 (reactor)
(d) (c)
UV
UV
SiO2
}
}
TiO2 (anatase)
(b) (a)
SiO2
800 600 400
-1
1000
200
447 612
TiO2 (rutile)
In situ Raman spectra obtained over preoxidized Pt/TiO2 catalysts under O2 flow at 30oC
H2 reduction
Peak (cm-1) 355 315 270 Assignment
350 C 250 C
Ti2O3
150 C 150 C
30 C SiO2 SiO
30oC
TiO2
30oC
2
150-250oC
800 600 400
-1
Ti2O3
1000
200
350-450oC
In situ Raman spectra obtained upon exposure of the Pt/TiO2 catalysts to H2/N2 mixture at 30-450 oC.
P25 PC
P25
(c)
460
UV
dTiO2
PC (b)
(a) UV
T= 150oC
800 600 400
-1
1000
200
In situ Raman spectra obtained upon exposure of the indicated Pt/TiO2 catalysts to H2/N2 mixture at 150 oC.
400
(*)
200
P25 PC
P25
(c)
440
(B)
UV
355 315270
PC
(b)
dTiO2
UV
(a)
CO2 or H2 production
The reducibility of Pt/TiO2 catalysts increases with decrease of particle size of the support.
UV
P25 AT
Temperature ( C)
CO-TPR over preoxidized Pt/TiO2 catalysts
100
0.5%Pt /10%MOx/Al2O3
Co Ni Ti Cr Mn Cu
Conversion of CO (%)
80 60 40 20 0 200 250
Fe Pt/Al2O3
300
350
400
o
450
500
Temperature ( C)
Conversion of CO as a function of reaction temperature obtained over 0.5%Pt/MOx/Al2O3
Mass of catalyst: 100 mg Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O
100
0.5%Pt /10%MOx/TiO2
Nd Ho Y
Conversion of CO (%)
80 60 40 20 Ce Gd Pt/TiO2
Experimental conditions
0 150 200 250 300 350
o
400
450
Temperature ( C)
Conversion of CO as a function of reaction temperature obtained over 0.5%Pt/MOx/TiO2
Mass of catalyst: 100 mg Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O
60
Conversion of CO (%)
40
20
Experimental conditions
0 200 250 300 350 400
o
450
500
Temperature ( C)
Conversion of CO as a function of reaction temperature obtained over Pt catalysts supported on mixed oxides
Mass of catalyst: 100 mg Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O 6% CO2 + 20% H2
Volcano-type correlation between TOF of metals and their respective CO heats of adsorption.
Grenoble, Estadt, Ollis, J. Catal. 67 (1981) 90.
alkali : Pt = 1:1
1E-4
80 60 40 20 0
alkali (wt. %) 0.0 alkali 0.34 Cs 0.10 K 0.018 Li 0.06 Na
o
rCO(mol.gcat s )
1E-5
alkali (wt. %) 0.0 % alkali 0.34% Cs 0.10% K 1E-6 0.018% Li 0.06% Na
1.8
2.0
2.2
-1
Temperature ( C)
1000/T(K )
Conversion of CO (%)
rCO(mol.gcat s )
-1 -1
1E-6
Temperature ( C)
Effect of addition of Cs on the catalytic performance of 0.5%/TiO2 catalysts
500
1000/T (K )
Arrhenius plot of reaction rates over Cspromoted 0.5%Pt/TiO2 catalysts
x% Cs
1.6 1.2 0.8 220 C 0.4 0.0 0.0 0.2 0.4 0.6
0.4 0.0 0.00
o o
x% Na
1.6 250 C
o
TOF (s )
-1
-1
250 C
TOF (s )
0.05
0.10
0.15
0.20
Cs content (wt.%)
Na content (wt.%)
Promoter Cs
Na
Li
Desorption temperature reflects the chemisorption strength of surface sites The adsorption strength of sites located at the metal-support interface is affected strongly by the presence of alkali promotes
none
100 200 300
o
400
Temperature ( C)
x% Cs
Cs content (wt.%) 0.68
0.12
K
100 ppm
0.34
Na
0.06
Li
0.017
0.17
none
100 200 300
o
400
500
500
Temperature ( C)
Temperature ( C)
Temperature ( C)
Ru/Na-TiO2
wt.% Na 0.2
280
Tmax ( C)
Promoter none Li Na K Cs
0.06 0.0
100 200 300 400
o
500
Temperature ( C)
Pd/Cs-TiO2
wt.% Cs 0.68
3
0.34 0.0
400
500
Temperature ( C)
TOF250 C (s )
o
-1
1.5
1.0
Promoter none Li Na K Cs
0.5
200
220
240
o
260
280
-Hads (CO), kJ/mol
Tmax( C)
Dependence of TOF at 250 oC on the desorption temperature of hydrogen adsorbed at the metal-support interface
500 ppm
0.68% Cs
CO2, H2 production
Alkali promotion of TiO2 affects the chemisorption strength of sites located at the metalsupport interface Alkali promotion also affects the reducibility of TiO2 Qualitatively similar results were obtained upon doping of TiO2 with alkaline earth metals.
0.20% Na
0.12% Na
CO2 H2
Temperature ( C)
CO H2O H2 CO2
CO H2O H2 CO2
Conversion of CO (%)
Conversion of CO (%)
-1
-1
200
250
300
o
350
Temperature ( C)
Temperature ( C)
Effect of space velocity on the catalytic performance of 0.5%Pt/1%CaO-TiO2 catalyst under realistic feed compositions
Conversion of CO (%)
T=300 C
Time-on-stream (h)
Long-term stability tests of Pt/TiO2 and Pt/TiO2(1%CaO) catalysts. Feed composition: 3%CO, 10% H2O, 20%H2, 6%CO2; T= 300 oC; SV= 29000 h-1.
400 C 350 C
1945
o
1525
Formates/carbonates (support)
1384
3711 3667
1690
1566
Absorbance (a.u.)
2120 2175
2062
1625 1690
CO(Pt) + OH(TiO2)
1560
[HCOO](Pt/TiO2)
100 C
1837
(formate mechanism)
75 C
2081 2112 3665 3727 3603
o
1579
2185
1435
25 C
4000
3500 2250
2000
1750
-1
1500
Wavenumber (cm )
FTIR spectra obtained upon heating the preoxidized Pt/TiO2(PC) catalyst under 1%CO flow from 25 to 450 oC.
O C
350 C
Pt-
Pt0 TiO2
iOx
Ti3+
e-
250 C
200 C
1830
100 C
o
2250
1750
Wavenumber (cm )
Pt/TiO2-Na(0.2%)
450 400
Pt/TiO2-Cs(0.68%)
450 400 350 2043 300
2056
350
Absorbance (a.u.)
Absorbance (a.u.)
300
300
Absorbance (a.u.)
250
250
1965 1755
200
150
100 1830 25
2030 1815
100
2025 1820
100
25
25
2200
2000
1800
1600
-1
2200
2000
1800
1600
-1
2200
2000
1800
1600
-1
wavenumber (cm )
wavenumber (cm )
wavenumber (cm )
FTIR spectra obtained following adsorption of CO (1%) at 25oC and subsequent heating at 450C under He flow
Pt/TiO2-WO3(4%)
450 400 350
2050
Pt/SiO2
400 350
Absorbance (a.u.)
Absorbance (a.u.)
X
2077
Absorbance (a.u.)
300
X
2085
250
200
150
150
100 1837
100
1628
25
25
2200
2000
1800
1600
-1
2200
2000
1800
1600
-1
2200
2000
1800
1600
-1
wavenumber (cm )
wavenumber (cm )
wavenumber (cm )
FTIR spectra obtained following adsorption of CO (1%) at 25oC and subsequent heating at 450C under He flow
Pt/YSZ
2045
Adsorption sites at the metal-support interface are directly related with catalytic activity The LF band in the (CO) region is the fingerprint of active WGS catalysts
250
Absorbance (a.u.)
Absorbance (a.u.)
250
200
150
200
2087
1975
1995
100
150
2091
100
1628
25
1827
25
2200
2000
1800
-1
1600
2200
2000
1800
1600
-1
wavenumber (cm )
wavenumber (cm )
FTIR spectra obtained following adsorption of CO (1%) at 25oC and subsequent heating at 450C under He flow
rCO(molgcat s )
-1 -1
rCO(mol.gcat s )
250 C O 230 C
1E-6
1E-6
-1 -1
k = k0 exp ( Ea / RT )
T=210 270 oC
1E-7
1E-7
1E-8 0,00
1E-8
0,02
0,04
0,06
0,04
0,08
2
0,12
0,16
0,20
PCO (atm)
3% CO, 10%H2O, 20%H2, x%CO2
1E-5
PH O (atm)
3% CO, 10%H2O, x%H2, 6%CO2
250 C O 230 C
O
rCO(mol.gcat s )
1E-6
rCO(mol.gcat s )
250 C O 230 C
1E-5
-1 -1
-1 -1
1E-6
1E-7
1E-7
1E-8
0,10
0,15
0,20
0,3
0,4
0,5
PCO (atm)
PH (atm)
k = k0 exp ( Ea / RT )
T=210 270 oC
rCO(molgcat s )
-1 -1
1E-5
3% CO, 10% H2O, 20% H2, 6% CO2 3% CO, 20% H2O, 20% H2, 6% CO2 3% CO, 10% H2O, 40% H2, 6% CO2 1.5% CO, 10% H2O, 20% H2, 6% CO2
a = 0.5 b=1
1E-6
c0 d = 0.7
Ea=10.8kcal/mol
1E-7 1,3 1,4 1,5 1,6 1,7 1,8 1,9 2,0 2,1 2,2
1000/T (K )
Fitting of experimental data to the power-low expression
-1
Conclusions
The WGS technology is well established and widely used in large scale steadystate operations, including manufacture of ammonia, methanol, refinery hydrogen Fischer-Tropsch synthesis, etc. Conventional catalysts and reactors cannot be used in fuel cell applications, mainly due to restrictions in volume and weight. Noble metal catalysts with proper structural and morphological characteristics may be considered as promising candidates as WGS catalysts for fuel cell applications.
References
Effect of morphological characteristics of TiO2-supported noble metal catalysts on their activity for the water-gas shift reaction, P. Panagiotopoulou, D.I. Kondarides, J. Catal. 225 (2004) 327-336. Effect of the nature of the support on the catalytic performance of noble metal catalysts for the Water-Gas Shift Reaction, P. Panagiotopoulou, D.I. Kondarides, Catal. Today 112 (2006) 49-52. Particle size effects on the reducibility of titanium dioxide and its relation to the Water-Gas Shift activity of Pt/TiO2 catalysts, P. Panagiotopoulou, A. Christodoulakis, D.I. Kondarides, S. Boghosian, J. Catal. 240 (2006) 114-125. Water-gas shift activity of doped Pt/CeO2 catalysts, P. Panagiotopoulou, J. Papavasiliou, G. Avgouropoulos, T. Ioannides, D.I. Kondarides, Chem. Eng. J.134 (2007) 16-22. A comparative study of the water-gas shift activity of Pt catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide carriers, P. Panagiotopoulou, D.I. Kondarides, Catal. Today, 127 (2007) 319-329. Effects of alkali additives on the physicochemical characteristics and chemisorptive properties of Pt/TiO2 catalysts, P. Panagiotopoulou, D.I. Kondarides, J. Catal. 260 (2008) 141-149. Kinetic and mechanistic studies of the water-gas shift reaction over Pt/TiO2 catalyst, C.M. Kalamaras, P. Panagiotopoulou, D.I. Kondarides, A.M. Efstathiou J. Catal. 264 (2009) 117-129. Effects of alkali-promotion of TiO2 on the chemisorptive properties and water-gas shift activity of supported noble metal catalysts, P. Panagiotopoulou, D.I. Kondarides, J. Catal. 267 (2009) 57-66. Chemical reaction engineering and catalysis issues in distributed power generation systems, P. Panagiotopoulou, D.I. Kondarides, X.E. Verykios, Ind. Eng. Chem. Res. 50 (2011) 523-530. Effects of promotion of TiO2 with alkaline earth metals on the chemisorptive properties and water-gas shift activity of supported platinum catalysts, P. Panagiotopoulou, D.I. Kondarides, Appl. Catal. B 101 (2011) 738-746.