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Novel Ceria-based

Low-temperature Shift Catalysts
for Fuel Cell Applications
Maria Flytzani-Stephanopoulos
Department of Chemical & Biological Engineering
Tufts University
Medford, Massachusetts

NSF--Fuel Cell Workshop
November 14-15, 2001
INTRODUCTION

™ Advanced low temperature water-gas shift (LTS)
catalysts are needed to supply essentially CO-free H2 for
PEM fuel cells
™ M or MOx/Ceria is a promising alternative to the
commercial LTS catalysts (Cu/ZnO/Al2O3)
„ Highly dispersed M or MOx on ceria
„ Stable in temperature excursions (to 650 oC)
„ Stable in condensed H2O and air
¾ Pt/Ceria1, CuxO/Ceria 2 , Au/Ceria3

1)T. Bunluesin, et al., Appl. Catal. B: 15(1998); 2) Y.Li et al, Appl. Catal. B, 27(2000)
3) Q. Fu, et. al. Catal. Letters, in press
PREPARATION METHOD

Urea Deposition-Precipitation
gelation/coprecipitation (DP)
(UGC)
M(NO3)x HAuCL4 Dropwise adding
(NH4)2Ce(NO3)6 La or Zr(NO3)x
Adjusted by
pH = 8 (NH4)2CO3
Ce(La)Ox
Urea
slurry, 60 oC
100 oC

Calcined S.A. CeO2 Filtered, washed 60 oC
T, oC (m2/g) (nm)
Dried overnight 120 oC
400 160 5
650 100 7 Calcined 400 or 650 oC
800 40 11
CHARACTERIZATION -- HRTEM & XRD

10 nm Au

CeO2

counts (a.u.)
5%AuCe(La)Ox, DP, 400 oC

10%CuCe(La)Ox, UGC 400 oC

Ce(La)Ox, UGC 400 oC
20 25 30 35 40 45 50 55 60
2-Theta

• Both ceria and metal are present as nanoparticles
(Au: 5nm; CuxO: 3 nm; CeO2: 5nm;)
• XPS: gold exists as Au and Au+, Cu exists as Cu2+ and Cu+.
WGS Activity of Au- or CuxO-Ceria
100 12

10%CuCe(La)Ox T = 200 oC
5%AuCe(La)Ox
80 5%AuCe(La)Ox
X-CO to CO2 (%)

Rate, µmol/s*gcat
60 8

40 Cu-ZnO-Al2O3 10%CuCe(La)Ox
Fuel Cell
Bull.
4
20 S.V. = 80, 000 h-1 Ce(La)Ox 30(2000)7
Cu/ZnO/Al O 5%Au/TiO2
2 3
(T-2650)
1%Pt/CeO2
0 This
200 300 400 500 600 work
Temperature, oC 0
Chem. Commun
2%CO-10%H2O-He
1997, 271
Both gold and copper oxide /ceria are promising LTS catalysts
Performance Stability in Hydrogen
50

40 5%AuCe(La)Ox
X-CO to CO2, %

30
10%CuCe(La)Ox

20

T = 250 oC
10
S.V = 15,000 h-1
5%CO-15%H2O-35%H2-He
0
0 20 40 60 80 100
Time-on-stream, h
H2-TPR 20%H2-N2, 50 mL/min, 5oC/min

140
Hydrogen consumption (A.U.)

10%CuCe(La)Ox

97

55
5%AuCe(La)Ox
487
Ce(La)Ox

0 200 400 600 800
o
Temperature, C

Surface oxygen of ceria is dramatically weakened by gold and copper oxide
Oxygen Storage Capacity
10%CO-10%O2, 50mL/min
Typical step sequences in OSC measurement Experimental setup
OSC -- CO2 produced during first CO and O2 steps

First CO step First O2 step

1000 5AuCe(La)Ox 1000

900 900
10CuCe(La)Ox
800

µ mol CO2 produced/gcat
800
Ce(La)Ox
µ mol CO2 produced/gcat

700 700

600 600

500
500
400
400
300
300
200
200
100
100
0
0 350 200
350 200 o
Temperature, C
Temperature, o C

Addition of metal increases the amount of CO2 produced in both
steps.
1st CO step vs. H2-TPR -- Dopant effect

1200 10%CuCe(Zr)Ox H2-TPR
10%CuCe(La)Ox
1000 H2 Consumption,
10%CuCeOx µmol/gcat
800 Sample up to 200 oC
µmolCO2/gcat

CuCe(Zr)Ox 1500
600 CuCe(La)Ox 1376
CuCeOx 1221
400

200

0
350 200 oC
100
Temperature,

The CO2 produced during 1st CO step agrees well with
H2-TPR result, reflecting oxygen availability.
1st O2 step vs. WGS activity -- Dopant effect
5%AuCe(Zr)Ox 100

450
5%AuCe(La)Ox S.V. = 80,000 h-1
5%AuCeOx
400 80 2%CO-10%H2O-He
5Au-Ce(La)Ox
350

X-CO to CO2 %
µ mol CO2 / g Cat

300 60

250 5Au-Ce(Zr)Ox
200 40
5%AuCe(La)Ox
150 5Au-CeOx
100 20
5%AuCe(Zr)Ox
50 5%AuCeOx
0
0
350 200 50 100 150 200 250 300 350
Temperature, Temperature, oC
oC

CO2 produced during 1st O2 step originates from carbon-
containing species left behind in CO step. It correlates well with
the WGS catalyst activity.
Water-gas Shift Mechanism on Ceria
CO + H2O ⇔ CO2 + H2
∆H = -41.2 kJ mol-1; ∆G = -28.6 kJ mol-1
Redox reaction mechanism on ceria-based catalysts:
H2O + [ ]-cat → H2 + O-cat
O-cat + CO → CO2 + [ ]-cat
k1k2PCOPH2O
Rate =
k1PCO + k2PH2O

Eapp(kJ/mol): (CO-rich condition)
Ce(10%La)Ox1: 58.5; 5%CuCe(La)Ox1: 30.4; Pd, Rh, Pt/CeO22: 46.2
1) Y.Li et al, Appl. Catal. B, 27(2000); 2)Bunluesin et al, Appl. Catal. B, 15(1998);
CONCLUSIONS

™ Nanostructured Au- and CuxO-ceria materials are very
attractive LTS catalysts
„ high activity and good stability
™ Gold or copper greatly increases the reducibility of ceria
(from 350-400oC to 40-150 oC)
™ OSC results have identified a strong dopant effect, which
correlates with WGS activity (La > Zr)