Water-gas shift: characterization and testing of nanoscale YSZ supported Pt catalysts
Michela Martinelli
1,2
, Gary Jacobs
1
, Uschi M. Graham
1
, Wilson D. Shafer
1
,
Donald C. Cronauer
3
, A. Jeremy Kropf
3
, Christopher L. Marshall
3
, Syed Khalid
4
,
Carlo G. Visconti
2
, Luca Lietti
2
, Burtron H. Davis
1,*
1
Center for Applied Energy Research, University of Kentucky, 2540 Research Park Dr.,
Lexington, KY 40511, USA
2
Politecnico di Milano, Dipartimento di Energia, Piazza Leonardo da Vinci, Milano 20133, Italy
3
Argonne National Laboratory, Argonne, IL 60439, USA
4
National Synchrotron Light Source, Brookhaven National Laboratory, Brookhaven Ave, Upton,
NY 11973, USA
*Corresponding author: burtron.davis@uky.edu ; 859-257-0251
Abstract
Nano-scale Y-doped zirconium oxide materials were prepared with high surface areas (150-200
m
2
/g) and small nano-crystallites (< 8 nm). A combination of XANES and EXAFS was used to
show that ZrO
2
exhibited the tetragonal phase, while the Zr
0.5
Y
0.5
O
1.75
support displayed the
cubic phase. A comparison with undoped zirconia suggests that the Zr
0.9
Y
0.1
O
1.95
support was
tetragonal in structure. A slight increase in d-spacing observed in HR-TEM for the Zr
0.9
Y
0.1
O
1.95
support relative to undoped ZrO
2
, along with a shift to lower 2θ in XRD, provide evidence that
Y-doping caused macrostrain. STEM imaging confirmed that the Pt clusters ranged from 0.5 to
2 nm over all three supports.
Catalyst reducibility was explored by H
2
-TPR, XANES at the Zr K-edge, and TPR-XANES at
the Pt L
III
edge. A higher concentration of surface defects for the 0.5%Pt/Zr
0.9
Y
0.1
O
1.95
catalyst
relative to 0.5%Pt/ZrO
2
was confirmed by DRIFTS of adsorbed CO, while a greater surface
mobility of surface formate was suggested based on forward formate decomposition experiments
in steam. The Y-doped Pt promoted catalysts displayed higher water-gas-shift activity relative to
the 0.5%Pt/ZrO
2
catalyst when the Y content was at or below 50%, with the best catalyst being
0.5%Pt/Zr
0.9
Y
0.1
O
1.95
.
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