Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations

Title
Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations
Authors
지호일Timothy C. DavenportSossina M. HaileChirrangjeevi Balaji Gopal
Issue Date
2016-08
Publisher
Physical chemistry chemical physics : PCCP
Citation
VOL 18, NO 31-21561
Abstract
The redox kinetics of undoped ceria (CeO2-delta) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 <= log(pO(2)/atm) <= -2.0 at 1400 degrees C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant k(chem) is found to obey the correlation log(k(chem)/cms(-1)) = (0.84 +/- 0.02) x log(pO(2)/atm) - (0.99 +/- 0.05) and increases with oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.
URI
http://pubs.kist.re.kr/handle/201004/66674
ISSN
1463-9076
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KIST Publication > Article
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