A Novel Analysis of Transient Isothermal 18O Isotopic Exchange on Commercial CexZr1−xO2-Based OSC Materials
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A novel methodology for the analysis of 18O2-transient isothermal isotopic exchange (TIIE) response curves obtained over commercial mixed metal oxides upon the gas switch 16O2/Ar (30 min) → 18O2/Kr/Ar (t) at constant T in a flow CSTR micro-reactor in the absence of external and internal mass transport resistances and grain boundary effects, is presented for the first time. The specific aim of this analysis was to derive quantitative descriptors of the16O/18O exchange under pseudo-equilibrium conditions for the transfer rates of oxygen between the gas and solid phases, enabling the assessment of differences in the kinetics of bulk oxygen diffusion over a series of commercial OSC materials used in various catalytic applications (e.g. TWC), without the need of performing any mathematical and kinetic modelling of the surface/bulk oxygen diffusion processes. Based on these descriptors, commercial OSC mixed metal oxides prepared by the same chemical synthesis route but varying the value of one of the synthesis parameters, and having the same at.% composition, were proved to possess largely different transient kinetic rates and other features of the transient response curves of 16O/18O exchange strongly related to the bulk oxygen diffusion in the solids. This novel 18O2-TIIE analysis is quick and provides a reliable means for proving or disproving likely infringement of patented commercial mixed metal oxides OSC materials.
KeywordsOSC Transient isothermal oxygen isotopic exchange Bulk oxygen diffusion
The Research Committee of the University of Cyprus, and the project “Materials and Processes for Energy and Environment Applications” (MIS 5002556) implemented under the “Action for the Strategic Development on the Research and Technological Sector”, funded by the Operational Program “Competitiveness, Entrepreneurship and Innovation” (NSRF 2014–2020) and co-financed by Greece and the European Union (European Regional Development Fund), are acknowledged for financial support. Dr. Klito Petallidou is acknowledged for the powder XRD work.
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