Acidity of surface-infiltrated binary oxides as a sensitive descriptor of oxygen exchange kinetics in mixed conducting oxides


Nicollet C., TOPARLI Ç. , Harrington G. F. , Defferriere T., Yildiz B., Tuller H. L.

NATURE CATALYSIS, vol.3, no.11, pp.913-920, 2020 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 3 Issue: 11
  • Publication Date: 2020
  • Doi Number: 10.1038/s41929-020-00520-x
  • Title of Journal : NATURE CATALYSIS
  • Page Numbers: pp.913-920

Abstract

Improving the kinetics of O-2 reduction on oxide surfaces is critical in many energy and fuel conversion technologies. Here we show that the acidity scale for binary oxides is a powerful descriptor for tuning and predicting oxygen surface exchange kinetics on mixed conducting oxides. By infiltrating a selection of binary oxides from strongly basic (Li2O) to strongly acidic (SiO2) onto the surface of Pr(0.1)Ce(0.9)O(2-delta)samples, it was possible to vary the chemical surface exchange coefficient k(chem) by 6 orders of magnitude, with basic oxides such as Li2O increasing k(chem) by nearly 1,000 times, with surface concentrations as low as 50 ppm impacting k(chem). Strikingly, although the pre-exponential ofk(chem)scales linearly with the acidity of the infiltrated binary oxide, there is nearly no change in the activation energy. The origin of these dramatic changes is proposed to arise from the systematic increase in electron concentration at the Pr0.1Ce0.9O2-delta surface with the decreasing acidity of the infiltrated binary oxide.