Mechanistic insights into temperature hysteresis in CO oxidation on Cu-TiO2 mesosphere

Abstract

This study employs in-situ X-ray absorption spectroscopy (XAS) and operando Raman to explore the reaction mechanism of copper/titanium dioxide microspheres (CuTMS) in CO oxidation. A temperature-dependent hysteresis behavior was observed during catalytic CO oxidation, which can be divided into two distinct regions. In the low-temperature region, the transformation of CuO → Cu2O → Cu2O/Cu on the surface of CuTMS is detected via in-situ XAS, highlighting the pivotal role of surface-adsorbed oxygen in initiating this conversion process. Conversely, in the high-temperature region, analysis of Raman peak areas suggests a variation in the {001} and {101} facets of anatase. Specifically, a decrease in the {001} facets from 17% to 10% indicates TiO2-mediated oxygen transportation, which facilitates the reoxidization of reduced Cu species. This integrated approach showcases significant potential for unraveling the mechanistic studies of catalytic reaction mechanisms in copper/titanium systems, including surface copper valence state changes, oxygen replenishment, and crystal structure distortion.