Localised Thermal Levering Events Drive Spontaneous Kinetic Oscillations in Catalysis

Abstract Unravelling kinetic oscillations, that arise spontaneously during catalysis, has been a challenge for decades; not only to understand these complex phenomena but also in an aim to exploit kinetics at the peak maxima. In this study, through temporally and spatially resolved operando analysis, we demonstrate that CO oxidation over Rh/Al2O¬3 involves a series of thermal levering events – CO oxidation, Boudouard reaction, and carbon combustion – which drive oscillatory CO2 formation. This catalytic sequence relies on harnessing localised temperature episodes at the nanoparticle level that provides an efficient means to drive unfavourable reactions, where the macroscopic conditions do not allow. This insight provides a new basis for coupling thermal events at the nanoscale for efficient harvesting of energy, essential for emerging net-zero carbon technologies.