In-Situ 2p3d Resonant Inelastic X-ray Scattering Tracking Cobalt Nanoparticle Reduction.

In-situ carbon-thermal reduction of cobalt oxide nanoparticles supported on carbon nanotubes was studied by cobalt 2p3d resonant inelastic X-ray scattering (RIXS). The in-situ 2p X-ray absorption spectroscopy (XAS) and RIXS measurements were performed at 500, 600, and 700 °C, where four consistent excitation energies were used for RIXS acquisitions. After 700 °C reduction, the XAS spectrum shows a cobalt metal-like shape, while the RIXS spectra reveal the minority cobalt monoxide phase. The holistic fit on both XAS and RIXS data reveals the respective contributions from metal and monoxide. We show that the relative precision to determine the monoxide content changes from ∼5.6% in XAS results to better than 0.8% in the RIXS analysis, suggesting that RIXS is a useful tool to track the oxidation state of nanoparticles under in situ conditions. We determined a relative radiative ratio () factor of approximately 5, where this factor gives the ratio between the relative strengths of the radiative decay channels compared to the nonradiative channels in CoO and Co metal.