Spin states investigation of delafossite oxides by means of X-ray absorption and photoemission spectroscopy

The d-electron occupancy of transition metal (TM) oxides is one of the most dominant factors in the catalytic activity in the oxygen evolution reaction (OER). To investigate the spin states and the local atomic structure around the TM atoms in delafossite oxides, CuCrO2, CuMnO2, AgFeO2, CuFeO2, AgCoO2, and CuCoO2, were investigated using X-ray absorption spectroscopy. Based on Shannon radii, the extracted TM-O bond lengths showed that TM = Co delafossite oxides are in the low spin (IS) state, while the other delafossite oxides are in the high spin state. Furthermore, non-splitting of Co 3s core level spectra were observed in photoemission spectroscopy, also indicating LS states. In the LS states, Fully-filled t(2g) orbital and its metallic surface states distributing normal to (001) surface is likely associated with high OER activity in TM = O delafossite oxides.