The spin state of antibonding orbital (e) occupancy in LaCoO is recognized as a descriptor for its oxygen electrocatalysis. However, the Co(III) cation in typical LaCoO (LCO) favors low spin state, which is mediocre for absorbing oxygen-containing groups involved in oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), thus hindering its further development in electrocatalysis. Herein, both experimental and theoretical results reveal the enhancement of bifunctional electrocatalytic activity in LaCoO by N doping. More specifically, electron energy loss spectroscopy and superconducting quantum interference devices magnetic analysis demonstrate that the Co(III) cation in N-doped LaCoO (LCON) achieves a moderate e occupancy (≈1) compared with its low spin state in LaCO. First-principle calculation results reveal that N dopants play a bifunctional role of tuning the spin-state transition of Co(III) cations and increasing the electrical conductivity of LCO. Thus, the optimized LCON exhibits an OER overpotential of 1.69 V at the current density of 50 mA/cm (1.94 V for pristine LCO) and yields an ORR limiting current density of 5.78 mA/cm (4.01 mA/cm for pristine LCO), which offers a new strategy to simultaneously modulate the magnetic and electronic structures of LCO to further enhance its electrocatalytic activity.
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