Transition metal single atom electrocatalysts (SACs) with metal-nitrogen-carbon (M-N-C) configuration show great potential in oxygen evolution reaction (OER), whereby the spin-dependent electrons must be allowed to transfer along reactants (OH- /H2 O, singlet spin state) and products (O2 , triplet spin state). Therefore, it is imperative to modulate the spin configuration in M-N-C to enhance the spin-sensitive OER energetics, which however remains a significant challenge. Herein, we report a local field distortion induced intermediate to low spin transition by introducing a main-group element (Mg) into the Fe-N-C architecture, and decode the underlying origin of the enhanced OER activity. We unveil that, the large ionic radii mismatch between Mg2+ and Fe2+ can cause a FeN4 in-plane square local field deformation, which triggers a favorable spin transition of Fe2+ from intermediate (dxy 2 dxz 2 dyz 1 dz2 1 , 2.96 μB ) to low spin (dxy 2 dxz 2 dyz 2 , 0.95 μB ), and consequently regulate the thermodyna-mics of the elementary step with desired Gibbs free energies. The as-obtained Mg/Fe dual-site catalyst demonstrates a superior OER activity with an overpotential of 224 mV at 10 mA cm-2 and an electrolysis voltage of only 1.542 V at 10 mA cm-2 in the overall water splitting, which outperforms those of the state-of-the-art transition metal SACs.
Keywords: Dual-site; Local field distortion; Overall water splitting; Oxygen evolution reaction; Spin regulation.
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