Improving Electrocatalytic Oxygen Evolution through Local Field Distortion in Mg/Fe Dual-site Catalysts

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-/H2O, 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 (dxy2dxz2dyz1dz21, 2.96 mu B) to low spin (dxy2dxz2dyz2, 0.95 mu B), 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. A regulation of the Fe spin state in a Mg-Fe dual-site catalyst is realized by taking advantage of the local crystal field distortion induced by the large ionic radii difference between Fe/Mg. The as-synthesized catalyst demonstrates a low overpotential of 224 mV at 10 mA cm-2 for oxygen evolution reaction and an electrolysis voltage of only 1.542 V at 10 mA cm-2 for the overall water splitting.image

Automated summary

A spin transition in a Mg-Fe dual-site catalyst is achieved by taking advantage of the local crystal field distortion induced by the large ionic radii difference between Fe/Mg. The as-synthesized catalyst demonstrates a low overpotential of 224 mV at 10 mA cm-2 for oxygen evolution reaction and an electrolysis voltage of only 1.542 V at 10 mA cm-2 for the overall water splitting.