Enhancing oxygen reduction reaction performance through eco-friendly chitosan gel-assisted molten salt strategy: Small NiCo alloy nanoparticles decorated with high-loading single Fe-NX

Abstract

We developed an effective and eco-friendly strategy using chitosan gel-molten salt to achieve high loading (2.23 At. %) of single Fe-N_X as assistive active sites. These sites were combined with small NiCo alloy NPs distributed on porous carbon aerogels to boost the ORR performance. The FeSAs-NiCo alloy@N-C sphere exhibits exceptional mass activity and specific activity of 3.705 A.mg^-1 and 8.79 mA.cm^-2_(ECSA), respectively, at 0.85 V versus RHE. It has a superior onset potential of 1.08 V versus RHE, surpassing that of its nanoparticle Fe counterpart and NiCo alloy@N-C sphere. The significant improvement in ORR performance of the FeSAs-NiCo alloy@N-C sphere could be attributed to the positive effects of increased lattice strain due to the single atoms of Fe-N_X hybridized with small NiCo alloy NPs. The chitosan gel-assisted molten salt strategy and assistive active sites of Fe-N_X hybridized with NiCo alloy NPs regulate the electronic properties of the FeSAs-NiCo alloy@N-C sphere, both geometrically via lattice strain mismatch and electronically through shifting of the d-band center. This could influence the binding energies for oxygen and/or oxygen reduction intermediate adsorption/desorption. The additional improvement in the ORR performance of the FeSAs-NiCo alloy@N-C sphere also benefits from having a lower electrochemical activation energy.

Keywords: Assistive active sites; Chitosan gel; NiCo alloy; Oxygen reduction reaction; Single atom catalysts.