One-Pot Synthesis of NiCo₂S₄ Hollow Spheres via Sequential Ion-Exchange as an Enhanced Oxygen Bifunctional Electrocatalyst in Alkaline Solution

Abstract

The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are considered to be cornerstones of many energy conversion and storage technologies. It is difficult studying high-performance nonprecious materials as cost-effective bifunctional electrocatalysts for both the OER and ORR in future practical applications. In this study, NiCo₂S₄ hollow spheres (NiCo₂S₄ HSs) were fabricated via an effective and facile one-pot "green" approach in an N, N-dimethylformamide-ethylene glycol binary solution. The obtained NiCo₂S₄ HSs had a high specific surface area as well as numerous active sites and showed a remarkable catalytic performance and durability toward both the OER and ORR in an alkaline electrolyte. For the ORR, NiCo₂S₄ HSs exhibited a positive half-wave potential of 0.80 V and demonstrated outstanding stability and enhanced methanol tolerance. For the OER, NiCo₂S₄ HSs presented a low overpotential (400 mV) at a current density of 10 mA cm^-2, small Tafel slope, and excellent stability in 0.1 M KOH. Moreover, regarding the overall electrocatalytic activity, the potential difference of NiCo₂S₄ HSs was 0.83 V, surpassing that of NiCo₂S₄ nanoparticles, binary counterparts (CoS, NiS), and most highly active bifunctional catalysts described in the literature. The superior catalytic performance of NiCo₂S₄ HSs is mainly ascribed to its unique hollow structure, which increases molecular diffusion and adsorption, as well as the synergistic effect of Ni and Co, which offers richer redox reaction sites. Importantly, this strategy may facilitate the design and preparation of excellent bifunctional nonprecious metal electrocatalysts in various domains.