Morphology Control of Carbon-Free Spinel NiCo2O4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media.

Abstract

Spinel NiCo2O4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo2O4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO2 hard templates, respectively, via hydrothermal methods followed by calcination. Whereas the hard-template yields spherelike dense structures, soft-template assists the formation of a unique nanoneedle cluster assembly containing abundant meso- and macropores. Furthermore, the effect of morphology of NiCo2O4 on their corresponding bifunctional catalytic performance was systematically investigated. The flowerlike nanoneedle assembly NiCo2O4 catalyst via the soft-template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V versus reversible hydrogen electrode, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo2O4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm2 at 1.6 V, showing no activity loss after 20 000 potential cycles (0-1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust three-dimensional architecture with increased surface areas and enhanced mass transfer. Importantly, the soft template can yield a high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.