Zirconium-Regulation-Induced Bifunctionality in 3D Cobalt–Iron Oxide Nanosheets for Overall Water Splitting

The design of high-efficiency non-noble bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is paramount for water splitting technologies and associated renewable energy systems. Spinel-structured oxides with rich redox properties can serve as alternative low-cost OER electrocatalysts but with poor HER performance. Here, zirconium regulation in 3D CoFe₂O₄ (CoFeZr oxides) nanosheets on nickel foam, as a novel strategy inducing bifunctionality toward OER and HER for overall water splitting, is reported. It is found that the incorporation of Zr into CoFe₂O₄ can tune the nanosheet morphology and electronic structure around the Co and Fe sites for optimizing adsorption energies, thus effectively enhancing the intrinsic activity of active sites. The as-synthesized 3D CoFeZr oxide nanosheet exhibits high OER activity with small overpotential, low Tafel slope, and good stability. Moreover, it shows unprecedented HER activity with a small overpotential of 104 mV at 10 mA cm⁻² in alkaline media, which is better than ever reported counterparts. When employing the CoFeZr oxides nanosheets as both anode and cathode catalysts for overall water splitting, a current density of 10 mA cm⁻² is achieved at the cell voltage of 1.63 V in 1.0 m KOH.