Mastering Surface Reconstruction of Metastable Spinel Oxides for Better Water Oxidation

Developing highly active electrocatalysts for oxygen evolution reaction (OER) is critical for the effectiveness of water splitting. Low-cost spinel oxides have attracted increasing interest as alternatives to noble metal-based OER catalysts. A rational design of spinel catalysts can be guided by studying the structural/elemental properties that determine the reaction mechanism and activity. Here, using density functional theory (DFT) calculations, it is found that the relative position of O p-band and M_Oh (Co and Ni in octahedron) d-band center in ZnCo_{2- x} Ni_x O₄ (x = 0-2) correlates with its stability as well as the possibility for lattice oxygen to participate in OER. Therefore, it is testified by synthesizing ZnCo_{2- x} Ni_x O₄ spinel oxides, investigating their OER performance and surface evolution. Stable ZnCo_{2- x} Ni_x O₄ (x = 0-0.4) follows adsorbate evolving mechanism under OER conditions. Lattice oxygen participates in the OER of metastable ZnCo_{2- x} Ni_x O₄ (x = 0.6, 0.8) which gives rise to continuously formed oxyhydroxide as surface-active species and consequently enhances activity. ZnCo_1.2 Ni_0.8 O₄ exhibits performance superior to the benchmarked IrO₂ . This work illuminates the design of highly active metastable spinel electrocatalysts through the prediction of the reaction mechanism and OER activity by determining the relative positions of the O p-band and the M_Oh d-band center.