Preferential Co substitution on Ni sites in Ni-Fe oxide arrays enabling large-current-density alkaline oxygen evolution

在Ni-Fe氧化物阵列中,Co优先取代Ni位点,从而实现大电流密度碱性析氧反应。

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Abstract

Developing low-cost and high-activity transition metal oxide electrocatalysts for an efficient oxygen evolution reaction (OER) at a large current density is highly demanded for industrial application and remains a big challenge. Herein, we report vertically aligned cobalt doped Ni-Fe based oxide (Co-NiO/Fe(2)O(3)) arrays as a robust OER electrocatalyst via a simple method combining hydrothermal reaction with heat treatment. Density functional theory calculation and XRD Rietveld refinement reveal that Co preferentially occupies the Ni sites compared to Fe in the Ni-Fe based oxides. The electronic structures of the Co-NiO/Fe(2)O(3) could be further optimized, leading to the improvement of the intrinsic electronic conductivity and d-band center energy level and the decrease in the reaction energy barrier of the rate-determining step for the OER, thus accelerating its OER electrocatalytic activity. The Co-NiO/Fe(2)O(3) nanosheet arrays display state-of-the-art OER activities at a large current density for industrial demands among Fe-Co-Ni based oxide electrocatalysts, which only require an ultra-low overpotential of 230 mV at a high current density of 500 mA cm(-2), and exhibit superb durability at 500 mA cm(-2) for at least 300 h without obvious degradation. The Co-NiO/Fe(2)O(3) nanosheet arrays also have a small Tafel slope of 33.9 mV dec(-1), demonstrating fast reaction kinetics. This work affords a simple and effective method to design and construct transition metal oxide based electrocatalysts for efficient water oxidation.

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