Spinel-Structured High-Entropy Oxide Nanofibers as Electrocatalysts for Oxygen Evolution in Alkaline Solution: Effect of Metal Combination and Calcination Temperature

Defect-engineering is a viable strategy to improve the activity of nanocatalysts for the oxygen evolution reaction (OER), whose slow kinetics still strongly limits the broad market penetration of electrochemical water splitting as a sustainable technology for large-scale hydrogen production. High-entropy spinel oxides (HESOs) are in focus due to their great potential as low-cost OER electrocatalysts. In this work, electrospun HESO nanofibers (NFs), based on (Cr,Mn,Fe,Co,Ni), (Cr,Mn,Fe,Co,Zn) and (Cr,Mn,Fe,Ni,Zn) combinations, with granular architecture and oxygen-deficient surface are produced by calcination at low temperature (600 or 500 degrees C), characterized by a combination of benchtop analytical techniques and evaluated as electrocatalysts for OER in alkaline medium. The variation of HESO composition and calcination temperature produces complex and interdependent changes in the morphology of the fibers, crystallinity and inversion degree of the spinel oxide, concentration of the oxygen-vacancies, cation distribution in the lattice, which mirror on different electrochemical properties of the fibers. The best electrocatalytic performance (overpotential and Tafel slope at 10 mA cm-2: 360 mV and 41 mV dec-1, respectively) pertains to (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4 NFs calcined at 500 degrees C and results from the lower outer 3d-electron number, eg filling closer to its optimal value and higher occupation of 16d sites by the most redox-active species. High-entropy spinel oxide nanofibers based on (Cr,Mn,Fe,Co,Ni), (Cr,Mn,Fe,Co,Zn) and (Cr,Mn,Fe,Ni,Zn) combinations are produced by electrospinning and calcination at 500 or 600 degrees C and evaluated as electrocatalysts for oxygen evolution reaction in alkaline medium. Their electrochemical properties mirror the interdependent changes in the fiber morphology, oxide crystallinity, spinel inversion degree, cation distribution and oxygen-vacancy concentration produced by the variation of metal combination and calcination temperature.image