Constructing oxygen vacancies by selective anion doping in high entropy perovskite oxide for water splitting

High entropy perovskite oxide (HEPO) is a potential electrocatalyst for the oxygen evolution reaction (OER), but insufficient activity remains a problem. Oxygen vacancies can activate the lattice oxygen to induce the lattice oxygen-mediated mechanism (LOM), which can avoid the kinetic limitation present in adsorbate evolution mechanism (AEM), thereby improving the OER activity. Herein, we select the appropriate doping element (S) through analysis of ionic radius, electronegativity, and oxygen vacancy formation energy, and report an effective two-step oxygen vacancy strategy for introducing oxygen vacancies into HEPO through electrospinning and sulfurization treatment. This strategy optimizes the eg orbital filling electron number and significantly increases the active area, oxygen vacancy content and electroconductivity. Furthermore, the apparent pH dependence and the TMA+ inhibition phenomenon suggest the involvement of the LOM. Consequently, the resulting S/LMO-E has a lower overpotential (314 mV at 10 mA cm−2) and faster kinetics, and shows excellent stability. Meanwhile, the water splitting is achieved at 1.59 V to afford 10 mA cm−2 current density for S/LMO-E⎪⎢Pt/C, which is smaller than that of RuO2⎪⎢Pt/C (1.62 V). This work provides an attractive OER electrocatalyst for efficient water splitting to produce renewable hydrogen and opens a new way for the design of effective and stable high entropy material electrocatalysts. [Display omitted]