Aluminum‐Tailored Energy Level and Morphology of Co3−xAlxO4 Porous Nanosheets toward Highly Efficient Electrocatalysts for Water Oxidation

: Tuning energy levels plays a crucial role in developing cost-effective, earth-abundant, and highly active oxygen evolution catalysts. However, to date, little attention has been paid to the effect of using heteroatom-occupied lattice sites on the energy level to engineer electrocatalytic activity. In order to explore heteroatom-engineered energy levels of spinel Co3 O4 for highly-effective oxygen electrocatalysts, herein Al atoms are directly introduced into the crystal lattice by occupying the Co2+ ions in the tetrahedral sites and Co3+ ions in the octahedral sites (denoted as Co2+Td and Co3+Oh , respectively). Experimental and theoretical simulations demonstrate that Al3+ ions substituting Co2+Td and Co3+Oh active sites, especially Al3+ ions occupying the Co2+Td sites, optimizes the adsorption, activation, and desorption features of intermediate species during oxygen evolution reaction (OER) processes. As a result, the optimized Co1.75 Al1.25 O4 nanosheet exhibit unprecedented OER activity with an ultralow overpotential of 248 mV to deliver a current of 10 mA cm-2 , among the best Co-based OER electrocatalysts. This work should not only provide fundamental understanding of the effect of Al-occupied different Co sites in Co3-x Alx O4 composites on OER performance, but also inspire the design of low-cost, earth-abundant, and high-active electrocatalysts toward water oxidation.