Confined cobalt single‐atom catalysts with strong electronic metal‐support interactions based on a biomimetic self‐assembly strategy

Abstract Designing high‐performance and low‐cost electrocatalysts for oxygen evolution reaction (OER) is critical for the conversion and storage of sustainable energy technologies. Inspired by the biomineralization process, we utilized the phosphorylation sites of collagen molecules to combine with cobalt‐based mononuclear precursors at the molecular level and built a three‐dimensional (3D) porous hierarchical material through a bottom‐up biomimetic self‐assembly strategy to obtain single‐atom catalysts confined on carbonized biomimetic self‐assembled carriers (Co SACs/cBSC) after subsequent high‐temperature annealing. In this strategy, the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups; meanwhile, the binding‐then‐assembling strategy also effectively suppressed the nonspecific adsorption of metal ions, ultimately preventing atomic agglomeration and achieving strong electronic metal‐support interactions (EMSIs). Experimental characterizations confirm that binding forms between cobalt metal and carbonized self‐assembled substrate (Co–O₄–P). Theoretical calculations disclose that the local environment changes significantly tailored the Co d‐band center, and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release. As a result, the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH (η₁₀ at 288 mV; Tafel slope of 44 mV dec⁻¹), better than other transition metal‐based catalysts and commercial IrO₂. Overall, we presented a self‐assembly strategy to prepare transition metal SACs with strong EMSIs, providing a new avenue for the preparation of efficient catalysts with fine atomic structures.