Molecular preassembly achieves precise electronic structure modulation of Co active centers for enhanced bifunctional oxygen electrocatalysis.

Developing highly efficient and stable electrocatalysts for the oxygen reduction and oxygen evolution reactions (ORR/OER) is crucial for advancing metal-air batteries. While cobalt based nitrogen doped carbon (Co@NC) materials show promise as bifunctional catalysts, their performance is restricted by the limited tunability of nitrogen coordination alone and an insufficient number of active sites. While coordination environment engineering and interface engineering are common optimization approaches, a single strategy often fails to fine-tune the electronic structure of Co active centers to the optimal state, and thus cannot fully satisfy the requirements of reversible oxygen electrocatalysis in metal-air batteries. To break through this bottleneck, we employ a molecular preassembly strategy that simultaneously achieves uniform heteroatom doping and the construction of tightly coupled Co2P/Co and CeO2/Co dual heterointerfaces from a pre-designed molecular precursor. This design overcomes the limitation of single-strategy electronic modulation, enabling more comprehensive and precise optimization of the electronic structure of the Co active centers in Co@NC materials, coupled with stepwise regulation of oxygen intermediate adsorption. As a result, the as-prepared CeO2/Co2P/Co@PSNC catalyst exhibits excellent bifunctional activity in both aqueous zinc-air batteries and organic lithium‑oxygen batteries.