Single-atom Zn with nitrogen defects on biomimetic 3D carbon nanotubes for bifunctional oxygen electrocatalysis

Single atoms catalysts (SACs) have promising development in electrocatalytic energy conversion. Nevertheless, rational design SACs with reversible oxygen electrocatalysis still remain challenge. Herein, we synthesized atomically dispersed Zn with N defect on three-dimensional (3D) biomimetic carbon nanotubes by secondary pyrolysis (Zn-N-C-2), which possesses excellent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalytic activities. The biomimetic 3D structure and unique "leaf-branch" system are beneficial to fully expose the active sites. Density functional theory (DFT) calculations show that Zn-N₃-D can optimize the charge distribution and facilitate electron transfer step of OH*→O*. Zn-N-C-2 exhibits higher ORR activity than commercial Pt/C with a half-wave potential (E_1/2) of 0.85 V and OER overpotential of 450 mV at 10 mA cm^-2. After being assembled into the air cathode of aqueous Zn-air battery (ZAB), it demonstrates superior performances with long-term charge and discharge for more than 200 h. This work not only clarifies the controlled synthesis of N-defects Zn SACs with excellent bifunctional electrocatalyst, but also provide in-depth understanding of structural-performance relationships by regulating local microenvironments.