Modulating the Bader Charge Transfer in Single p‐Block Atoms Doped Pd Metallene for Enhanced Oxygen Reduction Electrocatalysis

Abstract Metallene is considered as an emerging family of electrocatalysts due to its atomically layered structure and unique surface stress. Here we propose a strategy to modulate the Bader charge transfer (BCT) between Pd surface and oxygenated intermediates via p ‐ d electronic interaction by introducing single‐atom p ‐block metal (M=In, Sn, Pb, Bi) into Pd metallene nanosheets towards efficient oxygen reduction reaction (ORR). X‐ray absorption and photoelectron spectroscopy suggests that doping p ‐block metals could facilitate electron transfer to Pd sites and thus downshift the d ‐band center of Pd and weaken the adsorption energy of O intermediates. Among them, the developed Bi−Pd metallene shows extraordinarily high ORR mass activity of 11.34 A mg Pd −1 and 0.86 A mg Pd −1 at 0.9 V and 0.95 V in alkaline solution, respectively, representing the best Pd‐based ORR electrocatalysts ever reported. In the cathode of a Zinc‐air battery, Bi−Pd metallene could achieve an open‐circuit voltage of 1.546 V and keep stable for 760 h at 10 mA cm −2 . Theoretical calculations suggest that the BCT between Pd surface and *OO intermediates greatly affects the bond length between them ( d Pd‐*OO ) and Bi doping could appropriately reduce the amount of BCT and stretch the d Pd‐*OO, thus enhancing the ORR activity.