Zhu, XiaofengTan, XinWu, Kuang-HsuHaw, S-CPao, C-WSu, Bing-JianJiang, JunjieSmith, SeanChen, J-MAmal, RoseLu, Xunyu2023-06-191433-7851http://hdl.handle.net/1885/293555A considerable amount of platinum (Pt) is required to ensure an adequate rate for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Thus, the implementation of atomic Pt catalysts holds promise for minimizing the Pt content. In this contribution, atomic Pt sites with nitrogen (N) and phosphorus (P) co-coordination on a carbon matrix (PtNPC) are conceptually predicted and experimentally developed to alter the d-band center of Pt, thereby promoting the intrinsic ORR activity. PtNPC with a record-low Pt content (≈0.026 wt %) consequently shows a benchmark-comparable activity for ORR with an onset of 1.0 VRHE and half-wave potential of 0.85 VRHE. It also features a high stability in 15 000-cycle tests and a superior turnover frequency of 6.80 s−1 at 0.9 VRHE. Damjanovic kinetics analysis reveals a tuned ORR kinetics of PtNPC from a mixed 2/4-electron to a predominately 4-electron route. It is discovered that coordinated P species significantly shifts d-band center of Pt atoms, accounting for the exceptional performance of PtNPC.The work was supported by the Australian Research Council (ARC) under the ARC Training Centre for the Global Hydrogen Economy IC200100023application/pdfen-AU© 2021 Wiley-VCH GmbHatomiccatalystsbandcenterdopingintrinsic activity enhancementxygen reduction reaction202110.1002/anie.2021077902022-04-03