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Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d ‐Band Center via Local Coordination Tuning
Author(s) -
Zhu Xiaofeng,
Tan Xin,
Wu KuangHsu,
Haw ShuChih,
Pao ChihWen,
Su BingJian,
Jiang Junjie,
Smith Sean C.,
Chen JinMing,
Amal Rose,
Lu Xunyu
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202107790
Subject(s) - catalysis , chemistry , oxygen reduction reaction , kinetics , platinum , metal , oxygen reduction , cobalt , nitrogen , nanotechnology , inorganic chemistry , materials science , electrode , physics , electrochemistry , organic chemistry , quantum mechanics
A 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 V RHE and half‐wave potential of 0.85 V RHE . It also features a high stability in 15 000‐cycle tests and a superior turnover frequency of 6.80 s −1 at 0.9 V RHE . 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.