Indexed by: Research Article

First Author: Xie,Linfeng

Correspondence Author: Cai,Zhao,Li,Qing

Co-author: Huang,Yunhui,Yang,Feng,Cao,Ruiguo,Tanyuan,Lin,Zijie,Liang,Jiashun,Dr.,He,Zixu,Kun,Wang,Jing

Journal: Angewandte Chemie International Edition

Affiliation of Author(s): 华中科技大学

Place of Publication: 德国

Document Type: Article

Volume: 63

Issue: 44

Page Number: e202407658

ISSN No.: 1521-3773

Key Words: Pd metallene; p-d orbital hybridization; single-atom site; oxygen reduction reaction; Bader charge; zinc-air battery

DOI number: 10.1002/anie.202407658

Date of Publication: 2024-07-29

Impact Factor: 16.1

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 mgPd−1 and 0.86 A mgPd−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 (dPd-*OO) and Bi doping could appropriately reduce the amount of BCT and stretch the dPd-*OO, thus enhancing the ORR activity.