论文类型：Research Article
第一作者：Xie,Linfeng
通讯作者：Cai,Zhao,Li,Qing
合写作者：Huang,Yunhui,Yang,Feng,Cao,Ruiguo,Tanyuan,Lin,Zijie,Liang,Jiashun,Dr.,He,Zixu,Kun,Wang,Jing
发表刊物：Angewandte Chemie International Edition
所属单位：华中科技大学
刊物所在地：德国
文献类型：Article
卷号：63
期号：44
页面范围：e202407658
ISSN号：1521-3773
关键字：Pd metallene; p-d orbital hybridization; single-atom site; oxygen reduction reaction; Bader charge; zinc-air battery
DOI码：10.1002/anie.202407658
发表时间：2024-07-29
影响因子：16.1
摘要：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.