双功能
反键分子轨道
氧气
电子
吸附
化学
结晶学
无机化学
光化学
原子轨道
物理化学
催化作用
物理
有机化学
量子力学
作者
Yunlong Zhang,Bo Liu,Yunkun Dai,Lixiao Shen,Pan Guo,Yunfei Xia,Ziyu Zhang,Fantao Kong,Lei Zhao,Zhen‐Bo Wang
标识
DOI:10.1002/anie.202400577
摘要
Abstract Atomically dispersed metal‐nitrogen‐carbon (M‐N‐C) catalysts have exhibited encouraging oxygen reduction reaction (ORR) activity. Nevertheless, the insufficient long‐term stability remains a widespread concern owing to the inevitable 2‐electron byproducts, H 2 O 2 . Here, we construct Co‐N‐Cr cross‐interfacial electron bridges (CIEBs) via the interfacial electronic coupling between Cr 2 O 3 and Co‐N‐C, breaking the activity‐stability trade‐off. The partially occupied Cr 3d‐orbitals of Co‐N‐Cr CIEBs induce the electron rearrangement of CoN 4 sites, lowering the Co‐OOH* antibonding orbital occupancy and accelerating the adsorption of intermediates. Consequently, the Co‐N‐Cr CIEBs suppress the two‐electron ORR process and approach the apex of Sabatier volcano plot for four‐electron pathway simultaneously. As a proof‐of‐concept, the Co‐N‐Cr CIEBs is synthesized by the molten salt template method, exhibiting dominant 4‐electron selectively and extremely low H 2 O 2 yield confirmed by Damjanovic kinetic analysis. The Co‐N‐Cr CIEBs demonstrates impressive bifunctional oxygen catalytic activity (▵E=0.70 V) and breakthrough durability including 100 % current retention after 10 h continuous operation and cycling performance over 1500 h for Zn‐air battery. The hybrid interfacial configuration and the understanding of the electronic coupling mechanism reported here could shed new light on the design of superdurable M‐N‐C catalysts.
科研通智能强力驱动
Strongly Powered by AbleSci AI