Well-Defined Co2 Dual-Atom Catalyst Breaks Scaling Relations of Oxygen Reduction Reaction
Journal
Journal of the American Chemical Society
Journal Volume
146
Journal Issue
51
Start Page
35295
End Page
35304
ISSN
0002-7863
1520-5126
Date Issued
2024-12-11
Author(s)
Qidi Sun
Xian Yue
Linke Yu
Fu-Zhi Li
Yiwei Zheng
Meng-Ting Liu
Jian-Zhao Peng
Xile Hu
Lei Li
Jun Gu
Abstract
The 4-electron oxygen reduction reaction (ORR) under alkaline conditions is central to the development of non-noble metal-based hydrogen fuel cell technologies. However, the kinetics of ORR are constrained by scaling relations, where the adsorption free energy of *OOH is intrinsically linked to that of *OH with a nearly constant difference larger than the optimal value. In this study, a well-defined binuclear Co2 complex was synthesized and adsorbed onto carbon black, serving as a model dual-atom catalyst. This catalyst achieved a record half-wave potential of 0.972 V versus the reversible hydrogen electrode in an alkaline electrolyte. Density functional theory simulations and in situ infrared spectroscopy revealed that the dual-atom site stabilizes the *OOH intermediate through bidentate coordination, thereby reducing the free energy gap between *OOH and *OH. By altering the adsorption configuration of *OOH on the dual-atom site, the scaling relations are effectively disrupted, leading to a significant enhancement in ORR activity.
Publisher
American Chemical Society (ACS)
Type
journal article