J. Phys. Chem. C, 128, 1964−1970 (2024)
First-Principles Landscape of Single Atomic Catalysts to Metal Catalysts
Mengjiao Li1,2, Ruihu Lu2, Yu Mao2, Zhixin Hu1 and Ziyun Wang2
1 Center for Joint Quantum Studies and Department of Physics, Institute of Science, Tianjin University, Tianjin 300350, People’s Republic of China.
2 School of Chemical Sciences, University of Auckland, Auckland 1010, New Zealand.
* ziyun.wang@auckland.ac.nz, zhixin.hu@tju.edu.cn
Abstract
Catalyzing oxygen reduction toward water, while generating electrical energy, holds great potential in scaling ecofriendly energy conversation and storage technologies. Current studies have largely focused on single iron atomic catalysts and carbon-supported platinum nanoparticles. Consequently, the exploration of alternative catalysts has been restricted, leaving a wealth of potential undiscovered. Here, we reported a transition from metallic to covalent bonding in carbon-supported transition metal catalysts (TM@Cs), which can explain the formation of two high-activity regions that are centered around iron single atomic catalysts and Pt-NPs. In addition to the classical scaling relation (ΔG*OOH = ΔG*OH + 3.2), we identified a novel scaling relation (ΔG*OOH = 1.55ΔG*OH + 0.77) between *OOH and *OH adsorption energy, dictating the presence of the second oxygen reduction reaction (ORR) pathway. TM@Cs with a higher metal-tocovalent bond ratio demonstrate a strong adsorption, favoring this new ORR pathway and suggesting inferior activity compared to that along the traditional ORR pathway. By increasing the covalent bonds in TM@Cs, it is likely to diminish the adsorption strength, thereby transitioning from this new pathway back to the conventional pathway and showing an activity improvement. This work provides a deep understanding of carbon-supported metal catalysts in designing effective catalysts.
