Probing the active site in single-atom oxygen reduction catalysts via operando X-ray and electrochemical spectroscopy.
Hsiang-Ting LienSun-Tang ChangPo-Tuan ChenDeniz P WongYu-Chung ChangYing-Rei LuChung-Li DongChen-Hao WangKuei-Hsien ChenLi-Chyong ChenPublished in: Nature communications (2020)
Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt-nitrogen-carbon (Co-Nx/C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. Our results revealed the preferential adsorption of oxygen at the Co2+ center, with end-on coordination forming a Co2+-oxo species. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co-O species formation. These experimental findings, corroborated with first-principle calculations, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high-performance electrocatalysts for fuel cell applications.
Keyphrases
- transition metal
- high resolution
- single molecule
- low cost
- metal organic framework
- molecular dynamics
- highly efficient
- ionic liquid
- reduced graphene oxide
- gold nanoparticles
- single cell
- solid state
- electron transfer
- dual energy
- molecularly imprinted
- working memory
- room temperature
- mesenchymal stem cells
- magnetic resonance
- bone marrow
- carbon dioxide