Adjusting the local coordination environment of single-atom electrocatalysts is a viable way to improve catalytic performance. The diversity of coordination geometric structures is limited to the traditional in-plane configuration, with only a little consideration paid to out-of-plane configurations due to the lack of suitable carriers and fabrication methods. This study reports out-of-plane coordination of Co-based single-atom catalysts mediated by the conjugated bipyridine-rich covalent organic framework (COF). The bipyridine nitrogen on the COF layer backbone of these catalysts serves as the linker center for cobalt sites anchoring, while the complementary moieties are coordinated at the other side of the Co metal and reside beyond the COF backbone plane, thus yielding out-of-plane coordination. The electrochemical experiments and density functional theory calculations reveal that catalysts with multiple out-of-plane coordinations exhibit different electrocatalytic oxygen evolution activities and catalytic pathways. The out-of-plane coordination enabled by COFs provides a strategy for designing single-atom electrocatalysts, expanding the application of COFs in the field of electrocatalysis.
Keywords: covalent organic framework; electrocatalysts; local coordination environment; oxygen evolution reaction; single metal sites.
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