Fabricating Single-Atom Catalysts from Chelating Metal in Open Frameworks

In the present study, a highly efficient strategy is reported using open framework platforms with abundant chelating ligands to fabricate a series of stable metal single-atom catalysts (SACS). Here, the metal ions are initially anchored onto the active bipyridine sites through postsynthetic modification, followed by pyrolysis and acid leaching. The resulting single metal atoms are uniformly distributed on a nitrogen-doped carbon (N-C) matrix. Interestingly, each metal atom is found to be coordinated with five N atoms, in contrast to the average coordination number of four as previously reported. The as-prepared Fe SAC/N-C catalyst exhibits excellent oxygen reduction reaction (ORR) activity (with a half-wave potential of 0.89 V), outstanding stability, and good methanol tolerance. The density functional calculations reveal that the coordinated pyridine can favorably modulate the interaction strength of oxygen on the Fe ion and thus improve the ORR activity. More importantly, it is demonstrated that this strategy can be successfully extended to the preparation of other transition metal SACs, simply by altering the metal precursors used in the metalation step.