Enhanced Activity of C₂N‑Supported\nSingle Co Atom Catalyst by Single Atom Promoter

Abstract

The\nremarkable chemical activity of metal single-atom catalysts\n(SACs) lies in their unique electronic states associated with the\nlow-coordination nature of single-atom sites. Yet, electronic state\nmanipulation normally requires direct contact with other atoms, which\ninevitably changes the low-coordination environment. Herein, we found\nby first-principle calculations that the activity of a Co SAC for\nHCOOH dehydrogenation is appreciably enhanced via electronic state\nmanipulation by a noncontact single atom promoter. A Co atom and a\nSn/Ge/Pb atom are anchored in the same cavity of a graphitic C₂N monolayer. Surprisingly, the nonbonded promoter makes two\nfar splitting spin states of Co almost degenerate via charge redistribution\nof C₂N support. Further, the high-spin Co gives a remarkably\nlow reaction barrier comparable to Pt or Pd catalysts. Our results\ndemonstrate that the activity of a SAC can be tuned via a noncontact\npromoter, casting new insights into electronic state modulation of\nSACs on graphene-like support.