N-doping in Graphdiyne on Embedding of Metals and its Effect in Catalysis

Abstract As a rising-star in carbon materials family, graphdiyne (GDY) has drawn increasing attention for the naturally distributed pores and strong adsorption capacity for metal atoms. Hence it has been regarded as an ideal substrate for building atomic catalysts (ACs). While the effect of N-doping in GDY on the embedding of metal atom still remains to be uncovered. In this study, we systematically studied the doping of one and two N atoms in GDY on the stability, electronic and magnetic properties of transition metal atom (M = Cr, Mn, Fe, Co, Ni and Cu) anchored GDY-N substrates (M@xN-GDY). It was found that the doped sp-N could efficiently increase the electrons mobility by transforming the semi-conductive GDY to metallic, thus significantly boosting the stability of M@GDY by enhancing the binding strength of metal atoms. Moreover, the N-doping can alleviate O2 adsorption on M@GDY to a moderate extent, and therefore benefiting CO oxidization. Specifically, Fe@2N-GDY possesses the best catalytic performance with the lowest CO oxidization energy barrier for the rate determining step of 0.56 eV. Our work not only shed insight on heteroatom doping on the structure-performance relationship of GDY-based catalysts, but also extended the research scope of ACs.