Abstract
Tailoring the local chemistry environment to optimize the geometric and electronic properties of single atom catalysts has received much attention recently. Yet, most efforts have been devoted to establishing the preferable binding between the solid support and the single metal atom. In this work, a hybrid coordination environment was created for Fe-based single atom catalysts, comprising inorganic anchoring site from the support and organic ligands from the precursor. Using N,S co-doped graphene oxide as the support, Fe phthalocyanine was selectively anchored by the N/S sites, creating the unique N/S-Fe-N(4) active sites as evidenced by extended X-ray absorption fine structure and Mössbauer spectrometry. Compared with other analogues with different metal centers or support, N/S-Fe-N(4) showed much improved activity in oxygen reduction reaction, delivering onset and half-wave potentials of 1.02 and 0.94 V. This was superior over the state-of-the-art 20 wt % Pt/C and the classic Fe-N(4) carbon catalysts. Density functional theory calculations revealed that the interaction between phthalocyanine ligands and heteroatom dopant from the support pushed electrons of Fe site to para-position, facilitating O(2) adsorption and activation. This work shows the exciting opportunities of creating a hybrid coordination environment in single atom catalysts and paves a new avenue of improving their catalytic performance.