Engineering Molecular Heterostructured Catalyst for Oxygen Reduction Reaction

Introducing a second metal species into atomically dispersed metal–nitrogen–carbon (M–N–C) catalysts to construct diatomic sites (DASs) is an effective strategy to elevate their activities and stabilities. However, the common pyrolysis-based method usually leads to substantial uncertainty for the formation of DASs, and the precise identification of the resulting DASs is also rather difficult. In this regard, we developed a two-step specific-adsorption strategy (pyrolysis-free) and constructed a DAS catalyst featuring FeCo “molecular heterostructures” (FeCo-MHs). In order to rule out the possibility of the two apparently neighboring (in the electron microscopy image) Fe/Co atoms being dispersed respectively on the top/bottom surfaces of the carbon support and thus forming “false” MHs, we conducted in situ rotation (by 8°, far above the critical angle of 5.3°) and directly identified the individual FeCo-MHs. The formation of FeCo-MHs could modulate the magnetic moments of the metal centers and increase the ratio of low-spin Fe­(II)–N4 moiety; thus the intrinsic activity could be optimized at the apex of the volcano-plot (a relationship as a function of magnetic moments of metal–phthalocyanine complexes and catalytic activities). The FeCo-MHs catalyst displays an exceptional ORR activity (E 1/2 = 0.95 V) and could be used to construct high-performance cathodes for hydroxide exchange membrane fuel cells and zinc–air batteries.