Identifying the impact of the covalent-bonded carbon matrix to FeN4 sites for acidic oxygen reduction

Abstract The atomic configurations of FeN x moieties are the key to affect the activity of oxygen rection reaction (ORR). However, the traditional synthesis relying on high-temperature pyrolysis towards combining sources of Fe, N, and C often results in the plurality of local environments for the FeN x sites. Unveiling the effect of carbon matrix adjacent to FeN x sites towards ORR activity is important but still is a great challenge due to inevitable connection of diverse N as well as random defects. Here, we report a proof-of-concept study on the evaluation of covalent-bonded carbon environment connected to FeN 4 sites on their catalytic activity via pyrolysis-free approach. Basing on the closed π conjugated phthalocyanine-based intrinsic covalent organic polymers (COPs) with well-designed structures, we directly synthesized a series of atomically dispersed Fe-N-C catalysts with various pure carbon environments connected to the same FeN 4 sites. Experiments combined with density functional theory demonstrates that the catalytic activities of these COPs materials appear a volcano plot with the increasement of delocalized π electrons in their carbon matrix. The delocalized π electrons changed anti-bonding d-state energy level of the single FeN 4 moieties, hence tailored the adsorption between active centers and oxygen intermediates and altered the rate-determining step.