Identifying the impact of the covalent-bonded carbon matrix to FeN(4) sites for acidic oxygen reduction

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.