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

Abstract

The atomic configurations of FeNx 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 FeNx sites. Unveiling the effect of carbon matrix adjacent to FeNx 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 FeN4 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 FeN4 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 FeN4 moieties, hence tailored the adsorption between active centers and oxygen intermediates and altered the rate-determining step.