High Catalytic Activity of Co-centered 2D Metal Organic Frameworks toward Bifunctional Oxygen Evolution and Reduction Reactions: Rationalized by Spin Polarization Effect

CoX4 (X = NH, S, and O) motifs have demonstrated their high catalytic activity in the platforms of metal organic frameworks (MOFs), however, the underlying reason is still unrevealed. Herein, we propose monolayers constructed by linking TMN x O4‑x motifs (TM = Fe, Co, Ni, Cu) with trioxotriangulenes (TOTs) as suitable models to clarify the structure–property–performance relationship of 2D MOFs for the oxygen evolution/reduction reaction (OER/ORR). The highly robust catalytic activity of CoN x O4‑x for both the OER and the ORR has been confirmed, even surpassing that of most previously reported 2D MOFs and SACs. This activity is attributed to the moderate interaction between Co and the key intermediate species, which can be modulated by the coordinating atoms. We reveal spin momentum as a reliable activity descriptor in rationalizing the OER/ORR activity, which can be extended to many other 2D MOFs. The elucidated structure–activity relationship is significant for the development of effective bifunctional OER/ORR electrocatalysts.