Two-dimensional phthalocyanine-based covalent organic frameworks as high-performance electrocatalysts for oxygen reduction and oxygen evolution

It is crucial to use efficient catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in energy conversion devices, aiming to mitigate energy crises. The catalytic activity of MPc-PI-COF-1 and MPc-PI-COF-2 (M = Mn, Fe, Co) towards ORR and OER is investigated systematically based on DFT methods. Different M-N4 sites can adjust the binding strength of oxygen-containing intermediates to effect catalysis activity, while the different linkers have only a minor effect. FePc-PI-COF-1 and MnPc-based COFs have low ORR overpotential (ηORR) values, even lower than Pt(111). For OER, CoPc-based COFs have comparable OER overpotential (ηOER) values to that on RuO2(110). To sum up, MnPc-based COFs are efficient ORR catalysts, and CoPc-based COFs have high OER activity. FePc-PI-COF-1 could be served as an effective bifunctional catalyst with a ηORR value of 0.38 V and ηOER value of 0.56 V. Moreover, FePc-PI-COF-1 exhibits exceptional resistance to various impurity gases, indicating its strong tolerance against poisoning. These study offer valuable insights for the rational discovery of reticular materials as highly efficient electrocatalysts.