Bifunctional oxygen reduction/evolution reaction electrocatalysts achieved by axial ligand modulation on...

Exploring efficient and low-cost oxygen reduction and oxygen evolution reaction (ORR/OER) bifunctional catalysts is essential for the development of energy storage and conversion devices. Herein, enlightened by the experimentally synthesized cobalt(II) meso-tetraethynylporphyrins (Co-TEP) molecule, we designed a novel 2D covalent organic framework (COF), namely a 2D Co-TEP monolayer, by dimensional expansion. The 2D Co-TEP monolayer, with Co atoms distributed separately and stabilized by uniform pyrrolic-N coordination, features metal-nitrogen-carbon single-atom catalyst activity and shows tunable catalytic activity for the electrochemical ORR/OER by axial ligand (O, OH, Cl, CN, CH₃, NO, F) modulation. By means of the state-of-the-art constant-potential first-principles computations and microkinetic simulations, we demonstrated that 2D Co-TEP-CN exhibits good ORR/OER performance in both acidic and alkaline conditions. The difference between the onset-potential for the OER and the half-wave potential for the ORR is only 0.85 V at pH = 1, smaller than that of Pt/IrO₂ electrocatalysts. The good electrocatalytic performance is maintained by replacing the center metal atoms with Mn, Fe and/or Ni. Our investigation highlights the role of the pyrrolic-N coordination and the ligands in improving the catalytic activity of 2D COFs and provides new insights into the rational design of efficient bifunctional ORR/OER catalysts.