Theoretical Screening of Highly Efficient Single-Atom Catalysts Based on Covalent Triazine Frameworks for Oxygen Reduction.

Covalent triazine frameworks (CTFs) obtained from the trimerization of aromatic nitriles are expected to be the preferred carrier for single-atom catalysts (SACs). Using density functional theory methods, the oxygen reduction reaction (ORR) performance of a series of 3d, 4d, and 5d transition metals supported on the 6N or 9N pore of the CTF system [M-CTF(6N) or M-CTF(9N)] is explored. At first, 32 kinds of M-CTF(6N) and M-CTF(9N) are screened out with high thermodynamic and electrochemical stability. The binding energy of ORR intermediates and the change of Gibbs free energy in each step of the ORR are calculated. The overpotential of Pd-CTF(6N) is the lowest, which is 0.38 V. Considering that the ORR activity of M-CTFs is mainly limited by the strong binding of *OH, M-CTF(6N) and M-CTF(9N) are further modified by the OH ligand, namely, M-OH-CTF(6N) and M-OH-CTF(9N). After being modified by the OH ligand, due to the weakened binding strength of *OH, all these screened M-CTFs exhibit better ORR activity. Among them, the η values of Cu-OH-CTF(6N), Pd-OH-CTF(6N), Rh-OH-CTF(6N), Ir-OH-CTF(6N), Rh-OH-CTF(9N), and Ir-OH-CTF(9N) are 0.39, 0.38, 0.24, 0.30, 0.31, and 0.33 V, respectively, which possess better ORR activity than the Pt(111) surface (η = 0.45 V). This work highlights the great potential of CTFs as an efficient carrier for SACs.