Two-Dimensional Metal-Organic Frameworks as Ultrahigh-Performance Electrocatalysts for the Fuel Cell Cathode: A First-Principles Study

Except for metal-organic frameworks (MOFs) with traditional metal-nitrogen sites, MOFs with metal-oxygen sites may also possess good oxygen reduction reaction (ORR) catalytic activity due to their unique electronic structures. Herein, using density functional theory methods, the ORR performances of a series of M-3(HHTT)(2) (where M is a 3d, 4d, or Sd transition metal and HHTT is 2,3,7,8,12,13-hexahydroxytetraazanaphthotetraphene)) catalysts are explored. The binding energy (Delta E-species) results suggest that the binding energy of *OH (Delta E-*(OH)) shows a good linear relationship with the binding energies of *O and *OOH (Delta E-*O and Delta E-*OOH, respectively), indicating that Delta E-*OH can serve as a descriptor to reflect the catalytic activity of M-3(HHTT)(2). In addition, the volcano plot suggests that M-3(HHTT)(2) catalysts with a moderate binding strength of the intermediate *OH (0.6 eV < Delta E-*OH < 0.9 eV) show relatively high ORR activity. Therefore, four highly active ORR catalysts are screened out, namely, Fe-3(HHTT)(2), Co-3(HHTT)(2), Rh-3(HHTT)(2), and Ir-3(HHTT)(2), which possess very small overpotentials of 0.35, 0.24, 0.31, and 0.29 V, respectively. Their potential-determining step is the reduction of O-2 to the intermediate *OOH. It is encouraging that the theoretically lowest overpotential of this kind of catalyst is 0.21 V, which is superior to that on Pt(111). Moreover, Co-3(HHTT)(2) has excellent poisoning-tolerance ability for impurity gases (CO, NO, and SO2) as well as fuel molecules (CH3OH and HCOOH).