Design of high efficient oxygen reduction catalyst from the transition metal dimer phthalocyanine monolayer

Abstract Due to the large surface area, unique atomic configurations and dispersed metal sites, metal-organic porous monolayers provide a promising strategy for catalysis. Among them, the transition metal dimer phthalocyanine (TM2Pc) monolayer is one of the interesting members. Herein, we studied the oxygen reduction reaction (ORR) of TM2Pc with a series of transition metal dimers (M = Mn-Cu and Ru-Pd) by using the density functional theory. Volcano plot suggests that Fe2Pc has the best ORR activity. This is also confirmed by thermodynamic and kinetic study. Among the studied TM2Pc, Fe2Pc has the highest working potential of 0.98 V (smallest overpotential of 0.25 V), larger than 0.78 V for pure Pt. The energy barrier calculations show that for Fe2Pc, the rate-determining step is the *OOH hydrogenation to form *OH + *OH with an energy barrier of 0.25 eV, much smaller than 0.80 eV for pure Pt. Therefore, Fe2Pc has good ORR activity compared with pure Pt. These results also indicate that the introduction of transition metal dimer on phthalocyanine monolayer would provide a novel strategy for the design of high efficient ORR catalysts.