Theoretical study of metal-free catalytic for catalyzing CO-oxidation with a synergistic effect on P and N co-doped graphene

P and N co-doped graphene (PN x C y -G with x = 1, 2, 3 and y = 0, 1, 2) is designed to enhance graphene reactivity with a synergistic effect of the P and N atoms for the CO oxidation reaction, focusing on the influence of the N dopant concentration on graphene. The calculated results indicate that increasing two or three coordinated N to P can facilitate charge transfer from the surface onto O 2 molecules. However, the adsorbed O 2 molecule breaks apart on PN 3 -G surface, affecting CO oxidation performance. Furthermore, PN 2 C 1 -G exhibits excellent catalytic activity towards the oxidation of CO via the ER mechanism, which catalyzes CO oxidation with the rate-determining step of only 0.26 eV for the first and 0.25 eV for the second oxidation at 0 K. Additionally, the catalytic oxidation of PN 2 C 1 -G via Eley–Rideal mechanism prefers to occur at room temperature (298.15 K), with a rate-determining step of 0.77 eV. The reaction rates at 298.15 K is calculated to be 5.36 × 10 16 mol s –1 . The rate constants are obtained according to harmonic transition state theory, which could be supportive for catalytic oxidation of CO on the experiment.