LAUSR

Abstract The design of new cathode materials is vital to develop the high performance proton exchange membrane fuel cell (PEMFC). The adsorption properties of the species involved in the oxygen reduction reaction (ORR) and several ORR mechanisms on phosphorene were presented with using the first-principle calculations. Results show that the H adsorption is more preferable than O2, and the OOH spontaneously form from the adsorbed H and O2. The HOOH from the hydrogenation of the OOH species could be further hydrogenated into OH and H2O, and the OH would be finally hydrogenated into the (second) H2O. The reaction barrier of rate-determining step is 1.02 eV. Moreover, the presented kinetic processes are confirmed by the thermodynamic simulation from Gibbs free energy calculations and molecular dynamics simulations. These results indicate that phosphorene as one of new 2D materials could be a promising metal free cathode material for PEMFC.