Carbon-Free, Binder-Free MnO₂@Mn Catalyst for Oxygen Reduction Reaction

Reasonable design and feasible preparation of low-cost and stable oxygen reduction reaction (ORR) catalysts with excellent performance play a key role in the development of fuel cells and metal–air batteries. A 3D porous superimposed nanosheet catalyst composed of metal manganese covered with MnO₂ nanofilms (P-NS-MnO₂@Mn) was designed and synthesized by rotating disk electrodes (RDEs) through one-step electrodeposition. The catalyst contains no carbon material. Therefore, the oxidation and corrosion of the carbon material during use can be avoided, resulting in excellent stability. The structural and composition characterizations indicate that the nanosheets with sharp edges exist on the surface of the wall surrounding the macropore (diameter ∼ 5.07 μm) and they connect tightly. Both the nanosheets and the wall of the macropore are composed of metal manganese covered completely with MnO₂ film with a thickness of less than 5 nm. The half-wave potential of the synthesized P-NS-MnO₂@Mn catalyst is 0.86 V. Besides, the catalyst exhibits good stability with almost no decay after a 30 h chronoamperometric test. Finite element analysis (FEA) simulation reveals the high local electric field intensity surrounding the sharp edges of the nanosheets. Density functional theory (DFT) calculations reveal that the novel nanosheet structure composed of MnO₂ nanofilms covered on the surface of the Mn matrix accelerates the electronic transfer of the MnO₂ nanofilms during the ORR process. The high local electric field intensity near the sharp edge of the nanosheets effectively promotes the orbital hybridization and strengthens the adsorbing Mn–O bond between the active site Mn in the nanosheets and the intermediate OOH* during the ORR process. This study provides a new strategy for preparing transition metal oxide catalysts and a novel idea about the key factors affecting the catalytic activity of transition metal oxides for the ORR.