Manganese-based oxides are promising in electrocatalytic oxygen reduction reaction, but the activity and conductivity need further improvement. Herein manganese defected Mn3O4 was fabricated by solvothermal synthesis of manganese glycerate and then thermal calcination. The experimental and computational results reveal that manganese defects in Mn3O4 modify the electronic structure to improve conductivity and electronic delocalization, which helps to expose more surface Mn3+ as major active site, thereby facilitating O2 activation and OH* desorption, and reducing the Gibbs free energy variation in the rate-limiting step of ORR. Accordingly, the onset potential, half-wave potential and limiting current density of manganese defected Mn3O4 are 0.87 V, 0.65 V and 5.0 mA cm-2, better than that of normal Mn3O4 (0.77 V, 0.62 V and 2.6 mA cm-2). This work provides an effective approach to tune the defects and electronic structures of Mn3O4 for better electrochemical activity.

锰基氧化物在电催化氧还原反应中很有前景，但活性和电导率有待进一步提高。在此，通过溶剂热合成甘油酸锰并进行热煅烧来制备锰缺陷的Mn3O4。实验和计算结果表明，Mn3O4中的锰缺陷修饰了电子结构，从而改善了电导率和电子离域化，从而有助于暴露更多的表面Mn3 +作为主要活性位点，从而促进O2活化和OH *的解吸，并减少了吉布斯自由能的变化。在ORR的限速步骤中。因此，锰缺陷的Mn3O4的起始电势，半波电势和极限电流密度分别为0.87 V，0.65 V和5.0 mA cm-2，优于普通的Mn3O4（0.77 V，0.62 V和2.6 mA cm-2）。 。