Ag nanoparticle-loaded to MnO2 with rich oxygen vacancies and Mn3+ for the synergistically enhanced oxygen reduction reaction

Abstract

MnO2 is considered to be one of the most promising electrocatalysts for oxygen reduction reactions (ORR) in alkaline media and can be applied to various electrochemical energy conversion and storage devices. However, it is limited by the relatively slow kinetics of the cathodic electrochemical reactions. In addition, it is difficult to control the presence state of Ag during the modification of MnO2. To this end, an efficient ORR electrocatalyst of Ag nanoparticles supported by MnO2 nanorods was successfully synthesized by using NH3·H2O as a complexing agent to inhibit the Ag+ intercalating into the tunnels of MnO2. The half-wave potential (E1/2) and limiting current density (Jlim) of the obtained Ag/MnO2 electrocatalysts are 0.81 V and −5.6 mA cm−2, respectively, showing comparable ORR catalytic activity to commercial Pt/C catalysts. The excellent catalytic performances can be attributed to the presence of abundant oxygen vacancies and Mn3+ species on the MnO2 surface, as well as the synergistic effect between MnO2 substrates and Ag nanoparticles. Among them, oxygen vacancies enhances the adsorption of O2, Mn3+ facilitates the displacement of O22−/OH−, MnO2 inhibits the accumulation of peroxide species to improving the oxygen environment on the Ag surface and Ag accelerates the electron transfer in the whole process. This work provides a useful guide for the design of efficient Mn-based ORR electrocatalysts.