Preparation of nano manganese oxides by H2O2 in-situ oxidation: effect of regulation mechanism on physical and chemical properties

Abstract

Abstract Manganese oxides showed many special physicochemical properties in many fields such as electrochemistry, adsorption and catalysis. They were widely used in cathode materials for lithium batteries, molecular sieves, catalytic materials and adsorbents. In this paper, in situ oxidation of manganese sulfate solution was conducted with H2O2 as oxidant, and the characterization means of XRD, SEM and BET were used. The purpose was to study the effects of different regulation mechanisms on the physical and chemical properties of manganese oxides such as morphology, phase composition, surface properties and specific surface area. The adsorption properties of γ-MnO2 for Co and Ni in manganese ore leaching solution were tested. The results showed as follows. Under alkaline conditions, the main product of manganese sulfate solution oxidized by H2O2 was Mn3O4 spherical particles with a radius of about 50 nm, these particles had micropores or mesopores, the oxidation reaction rate was rapid, and the specific surface area and N2 adsorption capacity changed with the change of reaction conditions.The temperature had a great influence on the micro morphology of the product.The micro morphology was slender nanorod when the temperature was 20 °C. With the increase of temperature, the length of nanorod became shorter. When the temperature rises to 50 °C, the rod became spherical. When the pH value decreased from 9 to 7, the diffraction peak of each crystal plane in the product Mn3O4 decreased gradually. The diffraction peak of γ-MnO2 appeared when the pH value decreased to 5. All the products were γ-MnO2 when the pH value decreased to 3. With the increase of Mn2+ concentration, the grain size decreased and agglomeration was easy to occur. The optimum conditions were obtained as follows: the temperature was 30 °C, pH was 3, reaction time was 90 min, the mole ration of H2O2 to Mn2+ was 1:1, and Mn2+ concentration was 10 g l−1. Under the optimum conditions, γ-MnO2 with high specific surface area (172.41 m2 g−1) was prepared. This γ-MnO2 has a good adsorption effect on Co and Ni in manganese ore leaching solution, and the adsorption efficiency could be reached 94.75% and 95.67%. This study would provide a reference for the preparation of manganese oxides with different physical and chemical properties.