Use of Raw and Acid-Treated MnO2 as Catalysts for Oxidation of Dyes in Water: A Case Study with Aqueous Methylene Blue

Catalytic wet oxidation has become one of the best options for mineralization of dyes in water. In this work, mineralization of methylene blue in water was tried by using raw and acid-treated (0.50, 0.75, and 1.00 N H₂SO₄) MnO₂ as oxidation catalysts. Fourier transform infrared, scanning electron microscopy, surface area and cation exchange capacity measurements were used to characterize the catalysts. The acid-treated materials showed large increases in surface area while changes in other surface characteristics were moderate in nature. The oxidative destruction of the dye was possible at near room temperature and the process was optimized with respect to interaction time, dye concentration, catalyst loading, pH of the medium, and temperature. The dye (1.0 mg/L) was oxidized to the extents of 88.5%, 96.5%, 96.8%, and 97.7% with corresponding chemical oxygen demand (COD) reduction of 64.7%, 86.4%, 87.2%, and 88.2% by raw MnO₂, 0.50, 0.75, and 1.00 N acid-treated MnO₂(catalyst loading 2.5 g/L), respectively. The reduction in COD indicated oxidation of the dye to simpler organic compounds achieving mineralization to a large extent. The oxidation followed first-order kinetics and the catalysts could be used up to six repeated runs without much change in activity. Analysis of the intermediate products of oxidation helped in proposing the potential pathways for oxidative conversion of methylene blue.