Phase tunable nickel doped Mn3O4 nanoparticle synthesis by chemical precipitation: kinetic study on dye degradation.

Abstract

Nickel (Ni) doped Mn3O4 nanoparticles (NPs) were synthesized by a quick and facile chemical precipitation technique to investigate their performance in the degradation of methylene blue (MB) in the absence of light. XRD, FESEM, TEM, AAS, XPS, and FT-IR were used for the investigation of the structural, surface morphological, and elemental composition of Ni doped Mn3O4 NPs. XRD confirms the formation of a tetragonal phase structure of pure Mn3O4 and 1% and 3% Ni doped Mn3O4 NPs. However, mixed phases were found in the case of 5 to 10% Ni doped Mn3O4 NPs. Well-defined spherical-shaped morphology was presented through FESEM. Particle sizes decreased linearly (58.50 to 23.68 nm) upon increasing the doping concentration from 0% (pure Mn3O4) to 7% respectively, and then increased (48.62 nm) in the case of 10% doping concentration. TEM further confirmed spherical shaped 32 nm nanoparticles for 7% Ni doped Mn3O4. The elemental composition and oxidation state of the prepared NPs were confirmed by using XPS spectra. Mixed valence Mn2+ and Mn4+ states were found in pure Mn3O4 and 1% and 3% Ni doped Mn3O4 NPs in the ratio of 2MnO-MnO2. In addition, three different oxidation states Mn2+, Mn3+, and Mn4+ were found in 5 to 10% Ni doped Mn3O4 NPs. Moreover, as a dopant Ni exists as Ni2+ and Ni3+ states in all Ni doped Mn3O4 NPs. The synthesized NPs were then applied as potent oxidants for the degradation of MB at pH 3. With the increase of doping concentration to 7%, the degree of degradation was increased to 79% in the first 10 min and finally, it became about 98%. The degradation of MB follows the pseudo-first-order linear kinetics with a degradation rate of 0.0342 min-1.