Mn²⁺ effect on manganese oxides (MnO_x) nanoparticles aggregation in solution: Chemical adsorption and cation bridging

Manganese oxides (MnO_x) and Mn²⁺ usually co-exist in the natural environment, as well as in water treatments for Mn²⁺ removal. Therefore, it is necessary to investigate the influence of Mn²⁺ on the stability of MnO_x nanoparticles, as it is vital to their fate and reactivity. In this study, we used the time-resolved dynamic light scattering technique to study the influence of Mn²⁺ on the initial aggregation kinetics of MnO_x nanoparticles. The results show that Mn²⁺ was highly efficient in destabilizing MnO_x nanoparticles. The critical coagulation concentration ratio of Mn²⁺ (0.3 mM) to Na⁺ (30 mM) was 2^-6.64, which is beyond the ratio range indicated by the Schulze-Hardy rule. This is due to the coordination bond formed between Mn²⁺ and the surface O of MnO_x, which could efficiently decrease the negative surface charge of MnO_x. As a result, in the co-presence of Mn²⁺ and Na⁺, a small amount of Mn²⁺ (5 μM) could efficiently neutralize the negative charge of MnO_x, thereby decreasing the amount of Na⁺, which mainly destabilized nanoparticles through electric double-layer compression, required to initiate aggregation. Further, Mn²⁺ behaved as a cation bridge linking both the negatively charged MnO_x and humic acid, thereby increasing the stability of the MnO_x nanoparticles as a result of the steric repulsion of the adsorbed humic acid. The results of this study enhance the understanding of the stability of the MnO_x nanoparticles in the natural environment, as well as in water treatments.