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

Cheng, Haijun; Yang, Tao; Jiang, Jin; Lu, Xiaohui; Wang, Panxin; Ma, Jun

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

2020

Manganese oxides (MnOₓ) 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 MnOₓ 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 MnOₓ nanoparticles. The results show that Mn²⁺ was highly efficient in destabilizing MnOₓ 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 MnOₓ, which could efficiently decrease the negative surface charge of MnOₓ. 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 MnOₓ, 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 MnOₓ and humic acid, thereby increasing the stability of the MnOₓ 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 MnOₓ nanoparticles in the natural environment, as well as in water treatments.

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