Experimental and theoretical studies of methyl orange uptake by mn–rich synthetic mica: Insights into manganese role in adsorption and selectivity

Manganese–containing mica (Mn–mica) was synthesized at 200^◦C/96 h using Mn–carbonate, Al–nitrate, silicic acid, and high KOH concentration under hydrothermal conditions. Mn–mica was characterized and tested as a new adsorbent for the removal of methyl orange (MO) dye from aqueous solutions. Compared to naturally occurring mica, the Mn–mica with manganese in the octahedral sheet resulted in enhanced MO uptake by four times at pH 3.0 and 25^◦C. The pseudo-second order equation for kinetics and Freundlich equation for adsorption isotherm fitted well to the experimental data at all adsorption temperatures (i.e., 25, 40 and 55^◦C). The decrease of Langmuir uptake capacity from 107.3 to 92.76 mg·g⁻¹ within the temperature range of 25–55^◦C suggested that MO adsorption is an exothermic process. The role of manganese in MO selectivity and the adsorption mechanism was analyzed via the physicochemical parameters of a multilayer adsorption model. The aggregated number of MO ions per Mn–mica active site (n) was superior to unity at all temperatures signifying a vertical geometry and a mechanism of multi-interactions. The active sites number (D_M) of Mn–mica and the total removed MO layers (N_t ) slightly changed with temperature. The decrease in the MO adsorption capacities (Q_sat = n·D_M·N_t ) from 190.44 to 140.33 mg·g⁻¹ in the temperature range of 25–55^◦C was mainly controlled by the n parameter. The results of adsorption energies revealed that MO uptake was an exothermic (i.e., negative ∆E values) and a physisorption process (∆E < 40 kJ mol⁻¹). Accordingly, the adsorption of MO onto Mn–mica was governed by the number of active sites and the adsorption energy. This study offers insights into the manganese control of the interactions between MO ions and Mn–mica active sites.