Mechanistically understanding adsorption of methyl orange, indigo carmine, and methylene blue onto ionic/nonionic polystyrene adsorbents.

The involved interaction information concerning adsorbate-adsorbate and adsorbate-adsorbent is indispensable for developing and optimizing adsorption treatment of dye wastewater. Single and bi-solute adsorption of methyl orange (MO), indigo carmine (IC), and methylene blue (MB) on polystyrene anion exchanger (PsAX), defunctionalized version of PsAX (DF-PsAX), and hyper-cross-linked polystyrene adsorbent (MN200) were investigated to obtain a mechanistic understanding. Under acidic condition, higher adsorption efficiencies of PsAX due to extra intermolecular interactions of MO between the protonated tertiary amine group and the sulfate groups were observed, while strong alkaline condition is favorable for the adsorption of IC and MB by PsAX. MN200 exhibited much larger adsorption capacity toward MB than that toward MO or IC, because the fused-rings structure of MB is more polarizable and can form stronger nonionic intermolecular attractions with the matrix structure of polystyrene adsorbents. Bi-solute adsorption reveals that MO has obvious competitive effect toward IC adsorption at low concentrations, but it is not the case for the adsorption at high concentrations, where IC molecules can form intermolecular H-bonding interactions to defend the competition. the thermodynamic parameters confirm the endothermic and spontaneous nature of MO adsorption by PsAX, and ≈ 48 KJ mol-1 of the enthalpy change (∆H) imply the adsorption is not just physical absorption. Additionally, water/ethanol mixture solution of NaCl can almost thoroughly regenerate the exhausted PsAX, whereas only aqueous solution without ethanol is invalid.