Equilibrium and Molecular Mechanism of Anionic Dyes Adsorption onto Copper(II) Complex of Dithiocarbamate-Modified Starch

The assembly of dyes molecules on metal-polymer complexes is of interest due to their potential applications in photovoltaic cell, separation, and wastewater treatment. In the present work, the interaction of anionic dyes (acid orange 7, acid orange 10, acid green 25, and acid red 18) with the copper(II) complex of dithiocarbamate-modified starch (DTCSCu) was investigated. The sorption studies showed that the interaction mechanism was based on chelating adsorption. The equilibrium data fitted well with Langmuir-Freundlich isotherm, and the capacities followed the order AO7 > AG25 > AR18 > AO10. It was affected by the structure of the dye. The sulfonate groups located on benzene rings favored efficient adsorption. Despite the difference in capacity, the molar n(dye):n(Cu) ratios for acid orange 10, acid red 18, and acid green 25 were approximately 1:2 when the maximum capacities for the dyes were achieved at the optimal pH of 4. It suggested that one dye molecule bound to one dinuclear copper center oil DTCSCu. The molar n(dye):n(Cu) ratio for the smallest dye, acid orange 7 (AO7), approached 1:1, demonstrating two AO7 molecules binding to two copper ions of the dinuclear core. The dyes adsorption related to the dinuclear copper core available on the polymer was further verified by electron spin resonance studies. Such interaction resulted in the formation of a ternary dye-metal-polymer complex. The ternary complexes were more stable than DTCSCU, which favored the adsorptions.