Contamination by heavy metal ions, particularly in water resources, is a severe environmental problem. In this study, the interaction of metal ions, namely, Cadmium Cd(II), Mercury Hg(II), and Lead Pb(II), on lignin matrices was investigated based on theoretical calculations. Binding energy (ΔEBind) values proved that the Pb(II) interacted better with lignin matrices than Cd(II) or Hg(II), having energy values between -8.4 kcal mol-1 to -20.2 kcal mol-1. The Gibbs energy (ΔG) and enthalpy (ΔH) values for Pb(II) were <0, indicating that the process was spontaneous and released heat. However, the lignin matrices studied in this work did not interact efficiently with Cd(II) and Hg(II) ions because almost all ΔEBind, ΔG, and ΔH values were positive. The bond length of the interaction proved that the Pb ions yielded the smallest values, ratifying the values for the interaction energy. Analyses based on the quantum theory of atoms in molecules showed that the interactions between Pb(II) and the matrices were partially covalent, whereas the interactions of Cd(II) and Hg(II) were predominantly electrostatic, justifying the positive values of ΔEBind, ΔG, and ΔH. The natural bond orbital results showed that the ligand orbitals of the matrix interacted with the lone pair antibonding orbital (LP*) of the metal ions. The theoretical results of the study show the possibility of applying lignin to remove heavy metal ions, especially Pb, and providing information for research related to wastewater treatment.
Keywords: Biopolymers; DFT; Metallic cations; Simulations; Wastewater treatment.
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