A multi-scale computational investigation of cationic dye interaction with rutile TiO2: An interconnected simulation approach

Abstract

Metal oxides have increasingly been employed for water pollution remediation. In the present investigation, the adsorptive characteristics of three cationic dyes, rhodamine B (RB), safranin O (SO), and methylene blue (MB), on the (1 1 0) surface of rutile titanium dioxide in an aqueous milieu were scrutinized. Utilizing Density Functional Theory (DFT), the reactivity of these organic compounds was evaluated by computing parameters such as molecular frontier orbital energies, energy gap (ΔEgap), electronegativity (χ), chemical hardness (η), chemical softness (σ), electrophilicity (ω), nucleophilicity, electron transfer fraction (ΔN), and Fukui indices. Findings demonstrated that RB exhibited superior reactivity and adsorptive capacity in comparison to MB and SO. Self-Consistent Charge Density-Functional Tight-Binding (SCC-DFTB) simulations revealed that RB engaged in the most potent interactions with the TiO2(1 1 0) surface, with interaction energies following the sequence RB (−1.12 eV) > MB (−1.07 eV) > SO (−1.01 eV). Furthermore, the most energetically favorable adsorption configurations for these dyes were elucidated through Molecular Dynamics (MD) simulations. Adsorption energies calculated via MD simulations corroborated that the TiO2 (1 1 0) surface possessed high adsorptive capabilities for these cationic dyes, particularly a stronger affinity for RB. The study provides comprehensive insights into the molecular-level interactions between cationic dyes and rutile TiO2, thereby contributing valuable information for the optimization of metal oxide-based water pollution treatment technologies.