Comparative photocatalytic degradation of cationic rhodamine B and anionic bromocresol green using reduced ZnO: A detailed kinetic modeling approach

Abstract

The photocatalytic degradation of rhodamine B (RhB), a cationic dye, and bromocresol green (BCG), an anionic dye, was investigated using oxygen vacancy-enriched ZnO as the catalyst. These dyes were selected due to their differing charges and molecular structures, allowing for a deeper exploration of how these characteristics impact the degradation process. The catalyst was prepared by reducing ZnO with 10% H₂/Ar gas at 500 °C, and the introduction of oxygen vacancies was confirmed using various characterization techniques. A detailed kinetic model was developed to track dye degradation, accounting for adsorption and photocatalytic degradation simultaneously, both in solution and on the catalyst surface. The model incorporated the effect of pH on adsorption by considering the dissociation behavior of the dyes and their respective pK_a values. The study revealed that degradation primarily occurs on the catalyst surface at acidic pH, while at basic pH, degradation is more pronounced in the solution. DFT calculations supported these findings, showing that the electrostatic potential of the dyes shifts depending on pH, influencing their interaction with hydroxyl radicals or the catalyst surface. Quantum yield calculations indicate peak values of 6.32 10⁻⁵ molecules per photon for RhB at pH 11, and 4.20 10⁻⁵ for BCG at pH 3.