Computational investigation of metal doped coronene for acetophenone adsorption and sensing in wastewater treatment

Abstract Acetophenone (ACT) is a persistent organic pollutant in industrial wastewaters that poses serious risks to human health and the environment. In this study, we evaluated pristine coronene (CRO) and its aluminum- and zinc-doped forms (Al-CRO and Zn-CRO) as adsorbents and potential colorimetric/electrochemical sensing platforms for ACT using B97D/6-31G(d), B97D/LANL2DZ, and ωB97XD/6-31G(d). Statistical comparisons based on mean absolute deviation, root mean square deviation, and Pearson correlation coefficient confirmed the consistency of the main qualitative results at computational levels. Adsorption energy, electronic properties, optical response, and interaction mechanisms were examined using density functional theory (DFT), time-dependent DFT (TD-DFT), quantum theory of atoms in molecules (QTAIM), and NBO, NCI, and ELF/LOL analyses. QTAIM, NCI/RDG, and ELF/LOL analyses consistently identified weak physisorption in CRO@ACT, predominantly noncovalent adsorption with a localized Zn-O contribution in Zn-CRO@ACT, and a strong polarized coordination-type interaction in Al-CRO@ACT. Al-CRO exhibits strong charge-transfer-assisted, coordination-type adsorption, with Eads values from − 47.52 to -48.73 kcal.mol − 1 , accompanied by a reduced HOMO-LUMO gap and a predicted shift in the absorption maximum from 391 to 596 nm upon ACT binding. These results identify Al-CRO as a candidate for strong ACT adsorption/removal and for disposable adsorption-coupled colorimetric/electrochemical sensing due to its extremely long recovery time. Also, according to the theoretical results, Zn-CRO with Eads values from − 10.64 to -12.40 kcal.mol − 1 and faster desorption than Al-CRO (which may facilitate regeneration), along with a shift in the absorption wavelength from 346 to 410 (in the presence of ACT), is a candidate for experimental evaluation in the future.