Metal heteroatoms significantly enhance efficacy of TiO2 nanomaterials in promoting hydrolysis of organophosphates: Implications for mitigating pollution of plastic additives.

Abstract

Organophosphate esters (OPEs) are prevalent pollutants in the aquatic environment. OPEs are released from many sources, particularly, from the breakdown and weathering of plastic wastes, as OPEs are commonly used plastic additives. Metal oxide mineral nanoparticles play critical roles in the hydrolytic transformation of OPEs. While natural minerals often contain metal impurities, it is unclear how metal heteroatoms affect the efficiency of mineral nanoparticles in mediating hydrolysis reactions. Herein, we show that transition metal-doped anatase titanium dioxide (TiO₂) nanomaterials are more effective in catalyzing the hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE compound, with the relative effects of the heteroatoms following the order of Fe > Cr > Mn ≈ Ni > Co > Cu. With multiple lines of evidence based on spectroscopic analysis, kinetics modeling, and theoretical calculations, we show that metal doping increases the Lewis acidity of the TiO₂ nanomaterials by increasing the oxidation state of surface Ti atoms, inducing oxygen vacancies, and creating additional Lewis acid sites with stronger acidities. Moreover, the increased amounts of surface hydroxyl groups due to metal doping enhance inner-sphere complexation of pNPP through ligand exchange. The interesting observation that Fe-doped TiO₂ exhibited the highest catalytic efficiency may have important implications for reducing the risks of organophosphate plastic additives, as iron is the most common heteroatom of naturally occurring TiO₂ (nano)materials.