Enhanced immobilization of Arsenic(III) and Auto-oxidation to Arsenic(V) by titanium oxide (TiO2), due to Single-Atom vacancies and oxyanion formation

Pollution control of As(III), a naturally occurring carcinogen, has recently gained a global attention, while due to the dominance of neutral H3AsO3 over a wide pH range, As(III) immobilization by most minerals is not efficient as As(V) immobilization. TiO2 shows promise for controlling As(III) pollution, and herein, a comprehensive study about As(III) adsorption by TiO2 and oxyanion formation is conducted by means of DFT + D3 methods. Both anatase and rutile are effective for As(III) adsorption, while As(III) adsorption affinities differ significantly and are-1.48 and-3.79 eV for pristine surfaces, ascend to-3.85 and-5.08 eV for O vacancies, and further to-5.37 and-5.26 eV for Ti vacancies, respectively. The bidentate binuclear complexes dominate for pristine surfaces, and O vacancies prefer OAs insertion into TiO2 lattice, while for Ti vacancies, all As(III) centers are auto oxidized to As(V). Ti-3d, O-2p or/and As-4p rather than other orbitals contribute significantly to As adsorption, and O and Ti vacancies promote adsorption through stronger orbital hybridization. The superior adsorption for Ti vacancies originates from As(V) formation instead of bonding interactions. The formation of As oxyanions, which may occur spontaneously at pristine surfaces and is greatly promoted by O and Ti vacancies, enhances As (III) adsorption pronouncedly and becomes a viable strategy for As(III) immobilization. H2AsO3- and HAsO32- dominate for pristine surfaces and O vacancies, and for Ti vacancies, H2AsO4- and HAsO42-dominate over anatase whereas AsO43-also makes an important contribution over rutile. Results rationalize experimental observations available, and provide significantly new insights about the migration, bioavailability and fate of As(III) over TiO2 surfaces that facilitate the exploration of scavengers for As and other pollutants.

Automated summary

Pollution control of As(III), a naturally occurring carcinogen, is gaining global attention. TiO2 shows promise for controlling As(III) pollution, and the formation of As oxyanions enhances As(III) adsorption and immobilization.