How Doping Regulates As(III) Adsorption at TiO2 Surfaces: A DFT + U Study

The efficient adsorption and removal of As(III), which is highly toxic, remains difficult. TiO₂ shows promise in this field, though the process needs improvement. Herein, how doping regulates As(OH)₃ adsorption over TiO₂ surfaces is comprehensively investigated by means of the DFT + D3 approach. Doping creates the bidentate mononuclear (Ce doping at the Ti_5c site), tridentate (N, S doping at the O_2c site), and other new adsorption structures. The extent of structural perturbation correlates with the atomic radius when doping the Ti site (Ce >> Fe, Mn, V >> B), while it correlates with the likelihood of forming more bonds when doping the O site (N > S > F). Doping the O_2c, O_3c rather than the Ti_5c site is more effective in enhancing As(OH)₃ adsorption and also causes more structural perturbation and diversity. Similar to the scenario of pristine surfaces, the bidentate binuclear complexes with two Ti-O_As bonds are often the most preferred, except for B doping at the Ti_5c site, S doping at the O_2c site, and B doping at the O_3c site of rutile (110) and Ce, B doping at the Ti_5c site, N, S doping at the O_2c site, and N, S, B doping at the O_3c site of anatase (101). Doping significantly regulates the As(OH)₃ adsorption efficacy, and the adsorption energies reach -4.17, -4.13, and -4.67 eV for Mn doping at the Ti_5c site and N doping at the O_2c and O_3c sites of rutile (110) and -1.99, -2.29, and -2.24 eV for Ce doping at the Ti_5c site and N doping at the O_2c and O_3c sites of anatase (101), respectively. As(OH)₃ adsorption and removal are crystal-dependent and become apparently more efficient for rutile vs. anatase, whether doped at the Ti_5c, O_2c, or O_3c site. The auto-oxidation of As(III) occurs when the As centers interact directly with the TiO₂ surface, and this occurs more frequently for rutile rather than anatase. The multidentate adsorption of As(OH)₃ causes electron back-donation and As(V) re-reduction to As(IV). The regulatory effects of doping during As(III) adsorption and the critical roles played by crystal control are further unraveled at the molecular level. Significant insights are provided for As(III) pollution management via the adsorption and rational design of efficient scavengers.