Enhanced As(OH)3 adsorption by anatase TiO2 through facet control and Fe, N dual doping: A DFT+D3 study

Anatase and rutile, two major polymorphs of TiO 2 , have been used widely for environmental remediation, while anatase is apparently less effective for As(III) pollution management and needs substantial improvement. Herein, DFT calculations show that (001) rather than (101) and (100) facets of anatase are highly selective for As(III) adsorption. Facet control plays critical role during As(III) adsorption over pristine anatase surfaces and remains for mono doping, while diminishes substantially for dual doping. The second doping profoundly enhances As(III) adsorption for anatase facets with low activities and proves to be a viable strategy. Distinct from pristine surfaces where bidentate binuclear complexes prevail, monodentate complexes may become preferred due to doping, especially for dual doping where Fe site promotes adsorption via electronic effects. Doping causes As(III) oxidation when As centers interact directly with surfaces, and for mono doping, electron back -donation re -reduces As(V) to As(IV), while As(IV) occurs less for dual doping due to electron reservoir of Fe site that inhibits As (V) re -reduction. Regulatory mechanisms of facet control and effects of mono and dual doping for As(III) adsorption are further unraveled at molecular level. Results provide significant new insights for As(III) pollution management, and conduce to design As(III) scavengers and manage As -associated pollution.