Insights into the improving mechanism of defect-mediated As(V) adsorption on hematite nanoplates

Abstract

The fate of As(V) in subsurface environments is strongly affected by ubiquitous iron oxides. Defects are commonly present in natural hematite, while the impacts of defects on the active sites and complexation mechanism of hematite for As(V) remain poorly understood. In this study, the defect-rich hematite was employed to investigate the surface charge characteristics and As(V) adsorption behavior using potentiometric acid-base titration and CD-MUSIC model in comparison with corresponding defect-poor hematite. The total arsenate-active site density (5.7 sites/nm2) on defective hematite includes 1.2 sites/nm2 of original sites and 4.5 sites/nm2 of Fe vacancy-induced sites. The result revealed that the vacant Fe3+ sites in defective hematite was compensated by the protons in solution, thus resulting in a considerable increase in site density as well as positive charge. The CD-MUSIC modeling results demonstrated that the presence of Fe vacancies in hematite is beneficial to the improvement in affinity constants for both monodentate and bidentate arsenate complexes. The high adsorption capacity of defective hematite (2.60 μmol/m2) compared to defect-free hematite (1.33 μmol/m2) is attributed to its large affinity constants as well as its more active surface sites, thereby playing a vital role in reducing the threats of heavy metals in the environment.