Unveiling interfacial interaction between antimony oxyanions and boehmite nanorods: Spectroscopic evidence and density functional theory analysis

In natural environments, the fate and migratory behavior of metalloid contaminants such as antimony (Sb) significantly depend on the interfacial reactivity of mineral surfaces. Although boehmite (γ-AlOOH) is widely observed in (sub)surface environments, its underlying interaction mechanism with Sb o...

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Veröffentlicht in:Journal of hazardous materials 2024-05, Vol.469, p.133902-133902, Article 133902
Hauptverfasser: Lee, Seon Yong, Cho, Eun, Suh, Bong Lim, Choi, Jae-Woo, Lee, Seunghak, Kim, Jihan, Lee, Changha, Jung, Kyung-Won
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Sprache:eng
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Zusammenfassung:In natural environments, the fate and migratory behavior of metalloid contaminants such as antimony (Sb) significantly depend on the interfacial reactivity of mineral surfaces. Although boehmite (γ-AlOOH) is widely observed in (sub)surface environments, its underlying interaction mechanism with Sb oxyanions at the molecular scale remains unclear. Considering Sb-contaminated environmental conditions in this study, we prepared boehmite under weakly acidic conditions for use in the systematic investigation of interfacial interactions with Sb(III) and Sb(V). The as-synthesized boehmite showed a nanorod morphology and comprised four crystal facets in the following order: 48.4% (010), 27.1% (101), 15.0% (001), and 9.5% (100). The combined results of spectroscopic analyses and theoretical calculations revealed that Sb(III) formed hydrogen bonding outer-sphere complexation on the (100), (010), and (001) facets and that Sb(V) preferred to form bidentate inner-sphere complexation via mononuclear edge-sharing configuration on the (100), (001), and (101) facets and binuclear corner-sharing configuration on the (010) facet. These findings indicate that the facet-mediated thermodynamic stability of the surface complexation determines the interaction affinity toward the Sb species. This work is the first to document the contribution of boehmite to (sub)surface media, improving the ability to forecast the fate and behavior of Sb oxyanions at mineral–water interfaces. [Display omitted] •Interfacial interaction between boehmite nanorods (BNRs) and Sb(III/V) was studied.•XAS and DFT analyses show a molecular-scale interaction mechanism.•Affinity of BNRs was determined by energy-based geometric structures of Sb(III/V).•The (100), (010), and (001) facets preferred to form hydrogen bonding for Sb(III).•Four facets were functional to form a bidentate inner-sphere complex for Sb(V).
ISSN:0304-3894
1873-3336
DOI:10.1016/j.jhazmat.2024.133902