Sustainable hybrid biocomposite adsorbents for anion-selective or concerted removal of ionic pollutants: Organic dyes to arsenate

Abstract

The controlled removal of hazardous ionizable compounds ranging from organic dyes from the textile industry to inorganic anions such as fluoride, sulfate or arsenate in aqueous media presents challenges to this day. This study devised a synthetic strategy to enable anion selective or simultaneous adsorption of anionic and cationic species. Therefore, versatile ternary metal composites (TMCs) were prepared with variable aluminum salt precursors: TMC-S for Al2(SO4)3 and TMC-N for Al(NO3)3 with variable Al3+ content from high to low values (S1>S2>S3>S4; N1≫N3) for the respective TMCs. Characterization was achieved through complementary methods: pHPZC, TGA, PXRD, XPS, 27Al/13C NMR and IR spectroscopy. The TMC surface properties were assessed via dye adsorption with methylene blue (MB) as a model cation, whereas methyl orange (MO) and reactive Black 5 (RB5) served as model anion systems. Sulfate, fluoride and arsenate represented a variety of inorganic anion target pollutant species.The maximum equilibrium adsorption capacity of MO decreased (TMC-S1 to TMC-S4; 0.67 to 0.41 mmol/g), whereas the MB adsorption capacity increased from 0.03 to 0.47 mmol/g. The arsenate adsorption capacity also decreased with decreased aluminum concentration during synthesis from 0.71 mmol/g (TMC-S1) to 0.46 mmol/g (TMC-S4). Arsenate and fluoride were chemisorbed onto the Al-centers, in contrast to the dye probes, which undergo physisorption. Additionally, arsenate was selectively removed from saline samples of groundwater with up to 6000 mg/L sulfate species, which contributes to salinity without altering the adsorption properties. This study hereby highlights the unique role of variable aluminum salt during synthesis to enable facile tailoring of the adsorbent structure and selective anion adsorption (TMC-S1) versus a more general (less selective) adsorption of ionic species (TMC-S4) for multi-component pollutant removal.