An O/N/S-rich porous Fe-based metal-organic framework (MOF) for gold recovery from the aqueous phase with excellent performance.

Recovering gold from wastewater has both economic and environmental benefits. However, how to effectively recover it is challenging. In this work, a novel Fe-based metal-organic framework (MOF) was synthesized and decorated with 2,5-thiophenedicarboxylic acid to have a well-developed porous architecture to effectively recover Au(III) from water. The maximum Au(III) sorption capacity by the finally-synthesized porous material MIL-101(Fe)-TDCA reached 2350 mg/g at pH = 6.00 ± 0.15, which is one of the highest among all literature-reported relevant materials including MOFs, and high sorption strength can be maintained within a wide pH range from 2.0 to 10.0. Besides, Au(III) sorption efficiency at low concentrations (i.e., 3.5 × 10-4 mg/mL) reached over 99 %. Mechanically, outstanding Au(III) sorption by MIL-101(Fe)-TDCA resulted from the O/N/S-containing moieties on its surface, large surface area and porosity. The N- and S-containing functionalities (CS, CONH) served as electron donors to chelate Au(III). The O-containing (FeOFe, COFe, COOH, and coordinated H2 O) and N-containing (CONH) moieties on MIL-101(Fe)-TDCA interacted with OH groups on the hydrolyzed species of Au(III) (AuCl3(OH)- , AuCl2(OH)2- , and AuCl(OH)3- ) by hydrogen bond, which further increased Au(III) sorption. Furthermore, about 45.71 % of Au(III) was reduced to gold nanoparticles by CS groups on the decorated 2,5-dithiophene dicarboxylic acid during sorption on MIL-101(Fe)-TDCA. Over 98.35 % of Au(III) was selectively sorbed on MIL-101(Fe)-TDCA at pH 4.0, much higher than that of the coexisting heavy metal ions including Cu(II), Zn(II), Pb(II), and Ni(II) (<5 %), despite their same concentration at 0.01 mg/mL. Although sorption selectivity of a noble metal Pt(IV) by MIL-101(Fe)-TDCA is relatively poor (68.23 %), it could be acceptable. Moreover, reusability of MIL-101(Fe)-TDCA is also excellent, since above 90.5 % Au(III) still can be sorbed after two sorption-desorption cycles. Overall, excellent sorption performance and the roughly-calculated gold recycling benefits (26.30 %) highlight that MIL-101(Fe)-TDCA is a promising porous material for gold recovery from the aqueous phase.