RESUMO
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 × 104 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 H2O) 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.
RESUMO
A low-temperature plasma device was developed to introduce N-containing moieties into biochar type CS-300 to improve ciprofloxacin removal. The sorption capacity of ciprofloxacin by the treated biochars was 2.61-4.26 times that of CS-300, and the mechanisms were explained by X-ray photoelectron spectroscopy and site energy distribution analysis. The results showed that the π-π stacking mechanism dominated ciprofloxacin removal by biochars. Ammonia-plasma treatment introduced abundant amino and amide groups to CS-300. They increased the π electron density in the delocalized system in CS-300, thus enhancing ciprofloxacin removal by the π-π stacking mechanism. Plasma treatment also enhanced polar interactions between ciprofloxacin and CS-300 through hydrogen- and ionic bonding occurring at high-energy sites with energy over 10,000 J/mol, thereby increasing ciprofloxacin removal. The maximum removal efficiency of ciprofloxacin by the treated biochars reached 71.0-85.7% at pH 6, while that for CS-300 was only 31.6% and occurred at pH 4. This implied that plasma treatment not only greatly increased the maximum removal efficiency but also shifted the optimal pH from acidic to nearly-neutral condition. Our findings highlight that ammonia-plasma treatment is a promising technique to improve ciprofloxacin removal by biochars and the treated biochars have potential applications in its removal from water.
