skip to main content


Title: Efficient removal of heavy metals from polluted water with high selectivity for Hg( ii ) and Pb( ii ) by a 2-imino-4-thiobiuret chemically modified MIL-125 metal–organic framework
A highly porous adsorbent based on a metal–organic framework was successfully designed and applied as an innovative adsorbent in the solid phase for the heavy metal removal. MIL-125 was densely decorated by 2-imino-4-thiobiuret functional groups, which generated a green, rapid, and efficacious adsorbent for the uptake of Hg( ii ) and Pb( ii ) from aqueous solutions. ITB-MIL-125 showed a high adsorption affinity toward mercury( ii ) ions of 946.0 mg g −1 due to covalent bond formation with accessible sulfur-based functionality. Different factors were studied, such as the initial concentration, pH, contact time, and competitive ions, under same circumstances at the room temperature. Moreover, the experimental adsorption data were in excellent agreement with the Langmuir adsorption isotherm and pseudo-second order kinetics. At a high concentration of 100 ppm mixture of six metals, ITB-MIL-125 exhibited a high adsorption capacity, reaching more than 82% of Hg( ii ) compared to 62%, 30%, 2%, 1.9%, and 1.6% for Pb( ii ), Cu( ii ), Cd( ii ), Ni( ii ), and Zn( ii ), respectively.  more » « less
Award ID(s):
1900094
NSF-PAR ID:
10275606
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
RSC Advances
Volume:
11
Issue:
23
ISSN:
2046-2069
Page Range / eLocation ID:
13940 to 13950
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Heavy metal ions are highly toxic and widely spread as environmental pollutants. This work reports the development of two novel chelating adsorbents, based on the chemical modifications of graphene oxide and zirconium phosphate by functionalization with melamine-based chelating ligands for the effective and selective extraction of Hg( ii ) and Pb( ii ) from contaminated water sources. The first adsorbent melamine, thiourea-partially reduced graphene oxide (MT-PRGO) combines the heavier donor atom sulfur with the amine and triazine nitrogen's functional groups attached to the partially reduced GO nanosheets to effectively capture Hg( ii ) ions from water. The MT-PRGO adsorbent shows high efficiency for the extraction of Hg( ii ) with a capacity of 651 mg g −1 and very fast kinetics resulting in a 100% removal of Hg( ii ) from 500 ppb and 50 ppm concentrations in 15 second and 30 min, respectively. The second adsorbent, melamine zirconium phosphate (M-ZrP), is designed to combine the amine and triazine nitrogen's functional groups of melamine with the hydroxyl active sites of zirconium phosphate to effectively capture Pb( ii ) ions from water. The M-ZrP adsorbent shows exceptionally high adsorption affinity for Pb( ii ) with a capacity of 681 mg g −1 and 1000 mg g −1 using an adsorbent dose of 1 g L −1 and 2 g L −1 , respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb( ii ) from 1 ppm, 100 ppm and 1000 ppm concentrations is 40 seconds, 5 min and 30 min, respectively using an adsorbent dose of 1 g L −1 . In a mixture of six heavy metal ions at a concentration of 10 ppm, the removal efficiency is 100% for Pb( ii ), 99% for Hg( ii ), Cd( ii ) and Zn( ii ), 94% for Cu( ii ), and 90% for Ni( ii ) while at a higher concentration of 250 ppm the removal efficiency for Pb( ii ) is 95% compared to 23% for Hg( ii ) and less than 10% for the other ions. Because of the fast adsorption kinetics, high removal capacity, excellent regeneration, stability and reusability, the MT-PRGO and M-ZrP are proposed as top performing remediation adsorbents for the solid phase extraction of Hg( ii ) and Pb( ii ), respectively from contaminated water. 
    more » « less
  2. null (Ed.)
    Rice husks are an agricultural residue of great annual production and have a high cellulose content. In this study, we have prepared highly charged carboxyl cellulose nanofibers (CNFs) from rice husks using the TEMPO-oxidation method and the extracted CNFs were evaluated as an adsorbent for the removal of lead( ii ) and lanthanum( iii ) (Pb( ii ) and La( iii )) ions from contaminated water. Three different forms of nanocellulose adsorbents were prepared: suspension, freeze-dried, and nanocomposite containing magnetic nanoparticles, where their adsorption performance was tested against the removal of the two chosen heavy metal ions. The maximum adsorption capacity of rice husk based CNFs was found to be the highest in the nanocellulose suspension, i.e. , 193.2 mg g −1 for Pb( ii ) and 100.7 mg g −1 for La( iii ). The separation of the used adsorbent in the suspension was further facilitated by the gelation of the CNFs and metal cations, where the resulting floc could be removed by gravity-driven filtration. The absorption mechanism of the investigated CNF system is mainly due to electrostatic interactions between negatively charged carboxylate groups and multivalent metal ions. It was found that 90% lanthanum content in the form of lanthanum oxychloride (determined by X-ray powder diffraction) could be obtained by incinerating the CNF/LaCl 3 gel. This study demonstrates a viable and sustainable solution to upcycle agricultural residues into remediation nanomaterials for the removal and recovery of toxic heavy metal ions from contaminated water. 
    more » « less
  3. Abstract

    The new material polypyrrole/MoS42−(MoS4‐Ppy), prepared by ion‐exchange of NO3‐ of NO3‐Ppy with MoS42−, displays high acid stability and excellent uptake for heavy metal ions such as Hg2+, Ag+, Cu2+, and Pb2+. The different maximum adsorption capacities (qm) for Cu2+, Pb2+, Hg2+, and Ag+depend on the various binding modes arising from the different thiophilicity of these metal ions. The removals of Ag+and Pb2+reach >99.6% within 5 min, and for highly toxic Hg2+, >98% removal achieves at 1 min. At strong acid limit, the exceptionalqm(Ag+) of 725 mg g−1places the MoS4‐Ppy at the top of materials for such removal. Uptake kinetics of Ag+, Hg2+, and Pb2+is extremely fast: >99.9% removal rates at wide pH range (0.5–6) within 1–5 min. Also, at strongly acidic conditions (pH ≈ 1), for highly toxic Hg2+, <2 ppb concentration can be achieved, accepted as safe limit. The MoS4‐Ppy demonstrates an outstanding ability to separate low‐concentrated Ag+from high concentrated Cu2+especially under strong acidic conditions (pH ≈ 1), showing a large separation factor SFAg/Cu(KdAg/KdCu) of 105(>100). MoS4‐Ppy is a superior and novel sorbent material for water remediation applications as well as precious metals recovery.

     
    more » « less
  4. Abstract

    Biogenic thiols, such as cysteine, have been used to control the speciation of Hg(ii) in bacterial exposure experiments. However, the extracellular biodegradation of excess cysteine leads to the formation of Hg(ii)–sulfide species, convoluting the interpretation of Hg(ii) uptake results. Herein, we test the hypothesis that Hg(ii)–sulfide species formation is a critical step during bacterial Hg(ii) uptake in the presence of excess cysteine. An Escherichia coli (E. coli) wild-type and mutant strain lacking the decR gene that regulates cysteine degradation to sulfide were exposed to 50 and 500 nM Hg with 0 to 2 mM cysteine. The decR mutant released ∼4 times less sulfide from cysteine degradation compared to the wild-type for all tested cysteine concentrations during a 3 hour exposure period. We show with thermodynamic calculations that the predicted concentration of Hg(ii)–cysteine species remaining in the exposure medium (as opposed to forming HgS(s)) is a good proxy for the measured concentration of dissolved Hg(ii) (i.e., not cell-bound). Likewise, the measured cell-bound Hg(ii) correlates with thermodynamic calculations for HgS(s) formation in the presence of cysteine. High resolution X-ray absorption near edge structure (HR-XANES) spectra confirm the existence of cell-associated HgS(s) at 500 nM total Hg and suggest the formation of Hg–S clusters at 50 nM total Hg. Our results indicate that a speciation change to Hg(ii)–sulfide controls Hg(ii) cell-association in the presence of excess cysteine.

     
    more » « less
  5. Abstract

    In this study, Mg2+‐doped mesoporous TiO2photocatalysts derived from Mg2+adsorption (MA) process on MIL‐125, a metal‐organic framework material, were prepared and employed for photocatalytic reduction of CO2to produce CO. The Mg2+doping concentration was controlled by varying the Mg2+concentration in the Mg2+adsorption process. It was demonstrated that the Mg2+doping promoted the generation of surface Ti3+and significantly increased transient photocurrent density. Over a 4 h UV/Vis irradiation period, the best performing photocatalyst, 1MA, delivered a CO production rate ∼20 times higher than that of P25, a commercially available TiO2nanopowder. It is believed that the Mg2+adsorption process introduced more favorable properties to the TiO2photocatalysts, such as higher surface area and porosity for more reactive sites, and concentrated surface Ti3+centers for improved charge transfer.

     
    more » « less