Thallium(I) (Tl(I)) pollution has become a pressing environmental issue due to its harmful effect on human health and aquatic life. Effective technology to remove Tl(I) ions from drinking water can offer immediate societal benefits especially in the developing countries. In this study, a bio-adsorbent system based on nitro-oxidized nanocellulose (NOCNF) extracted from sorghum stalks was shown to be a highly effective Tl(I) removal medium. The nitro-oxidation process (NOP) is an energy-efficient, zero-waste approach that can extract nanocellulose from any lignocellulosic feedstock, where the effluent can be neutralized directly into a fertilizer without the need for post-treatment. The demonstrated NOCNF adsorbent exhibited high Tl(I) removal efficiency (>90% at concentration < 500 ppm) and high maximum removal capacity (Qm = 1898 mg/g using the Langmuir model). The Tl(I) adsorption mechanism by NOCNF was investigated by thorough characterization of NOCNF-Tl floc samples using spectroscopic (FTIR), diffraction (WAXD), microscopic (SEM, TEM, and AFM) and zeta-potential techniques. The results indicate that adsorption occurs mainly due to electrostatic attraction between cationic Tl(I) ions and anionic carboxylate groups on NOCNF, where the adsorbed Tl(I) sites become nuclei for the growth of thallium oxide nanocrystals at high Tl(I) concentrations. The mineralization process enhances the Tl(I) removal efficiency, and the mechanism is consistent with the isotherm data analysis using the Freundlich model. 
                        more » 
                        « less   
                    
                            
                            Aluminum-Crosslinked Nanocellulose Scaffolds for Fluoride Removal
                        
                    
    
            Anionic carboxylated cellulose nanofibers (CNF) are effective media to remove cationic contaminants from water. In this study, sustainable cationic CNF-based adsorbents capable of removing anionic contaminants were demonstrated using a simple approach. Specifically, the zero-waste nitro-oxidization process was used to produce carboxylated CNF (NOCNF), which was subsequently converted into a cationic scaffold by crosslinking with aluminum ions. The system, termed Al-CNF, is found to be effective for the removal of fluoride ions from water. Using the Langmuir isotherm model, the fluoride adsorption study indicates that Al-CNF has a maximum adsorption capacity of 43.3 mg/g, which is significantly higher than that of alumina-based adsorbents such as activated alumina (16.3 mg/g). The selectivity of fluoride adsorption in the presence of other anionic species (nitrate or sulfate) by Al-CNF at different pH values was also evaluated. The results indicate that Al-CNF can maintain a relatively high selectivity towards the adsorption of fluoride. Finally, the sequential applicability of using spent Al-CNF after the fluoride adsorption to further remove cationic contaminant such as Basic Red 2 dye was demonstrated. The low cost and relatively high adsorption capacity of Al-CNF make it suitable for practical applications in fluoride removal from water. 
        more » 
        « less   
        
    
                            - Award ID(s):
- 2216585
- PAR ID:
- 10519756
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Nanomaterials
- Volume:
- 14
- Issue:
- 12
- ISSN:
- 2079-4991
- Page Range / eLocation ID:
- 1032
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            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
- 
            Abstract The escalating presence of per‐ and polyfluoroalkyl substances (PFAS) in drinking water poses urgent public health concerns, necessitating effective removal. This study presents a groundbreaking approach, using viologen to synthesize covalent organic framework nanospheres: MELEM‐COF and MEL‐COF. Characterized by highly crystalline features, these nanospheres exhibit exceptional affinity for diverse anionic PFAS compounds, achieving simultaneous removal of multiple contaminants within 30 min. Investigating six anionic PFAS compounds, MEL‐ and MELEM‐COFs achieved 90.0–99.0% removal efficiency. The integrated analysis unveils the synergistic contributions of COF morphology and functional properties to PFAS adsorption. Notably, MELEM‐COF, with cationic surfaces, exploits electrostatic and dipole interactions, with a 2500 mg g−1adsorption capacity—surpassing all reported COFs to date. MELEM‐COF exhibits rapid exchange kinetics, reaching equilibrium within 30 min. These findings deepen the understanding of COF materials and promise avenues for refining COF‐based adsorption strategies.more » « less
- 
            This study reports on the highly simple fabrication of green carbon black (GCB) generated from scrap tires with acetic acid to improve the adsorption efficiency for water purification, which is thoroughly compared with conventional carbon black (CB) obtained from petrochemicals. Unlike traditional modification processes with strong acids or bases, the introduction of a relatively mild acid readily allowed for the effective modification of GCB to increase the uptake capability of metal ions and toxic organic dyes to serve as effective adsorbents. The morphological features and thermal decomposition patterns were examined by electron microscopy and thermogravimetric analysis (TGA). The surface functional groups were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The structural information (ratio of D-defects/G band-graphitic domains) obtained by Raman spectroscopy clearly suggested the successful fabrication of GCB (ID/IG ratio of 0.74), which was distinctively different from typical CB (ID/IG ratio of 0.91). In the modified GCB, the specific surface area (SBET) gradually increased with the reduction of pore size as a function of acetic acid content (52.97 m2/g for CB, 86.64 m2/g for GCB, 102.10-119.50 m2/g for acid-treated GCB). The uptake capability of the modified GCB (312.5 mg/g) for metal ions and organic dyes was greater than that of the unmodified GCB (161.3 mg/g) and typical CB (181.8 mg/g), presumably due to the presence of adsorbed acid. Upon testing them as adsorbents in an aqueous solution, all these carbon materials followed the Langmuir isotherm over the Freundlich model. In addition, the removal rates of cationic species (>70% removal of Cu2+ and crystal violet in 30 min) were much faster and far greater than those of anionic metanil yellow (<40% removal in 3 h), given the strong electrostatic interactions. Thus, this work demonstrates the possibility of recycling waste tires in the powder form of GCB as a cost-effective and green adsorbent that can potentially substitute traditional CB, and the modification strategy provides a proof of concept for developing simple fabrication guidelines of other carbonaceous materials.more » « less
- 
            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
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
 
                                    