Performance of Rod-Shaped Ce Metal-Organic Frameworks for Defluoridation.

The performance of a Ce(III)-4,4',4″-((1,3,5-triazine-2,4,6-triyl) tris (azanediyl)) tribenzoic acid-organic framework (Ce-H3TATAB-MOFs) for capturing excess fluoride in aqueous solutions and its subsequent defluoridation was investigated in depth. The optimal sorption capacity was obtained with a metal/organic ligand molar ratio of 1:1. The morphological characteristics, crystalline shape, functional groups, and pore structure of the material were analyzed via SEM, XRD, FTIR, XPS, and N2 adsorption-desorption experiments, and the thermodynamics, kinetics, and adsorption mechanism were elucidated. The influence of pH and co-existing ions for defluoridation performance were also sought. The results show that Ce-H3TATAB-MOFs is a mesoporous material with good crystallinity, and that quasi-second kinetic and Langmuir models can describe the sorption kinetics and thermodynamics well, demonstrating that the entire sorption process is a monolayer-governed chemisorption. The Langmuir maximum sorption capacity was 129.7 mg g-1 at 318 K (pH = 4). The adsorption mechanism involves ligand exchange, electrostatic interaction, and surface complexation. The best removal effect was reached at pH 4, and a removal effectiveness of 76.57% was obtained under strongly alkaline conditions (pH 10), indicating that the adsorbent has a wide range of applications. Ionic interference experiments showed that the presence of PO43- and H2PO4- in water have an inhibitory effect on defluoridation, whereas SO42-, Cl-, CO32-, and NO3- are conducive to the adsorption of fluoride due to the ionic effect.

Template-Free Synthesis of Magnetic La-Mn-Fe Tri-Metal Oxide Nanofibers for Efficient Fluoride Remediation: Kinetics, Isotherms, Thermodynamics and Reusability.

The occurrence of fluoride contamination in drinking water has gained substantial concern owing to its serious threat to human health. Traditional adsorbents have shortcomings such as low adsorption capacity and poor selectivity, so it is urgent to develop new adsorbents with high adsorption capacity, renewable and no secondary pollution. In this work, magnetic electrospun La-Mn-Fe tri-metal oxide nanofibers (LMF NFs) for fluoride recovery were developed via electrospinning and heat treatment, and its defluoridation property was evaluated in batch trials. Modern analytical tools (SEM, BET, XRD, FTIR) were adopted to characterize the properties of the optimized adsorbent, i.e., LMF11 NFs with a La:Mn molar ratio of 1:1. The surface area calculated via BET method and pHpzc assessed using pH drift method of LMF11 NFs were 55.81 m2 g-1 and 6.47, respectively. The results indicated that the adsorption amount was highly dependent on the pH of the solution, and reached the highest value at pH = 3. The kinetic behavior of defluoridation on LMF11 NFs was dominated by the PSO model with the highest fitted determination coefficients of 0.9999. Compared with the other three isotherm models, the Langmuir model described defluoridation characteristics well with larger correlation coefficients of 0.9997, 0.9990, 0.9987 and 0.9976 at 15 °C, 25 °C, 35 °C and 45 °C, respectively. The optimized LMF11 NFs exhibited superior monolayer defluoridation capacities for 173.30-199.60 mg F-/g at pH 3 at 15-45 °C according to the Langmuir isotherm model. A thermodynamic study proved that the defluoridation by LMF11 NFs is a spontaneous, endothermic along with entropy increase process. In addition, the LMF11 NFs still showed high defluoridation performance after three reused cycles. These findings unveil that the synthesized LMF11 NFs adsorbent is a good adsorbent for fluoride remediation from wastewater owing to its low cost, high defluoridation performance and easy operation.

Outstanding fluoride removal from aqueous solution by a La-based adsorbent.

A La-based adsorbent was prepared with La(NO3)3·6H2O, 2-methylimidazole and DMF via amide-hydrolysis and used for fluoride decontamination from aqueous water. The obtained adsorbent was lanthanum methanoate (La(COOH)3). The effects of pH value, initial F- concentration and interfering ions on defluoridation properties of as-prepared La(COOH)3 were assessed through batch adsorption tests. The adsorption kinetics, isotherm models and thermodynamics were employed to verify the order, nature and feasibility of La(COOH)3 towards fluoride removal. The results imply that La(COOH)3 is preferable for defluoridation over a wide pH range of 2 to 9 without interference. Simultaneously, the defluoridation process of La(HCOO)3 accords to the pseudo-second order model and Langmuir isotherm, revealing chemical adsorption is the main control step. The maximum fluoride capture capacities of La(COOH)3 at 30, 40 and 50 °C are 245.02, 260.40 and 268.99 mg g-1, respectively. The mechanism for defluoridation by La(COOH)3 was revealed by PXRD and XPS. To summarize, the as-synthesized La based adsorbent could serve as a promising adsorbent for defluoridation from complex fluoride-rich water.

Nanofibers with diameter below one nanometer from electrospinning.

Sub-nanometer materials have received wide attention due to their unique properties in recent years. Most studies focus on the preparation and properties investigation of the inorganic sub-nanometer materials, while there are few reports on organic especially polymeric sub-nanometer materials such as sub-nanometer fiber due to the obstacles with respect to fabricating such small nanofibers. In this work we prepare PAA nanofibers with diameters ranging from hundreds of nanometers down to sub-nanometer via electrospinning from a polyamic acid (PAA) with ultrahigh molecular weight. The morphologies and size of the electrospun ultrathin nanofibers are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). AFM images combined with theoretic calculations show that sub-nanometer fiber of approximate 0.17-0.63 nm only containing one molecular chain was generated via electrospinning from ultra-dilute PAA solutions for the first time. These quite small sub-nanometer fibers would open a new area of electrospinning and provide further explorations on the production and application of electrospun sub-nanometer fibers with single molecular chains.