Efficient Removal of Uranyl Ions Using PAMAM Dendrimer: Simulation and Experiment.

In this work, using atomistic molecular dynamics (MD) simulations and polymer-assisted ultrafiltration experiments, we explore the adsorption and removal of uranyl ions from aqueous solutions using poly(amidoamine) (PAMAM) dendrimers. The effects of uranyl ion concentration and the pH of the solution were examined for PAMAM dendrimers of generations 3, 4, and 5. Our simulation results show that PAMAM has a high adsorption capacity for the uranyl ions. The adsorption capacity increases with increasing concentration of uranyl ions for all 3 generations of PAMAM in agreement with experimental findings. We find that the number of uranyl ions bound to PAMAM is significantly higher in acidic solutions (pH < 3) as compared to neutral solutions (pH ∼ 7) for all uranyl ion concentrations. Additionally, we find an increase in the number of adsorbed uranyl ions to PAMAM with the increase in the dendrimer generation. This increase is due to the greater number of binding sites present for higher-generation PAMAM dendrimers. Our simulation study shows that nitrate ions form a solvation shell around uranyl ions, which allows them to bind to PAMAM binding sites, including the amide, amine, and carbonyl groups. In polymer-assisted ultrafiltration (PAUF) experiments, the removal percentage of uranyl ions by G3 PAMAM dendrimer increased from 36.3% to 42.6% as the metal ion concentration increased from 2.1 × 10-5 M to 10.5 × 10-5 M at a pH of 2. Our combined experiment and simulation study suggests that PAMAM is an effective adsorbent for removing uranyl ions from aqueous solutions.

Functionalized Carbon Nanotubes Encapsulated Alginate Beads for the Removal of Mercury Ions: Design, Synthesis, Density Functional Theory Calculation, and Demonstration in a Batch and Fixed-Bed Process.

Various nanomaterials have been envisaged mainly through batch studies for environmental remediation application. The real utilization of these new generation adsorbents in large scale pose a difficulty due to its low density and small size which makes it difficult for isolation after application. In this context, nanoadsorbents polymer composite beads can be seen as a way out. Here, functionalized CNTs (carbon nanotubes) have been fabricated into micro beads with sodium alginate. The alginate-functionalized CNT (Alg-f-CNT) beads were then comprehensively evaluated for batch and fixed-bed column separation of divalent mercury ions from an aqueous medium. The effects of process parameters such as pH, contact time, feed Hg2+ concentration, and temperature were studied. Simulation of the experimental data suggested that adsorption is an endothermic spontaneous process which follows the pseudo-second-order kinetic and Langmuir isotherm model. The desorption of the Hg2+ ion from used adsorbent was possible with 1 M HNO3. The breakthrough curves at different process parameters were investigated during fixed-bed column separation and found to be in good agreement with Thomas model. The regeneration and reusability of the adsorbent were tested up to five cycles without a significant decrease in the removal performance. Density functional theory studies revealed stronger interaction of Alg-f-CNT with Hg compared to free alginic acid and established the role of carboxyl and oxo groups present in the adsorbent in the coordination of the Hg2+ ions. The experimental results demonstrate that functionalized CNT-encapsulated alginate beads are a promising alternate material, which can be used to remove mercury in the fixed-bed column mode of the operation.

Interfacial Behavior of Cs+, K+, Na+, and Rb+ Extraction in the Presence of Dibenzo-18-Crown-6 from the Nitrobenzene-Water Biphasic System: Experimental, Quantum Chemical, and Molecular Dynamic Studies.

Extraction of metal ions (i.e., Cs+, K+, Na+, and Rb+) in the presence of ionophore such as dibenzo-18-crown-6 (DB18C6) from the nitrobenzene-water biphasic system is reported by COSMO-RS (conductor-like screening model for real solvents) predictions, molecular dynamics simulation, along with experimental validation. The predicted values of selectivity as obtained for the Na+-DB18C6 complex were 4.571, 4.877, and 4.947 at 298.15, 308.15, and 318.15 K, respectively. This was then confirmed by the experimental distribution coefficient (D) as obtained in the diluent systems along with by varying the metal ion to crown ether ligand (M-L) mole ratios: 10:1 (0.1 M M+ and 0.01 M DB18C6), 1:1 (0.01 M M+ and 0.01 M DB18C6), and 1:10 (0.001 M M+ and 0.01 M DB18C6). The experimentally determined values of D Na (i.e., 0.059, 0.060, and 0.056) were found to be very large as compared to the values of D Cs (i.e., 0.001, 0.010, and 0.024) in the nitrobenzene phase. It indicates an excellent extraction ability of DB18C6 for Na+. The rate of phase separation for the Cs+NO3 - system was slow as compared to other metal ion systems. The binding energies, free energies, and nonbonded interaction energies of the complexed metal ion in solution were calculated with both explicit and implicit solvent models. A higher interaction energy between Na+-DB18C6 complex and nitrobenzene was observed (i.e., -289.92 in the explicit model and -143.12 kcal/mol in the implicit model) when compared with other metal ions (i.e., Cs+, K+, and Rb+).