Layered hydrated-titanium-oxide-laden reduced graphene oxide composite as a high-performance negative electrode for selective extraction of Li via membrane capacitive deionization.

In this work, we initially prepared layered lithium titanate (Li2TiO3) using a solid-state reaction. Then Li+ of Li2TiO3 were acid-eluded with Hydrochloric acid to obtain hydrated titanium oxide (H2TiO3). Different weight percentages (50%, 60%, 70%, 80%, and 90%) of the as-prepared H2TiO3 were deposited on a conductive reduced graphene oxide (rGO) matrix to obtain a series of rGO/ H2TiO3 composites. Of the prepared composites, rGO/H2TiO3-60% showed excellent current density, high specific capacitance, and rapid ion diffusion. An asymmetric MCDI (membrane capacitive deionization) cell fabricated with activated carbon as the anode and rGO/H2TiO3-60% as the cathode displayed outstanding Li+ electrosorption capacity (13.67 mg g-1) with a mean removal rate of 0.40 mg g-1 min-1 in a 10 mM LiCl aqueous solution at 1.8 V. More importantly, the rGO/H2TiO3-60% composite electrode exhibited exceptional Li+ selectivity, superior cyclic stability up to 100,000 s, and a Li+ sorption capacity retention of 96.32% after 50 adsorption/desorption cycles. The excellent Li+ extraction obtained by MCDI using the rGO/H2TiO3-60% negative electrode was putatively attributed to: (i) ion exchange between Li+ and H+ of H2TiO3; (ii) the presence of narrow lattice spaces in H2TiO3 suitable for selective Li+ capture; (iii) capture of Li+ by isolated and hydrogen-bonded hydroxyl groups of H2TiO3; and (iv) enhanced interfacial contact and transfer of large numbers of Li+ ions from the electrolyte to H2TiO3 achieved by compositing H2TiO3 with a highly conductive rGO matrix.

Efficient lithium extraction using redox-active Prussian blue nanoparticles-anchored activated carbon intercalation electrodes via membrane capacitive deionization.

Global demand for lithium (Li) resources has dramatically increased due to the demand for clean energy, especially the large-scale usage of lithium-ion batteries in electric vehicles. Membrane capacitive deionization (MCDI) is an energy and cost-efficient electrochemical technology at the forefront of Li extraction from natural resources such as brine and seawater. In this study, we designed high-performance MCDI electrodes by compositing Li+ intercalation redox-active Prussian blue (PB) nanoparticles with highly conductive porous activated carbon (AC) matrix for the selective extraction of Li+. Herein, we prepared a series of PB-anchored AC composites (AC/PB) containing different percentages (20%, 40%, 60%, and 80%) of PB by weight (AC/PB-20%, AC/PB-40%, AC/PB-60%, and AC/PB-80%, respectively). The AC/PB-20% electrode with uniformly anchored PB nanoparticles over AC matrix enhanced the number of active sites for electrochemical reaction, promoted electron/ion transport paths, and facilitated abundant channels for the reversible insertion/de-insertion of Li+ by PB, which resulted in stronger current response, higher specific capacitance (159 F g-1), and reduced interfacial resistance for the transport of Li+ and electrons. An asymmetric MCDI cell assembled with AC/PB-20% as cathode and AC as anode (AC//AC-PB20%) displayed outstanding Li+ electrosorption capacity of 24.42 mg g-1 and a mean salt removal rate of 2.71 mg g min-1 in 5 mM LiCl aqueous solution at 1.4 V with high cyclic stability. After 50 electrosorption-desorption cycles, 95.11% of the initial electrosorption capacity was retained, reflecting its good electrochemical stability. The described strategy demonstrates the potential benefits of compositing intercalation pseudo capacitive redox material with Faradaic materials for the design of advanced MCDI electrodes for real-life Li+ extraction applications.

Preparation of highly stable zeolite-alginate foam composite for strontium(90Sr) removal from seawater and evaluation of Sr adsorption performance.

Alginate bead is a promising strontium (Sr) adsorbent in seawater, but highly concentrated Na ions caused over-swelling and damaged the hydrogel bead. To improve the mechanical stability of alginate bead, flexible foam-type zeolite-alginate composite was synthesized and Sr adsorption performance was evaluated in seawater; 1-10% zeolite immobilized alginate foams were prepared by freeze-dry technique. Immobilization of zeolite into alginate foam converted macro-pores to meso-pores which lead to more compact structure. It resulted in less swollen composite in seawater medium and exhibited highly improved mechanical stability compared with alginate bead. Besides, Sr adsorption efficiency and selectivity were enhanced by immobilization of zeolite in alginate foam due to the increase of Sr binding sites (zeolite). In particular, Sr selectivity against Na was highly improved. The 10% zeolite-alginate foam exhibited a higher log Kd of 3.3, while the pure alginate foam exhibited 2.7 in the presence of 0.1 M Na. Finally, in the real seawater, the 10% zeolite-alginate foam exhibited 1.5 times higher Sr adsorption efficiency than the pure alginate foam. This result reveals that zeolite-alginate foam composite is appropriate material for Sr removal in seawater due to its swelling resistance as well as improved Sr adsorption performance in complex media.

Highly stable and magnetically separable alginate/Fe3O4 composite for the removal of strontium (Sr) from seawater.

In this study, a highly stable alginate/Fe3O4 composite was synthesized, and systematically investigated for the practical application of strontium (Sr) removal in complex media, such as seawater and radioactive wastewater. To overcome the drawbacks of the use of alginate microspheres, high contents of alginic acid and Fe3O4 were used to provide a more rigid structure with little swelling and facile separation, respectively. The synthesized composite was optimized for particle sizes of <400 µm and 1% content of Fe3O4. The alginate/Fe3O4 composite showed excellent Sr uptake (≈400.0 mg/g) and exhibited outstanding selectivity for Sr among various cations (Na, Mg, Ca and K). However, in diluted Sr condition (50 mg/L), Ca significantly affected Sr adsorption, resulting in a decrease of Kd value from 3.7 to 2.4 at the 0.01 M Ca. The alginate/Fe3O4 composite could be completely regenerated using 0.1 M HCl and CaCl2. In real seawater spiked with 50 mg/L of Sr, the alginate/Fe3O4 composite showed 12.5 mg/g of Sr uptake, despite the highly concentrated ions in seawater. The adsorption experiment for radio-active 90Sr revealed a removal efficiency of 67% in real seawater, demonstrating the reliability of the alginate/Fe3O4 composite.

Investigation of the strontium (Sr(II)) adsorption of an alginate microsphere as a low-cost adsorbent for removal and recovery from seawater.

In this paper, we investigated alginate microspheres as a low-cost adsorbent for strontium (Sr(II)) removal and recovery from seawater. Alginate microspheres have demonstrated a superior adsorption capacity for Sr(II) ions (≈110 mg/g). A Freundlich isotherm model fits well with the Sr(II) adsorption of an alginate microsphere. The mechanism of Sr(II) adsorption is inferred as an ion exchange reaction with Ca(II) ions. The effects of the solution pH and co-existing ions in seawater are also investigated. Except for a pH of 1-2, Sr(II) adsorption capacity is not affected by pH. However, increasing the seawater concentration of metal cations seriously decreases Sr(II) uptake. In particular, highly concentrated (15,000 mg/L) Na(I) ions significantly interfere with Sr(II) adsorption. Sr(II) desorption was performed using 0.1 M HCl and CaCl2. Both regenerants show an excellent desorption efficiency, but the FTIR spectrum reveals that the chemical structure of the microsphere is destroyed after repeated use of HCl. Conversely, CaCl2 successfully desorbed Sr(II) without damage, and the Sr(II) adsorption capacity does not decrease after three repeated uses. The alginate microsphere was also applied to the adsorption of Sr(II) in a real seawater medium. Because of inhibition by co-existing ions, the Sr(II) adsorption capacity was decreased and the adsorption rate was retarded compared with D.I. water. Although the Sr(II) adsorption capacity was decreased, the alginate microsphere still exhibited 17.8 mg/g of Sr(II) uptake in the seawater medium. Considering its excellent Sr(II) uptake in seawater and its reusability, an alginate microsphere is an appropriate cost-effective adsorbent for the removal and recovery of Sr(II) from seawater.

Aminoclay-induced humic acid flocculation for efficient harvesting of oleaginous Chlorella sp.

Biofuels (biodiesel) production from oleaginous microalgae has been intensively studied for its practical applications within the microalgae-based biorefinement process. For scaled-up cultivation of microalgae in open ponds or, for further cost reduction, using wastewater, humic acids present in water-treatment systems can positively and significantly affect the harvesting of microalgae biomass. Flocculation, because of its simplicity and inexpensiveness, is considered to be an efficient approach to microalgae harvesting. Based on the reported cationic aminoclay usages for a broad spectrum of microalgae species in wide-pH regimes, aminoclay-induced humic acid flocculation at the 5g/L aminoclay loading showed fast floc formation, approximately 100% harvesting efficiency, which was comparable to the only-aminoclay treatment at 5g/L, indicating that the humic acid did not significantly inhibit the microalgae harvesting behavior. As for the microalgae flocculation mechanism, it is suggested that cationic nanoparticles decorated on macromolecular matters function as a type of network in capturing microalgae.