Functionalized Mesoporous Silicas with Crown Ether Moieties for Selective Adsorption of Lithium Ions in Artificial Sea Water

Moorthy, Madhappan Santha; Song, Hyun-Jin; Ha, Chang‐Sik

doi:10.1166/jnn.2014.9956

Cited by 21 publications

(12 citation statements)

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“…Improved studies have employed CEs modified with amine, vinyl, allyloxy methyl, carboxyl, , and hydroxyl (−OH) − groups, which were polymerized, ,, polymer-imprinted on magnetite, silanized on silica, , and tethered on multiwall carbon nanotube (MWCNT) or poly(glycidyl methacrylate) . However, most of them have low CE loading or experienced substantial CE loss during fabrication. − Furthermore, some were processed into resins, hydrogels, or films ,− that have poor mass-transport properties, limited by internal diffusion. , It is therefore important to develop a facile fabrication technique that would not only create covalent CE–matrix linkages but also minimize CE loss during fabrication and produce durable adsorbents with structures that promote Li + adsorption. To achieve these, this study (Figure ) demonstrates a very simple but highly effective method of preparing novel CE-based Li + adsorbents through modified CE/matrix blending, electrospinning, and aerosol cross-linking.…”

Section: Introductionmentioning

confidence: 99%

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li⁺ Adsorbents

Limjuco¹,

Nisola²,

Torrejos³

et al. 2017

ACS Appl. Mater. Interfaces

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Crown ether (CE)-based Li adsorbent microfibers (MFs) were successfully fabricated through a combined use of CE diols, electrospinning, and aerosol cross-linking. The 14- to 16-membered CEs, with varied ring subunits and cavity dimensions, have two hydroxyl groups for covalent attachments to poly(vinyl alcohol) (PVA) as the chosen matrix. The CE diols were blended with PVA and transformed into microfibers via electrospinning, a highly effective technique in minimizing CE loss during MF fabrication. Subsequent aerosol glutaraldehyde (GA) cross-linking of the electrospun CE/PVA MFs stabilized the adsorbents in water. The aerosol technique is highly effective in cross-linking the MFs at short time (5 h) with minimal volume requirement of GA solution (2.4 mL g MF). GA cross-linking alleviated CE leakage from the fibers as the CEs were securely attached with PVA through covalent CE-GA-PVA linkages. Three types of CE/PVA MFs were fabricated and characterized through Fourier transform infrared-attenuated total reflection, C cross-polarization magic angle spinning NMR, field emission scanning electron microscope, N adsorption/desorption, and universal testing machine. The MFs exhibited pseudo-second-order rate and Langmuir-type Li adsorption. At their saturated states, the MFs were able to use 90-99% CEs for 1:1 Li complexation, suggesting favorability of their microfibrous structures for CE accessibility to Li. The MFs were highly Li-selective in seawater. Neopentyl-bearing CE was most effective in blocking larger monovalents Na and K, whereas the dibenzo CE was best in discriminating divalents Mg and Ca. Experimental selectivity trends concur with the reaction enthalpies from density functional theory calculations, confirming the influence of CE structures and cavity dimensions in their "size-match" Li selectivity.

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Section: Introductionmentioning

confidence: 99%

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li⁺ Adsorbents

Limjuco¹,

Nisola²,

Torrejos³

et al. 2017

ACS Appl. Mater. Interfaces

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“…Pore size, surface area and pore volume of SBA15-Ca-40-700 were as 802.5 Å, 35 m 2 g −1 and 0.27 cm 3 g −1 , respectively, from N 2 sorption result (Figure 10, Table 3). On the other hand, SBA15-Li-40-700 and SBA15-K-40-700 retained 2D-hexagonal mesostructure as shown Figure 9d,e [60]. Table 3 summarizes pore size, surface area and pore volume for both samples.…”

Section: Resultsmentioning

confidence: 88%

“…Inset shows the magnified SAXS patterns in the q = 0.10-0.20 ranges for samples. The SAXS pattern of mesoporous silica, SBA-15 (Figure 1A(a)) showed three scattering peaks of the 100, 110 and 200 reflections of the hexagonal symmetry lattice of the SBA-15 [2,60]. Though the intensities of the scattering peaks were decreased after thermal treatment at 700 • C when the Si/Na ratio was decreased to 50 (Figure 1A(d)), well-resolved three scattering peaks (100, 110, 200) of the hexagonal symmetry were still observed.…”

Section: Resultsmentioning

confidence: 99%

“…Figure 8B shows the XRD patterns in the range of 2θ = 10-80 • for samples. SBA15-Li-40-700 and SBA15-K-40-700 synthesized after thermal treatment at 700 • C using Li + and K + as metal ion sources retained ordered mesostructures with two peaks of the 110 and 200 reflections of the hexagonal mesoporous materials [2,60], even though SBA15-K-40-700 has low intensity of the two peaks of the 110 and 200 reflections (Figure 8A(b)).…”

Section: Resultsmentioning

confidence: 99%

“…SBA-15 was synthesized by the similar method as reported elsewhere [2,60]; in a typical synthesis, 4 g of the triblock copolymer was dissolved in 125 g of DI water and 20 g of con. HCl was added with stirring at 35 • C for 1 h. 8.5 g of TEOS was added to the solution, followed by stirring the mixture at 35 • C for 24 h. Then, it was kept at 100 • C for 24 h in a Teflon bottle.…”

Section: Synthesis Of Sba-15mentioning

confidence: 99%

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SBA-15 with Crystalline Walls Produced via Thermal Treatment with the Alkali and Alkali Earth Metal Ions

et al. 2021

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Crystalline walled SBA-15 with large pore size were prepared using alkali and alkali earth metal ions (Na+, Li+, K+ and Ca2+). For this work, the ratios of alkali metal ions (Si/metal ion) ranged from 2.1 to 80, while the temperatures tested ranged from 500 to 700 °C. The SBA-15 prepared with Si/Na+ ratios ranging from 2.1 to 40 at 700 °C exhibited both cristobalite and quartz SiO2 structures in pore walls. When the Na+ amount increased (i.e., Si/Na increased from 80 to 40), the pore size was increased remarkably but the surface area and pore volume of the metal ion-based SBA-15 were decreased. When the SBA-15 prepared with Li+, K+ and Ca2+ ions (Si/metal ion = 40) was thermally treated at 700 °C, the crystalline SiO2 of quartz structure with large pore diameter (i.e., 802.5 Å) was observed for Ca+2 ion-based SBA-15, while no crystalline SiO2 structures were observed in pore walls for both the K+ and Li+ ions treated SBA-15. The crystalline SiO2 structures may be formed by the rearrangement of silica matrix when alkali or alkali earth metal ions are inserted into silica matrix at elevated temperature.

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Synthesis of benzo‐12‐crown‐4 ether immobilized silica for lithium‐ion adsorption

Jeong,

Lim,

et al. 2024

Bulletin Korean Chem Soc

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To develop an adsorbent for Li+ recovery from seawater and/or spent lithium batteries, a benzo‐12‐crown‐4 ether (B12C4) moiety was immobilized with silica (immobilization yield: 0.70 meq g−1). Compared to pure silica, the resulting adsorbent (FB12C4‐SG) had a reduced Brunauer–Emmett–Teller surface area (500 vs. 180 m2 g−1) and pore volume (0.75 vs. 0.26 cm3 g−1). The Li+ adsorption reached equilibrium at 31 mg g−1 after 2 h (1000 ppm Li+ solution). The adsorption behavior was well explained by pseudo‐second‐order kinetics and the Langmuir adsorption model (maximum adsorption capacity: 33 mg g−1). The material exhibited a Li+/Na+ adsorption selectivity factor of 4.2 and high chemical stability under acidic regeneration conditions (1.0 N HCl solution).

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Functionalized Mesoporous Silicas with Crown Ether Moieties for Selective Adsorption of Lithium Ions in Artificial Sea Water

Cited by 21 publications

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Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li⁺ Adsorbents

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li⁺ Adsorbents

SBA-15 with Crystalline Walls Produced via Thermal Treatment with the Alkali and Alkali Earth Metal Ions

Synthesis of benzo‐12‐crown‐4 ether immobilized silica for lithium‐ion adsorption

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Functionalized Mesoporous Silicas with Crown Ether Moieties for Selective Adsorption of Lithium Ions in Artificial Sea Water

Cited by 21 publications

References 0 publications

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li+ Adsorbents

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li+ Adsorbents

SBA-15 with Crystalline Walls Produced via Thermal Treatment with the Alkali and Alkali Earth Metal Ions

Synthesis of benzo‐12‐crown‐4 ether immobilized silica for lithium‐ion adsorption

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Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li⁺ Adsorbents

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li⁺ Adsorbents