Application of a Lithium-ion Selective Metallacrown to Extraction-Spectrophotometric Determination of Lithium in Saline Water

Katsuta, Shoichi; Saito, Yuki; Takahashi, Shingo

doi:10.2116/analsci.34.189

Cited by 9 publications

(9 citation statements)

References 25 publications

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“…To date, MOFs have not been utilized for lithium detection, so LMOF-321 sets the standard among this class of materials. LMOF-321 is well-matched with other types of inorganic and organic fluorescent sensor materials that target lithium, including fluoroionophores, nanoparticles, and metallacrown-complexes, ,,− among other compounds, ,,, presenting comparable quantitative detection values. The detection limit from LMOF-321, compared to known fluoroionophores for lithium sensing, was enhanced by a factor of 10 6 .…”

Section: Resultsmentioning

confidence: 86%

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Luminescent Metal–Organic Framework for Lithium Harvesting Applications

Rudd

Liu

Tan

et al. 2019

ACS Sustainable Chem. Eng.

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We have synthesized a stable luminescent metal–organic framework (LMOF) through modification of an established Zr-based structure. The three-dimensional porous network of LMOF-321 represents a step forward in the development of robust, dual-ligand Zr-MOFs. This material is based on Zr6-nodes, which underlie chemically and thermally stable frameworks. LMOF-321 exhibits notable durability in diverse types of water samples (deionized, acidic/basic, seawater). The porosity, luminescence, and specific functionality from LMOF-321 establishes itself as a fluorescent chemical sensor and adsorbent for aqueous analytes. Studies have been implemented to analyze interactions of LMOF-321 with Li+ and other metals commonly found in water. The fluorescence intensity from LMOF-321 is responsive to Li+ at a parts per billion level (3.3 ppb) and demonstrates high selectivity for Li+ over other light metals, with detection ratios of 6.2, 14.3, and 44.9 for Li+/Na+, Li+/Ca2+, and Li+/Mg2+, respectively. These performances were maintained in ion-doped deionized and seawater samples, highlighting the potential of LMOF-321 for field applications. The Li+ K SV value for LMOF-321 (6549 M–1) sets the standard for LMOF sensors. ICP-OES reveals the selective adsorption of Li+ over other light metals, consistent with fluorescence measurements. LMOF-321 has a maximum uptake capacity of 12.18 mg/g, on par with lithium extraction materials. The adsorption data was fitted using Langmuir adsorption model with a high correlation factor (>0.999). XPS and FTIR studies provide insight to help understand the interaction mechanism between Li+ and LMOF-321, focusing on the bis(sulfonyl)imide functionality in the pillaring coligand. No other MOFs have been utilized for both the detection and extraction of Li+, rendering this work one step further toward more efficient harvesting procedures.

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Section: Resultsmentioning

confidence: 86%

“…As stated above, select metallacrown-complexes have exhibited impressive detection limits in deionized, tap, lake, and saline water; , however, the recyclability of these materials were never discussed. Preproduction costs for lithium-ion batteries need to be diminished so focus can be applied toward research and development.…”

Section: Resultsmentioning

confidence: 99%

Luminescent Metal–Organic Framework for Lithium Harvesting Applications

Rudd

Liu

Tan

et al. 2019

ACS Sustainable Chem. Eng.

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“…When A – = picrate and organic solvent = dichloromethane, the K ex values are 1.0 × 10 8 and 1.4 × 10 3 for Li + and Na + , respectively, at 25 °C; the separation factor ( SF Li/Na ) defined as the ratio of K ex for Li + to that for Na + is 7.1 × 10 4 . Furthermore, an extraction spectrophotometric determination method for Li + was established using [{Ru(DMA)(pyO 2 )} 3 ], and was applied to the determination of Li + in seawater [ 11 ]. This method has excellent sensitivity and selectivity for Li + determination, but its drawback is that extraction is very slow, requiring 12 h of shaking for extraction equilibration.…”

Section: Introductionmentioning

confidence: 99%

Extraction spectrophotometry using a lithium-ion selective metallacrown: temperature effect on extraction reaction and application to determination of lithium in serum and seawater

Katsuta,

Maeda

2024

ANAL. SCI.

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A metallacrown-type ionophore, 2,3-pyridinediolate-bridged (3,5-dimethylanisole)ruthenium trinuclear complex, has a high extraction selectivity for Li+, but the extraction reaction is very slow. To solve this problem, the effect of temperature on the rapidity and equilibrium of the extraction of Li+ and Na+ as picrates from water to toluene with the metallacrown was investigated in this study. While the extraction of Li+ requires 6 h of shaking for equilibration at 25 °C, the distribution ratio becomes nearly constant after 4 h and 2 h of shaking at 37 °C and 50 °C, respectively. The extraction equilibrium constants (Kex) and associated thermodynamic parameters determined for Li+ and Na+ indicate that the extraction reactions are exothermic and enthalpy-driven: ΔH° = − 53 kJ/mol, ΔS° = − 0.03 kJ/(mol K) for Li+; ΔH° = − 28 kJ/mol, ΔS° = − 0.03 kJ/(mol K) for Na+. Although the extraction ability for Li+ and selectivity for Li+/Na+ decrease with increasing temperature, the values of Kex and Kex(Li+)/Kex(Na+) are 1.0 × 107 and 1.3 × 104, respectively, even at 50 °C, indicating that both are sufficiently high. In the determination of Li+ by extraction spectrophotometry using this metallacrown, extraction at 50 °C for 2 h was employed to speed up the analysis. The method was applied to seawater and serum samples containing a large amount of coexisting ions such as Na+ and Mg2+, and trace amounts (10−6–10−5 mol/L order) of Li+ in microvolume samples (sub-mL order) could be successfully determined. Graphical abstract

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“…Although various analytical methods, including inductively coupled plasma (ICP), glow discharge optical emission spectroscopy (GD-OES), electrochemical analytical methods, and various microscopy methodologies, have been used for lithium quantification, these methods are limited because they are time-consuming, expensive, and complicated. , In addition, compared to other alkali metals, the high charge density of Li + (hard acid) enables it to successfully be bound with the hard donor oxygen and nitrogen atoms present in the receptors . However, lithium ions generally exhibit poor coordination ability due to their small size and strong hydration in aqueous medium, making it more challenging to develop selective sensors for this purpose. − Thus, the selective detection of the well solvated lithium ion in an aqueous environment containing competing ions such as Na + or Mg 2+ is also a challenging task …”

Section: Introductionmentioning

confidence: 99%

Dual-Emission Metal–Organic Framework for Highly Selective Ratiometric Sensing of Lithium(I) Ions in Aqueous Solution

Chen

Jiang

Cheng

et al. 2023

ACS Sustainable Chem. Eng.

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The development of highly selective and sensitive detection methods for lithium ions in various environments, such as aqueous or battery application, is highly sought. However, it remains elusive due to the small radius and weak coordination ability of lithium ions. Considering a metal−organic framework (MOF) possesses plentiful open coordination sites and an adjustable pore size, the welldesigned MOF would be an ideal platform for the selective detection of Li + . Herein, a novel dual-emission luminescent metal−organic framework with three-dimensional structure, namely, Co−HIAT, was prepared by the hydrothermal method and structurally characterized. The Co−HIAT MOF displays the ligand-based emission at 340 nm and the charge transition emission between the metal ions and ligand at 410 nm simultaneously. Hence, the first example of ratiometric fluorescence detecting of Li + can be achieved by measuring the ratio of fluorescence at 410 to 340 nm in the fluorescent spectra of the Co−HIAT, which exhibits the outstanding sensitivity and selectivity, giving a detection limit down to 0.17 μM. Detailed experimental studies showed that the sensing mechanism involves the strong interactions of Li + with the reasonable hydroxyl and carboxyl oxygen atoms in the Co−HIAT framework, which is responsible for the ratiometric change in fluorescence emission properties in the inclusion of Li + . It is worth noting that electrochemical experiments further confirmed its superior affinity for lithium ions. This work represents an important and feasible pathway to design MOFs for the detection of Li + .

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Application of a Lithium-ion Selective Metallacrown to Extraction-Spectrophotometric Determination of Lithium in Saline Water

Cited by 9 publications

References 25 publications

Luminescent Metal–Organic Framework for Lithium Harvesting Applications

Luminescent Metal–Organic Framework for Lithium Harvesting Applications

Extraction spectrophotometry using a lithium-ion selective metallacrown: temperature effect on extraction reaction and application to determination of lithium in serum and seawater

Dual-Emission Metal–Organic Framework for Highly Selective Ratiometric Sensing of Lithium(I) Ions in Aqueous Solution

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