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Phase Chemistry for Hydration Sensitive (De)intercalation of Lithium Aluminum Layered Double Hydroxide Chlorides.

ABSTRACT: Lithium aluminum layered double hydroxide chlorides (LADH-Cl) have been widely used for lithium extraction from brine. Elevation of the performances of LADH-Cl sorbents urgently requires knowledge of the composition-structure-property relationship of LADH-Cl in lithium extraction applications, but these are still unclear. Herein, combining the phase equilibrium experiments, advanced solid characterization methods, and theoretical calculations, we constructed a cyclic work diagram of LADH-Cl for lithium capture from aqueous solution, where the reversible (de)hydration and (de)intercalation induced phase evolution of LADH-Cl dominates the apparent lithium "adsorption-desorption" behavior. It is found that the real active ingredient in LADH-Cl type lithium sorbents is a dihydrated LADH-Cl with an Al:Li molar ratio varying from 2 to 3. This reversible process indicates an ultimate reversible lithium (de)intercalation capacity of ∼10 mg of Li per g of LADH-Cl. Excessive lithium deintercalation results in the phase structure collapse of dihydrated LADH-Cl to form gibbsite. When interacting with a concentrated LiCl aqueous solution, gibbsite is easily converted into lithium saturated intercalated LADH-Cl phases. By further hydration with a diluted LiCl aqueous solution, this phase again converts to the active dihydrated LADH-Cl. In the whole cyclic progress, lithium ions thermodynamically favor staying in the Al-OH octahedral cavities, but the (de)intercalation of lithium has kinetic factors deriving from the variation of the Al-OH hydroxyl orientation. The present results provide fundamental knowledge for the rational design and application of LADH-Cl type lithium sorbents.

SUBMITTER: Li D

PROVIDER: S-EPMC10786131 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

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Phase Chemistry for Hydration Sensitive (De)intercalation of Lithium Aluminum Layered Double Hydroxide Chlorides.

Li Dongdong D Zhang Ning N Gao Dandan D Zhuang Ziyu Z Zeng Dewen D

ACS materials Au 20231006 1

Lithium aluminum layered double hydroxide chlorides (LADH-Cl) have been widely used for lithium extraction from brine. Elevation of the performances of LADH-Cl sorbents urgently requires knowledge of the composition-structure-property relationship of LADH-Cl in lithium extraction applications, but these are still unclear. Herein, combining the phase equilibrium experiments, advanced solid characterization methods, and theoretical calculations, we constructed a cyclic work diagram of LADH-Cl for ...[more]

PMID: 38221919

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Project description:Environmental pollution resulting from the use of pesticides such as fenuron poses significant health risks due to the carcinogenic and teratogenic properties of these compounds. There is an urgent need to develop rapid and cost-effective detection methods for quantifying fenuron. In this study, an inorganic-organic composite material was obtained by intercalating sodium dioctylsulfosuccinate (DSS) within the interlayer space of a nickel-aluminum-layered double hydroxide (NiAl-LDH). The pristine and modified LDHs (NiAl-LDH) were characterized using Fourier transform infrared, X-ray diffraction, and thermogravimetric analysis, confirming the successful intercalation of DSS in the mineral structure. The modified LDH was used to elaborate a sensor for detecting fenuron herbicide via differential pulse voltammetry (DPV) employing a carbon paste electrode (CPE). The electrochemical procedure for fenuron analysis consisted of immersing the working electrode in an electrolytic solution containing the appropriate amount of fenuron, followed by voltammetry detection without any preconcentration step. Compared to CPE modified by pristine LDH, the peak current obtained on the organo-LDH-modified CPE was twice as high. The increase in the fenuron signal was attributed to the high organophilic feature of this composite material induced by DSS modification. To optimize the sensitivity of the organo-LDH modified electrode, the effects of several experimental parameters such as pH of the medium and proportion of the modifier in the paste on the stripping response were examined. Linear calibration curves were obtained for the fenuron concentrations ranging from 0.5 × 10-6 to 1 × 10-6 mol.L-1 and 1 × 10-6 to 5 × 10-6 mol.L-1. The limit of detection (LOD) calculated on the basis of a signal-to-noise ratio of 3 was found to be 1.8 × 10-8 mol.L-1 for the low concentration range with a limit of quantification (LOQ) which was 6 × 10-8 mol.L-1. Furthermore, the interference effect of several inorganic ions and other pesticides potentially affecting fenuron stripping was explored, and the method's applicability was confirmed by determining fenuron levels in a river sample taken from down-town Yaoundé.

Dataset Information

Phase Chemistry for Hydration Sensitive (De)intercalation of Lithium Aluminum Layered Double Hydroxide Chlorides.

Publications

Phase Chemistry for Hydration Sensitive (De)intercalation of Lithium Aluminum Layered Double Hydroxide Chlorides.

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