Direct Extraction of Sodium Hydroxide by Calix[4]pyrrole-Based Ion-Pair Receptors

Inhong Hwang; Sheng Yin Huang; Scott Smith; Vincent Lynch; Radu Custelcean; Bruce A. Moyer; Nitesh Kumar; Vyacheslav S. Bryantsev; Jonathan L. Sessler

doi:10.1021/jacs.3c03547

Direct Extraction of Sodium Hydroxide by Calix[4]pyrrole-Based Ion-Pair Receptors

Inhong Hwang, Sheng Yin Huang, Scott Smith, Vincent Lynch, Radu Custelcean, Bruce A. Moyer, Nitesh Kumar, Vyacheslav S. Bryantsev, Jonathan L. Sessler

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

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Abstract

Described in this work are calix[4]pyrrole-based ion-pair receptors, cis/trans-1 and cis/trans-2, designed for the extraction of sodium hydroxide. An X-ray diffraction analysis of a single crystal of the cis-1·NaOH isomer isolated from a mixture of cis/trans-1 revealed a unique dimeric supramolecular structure. An average dimer in toluene-d₈ solution was inferred on the basis of diffusion-ordered spectroscopy (DOSY). Support for the proposed stoichiometry came from density functional theory (DFT) calculations. The structural stability of the dimeric cis-1·NaOH complex in toluene solution was further confirmed by ab initio molecular dynamics (AIMD) simulation with explicit representation of solvent. Under conditions of liquid-liquid extraction (LLE), purified receptors cis- and trans-2 were both found to remove NaOH from a pH 11.01 aqueous source phase into toluene with extraction efficiencies (E%) of 50-60% when used equimolar to NaOH. However, in all cases, precipitation was observed. Complexities associated with precipitation could be avoided by immobilization of the receptors onto a chemically inert poly(styrene) resin by means of solvent impregnation. The use of solvent-impregnated resins (SIRs) eliminated precipitation in solution while retaining the extraction efficiency toward NaOH. This allowed both the pH and salinity of the alkaline source phase to be lowered.

Original language	English
Pages (from-to)	14387-14394
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	145
Issue number	26
DOIs	https://doi.org/10.1021/jacs.3c03547
State	Published - Jul 5 2023

Funding

J.L.S. acknowledged the support from the Robert A. Welch Foundation (F-0018). The work at the Oak Ridge National Laboratory was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory and the National Energy Research Scientific Computing Center (NERSC), which are supported by the Office of Science of the U.S. Department of Energy under Contracts No. DE-AC05-00OR22725 and No. DE-AC02-05CH11231, respectively.

Funders	Funder number
CADES
Data Environment for Science
U.S. Department of Energy
Welch Foundation	F-0018
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory	DE-AC05-00OR22725, DE-AC02-05CH11231
Chemical Sciences, Geosciences, and Biosciences Division

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title = "Direct Extraction of Sodium Hydroxide by Calix[4]pyrrole-Based Ion-Pair Receptors",

abstract = "Described in this work are calix[4]pyrrole-based ion-pair receptors, cis/trans-1 and cis/trans-2, designed for the extraction of sodium hydroxide. An X-ray diffraction analysis of a single crystal of the cis-1·NaOH isomer isolated from a mixture of cis/trans-1 revealed a unique dimeric supramolecular structure. An average dimer in toluene-d8 solution was inferred on the basis of diffusion-ordered spectroscopy (DOSY). Support for the proposed stoichiometry came from density functional theory (DFT) calculations. The structural stability of the dimeric cis-1·NaOH complex in toluene solution was further confirmed by ab initio molecular dynamics (AIMD) simulation with explicit representation of solvent. Under conditions of liquid-liquid extraction (LLE), purified receptors cis- and trans-2 were both found to remove NaOH from a pH 11.01 aqueous source phase into toluene with extraction efficiencies (E%) of 50-60% when used equimolar to NaOH. However, in all cases, precipitation was observed. Complexities associated with precipitation could be avoided by immobilization of the receptors onto a chemically inert poly(styrene) resin by means of solvent impregnation. The use of solvent-impregnated resins (SIRs) eliminated precipitation in solution while retaining the extraction efficiency toward NaOH. This allowed both the pH and salinity of the alkaline source phase to be lowered.",

author = "Inhong Hwang and Huang, {Sheng Yin} and Scott Smith and Vincent Lynch and Radu Custelcean and Moyer, {Bruce A.} and Nitesh Kumar and Bryantsev, {Vyacheslav S.} and Sessler, {Jonathan L.}",

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AU - Hwang, Inhong

AU - Huang, Sheng Yin

AU - Smith, Scott

AU - Lynch, Vincent

AU - Custelcean, Radu

AU - Moyer, Bruce A.

AU - Kumar, Nitesh

AU - Bryantsev, Vyacheslav S.

AU - Sessler, Jonathan L.

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Direct Extraction of Sodium Hydroxide by Calix[4]pyrrole-Based Ion-Pair Receptors

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