Ion Chromatography Using a Zirconia Stationary Phase Modified with Ion-exchange Functionality

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  • MORI Masanobu
    Faculty of Science and Technology, Kochi University
  • MASUNO Tomoe
    Department of Environmental Engineering Science, Gunma University
  • KANAI Asako
    Department of Environmental Engineering Science, Gunma University
  • KOZAKI Daisuke
    Faculty of Science and Technology, Kochi University

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  • イオン交換基を修飾したジルコニア固定相を用いるイオンクロマトグラフィー
  • イオン コウカンキ オ シュウショク シタ ジルコニア コテイソウ オ モチイル イオンクロマトグラフィー

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Abstract

<p>Recently, to create a new ion chromatography (IC), the authors have been studying ion separations using zirconia (ZrO2) as a stationary phase that indicates excellent chemical and thermal resistances. In this paper, we summarize the retention behaviors of inorganic ions by modifying phosphoric acid, α-hydroxy acid and diallylamine-maleic acid copolymer (DAM) to a zirconia-packed column, as well as those by an unmodified zirconia. In the unmodified zirconia, which has an equal adsorption point at pH 6 to 7, anions were retained to the stationary phase in the acidic eluent condition; in contrast, cations were retained in the basic eluent condition. The zirconia phase could selectively retain the fluoride ion based on ligand exchanges to the hydroxyl-group bound to zirconia or H2O coordinated to zirconia in the basic condition. When phosphoric acid and citric acid were modified on the zirconia, they functioned as cation-exchangers, and sould separate divalent cations (Mg2+, Ca2+, Ba2+, Mn2+, Zn2+ and Cd2+). There were no differences in the selectivity for cations between two modified columns, but a citric acid-modified zirconia column showed approximately twice the retention volume for cations as compared with phosphate-modified. It seemed to be taken into not only electrostatic adsorption, but also chelating formation. In addition, when a zwitterionic compound DAM was modified to zirconia, the amine groups in the molecule functioned as an anion exchanger and separated monovalent anions (Cl−, NO3− and ClO4−) in the acidic eluent condition. Accordingly, this study could demonstrate that the ion-exchange-modified zirconia stationary phases had potential as ion-exchange column by modifying phosphate, organic carboxylic acid and DAM, and the cation-exchange modified zirconia column provided the stable retention of cation at a higher column temperature (e.g., 80 °C).</p>

Journal

  • BUNSEKI KAGAKU

    BUNSEKI KAGAKU 68 (4), 241-251, 2019-04-05

    The Japan Society for Analytical Chemistry

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