SYNTHESIS AND CHARACTERIZATION OF Zn-Al LAYERED DOUBLE HYDROXIDES INTERCALATED WITH 1- TO 19-CARBON CARBOXYLIC ACID ANIONS

被引:18
作者
Kuehn, Thomas [1 ]
Poellmann, Herbert [2 ]
机构
[1] Univ Halle Wittenberg, D-06108 Halle, Germany
[2] Univ Halle Wittenberg, D-06120 Halle, Germany
关键词
Anion Exchange; Carboxylic Acid Anion; Hydrotalcite; LDH; SURFACTANTS; INTERLAYER; EXCHANGE;
D O I
10.1346/CCMN.2010.0580502
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Layered double hydroxides (LDHs) are layered ion exchangers, with a large surface-charge density, which react easily with organic anions. Various types of organics are rapidly substituted in the interlayer space of inorganic precursor LDHs. ZnAl-LDHs were intercalated with 1- to 19-carbon monocarboxylic acid anions by anion exchange of NO3--saturated LDH precursor phases in order to study the dependence of exchange reactions on synthesis parameters (temperature, pH, and interlayer anion). The carboxylic acid anion-LDHs synthesized were characterized using X-ray diffraction, infrared spectroscopy, thermal analysis, scanning electron microscopy, chemical analysis, and N-2 adsorption. Carboxylic anion quantities in excess of the LDH anion exchange capacity easily replaced exchangeable nitrate anions at moderate pH. The intercalated LDH interlayer space depended on the alkyl chain length and orientation (inclination angle) of the carboxylic-acid anion. The lattice parameter c(0) ranged from 3.4 to 13.5 nm, but the a(0) lattice parameter remained constant at 0.31 nm. Crystallographic analyses indicated a monomolecular arrangement of intercalated short-chain fatty-acid anions. At pH < 7, intercalated long-chain carboxylates showed a preferred bimolecular interlayer orientation. Carboxylic-acid anion exchange with LDHs at pH 7 resulted in the formation of two different sets of basal spacings, which indicated the coexistence of LDHs intercalated with monomolecular and bimolecular arrangements of interlayer carboxylic compounds. Thermal treatment of the carboxylic acid anion-intercalated LDHs indicated stability up to similar to 140 degrees C. The release of interlayer water led to distortion of the crystallographic units and resulted in smaller basal spacings without collapse of the layered structure. Heat treatment re-oriented alkyl-chain carbon carboxylates (with > 10 carbons) to a more upright interlayer position.
引用
收藏
页码:596 / 605
页数:10
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