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Nanometer-scale chemical modification of nano-ball allophane

Published online by Cambridge University Press:  01 January 2024

Zaenal Abidin ,
Naoto Matsue  and
Teruo Henmi
Zaenal Abidin
Affiliation:
Applied Chemistry for Environmental Industry Laboratory, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama 790-8566, Japan Inorganic Chemistry Laboratory, Department of Chemistry, Faculty of Mathematics and Natural Science, Bogor Agricultural University, Kampus IPB Darmaga Jl. Meranti Bogor, West of Java, 16680 Indonesia
Naoto Matsue
Affiliation:
Applied Chemistry for Environmental Industry Laboratory, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama 790-8566, Japan
Teruo Henmi*
Affiliation:
Applied Chemistry for Environmental Industry Laboratory, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama 790-8566, Japan
*
*E-mail address of corresponding author: henmi@agr.ehime-u.ac.jp
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Abstract

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Nano-ball allophane is a hydrous Al silicate with a hollow-sphere morphology that contains some defects or pores along the spherule walls. Enlargement of the pore openings by dilute alkali treatment was confirmed by cation exchange capacity determinations using various alkylammonium cations as replacement cations. An allophane sample with a low Si/Al ratio (0.67) was equilibrated with 10 mM CaCl2 (pH = 6.0) and the Ca2+ retained was extracted using aqueous 1 M NH4C1 or alkylammonium chloride salts. The Ca2+ extracted by NH4+ was 15.1 cmolc kg−1, but CH3NH3+${\rm{C}}{{\rm{H}}_3}{\rm{NH}}_3^ + $ (mean diameter = 0.38 nm) only extracted 7.9 cmolc kg−1 of Ca2+. After 10 mM NaOH treatment (0.25 g:100 mL) of the allophane, the Ca2+ extracted by NH4+${\rm{NH}}_4^ + $ was 29.7 cmolc kg−1, 29.6 cmolc kg−1 by CH3NH3+${\rm{C}}{{\rm{H}}_3}{\rm{NH}}_3^ + $, and 29.4 cmolc kg−1 by (CH3)2NH2+${{\rm{(C}}{{\rm{H}}_3}{\rm{)}}_2}{\rm{NH}}_2^ + $. The extraction of Ca2+ by the large C2H5NH3+${{\rm{C}}_2}{{\rm{H}}_5}{\rm{NH}}_3^ + $ cation (mean diameter = 0.46 nm) only decreased to 26.1 cmolc kg−1, indicating that pore diameters were enlarged from ∼0.35 to 0.45 nm. The significant increase in Ca2+ retention after NaOH treatment was attributed to the dissociation of increased numbers of newly exposed silanol groups in the enlarged pores. The low Si/Al ratio of the NaOH-dissolved material (0.35) and the decreased intensity of the 348 cm−1 IR band also suggested selective dissolution of the pore region. For allophane with a high Si/Al ratio (0.99) and much accessory polymeric Si, dissolution of polymeric Si and of the pore region occurred simultaneously. Alkali treatment produced a smaller increase in pore size and Ca2+ retention for allophanes with large Si/Al ratios than for allophanes with small Si/Al ratios. It was concluded that by altering the dilute alkali treatment conditions and varying the Si/Al ratio of allophane, the extent of structural modification or pore enlargement of the hollow spheres might be controlled.

Keywords

AlkylammoniumAllophaneDilute AlkaliDissolutionPore Size
Type
Research Article
Information
Clays and Clay Minerals , Volume 55 , Issue 4 , August 2007 , pp. 443 - 449
Copyright
Copyright © 2007, The Clay Minerals Society

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