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Adsorption and stacking behaviour of zwitterionic porphyrin on the clay surface

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Abstract:

Zwitterionic porphyrin (tetrakis {4-(2-carboxyethyl)pyridinio}porphyrin (TPyCP)) with four pyridinium and carboxyl groups in the molecule was synthesized. The adsorption behaviour of TPyCP on the montmorillonite clay surface was examined in an aqueous colloidal solution. While the adsorption maximum λmax of TPyCP was 424 nm in water, it shifted to longer wavelengths on complex formation with clay. The λmax on the exfoliated clay surface was 450 nm, and that in the stacked clay sheets was 471 nm, respectively. Under alkaline conditions ([NaOH] = 2 × 10–4 M), the stacking behaviour of the clay was completely suppressed. It emerged that anionic parts in the porphyrin molecule can suppress the stacking of clay sheets. Judging from the quantitative analysis, the maximum adsorption amount of TPyCP was 100% vs. cation exchange capacity (CEC) of the clay. As the adsorption density of TPyCP increased, λmax shifted slightly to longer wavelengths due to the interactions between adjacent porphyrins. When the loading level of TPyCP was 200% vs. CEC, the stacking of TPyCP was indicated. The average stacking layer number was calculated to be 1.48. On the other hand, it is known that tetra cationic porphyrins without anionic parts do not form such stacking structures. Thus, it seems that zwitterionic porphyrin has the potential to form a three dimensional structure through electrostatic interactions between porphyrins on the clay surface.

Keywords: ELECTROSTATIC INTERACTION; MONTMORILLONITE; ORGANIC DYE; SIZE-MATCHING RULE; ZWITTERIONIC PORPHYRIN

Document Type: Research Article

DOI: https://doi.org/10.1180/claymin.2012.047.2.07

Publication date: 2012-06-01

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