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Polymerization of Benzene and Aniline on Cu(II)-Exchanged Hectorite Clay Films: A Scanning Force Microscope Study

Published online by Cambridge University Press:  28 February 2024

Michael P. Eastman
Department of Chemistry, Northern Arizona University, Flagstaff, Arizona 86011
Michael E. Hagerman
Department of Chemistry, Northern Arizona University, Flagstaff, Arizona 86011
Jennifer L. Attuso
Department of Chemistry, Northern Arizona University, Flagstaff, Arizona 86011
Edlin D. Bain
Department of Chemistry, Northern Arizona University, Flagstaff, Arizona 86011
Timothy L. Porter
Department of Physics, Northern Arizona University, Flagstaff, Arizona 86011


The technique of scanning force microscopy (SFM) was used to study the nanometer-scale structure of Cu(II)-exchanged hectorite thin films. Supporting data were also obtained from Electron Spin Resonance (ESR) and X-ray diffraction (XRD) techniques. The surfaces studied included pure Cu(II)-exchanged hectorite, Cu(II)-exchanged hectorite exposed to benzene and Cu(II)-exchanged hectorite exposed to aniline. SFM images of the unexposed Cu(II)-exchanged hectorite surface revealed a smooth surface composed of interlocking platelets. The lateral dimension of these platelets ranged from a few nm to about 1 μm. After exposure to refluxing benzene, the SFM showed that the platelets underwent vertical shifts in position. This is believed to have occurred from intercalated benzene that polymerized in the interlayer region. No SFM evidence was obtained for benzene polymerization on the surface of the hectorite. Hectorite films exposed to aniline at room temperature revealed a post-polymerization structure on the hectorite surface consisting of small polymer bundles. The diameter of these bundles was measured to be 300–3000 Å, similar to the structure seen on electropolymerized polyaniline films. Aniline polymerized on the surface of hectorite films at 180 °C revealed a structure similar to undoped n-methyl-pyrrolidinone (NMP) cast polyaniline films. In this case, the polymer bundles are only 300 Å in dimension on average. XRD and ESR data also indicated interlayer aniline polymerization in Cu(II) exchanged hectorite. Mechanistic considerations affecting these polymerization reactions are presented.

Research Article
Copyright © 1996, The Clay Minerals Society

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Eastman, M.P., Patterson, D.E. and Pannell, K.H.. 1984. Reaction of benzene with Cu(II)- and Fe(III)-exchanged hectorites. Clays Clay Miner 32: 327333.CrossRefGoogle Scholar
Goddard, R., Haenel, M.W., Herndon, W.C., Krüger, C. and Zander, M.. 1995. Crystallization of large planar polycyclic aromatic hydrocarbons: The molecular and crystal structures of hexabenzo[bc,ef,hi,kl,no,qr] coronene and benzo[1,2,3-bc: 4,5,6-b'c']dicoronene. J Am Chem Soc 117: 3141.CrossRefGoogle Scholar
Langer, J.J.. 1990. A process leading to the domain structure of aniline black (polyaniline). Synth Met 36: 3540.CrossRefGoogle Scholar
Martin, C.R.. 1995. Template synthesis of electrically conductive polymer nanostructures. Acc Chem Res 28: 6168.CrossRefGoogle Scholar
McBride, M.B., Pinnavaia, T.J. and Mortland, M.M.. 1975. Electron spin resonance studies of cation orientation in restricted water layers on phyllosilicate (smectite) surfaces. J Phys Chem 22: 24302435.CrossRefGoogle Scholar
Mehrotra, V. and Giannelis, E.P.. 1992. Nanometer scale multilayers of electroactive polymers: intercalation of polypyrrole in mica-type silicates. Solid State Ionics 51: 115122.CrossRefGoogle Scholar
Mortland, M.M. and Pinnavaia, T.J.. 1971. Formation of copper(II) arene complexes in the interlamellar surfaces of montmorillonite. Nature 229: 7577.Google Scholar
Pinnavaia, T.J., Hall, P.L., Cady, S.S. and Mortland, M.M.. 1974. Aromatic radical cation formation on the intracrystal surfaces of transition metal layer silicates. J Chem Phys 78: 994999.CrossRefGoogle Scholar
Porter, T.L., Minore, D., Stein, R. and Myrann, M.. 1995. Scanning probe microscope and effective medium theory study of free-standing polyaniline thin films. J Polym Sci 33: 21672173.CrossRefGoogle Scholar
Porter, T.L., Sykes, A.G. and Caple, G.. 1994. Scanning probe microscope imaging of polyaniline thin films in non-contact mode. Surface and Interface Anal 21: 814817.CrossRefGoogle Scholar
Rupert, J.P.. 1973. Electron spin resonance spectra of interlamellar copper(II)-arene complexes on montmorillonite. J Chem Phys 77: 784790.CrossRefGoogle Scholar
Soma, Y., Soma, M. and Harada, I.. 1983. Resonance raman spectra of benzene adsorbed on Cu2+ montmorillonite. Formation of poly(p-phenylene) cations in the interlayer of the clay mineral. Chem Phys Lett 99: 153156.CrossRefGoogle Scholar
Wu, C.G. and Bein, T.. 1994a. Conducting carbon wires in ordered, nanometer-sized channels. Science 266: 10131015.CrossRefGoogle ScholarPubMed
Wu, C.G. and Bein, T.. 1994b. Polyaniline wires in oxidant-containing mesoporous channel hosts. Chem Mater 6: 11091112.CrossRefGoogle Scholar