LAYERED MATERIALS AS TEMPLATES FOR PYRROLE POLYMERIZATION Garrido, F. M. S.*; Peres, R.C.D.; Medeiros, M.E.; Santos, A.M.; Malta, L.F.B.

Instituto de Química, UFRJ , Centro de Tecnologia, Bloco A, Ilha do Fundão, Rio de Janeiro, RJ, Brasil. chico@iq.ufrj.br Recently, there has been tremendous interest in the development of conducting structures with nanometer dimensions. These nanostructured-conducting materials could find many attractive applications such as electrochromic devices, supercapacitors, polymeric electrodes and sensors [1-3]. Many nanotubes and nanowires of polymers, metals and carbons have been produced through template approach with layered inorganic solids, zeolites and mesoporous materials [1-3]. The advantages of template-mediated synthesis are: (1) clear size distinction of nanostructures, (2) low processing temperature, (3) easier separation of nanowires from the template, and (4) inexpensive and cost-effective synthesis [3]. In this article, we describe the templated-mediated synthesis of polypyrrole (PPy) using two different layered solids as templates. The layered material alfa-Zr(HPO4)2.H2O (ZrP) or its Cu2+ 100% exchanged form (ZrPCu) was used first. In these synthesis 0.17g of one of these solids was allowed to disperse in 5mL of acetone for 15min at 25 oC, in the presence of ultrasonication. Following, 5mL of a 30% (v/v) solution of pyrrole was added and after another section of ultrasonication (60min) the acetone was eliminated by evaporation and the resulting solid was dried at 140 oC over night. In the synthesis of ZrP/PPy a light brown solid was first formed, and a black lustrous solid was obtained after dried at 140 oC in air, the PPy content in this nanocomposite was around 13% in mass. When ZrPCu was used as template a black solid (ZrPCu/PPy) was formed during the 60min of ultrasonication. After dried ZrPCu/PPy at 140 oC an increase of 25% in mass was observed, if compared with ZrPCu dried at the same temperature. The formations of nanocomposites were characterized by infrared spectroscopy (FT-IR). The FT-IR spectra of ZrP and ZrP/PPy can be seen in Fig. 1. The formation of PPy was confirmed by the bands at 1705 (oxidized PPy), 1598 (C-C & C=C str.), 1435 (C-N str.), 1256 (C-H def), 1226 (N-H def), 770 and 714cm-1 [5]. Most of vibrational bands of ZrP were significantly perturbed, reflecting the interactions of PPy with the inorganic matrix; it is interesting to note that the position of vibrational band at 595cm-1 (associated with the P-O deformation of O3POH group) was not affected. The FT-IR spectra of ZrPCu and ZrPCu/PPy can be seen in Fig. 2. The bands confirmed the formation of PPy at 1701, 1421, 780 and 730cm-1. The presence of a band at 598cm-1 for ZrPCu/PPy suggests the protonation of inorganic matrix PO4 groups; this observation is consistent with the chemical reduction of at least part of Cu2+ ions. The interaction of PPy with the inorganic matrix is confirmed by the modification in the position of matrix bands, especially at 650 to 400cm-1. Another layered material studied was VO(PO3CH2CH2CHOOH).CH3CH2OH 100% Cu2+ exchanged form (VOPCu). In this synthesis 0,400g of VOPCu was put in contact with pyrrole vapor at 25 oC for one (VOPCu/PPy1) and five (VOPCu/PPy5) days. For VOPCu/PPy1 a dark green color was observed and for VOPCu/PPy5 a dark gray color. The FT-IR spectra of VOPCu, VOPCu/PPy1 and VOPCu/PPy5 can been seen in Fig. 3. For VOPCu/PPy1 spectrum no significant differences were observed if compared with VOPCu spectrum. In the VOPCu/PPy5 spectrum the bands at 1567, 1163, 1132, 952 cm-1 can be attributed to PPy. The matrix/ polymer interaction is confirmed by modification in the intensity and position of matrix bands at 900 to 500cm-1. Our results showed the synthesis of polypyrrole (PPy) using different layered solids as templates. The role of Cu2+ in the formation of PPy at room temperature is confirmed. The molecular interaction between the polymer and the inorganic matrix is made evident. An increase in the formation rate of PPy under ultrasonication was observed. References: [1] A. Malinauskas, Polymer 43 (2001) 3957-3972. [2] J. Jang, B. Lim, J. Lee and T. Hyeon, Chem. Comm. (2001) 83-84. [3] J.K. Park, S.H. Lee, B. Kim and Y Park, Appl. Phys. Lett. 81 (2002) 4625-4627. .W. [4] C.W. Kwon, S. Mornet, A. Poquet, G. Campet, J. Portier and J.H. Choy; Electrochem. Comm. 4 (2002) 197-200. Figure 1 – Infrared spectra of ZrP and ZrP/PPy. Figure 2 – Infrared spectra of ZrPCu and ZrPCu/PPy. Figure 3 – Infrared spectra of VOPCu; VOPCu/PPy1 and VOPCu/PPy5.

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