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Conducting polymers have attracted significant attention due to their easy fabrication, morphology modification, and their electrical properties. Amongst them, polypyrrole (PPy) has attractive thermoelectric (TE) properties. Engineering of this polymer in one-dimensional (1D) nanostructured form is found to enhance its TE performance. This was achieved in the present work by using multi-walled carbon nanotubes (MWCNTs) as a core template to direct the self-assembly of PPy and also to further enhance its TE performance. The growth of PPy on the sidewalls of MWCNTs was performed in an acidic medium based oxidative in situ polymerization. Various concentrations of MWCNTs within the range 1.1–14.6 wt.% were used to form the MWCNTs/PPy nanocomposites in 1D core-shell structures. The morphology and microstructure results of the produced nanocomposite samples showed that this MWCNTs were successfully coated by thick and thin layers of PPy. At low concentrations of MWCNTs, thick layers of PPy are formed. While at high concentrations thin layers are coated. The formed 1D nanocomposites have enhanced TE performance, particularly those containing higher contents of MWCNTs. The power factor and figure of merit values for the formed 1D nanocomposites recorded around 0.77 µV/mK2 and 1 × 10−3 at room temperature (RT), respectively. This enhancement was attributed to the perfect coating and good interaction between PPy and MWCNT through π–π stacking between the polymer chains and these nanotubes. These results might be useful for developing future TE materials and devices.

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