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. 2024 Mar 7;29(6):1197.
doi: 10.3390/molecules29061197.

Exploring the Influence of Morphology on Bipolaron-Polaron Ratios and Conductivity in Polypyrrole in the Presence of Surfactants

Thaneeya Samwang  1   2 , Nozomi Morishita Watanabe  1 , Yukihiro Okamoto  1 , Hiroshi Umakoshi  1
Affiliations

Exploring the Influence of Morphology on Bipolaron-Polaron Ratios and Conductivity in Polypyrrole in the Presence of Surfactants

Thaneeya Samwang et al. Molecules. .

Abstract

This research aims to deepen the understanding of the relationship between conductivity and morphology in polypyrrole (PPy) via a comparison of the bipolaron to polaron ratios with a focus on the C-H deformation area. PPy samples were synthesized with different surfactants: sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and tween 80 (TW). This study revealed that SDS significantly altered the bipolaron and polaron in the C-H deformation region and showed higher conductivity than other surfactants. Notably, the morphological shifts to a sheet-like structure when using ammonium sulfate (APS) contrasted with the particle-like form observed with ferric chloride (FeCl3). These results showed that if the oxidant changed, the bipolaron and polaron ratios in C-H deformation were unrelated to PPy morphology. However, this work showed a consistent relationship between SDS use, the bipolaron and polaron ratios in the C-H deformation, and the conductivity properties. Moreover, the natural positive charge of PPy and negatively charged SDS molecules may lead to an electrostatic interaction between PPy and SDS. This work assumes that this interaction might cause the transformation of polaron to bipolaron in the C-H deformation region, resulting in improved conductivity of PPy. This work offers more support for the future investigation of PPy characteristics.

Keywords: C-H deformation; Raman spectra; bipolaron and polaron ratio; polypyrrole; sodium dodecyl sulfate; surfactant.

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Conflict of interest statement

The authors declare no conflicts of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Figure 1
Figure 1
(a) Illustration of the pyrrole polymerization and (b) the molecular configuration of dimers with different interaction sites.
Scheme 1
Scheme 1
Illustration of the relationship between PPy properties.
Figure 2
Figure 2
Average size, PdI, and zeta potential determined from the zetasizer: (a) average size and PdI, (b) zeta potential.
Figure 3
Figure 3
SEM image at 10,000 magnifications comparing the original picture (left) and the analyzed picture (right): (a) PPy*, (b) Py-SDS-APS, (c) Py-CTAB-APS, (d) Py-TW-APS (the analyzed picture received from the red triangle area), (e) Py-SDS-Fe, and (f) Py-CTAB-Fe. The red arrows show where the boundaries were found from the analysis, representing the shape correlated to the SEM picture.
Figure 3
Figure 3
SEM image at 10,000 magnifications comparing the original picture (left) and the analyzed picture (right): (a) PPy*, (b) Py-SDS-APS, (c) Py-CTAB-APS, (d) Py-TW-APS (the analyzed picture received from the red triangle area), (e) Py-SDS-Fe, and (f) Py-CTAB-Fe. The red arrows show where the boundaries were found from the analysis, representing the shape correlated to the SEM picture.
Figure 4
Figure 4
(a) I/V graph data determined from the autopolarization machine using the LSV mode; the dashed line refers to the slope fitted from Origin software (OriginPro 2023, Student version 10.0.0.154), and (b) conductivity calculated from resistance based on each sample.
Figure 5
Figure 5
(a) Raman spectra and (b) bipolaron/polaron ratios of the samples. Samples composed of PPy were synthesized with SDS, CTAB, and Tween80 as surfactants and APS and FeCl3 as oxidizing agents.
Figure 6
Figure 6
(a) UV-Vis-NIR absorption ranged between 250 and 1000 nm, (b) bandgap calculated from UV-Vis-NIR absorbance.
Scheme 2
Scheme 2
Illustration of the formation of PPy within a surfactant structure. This image depicts the micelles formed by the surfactants in an aqueous solution. The hydrophilic heads of the surfactants are oriented outward (circle with pink, yellow, and green), whereas the hydrophobic tails face inward (gray stick), forming the core of the micelle. The polymerization of Py occurs inside these micelle structures, with Py monomers linked together to form polymer chains. PPy chains were confined within the hydrophobic core of the surfactant micelles.
Figure 7
Figure 7
The relationship between the bipolaron and polaron ratio (B/P ratio) in the C–H deformation region and conductivity and bandgap.
Scheme 3
Scheme 3
(a) Two-electrode cell construction for resistance measurement and (b) half-side view of the cells.
See this image and copyright information in PMC

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