Polymerization of Poly(3,4-ethylenedioxythiophene) on Sulfated Cellulose Nanofiber and Its Conducting Property

Recent research on incorporating biomass resources into functional polymers has garnered significant attention. Poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) is the most commercially successful conducting polymer composed of over 70 wt% petroleum-derived PSS, which presents an opportunity for partial replacement with biomass-based resources. In this study, a complex of PEDOT and sulfated cellulose nanofiber (PEDOT:s-CNF) was synthesized, and the relationship between its conductivity and doping conditions was investigated. PEDOT was synthesized on s-CNF, which was used in place of PSS, and the results indicate that conductivity increases as PEDOT polymerization progresses; however, excessive polymerization reduces electrical conductivity. Based on X-ray photoelectron spectroscopy and zeta potential measurements, the doping concentration decreases as PEDOT polymerization progresses to an excess state. This decrease is attributed to the depletion of sulfate groups, which act as dopants on s-CNFs, occurring as a consequence of the addition of PEDOT monomers. Enhancing the degree of sulfate group substitution on s-CNFs and incorporating additional dopants containing sulfonic groups improved conductivity. Specifically, adding p-toluenesulfonic acid (PTSA) as a dopant increased conductivity, reaching approximately 10 mS cm^-1. However, at higher PTSA concentrations, the strong acidity of sulfonic groups reduced the degree of sulfate group dissociation, leading to a decline in doping efficiency.