Oxygenation of conducting polymers facilitated by structure‐breaking anions

Abstract

Conducting polymers are an interesting class of materials that can be tuned to have a range of properties through counterion doping. For most conducting polymers, the insertion of anions (the doping process) leads to the formation of carbocations (positive charge carriers) along the conjugated polymer backbone. In this research, we report on a scenario that arises where certain (commonly used) anions in water induce oxygenation of the conducting polymers heteroatom. This is in contrast to the widely reported doping process, and the recently reported hydrolysis of conducting polymers. We observe that the transition between these different conducting polymer-interactions/reactions is well described by the concept of structure-making and structure-breaking anions. Poly(3,4-propylenedioxy thiophene dimethyl) (PProDOT-Me 2 ), polypyrrole (PPy), and poly(3,4-ethylenedioxy thiophene) (PEDOT) thin films are exposed to a range of anions in water. Both PProDOT-Me 2 and PPy are susceptible to oxygenation, while in contrast PEDOT is doped, when exposed to structure-breaking anions. All the polymers show hydrolysis for structuremaking anions. The knowledge of the interaction and/or reaction of conducting polymers with anions in water is not only critical to their application in devices for aqueous environments (i.e., sensing), but also for their processing and fabrication using water.

Charge transport mechanism in dodecylbenzenesulfonic acid doped polyaniline/carbon black composites

“…Conducting polymers (CPs) are analogous to those of metals or semi-conductors having conjugated backbone of enriched electrons with the ability to conduct. 1 The existence of conjugated backbone within the conducting polymers (CPs) provides them with the property of electrical conductivity. 2 Ever since their discovery, CPs are of significant interest due to their ease of synthesis, good process ability, lightweight, less toxicity, and high thermal conductivity.…”

Surface Doping in Poly(3,4-ethylenedioxythiophene)-Based Nanoscale Films: Insights for Polymer Electronics

“…Because the synthesis of samples with a higher percentage of Tos clearly pointed toward metastable states, ab initio molecular dynamic simulation was carried out at zero temperature and pressure using a Langevin thermostat so as to optimize the atomic configuration, achieve local minima in the energy landscape, and set the scene for calculation of the ground-state electronic structure . The simulations were terminated when the energies converge to less than 0.0001 eV/atom. , …”

“…The exploration of doped PEDOT nanofilms is not limited to the experimental domain, with a range of computations and simulations deployed for greater understanding. − More specifically, the combination of computation and experimentation can be used to garner a deeper understanding of doped PEDOT. , Two experimental techniques that being exploited for this are X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy (XPS and UPS, respectively). These techniques interrogate the outermost nanoscale region of a material.…”

“…40 The simulations were terminated when the energies converge to less than 0.0001 eV/atom. 23,41 It is well-known that, in the context of a linear combination of atomic orbitals (LCAO), the molecular orbital can be square integrated over all space and thus the overlap population (OP) obtained. Mulliken partitioned the integration and attributed the OP to bonding.…”

Recent advances in the aqueous applications of PEDOT

“… 22 They showed the classification of ions as structure-breaking or structure-making in water to be important for understanding how CPs interacts with ions in water. 23 How these mechanisms on an atomic/molecular level impact on the deployment of PEDOT-based devices in water applications is of growing importance/interest. Therefore, this mini-review will present a brief overview of the recent key literature demonstrating the use of PEDOT in water-based applications.…”