A Comparative Study of Biomimetic Synthesis of EDOT-Pyrrole and EDOT-Aniline Copolymers by Peroxidase-like Catalysts: Towards Tunable Semiconductive Organic Materials.

It has been two decades since biomimetic synthesis of conducting polymers were first reported, however, the systematic investigation of how catalysts influence the properties of the conducting polymers has not been reported yet. In this paper, we report a comparative study between peroxidase-like catalyst, dopants, and their effect on the properties of poly (3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPY), and polyaniline (PANI). We also investigate the EDOT-Pyrrole and EDOT-Aniline copolymerization by enzymomimetic synthesis using two catalysts (Ferrocene and Hematin). It was found that, chemically, there are no detectable effects, only having small contributions in molar ratios greater than 0.7-0.3. Spectroscopic data provide solid evidence concerning the effect in the variation of the molar fractions, finding that, as the molar fraction of EDOT decreases, changes associated with loss of the conjugation of the structure and the oxidation state of the chains were observed. The electrical conductivity was considerably modified depending on the type of catalyst. Hematin produces conductive homopolymers and copolymers when doped with p-toluene sulfonic acid (TSA), while ferrocene produces low conductive copolymers under the same conditions. The mole fraction affects conductivity significantly, showing that as the EDOT fraction decreases, the conductivity drops drastically for both EDOT-PY and EDOT-ANI copolymers. The type of dopant also notably affects conductivity; the best values were obtained by doping with TSA, while the lowest were obtained when doping with polystyrene sulfonate (PSS). We also draw a biomimetic route to tailor the fundamental properties of conducting homopolymers and copolymers for their design and scaled-up production, as they have recently been found to have use in a broad range of applications.

Synthesis and Vulcanization of Polymyrcene and Polyfarnesene Bio-Based Rubbers: Influence of the Chemical Structure over the Vulcanization Process and Mechanical Properties.

The overuse of fossil-based resources to produce thermoplastic materials and rubbers is dramatically affecting the environment, reflected in its clearest way as global warming. As a way of reducing this, multiple efforts are being undertaken including the use of more sustainable alternatives, for instance, those of natural origin as the main feedstock alternative, therefore having a lower carbon footprint. Contributing to this goal, the synthesis of bio-based rubbers based on ß-myrcene and trans-ß-farnesene was addressed in this work. Polymyrcene (PM) and polyfarnesene (PF) were synthesized via coordination polymerization using a neodymium-based catalytic system, and their properties were compared to the conventional polybutadiene (PB) and polyisoprene (PI) also obtained via coordination polymerization. Moreover, different average molecular weights were also tested to elucidate the influence over the materials' properties. The crosslinking of the rubbers was carried out via conventional and efficient vulcanization routes, comparing the final properties of the crosslinking network of bio-based PM and PF with the conventional fossil-based PB and PI. Though the mechanical properties of the crosslinked rubbers improved as a function of molecular weight, the chemical structure of PM and PF (with 2 and 3 unsaturated double bonds, respectively) produced a crosslinking network with lower mechanical properties than those obtained by PB and PI (with 1 unsaturated double bond). The current work contributes to the understanding of improvements (in terms of crosslinking parameters) that are required to produce competitive rubber with good sustainability/performance balance.

Biomimetic Synthesis of PANI/Graphitic Oxidized Carbon Nitride for Supercapacitor Applications.

Polyaniline (PANI) composites have gained momentum as supercapacitive materials due to their high energy density and power density. However, some drawbacks in their performance remain, such as the low stability after hundreds of charge-discharge cycles and limitations in the synthesis scalability. Herein, we report for the first time PANI-Graphitic oxidized carbon nitride composites as potential supercapacitor material. The biomimetic polymerization of aniline assisted by hematin, supported by phosphorous and oxygen-modified carbon nitrides (g-POCN and g-OCN, respectively), achieved up to 89% yield. The obtained PAI/g-POCN and PANI/g-OCN show enhanced electrochemical properties, such as conductivity of up to 0.0375 S/cm, specific capacitances (Cs) of up to 294 F/g (at high current densities, 5 A/g) and a stable operation after 500 charge-discharge cycles (at 3 A/g). In contrast, the biomimetic synthesis of Free PANI, assisted by stabilized hematin in cosolvents, exhibited lower performance properties (65%). Due to their structural differences, the electrochemical properties of Free PANI (conductivity of 0.0045 S/cm and Cs of up to 82 F/g at 5 A/g) were lower than those of nanostructured PANI/g-POCN and g-OCN supports, which provide stability and improve the properties of biomimetically synthesized PANI. This work reveals the biomimetic synthesis of PANI, assisted by hematin supported by modified carbon nitrides, as a promising strategy to produce nanostructured supercapacitors with high performance.