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.

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.

Ultrasound-Assisted Surface Modification of MWCNT Using Organic Acids.

In the present work, multiple-wall carbon nanotubes (MWCNTs) were surface modified in an environmentally friendly way, using low-frequency ultrasonic energy. This type of modification was carried-out using two different types of organic acids, citric acid (CA) and oxalic acid (OA). The modification of the MWCNTs was confirmed by Fourier-transform infrared spectroscopy (FTIR), where functional groups such as OH, C=O, O-C=O and COOH were detected. By means of Raman spectroscopy, an increase in carbon surface defects was found. On the other hand, using X-ray photoelectron spectroscopy (XPS), oxidation was evidenced on the surface of the modified MWCNT. In both Raman spectroscopy and XPS, the results indicate a greater modification when CA is used, possibly due to the fact that CA has a larger number of functional groups. MWCNT-CA showed good dispersion in methanol, while MWCNT-OA showed good stability in methanol and ethanol. Finally, a 20% removal of creatinine efficiency improvement was found with respect to the unmodified MWCNTs, while no improvement was found in the case of urea and uric acid.

Laser-Induced Deposition of Carbon Nanotubes in Fiber Optic Tips of MMI Devices.

The integration of carbon nanotubes (CNTs) into optical fibers allows the application of their unique properties in robust and versatile devices. Here, we present a laser-induced technique to obtain the deposition of CNTs onto the fiber optics tips of multimode interference (MMI) devices. An MMI device is constructed by splicing a section of no-core fiber (NCF) to a single-mode fiber (SMF). The tip of the MMI device is immersed into a liquid solution of CNTs and laser light is launched into the MMI device. CNTs solutions using water and methanol as solvents were tested. In addition, the use of a polymer dispersant polyvinylpyrrolidone (PVP) in the CNTs solutions was also studied. We found that the laser-induced deposition of CNTs performed in water-based solutions generates non-uniform deposits. On the other hand, the laser-induced deposition performed with methanol solutions generates uniform deposits over the fiber tip when no PVP is used and deposition at the center of the fiber when PVP is present in the CNTs solution. The results show the crucial role of the solvent on the spatial features of the laser-induced deposition process. Finally, we register and study the reflection spectra of the as-fabricated CNTs deposited MMI devices.