Tomasz Rębiś

High performance PEDOT/lignin biopolymer composites for electrochemical supercapacitors

Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge–discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g−1) compared to reference PEDOT electrodes (80.4 F g−1). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.

Spectroelectrochemical investigation of redox states in a polypyrrole/lignin composite electrode material

We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation–reduction of these groups during charge–discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm−1, which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm−1 which is due to hydroquinone moieties.

Hybrid materials from organic electronic conductors and synthetic-lignin models for charge storage applications

Homopolymers and copolymers of the monolignols syringol (S) and guaiacol (G) were prepared as well-defined lignin model compounds. Polymerisation was performed by phenol–formaldehyde condensation, also including the monomer hydroquinone (HQ) to extend the range of redox processes in these synthetic lignins (SLig). The chemical structures of the SLig samples were characterized by 13C and quantitative 31P NMR, and the molecular weight was monitored by size exclusion chromatography (SEC). Subsequently, SLig were incorporated into two different electron-conducting matrix – single-wall carbon nanotubes (SWNT) and polypyrrole (PPy), respectively. As a result, the hybrid materials, with a controlled amount of SWNT or with an unknown amount of PPy, were assembled and compared. The charge storage properties in the investigated materials are attributed to contributions from both the double-layer capacitance of the conducting matrix, and the faradaic reactions provided by quinone groups immobilized in the electrodes. The results indicate a considerable improvement of charge capacity, with the synthetic lignins incorporated in the hybrid materials. With a PPy carrying S, G and HQ, better performance is obtained than has previously been obtained with lignin derivatives, showing a maximum capacity of 94 mA h g−1. Moreover, a low amount of electronic conductor (20% wt of SWNT) is adequate to perform efficient electron communication between redox active quinones and the electrode surface, providing 72 mA h g−1.

Electrocatalysis of NADH oxidation using electrochemically activated fluphenazine on carbon nanotube electrode.

Electrocatalytic determination of NADH using a hybrid surface-modified electrode with multi-wall carbon nanotubes (MWCNTs) and a novel electrogenerated redox mediator is described. The redox mediator precursor - fluphenazine (Flu) was adsorbed on MWCNT-modified glassy carbon (GC) electrode which was then subjected to electrochemical activation in 0.1 M H2SO4 using cyclic voltammetry (CV) over a range of potentials -0.2 to 1.5 V vs. Ag/AgCl (6 scans at 100 mV s(-1)). Cyclic voltammograms of Flu indicated the formation of a stable electroactive material presenting one reversible redox couple at the formal potential of -0.115 vs. Ag/AgCl in a phosphate buffer (pH7.0) as a supporting electrolyte. The peaks increased linearly with increasing scan rate indicating electroactive molecules anchored to the electrode surface. The GC/MWCNT/Flu electrode efficiently catalyzed the oxidation of NADH with a decrease in the overpotential of about 600 mV and 150 mV compared to the bare GC and GC/MWCNT electrode, respectively. This modified electrode was successfully used as the working electrode in the chronoamperometric analysis. The peak current response to NADH was linear over its concentration range from 15 μM to 84 μM, and correlation coefficient 0.998. The limits of detection (5 μM) and quantitation (15 μM) were evaluated.

Electrode Modified by Reduced Graphene Oxide for Monitoring of Total Thallium in Grain Products

Grain products and the associated industry have a notable economic and social impact all over the world. The toxicological safety of grain products is a nutritional prerogative. This study focused on the determination of thallium content in grain product samples collected from a commercial brand commonly available in Poland. The samples were analyzed with the use of differential pulse anodic stripping voltammetry (DPASV) with graphene oxide based on glassy carbon. The stripping anodic peak current of thallium was linear over its concentration range from 9.78 × 10−9 to 97.8 × 10−9 M. The limit of detection (LOD) was calculated according to the formula LOD = (κ × SDa)/b, where κ is 3.3, SDa is the standard deviation of the intercept, and b is the slope. The determined value of LOD was 1.229 µg L−1 (6.01 × 10−9 M). The proposed method was successfully applied for the determination of thallium ions in samples of actual grain products. The obtained results confirmed that thallium was present in the studied cereal samples (average content at 0.0268 ± 0.0798 mg/kg). Thallium has a half-life of 60 days; therefore, the consumption of foods with thallium content of approximately 0.08 mg/kg has the potential for harmful bioaccumulation in the body. Thallium contamination in cereal products should be a critical parameter for health environmental regulations.