Electrochemical Sensing of Nitrite Ions Using Modified Electrode by Poly 1,8-Diaminonaphthalene/Functionalized Multi-Walled Carbon Nanotubes.

A novel electrochemical sensor based on conducting polymer and multi-walled carbon nanotubes was reported for the detection of nitrite ions (NO2 -). The hybrid material poly 1,8-Diaminonaphthalene (poly 1,8-DAN)/functionalized multi-walled carbon nanotubes (f-MWCNT) was prepared by using a simple electrochemical approach which is based on the deposition of functionalized multi-walled carbon nanotubes (f-MWCNT) on the surface of the electrode followed by the electropolymerization of 1,8-DAN using cyclic voltammetry. The morphology and the electro-catalytic properties of the obtained electrodes were investigated with Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM), Cyclic Voltammetry (CV), and Electrochemical Impedance Spectroscopy (EIS) showing an improvement of the electronic transfer due to the synergic effect between the proprieties of poly 1,8-DAN and f-MWCNT. Under the optimum experimental conditions, the poly 1,8-DAN/f-MWCNT/CPE exhibited excellent electro-catalytic activity towards nitrite detection. The nitrite anodic peak potential decreased by 210 mV compared to the bare carbon paste electrode. The calibration plot of nitrite detection was linear in the range of concentration from 300 to 6500 nM with a low detection limit of 75 nM.

Interfacial charge storage mechanisms of composite electrodes based on poly(ortho-phenylenediamine)/carbon nanotubes via advanced electrogravimetry.

To reach a deeper understanding of the charge storage mechanisms of electrode materials is one of the challenges toward improving their energy storage performance. Herein, we investigate the interfacial ion exchange of a composite electrode made of carbon nanotube/poly(ortho-phenylenediamine) (CNT/PoPD) in a 1M NaCl aqueous electrolyte via advanced electrogravimetric analyses based on electrochemical quartz crystal microbalance (EQCM). Classical EQCM at different scan rates of the potential revealed the complex electrogravimetric behavior likely due to multi-species participation at different temporal scales. Thereafter, in order to better understand the behavior of each species (ions, counter ions, and co-ions) in the charge compensation mechanism, the electrogravimetric impedance spectroscopy analysis (also called ac-electrogravimetry) was pursued. Ac-electrogravimetry revealed the role of each species where Na+ cations and Cl- anions as well as protons participate in the charge compensation mechanism of the CNT/PoPD composite with different kinetics and proportions. The water molecules with opposite flux direction with the cations are also detected, suggesting their exclusion during cationic species transfer. Having analyzed ac-electrogravimetry responses in depth, the synergistic interaction between the CNT and PoPD is highlighted, revealing the improved accessibility of species to new sites in the composite.

Aqueous Multivalent Charge Storage Mechanism in Aromatic Diamine-Based Organic Electrodes.

Rechargeable batteries employing aqueous electrolytes are more reliable and cost-effective as well as possess high ionic conductivity compared to the flammable organic electrolyte solutions. Among these types of batteries, aqueous batteries with multivalent ions attract more attention in terms of providing high energy density. Herein, electrochemical behavior of an organic electrode based on a highly aromatic polymer containing 2,3-diaminophenazine repeating unit, namely poly(ortho-phenylenediamine) (PoPD), is tested in two different multivalent ions (Zn2+ and Al3+) containing aqueous electrolytes, that is, in zinc sulfate and aluminum chloride solutions. PoPD is synthesized via electropolymerization, and its ion transport and storage mechanism are comprehensively investigated by structural and electrochemical analyses. The electrochemical quartz crystal microbalance, time-dependent Fourier transform infrared, and electrochemical impedance spectroscopy analyses as well as ex situ X-ray diffraction observations established that along with the Zn2+ or Al3+ ions, reversible proton insertion/extraction also takes place. Contrary to the most of the organic electrodes that requires the use of conductive carbon additives, the electrodeposited PoPD electrode is intrinsically electrically conductive enough, resulting in a binder and additive free electrode assembly. In addition, its discharge products do not dissolve in aqueous medium. As a whole, the resulting PoPD electrode delivers excellent rate performances with prolonged cycle life in which discharge capacities of ∼110 mAh g-1 in 0.25 M AlCl3 and ∼93 mAh g-1 in 1 M ZnSO4 aqueous electrolyte after 1000 cycles at a current density of 5C have been achieved.

Designing New Material Based on Functionalized Multi-Walled Carbon Nanotubes and Cu(OH)2-Cu2O/Polypyrrole Catalyst for Ethanol Oxidation in Alkaline Medium.

In this work, copper(II) hydroxide (Cu(OH)2) and copper oxide (Cu2O) nanostructures are deposited on functionalized multi-walled carbon nanotubes/polypyrrole to report an efficient electrocatalyst for ethanol oxidation in alkaline medium. In the first step, the deposition of functionalized multi-walled nanotubes of carbon (F-MWCNTs) on the electrode surface was carried out using drop casting mode followed by the electrodeposition of polypyrrole (PPy) and copper nanoparticles (Cu-Nps) using galvanostatic mode. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were performed in order to study the morphology and the structure of the elaborated catalysts. Electrochemical characterization conducted by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that the introduction of functionalized multi-walled carbon nanotubes enhances the electric properties of the nanocomposites and offers a large active surface area. The prepared electrocatalyst was then tested in a solution of 0.1 M NaOH containing 0.2 M of ethanol showing high performance (7 mA cm-2 at 0.85 V vs Ag/AgCl) and good stability (over 1800 s) toward ethanol oxidation.

Electrochemical sensor based on low silica X zeolite modified carbon paste for carbaryl determination.

A new and simple approach for carbaryl determination in natural sample was proposed using Low Silica X (LSX) zeolite modified carbon paste electrode. LSX zeolite with a porous structure was incorporated into carbon paste electrode in the appropriate portion. The prepared electrode was then characterized using scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Various experimental parameters as the zeolite amounts, pH, accumulation time, and differential pulse voltammetric parameters were optimized. Under optimal conditions, a linear response was obtained in the range of 1-100 µM of carbaryl using differential pulse voltammetry with detection limit of 0.3 µM (S/N = 3). The sensors showed good selectivity, stability, and reproducibility and has been successfully applied for detection of carbaryl in tomato samples with good recoveries.

Investigation of amperometric detection of phosphate Application in seawater and cyanobacterial biofilm samples.

Detection of phosphate using amperometry was investigated. The phosphomolybdate complex, formed by addition of nitric acid, ammonium molybdate and phosphate, was reduced at a carbon paste electrode polarised at +0.3V (versus Ag/AgCl). The major characteristics observed were simplicity of the equipment, a limited consumption of reagents and a low detection limit (0.3mumoll(-1)), with a linear range between 1 and 20mumoll(-1). The interference of silicate was completely eliminated using an appropriate concentration of nitric acid and ammonium molybdate. The amperometric detection of orthophosphate in seawater using the batch injection analysis (BIA) technique was reported. Moreover, a carbon paste microelectrode was constructed. Its use allows the analysis of small volume of samples with little dilution in supporting electrolyte. This method was applied to the determination of orthophosphate in cyanobacterial biofilms collected from Roman catacombs. There was a good statistical correlation between results obtained with the proposed method and the standard spectrophotometric method.

Determination of mercury(II) by invertase enzyme inhibition coupled with batch injection analysis.

The determination of mercury(II) ions at the trace level by inhibition of the invertase enzyme-catalysed hydrolysis of sucrose into glucose and fructose coupled to electrochemical batch injection analysis was investigated using two approaches. In the first, the glucose produced was detected by injection of 100 microliters samples into the batch injection cell containing a platinum electrode modified by immobilised glucose oxidase. In the second, the glucose and fructose present in injected samples were oxidised directly at a copper-modified glassy carbon electrode. The experimental parameters were optimised and the degree of enzyme inhibition by mercury(II) ions under both conditions was measured. Mercury concentrations in the ng ml-1 range were determined by these two techniques with low sample and reagent consumption. Comparison is made between the two methods and perspectives as a screening test for field application are indicated.