Nitrite anodic oxidation at Ni(II)/Ni(III)-decorated mesoporous SnO2 and its analytical applications.

Hydrothermally formed mesoporous SnO2 was used as a support for nickel chemical deposition and, after subsequent thermal treatment, a high specific surface area (36 m2 g-1) Ni/SnO2 material was obtained. XPS analysis has shown that in the Sn 3d region the spectrum is similar to that of pristine SnO2, whereas Ni species are present on the surface as NiO, Ni2O3 and Ni(OH)2. Mixing Ni/SnO2 with a small amount of Black Pearls (BP) leads to a significant enhancement of the resulting Ni/SnO2-BP composite activity for nitrite anodic oxidation, presumably due to the higher surface area (115 m2 g-1), to better electrical conductivity and to a certain contribution of the BP to an increase in surface density of the active sites. Ni/SnO2-BP also outperforms pristine BP (in terms of Tafel slopes and electron-transfer rates), most likely due to the fact that the Ni(II)/Ni(III) couple can act as an electrocatalyst for nitrite oxidation. A voltammetric method is proposed for the determination of nitrite, over a concentration range of three orders of magnitude (0.05 to 20 mM), with good reproducibility, high stability and excellent sensitivity. The high upper limit of the dynamic range of the analytically useful response might provide a basis for the reliable quantification of nitrite in wastewater.

Sinusoidal voltage electrodeposition of PEDOT-Prussian blue nanoparticles composite and its application to amperometric sensing of H2O2 in human blood.

A selective electrochemical sensor based on poly(3,4-ethylenedioxythiophene) (PEDOT) - Prussian blue nanoparticles (PBNPs) for hydrogen peroxide (H2O2) determination was prepared by innovative sinusoidal voltage (SV) method. The successful incorporation of citrate-stabilized PBNPs into PEDOT matrix was confirmed by energy dispersive X-ray analysis (EDX), Raman spectroscopy, UV-Vis spectroelectrochemistry and cyclic voltammetry measurements. The SV preparation method provides a PEDOT-PBNPs coating with rough surface morphology and good electrocatalytic activity toward H2O2 reduction. The amperometric response of PEDOT-PBNPs-based sensor at -50 mV vs. Ag/AgCl is linear within the range of concentrations from 5 µM to 1 mM H2O2 with a detection limit of 1.4 µM H2O2. The proposed Pt/PEDOT-PBNPs sensor displays good repeatability, reproducibility, operational stability as well as good selectivity toward H2O2 determination in the presence of interfering species like dopamine (DA), uric acid (UA), KNO2 glucose (Glu), KNO3 and ascorbic acid (AA), and was successfully applied to H2O2 determination in human blood samples without biofouling.

Hemin interaction with bare and 4,4'-thio-bis-benzene-thiolate covered n-GaAs (110) electrodes.

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) investigations on the redox behavior of hemin at bare and 4,4'-thio-bis-benzene-thiolate (TBBT) covered n-GaAs (110) electrodes in dimethylsulfoxide (DMSO) revealed the high irreversibility of the electroreduction process, which appeared to be closely related to the stable adsorbed species strongly interfering with the electronic properties of the semiconducting substrate. The subsequent exploration of the hemin-modified electrodes by second harmonic generation (SHG), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements pointed to significant differences between the iron protoporphyrin species adsorbed on the bare- and TBBT-GaAs (110) electrodes. Only Fe(2+) species having a flat configuration with the porphyrin plane oriented parallel to the surface were detected on GaAs, unlike the TBBT-GaAs, where Fe(2+) and Fe(3+) species having both flat and vertical adsorption positions could be observed. These differences originate from the mutual interactions between the solvent, hemin and dithiolate molecules as well as their competition for the surface sites found to play a key role in the electrochemical process under discussion.