Redox

About: Redox is a research topic. Over the lifetime, 26853 publications have been published within this topic receiving 862368 citations. The topic is also known as: reduction-oxidation & reduction-oxidation reaction.

Effects of humic substances and quinones at low concentrations on ferrihydrite reduction by Geobacter metallireducens.

Abstract: Humic substances (HS) and quinones can accelerate dissimilatory Fe(III) reduction by electron shuttling between microorganisms and poorly soluble iron(III) (hydr)oxides. The mechanism of electron shuttling for HS is not fully understood, but it is suggested that the most important redox-active components in HS are also quinones. Here we studied the influence of HS and different quinones at low concentrations on ferrihydrite reduction by Geobacter metallireducens. The aquatic HS used were humic and fulvic acids (HA and FA) isolated from groundwater of a deep aquifer in Gorleben (Niedersachsen, Germany). HA stimulated iron reduction stronger than FA down to total HA concentrations as low as 1 mg/L. The quinones studied showed large differences: some had strong accelerating effects, whereas others showed only small effects, no effects, or even inhibitory effects on the kinetics of iron reduction. We found that the redox potentials of the most active quinones fall in a narrow range of -137 to -225 mV vs NHE at pH 7. These results give evidence that the kinetic of microbial iron reduction mediated by electron shuttles is mainly controlled by thermodynamic parameters, i.e., by the redox potential of the shuttle compound, rather than by the proportion of dissolved vs adsorbed compound.

Isopropanol oxidation by pure metal oxide catalysts: number of active surface sites and turnover frequencies

Abstract: The objective of the present study was to determine the number of active surface sites and their nature, redox or acidic, for bulk metal oxide catalysts using isopropanol as a chemical probe molecule. Isopropanol oxidation activity on the following metal oxides was investigated: MgO, CaO, SrO, BaO, Y 2 O 3 , La 2 O 3 , CeO 2 , TiO 2 , ZrO 2 , HfO 2 , V 2 O 5 , Nb 2 O 5 , Ta 2 O 5 , Cr 2 O 3 , MoO 3 , WO 3 , Mn 2 O 3 , Fe 2 O 3 , Co 3 O 4 , Rh 2 O 3 , NiO, PdO, PtO, CuO, Ag 2 O, Au 2 O 3 , ZnO, Al 2 O 3 , Ga 2 O 3 , In 2 O 3 , SiO 2 , SnO 2 and Bi 2 O 3 . On average, the number of active surface sites for isopropanol dissociative adsorption on these catalysts was ∼2–4 μmol/m 2 . The number of active surface sites enabled quantification of the turnover frequency (TOF) for these catalysts. The TOF values for the various pure metal oxides were normalized at 200 °C. The TOFs of catalysts showing redox activity vary by six-orders of magnitude (10 2 to 10 −4 s −1 ). For catalyst showing acidic activity, the TOFs varied by over eight-orders of magnitude (10 1 to 10 −7 s −1 ). The reaction products from isopropanol oxidation at low conversions reflected the nature of the active surface sites, redox or acidic, on these catalysts. Redox surface sites yield acetone and acidic surface sites yield propylene. Small amounts of isopropyl ether formation are sometimes also observed via bimolecular recombination of surface isopropoxide species on acidic surface sites. All catalysts with the exception of Fe 2 O 3 and TiO 2 , exhibited extremely high selectivity to either redox or acidic products. Except for the sharp decrease in TOFs towards redox products with increasing bulk M–O heats of formation at low −Δ H f , no correlations were found between the TOFs and bulk metal oxide properties (TPR–H 2 and −Δ H f ). However, an inverse relation was found between the TOFs (redox) and the surface isopropoxide intermediate decomposition temperature at low decomposition temperatures. At moderate and high decomposition temperatures, the TOFs (redox) were almost independent of the surface isopropoxide decomposition temperature. The selectivity of the metal oxide catalysts was found to be independent of the TOFs.

Cyclic voltammetric studies of charge transfer reactions at highly boron-doped polycrystalline diamond thin-film electrodes

Abstract: Cyclic voltammetry and ac impedance analysis were used to measure the background current response and capacitance of interfaces formed at as grown (untreated) boron-doped polycrystalline diamond thin-film electrodes in contact with aqueous electrolytes. The diamond films (∼1 cm 2 , 15 μm thick ; carrier concentration, ∼10 17 cm -3 ) were grown on conducting Si substrates by plasma-enhanced chemical vapor deposition. Cyclic voltammetry was also used to determine the charge transfer reactions of several redox analytes at as grown and chemically wet etched diamond thin-film electrodes and to study the effect of surface pretreatment, including Fe(CN) 6 3-/4- , IrCl 6 2-/3- , Ru(NH 3 ) 6 3+/2+ , dopamine, 4-methylcatechol, MV 2+/+/0 , and ferrocene. The electrochemical response exhibited by the films is explained using two models : (i) traditional electron transfer at a p-type semiconductor-electrolyte interface and (ii) electron transfer at a composite electrode composed of nondiamond carbon impurities contained within a diamond matrix such that k° nondiamond >> k° diamond.