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.

Water-oxidation catalysis by manganese in a geochemical-like cycle

Abstract: Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn₄CaO₄ cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn²⁺.

Novel electrochemical approach to assess the redox properties of humic substances.

Abstract: Two electrochemical methods to assess the redox properties of humic substances (HS) are presented: direct electrochemical reduction (DER) on glassy carbon working electrodes (WE) and mediated electrochemical reduction (MER) and oxidation (MEO) using organic radicals to facilitate electron transfer between HS and the WE. DER allows for continuous monitoring of electron and proton transfer to HS by chronocoulometry and automated acid titration, respectively, and of changes in bulk HS redox potential Eh. Leonardite Humic Acid (LHA) showed an H+/e− ratio of unity and a decrease in potential from Eh = +0.18 to −0.23 V upon transfer of 822 μmole- gLHA−1 at pH 7, consistent with quinones as major redox-active functional moieties in LHA. MER and MEO quantitatively detected electrons in LHA samples that were prereduced by DER to different extents. MER and MEO therefore accurately quantify the redox state of HS. Cyclic DER and O2-reoxidation revealed that electron transfer to LHA was largely reversible. However, LH...

An Electrochemical Model for Prediction of Corrosion of Mild Steel in Aqueous Carbon Dioxide Solutions

Abstract: A predictive model was developed for uniform carbon dioxide (CO2) corrosion, based on modeling of individual electrochemical reactions in a water-CO2 system. The model takes into account the electrochemical reactions of hydrogen ion (H+) reduction, carbonic acid (H2CO3) reduction, direct water reduction, oxygen reduction, and anodic dissolution of iron. The required electrochemical parameters (e.g., exchange current densities and Tafel slopes) for different reactions were determined from experiments conducted in glass cells. The corrosion process was monitored using polarization resistance, potentiodynamic sweep, electrochemical impedance, and weight-loss measurements. The model was calibrated for two mild steels over a range of parameters: temperature (t) = 20°C to 80°C, pH = 3 to 6, partial pressure of CO2 (PCO2) = 0 bar to 1 bar (0 kPa to 100 kPa), and ω = 0 rpm to 5,000 rpm (vp = 0 m/s to 2.5 m/s). The model was applicable for uniform corrosion with no protective films present. Performance of...

Experimental and Calculated Electrochemical Potentials of Common Organic Molecules for Applications to Single-Electron Redox Chemistry

Abstract: Herein, we report half-peak potentials for over 180 organic substrates obtained via cyclic voltammetry. These values are of great use in assessing the thermodynamics of an electron-transfer process. In addition, we disclose a simple computational method to determine redox potentials of organic substrates.