Topic
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.
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TL;DR: Redox states of cysteine/cystine and GSH/GSSG provide an approach to clinically distinguish between increased causative oxidative events and decreased GSH antioxidant function, and can be used to assess efficacy of intervention strategies against oxidative stress prior to or early after onset of clinical symptoms in aging and age-related disease.
374 citations
TL;DR: In this paper, a metal-organic framework-derived nitrogen-doped nanoporous carbon was used as an electrocatalyst for the nitrogen reduction reaction (NRR) by using renewable electricity.
373 citations
TL;DR: Investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 °C and higher is a highly stable atomic species, which at 70 °C is formed only at the perimeter of the Au-oxide interface and whose reactive removal by CO is activated, but not its formation, and that surface lattice oxygen represents the Oact species for the CO oxidation.
Abstract: Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently.This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even ...
372 citations
TL;DR: This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding Cu(II)-mediated C-H oxidation reactions.
Abstract: Copper(II)-mediated C–H oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from CuII-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Under basic conditions, the benzamide group undergoes directed C–H methoxylation or chlorination. Under acidic conditions, the quinoline group undergoes nondirected chlorination. Experimental and computational mechanistic studies implicate an organometallic C–H activation/functionalization mechanism under the former conditions and a single-electron-transfer mechanism under the latter conditions. This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding CuII-mediated C–H oxidation reactions.
370 citations
TL;DR: In this article, two aluminophosphate molecular sieves containing isolated, four-coordinated Co(III or Mn(III) ions are substituted into the framework and act, in concert with the surrounding framework structure, as regioselective catalysts for the oxidation of linear alkanes by molecular oxygen.
Abstract: Terminally oxidized hydrocarbons are of considerable interest as potential feedstocks for the chemical and pharmaceutical industry, but the selective oxidation of only the terminal methyl groups in alkanes remains a challenging task. It is accomplished with high efficiency and selectivity by some enzymes; but inorganic catalysts, although inferior in overall performance under benign conditions, offer significant advantages from a processing standpoint1. Controlled partial oxidation is easier to achieve with ‘sacrificial’ oxidants, such as hydrogen peroxide2, alkyl hydroperoxides oriodosylbenzene3, than with molecular oxygen or air. These sacrificial oxidants, themselves the product of oxidation reactions, have been used in catalytic systems involving tailored transition-metal complexes in either a homogeneous state4,5,6, encapsulated in molecular sieves7,8,9 or anchored to the inner surfaces of porous siliceous supports10. Here we report the design and performance of two aluminophosphate molecular sieves containing isolated, four-coordinated Co(III) or Mn(III) ions that are substituted into the framework and act, in concert with the surrounding framework structure, as regioselective catalysts for the oxidation of linear alkanes by molecular oxygen. The catalysts operate at temperatures between 373 K and 403 K through a classical free-radical chain-autoxidation mechanism. They are thus able to use molecular oxygen as oxidant, which, in combination with their good overall performance, raises the prospect of using this type of selective inorganic catalyst for industrial oxidation processes.
369 citations