EPR Monitoring of Redox Processes in Transition Metal Oxide Catalysts

Łabanowska, Maria

doi:10.1002/1439-7641(20011217)2:12<712::aid-cphc712>3.0.co;2-h

Cited by 54 publications

(32 citation statements)

References 59 publications

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“…30,31 At present, a common route to drive selective oxidation by transition metals is to modify the oxidation state of the catalytically active metal centre. [32][33][34][35] However, the diradical nature of molecular oxygen means that it can also react with organic substrates via autoxidation pathways. 36,37 As these are not driven by catalysts, autoxidation reactions are difficult to study unambiguously.…”

Section: Introductionmentioning

confidence: 99%

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

Liu

Ryabenkova

Conte

2015

Phys. Chem. Chem. Phys.

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The activation and use of oxygen for the oxidation and functionalization of organic substrates is among the most important reactions in a chemist's toolbox. Nevertheless, despite the vast literature on catalytic oxidation, the phenomenon of autoxidation, an ever-present background reaction that occurs in virtually every oxidation process, is often neglected. In contrast, autoxidation can affect the selectivity to a desired product, to those dictated by pure freeradical chain pathways, thus affecting the activity of any catalyst used to carry out a reaction.This critical review compares catalytic oxidation routes by transition metals versus autoxidation, particularly focusing on the industrial context, where highly selective and "green" processes are needed. Furthermore, the application of useful tests to discriminate between different oxygen activation routes, especially in the area of hydrocarbon oxidation, with the aim of an enhanced catalyst design, is described and discussed. In fact, one of the major targets of selective oxidation is the use of molecular oxygen as ultimate oxidant, combined with the development of catalysts capable to perform the catalytic cycle in a real energy and cost effective manner on a large scale. To achieve this goal, insights from metallo-proteins that could find application in some areas of industrial catalysis are presented, as well as considering the physicochemical principles that are at the fundament of oxidation and autoxidation processes.3

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Section: Introductionmentioning

confidence: 99%

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

Liu

Ryabenkova

Conte

2015

Phys. Chem. Chem. Phys.

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“…The α-MoO 3 compound is a layered oxide that has attracted interest for a range of applications including catalysis 1 , and cathode materials for lithium-ion batteries 2 and electrochemical supercapacitors 3 . As shown in Fig.…”

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confidence: 99%

Structural and vibrational properties ofα-MoO3from van der Waals corrected density functional theory calculations

et al. 2012

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“…transition from O − to O 2− . However, as it was shown in [36], the incorporation of oxygen into external layers of the vanadia crystallites at higher temperatures of around 473 K, led to an immediate formation of the O 2− ions. The ESR signals characteristic of O − or O 2 − are not observed at this temperature.…”

Section: Nature Of the Surface Oxygen Speciesmentioning

confidence: 65%

“…Thorough discussion concerning the influence of oxygen chemisorption and the different forms of surface oxygen on the activity and selectivity of the catalyst in the oxidation of hydrocarbons can be found in the reviews [32,33]. Presence of the electrophillic oxygen on the surface of many oxide systems was confirmed by the ESR studies [34][35][36]. However, these studies were carried out at low temperatures and for low concentrations of oxygen to assure a good quality of the ESR spectra.…”

Section: Introductionmentioning

confidence: 99%