Low‐Temperature Activation of Dioxygen and Hydrocarbon Oxidation Catalyzed by a Phosphovanadomolybdate: Evidence for a Mars–van Krevelen Type Mechanism in a Homogeneous Liquid Phase

Am, Khenkin; Neumann, Ronny

doi:10.1002/1521-3773(20001117)39:22<4088::aid-anie4088>3.0.co;2-#

Cited by 82 publications

(22 citation statements)

References 21 publications

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“…Particularly, for liquid-phase aerobic oxidations, PMoV 2 takes a catalytic effect through Mars-van Krevelen-type mechanism, where the lattice oxygen of PMoV 2 selectively oxygenates organic substrates via a valence variation between V 5+ and V 4+ 2732. Neumann and co-workers2732333435 have systematically studied series of PMoV 2 -catalyzed homogeneous oxidations, and based on the Mars-van Krevelen mechanism they propose that the isomers of PMoV 2 with vanadium atoms in adjacent positions ( i.e. V-O-V structure) are more likely to form bridge defects, favoring higher activity in oxygen-transfer reactions.…”

Section: Discussionmentioning

confidence: 99%

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

Long

Zhou

Chen

et al. 2014

Sci Rep

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Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

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Section: Discussionmentioning

confidence: 99%

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

Long

Zhou

Chen

et al. 2014

Sci Rep

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“…84 Interestingly, despite the fact that this mechanism is exclusively regarded to take place for gas/solid reactions, convincing evidence that it can also operate for liquid/solid reactions has been found when phosphovanadomolybdates (H 5 PV 2 Mo 10 O 40 ) are used for C-H activation of anthracene and xanthene in the liquid phase. 85 From the mechanistic and classification point of view, oxygen activation routes that lead to the formation of metal oxo and dioxo species (Scheme 1) are usually classed as heterolytic oxygen activation. 86,87 That is a two electron process in a reaction pathway where ionic species may be present, but not free-radical species.…”

Section: Oxygen Activation By a Metalmentioning

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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“…The relevant properties related to developing functional materials are (i) catalytic activity for chemical transformations [7], (ii) molecule-based conductivity [8], (iii) magnetism [9], as well as (iv) photochromism, electrochromism, and luminescence [10]. Obviously, polyoxometalates are extremely versatile inorganic building block for the construction of functional materials.…”

Section: Introductionmentioning

confidence: 99%

Stable multilayer films based on photoinduced interaction between polyoxometalates and diazo resin

Zhang

Cao

et al. 2004

Materials Letters

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Low‐Temperature Activation of Dioxygen and Hydrocarbon Oxidation Catalyzed by a Phosphovanadomolybdate: Evidence for a Mars–van Krevelen Type Mechanism in a Homogeneous Liquid Phase

Cited by 82 publications

References 21 publications

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

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

Stable multilayer films based on photoinduced interaction between polyoxometalates and diazo resin

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