A5055637580- Polyoxometalates: Synthesis and Applications
- Oxidative Organic Chemistry Reactions
- Metal-Organic Frameworks: Synthesis and Applications
- Chemical Synthesis and Reactions
- Porphyrin and Phthalocyanine Chemistry
- Catalytic Processes in Materials Science
- Mesoporous Materials and Catalysis
- Metal-Catalyzed Oxygenation Mechanisms
- Carbon dioxide utilization in catalysis
- Catalysis and Oxidation Reactions
- Catalysis and Hydrodesulfurization Studies
- Organic Chemistry Cycloaddition Reactions
- Vanadium and Halogenation Chemistry
- Advanced Battery Materials and Technologies
- Thermal Expansion and Ionic Conductivity
- Advanced Nanomaterials in Catalysis
- Nanomaterials for catalytic reactions
- Coenzyme Q10 studies and effects
- Advancements in Battery Materials
- Multicomponent Synthesis of Heterocycles
- Bioactive Compounds and Antitumor Agents
- Sulfur-Based Synthesis Techniques
- Advanced battery technologies research
- Covalent Organic Framework Applications
- Zeolite Catalysis and Synthesis
Boreskov Institute of Catalysis
2013-2024
Novosibirsk Tuberculosis Research Institute
2020
Centre National de la Recherche Scientifique
2005-2013
Université Claude Bernard Lyon 1
2007-2013
Institut de Recherches sur la Catalyse et l'Environnement de Lyon
2005-2007
In this short review paper, we survey our recent findings in the catalytic applications of mesoporous metal–organic frameworks MIL-101 family (Fe- and Cr-MIL-101) demonstrate their potential two types liquid-phase processes: (i) selective oxidation hydrocarbons with green oxidants—O 2 tert -butyl hydroperoxide—and (ii) coupling reaction organic oxides CO . A comparison conventional single-site catalysts is made special attention to issues catalyst's resistance metal leaching nature catalysis.
Iron tetrasulfophthalocyanine (FePcS) has been irreversibly inserted into nanocages of the metal organic framework MIL-101 to give a hybrid material FePcS/MIL-101 which demonstrated superior catalytic performance in selective oxidation aromatic substrates with tBuOOH than homogeneous FePcS.
The decomposition of hydrogen peroxide (H2O2) is the main undesired side reaction in catalytic oxidation processes industrial interest that make use H2O2 as a terminal oxidant, such epoxidation alkenes. However, mechanism responsible for this still poorly understood, thus hindering development design rules to maximize efficiency oxidations terms product selectivity and oxidant utilization efficiency. Here, we thoroughly investigated using Zr-monosubstituted dimeric Lindqvist tungstate,...
Zr-monosubstituted Lindqvist-type polyoxometalates (Zr-POMs), (Bu4N)2[W5O18Zr(H2O)3] (1) and (Bu4N)6[{W5O18Zr(μ-OH)}2] (2), have been employed as molecular models to unravel the mechanism of hydrogen peroxide activation over Zr(IV) sites. Compounds 1 2 are hydrolytically stable catalyze epoxidation C═C bonds in unfunctionalized alkenes α,β-unsaturated ketones, well sulfoxidation thioethers. Monomer is more active than dimer 2. Acid additives greatly accelerate oxygenation reactions increase...
Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, spectroscopic tools. following facts point out a nucleophilic character the peroxo species responsible for superior formation sulfones: (1)...
Abstract The catalytic performance of Zr‐abtc and MIP‐200 metal–organic frameworks consisting 8‐connected Zr 6 clusters tetratopic linkers was investigated in H 2 O ‐based selective oxidations compared with that 12‐coordinated UiO‐66 UiO‐67. demonstrated advantages both substrate conversion product selectivity for epoxidation electron‐deficient C=C bonds α,β‐unsaturated ketones. significant predominance 1,2‐epoxide carvone epoxidation, coupled high sulfone thioether oxidation, points to a...
2,3,5-Trimethylbenzoquinone (precursor of vitamin E) and 2-methylnaphthoquinone (vitamin K3) were obtained in good yields by oxidation 2,3,6-trimethylphenol 2-methyl-1-naphthol, respectively, with tBuOOH catalyzed supported iron tetrasulfophthalocyanine. The mechanism this heterogeneous was studied using 18O2labeling experiments, EPR spectroscopy spin traps, kinetic studies, complete analysis reaction products including minor ones. experiments did not indicate the involvement O2 oxidative...
High yields of epoxides were obtained in the oxidation a large range olefins using 1.2-2 equiv. H2O2 presence iron helmet phthalocyanines. The involvement high-valent oxo species was evidenced cryospray mass spectrometry.
The oxidation of thioethers by the green oxidant aqueous H2 O2 catalysed tetratitanium-substituted Polyoxometalate (POM) (Bu4 N)8 [{γ-SiTi2 W10 O36 (OH)2 }2 (μ-O)2 ], as a model catalyst comprising tetrameric titanium centres, was investigated kinetic modelling and DFT calculations. Several mechanisms sulfoxidation were evaluated using methyl phenyl sulfide (PhSMe) substrate in experiments dimethyl first mechanism assumes that active hydroperoxo species forms directly through interaction Ti2...
Mesoporous zirconium-silicates have been prepared using two different methodologies, evaporation-induced self-assembly and solventless organometallic precursor dry impregnation of commercial SiO2. The samples were characterized by elemental analysis, XRD, N2 adsorption, TEM, DRS UV–vis Raman spectroscopic techniques. catalytic performance the Zr-Si catalysts was assessed in epoxidation three representative alkenes, cyclohexene, cyclooctene caryophyllene, as well oxidation methyl phenyl...
The controlled oxidation at only one position of compounds with several oxidizable sites, while keeping the other sites intact, has been demonstrated for phenols bearing alcohol or olefinic functional groups. Iron tetrasulfophthalocyanine supported on silica was found to be an efficient catalyst preparation functionalized quinones under mild conditions, tert-butylhydroperoxide as oxidant. A novel rapid and one-pot procedure covalent grafting iron onto developed. characterized by chemical...
In this work, we elaborated heterogeneous catalysts on the basis of Venturello complex [PO4{WO(O2)2}4]3- (PW4) and nitrogen-free or nitrogen-doped carbon nanotubes (CNTs N-CNTs) for epoxidation alkenes sulfoxidation thioethers with aqueous hydrogen peroxide. Catalysts PW4/CNTs PW4/N-CNTs (1.8 at. % N) containing 5-15 wt. PW4 differing in acidity have been prepared characterized by elemental analysis, N2 adsorption, IR spectroscopy, HR-TEM, HAADF-STEM. Studies STEM HAADF mode revealed a...
The divanadium-substituted polyoxometalate (Bu<sub>4</sub>N)<sub>5−n</sub>H<sub>n</sub>[γ-PW<sub>10</sub>V<sub>2</sub>O<sub>40</sub>] (<italic>n</italic> = 1–2) is an efficient and recyclable catalyst used for the synthesis of coenzyme Q<sub>0</sub> using hydrogen peroxide as a green oxidant.
Oxidation of 2-methyl-1-naphthol (MNL) with molecular oxygen proceeds efficiently under mild reaction conditions (3 atm O(2), 60-80 °C) in the absence any catalyst or sensitizer and produces 2-methyl-1,4-naphthoquinone (MNQ, menadione, vitamin K(3)) selectivity up to 80% nonpolar solvents. (1)H NMR (1)H,(1)H-COSY studies revealed formation 2-methyl-4-hydroperoxynaphthalene-1(4H)-one (HP) during course. Several mechanistic hypotheses, including conventional radical autoxidation, electron...
A mixed Ti,Zr‐based metal–organic framework, PCN‐415 (Porous Coordination Network), and the corresponding Ti,Zr‐oxocluster [Ti 8 Zr 2 O 12 (CH 3 COO) 16 ] have been synthesized comprehensively characterized by powder X‐Ray diffraction (PXRD), low‐temperature nitrogen adsorption, scanning electron microscopy, thermogravimetric analysis, Fourier‐transform infrared spectroscopy, Raman spectroscopy. The catalytic performance of both was evaluated in selective oxidation representative thioethers,...
The oxidation of 2-allylphenol and different phenols bearing alcohol functional groups with aqueous H2O2 as oxidant heterogeneous titanium-silicate Ti-MMM-2 catalyst exhibits an unusual selectivity affording the corresponding p-quinones good to moderate yield keeping other oxidizable sites intact. use hydrogen peroxide is a green alternative stoichiometric hypervalent iodine compounds that provides better yields structurally complex quinones in one step.
Nb‐monosubstituted polyoxotungstates of the Lindqvist and Keggin structures, (Bu 4 N) 3 [Nb(O)W 5 O 18 ] ( 1 ) [PW 11 NbO 40 2 ), respectively, catalyze oxidation organic sulfides with aqueous H in acetonitrile. The corresponding peroxo complexes [Nb(O )W Nb(O )O 39 formed upon interaction , are able to oxidize sulfoxides sulfones under stoichiometric conditions. product analysis thianthrene 5‐oxide, competitive sulfide–sulfoxide Hammett plot implicated electrophilic oxidative properties a...