- Non-hydrolytic synthesis of mesoporous silica-titania catalysts for the mild oxidation of sulfur compounds with hydrogen peroxide
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A SiO2-TiO2 mesoporous xerogel prepared in one-step by a non-hydrolytic route shows excellent performance in the mild oxidation of sulfides, sulfoxides and thiophenes with aqueous solutions of H 2O2. The Royal Society of Chemistry.
- Cojocariu, Ana Mihaela,Mutin, P. Hubert,Dumitriu, Emil,Fajula, Francois,Vioux, Andre,Hulea, Vasile
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- Unique Thia-Baeyer–Villiger-Type Oxidation of Dibenzothiophene Sulfoxides Derivatives
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The present research has demonstrated that selective C?S bond cleavages of dibenzothiophene and its derivatives are feasible by thia-Baeyer–Villiger type oxidation, i. e. the oxygen insertion process within a sulfoxide-carbon linkage, in the presence of porphyrin iron (III) and by ultraviolet irradiation originating from sunlight, high pressure Hg-lamp or residentially germicidal ultraviolet lamp under very mild conditions. This reaction with tert-butylhydroperoxide at 30.0 °C leads to dibenzo[1,2]oxathiin-6-oxide (PBS) in 83.2 % isolated yield or its hydrated products, 2-(2-hydroxyphenyl)-benzenesulfinic derivatives (HPBS) in near 100 % yield based HPLC data. PBS and HPBS are a type of biological products detected on the C?S bond cleavage step through various oxidative biodesulfurization (OBDS) pathways, and are useful synthetic intermediates and fine chemicals. These observations may contribute on understanding delicately molecular aspect of OBDS in the photosynthesis system, expanding the C-S cleavage chemistry of S-heterocyclic compounds and approaching toward biomemic desulfurization with respect to converting sulfur contaminants to chemically beneficial blocks as needed and performing under the ambient conditions.
- Kong, Yang,Li, Jie,Markó, István E.,Shi, Wenjun,Zhou, Xinrui
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- Oxidation of dibenzothiophene by hydrogen peroxide catalyzed by solid bases
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The removal of sulfur compounds from hydrocarbon-based distillate fuels is essential due to environmental concerns (i.e., acid rain and airborne particulate material production), and because a few parts per million of sulfur are enough to poison the catalysts used for the purification of the exhaust gases of diesel cars. The oxidation of dibenzothiophene (DBT) by H2O2 at 333 K was investigated using the catalysts (hydrotalcite (HT) and MgLa mixed oxide) and solvents (methanol, acetonitrile, benzonitrile, acrylonitrile, and 3-methoxypropionitrile). High activity was found only after calcinations followed by rehydration of HT. Acetonitrile was the best solvent, while much lower reaction rates were observed in methanol. The decomposition of H2O2 into oxygen was observed for HT, and was the major reaction at > 353 K. This reaction did not occur in the absence of nitrile, and was faster over MgLa mixed oxide of higher basic strength. The activity increased with increasing Mg/Al ratio due to a lower rate of H2O2 decomposition attributed to a lower basicity of the solid.
- Figueras,Palomeque,Clacens
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- Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil
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Aiming at the deep desulfurization of the diesel oil, a comparison of the catalytic effects of several Keggin type POMs, including H3PWxMo12-xO40 (x = 1, 3, 6), Cs2.5H0.5PW12O40, and H3PW12O40, was made, using the solution of DBT in normal octane as simulated diesel oil, H2O2 as oxidant, and acetonitrile as extractant. H3PW6Mo6O40 was found to be the best catalyst, with a desulfurization efficiency of 99.79% or higher. Hence, it is promising for the deep desulfurization of actual ODS process. The role of the main factors affecting the process including temperature, O/S molar ratio, initial sulfur concentration, and catalyst dosage, was investigated, whereby the favourable operating conditions were recommended as T = 60 °C, O/S = 15, and a catalyst dosage of 6.93 g (H3PW6Mo6O40)/L (simulated diesel). With the aid of GC-MS analysis, sulfone species was confirmed to be the only product after reaction for 150 min. Furthermore, macro-kinetics of the process catalyzed by H3PW6Mo6O40 was studied, from which the reaction orders were found to be 1.02 to DBT and 0.38 to H2O2, and the activation energy of the reaction was found to be 43.3 kJ/mol. Moreover, the catalyst recovered demonstrated almost the same activity as the fresh.
- Wang, Rui,Zhang, Gaofei,Zhao, Haixia
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- Synergy between bis(dimethyldioctylammonium) molybdate and tetraethylene glycol monooctyl ether: A winning combination for interfacial catalysis in thermo-controlled and switchable microemulsions
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A simple thermo-responsive one-phase microemulsion (μem) is designed to enable the dark singlet oxidation of organic substrates while allowing a straightforward separation of the catalytic surfactant and products in two distinct phases by cooling down the reaction medium. This latter is prepared by combining a small amount (1%) of the catalytic surfactant bis(dimethyldioctylammonium) molybdate, [DiC8]2[MoO4], with the nonionic amphiphile tetraethylene glycol monooctyl ether, C8E4. Tensiometry and dynamic light scattering are used to rationalize the synergy between the two surfactants which strongly interact. The oxidation takes place in the effective one-phase Winsor IV system which separates into two phases (μem + oil, i.e. Winsor I) just by temperature change thanks to the presence of the thermosensitive C8E4. The thermal-controlled nanostructured reaction medium is applied to the ene reaction, [4+2] cycloaddition and sulfide oxidation.
- Hong, Bing,Leclercq, Lo?c,Collinet-Fressancourt, Marion,Lai, Jonathan,Bauduin, Pierre,Aubry, Jean-Marie,Nardello-Rataj, Véronique
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- Performance evaluation of the carbon nanotubes supported Cs2.5H0.5PW12O40 as efficient and recoverable catalyst for the oxidative removal of dibenzothiophene
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With the issues of increasingly stringent legislations on sulfur level in transportation fuels, clean fuels research including desulfurization has become a more important subject of environmental catalysis studies. Oxidative desulfurization (ODS) combined with extraction is one of the most promising desulfurization processes. With the loading of Cs2.5H0.5PW12O40, a new multi-walled carbon nanotube (MWNT) supported catalyst (Cs2.5H0.5PW12O40/MWNT) has been developed in this study. Through experimental evaluations, Cs2.5H0.5PW12O40/MWNT was found to be very effective for the oxidative removal of DBT, with a desulfurization efficiency of up to 100%. Factors affecting the process, including reaction temperature, O/S molar ratio, initial sulfur content, catalyst dosage, and pre-immersion time of the catalyst in H2O2 solution, were evaluated, and the favourable operating conditions were determined. Sulfone species was confirmed by GC-MS analysis to be the only product from DBT oxidation by H2O2 in the presence of Cs2.5H0.5PW12O40/MWNT after 160 min. Moreover, the new catalyst developed is recoverable. The recovered Cs2.5H0.5PW12O40/MWNT demonstrates quite close catalytic activity to that of the fresh. As a whole, Cs2.5H0.5PW12O40/MWNT has a high potential for using as an effective catalyst for deep desulfurization of diesel.
- Wang, Rui,Yu, Fengli,Zhang, Gaofei,Zhao, Haixia
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- One-pot extractive and oxidative desulfurization of liquid fuels with molecular oxygen in ionic liquids
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Benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethlydibenzothiophene (4,6-DMDBT) were extracted from an oil phase to ionic liquid phase, and then oxidized to the corresponding sulfone by the cheap catalyst, N-hydroxyphthalimide (NHPI), using molecular oxygen as the oxidant in one-pot. The system can be recycled 5 times without a significant decrease in desulfurization.
- Wang, Jianlong,Guo, Qingping,Zhang, Changming,Li, Kaixi
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- Selective oxidation of sulfides to sulfoxides and sulfones by microwave thermolysis on wet silica-supported sodium periodates
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A variety of symmetrical and unsymmetrical sulfides have been selectively and expeditiously oxidized to either sulfoxides or sulfones in good yields using wet silica-supported sodium periodate under microwave thermolysis conditions.
- Varma, Rajender S.,Saini, Rajesh K.,Meshram, Harshadas M.
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- Efficient molybdenum catalyzed chemoselective, solvent-free oxidation of sulfides to sulfones at room temperature
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An effcient and reusable molybdenum-based catalyst has been prepared by tethering dioxomolybdenumacetylacetonate complex, MoO2(acac)2, via postsynthesis modifcation of zeolite beta. The catalyst has been characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and inductively coupled plasma (ICP). The catalyst exhibited very high activity for the selective oxidation of sulfdes to sulfones at room temperature. The catalyst can be recycled and reused four times without signifcant loss of activity.
- Hadigavabar, Ali Dadashi,Tabatabaeian, Khalil,Zanjanchi, Mohammad Ali,Mamaghani, Manouchehr
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- Tungstophosphoric Acid-catalyzed Oxidative Desulfurization of Light Oil with Hydrogen Peroxide in a Light Oil/Acetic Acid Biphasic System
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Dibenzothiophenes were oxidized effectively with H2O 2 in the presence of 12-tungstophosphoric acid in the tetradecane/ AcOH biphasic system to give their corresponding sulfones as the major products. The oxidation proceeded in the AcOH phase and most of the sulfones distributed there, resulting in the successive removal of the sulfur compounds from the tetradecane phase. This biphasic oxidation system can effectively reduce the sulfur content in light oil.
- Yazu, Kazumasa,Furuya, Takeshi,Miki, Keiji,Ukegawa, Koji
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- Oxidation of dibenzothiophene with cumene hydroperoxide on MoO3/SiO2 modified with alkaline earth metals
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Catalytic oxidation of dibenzothiophene (DBT) in decalin was performed using an oil-soluble oxidant, cumene hydroperoxide (CHP), over molybdenum oxide (MoO3) supported on silica. The effects of MoO3 loading, reaction time and the molar ratio of CHP/DBT were investigated. At a MoO3 loading of 15 wt%, the conversion of DBT reached 82% at 70 °C, WHSV 30 h-1, and O/S molar ratio 3. Alkaline earth metals, such as Ca, Ba, Sr and Mg were introduced on the surface of silica, prior to the impregnation of MoO3. The results showed that the activity in the oxidation of DBT with CHP decreased in the order: MoO3/Ca-SiO2 > MoO3/Ba-SiO2 > MoO3/SiO2 > MoO3/Sr-SiO2 > MoO3/Mg-SiO2. The MoO3/Ca-SiO2 catalysts were characterized by XRD. The DBT conversions on MoO3/Ca-SiO2 catalysts with various Ca/Mo ratios were studied. When the Ca/Mo ratio was 0.05, the DBT conversion was the highest (95%) at 60 °C, WHSV 30 h-1, and O/S molar ratio 3.0.
- Chang, Jie,Wang, Anjie,Liu, Jing,Li, Xiang,Hu, Yongkang
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- Polyoxometalate [γ-SiW10O34(H 2O)2]4- on MCM-41 as catalysts for sulfide oxygenation with hydrogen peroxide
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The polyoxometalate (POM) catalyst, [γ-SiW10O 34(H2O)2]4-, was introduced into the pores of both as-synthesized (I) and amine functionalized MCM-41 (II). The resultant catalysts were characterized with powder X-ray diffraction, nitrogen sorption, and diffuse-reflectance UV-vis spectroscopy. Both catalysts were tested for reusability through repeated catalytic conversions of methyl phenyl sulfide to methyl phenyl sulfone with hydrogen peroxide. While the physisorbed catalyst (I) exhibits steadily decreasing turnover frequency (TOF), the POM catalyst supported on MCM-41 functionalized with a protonated amine (II) exhibits markedly improved reusability. This chemisorbed catalyst effectively showed no change in TOF between the second (21) and the sixth reactions (22). Additionally, sulfoxidations with catalyst II were investigated with a small set of substrates focusing on compounds including dibenzothiophene, which serves as a model refractory sulfide.
- Thompson, Dylan J.,Zhang, Yang,Ren, Tong
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- Synthesis and characterization of PMoV/Fe3O4/g-C3N4 from melamine: An industrial green nanocatalyst for deep oxidative desulfurization
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A facile approach to the preparation of a novel magnetically separable H5PMo10V2O40/Fe3O4/g-C3N4 (PMoV/Fe3O4/g-C3N4) nanocomposite by chemical impregnation is demonstrated. The prepared nanocomposite was characterized and its acidity was measured by potentiometric titration. PMoV/Fe3O4/g-C3N4 showed high catalytic activity in the selective oxidative desulfurization of sulfides to their corresponding sulfoxides or sulfones. The catalytic oxidation of a dibenzothiophene (DBT)-containing model oil and that of real oil were also studied under optimized conditions. In addition, the effects of various nitrogen compounds, as well as the use of one- and two-ring aromatic hydrocarbons as co-solvents, on the catalytic removal of sulfur from DBT were investigated. The catalyst was easily separated and could be recovered from the reaction mixture by using an external magnetic field. Additionally, the remaining reactants could be separated from the products by simple decantation if an appropriate solvent was chosen for the extraction. The advantages of this nanocatalyst are its high catalytic activity and reusability; it can be used at least four times without considerable loss of activity.
- Rafiee, Ezzat,Khodayari, Maryam
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- Extraction and oxidative desulfurization of diesel fuel catalyzed by a Bronsted acidic ionic liquid at room temperature
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The Bronsted acidic ionic liquids 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]) and N-butylpyridinium hydrogen sulfate ([C4Py][HSO4]) were used as extractant and catalyst for desulfurization of diesel. The results show that [BMIM][HSO 4] is better as extractant and catalyst than [C4Py] [HSO4] during the desulfurization process. The sulfur removal of dibenzothiophene (DBT) in n-octane was 99.6% in 90 min under the conditions of Vmodel oil/VIL = 2:1 and H2O2/DBT molar ratio at 5 (O/S = 5), at room temperature. The sulfur removal of four sulfur compounds by extraction and catalytic oxidation process followed the order of DBT > benzothiophene (BT) > thiophene (TS) > 4,6-dimethyldibenzothiophene (4,6-DMDBT). Moreover, the [BMIM][HSO4] can be recycled for at least 6 times with a little decrease in the desulfurization activity. The sulfur removal of diesel fuel containing sulfur content of 97 ppm is 85.5%, which was much better than desulfurization performance by simple extraction with IL (11.0%). In this extraction and oxidative desulfurization process, DBT was oxidized to corresponding sulfone by H2O2 with Bronsted acidic IL [BMIM][HSO 4] which served as not only extractant but also catalyst. The Royal Society of Chemistry 2010.
- Gao, Hongshuai,Guo, Chen,Xing, Jianmin,Zhao, Junmei,Liu, Huizhou
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- Solvent-free chemoselective oxidation of thioethers and thiophenes by mechanical milling
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Organosulphur compounds can be easily and selectively oxidized to sulfones using a small excess of Oxone (1.6 eq.) under solventless mechanical milling conditions. This green procedure has been efficiently applied to a series of model compounds and to the desulphurization of medium/high sulphur content paraffins (up to 3000 mg kg-1).
- Cravotto, Giancarlo,Garella, Davide,Carnaroglio, Diego,Gaudino, Emanuela Calcio,Rosati, Ornelio
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p. 11632 - 11634,3
(2012)
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- Oxidation of sulfides to sulfoxides and sulfones with 30% hydrogen peroxide under organic solvent- and halogen-free conditions
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Aromatic and aliphatic sulfides are oxidized to sulfoxides or sulfones in high yield with 30% hydrogen peroxide under organic solvent- and halogen-free conditions. Dialkyl and alkyl aryl sulfides are cleanly oxidized to sulfoxides using aqueous hydrogen peroxide without catalysts. The best catalyst for the sulfone synthesis consists of sodium tungstate, phenylphosphonic acid, and methyltrioctylammonium hydrogensulfate. Co-existing primary or secondary alcohol or olefinic moieties are unaffected under such conditions.
- Sato, Kazuhiko,Hyodo, Mamoru,Aoki, Masao,Zheng, Xiao-Qi,Noyori, Ryoji
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- A promising PET tracer for imaging of α7 nicotinic acetylcholine receptors in the brain: Design, synthesis, and in vivo evaluation of a dibenzothiophene-based radioligand
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Changes in the expression of α7 nicotinic acetylcholine receptors (α7 nAChRs) in the human brain are widely assumed to be associated with neurological and neurooncological processes. Investigation of these receptors in vivo depends on the availability of imaging agents such as radioactively labelled ligands applicable in positron emission tomography (PET). We report on a series of new ligands for α7 nAChRs designed by the combination of dibenzothiophene dioxide as a novel hydrogen bond acceptor functionality with diazabicyclononane as an established cationic center. To assess the structure-activity relationship (SAR) of this new basic structure, we further modified the cationic center systematically by introduction of three different piperazine-based scaffolds. Based on in vitro binding affinity and selectivity, assessed by radioligand displacement studies at different rat and human nAChR subtypes and at the structurally related human 5-HT3 receptor, we selected the compound 7-(1,4-diazabicyclo[3.2.2]nonan-4-yl)-2-fluorodibenzo-[b,d]thiophene 5,5-dioxide (10a) for radiolabeling and further evaluation in vivo. Radiosynthesis of [18F]10a was optimized and transferred to an automated module. Dynamic PET imaging studies with [18F]10a in piglets and a monkey demonstrated high uptake of radioactivity in the brain, followed by washout and target-region specific accumulation under baseline conditions. Kinetic analysis of [18F]10a in pig was performed using a two-tissue compartment model with arterial-derived input function. Our initial evaluation revealed that the dibenzothiophene-based PET radioligand [18F]10a ([18F]DBT-10) has high potential to provide clinically relevant information about the expression and availability of α7 nAChR in the brain.
- Teodoro, Rodrigo,Scheunemann, Matthias,Deuther-Conrad, Winnie,Wenzel, Barbara,Fasoli, Francesca Maria,Gotti, Cecilia,Kranz, Mathias,Donat, Cornelius K.,Patt, Marianne,Hillmer, Ansel,Zheng, Ming-Qiang,Peters, Dan,Steinbach, J?rg,Sabri, Osama,Huang, Yiyun,Brust, Peter
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- Selective sulfoxidation with hydrogen peroxide catalysed by a titanium catalyst
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A moisture-tolerant cyclopentadienyl-silsesquioxane titanium complex efficiently catalyses the selective oxidation of various types of sulfides to either sulfoxides (TOFs up to 32 530 h-1) or sulfones with H2O2 (30% in water) under mild conditions.
- Postigo, Lorena,Ventura, Maria,Cuenca, Toms,Jimnez, Gerardo,Royo, Beatriz
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- Catalytic performance of ammonium salt of molybdenum heteropoly acid supported silica for oxidative desulfurization of benzothiophene, dibenzothiophene and 4,6-dimethyldibenzothiophene in model oil
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An ammonium salt of molybdenum heteropoly acid was loaded on silica support (HPA-SiO2), used as catalyst in oxidative desulfurization for removing benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) from model oil. The structural properties of prepared catalyst were studied by using various analytical techniques; Fourier transforms infrared spectroscopy, X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The results showed that the ammonium salt of molybdenum heteropoly acid highly dispersed on SiO2. The final catalyst exhibits good catalytic activity of oxidative desulfurization. The 94.6 % of thiophene compounds of the model oil were removed under optimal conditions; temperature at 80 °C, reaction time 100 min. The oxidation is decreased in order of DBT > 4,6-DMDBT > BT.
- Pant, Deeptiraj,Thakur, Ramswaroop Singh,Lal, Sunder
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- Oxidative Desulfurization of Dibenzothiophene Using Cobalt (II) Complexes with Substituted Salen-Type Ligands as Catalysts in Model Fuel Oil
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Three cobalt(II)-salen complexes (CoL1, CoL2 and CoL3) were synthesized via the reaction of the three tetradentate ligands as N,N′-ethylenebis(salicylimine) L1, N,N′-ethylenebis(3-tert-butylsalicylimine) L2 and N,N′-ethylenebis(3,5-di-tert-butylsalicylimine) L3, with a stoichiometric amount of cobalt(II) acetate tetrahydrate, respectively. All the three complexes were studied as oxidative desulfurization catalyst on dibenzothiophene taken in model fuel oil n-dodecane. The acetonitrile used as an extracting solvent and H2O2 as an oxidant. Comparatively CoL3 proved to be the best catalyst which showed the 76% DBT removal at the optimized conditions. The nth-order kinetic model is the best way to represent oxidation kinetics of complexes. Graphic Abstract: [Figure not available: see fulltext.]This cobalt(II) Schiffs base complexes were studied as catalyst for oxidative desulfurization of dibenzothiphene (DBT) taken as model sulphur compounds in fuel model oil (n-dodecane) using H2O2 as oxidant and acetonitrile as extracting solvent for DBT sulfone in a batch experiment.
- Tripathi, Deependra,Singh, Raj K.
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- A new halide-free efficient reaction-controlled phase-transfer catalyst based on silicotungstate of [(C18H37)2(CH 3)2N]3[SiO4H(WO5) 3] for olefin epoxidation, oxidation of sulfides and alcohols with hydrogen peroxide
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A new reaction-controlled phase-transfer catalyst based on silicotungstate of [(C18H37)2(CH3) 2N]3[SiO4H(WO5)3] for oxidation of hydrocarbons is developed. The catalyst is a new heteropoly compound with silicon as heteroatom, which is different to the previously reported reaction-controlled phase transfer catalysts that were composed of quaternary ammonium heteropolyoxotungstates of [π-C5H 5N(CH2)15CH3]3[PW 4O16] and [π-C5H5N(CH 2)15CH3]3[PW4O 32] with phosphorus as heteroatom. The oxidation of various alkenes (such as linear terminal olefins, internal olefins, cyclic olefins and unactivated alkenes) to epoxides, sulfides to sulfoxides and sulfones, alcohols to carbonyl compounds, are successfully catalyzed by this recyclable and environmentally benign catalyst using H2O2 as oxidant and ethyl acetate as solvent. This catalyst is not only capable of catalyzing homogeneous oxidation of organic substrates with unique reaction-controlled phase-transfer character, but also avoids the use of toxic solvents. The catalyst could be easily recovered and reused after reaction, and the epoxidation of cyclohexene was performed twenty times without obvious loss in activity. The fresh catalyst and the used one were characterized by ICP, IR, UV-vis, 29Si MAS NMR and 183W NMR in detail. the Partner Organisations 2014.
- Ma, Baochun,Zhao, Wei,Zhang, Fuming,Zhang, Yingshuai,Wu, Songyun,Ding, Yong
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- Novel yellow phosphorescent iridium complexes with dibenzothiophene-S,S-dioxide-based cyclometalated ligand for white polymer light-emitting diodes
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We have designed and synthesized two novel yellow phosphorescent iridium complexes using dibenzothiophene-S,S-dioxide-based cyclometalated ligand for the first time, which are capable of producing highly efficient yellow and white polymer light-emitting devices (PLEDs). The resulted iridium complexes display good thermal stability and high photoluminescence quantum yields. Both yellow and white PLEDs are fabricated with an identical single-emission-layer configuration of ITO/PEDOT:PSS/emission layer (EML)/CsF/Al. For the yellow phosphorescent PLEDs based on (p-CzFSOPy)2IrPic, the best device performances with a peak luminous efficiency (LE) of 13.3 cd/A and a peak external quantum efficiency (EQE) of 5.3% are achieved. More importantly, the two-element WPLEDs containing iridium (III)bis (2-(4,6-difluorophenyl)-pyridinato-N,C2′) picolinate (FIrpic) as blue and (p-CzFSOPy)2IrPic as yellow phosphors doped into a PVK:OXD-7 matrix at an appropriate ratio exhibited a maximum LE of 19.2 cd/A, a maximum EQE of 9.6%, an extremely high luminance of 18717 cd/m2 and Commission Internationale de L'Eclairage (CIE) coordinate of (0.317, 0.448). Moreover, at a luminance for practical application of 1000 cd/m2, the LE still remains as high as 19.0 cd/A, with a very slight decrease.
- Liang, Aihui,Luo, Ming,Liu, Yusheng,Wang, Han,Wang, Zhiping,Zheng, Xiaoyan,Cao, Tian,Liu, Dewang,Zhang, Yong,Huang, Fei
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- An environmentally benign and selective electrochemical oxidation of sulfides and thiols in a continuous-flow microreactor
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A practical and environmentally benign electrochemical oxidation of thioethers and thiols in a commercially-available continuous-flow microreactor is presented. Water is used as the source of oxygen to enable the oxidation process. The oxidation reaction utilizes the same reagents in all scenarios and the selectivity is solely governed by the applied potential. The procedure exhibits a broad scope and good functional group compatibility providing access to various sulfoxides (15 examples), sulfones (15 examples) and disulfides (6 examples). The use of continuous flow allows the optimal reaction parameters (e.g. residence time, applied voltage) to be rapidly assessed, to avoid mass- and heat-transfer limitations and to scale the electrochemistry.
- Laudadio, Gabriele,Straathof, Natan J. W.,Lanting, Menno D.,Knoops, Benny,Hessel, Volker,No?l, Timothy
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- A Mn(III) polyoxotungstate in the oxidation of organosulfur compounds by H2O2 at room temperature: An environmentally safe catalytic approach
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The tetrabutylammonium (TBA) salt of a Keggin-type polyoxometalate (POM), with the chemical formula TBA4H2[BW11Mn(H2O)O39]·H2O, TBABW11Mn, was evaluated as a catalyst in the oxidation by hydrogen peroxide of several organosulfur compounds, namely benzothiophene (BT), 2-methylbenzothiophene (2-MBT), 3-methylbenzothiophene (3-MBT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-diethyldibenzothiophene (4,6-DEDBT), in acetonitrile at room temperature. All compounds were oxidized to their corresponding sulfones with high conversion and selectivity. Following the excellent results achieved, the BW11Mn/H2O2 in CH3CN system was tested in the oxidation of model fuels (MFs) consisting of a mixture of BTs and DBTs in hexane (MF1 containing mainly BTs and MF2 containing predominantly DBTs). In both cases, the organosulfur compounds from the model fuels were fully converted into their corresponding sulfones. Envisaging the development of a promising desulfurization procedure, the extraction of sulfur compounds from MF2 was attempted after the catalytic oxidation process. More than 98 mol% was removed using an ethanol/H2O mixture.
- Duarte, Tiago A.G.,Pires, Sónia M.G.,Santos, Isabel C.M.S.,Sim?es, Mário M.Q.,Neves, M. Gra?a P.M.S.,Cavaleiro, Ana M.V.,Cavaleiro, José A.S.
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- Deep oxidative desulfurization of dibenzothiophene with molybdovanadophosphoric heteropolyacid-based catalysts
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Three hydrophobic Keggin-type heteropolyacid catalysts, [C 3H3N2(CH3)(C2H 4)]5PMo10V2O40 ([C 2mim]PMoV), [C3H3N2(CH 3)(C4H8)]5PMo10V 2O40 ([C4mim]PMoV) and [C3H 3N2(CH3)(C6H12)] 5PMo10V2O40 ([C6mim]PMoV) , were synthesized by reacting molybdovanadophosphoric acid with imidazolium bromides, and characterized by spectroscopic methods. Their use as catalysts in the extractive catalytic oxidative desulfurization process using hydrogen peroxide as the oxidant and acetonitrile as phase transfer agent was studied. The catalytic properties decreased in the order: [C6mim]PMoV > [C4mim]PMoV > [C2mim]PMoV. The main factors influencing the rate of removal of dibenzothiophene (DBT) were investigated, including reaction temperature, the amounts of catalyst, H2O2 and acetonitrile. Nearly 100 % sulfur removal rate was achieved under optimal conditions. The catalyst could be recycled six times with only a slight decrease in activity. A reaction mechanism for DBT oxidation is proposed, in which the Keggin anions first obtain active oxygen from H2O2, then the DBT is oxidized to dibenzothiophene sulfones.
- Zhuang, Jiangzhou,Hu, Bing,Tan, Junjun,Jin, Xiaoying
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- An efficient method for the oxidation of organic sulfides to sulfones
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Mild and safe oxidation of dialkyl-, diaryl- and alkyl-aryl sulfides (1a-m) to the corresponding sulfones (2a-m)by using urea-hydrogen peroxide/formic acid system is reported. Wiley-VCH Verlag GmbH, 1999.
- Balicki, Roman
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- Application of VIVO(acac)2 type complexes in the desulfurization of fuels with ionic liquids
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The acetylacetonate complexes of oxovanadium(IV): VO(X-acac)2 (X = Cl, CH3 and CH3CH2) were structurally characterized in several alkylimidazolium ionic liquids by visible absorption and EPR spectroscopies. VO(Me-acac)2 and VO(Et-acac)2 showed solvatochromism in the selected ionic liquids (a λ1 shift of ca. 120 nm was observed) and most complexes showed two species in the anisotropic EPR spectra in several ionic liquids. It was shown that the ionic liquids anions have coordinating ability and the basicity order found was: NTf2- - 4 -, in agreement with previous findings. An extraction and catalytic oxidation desulfurization (ECODS) system composed of VO(X-acac)2, H2O2 and ionic liquids was tested in the removal of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) from a model oil (n-octane) at ambient temperature. The influence of the catalyst, ionic liquid, substrate and the molar ratio of the oxidant (H2O2) and the S-containing molecule were examined. The reaction rates of the oxidative desulfurization reaction were found to increase with the molar ratio of H2O2 and the S-containing molecule, as expected, however a ratio of 4 was enough to achieve >95% conversion to sulfone. The ionic liquid that showed the best performance with all substrates was bmimNTf2. In bmimOTf and bmimBF4 the activity of all catalysts in the ECODS system was low to moderate, which is probably due to the higher coordinating ability of these anions.
- Mota, Andreia,Butenko, Nataliya,Hallett, Jason P.,Correia, Isabel
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- Efficient mesoporous silica-titania catalysts from colloidal self-assembly
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Mesoporous silica-titania materials of tunable composition and texture, which present a high catalytic activity in the mild oxidation of sulfur compounds, have been obtained by combining the spray-drying process with the colloidal self-assembly of α-chitin nanorods (biopolymer acting as a template) and organometallic oligomers.
- Sachse, Alexander,Hulea, Vasile,Marcotte, Nathalie,Boltoeva, Maria Yu,Belamie, Emmanuel,Alonso, Bruno,Kostov, Krassimir L.
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p. 10648 - 10650,3
(2012)
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- Imidazolium perrhenate ionic liquids as efficient catalysts for the selective oxidation of sulfides to sulfones
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A series of imidazolium perrhenate ionic liquids (IPILs) have been synthesized and used as efficient catalysts for the oxidation of sulfides to sulfones with aqueous hydrogen peroxide under mild conditions. Various sulfones are obtained in good to excellent yields. IPILs are stable and can be reused at least ten times without detectable activity loss. Furthermore, this system provides a reasonably environmentally benign chemical process in terms of potential industrial application.
- Zhang, Bo,Li, Su,Yue, Shuang,Cokoja, Mirza,Zhou, Ming-Dong,Zang, Shu-Liang,Kühn, Fritz E.
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- The adsorptive extraction of oxidized sulfur-containing compounds from fuels by using molecularly imprinted chitosan materials
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An innovative approach for desulfurisation of fuels is proposed. It relies on the formation of recognition sites, complementary to oxidized sulfur-containing compounds, on cross-linked chitosan microspheres and electrospun chitosan nanofibers using the molecularly imprinted polymer technique. Benzothiophene sulfone (BTO2), dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO 2) were used as templates for the preparation of molecularly imprinted polymers (MIPs). The possible molecular interactions between imprinted chitosan adsorbent and oxidized sulfur-containing compounds were investigated by molecular modeling using density functional theory (DFT) and results indicated that interactions took place via hydrogen bonding. The molecularly imprinted polymer adsorbents (cross-linked microspheres and electrospun nanofibers) gave better selectivity for the target sulfonated compounds and the adsorption isothermal studies followed the Freundlich model. Maximum adsorption capacities of 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g were observed for model BTO2, DBTO2 and 4,6-DMDBTO2 respectively at 1 mL/h when imprinted nanofibers were employed, and the imprinted microspheres gave maximum adsorption capacity of 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g for BTO 2, DBTO2 and 4,6-DMDBTO2 respectively. Application of the nanofibers to oxidized hydro-treated fuel under continuous flow adsorption system at 1 mL/h indicated that 84% of sulfur was adsorbed, with adsorption capacity of 2.2 ± 0.2 mg/g.
- Ogunlaja, Adeniyi S.,Coombes, Matthew J.,Torto, Nelson,Tshentu, Zenixole R.
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- Binuclear manganese complexes as catalysts in the selective and efficient oxidation of sulfides to sulfones
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The binuclear Mn(IV)-Mn(IV) manganese complex 1 catalyzes the periodic acid oxidation of sulfides to sulfones under mild conditions. The reaction was found to be highly selective giving almost quantitative yields of the sulfones even in the presence other easily oxidized groups. Only amines were found to hinder the reaction.
- Barton, Derek H. R.,Li, Wenge,Smith, Jason A.
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- Deep oxidative desulfurization with task-specific ionic liquids: An experimental and computational study
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A series of task-specific acidic ionic liquids (TSILs), immiscible with oil, halogen-free and containing -COOH group in the cations, were used for oxidative desulfurization as both the catalyst and extractant. The removal of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) from model diesel at 298 K could reach 96.7% and 95.1%, respectively. The TSIL could be recycled 5 times without any apparent loss of the catalytic activity. Meanwhile, the structures, acidities and interactions between the cation and the anion of TSILs have been investigated by density functional theory (DFT) method, and found that catalytic properties of TSILs are close related to the structures, acidities and extraction capabilities. Furthermore, an oxidative desulfurization mechanism has been proposed.
- Gui, Jianzhou,Liu, Dan,Sun, Zhaolin,Liu, Daosheng,Min, Dayoung,Song, Busub,Peng, Xilai
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- A mild and efficient procedure for the oxidation of organic sulfides to sulfones by use of urea-hydrogen peroxide/trifluoroacetic anhydride system
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Selective, mild and safe oxidation of dialkyl-, diaryl- and alkyl-aryl sulfides to the corresponding sulfones was achieved by using of urea- H2O2/trifluoroacetic anhydride system.
- Balicki, Roman
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- Oxidation of organic sulfur compounds with hydrogen peroxide in the presence of crown ethers
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It was first shown that crown ethers catalyze the oxidation of organic sulfur compounds (methyl phenyl sulfide to sulfoxide and sulfone, benzothiophene and dibenzothiophene to sulfones) with hydrogen peroxide. Nauka/Interperiodica 2007.
- Anisimov,Tarakanova,Tkhai, Fat Vin,Kulikov,Seleznev
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- Vanadium and titanium oxide supported on mesoporous CMK-3 as new catalysts for oxidative desulfurization
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Vanadium supported-CMK-3 catalysts with vanadium loading of 1–7?wt.% were studied in the oxidative desulfurization (ODS) of dibenzothiophene as a model sulfur compound. The activity was compared with titanium supported-CMK-3. Structural and textural characterization of the catalysts was performed by means of N2 adsorption, XRD, UV–vis–DRS, Raman spectroscopy, XPS, TEM and TPR. The dispersion and the nature of the vanadium species depend on the V loading, so does the catalyst activity. Vanadium supported-CMK-3 with 7?wt.% of vanadium loading was the most active catalyst for ODS of DBT using hydrogen peroxide (H2O2) as oxidant and acetonitrile as solvent. 100% of DBT elimination was attained at short time in mild conditions. Carbon ordered mesoporous CMK-3 with high surface area and high pore volume promotes a very good anchorage of metallic oxides in the carbons framework reaching high active sites distribution and more stable nanoclusters. The reusability of the catalyst indicates that V-CMK-3 is a potential catalyst for the ODS of dibenzothiophene.
- Rivoira, Lorena,Juárez, Juliana,Falcón, Horacio,Gómez Costa, Marcos,Anunziata, Oscar,Beltramone, Andrea
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- Anchorage of a ruthenium complex into modified MOF: Synergistic effects for selective oxidation of aromatic and heteroaromatic compounds
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The structure of IRMOF-3 was modified with pyridine-2-aldehyde and then the Schiff base moieties were used to anchor ruthenium complex to this metal-organic framework. The prepared catalyst was characterized by X-ray powder diffraction (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and FTIR methods. The results show that the prepared catalyst acquires a high potential for selective oxidation of aromatic and heteroaromatic compounds under mild conditions and easy workups.
- Tabatabaeian, Khalil,Zanjanchi, Mohammad Ali,Mahmoodi, Nosrat. O.,Eftekhari, Tooraj
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p. 101013 - 101022
(2015)
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- Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
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Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is
- Li, Chifeng,Mizuno, Noritaka,Murata, Kei,Ishii, Kazuyuki,Suenobu, Tomoyoshi,Yamaguchi, Kazuya,Suzuki, Kosuke
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- Metal and solvent free selective oxidation of sulfides to sulfone using bifunctional ionic liquid [pmim]IO4
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The oxidation of organo-sulfides to sulfones has been accomplished using an easily accessible bifunctional ionic liquid, [pmim]IO4 in the absence of any other oxidants, metal and organic solvent at ambient temperature. A variety of sulfides including dialkyl, aryl-alkyl, diaryl, and aryl-hetero aryl have been oxidized to the corresponding functionalized sulfones in high yields by this procedure.
- Ahammed, Sabir,Kundu, Debasish,Siddiqui, Mohammad Nahid,Ranu, Brindaban C.
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- Oxidation of refractory sulfur-containing compounds with molecular oxygen catalyzed by vanadoperiodate
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A new vanadoperiodate [HIV9O28]3- has been synthesized by a simple, one-pot stoichiometric reaction of HIO4·2H2O with NaVO3 in aqueous solution and then isolated as [C8H17/
- Tang, Nanfang,Jiang, Zongxuan,Li, Can
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- Substrate specificity and ionization potential in chloroperoxidase- catalyzed oxidation of diesel fuel
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Straight-run diesel fuel containing 1.6% of sulfur was enzymatically oxidized with chloroperoxidase from Caldariomyces rumago. Most organosulfides and thiophenes were transformed to form sulfoxides and sulfones. The oxidized organosulfur compounds can be effectively removed by distillation. The resulting fraction after distillation contained only 0.27% sulfur, while the untreated straight-run diesel fuel after the same distillation process still showed 1.27% sulfur. To know the chemical nature of the products, nine organosulfur compounds and 12 polycyclic aromatic compounds (PACs) were transformed by chloroperoxidase in the presence of chloride and hydrogen peroxide. Organosulfur compounds were only oxidized to form sulfoxides and sulfones, and no chlorinated derivatives were detected, except for bithiophene. In contrast, PACs were exclusively chlorinated, and no oxidized derivatives could be found. No enzymatic activity was detected on PACs with an ionization potential higher than 8.52 eV, while in the lower region it was found that the higher the ionization potential of the PAC the lower the specific activity. On the other hand, the substrate ionization potential did not seem to influence chloroperoxidase activity in the oxidation of organosulfur compounds. All organosulfur compounds tested were oxidized by chloroperoxidase. From double-substrate experiments, it appears that organosulfur compounds are oxidized by both compound I and compound X enzyme intermediates, while PACs react only with the halogenating intermediate, compound X. Straight-run diesel fuel containing 1.6% of sulfur was enzymatically oxidized with chloroperoxidase from Caldariomyces fumago. Most organosulfides and thiophenes were transformed to form sulfoxides and sulfones. The oxidized organosulfur compounds can be effectively removed by distillation. The resulting fraction after distillation contained only 0.27% sulfur, while the untreated straight-run diesel fuel after the same distillation process still showed 1.27% sulfur. To know the chemical nature of the products, nine organosulfur compounds and 12 polycyclic aromatic compounds (PACs) were transformed by chloroperoxidase in the presence of chloride and hydrogen peroxide. Organosulfur compounds were only oxidized to form sulfoxides and sulfones, and no chlorinated derivatives were detected, except for bithiophene. In contrast, PACs were exclusively chlorinated, and no oxidized derivatives could be found. No enzymatic activity was detected on PACs with an ionization potential higher than 8.52 eV, while in the lower region it was found that the higher the ionization potential of the PAC the lower the specific activity. On the other hand, the substrate ionization potential did not seem to influence chloroperoxidase activity in the oxidation of organosulfur compounds. All organosulfur compounds tested were oxidized by chloroperoxidase. From double-substrate experiments, it appears that organosulfur compounds are oxidized by both compound I and compound X enzyme intermediates, while PACs react only with the halogenating intermediate, compound X.
- Ayala, Marcela,Robledo, Norma R.,Lopez-Munguia, Agustin,Vazquez-Duhalt, Rafael
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- Ultrasound-assisted oxidative desulfurization process of liquid fuel by phosphotungstic acid encapsulated in a interpenetrating amine-functionalized Zn(II)-based MOF as catalyst
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In this work, ultrasound-assisted oxidative desulfurization (UAOD) of liquid fuels performed with a novel heterogeneous highly dispersed Keggin-type phosphotungstic acid (H3PW12O40, PTA) catalyst that encapsulated into an amino-functionalized MOF (TMU-17-NH2). The prepared composite exhibits high catalytic activity and reusability in oxidative desulfurization of model fuel. Ultrasound-assisted oxidative desulfurization (UAOD) is a new way to performed oxidation reaction of sulfur-contain compounds rapidly, economically, environment-friendly and safely, under mild conditions. Ultrasound waves can be apply as an efficient tool to decrease the reaction time and improves oxidative desulfurization system performance. PTA@TMU-17-NH2 could be completely performed desulfurization of the model oil by 20?mg of catalyst, O/S molar ratio of 1:1 in presence of MeCN as extraction solvent. The obtained results indicated that the conversions of DBT to DBTO2 achieve 98% after 15?min in ambient temperature. In this work, we prepared TMU-17-NH2 and PTA/TMU-17-NH2 composite by ultrasound irradiation for first time and employed in UAOD process. Prepared catalyst exhibit an excellent reusability without PTA leaching and loss of activity.
- Afzalinia, Ahmad,Mirzaie, Abbas,Nikseresht, Ahmad,Musabeygi, Tahereh
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- Synthesis and non-parametric evaluation studies on high performance of catalytic oxidation-extraction desulfurization of gasoline using the novel TBAPW11Zn?TiO2?PAni nanocomposite
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In this work, the new catalyst (assigned as TBAPW11Zn?TiO2?PAni) was successfully designed and synthesized on the basis of quaternary ammonium salt of zinc monosubstituted phosphotungstate [(n-C4H9)4N][PW11ZnO39] (TBAPW11Zn), titanium dioxide (TiO2), and polyaniline (PAni). This study reports the catalytic oxidation-extraction desulfurization (ECODS) of sulfur-containing molecules from real and the simulated (Th, BT, and DBT) gasoline using new organic–inorganic hybrid catalyst (TBAPW11Zn?TiO2?PAni). The ECODS results were shown that the concentration of sulfur compounds (SCs) of real gasoline was lowered from 0.4992 to 0.0122 wt.% with 97% efficiency at 35 °C after 1 h. Furthermore, the synthesized heterogeneous nanocatalyst showed high stability and reusability after five times without significant loss of activity. The high performance of TBAPW11Zn?TiO2?PAni/H2O2/CH3CO2H system can be a promising route with a superb potential in the generation of ultra-low-sulfur gasoline. Also the Mann–Whitney U-test results show that there is not a significant difference between the mean of sulfur percentage for DBT & BT, BT & Th and DBT & Th in the presence of the catalyst. Based on the Kruskal–Wallis test results, we can conclude that the temperature, time and amount of catalyst have a significant effect on ECODS efficiency of TBAPW11Zn?TiO2?PAni nanocomposite.
- Khanmohammadi Khorrami, Mohammad Reza,Shokri Aghbolagh, Zahra
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- Highly efficient deep desulfurization of fuels by chemical oxidation
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This paper describes the oxidation of several model S-containing molecules with hydrogen peroxide in L-L phase system using a heterogeneous catalyst under atmospheric pressure in the 333-353 K temperature range. Molybdenum and tungsten compounds are prepared by anion exchange with alkylammonium derivatives covalently anchored to silica gel. These solids are robust heterogeneous catalysts able to activate selectively hydrogen peroxide to remove sulfur compounds via oxidation (ODS). The influence of several reaction variables (the reaction temperature, the nature of the substrate, the solvent, the molar ratio of the oxidant (H2O2), the S-containing molecule, the catalysts nature and the reuse of the catalysts) on the performance was examined. The potential of this methodology is illustrated by the complete S removal from a 0.2 wt% dibenzothiophene mixture at 353 K in less than 1 h of reaction. Molybdenum catalysts exposed to hydrogen peroxide form peroxomolybdates moieties which are more active than acid precursors. The activated Mo catalysts are very active in ODS reaction and can be reused four times without lose of activity.
- Capel-Sanchez,Perez-Presas,Campos-Martin,Fierro
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- The development of catalytic oxovanadium(IV)-containing microspheres for the oxidation of various organosulfur compounds
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The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO 4 with poly[allylSB-co-EGDMA]. XPS
- Ogunlaja, Adeniyi S.,Khene, Samson,Antunes, Edith,Nyokong, Tebello,Torto, Nelson,Tshentu, Zenixole R.
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- Vanadium Containing Metal-organic Frameworks as Highly Efficient Catalysts for the Oxidation of Refractory Aromatic Sulfur Compounds
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The wet impregnation method was applied to prepare vanadium species on the chromium(III) terephthalate metal-organic framework (MIL-101) and on the aluminum fumarate metal-organic framework (A520), two highly efficient catalysts, as well as vanadium species on the zinc terephthalate metal-organic framework (MOF-5), using vanadium(V) oxytributoxide as a precursor. The prepared catalysts were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX), N2 sorption measurement (BET), thermal analysis (TGA-DTA), and X-ray photoelectron spectroscopy (XPS). The prepared materials were utilized as catalysts for the oxidation of the refractory aromatic sulfur compound, dibenzothiophene (DBT), in a model diesel fuel. The catalytic oxidation of DBT to DBT-sulfone was performed in the presence of tert-butyl hydroperoxide (TBHP) under mild operating conditions. The heterogeneous catalysts, OV(OtBu)3?x(OH)x@MIL-101(Cr), OV(OtBu)3?x(OH)x@A520, and OV(OtBu)3?x(OH)x@MOF-5 demonstrated activities of 98, 98, and 10 %, respectively, in the oxidative desulfurization (ODS) process at 60 °C. The catalysts were recycled easily and reused without a significant decrease in their activity. The oxidation of DBT to DBT-sulfone was investigated using gas chromatography, and the formation of DBT-sulfone was confirmed by FT-IR and 1H NMR spectroscopies.
- Jamali, Marjan Abdi,Arvani, Alireza,Amini, Mostafa M.
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- Visible-light-promoted aerobic oxidation of sulfides and sulfoxides in ketone solvents
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Simple and readily available ketones have been identified to promote the visible-light-promoted aerobic oxidation of sulfides and sulfoxides to sulfones. We report a simple and environmental-friendly oxidation protocol of sulfides to sulfones. Various sulfides were efficiently oxidized into sulfones with O2 as sustainable terminate oxidant, readily available thioxanthone as the photocatalyst and 3-pentanone (DEK) as the solvent. The protocol tolerates diverse functional groups, including halogens, ketone, ester, cyano, heterocycle and even cyclopropyl groups. The detection of the aerobic oxidation reaction in DEK by GC and HRMS disclosed that the key active intermediates were generated.
- Li, Xiaotong,Wang, Yu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
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- Niobium(V) oxido tris-carbamate as easily available and robust catalytic precursor for the selective sulfide to sulfone oxidation
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The oxidation of the sulfide function promoted by a variety of vanadium compounds has been largely explored, whereas the use of homogeneous catalytic systems based on the heavier group 5 metals remains less explored. We report the use of easily available niobium and tantalum carbamates, i.e. [M(O2CNMe2)5] (M = Nb, 1; M = Ta, 2), [Nb(O2CNMe2)4], 3, [NbO(O2CNEt2)3], 4, and [NbCl3(O2CNEt2)2], 5, as effective catalysts for the conversion of a series of alkyl aryl and aromatic sulfides into the corresponding sulfones. NMR investigations on the performant niobium catalyst 4 unexpectedly revealed the substantial stability of this compound in the protic catalytic environment, and a plausible catalytic cycle was obtained by DFT studies. The two active catalytic species, i.e. 4 and its minor mono-methoxide derivative, presumably interconvert to each other exploiting the versatile coordination of the carbamato ligand.
- Bresciani, Giulio,Ciancaleoni, Gianluca,Crucianelli, Marcello,Gemmiti, Mario,Marchetti, Fabio,Pampaloni, Guido
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- Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
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A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is
- Liu, Kai-Jian,Wang, Zheng,Lu, Ling-Hui,Chen, Jin-Yang,Zeng, Fei,Lin, Ying-Wu,Cao, Zhong,Yu, Xianyong,He, Wei-Min
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supporting information
p. 496 - 500
(2021/01/28)
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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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- Oxovanadium and dioxomolybdenum complexes: synthesis, crystal structure, spectroscopic characterization and applications as homogeneous catalysts in sulfoxidation
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New oxovanadium and dioxomolybdenum Schiff base complexes, [VO(L)(OCH3)] n and [MoO2(L)(CH3OH)], were synthesized by treating an ONO donor Schiff base (H2L) derived by condensation of 3-ethoxysalicylaldehyde and nicotinic hydrazide with oxo and dioxo acetylacetonate salts of vanadium and molybdenum (VO(acac)2 and MoO2(acac)2), respectively. The synthesized ligand and complexes were characterized by FTIR, multinuclear (1H, 13C) NMR, elemental and single crystal X-ray diffraction analysis. In both complexes, the geometry around the central metal ions was distorted octahedral as revealed by diffraction studies. Theoretical calculations of the synthesized compounds were carried out by DFT at B3LYP/Def2-TZVP level of theory, which showed good correlation with the experimental results. Moreover, the catalytic efficiency of both complexes was investigated by oxidizing aryl and alkyl sulfides in the presence of 30% H2O2 in ethanol.
- Kargar, Hadi,Kaka-Naeini, Azar,Fallah-Mehrjardi, Mehdi,Behjatmanesh-Ardakani, Reza,Amiri Rudbari, Hadi,Munawar, Khurram Shahzad
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p. 1563 - 1583
(2021/05/11)
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- New oxovanadium and dioxomolybdenum complexes as catalysts for sulfoxidation: experimental and theoretical investigations of E and Z isomers of ONO tridentate Schiff base ligand
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A new ONO-tridentate Schiff base ligand (H2L) derived by the condensation of nicotinic hydrazide with 5-chlorosalicylaldehyde has been prepared and characterized by combustion analysis (CHN), FT-IR and multinuclear (1H and 13C) NMR spectroscopy. The crystalline nature and molecular structure of the ligand were confirmed by single-crystal X-ray diffraction analysis. Furthermore, the optimized structural parameters of the four possible configurations of the ligand including Z and E stereoisomers each containing two tautomeric forms (enol and keto) have also been investigated. The theoretical parameters were calculated by performing the DFT method using the B3LYP/Def2-TZVP level of theory. In addition to this, dioxomolybdenum(VI) (MoO2L) and oxovanadium(V) (VOL) complexes with the entitled Schiff base ligand have also been prepared and characterized by different techniques. Then, the catalytic efficiencies of synthesized VOL and MoO2L complexes were also explored for the oxidation of sulfides using 30% aqueous H2O2 as a source of oxygen. These homogeneous catalysts showed excellent catalytic activities in the oxidation of both aromatic and aliphatic sulfides.
- Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Moghimi, Atefeh,Munawar, Khurram Shahzad,Rudbari, Hadi Amiri
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- Polyoxometalate-Based Organic-Inorganic Hybrids as Heterogeneous Catalysts for Cycloaddition of CO2with Epoxides and Oxidative Desulfurization Reactions
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Self-assembly of polyoxometalates, transition metal salts, and 2,6-bis(2′-pyridyl)-4-hydroxypyridine (LOH) obtained four organic-inorganic hybrids [Co2.5(LOH)(LO)2(H2O)2(PW12O39)]·3CH3CN·2OH (1), [Zn1.5(LOH)3]·(PMo12O40)·CH3OH·2H2O (2), [Cd1.5(LOH)3]·(PW12O40)·2CH3OH·1.5H2O (3), and [Mn(LOH)2]·(PW12O40)·2CH3CN·H3O (4). Hybrid 1 exhibits an extended chain, which could be further connected into a 3D supramolecular architecture by H-bonds. Hybrids 2-4 feature monomolecular structures, which are further bridged via H-bonds to yield charming 3D supramolecular structures. Noteworthy, 1 and 2 can be employed as recyclable and highly efficient heterogeneous catalysts. The activated 1 displays a high catalytic activity for the cycloaddition reaction of CO2 and epoxides. Hybrid 2 exhibits an excellent catalytic performance for the oxidative desulfurization reaction.
- Zhao, Yu-Qing,Liu, Ying-Ying,Ma, Jian-Fang
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supporting information
p. 1019 - 1027
(2021/01/13)
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- Self-Assembled Polyoxometalate-Based Metal-Organic Polyhedra as an Effective Heterogeneous Catalyst for Oxidation of Sulfide
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Two polyoxovanadate-based metal-organic polyhedra with octahedral (oct) and rhombic dodecahedral (rdo) geometries have been constructed from a concave molecular building block and linear and triangular carboxylate ligands. VMOP-7 is constructed from {V5O9Cl} SBU and a linear anthracene-9,10-dicarboxylic acid ligand in which all the anthracene groups are perpendicular to the edge of the octahedron. Such an arrangement mode can effectively reduce the steric hindrance between ligands. VMOP-8 is constructed from {V5O9Cl} SBU and a triangular biphenyl 3,4,5-tricarboxylate ligand, which exhibits an elongated rhombic dodecahedral configuration due to the geometry of the ligand. Furthermore, VMOP-8 can serve as a heterogeneous catalyst and exhibits efficient and common catalytic activity for oxidative desulfurization.
- Gan, Hong-Mei,Qin, Chao,Zhao, Liang,Sun, Chunyi,Wang, Xing-Long,Su, Zhong-Min
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p. 1028 - 1034
(2021/01/26)
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- Assembly of polyoxometalate-thiacalix[4]arene-based inorganic-organic hybrids as efficient catalytic oxidation desulfurization catalysts
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Self-assembly of polyoxometalates, Ni(ii)/Ag(i) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene (L) yielded three inorganic-organic hybrids, namely, [Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O (1), [Ni3L2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2) and [Ag3L(PMo12O40)] (3). In hybrids (1) and (2), Ni(ii) cations are linked by L ligands to produce layered frameworks, and H bonds among the [PMo12O40]3?/[PW12O40]3?anions and L ligands lengthen the structures to form 3D supramolecular architectures. Hybrid (3) exhibits a 3D architecture, of which Ag(i) cations not only coordinated with the N and O atoms of L ligands and [PMo12O40]3?anions simultaneously, but also connected each other by Ag-Ag interactions. It is worth mentioning that1and3as recyclable catalysts show excellent heterogeneous catalytic activity in oxidation desulfurization reactions.
- Li, Jie,Du, Peng,Liu, Ying-Ying,Ma, Jian-Fang
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supporting information
p. 1349 - 1356
(2021/02/09)
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- A μ-AsO4-Bridging Hexadecanuclear Ni-Substituted Polyoxotungstate
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A novel tetrahedral μ-AsO4-bridging hexadecanuclear Ni-substituted silicotungstate (ST) Na21H10[(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]·60H2O (1) was made by the reactions of trivacant [A-α-SiW9O34]10- ({SiW9}) units with Ni2+ cations and Na3AsO4·12H2O and characterized by IR spectrometry, elemental analysis, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). 1 contains a novel polyoxoanion [(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]31- built by four trivacant Keggin [A-α-SiW9O34]10- fragments linked through an unprecedented [(AsO4){Ni8(OH)6(H2O)2(CO3)2}2]9+ cluster, where the tetrahedral AsO4 acts as an exclusively μ2-bridging unit to link multiple Ni centers; such a connection mode appears for the first time in polyoxometalate chemistry. Furthermore, the electrochemical and catalytic oxidation properties of compound 1 have been investigated.
- Lian, Chen,Li, Hai-Lou,Yang, Guo-Yu
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p. 3996 - 4003
(2021/04/07)
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- In Situ Generated Organic Peroxides in Oxidative Desulfurization of Naphtha Reformate
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Abstract: The paper describes a method developed for the oxidation of organosulfur compounds using organic peroxides generated in situ under the action of atmospheric oxygen on gasoline fraction after reforming. Naphtha reformate that contained dibenzothiophene as a model substrate was subjected to oxidative desulfurization by organic peroxides generated in situ under atmospheric oxygen. The study examined various catalytic systems, including immobilized Anderson-type polyoxometalates, and initiators, which, in combination, provided effective generation of alkyl hydroperoxides, selective oxidation of organosulfur compounds in the hydrocarbon feedstock, and a high conversion rate.
- Akopyan, A. V.,Anisimov, A. V.,Eseva, E. A.,Sinikova, N. A.
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p. 472 - 482
(2021/06/01)
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- In Situ Implanting of Single Tungsten Sites into Defective UiO-66(Zr) by Solvent-Free Route for Efficient Oxidative Desulfurization at Room Temperature
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Design of single-site catalysts with catalytic sites at atomic-scale and high atom utilization, provides new opportunities to gain superior catalytic performance for targeted reactions. In this contribution, we report a one-pot green approach for in situ implanting of single tungsten sites (up to 12.7 wt.%) onto the nodes of defective UiO-66(Zr) structure via forming Zr-O-W bonds under solvent-free condition. The catalysts displayed extraordinary activity for the oxidative removal of sulfur compounds (1000 ppm S) at room temperature within 30 min. The turnover frequency (TOF) value can reach 44.0 h?1 at 30 °C, which is 109.0, 12.3 and 1.2 times higher than that of pristine UiO-66(Zr), WO3, and WCl6 (homogeneous catalyst). Theoretical and experimental studies show that the anchored W sites can react with oxidant readily and generate WVI-peroxo intermediates that determine the reaction activity. Our work not only manifests the application of SSCs in the field of desulfurization of fuel oil but also opens a new solvent-free avenue for fabricating MOFs based SSCs.
- Chen, Wenxing,Chu, Hongqi,Li, Yadong,Wang, Dagang,Wang, Hanlu,Wang, Jin,Wei, Jinshan,Ye, Gan
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supporting information
p. 20318 - 20324
(2021/07/25)
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- Single-Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11? Tungstophosphate Nanoclusters
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A series of eleven lanthanide containing di-Zinc (II) substituted heterometallic 3d–4f sandwich-type tungstophosphate nanoclusters [Ln{PZn2W10O38(H2O)2}2]11? (Ln=NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII) have been synthesized by a single step reaction procedure. These clusters were characterized by various analytical techniques such as single crystal X-ray diffraction (SC-XRD), fourier transform infrared (FT-IR) spectroscopy, high-resolution electro-spray ionization mass spectrometry (HR-ESI-MS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), solid UV/Vis, photoluminescence spectroscopy, powder X-ray diffraction (P-XRD) and thermogravimetric analysis (TGA). All the polyanions are isostructural and consists of a lanthanide ion sandwiched between two units of (1,5) isomer of di-Zn substituted α-Keggin type tungstophosphate. The complexes Sm-2 a, Eu-3 a, Tb-5 a, and Dy-6 a show good photoluminescence behavior. The catalytic properties were examined for the oxidation of thioethers. The catalyst is stable with a high turn over frequency (TOF) of 6250 h?1 and can be recovered even after 5 consecutive cycles. Furthermore, magnetic properties revealed that Gd-4 a, Tb-5 a, Dy-6 a, Er-8 a, and Yb-10 a show single-molecule magnetic properties.
- Das, Vivek,Khan, Imran,Hussain, Firasat,Sadakane, Masahiro,Tsunoji, Nao,Ichihashi, Katsuya,Kato, Chisato,Inoue, Katsuya,Nishihara, Sadafumi
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p. 3819 - 3831
(2021/09/22)
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- Magneli-type tungsten oxide nanorods as catalysts for the selective oxidation of organic sulfides
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Selective oxidation of thioethers is an important reaction to obtain sulfoxides as synthetic intermediates for applications in the chemical industry, medicinal chemistry and biology or the destruction of warfare agents. The reduced Magneli-type tungsten oxide WO3?xpossesses a unique oxidase-like activity which facilitates the oxidation of thioethers to the corresponding sulfoxides. More than 90% of the model system methylphenylsulfide could be converted to the sulfoxide with a selectivity of 98% at room temperature within 30 minutes, whereas oxidation to the corresponding sulfone was on a time scale of days. The concentration of the catalyst had a significant impact on the reaction rate. Reasonable catalytic effects were also observed for the selective oxidation of various organic sulfides with different substituents. The WO3?xnanocatalysts could be recycled at least 5 times without decrease in activity. We propose a metal oxide-catalyzed route based on the clean oxidant hydrogen peroxide. Compared to other molecular or enzyme catalysts the WO3?xsystem is a more robust redox-nanocatalyst, which is not susceptible to decomposition or denaturation under standard conditions. The unique oxidase-like activity of WO3?xcan be used for a wide range of applications in synthetic, environmental or medicinal chemistry.
- D?ren, René,Hartmann, Jens,Leibauer, Benjamin,Panth?fer, Martin,Mondeshki, Mihail,Tremel, Wolfgang
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p. 14027 - 14037
(2021/10/19)
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- Optimization study on deep extractive oxidative desulfurization with tetrabutylammonium bromide/polyethylene glycol des
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Green, efficient and inexpensive desulfurizing solvents have always been a considerable focus of petroleum desulfurization research. In this study, a series of deep eutectic solvents (DESs) based on tetrabutylammonium bromide (TBAB)/polyethylene glycol 200 (PEG-200) with different molar ratios were synthesized and characterized by Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy. Dibenzothiophene (DBT) was removed deeply as the classic sulfide in model oil, and H2O2 was fully utilized by the new TBAB/PEG-200 desulfurization system in step extractive oxidative desulfurization. The reaction conditions were optimized further, and O/S = 8, DES/oil = 1?:?5, 40 °C and 75 minutes were chosen as the best reaction conditions. Meanwhile, other organic sulfides in crude oil were also removed, and the removal rates of DBT, 4,6-dimethyldibenzothiophene and benzothiophene were 99.65%, 96.71% and 93.52%, respectively. The DES was reused 7 times, and the desulfurization efficiency of the regenerated DES for DBT was maintained at 98.14%. Finally, the possible mechanism of the synergistic effect of two kinds of hydrogen bonds and the oxidant was proposed.
- Guo, Yanwen,Hu, Bing,Li, Jingwen,Liu, Xingjian
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p. 31727 - 31737
(2021/11/30)
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- Preparation method of polysulphone compound
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The invention belongs to the technical field of chemical synthesis, and discloses a preparation method of a polysulphone compound. The preparation method comprises the following steps: reacting a cyclic diaryliodonium salt compound with sodium formaldehyde sulfoxylate dehydrate, and carrying out two-step reaction to prepare the polysulphone compound. The cyclic diaryliodonium salt reacts with thesodium formaldehyde sulfoxylate dehydrate for 10-120 minutes at 20 DEG C, and reacts in a microwave reactor for 10 minutes to generate the corresponding polycyclic sulfone compound. The method has theadvantages of mild reaction conditions, accessible reagents, wide substrate application range, simple operation, quick reaction and the like.
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Paragraph 0021-0026
(2020/07/21)
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- Ionic liquids vs conventional solvents: A comparative study in the selective catalytic oxidations promoted by oxovanadium(IV) complexes
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Two oxovanadium(IV) complexes containing 4-acyl-5-pyrazolonate-κ2-O,O' bidentate ligands with different chain lengths in the acyl moiety, namely HQC6 (complex I) and HQC17 (complex II), have been synthetized and full characterized, to study their catalytic activity toward the mild and selective oxidation of olefins or model organosulphur substrates, promoted by H2O2 or tert-butyl hydroperoxide (TBHP). The influence due to the type of solvent, likewise ionic liquids (ILs) or conventional medium, was analysed. H2O2 has proven less efficient, in comparison to TBHP. Quantum-chemical calculations have shown that, the key catalytic species involved and, consequently, the actual mechanism might be slightly different according to the oxidant used, i.e. the peroxo VO(QMe)(O2) adduct in the case of H2O2 and the tert-butylperoxo VO(QMe)2(OOt-Bu) adduct in the case of TBHP. Preliminary calculations suggested that, in ionic liquids, the VO(QMe)2 complex might reveal relatively unstable, hence qualitatively explaining the moderate efficiency observed in these media.
- Aschi, Massimiliano,Campitelli, Patrizio,Crucianelli, Marcello,Di Nicola, Corrado,Marchetti, Fabio,Pettinari, Riccardo
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- Ag?CeO2 nanoparticles with “rice ball” configuration as an efficient and heterogeneous nanocatalyst for the selective oxidation of sulfides to sulfones with 30% H2O2
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Abstract: Ag?CeO2 with a rice-ball configuration as a heterogeneous and highly efficient catalyst was described for activation of H2O2 in the selective oxidation of aromatic and aliphatic sulfides to their corresponding sulfones. Ag nanoparticles in the CeO2–Ag interface increase the oxygen vacancy defects on the surface of CeO2 and oxygen vacancy defects promote the reduction of Ce4+ to Ce3+ to keep the electroneutrality. Generated Ce3+ species act as the active sites in the interface of CeO2–Ag to promote the oxidation of sulfides to sulfones. Compatibility with various aromatic and aliphatic sulfides, excellent selectivity, high yield of product, simple experimental procedure, and mild reaction conditions are some of the precious advantages of Ag?CeO2/H2O2 catalyst system. Graphic abstract: [Figure not available: see fulltext.]
- Bahrami, Kiumars,Ghorbani, Somayeh,Parnian, Rouhallah,Soleimani, Ebrahim
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- ORGANIC OPTOELECTRONIC DEVICE AND DISPLAY DEVICE
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An organic optoelectronic device and a display device including the organic optoelectronic device, the organic optoelectronic device including an anode and a cathode facing each other, a light emitting layer between the anode and the cathode, a hole transport layer between the anode and the light emitting layer, and a hole transport auxiliary layer between the light emitting layer and the hole transport layer, wherein the light emitting layer includes a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2, and the hole transport auxiliary layer includes a third compound represented by Chemical Formula 3,
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Paragraph 0328-0330
(2020/05/29)
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- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
- Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
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supporting information
p. 433 - 438
(2020/02/13)
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- Highly efficient oxidative desulfurization of dibenzothiophene using Ni modified MoO3 catalyst
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Ni modified MoO3 (Ni-MoO3) had been synthesized by a facile one-step hydrothermal technique and was used for oxidative desulfurization (ODS) of dibenzothiophene (DBT) in the decalin/acetonitrile biphasic system with H2O2 as oxidant, the effect of different operating conditions was investigated. Under the optimal reaction condition, Ni-MoO3 catalyst showed excellent ODS performance toward DBT, the highest sulfur removal efficiency can be up to 99.8% and sulfur content was wiped out from 5000 to 10 ppm, which is more effective than the recent reported MoO3-based catalysts. The reaction kinetics obeyed the pseudo-first-order equation with an apparent rate constant of 0.076 min?1, which is twice that of pure MoO3 (0.035 min?1). The ODS mechanism of DBT with Ni-MoO3 was explored by combining radical scavenger, FT-IR experiments and theoretical analysis, proving that surface oxygen vacancies and Lewis acid sites play important roles in the high-efficiency ODS reaction with Ni-MoO3 catalyst.
- Cao, Ying,Wang, Huixiang,Ding, Ruimin,Wang, Liancheng,Liu, Zhong,Lv, Baoliang
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- Two polyoxometalate-based inorganic-organic hybrids and one coordination polymer assembled with a functionalized calix[4]arene: Catalytic and electrochemical properties
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Self-assembly of 4-pyridyl-functionalized calix[4]arene ligand 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26,27,28-tetrakis[(4-pyridylmethyl)oxy]calix[4]arene (L), Ag(I)/Cd(II) cations and polyoxometalate obtained two inorganic-organic hybrids [Ag3(L)2][PMo12O40]·CH3CN·4H2O (1), [Ag3(L)2][PMo12O40]·2DMA·0.5EtOH (2) and one complex [Cd3(L)2Cl6]·4CH3CN·4H2O (3) (DMA = N,N-dimethylacetamide). Hybrids 1 and 2 have fascinating one-dimensional chains, which are linked by hydrogen bonds between the C atoms of L ligands and the O atoms of [PMo12O40]3? anions to generate supramolecular layers. 3 displays a thick layer containing trinuclear Cd(II) clusters. Noteworthy, hybrid 1 exhibits excellent heterogeneous catalytic activity for oxidative desulfurization reaction and obvious electrocatalytic activity for oxidize ascorbic acid and reduce NaBrO3. Complex 3 shows heterogeneous catalytic ability for Knoevenagel condensation reaction.
- Li, Zhuo,Liu, Ying-Ying,Xu, Guo-Hai,Ma, Jian-Fang
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- Synergistic effects of MOF-76 on layered double hydroxides with superior activity for extractive catalytic oxidative desulfurization
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The combination of metal-organic frameworks (MOFs) with layered double hydroxides (LDHs) has been greatly limited by the agglomeration of pure MOFs and the height of the LDH gallery, so there are few reports on the combination of MOFs and LDHs. In this work, for the first time, the combination of MOF-76 with a layered double hydroxide (MOF-76?LDH) was used for desulfurization under room temperature and pressure conditions without the necessity of protecting with nitrogen. The structure of the heterogeneous catalyst was characterized using FT-IR, XRD, TG, BET, SEM, EDX, XPS, fluorescence and ICP-AES. The as-prepared catalyst exhibited superior activity in deep desulfurization of DBT (dibenzothiophene), BT (benzothiophene) and 4,6-DMDBT (4,6-dimethyldibenzothiophene). The above sulfides could be completely converted into their corresponding sulfones and sulfoxides at 60 °C in 25, 40 and 55 minutes, respectively. 49 wt% MOF-76?LDH exhibited a high desulfurization capacity (100%), much higher than that of LDH (16.3%), MOF-76 (48%) and MOF-76 + LDH (50.3%). Because MOF-76?LDH has a special one-dimensional channel on the surface of the material, it can efficiently promote the degradation of H2O2 into hydroxyl radicals (OH) and further improve the desulfurization effect. The catalyst is easy to recycle and can be reused at least 5 times, and the catalytic effect is not significantly reduced. This provides a completely new route for the synthesis of MOF-LDH advanced functional materials.
- Li, Xiaonan,Liu, Siqi,Zhang, Hong
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supporting information
p. 6269 - 6276
(2020/05/13)
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- Efficient Catalytic Oxidative Desulfurization toward Thioether and Sulfur Mustard Stimulant by Polyoxomolybdate-Resorcin[4]arene-Based Metal-Organic Materials
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The design and synthesis of effective and recyclable oxidative desulfurization catalysts is of great importance in view of environmental protection and human health. Herein, a family of polyoxomolybdate-based inorganic-organic hybrid materials, namely, [Mn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (3), and [Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4), were assembled by the functionalized resorcin[4]arene ligand (TMR4A) with polyoxomolybdate and metal ions under solvothermal conditions. In isostructural 1-3, the [M(TMR4A)(H2O)4]2+ species (M = MnII, NiII, ZnII) and [Mo6O19]2- anions are held together via C-H···O hydrogen bonds to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H2O)2]2+ cations were linked by one [β-Mo8O26]4- anion to produce an attractive molecular dimer. Remarkably, 1-4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard simulant. Moreover, their electrochemical properties were also studied.
- Guo, Ting-Ting,Ma, Jian-Fang,Yang, Jin,Yu, Ming-Yue
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supporting information
(2020/04/02)
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- A safe and compact flow platform for the neutralization of a mustard gas simulant with air and light
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A low footprint, mobile, robust and frugal chemical neutralization technology is reported for the oxidative neutralization of a mustard gas simulant. It relies on the inherent properties of a highly engineered continuous flow setup and carefully optimized and simple, yet robust, experimental conditions. The neutralization protocol uses only non-toxic, widely available and cheap chemicals. The continuous flow setup integrates a singlet oxygen generator and exploits its oxidative power to neutralize 2-chloroethyl ethyl sulfide (CEES), the most common thioether mustard gas simulant. The flow reactor can be connected to either pressurized oxygen or air and handles CEES as a 1 M solution in EtOH containing a trace amount (0.06 molpercent) of a non-toxic and widely available photosensitizer (Methylene Blue). Upon irradiation with visible light (orange or white light), total and highly selective neutralization towards the corresponding non-toxic sulfoxide (1-chloro-2-(ethylsulfinyl)ethane, CEESO) is obtained with reactor effluents containing less than 1percent of the corresponding potentially toxic sulfone (1-chloro-2-(ethylsulfonyl)ethane, CEESO2). With a low footprint (L × W × H 94 × 42 × 40 cm), this neutralization technology can be equipped on a vehicle for on-site interventions, localized at a neutralization facility or both. This experimental work is also supported with the computational rationalization of the reactivity of CEES towards singlet oxygen.
- Bianchi, Pauline,Emmanuel, Noémie,Legros, Julien,Monbaliu, Jean-Christophe M.
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supporting information
p. 4105 - 4115
(2020/07/30)
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- Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
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Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to couple various inactivated arenes to prepare sulfones at ambient temperature.
- Zhang, Zhiguo,Wang, Songnan,Zhang, Yong,Zhang, Guisheng
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p. 3919 - 3926
(2019/03/29)
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- Sulfoxide and sulfone compounds, as well as selective synthesis method and application thereof
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The invention discloses a method for selectively synthesizing a sulfoxide compound shown as a formula (II) and a sulfone compound shown as a formula (III). In a reaction solvent, thioether (I) is usedas a reaction raw material and oxygen as an oxidation reagent, under the catalytic action of visible light and a photosensitive reagent; under the assistance of an additive, when a large-polarity proton-containing additive such as an acid and an alcohol or a solvent or an additive with excellent electron donating ability is used, a sulfoxide compound (II) is selectively generated; and when a small-polarity aprotic additive or a solvent is used, a sulfone compound (III) is selectively generated. The synthesis method has the advantages of easily available and cheap raw materials, simple reaction operation, mild reaction conditions, high yield and excellent functional group tolerance. According to the invention, synthesis and modification of some medicines are realized, and an efficient method for selectively constructing sulfoxide and sulfone compounds is provided for medicinal chemistry research.
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Paragraph 0049-0052; 0089-0092
(2019/12/02)
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- Photophysical properties and optical power limiting ability of Pt(II) polyynes bearing fluorene-type ligands with ethynyl units at different positions
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Two series of Pt(II) polyynes bearing fluorene-type ligands with ethynyl units at different positions have been synthesized. In the absorption spectra, the Pt(II) polyynes bearing fluorene-type ligands with ethynyl units at 3,6-position have blue-shift with respect to the corresponding analogs bearing fluorene-type ligands with ethynyl units at 2,7-position, showing better transparency in the visible light region. Moreover, the Pt(II) polyynes bearing fluorene-type ligands with ethynyl units at 3,6-position show stronger triplet emission than corresponding analogs bearing fluorene-type ligands with ethynyl units at 2,7-position in the photoluminescent (PL) spectra. Furthermore, these Pt(II) polyynes were applied to optical power limiting (OPL) field. The Pt(II) polyynes bearing fluorene-type ligands with ethynyl units at 2,7-position show better OPL performance than the corresponding analogs with fluorene-type ligands of ethynyl units at 3,6-position. Therefore, changing the position of the ethynyl units in fluorene-type ligands can not only effectively control the photophysical properties of the Pt(II) polyynes, but also has an important effect on their OPL ability.
- Tian, Zhuanzhuan,Yang, Xiaolong,Liu, Boao,Zhong, Daokun,Zhou, Guijiang
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supporting information
p. 28 - 36
(2019/06/05)
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- Double-(S, S - dioxo - dibenzo thiophene) and high output compound and its preparation method and application
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The invention discloses a bi(S,S-dioxo-dibenzothiophene) five-membered ring compound and a preparation method and application thereof. The existence of bi-sulfuryl in the bi(S,S-dioxo-dibenzothiophene) five-membered ring compound is more beneficial for improving the electron affinity of molecules. Alkyl chains are introduced on a five-membered ring, so that the solubility of monomers in an organic solvent can be obviously improved. The plane conjugacy of the compound is better, and is beneficial for the transmission of a current carrier. Higher D-A mutual effect existing in the molecules of the compound endows higher fluorescence of the material. The bi(S,S-dioxo-dibenzothiophene) five-membered ring compound is synthesized and obtained through common organic chemistry reactions such as substitution reactions, Suzuki coupling and ring-closure reactions and oxidation reactions. The compound has good solubility in the organic solvent, and is suitable for solution processing. The compound has wide application prospects in the fields of organic luminescence display, organic photovoltaic cells and organic field-effect tubes.
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Paragraph 0107-0110
(2019/06/26)
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- Water-soluble polymer anchored peroxotitanates as environmentally clean and recyclable catalysts for mild and selective oxidation of sulfides with H2O2 in water
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Anchoring of peroxotitanium (pTi) species to linear water-soluble acrylic acid based polymers, poly(sodium acrylate) (PA) and poly(sodium methacrylate) (PMA) led to the successful synthesis of a pair of new, water-tolerant and recyclable catalysts of the type [Ti2(O2)2O2(OH)2]4-—L (L = PA or PMA), highly effective in chemoselective sulfoxidation of organic sulfides with 30% H2O2 in aqueous medium at ambient temperature. The catalytic protocol is high yielding (TOF up to 11,280 h?1), operationally simple as well as environmentally clean and safe, being free from halide, or any other toxic auxiliaries. The catalysts are sufficiently stable to afford easy recyclability for at least 10 consecutive reaction cycles of sulfoxidation with consistent activity selectivity profile. Oxidation of dibenzothiophene (DBT) to respective high purity sulfoxide or sulfone could also be accomplished using the same catalysts by variation of reaction conditions.
- Ahmed, Kabirun,Saikia, Gangutri,Paul, Sivangi,Baruah, Satyajit Dey,Talukdar, Hiya,Sharma, Mitu,Islam, Nashreen S.
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- Method for preparing aryl sulfone compound as well as method for extracting catalyst and aryl sulfone compound
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The invention provides a preparation method of an aryl sulfone compound, which is characterized in that in an organic solvent and under an aerobic atmosphere, a catalytic system composed of a metal-ligand-TEMPO is used for catalytic oxidation of a thioether compound to obtain the aryl sulfone compound. The preparation method is simple, green, and efficient, the reaction condition is mild, and theapplication range is wide; the invention also provides a method for extracting a catalyst and the product aryl sulfone compound used in the preparation process. The ethyl acetate is added to a reaction mixture, steps of filtering and condensation under reduced pressure are carried out to obtain a filtrate and the catalyst, and silica gel column chromatography and concentration extraction are carried out to obtain the aryl sulfone compound. The extraction method is simple, and the extracted catalyst has high activity and good cycle stability, and the extraction rate of the product aryl sulfonecompound is high.
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Paragraph 0080-0083
(2019/02/13)
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- Selective Late-Stage Oxygenation of Sulfides with Ground-State Oxygen by Uranyl Photocatalysis
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Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with ground-state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO22+) enabled the efficient synthesis of sulfones. The ligand-to-metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a UV center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom- and step-efficient manner.
- Li, Yiming,Rizvi, S. Aal-e-Ali,Hu, Deqing,Sun, Danwen,Gao, Anhui,Zhou, Yubo,Li, Jia,Jiang, Xuefeng
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supporting information
p. 13499 - 13506
(2019/08/21)
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- Oxidative desulfurization of dibenzothiophene by central metal ions of chlorophthalocyanines-tetracarboxyl complexes
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Oxidative desulfurization (ODS) is one of the most promising methods of ultra low sulfur diesel (ULSD). Herein, metallophthalocyanine(MPc(COOH)4Cl8, M = Mn(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ)) composites are synthesized by a facile in situ solid method and characterized by elemental analysis, UV–Vis, XPS and IR spectra. The simulated bionic catalytic system is composed of MPc(COOH)4Cl8 and molecular O2, which exhibited great activity for ultra-deep removal of dibenzothiophene (DBT) from the model oil containing n-octane. The catalytic activity of MPc(COOH)4Cl8 for the degradation of DBT in fuel was significantly improved at room temperature with natural light irradiation. After 90 min of catalytic reaction, the sulfur content in the model fuel decreased from (800 ppm) to 20 ppm. Catalytic activity studies revealed that the central metal ions of phthalocyanine structures presented a significant influence in the catalytic activity for the degradation of DBT. Additionally, mechanistic studies revealed that the ‘?O2-MPcTcCl8+’ species was the key active intermediate. The metallophthalocyanine composites as active photocatalysts offer great potential for degradation of thiophene derivatives in fuel.
- Gao, Min,Zhang, Gai,Tian, Min,Liu, Bulei,Chen, Weixing
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- Molybdenum Dioxide in Carbon Nanoreactors as a Catalytic Nanosponge for the Efficient Desulfurization of Liquid Fuels
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The principle of a “catalytic nanosponge” that combines the catalysis of organosulfur oxidation and sequestration of the products from reaction mixtures is demonstrated. Group VI metal oxide nanoparticles (CrOx, MoOx, WOx) are embedded within hollow graphitized carbon nanofibers (GNFs), which act as nanoscale reaction vessels for oxidation reactions used in the decontamination of fuel. When immersed in a model liquid alkane fuel contaminated with organosulfur compounds (benzothiophene, dibenzothiophene, dimethyldibenzothiophene), it is found that MoO2@GNF nanoreactors, comprising 30 nm molybdenum dioxide nanoparticles grown within the channel of GNFs, show superior abilities toward oxidative desulfurization (ODS), affording over 98% sulfur removal at only 5.9 mol% catalyst loading. The role of the carbon nanoreactor in MoO2@GNF is to enhance the activity and stability of catalytic centers over at least 5 cycles. Surprisingly, the nanotube cavity can selectively absorb and remove the ODS products (sulfoxides and sulfones) from several model fuel systems. This effect is related to an adsorptive desulfurization (ADS) mechanism, which in combination with ODS within the same material, yields a “catalytic nanosponge” MoO2@GNF. This innovative ODS and ADS synergistic functionality negates the need for a solvent extraction step in fuel desulfurization and produces ultralow sulfur fuel.
- Astle, Maxwell A.,Rance, Graham A.,Loughlin, Hannah J.,Peters, Thomas D.,Khlobystov, Andrei N.
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- Hydroxyl free radical route to the stable siliceous Ti-UTL with extra-large pores for oxidative desulfurization
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A facile and mild method was successfully developed to prepare the stable, highly siliceous Ti-UTL zeolite with extra-large pores. The hydroxyl free radical (OH) was introduced for the first time to effectively promote the isomorphous substitution of Si for framework Ge under room temperature and neutral conditions, resulting in a stable titanosilicate with an outstanding catalytic activity for oxidative desulfurization.
- Shi, Dier,Xu, Le,Chen, Pohua,Ma, Tianqiong,Lin, Cong,Wang, Xiaoge,Xu, Diming,Sun, Junliang
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supporting information
p. 1390 - 1393
(2019/02/05)
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- A novel high-performance SnO2 catalyst for oxidative desulfurization under mild conditions
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The catalyst SnO2 was prepared by a precipitation method, and then aged and calcined at the optimal temperature of 673 K. The reaction conditions were optimized and the oxidation desulfurization efficiency of the obtained catalyst were evaluated. The sulfur removal rate was 99.8% at the optimum reaction conditions of 0.08 g catalyst, 333 K, O/S = 10, 2 h. The catalytic site in the ODS process of the SnO2 catalyst may be Sn4+/Sn2+ Lewis acids. Furthermore, no significant catalytic performance decrease was observed over 14 reuse cycles. The excellent activity and reusability of the catalyst was attributed to the beneficial effects upon specific surface area and acidic-site strength of the appropriate heat treatment temperature.
- Liu, Aili,Zhu, Mingyuan,Dai, Bin
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- Boosting oxidative desulfurization of model fuel by POM-grafting ZIF-8 as a novel and efficient catalyst
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In this article, a water-soluble Keplerate-type polyoxometalate (POM), known as {Mo132} nanoballs, was supported over the zeolitic imidazolate framework-8 (ZIF-8) to achieve a highly efficient heterogeneous nano-structure catalyst (ZIF-8@{Mo132}) evaluated in oxidative desulfurization (ODS) of dibenzothiophene (DBT) presenting in model fuel. The ZIF-8@{Mo132} nano-structured catalyst was characterized using various methodologies including FT-IR, XRD, SEM, TGA, UV–Vis spectra of solid state and N2 adsorption–desorption confirming the incorporation of the {Mo132} nanoballs over the ZIF-8. The catalytic ODS performances of the as-synthesized catalyst revealed that high DBT removal efficiency around 87% and 92% after 6 and 12 h of reaction, respectively, in the presence of tert-butyl hydroperoxide (TBHP) as an oxidant, while they were only around 40% and 55% for pristine ZIF-8 at the same condition. The reaction mechanism suggested that the presence of Mo atoms enhances the formation of metal-peroxide formed by nucleophilic attack of TBHP and consequently enhancing DBT removal from a model fuel. Thin-layer chromatography (TLC) and gas chromatography (GC) were implemented for DBT concentration determination. In addition, the operating variables, including catalyst dosage, temperature, initial concentration of DBT, and oxidant to sulfur (O/S) ratio affecting the ODS efficiency were investigated to find the optimum condition. Finally, the remarkable heterogeneous catalyst indicated recyclability for various catalytic cycles.
- Ghahramaninezhad, Mahboube,Pakdel, Fatemeh,Niknam Shahrak, Mahdi
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p. 364 - 372
(2019/06/27)
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- Highly stable polyoxometalate-resorcin[4]arene-based inorganic-organic complexes for catalytic oxidation desulfurization
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Self-assembly of a resorcin[4]arene-based ligand (TMR4A) with metal salts and H3PMo12O40·xH2O offers two isostructural complexes, namely, [Ni2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN (1) and [Co2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN (2). In both 1 and 2, one Cl? anion bridges two metal cations, and each metal cation is further chelated by four 2-mercaptopyridine N-oxide groups of one TMR4A, producing a [M2Cl(TMR4A)2]3+ dimer (M?=?Ni or Co). The negative [PMo12O40]3? as a counter-anion balances the positive charge. Markedly, 1 and 2 exhibit high stability in aqueous solutions with different pH values and in organic solvents. Remarkably, the efficient heterogeneous catalytic capability for oxidative desulfurization was studied by suing 1 and 2 as recycled catalysts. Moreover, the electrochemical behaviors of the two compounds were discussed as well.
- Yu, Ming-Yue,Yang, Jin,Xu, Xianxiu,Ma, Jian-Fang,Wang, Zhenxing
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- Polyoxometalate-Bridged Cu(I)- And Ag(I)-Thiacalix[4]arene Dimers for Heterogeneous Catalytic Oxidative Desulfurization and Azide-Alkyne "click" Reaction
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Two remarkable polyoxometalate-bridged Cu(I)- and Ag(I)-thiacalix[4]arene dimers, namely, [Cu4(SiW12O40)(L)2(DMF)2]·2EtOH·DMF (1-Cu) and [Ag4(PMo12O40)(L)2]·OH (1-Ag), were prepared by using a new thiacalix[4]arene, metal cation and polyoxometalate (L = tetra[2-(ethylthio)-1-methyl-1H-imidazole]-thiacalix[4]arene). In 1-Cu and 1-Ag, two thiacalix[4]arenes were linked together by one [SiW12O40]4- or [PMo12O40]3- anion via two metal cations to give a molecular dimer. Further, adjacent dimers were extended into a high-dimensional supramolecular architecture through hydrogen bonds. Markedly, these molecular dimers are exceedingly stable in organic solvents and then were employed as efficient catalysts for catalytic oxidation desulfurization as well as the azide-alkyne "click" reaction.
- Yu, Ming-Yue,Guo, Ting-Ting,Shi, Xiao-Chuan,Yang, Jin,Xu, Xianxiu,Ma, Jian-Fang,Yu, Zhen-Tao
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p. 11010 - 11019
(2019/08/26)
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- Synthesis of N-benzylated cobalt phthalocyaninetetrasulfonamide and its application in oxidative desulfurization catalysis
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The FeCl2/K2CO3 catalyst system was used successfully for the synthesis of oil soluble N-benzylated cobalt phthalocyaninetetrasulfonamide by the reaction of benzyl alcohol on water-soluble cobalt phthalocyaninetetrasulfonamide via heating at 135 °C for 20 h under N2. The new oil-soluble peripherally N-benzylated phthalocyanine was characterized by elemental analysis, FT-IR, UV–vis, TG and mass spectrometry. The catalytic activity of this new cobalt complex for oxidation of dibenzothiophene (DBT) was evaluated in n-dodecane (a middle distillate model compound) using H2O2 as an oxidant. The acetonitrile was taken as an extracting solvent for further extracting DBT sulfoxide and sulfone. The novel peripherally substituted cobalt(II) complex showed better oxidative desulfurization catalytic activity than cobalt phthalocyanine and cobalt phthalocyaninetetrasulfonamide. DBT oxidation kinetics were evaluated by lumped nth- and first-order kinetic models. The maximum removal of the DBT was found to be 85% at the optimized dose and experimental conditions.
- Tripathi, Deependra,Negi, Himani,Singh, Raj K.,Singh, Udai P.,Srivastava, Vimal C.
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p. 2982 - 2996
(2019/11/14)
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- A new phosphotungstate-supported rhenium carbonyl derivative: Synthesis, characterization and catalytic selective oxidation of thiophenes
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A monomeric phosphotungstate-supported rhenium carbonyl derivative, [N(CH3)4]6H4[P2W17O62{Re(CO)3}2]·25H2O (1), has been synthesized in a conventional solution system and structurally characterized by single crystal X-ray diffraction crystallography, IR spectroscopy, thermogravimetric (TG) analyses, X-ray powder diffraction (XRPD), and electrospray ionization mass spectrometry (ESI-MS). To our knowledge, this is the first time that the {Re2} fragment existing in the polyoxoanion has been observed in polyoxometalate-supported metal carbonyl derivatives. Moreover, UV-vis spectroscopy was employed to elucidate the stability of the polyoxoanion, and its electrochemical properties were also investigated. In particular, complex 1 could act as an efficient homogeneous catalyst for selective oxidation of thiophenes. For example, dibenzothiophene (DBT) undergoes up to 99% conversion and 99% sulfone selectivity in acetonitrile with 30% H2O2 as an oxidant.
- Lu, Jingkun,Feng, Junwei,Ma, Xinyi,Wang, Ping,Xu, Baijie,He, Peipei,Jia, Jiage,Ma, Pengtao,Niu, Jingyang,Wang, Jingping
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p. 7322 - 7328
(2019/12/09)
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- Oxygenation of sulfides catalysed by SBA-15-immobilized molybdenum(VI) complex of a bis(phenol) diamine ligand using aqueous hydrogen peroxide as a green oxidant
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A highly efficient and reusable molybdenum-based catalyst has been synthesized by covalent grafting of a bis(phenol) diamine ligand, namely 2-(((2-bromoethyl)(2-((3,5-di-tert-butyl-2-hydroxybenzyl)amino)ethyl)amino)methyl)-4,6-di-tert-butylphenol, onto functionalized ordered mesoporous silica (SBA-15) followed by complexation with MoO2(acac)2. The resulting organic–inorganic hybrid material was found to be a highly effective catalyst for oxygenation of various sulfides to their corresponding sulfoxides or sulfones. The catalyst was characterized using transmission and scanning electron microscopies, X-ray photoelectron, Fourier transform infrared and atomic absorption spectroscopies, Brunauer–Emmett–Teller surface area analysis and thermogravimetric analysis. Mild reaction conditions, high selectivity and easy recovery and reusability of the catalyst render the presented protocol very useful for addressing industrial needs and environmental concerns.
- Saberikia, Iraj,Safaei, Elham,Karimi, Babak,Lee, Yong-Iii
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- An Efficient Oxidation of Sulfides to Sulfones with Urea-Hydrogen Peroxide in the Presence of Phthalic Anhydride in Ethyl Acetate
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A metal-free, environmentally benign oxidation of substituted sulfides directly to their corresponding sulfones is described. Using urea-hydrogen peroxide and phthalic anhydride in ethyl acetate clean conversion into the sulfone was achieved without observation of the possible sulfoxide oxidation product.
- Lutz, Marlon,Wenzler, Marta,Likhotvorik, Igor
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supporting information
p. 2231 - 2234
(2018/04/16)
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- Reusable BNPs-SiO2@(CH2)3NHSO3H-catalysed selective oxidation of sulfides to sulfones
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Reusable boehmite nanoparticles–silica–NHSO3H (BNPs-SiO2@(CH2)3NHSO3H) was found to be an efficient heterogeneous nanocatalyst for the selective oxidation of sulfides to sulfones in the presence of H2O2. Excellent yields, easy and quick isolation of products, short reaction times and excellent selectivity are the main advantages of this method. The catalyst was characterized using Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, X-ray diffraction, and transmission and scanning electron microscopies.
- Bahrami, Kiumars,Khodamorady, Minoo
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