Deep oxidative desulfurization of benzothiophene and dibenzothiophene with a peroxophosphotungstate–ionic liquid brush assembly

Deep oxidative desulfurization of benzothiophene and dibenzothiophene with a peroxophosphotungstate–ionic liquid brush assembly

Type	Journal Article
Author	Xian-Ying Shi
Author	Man Sun
URL	http://onlinelibrary.wiley.com/doi/10.1002/aoc.3344/abstract?userIsAuthenticated=false&deniedAccessCustomisedMessage=
Volume	29
Issue	9
Pages	633-637
Publication	Applied Organometallic Chemistry
Date	September 1, 2015
Abstract	Describes development of an innovative, efficient and reusable heterogeneous catalytic assembly of peroxophosphotungstate held in an ionic liquid brush. An extraction and catalytic oxidative desulfurization (ECODS) procedure was developed for a model oil of benzothiophene (BT) and dibenzothiophene (DBT) using 30 wt% hydrogen peroxide as terminal oxidant and methanol as solvent under mild conditions. Researchers examined a number of factors affecting sulfur removal. The highest sulfur removal can reach 100% for BT in 7 h at 70 °C when the molar ratio of H2O2, S and catalyst is 10:1:0.025. The sulfur removal for DBT can also reach 100% in 4 h at 50 °C with the same molar ratio of H2O2, S and catalyst. Results showed that the ECODS process has no apparent scale-up effect. The catalyst can be easily recovered and recycled five times without a significant decrease in activity.

Deep oxidative desulfurization catalyzed by an ionic liquid-type peroxotungsten catalyst

Deep oxidative desulfurization catalyzed by an ionic liquid-type peroxotungsten catalyst

Type	Journal Article
Author	Jizhong Chen
Author	Chen Chen
URL	http://pubs.rsc.org/en/content/articlelanding/2015/ra/c5ra00136f
Volume	5
Issue	33
Pages	25904-25910
Publication	RSC Advances
Date	2015-03-11
Abstract	Researchers synthesized novel peroxotungsten anion-based ionic liquid-type catalysts for the deep desulfurization of model oil containing dibenzothiophene (DBT) with H2O2 as an oxidant. They studied the effects of the temperature, H2O2/DBT molar ratio, and catalyst loading on the desulfurization activity. The catalysts exhibited excellent desulfurization activity under solvent-free and mild reaction conditions. The catalyst could be recycled at least ten times without any decrease in activity. Researchers observed that the H-bonding interaction between the H2-proton in imidazolium and the basic S atom in the DBT molecule played an important role in enhancing catalytic activity. On the basis of the activity measurements and characterization of the catalyst, they propose reaction mechanism for the oxidative desulfurization process.

Deep desulfurization by oxidation using an active ionic liquid-supported Zr metal–organic framework as catalyst

Deep desulfurization by oxidation using an active ionic liquid-supported Zr metal–organic framework as catalyst

Type	Journal Article
Author	Jianxiang Wu
Author	Yilong Gao
URL	http://onlinelibrary.wiley.com/doi/10.1002/aoc.3251/abstract
Volume	29
Issue	2
Pages	96-100
Publication	Applied Organometallic Chemistry
Date	February 1, 2015
Abstract	Reports synthesis of a Zr metal–organic framework (UIO-66) with zirconium tetrachloride and terephthalic acid using the solvent method. Various masses of 1-methylimidazolium-3-propylsulfonate hydrosulfate (PSMIMHSO4) were supported on the UIO-66 as catalysts, which were used for catalytic oxidative desulfurization. Researchers achieved sulfur removal using 400 mg of 40% PSMIMHSO4 supported on the UIO-66 of greater than 94% at 313 K for 20 min with an O/S molar ratio of 7:1. Results offer valuable information for the design of water-stable metal–organic frameworks with permanent porosity in applications of catalytic oxidative desulfurization.

Controllable Fabrication of Tungsten Oxide Nanoparticles Confined in Graphene-Analogous Boron Nitride as an Efficient Desulfurization Catalyst

Controllable Fabrication of Tungsten Oxide Nanoparticles Confined in Graphene-Analogous Boron Nitride as an Efficient Desulfurization Catalyst

Type	Journal Article
Author	Peiwen Wu
Author	Wenshuai Zhu
URL	http://onlinelibrary.wiley.com/doi/10.1002/chem.201501413/abstract
Publication	Chemistry – A European Journal
Date	September 9, 2015
Abstract	While tungsten oxide nanoparticles (WOxNPs) are attracting increasing attention, low stability and poor dispersion of WOxNPs hinder their catalytic applications. Researchers confined WOxNPs in graphene-analogous boron nitride (g-BN) using a one-step, in situ method at high temperature, enhancing the interactions between WOxNPs and the support and control the sizes of WOxNPs in a range of about 4–5 nm. They applied the catalysts to catalytic oxidation of aromatic sulfur compounds in which they showed high catalytic activity.

Application of a H4SiMo12O40@SiO2 catalyst with a hollow core–shell structure to oxidative desulfurization

Application of a H4SiMo12O40@SiO2 catalyst with a hollow core–shell structure to oxidative desulfurization

Type	Journal Article
Author	Xiaotian Zhang
Author	Guangqin Luo
URL	http://pubs.rsc.org/en/content/articlelanding/2015/ra/c5ra14307a
Volume	5
Issue	93
Pages	76182-76189
Publication	RSC Advances
Date	2015-09-08
Abstract	Designing an oxidative desulfurization catalyst with superior recyclability is an ongoing challenge. Researchers fabricated a H4SiMo12O40@SiO2 catalyst with a core–shell structure to desulfurize a model oil. Characterization results revealed that the synthesized H4SiMo12O40@SiO2 catalyst presents a hollow spherical structure and that the active H4SiMo12O40 species is incorporated into the mesoporous SiO2 shell. Under optimal reaction conditions, the desulfurization rate of dibenzothiophene is nearly 100%, and the activation energy of the oxidation reaction of dibenzothiophene is 22.08 kJ mol−1. Results demonstrated the excellent catalytic activity of H4SiMo12O40@SiO2 for oxidative desulfurization.

A Polyoxometalate-Encapsulating Cationic Metal–Organic Framework as a Heterogeneous Catalyst for Desulfurization

A Polyoxometalate-Encapsulating Cationic Metal–Organic Framework as a Heterogeneous Catalyst for Desulfurization

Type	Journal Article
Author	Xiu-Li Hao
Author	Yuan-Yuan Ma
URL	http://onlinelibrary.wiley.com/doi/10.1002/chem.201405825/abstract
Volume	21
Issue	9
Pages	3778-3784
Publication	Chemistry – A European Journal
Date	February 23, 2015
Abstract	Researchers hydrothermally synthesized a novel cationic triazole-based metal–organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ=4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl]. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other: straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction suggests that it is an effective and size-selective heterogeneous catalyst. It also exhibits distinct structural stability in the catalytic reaction system.

An inexpensive N-methyl-2-pyrrolidone-based ionic liquid as efficient extractant and catalyst for desulfurization of dibenzothiophene

An inexpensive N-methyl-2-pyrrolidone-based ionic liquid as efficient extractant and catalyst for desulfurization of dibenzothiophene

Type	Journal Article
Author	Fa-tang Li
Author	Biao Wu
URL	http://www.sciencedirect.com/science/article/pii/S1385894715005094
Volume	274
Pages	192-199
Publication	Chemical Engineering Journal
Date	August 15, 2015
Abstract	The oxidative desulfurization of DBT using H2O2 as oxidant and ILs as extractants are investigated. The scavenger experiments and electron paramagnetic resonance (EPR) measurement verify the active species is hydroxyl radical (OH) responsible for the oxidation of DBT. FeCl3-based ILs show much better effects in catalyzing H2O2 to generate OH than ZnCl2-based ILs. Inexpensive N-methyl-pyrrolidone (NMP)-based ionic liquids (ILs) are synthesized by coordinating N-methyl-pyrrolidone with anhydrous FeCl3 or ZnCl2. The process and mechanism for extraction and catalytic oxidation of DBT in an oil–ionic liquid–H2O2 system are proposed. The C5H9NO·0.3FeCl3 IL shows excellent recycling performance. After six-run experiment, there is only little loss in activity, which can be ascribed to the high solubility (18,190 ppm) of dibenzothiophene-sulfone (DBTO2), the main oxidation product of DBT, in the IL.