Benzothiophene Research Articles

Enhancing performance of ternary blend photovoltaics by tuning the side chains of two-dimensional conjugated polymer

Abstract We prepared the ternary blends active layer by incorporating a new two-dimensional donor-acceptor (D/A) conjugated polymer (BDTTBO) comprising benzo-dithiophene-thiophene-thiophene-benzo oxadiazole chemical units that has three different conjugated side chains bithiophene (BT), benzothiophene (BzT) and thienothiophene (TT) BDTTBO-BT, BDTTBO-BzT and BDTTBO-TT into poly (benzodithiophene-fluorothienothiophene) (PTB7-TH) and PC71BM as for organic photovoltaics (OPVs). We expected that incorporating these BDTTBO with different side chains into the blend of PTB7-TH and PC71BM not only can broaden the absorption of solar spectrum thereby increasing short-circuit current density but also tune the packing of PTB7-TH and the dispersion of PC71BM. In particular, we found that incorporating 10% of BDTTBO-BT to form the PTB7-TH: BDTTBO-BT: PC71BM ternary blend (active layer) device could improve the power conversion efficiency to 10.4% from 9.0% for the binary blend of PTB7-TH: PC71BM device—a relative increase of 15%. We examined the packing orientations of the PBDTTBO: PTB7-TH:PC71BM ternary blend films using synchrotron two-dimensional grazing-incidence wide-angle X-ray scattering, and found that the incorporation of 10% relatively higher crystallinity PBDTTBO-BT, PBDTTBO-BzT or PBDTTBO-TT not only altered the packing orientation of PTB7-TH substantially but also reduced PC71BM cluster size in the ternary blend system, as compared to that in the case of PTB7-TH with PC71BM binary blend, thereby providing more pathways for electrons and thus enhancing the carrier transport in the ternary blend, as evidenced by the carrier mobility.

Oxidative desulfurization of model and real oil samples using Mo supported on hierarchical alumina–silica: Process optimization by Box–Behnken experimental design

Abstract The catalytic performance of Mo supported on hierarchical alumina–silica (Si/Al = 15) with Mo loadings of 3, 6 and 15 wt% was investigated for the oxidative desulfurization (ODS) of model and real oil samples. Hierarchical alumina–silica (hAl–Si) was synthesized by economical and ecofriendly silicate-1 seed-induced route using cetyltrimethylammonium bromide (CTAB) as mesoporogen. The effect of CTAB on the structure of catalyst was studied by characterization techniques. The results revealed that 6%Mo/hAl–Si had the highest sulfur removal compared to the other catalyst loadings. The effect of operating parameters was evaluated using Box–Behnken experimental design. The optimal desulfurization conditions with the 6%Mo/hAl–Si catalyst were determined at oxidation temperature of 67 °C, oxidation time of 42 min, H2O2/S molar ratio of 8 and catalyst dosage of 0.008 g·ml−1 for achieving a conversion of 95%. Under optimal conditions, different sulfur-containing compounds with initial concentration of 1000 ppm, Dibenzothiophene (DBT), Benzothiophene (BT) and Thiophen (Th), showed the catalytic oxidation reactivity in the order of DBT > BT > Th. According to the regeneration experiments, the 6%Mo/hAl–Si catalyst was reused 4 times with a little reduction in the performance. Also, the total sulfur content of gasoline and diesel after ODS process reached 156.6 and 4592.2 ppm, respectively.

Synthesis and Antimicrobial Schreening of New 4,5,6,7-Tatra Hydro Benzo Thiophene Derivatives

A group of derivatives for compounds 2-Amino-3-carboxy-4,5,6,7-tetra hydrobenz -othiophene bearing different heterocyclic moieties such as Schiff bases. B-Lactum, 4-thiazolidinone.1,3-oxazepan. The newly synthesized derivatives have been supported by spectral data FT-IR, H1-NMR. All the synthesized compounds were screened for their antimicrobial activities against gram-positive and gram-negative bacteria as reference.

Synthesis and Antimicrobial Schreening of New 4,5,6,7-Tatra Hydro Benzo Thiophene Derivatives

A group of derivatives for compounds 2-Amino-3-carboxy-4,5,6,7-tetra hydrobenz -othiophene bearing different heterocyclic moieties such as Schiff bases. B-Lactum, 4-thiazolidinone.1,3-oxazepan. The newly synthesized derivatives have been supported by spectral data FT-IR, H1-NMR. All the synthesized compounds were screened for their antimicrobial activities against gram-positive and gram-negative bacteria as reference.

Desulfurization by liquid phase adsorption: Role of exposed metal sites in metal-organic frameworks

A highly porous 3D metal-organic framework {H3[(Cd4Cl)3(ttpa)8(H2O)12]⋅nH2O}∞ (1) with a 3,8-connected framework (H3ttpa = tris-[4-tetrazolylphenyl]amine) was prepared by in situ chemical synthesis using solvothermal method. With the open metal sites, the complex 1 can act as an efficient adsorbent for the removal of benzothiophene (BT) and dibenzothiophene (DBT) from isooctane.

The distribution and δ34S values of organic sulfur compounds in biodegraded oils from Peace River (Alberta Basin, western Canada)

The heavy sulfur-rich oils of the Peace River oil sands were formed by severe anaerobic biodegradation. To investigate the impacts of biodegradation on organic sulfur compounds (OSCs) we have measured the distribution and δ34S values of alkylated thioaromatics detected in four oils from each of two Peace River wells (A and B). The fluid composition of the Peace River oil sands can be highly complex due to the variable contributions of sources, thermal maturity and secondary alteration. Nevertheless, a previous multi-molecular investigation of samples from well B oils (PR2 oil-leg of Marcano et al., 2013, Organic Geochemistry 59, 114–132) indicated that the oils had biodegradation levels (BLs) of 5–6, with biodegradation increasing down the oil column. The hydrocarbon composition of oils isolated from well A were biodegraded to a lesser degree than well B (i.e., the presence of isoprenoids and high molecular weight [MW] n-alkanes suggests BLs of ∼3–4). The concentrations of C1–C3 alkylated benzothiophenes (BTs) and C1–C3 alkylated dibenzothiophenes (DBTs) declined sharply through both wells consistent with increased biodegradation, although other alteration impacts (e.g., water washing) might also contribute. The rates of decrease recorded for selected isomers showed variable responses (e.g., 3&4-mBT > 2-mBT; 4-eDBT > 1,3-dmDBT) which implies different susceptibilities to biodegradation and which may contribute additional useful molecular parameters for evaluating the BL of biodegraded S-rich petroleum. The S-isotopic measurements showed a 34S enrichment in several alkyl BTs down the oil leg in well B, with their δ34S values increasing by up to 6‰, consistent with the microbial utilisation of 32S (n.b., the δ34S values of alkyl BTs were not measured in well A oils because of low aromatic sub-fraction concentrations). In contrast, there was little variation in the δ34S values of alkyl DBTs down both wells indicating negligible S-isotopic fractionation of these OSCs in the deeper more biodegraded oils, possibly because of their higher MW and resistance to biodegradation. The δ34SDBT (and bulk δ34S) values of the well B oils were generally slightly enriched than the well A oils probably due to differences in the relative contribution of the major Devonian and Jurassic source rocks.

Sonochemical Degradation of Benzothiophene (BT) in Deionized Water, Natural Water and Sea Water.

This paper deals with the sonochemical water treatment of polycyclic aromatic sulfur hydrocarbons (PASHs), one of the most common impurities found in waste water coming from petroleum industry. The best fit of the experimental data appears to be the kinetic parameters determined using the Michaelis-Mentonmodel in the concentrations range of the study. For the initial increase in the degradation rates, it is simply considered that the more the bulk concentration increases, the more the concentration in the interfacial region increases. This will be explained by Michaelis-Menton kinetics. The influence of organic compounds in the water matrix as a mixture with Benzothiophene (BT) was also evaluated. The results indicated that BT degradation is unaffected by the presence of bisphenol A (BPA). Finally, the results indicated that ultrasonic action is involved in oxidation rather than pyrolitic processing in the BT sonochemical degradation.

Shifting Desulfurization Equilibria in Ionic Liquid–Oil Mixtures

Ionic liquids (ILs) and deep eutectic solvents have been used for the extraction of molecules, particularly natural products. An often studied system is that for thiophene removal from oil. In the current study, ILs have been used for the removal of thiophene (Th), benzothiophene (BT), and dibenzothiophene by liquid–liquid extraction. The equilibrium can be shifted by polymerizing the thiophenic compounds both electrochemically and chemically. A 1:1 mixture of 1-butyl-3-methylimidazolium chloride (Bmim)Cl and FeCl3 was used to extract Th and BT from alkane layers using electropolymerization to shift the position of the equilibrium. While the process could be carried out, the kinetics of polymer formation were too slow to make this a viable process. The final part of the study used a 1:2 (Bmim)Cl/FeCl3 mixture to chemically remove sulfur-containing compounds from alkane layer. It was shown that the chemical polymerization reaction of Th is around 1500 times faster than electrochemical polymerization. Issues associated with the regeneration of the liquid are discussed.

Adducts of triangular silver(i) 3,5-bis(trifluoromethyl)pyrazolate with thiophene derivatives: a weak interaction model of desulfurization.

π-Acidic triangular silver(i) 3,5-bis(trifluoromethyl)pyrazolate (Ag3pz3) can form 1 : 1 adducts with dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (DMDBT), benzothiophene (BT), and 2,5-dimethylthiophene (DMT), which are stabilized by weak AgS and AgC contacts and sometimes by π-π stacking and, therefore, may represent a weak interaction model for some adsorptive desulfurization processes.

Deep oxidative desulfurization of model fuels catalysed by immobilized ionic liquid on MIL-100(Fe).

Deep desulfurization of fossil fuels has become urgently required because of the serious pollution by the large-scale use of fossil fuels. In this study, [PrSO3HMIm]HSO4@MIL-100(Fe) was synthesized by wet-impregnation of the ionic liquid (IL) of [PrSO3HMIm]HSO4 on MIL-100(Fe). The construction of [PrSO3HMIm]HSO4@MIL-100(Fe) was then confirmed by X-ray powder diffraction, N2 adsorption–desorption experiments, infrared spectroscopy and elemental analysis, and then applied in the oxidative desulfurization of model fuels. In comparison with the corresponding IL, [PrSO3HMIm]HSO4@MIL-100(Fe) showed an enhanced performance in the desulfurization rate of model fuels due to the increase of the mass transfer rate. Under the optimized conditions (oxidant to sulphur ratio = 25, oil to acetonitrile ratio = 1, and temperature = 60 °C), a sulphur removal rate of 99.3% was observed (initial sulphur concentration = 50 ppm). The sulphur removal of three sulphur compounds by catalytic oxidation and extraction followed the order of dibenzothiophene (DBT) > thiophene (T) > benzothiophene (BT).

Highly efficient adsorption of benzothiophene from model fuel on a metal-organic framework modified with dodeca-tungstophosphoric acid

Reduction of sulfur-containing compounds from fossil fuel is vital. This work reports on the adsorptive removal of benzothiophene (BT) from liquid fuel using a highly porous metal-organic framework based on a bicomponent zirconium(IV) benzene-tricarboxylate Zr(BTC), and its post-synthetically modified hybrid form with dodeca-tungstophosphoric acid (HPW/Zr(BTC). The HPW loading for the high-performing hybrid adsorbents was 0.5–2.0 wt/wt of W/Zr. Temperature and concentration dependent BT adsorption data were in good agreement with the non-linear Langmuir model combined with a van’t Hoff description of the heat of adsorption. The maximum predicted adsorption capacities were estimated to be 290 and 238 mg.g−1 for HPW(1.5)/Zr(BTC) and Zr(BTC) comparable to the contemporary reported adsorbents. The adsorption kinetics followed a pseudo-second order model, which was related to the low concentration of BT used for these studies. Although the highly porous Zr(BTC) had good adsorptive sites, its adsorption capacity was enhanced by incorporation of HPW, this was attributed to availability of added acid sites for adherence of basic BT. The adsorption findings were further corroborated with DFT calculations, which showed favorable BT adsorption with calculated binding energies of −140.2 and −47.3 kJ.mol−1 for HPW(1.5)/Zr(BTC) and Zr(BTC), respectively. Much of adsorption sites were retained after regeneration of adsorbents.

Activity and stability of amino-functionalized SBA-15 immobilized 12-tungstophosphoric acid in the oxidative desulfurization of a diesel fuel model with H2O2

In this study, the stability and the catalytic activity of an ordered mesoporous SBA-15 immobilized 12-tungstophosphoric acid (H3PW12O40, HPW) in the oxidative desulfurization (ODS) of benzothiophene (BT) and dibenzothiophene (DBT) were improved by a post-synthesis-grafting method. In this method, SBA-15 was functionalized to provide a large number of amine groups for the immobilization of HPW through electrostatic binding with (3-aminopropyl) triethoxysilane (APTES) using triflic acid as a protonated agent. The materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N2 adsorption–desorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results show that the structure of functionalized SBA-15 support and the active phase of the HPW remained intact after immobilization. The synthesized PW–H3N+-SBA-15 catalyst showed a high catalytic activity for ODS, achieving BT and DBT conversion of 99.9% and 100% with the reaction conditions of reaction temperature of 50 °C, H2O2 dosage of 1 mL, catalyst dosage of 0.03 g, and reaction time 5 and 1 h, respectively. The catalyst also showed a high reusability after up to four cycles, for which the conversion of the fourth reaction was 90.0% for both BT and DBT.

Catalytic Oxidative/Extractive Desulfurization of Model Oil using Transition Metal Substituted Phosphomolybdates-Based Ionic Liquids

Polyoxometalates based ionic liquids (POM-ILs) exhibit a high catalytic activity in oxidative desulfurization. In this paper, four new POM-IL hybrids based on transition metal mono-substituted Keggin-type phosphomolybdates, [Bmim]5[PMo11M(H2O)O39] (Bmim = 1-butyl 3-methyl imidazolium; M = Co2+, Ni2+, Zn2+, and Mn2+), have been synthesized and used as catalysts for the oxidation/extractive desulfurization of model oil, in which ILs are used as the extraction solvent and H2O2 as an oxidant under very mild conditions. The factors that affected the desulfurization efficiency were studied and the optimal reaction conditions were obtained. The results showed that the [Bmim]5[PMo11Co(H2O)O39] catalyst demonstrated the best catalytic activity, with sulfur-removal of 99.8%, 85%, and 63% for dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and benzothiophene (BT), respectively, in the case of extraction combining with a oxidative desulfurization system under optimal reaction conditions (5 mL model oil (S content 500 ppm), n(catalyst) = 4 μmol, n(H2O2)/n(Substrate) = 5, T = 50 °C for 60 min with [Omim]BF4 (1 mL) as the extractant). The catalyst can be recycled at least 8 times, and still has stability and high catalytic activity for consecutive desulfurization. Probable reaction mechanisms have been proposed for catalytic oxidative/extractive desulfurization.

Encapsulation of the Sulfur Compounds by Cucurbit[7]uril: A Quantum Chemistry Study.

Benzothiophene (BT) and dibenzothiophene (DT) are the most important contaminants in the petroleum derivatives responsible for serious environmental and health problems. Therefore, we have investigated the absorption of these compounds for the first time by considering cucurbit[7]uril (CB[7]) as the host molecule and using the theoretical levels of density functional theory//B3LYP-D3/6-31G(d). BT and DT absorbed into CB[7] do not undergo a significant structural change in the CB[7] structure. The energy gap of the S-compounds@CB[7] in water and hexane solvents was approximately 5 eV, and this large value implies that the complexes have high chemical stability. Moreover, the absorption of the BT and DT into CB[7] in the water and hexane solvents is a favorable process, whereas the lowest binding energy was observed between the dibenzothiophene and CB[7] in the DT@CB[7] complex. The solvation enthalpy shows a preferential solvation of the complexes in water than in hexane solvent. This trend is confirmed by the AIM analysis that shows the highest stability for the DT@CB[7] system with the contribution of cooperative hydrogen bonding. The transfer free energy of S-compounds@CB[7] complexes from hexane to water are -66.12 and -59.56 kcal/mol for BT@CB[7] and DT@CB[7], respectively, implying the spontaneous transference of these complexes from hexane to water solvent. Overall, our results show that the cucurbiturils can be a new class of host molecules to be used in the removal of S-compounds from petroleum derivatives. Finally, a schematic flow diagram of the desulfurization process by cucurbiturils was proposed.

Development of a novel double-templated mesoporous carbon with outstanding desulfurization capacity

Abstract High specific surface area and considerable pore size are of crucial importance for adsorbents. The coexistence of the two properties, however, is acknowledged to be a tough task to be realized when preparing porous sorbents. In order to develop such adsorbents that incorporate both decent specific area and impressive pore size, a novel inorganic double-templated MgO CaCO3 assembly was for the first time contrived and utilized to synthesize carbon materials. The as generated double-templated mesoporous carbons (DMCs) possess a tunable pore size (5.13–8.28 nm) and comparatively high specific surface area (688–857 m2/g). As a result of the excellent porous properties, DMCs exhibit an outstanding benzothiophene (BT) capture ability.

Combining the Photocatalysis and Absorption Properties of Core-Shell Cu-BTC@TiO₂ Microspheres: Highly Efficient Desulfurization of Thiophenic Compounds from Fuel.

A core-shell Cu-benzene-1,3,5-tricarboxylic acid (Cu-BTC)@TiO2 was successfully synthesized for photocatalysis-assisted adsorptive desulfurization to improve adsorptive desulfurization (ADS) performance. Under ultraviolet (UV) light irradiation, the TiO2 shell on the surface of Cu-BTC achieved photocatalytic oxidation of thiophenic S-compounds, and the Cu-BTC core adsorbed the oxidation products (sulfoxides and sulfones). The photocatalyst and adsorbent were combined using a distinct core-shell structure. The morphology and structure of the fabricated Cu-BTC@TiO2 microspheres were verified by scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive x-ray spectroscopy, X-ray powder diffraction, nitrogen adsorption-desorption and X-ray photoelectron spectroscopy analyses. A potential formation mechanism of Cu-BTC@TiO2 is proposed based on complementary experiments. The sulfur removal efficiency of the microspheres was evaluated by selective adsorption of benzothiophene (BT) and dibenzothiophene (DBT) from a model fuel with a sulfur concentration of 1000 ppmw. Within a reaction time of 20 min, the BT and DBT conversion reached 86% and 95%, respectively, and achieved ADS capacities of 63.76 and 59.39 mg/g, respectively. The BT conversion and DBT conversion obtained using Cu-BTC@TiO2 was 6.5 and 4.6 times higher, respectively, than that obtained using Cu-BTC. A desulfurization mechanism was proposed, the interaction between thiophenic sulfur compounds and Cu-BTC@TiO2 microspheres was discussed, and the kinetic behavior was analyzed.

Catalytic oxidative desulfurization of model and real diesel over a molybdenum anchored metal-organic framework

In this work, we report the catalytic performance of a MoO2Cl2 anchored metal-organic framework, [email protected], in the oxidative desulfurization (ODS) process on a continuous fixed-bed reactor. [email protected] was examined as a catalyst in the oxidation of model oils containing dibenzothiophene (DBT), benzothiophene (BT) or 4,6-dimethyldibenzothiophene (4,6-DMDBT). In a 50-h ODS reaction of DBT at 70 °C, with tert-butyl hydroperoxide (TBHP) as the oxidant, a constant high DBT conversion of nearly 80% was observed along with a high oxidant utility of over 85%, where DBT was converted rapidly into DBT sulfone. XRD and ICP analysis show that the structure of [email protected] was well preserved, with no significant leaching of Mo species. In addition, [email protected] can also oxidize a hydrogenated diesel oil, and 74% sulfur removal efficiency was achieved, with an extraction recovery of 92.5% after acetonitrile extraction. Spectroscopic characterization confirmed the formation of a molybdenum peroxide complex from MoO2Cl2 under TBHP treatment, a plausible catalytic process was proposed based on the experiment evidence as well as FT-IR and FT-FIR characterization results.

Extractive-Catalytic Oxidative Desulfurization with Graphene Oxide-Based Heteropolyacid Catalysts: Investigation of Affective Parameters and Kinetic Modeling

Different tungsten and molybdenum containing heteropolyacid (HPA) catalysts (H3PMo12O40:Mo12, H3PMo8W4O40:Mo8W4, H3PMo6W6O40:Mo6W6, H3PW12O40:W12) were immobilized on graphene oxide (GO) to obtain HPA–GO heterogeneous catalysts (Mo12–GO, Mo8W4–GO, Mo6W6–GO, and W12–GO). The synthesized catalysts were applied in removal of sulfur containing compounds [benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT)] with combined extraction–oxidation process using a batch reactor. The sulfur removal efficiency was gradually increased with increasing the ratio of molybdenum ions in the HPAs and complete sulfur removal efficiency for DBT was obtained for Mo12–GO. The roles of affecting parameters such as extracting solvent, catalyst calcination, and feed concentration were also investigated. Among different extracting solvents including acetonitrile, DMF, NMP, methanol, water, and ethylene glycol, acetonitrile represented the best ECOD performance as the extracting solvent. The performance of non-calcined catalyst for sulfur removal was slightly better than that by the calcined one. It was also found that the high sulfur removal activity of the extractive-catalytic oxidative process (ECOD) was retained even at high feed concentration. The kinetic model was evaluated considering mass transfer coupled with chemical reaction, in which the catalytic oxidation reaction was recognized as the rate-controlling step. The kinetic parameters such as rate constants and apparent activation energy were determined.

Catalytic oxidative desulfurization of fuels in acidic deep eutectic solvents with [(C6H13)3P(C14H29)]3PMo12O40 as a catalyst

Deep eutectic solvents (DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry. The oxidative desulfurization results showed that benzothiophene (BT) could be completely removed by employing a [(C6H13)3P(C14H29)]3PMo12O40, DES (ChCl/2Ac) and H2O2 system. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and H2O2/S (O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene (DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(C6H13)3P(C14H29)]3PMo12O40 was stable during the reaction process and the oxidative product was dibenzothiophene sulfone (DBTO2). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.

A New Strategy for Fuel Desulfurization by Molecular Inclusion with Copper(II)-β-cyclodextrin@SiO2@Fe3O4 for Removing Thiophenic Sulfides

Developing a new and environment-friendly desulfurization strategy for removing thiophenic sulfides from fuel is currently necessary. Fuel desulfurization by molecular inclusion with a novel cyclodextrin-based magnetic nanomaterial copper(II)-β-cyclodextrin@silica@ferroferric oxide (Cu(II)-β-CD@SiO2@Fe3O4) was proposed for the efficient removal of thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) in fuel. Cu(II)-β-CD@SiO2@Fe3O4 was successfully prepared by the reaction between mono-6-O-toluenesulfonyl-Cu(II)-β-CD and 3-aminopropyltrimethoxysilane functionalized SiO2@Fe3O4, and the structural characterization illustrated that the active desulfurization component Cu(II)-β-CD was evenly immobilized on the surface of SiO2@Fe3O4. Furthermore, Cu(II)-β-CD@SiO2@Fe3O4 showed outstanding desulfurization performance for thiophenic sulfides in the order BT > DBT > T on account of the varying molecular inclusion ability of Cu(II)-β-CD for the three types of thiophenic sulfides. The optimum immobilized lo...