Desulfurization of simulated and commercial liquid fuel on nano-ZnO fabricated walnut shells.

The current investigation involved the development of activated carbon, juglans regia activated carbon (JRACs), from walnut shells, scientifically known as Juglans regia. The ZnO nanorods were loaded on the activated carbon and referred to as ZnO@JRACs. Desulfurization efficiency was assessed through batch adsorption and compared to commercial activated carbon known as DARCO. The materials were characterized using PXRD (powder X-ray diffraction), FTIR (Fourier-transform infrared spectroscopy), ICP-AES (inductively coupled plasma atomic emission spectroscopy), BET (Brunauer-Emmett-Teller) surface area analysis, TEM (transmission electron microscopy) imaging, and TGA (thermal gravimetric analysis). The findings indicated that the materials have oxygen functionalities, a porous morphology, and a substantial specific surface area (BET) of 1269.92 m2/g for ZnO@JRACs. Zn atom concentration in the ZnO@JRACs surface was determined to be 1.16 atomic percent using ICP-AES. Desulfurization experiments were conducted on three liquid fuels, namely a single component model fuel, MSF (multicomponent simulated fuel), and commercial fuel (kerosene), under optimized conditions (8 g/L adsorbent dosage in 10 mL of fuel, 15 min of contact time at room temperature). The conditions effectively removed ~ 98.9% of dibenzothiophene (DBT) from the single component model fuel. The observed order for adsorption capacity is as follows: ZnO@JRACs (63.6 mg g-1) > JRACs (46.3 mg g-1) > DARCO (26.1 mg g-1). The analysis of multicomponent simulated fuel (MSF) using gas chromatography-flame photometric detector (GC-FPD) revealed significant removal percentages for different types of thiophenic sulfur. Specifically, the removal percentages were ~ 46.2%, 97.6%, and 99.4% for benzothiophene, dibenzothiophene, and 4, 6-dimethyldibenzothiophene, respectively. Kinetic studies have shown that the adsorption process is governed by a pseudo second-order reaction. Additional thermodynamic studies were conducted to further investigate the mechanism of adsorption. The spent synthesized composite ZnO@JRACs were thermally regenerated and can be reused for up to four cycles.

Dibenzothiophene S, S-Dioxide-Containing Dipolar Molecules As Efficient Hole-Transport Materials for p-i-n Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (OIH-PSCs) have developed rapidly in the past decade, and the commercialization of OIH-PSCs demands low-cost hole-transport materials (HTMs) with high performance and stability. The present study synthesized two organic HTMs containing dibenzothiophene S-dioxide as the acceptor unit and triphenylamine as the donor (denoted by TPAF-SO2 and TPA-SO2). In TPAF-SO2, the methoxy group and adjacent fluorine atom were introduced to decrease the highest occupied molecular orbital energy level. In TPA-SO2, the methyl sulfide group is the end group that can passivate the lead ion. TPAF-SO2 and TPA-SO2 exhibit hole-transport mobilities as high as 1.12 × 10-3 and 2.31 × 10-3 cm2 v-1 s-1, respectively, and strongly passivate Pb vacancies. Compared with TPAF-SO2, TPA-SO2 is more suitable for the growth of perovskite crystals. The perovskite grown on the latter has a lower trap density and higher carrier mobility; thus, both the nonradiative recombination and the charge-transport loss are decreased. The OIH-PSC based on TPA-SO2 as the HTM achieved a power conversion efficiency (PCE) as high as 22.08%, whereas the device based on TPAF-SO2 achieved a PCE of only 18.42%. In addition, the unencapsulated device based on TPA-SO2 can maintain 85% of the initial PCE after being stored in N2 for 1200 h, whereas the device based on TPAF-SO2 decayed rapidly to zero in 800 h under the same conditions.

Dibenzo-Fused Heterocycles: A Decade Update on the Syntheses of Carbazole, Dibenzofuran, and Dibenzothiophene.

Polycyclic heterocycles are the most common and critical structural motifs found in a variety of natural products, medicines, fertilizers, and advanced materials. Because of their widespread use in biologically active compounds and material chemistry, functionalised dibenzo heterocyclic compounds, especially dibenzofuran, dibenzothiophene, and carbazole derivatives, garnered much attention over time. Scientists are especially interested in elucidating more efficient techniques for developing these industrially essential compounds. Dibenzo-fused heterocycles can rapidly be synthesised using highly efficient transition metal-catalysed strategies as well as by economic metal-free reaction conditions. This review includes a detailed overview of the most recent significant synthetic techniques, both metal-catalysed and metal-free, to produce these industrially significant and medicinally important dibenzo-fused heterocycles.

SBA-15 Type Mesoporous Silica Modified with Vanadium as a Catalyst for Oxidative and Extractive Oxidative Desulfurization Processes.

One of the current challenges is the reduction of sulfur emitted into the atmosphere, usually in the form of sulfur oxides generated by fossil fuel combustion. To achieve this goal, the sulfur content should be reduced in fuel. In this context, vanadium-containing materials based on SBA-15 mesoporous silica supports and two different sources of vanadium were prepared, characterized, and applied as catalysts for oxidative desulfurization (CODS) and extractive oxidative desulfurization processes (ECODSs). The novelty of this work was the comparative study of vanadium-containing materials in two desulfurization systems. The properties of the catalysts, the concentration and state of vanadium species, and their role in the catalytic process were examined by low-temperature nitrogen physisorption, XRD, UV-Vis, XPS, and chemisorption of pyridine combined with FTIR spectroscopy. The catalytic performance of the material prepared using ammonium metavanadate was superior to that of the catalyst obtained using vanadium(IV) oxide sulfate, which was explained by a higher concentration of vanadium species on the surface of the support and their lower oxidation state in the former. Both types of catalysts showed high activity and stability in the ECODS process.

The Sulfur Conversion Functional Microbial Communities in Biogas Liquid Can Participate in Coal Degradation.

The addition of biogas liquid is a practical way to improve the yield of biological coalbed methane. The microbial composition in biogas liquid is complex, and whether it could participate in the sulfur conversion of coal remains unknown. In this study, sulfur conversion-related microbial communities were enriched from biogas liquid, which was dominated by genera Anaerosolibacter, Bacillus, Hydrogenispora, and Oxobacter. The co-culture of these groups with coal significantly changed the coal microbial community composition but did not increase the content of CH4 and H2S. The changed microbial communities mainly belonged to phyla Firmicutes, Proteobacteria, and Actinobacteriota, and increased the relative abundance of genera Bacillus, Thermicanus, Hydrogenispora, Oxobacter, Lutispora, Anaerovorax, Desulfurispora, Ruminiclostridium, and Fonticella. From the microscopic structure of coal, an increase in the number of holes and roughness on the surface of the coal was found but the change of surface functional groups was weak. In addition, the addition of S-related microbial communities increased the contents of phoxim, methylthiobenzoylglycine and glibornuride M5 in aromatic compounds, as well as the content of lauryl hydrogen sulfate in alkyl compounds. Furthermore, the dibenzothiophene degradation-related microbial communities included Bacillus, Brevibacillus, Brevundimonas, Burkholderia-Caballeronia-Paraburkholderia, and Thermicanus, which can break C-S bonds or disrupt benzene rings to degrade dibenzothiophene. In conclusion, the S-related microbial communities in biogas liquid could rebuild the coal microbial community and be involved in the conversion process of organic sulfur in coal.

SERS characterization of biochemical changes associated with biodesulfurization of dibenzothiophene using Gordonia sp. HS126-4N.

In this study, Gordonia sp. HS126-4N was employed for dibenzothiophene (DBT) biodesulfurization, tracked over 9 days using SERS. During the initial lag phase, no significant spectral changes were observed, but after 48 h, elevated metabolic activity was evident. At 72 h, maximal bacterial population correlated with peak spectrum variance, followed by stable spectral patterns. Despite 2-hydroxybiphenyl (2-HBP) induced enzyme suppression, DBT biodesulfurization persisted. PCA and PLS-DA analysis of the SERS spectra revealed distinctive features linked to both bacteria and DBT, showcasing successful desulfurization and bacterial growth stimulation. PLS-DA achieved a specificity of 95.5 %, sensitivity of 94.3 %, and AUC of 74 %, indicating excellent classification of bacteria exposed to DBT. SERS effectively tracked DBT biodesulfurization and bacterial metabolic changes, offering insights into biodesulfurization mechanisms and bacterial development phases. This study highlights SERS' utility in biodesulfurization research, including its use in promising advancements in the field.

Poly(Dibenzothiophene-Terphenyl Piperidinium) for High-Performance Anion Exchange Membrane Water Electrolysis.

The anion exchange membrane water electrolysis is widely regarded as the next-generation technology for producing green hydrogen. The OH- conductivity of the anion exchange membrane plays a key role in the practical implementation of this device. Here, we present a series of Z-S-x membranes with dibenzothiophene groups. These membranes contain sulfur-enhanced hydrogen bond networks that link surrounding surface site hopping regions, forming continuous OH- conducting highways. Z-S-20 has a high through-plane OH- conductivity of 182±28 mS cm-1 and ultralong stability of 2650 h in KOH solution at 80 °C. Based on rational design, we achieved a high PGM-free alkaline water electrolysis performance of 7.12 A cm-2 at 2.0 V in a flow cell and demonstrated durability of 650 h at 2 A cm-2 at 40 °C with a cell voltage increase of 0.65 mV/h.

Efficient and promising oxidative desulfurization of fuel using Fenton like deep eutectic solvent.

Oxidative desulfurization (ODS) has emerged as a prominent technique for the removal of sulfur compounds from fuels, aiming to comply with stringent environmental regulations and minimize sulfur dioxide emissions. Herein, Fenton-like deep eutectic solvents (DESs) were synthesized as a catalyst and reaction medium and their application for the ODS process was investigated. The study encompassed the optimization of DES composition, reaction conditions, and the influence of different parameters on the desulfurization efficiency. The experimental findings demonstrated that the Fenton-like DES exhibited outstanding catalytic activity in the oxidative desulfurization of fuel. The optimized conditions involved conducting the reaction at room temperature for 2.5 h, using 200 mg of the prepared DES (HNFM-FeCl4) as both the extraction solvent and catalyst. An oxidant-to-sulfur (O/S) ratio of approximately 3:1 was maintained, with a 30 wt% H2O2 solution utilized as the oxidant. The analysis of the reaction products using GC-MS revealed a remarkable yield of 98% for dibenzothiophene sulfone. The DES provided a suitable medium for the reaction, enhancing the solubility and availability of sulfur compounds. The iron catalyst, in the presence of hydrogen peroxide, facilitated the oxidation of sulfur-containing compounds to their corresponding sulfones, which can be easily separated from the fuel phase. The DES catalysts exhibited stability and recyclability, making them suitable for practical applications in fuel desulfurization processes.

Exploring the effects of mono-bromination on hole-electron transport and distribution in dibenzofuran and dibenzothiophene isomers: a first-principles study.

CONTEXT: This study delves into hole-electron transport and distribution properties inherent in mono-brominated dibenzofuran (DBF) and dibenzothiophene (DBT) isomers. As determined by frontier molecular orbitals, all brominated structures have narrower bandgaps than their primary structures. The TD-DFT calculation showed that 2BDBT had the highest absorption wavelength of all molecules at 315.35 nm. Notably, the study unveils remarkably low electron and hole reorganization energies due to bromine substitution in DBF and DBT molecules. Specifically, the 4BDBF has the lowest hole reorganization energy of all DBF configurations, 0.229 eV. In addition, 3BDBF has 0.226 eV less electron reorganization energy than all other molecules. Compared to DBT, 3BDBT has the lowest electron reorganization energy of 0.254 eV. Overall, this research sheds significant light on the fundamental electronic and hole transport characteristics of bromine-substituted DBF and DBT isomers, highlighting their promising role in polymer design as donors/acceptors for advanced organic electronic applications. METHODS: Molecular structures were optimized using Density Functional Theory (DFT) B3LYP/6-311 + + G (d, p) level of theory, and the study further elucidates these molecules' energy levels and absorption spectra through Time-Dependent Density Functional Theory TD-DFT; these calculations were performed using Gaussian 09W software package. The key parameters such as reorganization energies, Electron Localization Function map, Laplacian Bond Order, and NCI-RDG were meticulously examined for the molecules with the results of DFT calculations were analyzed and displayed by utilizing the software packages VMD 1.9.4 and Multiwfn 3.8, aiming to comprehend their charge transport and distribution properties.

Interplay Between Ni and Brønsted and Lewis Acid Sites in the Hydrodesulfurization of Dibenzothiophene.

Ni-MoS2/γ-Al2O3 catalysts are commonly used in hydrotreating to enhance fossil fuel quality. The extensive research on these catalysts reveals a gap in understanding the role of Ni, often underestimated as an inactive sulfide phase or just a MoS2 promoter. In this work, we focused on analyzing whether well-dispersed supported nickel nanoparticles can be active in the hydrodesulfurization of dibenzothiophene. We dispersed Ni by Strong Electrostatic Adsorption (SEA) method across four supports with different types of acidity: silica (~ neutral acidity), γ-Al2O3 (Lewis acidity), H+-Y zeolite, and microporous-mesoporous H+-Y zeolite (both with Brønsted-Lewis acidity). Our findings reveal that Ni is indeed active in dibenzothiophene hydrodesulfurization, even with alumina and silica as supports, although their catalytic activity declines abruptly in the first hours. Contrastingly, the acid nature of zeolites imparts sustained stability and performance, attributed to robust metal-support interactions. The efficacy of the SEA method and the added mesoporosity in zeolites further amplify catalytic efficiency. Overall, we demonstrate that Ni nanoparticles may perform as a hydrogenating metal in the same manner as noble metals such as Pt and Pd perform in hydrodesulfurization. We discuss some of the probable reasons for such performance and remark on the role of Ni in hydrotreatment.

Oxidative desulfurization of fuels using alcohol-based DESs.

The presence of sulfur-containing compounds in fuel oil has become a major global issue due to their release of toxic sulfur dioxide. Hydrodesulfurization is a commonly used method for removing sulfur from fuel. However, new desulfurization techniques have been developed recently as hydrodesulfurization (HDS) is ineffective in removing refractory sulfur, e.g., BT, DBT, 4-MDBT. In this study, a series of deep eutectic solvent (DES) using ChCl, salicylic acid, oxalic acid, citric acid, and adipic acid as hydrogen bond acceptors and MeOH, EtOH, BuOH, EG, DEG, and TEG as hydrogen bond donors on different mole ratios were synthesized and then investigated the efficiency of these DESs in extracting sulfur from model and diesel fuel. Densities, viscosity, refractive index, and FTIR spectra of synthesized DESs were recorded. It also included oxidative desulfurization, which is a promising approach offering high selectivity, mild reaction conditions, low cost, and high efficiency. Hydrogen peroxide was selected as the oxidant in this study due to its excellent performance, commercial availability, and high proportion of active oxygen. [Citric acid: TEG] [1:7] and [adipic acid: TEG] [1:8] were found to be the most effective, removing up to 44.07% and 42.53% sulfur from model oil during single-stage extraction at 30 °C using a solvent-to-feed ratio of 1.0 and was increased to 86.87% and 85.06% using successive extraction up to the fourth stage. On oxidation, extraction efficiencies were reported to be 98.98%, 87.79%, and 56.25% and 96.96%, 81.22%, and 44.51% for model oil containing DBT and diesel 1 and diesel 2 with DES [citric acid: TEG] [1:7] and [adipic acid: TEG] [1:8] respectively at 30 °C using a solvent-to-feed ratio of 1.0. The study found that [citric acid: TEG] [1:7] exhibits better extraction performance in the deep desulfurization of fuels at an extraction temperature of 30 °C.

Surface enhanced Raman spectroscopy for the characterization of the metabolites of the biodesulfurization of dibenzothiophene carried out by Tsukamurella paurometabola.

Large amount of sulphur is released by the combustion of fossil fuels in the form of SoX which affects human health and leads to acid rain. To overcome this issue, it is essential to eliminate sulphur moieties from heterocyclic organo-sulphur compounds like Dibenzothiophene (DBT) present in the petrol. In this study Surface enhanced Raman scattering (SERS) spectroscopy is used to analyze the desulfurizing activity of Tsukamurella paurometabola bacterial strain. The most prominent SERS peaks observed at 791, 837, 944 and 1032 cm-1, associated to C-S stretching, are solely observed in dibenzothiophene and its metabolite-I (DBTS) but absent in 2-Hydroxybiphenyl (metabolite-II) and extraction sample of supernatant as a result of biodesulfurization. Moreover, the SERS peaks observed at 974 (characteristic peak of benzene ring) and 1015 cm-1 is associated to C-C ring breathing while 1642 and 1655 cm-1 assigned to CC bonds of aromatic ring. These peaks are only observed in 2-Hydroxybiphenyl (metabolite-II) and extraction sample of supernatant as a result of biodesulfurization. Notably, these peaks are absent in the Dibenzothiophene and its metabolite-I which indicate that aromatic ring is carrying sulfur in this fraction. Moreover, multivariate data analytical tools like principal component analysis (PCA) and PCA-loadings are applied to further differentiate between dibenzothiophene and its metabolites that are Dibenzothiophene sulphone (metabolite-I) and 2-Hydroxybiphenyl (metabolite-II).

Visible light to the second near-infrared light-harvesting donor-acceptor1-donor-acceptor2-type terpolymers for boosted photocatalytic hydrogen evolution via dual-sulfone-acceptor engineering.

Developing visible to near-infrared light-absorbing conjugated polymer photocatalysts is crucial for enhancing solar energy utilization efficiency, as most conjugated organic polymers only absorb light in the visible range. In this work, we firstly developed a novel thiophene S,S-dioxide (TDO) monomer with the stronger electron-withdrawing character, and then prepared a series of donor-acceptor1-donor-acceptor2-type (D-A1-D-A2-type) conjugated terpolymers (THTDB-1-THTDB-5) by statistically adjusting the molar ratio of two sulfone-based acceptor monomers, dibenzothiophene-S,S-dioxide (BTDO, A1) and TDO (A2). These terpolymers demonstrate a gradually expanding absorption range from visible light to the second near-infrared (Vis-to-NIR-II) region with the gradual increase of the TDO contents in the polymer skeleton, showcasing excellent absorption properties and efficient light-capturing capabilities. The optimized D-A1-D-A2 polymer photocatalyst THTDB-4 exhibits a high hydrogen evolution rate of 21.27 mmol g-1 h-1 under visible light without any co-catalyst. The dual-sulfone-acceptor engineering offers a viable approach for developing efficient the longer Vis-to-NIR-II light-harvesting polymer photocatalysts.

In Situ Generation of H2O2 over MoOx Decorated on Cu2O@CuO Core-Shell Particle Nanoarchitectonics for Boosting Photocatalytic Oxidative Desulfurization.

Photocatalytic oxidation desulfurization (PODS) has emerged as a promising, ecofriendly alternative to traditional, energy-intensive fuel desulfurization methods. Nevertheless, its progress is still hindered due to the slow sulfide oxidation kinetics in the current catalytic systems. Herein, we present a MoOx decorated on a Cu2O@CuO core-shell catalyst, which enables a new, efficient PODS pathway by in situ generation of hydrogen peroxide (H2O2) with saturated moist air as the oxidant source. The photocatalyst delivers remarkable specific activity in oxidizing dibenzothiophene (DBT), achieving a superior rate of 7.8 mmol g-1 h-1, while maintaining a consistent performance across consecutive reuses. Experimental investigations reveal that H2O2 is produced through the two-electron oxygen reduction reaction (ORR), and both H2O2 and the hydroxyl radicals (•OH) generated from it act as the primary reactive species responsible for sulfide oxidation. Importantly, our catalyst accomplishes complete PODS of real diesel fuel, underscoring an appealing industrial prospect for our photocatalyst.

Exploring the impact of competitive compounds and catalyst synthesis method in DBT oxidative desulfurization using MoO3-V2O5/Al2O3 catalyst.

This research endeavors to address the pressing challenge of reducing sulfur content in fuels, an environmental imperative. It does so by employing bimetallic catalysts to enhance the efficiency of oxidative desulfurization (ODS) processes. This involves utilizing successive impregnation and co-impregnation methods to prepare a MoO3-V2O5/Al2O3. The catalysts underwent characterization using various techniques including X-ray diffraction (XRD), N2 adsorption-desorption, UV-vis (DRS), temperature-programmed desorption (NH3-TPD), Raman, Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), and energy dispersive spectrum (EDS). The catalyst was utilized for the evaluation of the ODS process of dibenzothiophene (DBT). The effects of oxidants, namely H2O2 and t-butyl hydroperoxide (TBHP), were studied in the ODS. The catalyst prepared using the co-impregnation method (5M-15V-co) demonstrated significant acidic sites and exhibited remarkable efficiency in oxidative desulfurization. Remarkably, this catalyst achieved 100% oxidation of sulfur components within 30 min (min). To assess the catalyst's performance further, competitive compounds including nitrogen-containing compounds (NCCs) and saturated and unsaturated hydrocarbon compounds (HCs) were employed in the ODS. Initially, the introduction of NCCs led to a decrease in the sulfur removal rate; however, the catalyst successfully oxidized DBT completely within 60 min. When cyclohexene was present as an olefinic hydrocarbon compound, the catalyst oxidized DBT by approximately 75%, whereas DBT oxidation reached 100% within 20 min when p-xylene was introduced to the catalytic reactor. Additionally, as the O/S ratio increased from 2/5 to 10, the sulfur removal rate improved from 30 to 90%, indicating that HCs and NCCs compete with sulfur in terms of oxidant consumption.

The Effect of Mesoporous Structure of the Support on the Oxidation of Dibenzothiophene.

A source of Brønsted acid centers, generated on the surface of two mesoporous silica supports of different structures (SBA-15 and MCF), was 3-(trihydroxysilyl)-1-propanesufonic acid (TPS). The materials obtained were characterized and applied as catalysts for the oxidative desulfurization of dibenzothiophene (DBT) with hydrogen peroxide as a model ODS (oxidative desulfurization) process. The properties of the materials were examined via nitrogen physisorption, XRD (X-ray Diffraction) and elemental analysis showing the preservation of the support structure after modification with organosilane species. Due to the aggregation of catalyst particles in the reaction mixture, the SBA-15 based catalyst was not very effective in DBT oxidation. Contrary, TPS/MCF catalyst exhibited a very good activity (almost total conversion of DBT after 1 h in optimized reaction conditions) and stability in dibenzothiophene oxidation in mild reaction conditions.

Donor-Acceptor Copolymers with 9-(2-Ethylhexyl)carbazole or Dibenzothiophene-5,5-dioxide Donor Units and 5,6-Difluorobenzo[c][1,2,5]thiadiazole Acceptor Units for Photonics.

Semiconducting polymers, particularly of the third generation, including donor-acceptor (D-A) copolymers, are extensively studied due to their huge potential for photonic and electronic applications. Here, we report on two new D-A copolymers, CP1 and CP2, composed of different electron-donor (D) units: 9-(2-ethylhexyl)carbazole or dibenzothiophene-5,5-dioxide, respectively, and of 4,7-bis(4'-(2-octyldodecyl)thiophen-2'-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole building block with central 5,6-difluorobenzo[c][1,2,5]thiadiazole electron-acceptor (A) units, which were synthesized by Suzuki coupling in the high-boiling solvent xylene and characterized. The copolymers exhibited very good thermal and oxidation stability. A copolymer CP1 with different molecular weights was prepared in order to facilitate a comparison of CP1 with CP2 of comparable molecular weight and to reveal the relationship between molecular weight and properties. The photophysical, electrochemical, and electroluminescence properties were examined. Intense red photoluminescence (PL) with higher PL efficiencies for CP1 than for CP2 was observed in both solutions and films. Red shifts in the PL thin film spectra compared with the PL solution spectra indicated aggregate formation in the solid state. X-ray diffraction measurements revealed differences in the arrangement of molecules in thin films depending on the molecular weight of the copolymers. Light-emitting devices with efficient red emission and low onset voltages were prepared and characterized.

Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways.

A series of petroleum coke (petcoke)-derived solid acid catalysts were prepared via nitric acid treatment with or without ball milling pretreatment. The inherent sulfur in petcoke was converted to sulfonic groups, which were active sites for the esterification of octanoic acid and methanol at 60 °C, with ester yields of 14-43%. More specifically, samples without ball milling treated at 120 °C for 3 h had a total acidity of 4.67 mmol/g, which was 1.6 times that of the samples treated at 80 °C, despite their -SO3H acidities being similar (~0.08 mmol/g). The samples treated for 24 h had higher -SO3H (0.10 mmol/g) and total acidity (5.25 mmol/g) but not increased catalytic activity. Ball milling increased the defects and exposed aromatic hydrogen groups on petcoke, which facilitated further acid oxidation (0.12 mmol -SO3H/g for both materials and total acidity of 5.18 mmol/g and 5.01 mmol/g for BP-N-3/120 and BP-N-8/90, respectively) and an increased ester yield. DFT calculations were used to analyze the pathways of sulfonic acid group formation, and the reaction pathway with NO2• was the most thermodynamically and kinetically favourable. The activities of the prepared catalysts were related to the number of -SO3H acid sites, the total acidity, and the oxygen content, with the latter two factors having a negative impact.

Searching for bacteria able to metabolize polycyclic aromatic sulfur compounds in 12-years periodically fed bioreactor.

Biodesulfurization is a promising alternative for removing sulfur molecules from the polycyclic aromatic sulfur compounds (PASC) found in petroleum. PASC consists of recalcitrant molecules that can degrade fuel quality and cause a range of health and environmental problems. Therefore, identifying bacteria capable of degrading PASC is essential for handling these recalcitrant molecules. Microorganisms in environments exposed to petroleum derivatives have evolved specific enzymatic machinery, such as the 4S pathway associated with the dszABC genes, which are directly linked to sulfur removal and utilization as nutrient sources in the biodesulfurization process. In this study, bacteria were isolated from a bioreactor containing landfarm soil that had been periodically fed with petroleum for 12 years, using a medium containing dibenzothiophene (DBT), 4.6-dimethylbenzothiophene, 4-methylbenzothiophene, or benzothiophene. This study aimed to identify microorganisms capable of degrading PASC in such environments. Among the 20 colonies isolated from an inoculum containing DBT as the sole sulfur source, only four isolates exhibited amplification of the dszA gene in the dszABC operon. The production of 2-hydroxybiphenyl (HPB) and a decrease in DBT were detected during the growth curve and resting cell assays. The isolates were identified using 16S rRNA sequencing belonging to the genera Stutzerimonas and Pseudomonas. These isolates demonstrated significant potential for biodesulfurization and/or degradation of PASC. All isolates possessed the potential to be utilized in the biotechnological processes of biodesulfurization and degradation of recalcitrant PASC molecules.

Mesoporous SnO2-MoO3 catalyst for diesel oxidative desulfurization: Impact of the SnO2/MoO3 ratio on catalytic efficiency.

Vehicular SOx emissions have a huge detrimental impact on public health, catalytic converters, and the environment. Developing strategies to remove sulfur from diesel and thus safeguard the above is imperative. A series of SnO2-MoO3 mixed oxides and mono oxides MoO3 and SnO2 were prepared by soft template method, calcined at 450 °C and successfully tested in model diesel oxidative desulfurisation (ODS). The impact of the SnO2/MoO3 mole ratio (hereinafter denoted as Sn/Mo) on catalytic efficiency was investigated, among other catalytic parameters. The obtained samples were analyzed using X-ray diffraction (XRD), Raman spectrocscopy, scanning electron microscopy (SEM), N2-physisorption and titration method for acidic properties. The study demonstrates that mixing SnO2 and MoO3 improves acidic sites, crystallinity, and morphological properties of pure SnO2. The addition of MoO3 increased oxygen vacancies and the surface area of SnO2. High acidic site densities of 49.3, 47.4, and 46.7 mEqg-1 were observed for the catalysts with 2:1, 1:1, and 1:2 Sn/Mo mole ratio, respectively. The catalytic efficiency increased with an increase in Sn content with the highest catalytic efficiency of 99.8% for the dibenzothiophene (DBT) oxidation achieved in 30 min for Sn/Mo (2:1) catalyst compared to 92 and 70% for Sn/Mo 1:1 and 1:2 catalysts, respectively. The rate constant for the reaction was 0.057 min-1, which is eight times that of MoO3; 0.007 min-1 and three times that of SnO2; 0.017 min-1. The ODS mechanism utilizing the SnO2-MoO3 catalyst was proposed. The prepared SnO2-MoO3 catalyst demonstrated a high potential for industrial desulfurisation applications.