Search Results (63)

The synthesis of n-bromobutane from n-butanol is a classic undergraduate organic chemistry experiment, primarily intended to illustrate the bimolecular nucleophilic substitution (S_N2) mechanism. However, this experiment is commonly plagued by low yields and the formation of byproducts (e.g., n-butene and di-n-butyl ether), which confuse students. To reveal the molecular origin of these competitive pathways, this study employs density functional theory (DFT) calculations to systematically investigate the reaction mechanism under acid catalysis. Four potential reaction pathways were explored: S_N2 substitution, E2 elimination, intermolecular etherification, and a high-energy E2 pathway. The computational results indicate that the S_N2 pathway to n-bromobutane is kinetically and thermodynamically favorable due to its low energy barrier. In contrast, the E2 elimination pathway possesses a higher energy barrier (18.8 kcal/mol vs. 13.5 kcal/mol for S_N2), explaining why elevated temperatures favor the formation of n-butene. Moreover, the etherification pathway was found to be the most energetically demanding, consistent with the trace amounts of di-n-butyl ether observed experimentally. These findings provide a quantitative molecular-level rationale for the strict temperature control and standardized reagent addition sequences in the laboratory protocol. By visualizing the potential energy surfaces, this computational approach bridges the gap between theoretical mechanism and practical operation, offering a valuable pedagogical tool for enhancing student understanding. Full article

Traditional oxidative dehydrogenation of n-butene has typically required relatively high operating temperatures (400–500 °C), which has driven increasing interest in the development of catalysts capable of delivering high activity at lower temperatures. In this study, zinc ferrite (ZnFe₂O₄-ST) was successfully synthesized via hydrothermal hydrolysis of Zn–Fe oleate and demonstrated remarkable catalytic performance for the oxidative dehydrogenation of n-butene under mild conditions. At 300 °C, ZnFe₂O₄-ST achieved a conversion of 72.9% with 92.1% selectivity toward 1,3-butadiene, a result that, to the best of our knowledge, ranks among the best reported in the literature. By contrast, ZnFe₂O₄ prepared by conventional coprecipitation (17.2% conversion with 91.3% selectivity) and sol-gel (10.1% conversion with 86.4% selectivity) methods showed much lower activities, highlighting the critical influence of synthesis strategy on catalytic performance. To better understand the origin of these differences, a detailed structural and physicochemical characterization was undertaken using X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), N₂ adsorption–desorption, X-ray photoelectron spectroscopy (XPS), H₂-temperature-programmed reduction (H₂-TPR), temperature-programmed re-oxidation (TPRO), and NH₃-temperature-programmed desorption (NH₃-TPD). These analyses revealed that the as-synthesized ZnFe₂O₄-ST possessed a significantly smaller average particle size, a larger specific surface area, and superior reducibility compared with the other samples. These properties are believed to be the key factors underpinning its outstanding catalytic behavior and provide important insights into the design of efficient low-temperature catalysts for selective oxidative dehydrogenation. Full article

Rice volatiles play a crucial role in mediating resistance to the brown planthopper (Nilaparvata lugens Stål, Hemiptera: Delphacidae), a major pest of rice crops. In this study, we analyzed secondary metabolites from rice plants to identify compounds associated with insect behavior. A total of 31 volatile metabolites were detected, among which 16 differed significantly between 51 resistant or susceptible varieties. Fifteen volatiles were more abundant in susceptible plants, while one was enriched in resistant varieties. Electrophysiological (EAG) and Y-tube olfactometer assays revealed that both male and female adults exhibited positive chemotaxis toward five volatiles: Cyclohexanone, 2,2,6-trimethyl-; 3-Cyclohexen-1-one, 3,5,5-trimethyl-; (+)-Isomenthol; Benzoic acid, 2-hydroxy-, methyl ester; and 2-Methoxy-4-vinylphenol. In contrast, male adults were repelled by Benzaldehyde, 3-ethyl-, and 3-Buten-2-one, 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-. These results indicate that characteristic volatiles serve as functional cues for host selection and may act as phytochemical markers for assessing rice resistance. The findings provide new insights into plant–insect chemical interactions and suggest potential strategies for environmentally friendly pest management, including the use of attractant- or repellent-based approaches and breeding for optimized volatile profiles to control N. lugens. Full article

Accurate knowledge of phase behavior in polyolefin–solvent mixtures is critical for ensuring stable operation and safe scale-up of industrial solution polymerization processes. The binary (n-hexane + ethylene/1-octene copolymer, POE96k-10) and ternary (α-olefin + n-hexane + POE96k-10) phase behaviors were investigated via a visual high-pressure cell (POE96k-10: M_w = 96 kg·mol^–1, M_w/M_n = 3.87, 1-octene mole fraction = 10.31 mol%) at temperatures of 380~480 K and pressures as high as 14 MPa. To systematically analyze the effects of α-olefin mass fraction and type on phase transition, four industrially relevant α-olefins (ethylene, 1-butene, 1-hexene, and 1-octene) were investigated. The results show that the phase transition temperature and pressure for liquid–liquid and liquid–vapor transitions show an approximately linear dependence on α-olefin mass fraction. Ethylene, 1-butene, and 1-hexene lower the phase transition temperature, whereas 1-octene increases it. Ethylene exhibits a strong anti-solvent effect, significantly lowering the transition temperature while increasing the phase transition pressure. The modified Sanchez-Lacombe equation of state (MSL EOS) effectively correlates and reproduces the phase equilibrium data of the α-olefin + n-hexane + POE96k-10 ternary systems, though its accuracy decreases with increasing α-olefin chain length. Full article

The identification of key active sites that determine oligomerization degree is a key focus of research in olefin oligomerization. The Ni/S-HZSM-5 catalyst has attracted widespread attention due to its excellent performance in this reaction. However, the interaction between SO₄²⁻ and Ni²⁺ on the ZSM-5 support, especially quantitatively regulating their ratio, has been rarely investigated. In this study, we prepared a series of Ni/S-HZSM-5-x catalysts by fixing the Ni loading and varying the Ni/S molar ratio in the initial feedstock. Then, the obtained catalysts were characterized to systematically investigate how the Ni/S ratio affects their structure, properties, and n-butene oligomerization performance. The results indicate that tuning the Ni/S ratio enables the targeted regulation of surface acidity and electronic properties of the catalysts. The Ni/S ratio influenced the interaction between the Ni cation and SO₄²⁻-SO₃²⁻ complex, which in turn altered the Lewis acidity of the catalysts. Further evaluation results reveal that n-butene conversion is positively correlated with the catalyst’s acidity, and the Ni²⁺/Ni⁺ ratio is positively correlated with the carbon chain length of the products. The surface form of NiSO₄ is the primary factor determining Lewis acidity, which is directly associated with the chain-growth ability of the catalyst. Full article

Unexpected activation of the tetrabutylammonium cation in the presence of hexachloroplatinate(IV) under light to give a dinuclear complex of trans-μ²:η²,η²-1,3-butadiene-bis(trichloroplatinate(II)) along with a proposed mechanism of the activation has been reported. The mechanism has been investigated using a combination of photodissociation photodetachment mass spectrometry, and frozen-matrix EPR spectroscopy, in addition to 1D and 2D NMR spectroscopy. In addition to the Bu₄N⁺ salts of [PtCl₆]²⁻ that were part of the original observations, the reactivity of Bu₄P⁺, Pr₄N⁺, and Pe₄N⁺ (Pe = pentyl) salts has also been investigated, and, in addition, the possible involvement of η²-butene complex intermediates has been investigated. The combined results provide additional evidence and support for the originally proposed mechanism of activation of the Bu₄N⁺ cation. Full article

1,3-butadiene (BD) is a volatile organic pollutant. Upon inhalation, it is metabolically activated to reactive epoxides which alkylate genomic DNA and form potentially mutagenic monoadducts and DNA–DNA crosslinks including N7-(1-hydroxyl-3-buten-1-yl)guanine (EB-GII) and 1,4-bis-(guan-7-yl)-2,3-butanediol (bis-N7G-BD). While metabolic activation resulting in mutagenicity is a well-established mode of action for 1,3-butadiene, characterization of the extent of inter-individual variability in response to BD exposure is a gap in our knowledge. Previous studies showed that population-wide mouse models can be used to evaluate variability in 1,3-butadiene DNA adducts; therefore, we hypothesized that this approach can be used to also study variability in the formation and loss of BD DNA adducts across tissues and between sexes. To test this hypothesis, female and male mice from five genetically diverse Collaborative Cross (CC) strains were exposed to filtered air or 1,3-butadiene (600 ppm, 6 h/day, 5 days/week for 2 weeks) by inhalation. Some animals were kept for two additional weeks after exposure to study DNA adduct persistence. EB-GII and bis-N7G-BD adducts were quantified in liver, lungs and kidney using established isotope dilution ESI-MS/MS methods. We observed strain- and sex-specific effects on both the accumulation and loss of both DNA adducts, indicating that both factors play important roles in the mutagenicity of 1,3-butadiene. In addition, we quantified the intra-species variability for each adduct and found that for most tissues/adducts, variability values across strains were modest compared to default uncertainty factors. Full article

This study explores the catalytic performance of V³⁺-modified Mg/Al hydrotalcite-derived materials in the oxidative dehydrogenation (ODH) of n-butane, compared with catalysts derived from pyrovanadate and decavanadate precursors. Different methods for preparing hydrotalcite-like materials were applied to obtain vanadium-containing Mg-Al mixed oxide catalysts for n-butane ODH. The hydrotalcite-like precursors were doped with vanadates (V⁵⁺) via ion exchange or co-precipitation or with V³⁺ cations incorporated into brucite-like layers. During calcination in air or argon flow, different vanadium-containing phases were obtained. Our findings demonstrate that V³⁺-doped hydrotalcites exhibit superior activity and selectivity toward the total C₄H₈ products, with enhanced selectivity for 1,3-butadiene. The highest n-butane conversion was observed for catalysts with an MgO structure and vanadium dispersed in the oxide matrix. A similar conversion level (~44%) was obtained for a spinel-like Mg₂VO₄ catalyst, but only a 15% level was found for the highly crystalline α-Mg₂V₂O₇ catalyst. In contrast, the highest selectivities toward dehydrogenated products were observed for V³⁺-containing and α-Mg₂V₂O₇ catalysts. NH₃- and CO₂-temperature programmed desorption (TPD) analyses showed that high basicity combined with low acidity favors the formation of butene isomers and 1,3-butadiene. This work highlights the strategic potential of tailoring vanadium speciation and hydrotalcite-based catalyst design for low-carbon chemical manufacturing, supporting the transition toward a circular economy. Full article

In the dimethyl ether (DME)-to-olefin (DTO) reaction over 20 types of P-loaded ferrierite zeolites with different P loading amounts, the synthesis of n-butenes such as 1-butene, trans-2-butene, and cis-2-butene was investigated to maximize the n-butene yield by optimizing the P loading amount. The zeolites were characterized using X-ray diffractometry (XRD), N₂ adsorption-desorption isotherms, and NH₃ temperature-programmed desorption (NH₃-TPD). Micropore and external surface areas, total pore and micropore volumes, and weak and strong acids affected the DTO reaction’s characteristics. The P-loaded ferrierite zeolite with a P loading of 0.3 wt.% calcined at 500 °C exhibited an n-butene yield of 35.7 C-mol%, which exceeds the highest yield reported to date (31.2 C-mol%). Multiple regression analysis using the obtained data showed that the strong acid/weak acid ratio and total pore volume had a high correlation with the n-butene yield, with a contribution rate of 64.3%. Based on the multiple regression analysis results, the DTO reaction mechanism was discussed based on the proposed reaction model involving the dual-cycle mechanism. Full article

The dehydrogenation of n-butane to butenes is a crucial process for producing valuable petrochemical intermediates. This study explores the role of oxyphilic metal promoters (Sn, Zn, and Ga) in enhancing the performance and stability of Pt@MFI catalysts for n-butane dehydrogenation. The presence of Sn in the catalyst inhibits the agglomeration of Pt clusters, maintaining their subnanometric particle size. PtSn@MFI exhibits superior stability and selectivity for butenes while suppressing cracking reactions, with selectivity for C1–C3 products as low as 2.1% at 550 °C compared to over 30.5% for Pt@MFI. Using a combination of high-angle annular dark-field scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy, we examined the structural and electronic properties of the catalysts. Our findings reveal that Zn tends to consume hydroxyl groups and substitute framework sites, and Ga induces more defective sites in the zeolite structure. In contrast, the interaction between SnO_x and the zeolite framework does not depend on reactions with hydroxyl groups. The incorporation of Sn significantly prevents Pt particle agglomeration, maintaining smaller Pt particle sizes and reducing coke formation compared to Zn and Ga promoters. Theoretical calculations showed that Sn increases the positive charge on Pt clusters, enhancing their interaction with the zeolite framework and reducing sintering, albeit with a slight increase in the energy barrier for C-H activation. These results underscore the dual benefits of Sn as a promoter, offering enhanced structural stability and reduced coke formation, thus paving the way for the rational design of more effective and durable catalysts for alkane dehydrogenation and other high-value chemical processes. Full article

The Lewis acidic framework Ti sites in Ti-Beta and Si-Beta catalysts were compared by FT-IR and NMR characterization methods before they were applied to the conversion of four butenes. The results showed that Si-Beta has fewer Lewis acid sites and abundant weak Brønsted acidic silanol nests, which play an important role in conversions between n-butene, cis-2-butene, and trans-2-butene. The conversions for these butenes over Si-Beta were always higher than those over a series of Ti-Beta catalysts with gradient-varied Lewis acidic framework Ti sites and silanols. This is because isobutene can only oligomerize, which requires stronger acidity, so its conversion over Si-Beta was lower than those over Ti-Beta zeolites. For a series of Ti-Beta catalysts with different abundances of Lewis acidic Ti sites, the more Lewis acid sites it had, the higher the conversions for the four butenes. Full article

FER zeolites have a unique framework structure and acid distribution, and are widely studied as a catalyst for reactions such as n-butene skeletal isomerization and dimethyl ether carbonylation. The Brönsted acid site (BAS) located in the 10-member ring (10-MR) of FER zeolites serves as the active site for the isomerization reaction of skeletal n-butene to produce isobutene. This study prepared five types of FER zeolites using different methods: using pyrrolidine (PY) alone as a template; using Na-form FER as seeds (SN) or H-form FER as seeds without organic structure directing agents (OSDAs); and combining the seeds of SN or SH with PY as OSDAs. The differences in the structure and acid distribution of the five zeolites were investigated, as well as their catalytic performance for the skeletal isomerization of n-butene. Experiments and characterization results showed that under hydrothermal synthesis conditions, the FER-PY+SH zeolites synthesized by using both H-form zeolites seeds and pyridine exhibited the highest aluminum concentrations at T1 and T3 sites, along with the greatest BAS located in the 10-MR. This unique composition contributed to the highest selectivity of isobutene. The FER-PY+SH catalyst was continuously used for 720 h at 350 °C, 0.1 MPa, and an n-butene mass space velocity of 2.0 h⁻¹ for three cycles of 2160 h. During this period, the conversion of n-butene was over 39%, while the selectivity of isobutene exceeded 95%. The FER-PY+SH catalyst exhibited excellent stability and activity. Full article

1,3-Butadiene (BD) is classified as a human carcinogen, and occupational exposure should be minimized. This study examined the effectiveness of personal protective equipment (PPE) during the clean-up and repair of a storage tank containing sludge contaminated with BD. A total of 66 workers participated, providing repeat urine samples before and after the shift. Overall, 1286 samples were analyzed for 1,2-dihydroxy-4-(N-acetylcysteinyl)butane (DHBMA) and the isomers 2-hydroxy-1-(N-acetylcysteinyl)-3-butene and 1-hydroxy-2-(N-acetylcysteinyl)-3-butene (MHBMA). Both DHBMA and MHBMA are urinary metabolites of BD and serve as biomarkers for recent BD exposure. Established correlations between the urinary concentrations of these biomarkers and airborne BD levels allowed for exposure assessment. However, conclusions regarding the exceedances of occupational exposure limits can vary depending on whether DHBMA or MHBMA levels are considered. This study investigated this discrepancy by estimating the apparent urinary half-lives of DHBMA and MHBMA using sequential individual post- and pre-shift samples. The results indicated that the longer urinary half-life of MHBMA (19.7 ± 3.1 h) led to its accumulation during the work week, in contrast to DHBMA, which has a shorter half-life (10.3 ± 1.9 h) and showed limited accumulation. When the kinetic information was used to adjust for the MHBMA build-up over the week, the discrepancy with DHBMA resolved, confirming that exposure limit values were not exceeded and validating the effectiveness of the PPE used. In the context of biomonitoring, this study provides valuable insights into biomarker selection based on specific objectives. MHBMA is recommended for scenarios with uncertain exposure timing and activities, whereas DHBMA is the preferred biomarker for evaluating the effectiveness of protective measures in known exposure settings. Full article

This paper investigates the use of loaded Co/BETA molecular sieve catalysts for the selective oligomerization of isobutylene. The physicochemical properties of Co/BETA molecular sieves were characterized using XRD, BET, NH3-TPD, FT-IR, XPS, and Py-FTIR. The effects of different active component loadings, reaction temperatures, and reaction air velocities on the selective oligomerization of isobutylene were investigated in a fixed-bed reactor. The results showed that the catalytic effect was optimal when the Co loading was 6%, the reaction temperature was 60 °C, the reaction pressure was 1 MPa, and the reaction air speed was 1 h⁻¹. The isobutylene conversion was greater than 74%, the C₈⁼ selectivity was approximately 70%, and the C₈⁼ yield reached 51.69% with minimal loss of n-butene, providing good catalytic capacity and efficiency. Full article

4-(2-furyl)-3-buten-2-one (FAc) is obtained by aldol condensation of furfural and acetone and has been used in hydrodeoxygenation reactions to obtain fuel products using noble metal catalysts. The hydrogenation of FAc in the aqueous phase using metallic- and Re oxide-supported catalysts on graphite was studied, within a temperature range of 200–240 °C, in a batch reactor over a 6 h reaction period. The catalysts were characterized using N₂ adsorption–desorption, TPR-H₂, TPD-NH₃, XRD, and XPS analyses. Catalytic reactions revealed that metallic rhenium and rhenium oxide-supported catalysts are active for the hydrogenation and Piancatelli rearrangement of FAc. Notably, metallic rhenium exhibited a fourfold higher initial rate than rhenium oxide, which was attributed to the higher dispersion of Re in the Re/G catalyst over graphite. Re/G and ReOx/G catalysts tended to rearrange and hydrogenate FAc to 2-(2-oxopropyl)cyclopenta-1-one in water. Full article