Aromatic Reactions Research Articles

Triflyl [18F]Fluoride as a Solution for Base‐sensitive Late‐stage Nucleophilic Aromatic 18F‐Fluorination Reactions

Fluorine‐18 is the predominant radionuclide used to label Positron Emission Tomography (PET) tracers. One outstanding challenge in nucleophilic aromatic radiofluorination reactions is the sensitivity of precursors and catalysts for basic reaction conditions, which are necessary for the work‐up of [18F]fluoride, resulting in limited reproducibility. Triflyl [18F]fluoride is a new [18F]fluoride source that allows freedom in choice of type and amounts of base and cryptand. The aim of the current work is to explore the scope and limitations of triflyl [18F]fluoride in the late‐stage nucleophilic aromatic 18F‐fluorination of various functionalized precursors, exploring reduced amounts of base and cryptand. The assessment allowed for the application of this new nucleophilic [18F]fluoride reagent to the successful radiosynthesis of boron, stannane, hypervalent iodonium ylide and phenol substrates bearing electron‐deficient, ‐neutral and ‐rich functional groups as well as the clinically relevant PET tracers [18F]FPEB, [18F]mFBG and [18F]SynVesT‐1.

Hydrogen isotope fractionation during aromatization to form alkylnaphthalene: Insights from pyrolysis experiments of 1-n-butyldecalin

Alkylnaphthalene homologues are important components of aromatic fraction in sedimentary organic matter and contain significantly geochemical information relative to formation and evolution of the host organic matter. They mainly originate from hydrocarbon aromatization reaction which involves the dehydrogenation of aliphatic rings resulting in the fractionation of stable hydrogen isotopes between aromatic hydrocarbons and their precursors. To examine these processes, this study thermally pyrolysed 1-n-butyldecalin (BD) at different time intervals under 360 °C/50 MPa to study the aromatization and hydrogen isotope fractionation during alkylnaphthalene formation and evolution. The relative content of aromatic products, such as naphthalene (N) and 1-methylnaphthalene (1-MN), increases with increasing aromatization. Sulfur enhanced the degree of aromatization during BD thermal evolution, resulting in greater N and 1-MN formation. For the compounds with the same carbon skeleton, i.e. tran-1-methyldecalin (1-MD), 5-methyltetraline (5-MT) and 1-MN, the 2H enrichment follows the order δ2H1-MD < δ2H5-MT < δ2H1-MN during the low thermal conversion of BD. However, the order was subsequently destroyed with increasing aromatization. The results indicate that hydrocarbon aromatization can enrich aromatic hydrocarbon in 2H, resulting in a higher δ2H value of higher aromatic-ring-number hydrocarbon than that of a lower aromatic-ring-number at low aromatization. However, 2H enrichment will decrease and even result in a reverse order with enhanced aromatization. Our findings are beneficial for understanding genetic mechanism and hydrogen isotope fractionation effect during the formation and evolution of aromatic hydrocarbons.

Hydrogen-Bond-Assisted Catalysis: Hydroxylation of Paclitaxel by Human CYP2C8.

Paclitaxel (PTX, or Taxol), a chemotherapeutic agent widely employed in the treatment of various cancers, undergoes metabolic transformations through the cytochrome P450 enzymes CYP3A4 and CYP2C8. CYP3A4 catalyzes the aromatic hydroxylation reaction of PTX, whereas CYP2C8 demonstrates a distinct reactivity pattern, producing 6α-hydroxypaclitaxel via alkane hydroxylation. Despite the significant impact of PTX metabolism on its anticancer efficacy, the detailed mechanisms underlying these transformations have remained largely unclear. In this study, we employed hybrid quantum mechanics and molecular mechanics (QM/MM) calculations to elucidate the mechanism of PTX metabolism by human CYP2C8. Our QM/MM results reveal that the hydroxylation of PTX by CYP2C8 follows an atypical rebound mechanism. Either of the two hydrogen atoms at the C6 position of PTX can be abstracted, leading to a common radical intermediate. Although the subsequent rebound barrier is unusually high, stereochemical scrambling is unlikely, as the rebound barrier for the formation of the 6α-hydroxylated PTX─the actual product─is significantly lower than that for the 6β-hydroxylated metabolite. Thus, product selectivity is determined by the non-rate-determining rebound step. Furthermore, the hydroxyl group at the C7 position of PTX plays a catalytic role by facilitating the hydrogen abstraction and rebound steps. Our study also confirms a pronounced stability of the transition state in the high-spin sextet spin state, enabled by the enzyme's specific substrate positioning.

Synthesis and properties of modified polyimides containing multiple side methyl and biphenyl structures

With the rapid development of 5 G technology and microelectronics, there is an urgent demand to design and develop modified polyimide films with low dielectric constant as flexible matrix materials. In this work, a diamine containing multiple side methyl and biphenyl groups was synthesized by aromatic nucleophilicsubstitution reaction and oxidation-reduction reaction, respectively. Furthermore, this monomer was used to polymerize with four different commercially available dianhydrides (ODPA, BTDA, BPDA, and PMDA) to produce a class of polyimides (PI 3a∼3d). The structures of the diamine and its PIs are characterized, and the relationship between the structure and properties of the obtained PI films is investigated. These modified PIs are easy to cast into films and have low dielectric constants and water absorption. Their dielectric constants and dielectric losses are in the range of 2.66–2.91 and 0.00579–0.00677 at 1 MHz, respectively. Meanwhile, these PIs also maintains good thermal stability, with glass transition temperatures (T g) higher than 284 °C and 10% weight loss temperatures in the range of 496–505 °C at N2.

Catalytic co-pyrolysis of yellow poplar and HDPE using MOF-incorporated HY zeolite catalysts

Catalytic co-pyrolysis of yellow poplar and high-density polypropylene (HDPE) was conducted using metal oxide on hydrogen y-type (HY) zeolite to selectively produce monoaromatic hydrocarbons. The reaction was investigated using a tandem micro-reactor connected to a gas chromatography–mass spectrometry (GC–MS) system, encompassing both in-situ and ex-situ studies. Fe oxide/HY and Cu oxide/HY catalysts, prepared via a metal–organic framework (MOF)-incorporated technique, demonstrated excellent metal dispersion and enhanced electron density. The Cu oxide/HY catalyst showed significant production of benzene, toluene, ethylbenzene, and xylene, reaching up to 28% in in-situ studies. Owing to its strong acid sites, this catalyst facilitated the formation of aromatic compounds. In ex-situ studies, furan and acetaldehyde were consumed through the Diels–Alder reaction. The increase in aromatic compounds was highlighted by a synergistic effect percentage as high as 175%. The mechanism of aromatic formation was elucidated through dealkylation, Diels–Alder, and aromatization reactions. The Cu oxide/HY catalyst, combined with the MOF-incorporated preparation technique presents a promising system for catalytic co-pyrolysis of biomass and HDPE. This approach will facilitate efficient and sustainable aromatic hydrocarbon production from renewable and plastic waste sources.

Accurate carbon structure for prediction of reaction pathway during bio-coal production using torrefaction

The structural parameters of carbon were accurately determined through correction by employing a linear correlation method. Further, the nuclear Overhauser effect (NOE) was reduced in solid 13C-nuclear magnetic resonance spectra using a solid cross-polarization/magic angle spinning (CP/MAS) probe and the total suppression of sidebands sequence (TOSS). The reaction pathway during torrefaction was inferred from analysis of the accurate bond behavior and product distribution. The results show that torrefaction has a significant influence on the structural evolution of biomass. After correction, the relative deviations in the H/C ratio and aromaticity of the carbon structure decreased below 20 %. During torrefaction, the aliphatic carbon bonds were cleaved and aromatic carbon bonds were formed by dehydration, deoxygenation, oligomerization, aromatization, and Diels-Alder reaction. Torrefaction of biomass is divided into three stages. The first stage occurs below 220 °C, with disruption of the hydrogen bonds, a decrease in the number of Cal-O bonds, and the release of some CO2, CO, and furaldehyde. The second stage proceeds in the 220–260 °C range, where β-O-α bonds and glycoside bonds are broken, with the generation of ketones, furan, phenols, CO, and CO2. In the third stage between 260 and 300 °C, Cal-O and Cal-Cal bonds are broken. Bio-coal is composed of monomers of C20H14O3 with two aromatic rings linked by one aromatic ring. This significant, fundamental study enables accurate calculation and simulations for optimizing the industrial utilization of biomass.

Fe-ZSM-5 outperforms Al-ZSM-5 in paraffin cracking by increasing the olefinicity of C3-C4 products

Iron-modified Al-ZSM-5 increases selectivity to propene, a key petrochemical resulting from fluid catalytic cracking (FCC). However, the type and role of active iron species remain unclear, hindering efforts to streamline the design of selective FCC additives. Here, we investigated Al-free Fe-ZSM-5 catalysts containing iron species in the form of framework Fe3+, extra-framework Fe3+, oxidic clusters, and oxide micro aggregates in n-octane cracking (FCC model) to assess their effect on catalytic cracking. DR-UV–Vis spectroscopy, 57Fe Mössbauer Spectroscopy, FTIR studies of pyridine adsorption, and n-octane cracking tests at 500 °C revealed that framework-associated coordinatively unsaturated Fe3+ species, which induce strong Lewis acidity, are responsible for paraffin cracking initiation, whereas bulk iron oxides on the zeolite surface are inactive. In comparison with Al-ZSM-5, Fe-ZSM-5 increases the olefinicity of the valuable C3-C4 fractions (selectivity to propene and butenes) and promotes aromatization reactions due to the lower relative strength of Fe-induced Brønsted acid sites and dehydrogenation properties. As shown by our 57Fe Mössbauer study (performed at −269 °C) of the catalyst in calcined, spent, and regenerated states, Fe-ZSM-5 deactivation is associated with the loss of tetrahedrally coordinated Fe3+ species. Therefore, tuning Fe-ZSM-5 C3-C4 selective FCC additives requires stabilizing framework Brønsted and framework-associated Lewis acid sites while decreasing the concentration of iron oxide species. Ultimately, these findings may enable us to meet the demand for propene derived from FCC cracking, which is expected to grow in the foreseeable future.

Divergent Reactivity of Iminyl Radicals in Four Interrupted Pathways for the Synthesis of Cyclic/Acyclic Ketones and N-Heterocycles from Vinyl Azides and Phenylacetic Acids.

Herein, we report the Ag-catalyzed substrate-controlled interrupted radical pathways of the iminyl radical. The benzylic groups played a crucial role in pathway selection involving a series of dimerization and hydrolysis, a 1,5-H shift followed by cascade radical cyclization, and direct N-(sp2)/aromatization reactions that provide access to diverse cyclic/acyclic ketones, quinolines, and phenanthridine derivatives. Contrary to previous reports, mechanistic investigations with high-resolution mass spectrometry analysis uncovered the involvement of rare azine, oxime, and β-functionalized vinyl azide intermediates.

Synthesis Route to Single-Walled Zeolite Nanotubes Enabled by Tetrabutylammonium Hydroxide.

Single-walled zeolite nanotubes (ZNT) were recently synthesized in a narrow compositional window. ZNT structural features-thin zeolitic walls and large mesopores-can allow for easy access of small molecules to zeolite micropores, but they also impart processing limitations for these materials, such as challenges with conventional aqueous ion-exchange conditions. Conventional solid- and liquid-phase ion exchange of calcined NaOH-derived ZNT (NaH-ZNT) results in structural degradation to either 2D sheet-like phases, 3D nanocrystals, or amorphous phases, motivating different direct synthesis routes and unconventional ion-exchange procedures of uncalcined ZNT precursors. Here, a modified synthesis route for ZNT synthesis is introduced that facilitates facile ion exchange as well as incorporation of additional non-Al heteroatoms in the zeolite framework. Tetrabutylammonium hydroxide (TBAOH) is used as a hydroxide source and co-OSDA, enabling synthesis of new compositions of ZNT, otherwise unachievable by post-modification of previously reported NaH-ZNT. By varying the gel composition, synthesis temperature, crystallization time, hydroxide source, silicon source, and aluminum source, productive conditions for the new TBAOH synthesis are developed, leading to increased strong acid site density in the ZNT. The collected results demonstrate the sensitivity of the ZNT synthesis to many key parameters and show that the ZNT forms only when Si/(Al + T) ∼ 30 in these synthesis gels and with specific Si and Al sources, and always in the presence of trace Na+. Catalytic testing, via the tandem CO2 hydrogenation to methanol and methanol to aromatics reaction, shows that ZNTs provide adequate catalytic activity (acidity), relative to their conventional 3D counterparts in converting methanol to aromatic compounds.

Fully-Exposed Pt Cluster@Zeolite catalysts for efficient n-Hexane aromatization

The exploration of Pt cluster catalysts with minimal or fully exposed Pt atoms for specific reactions is meaningful but challenging, aiming to maximize Pt atomic utilization. To answer the above question, we design 4Pt cluster catalysts within a KL zeolite (Ptn@KL, n represents Pt atom numbers) for an n-hexane aromatization (n-HAM) reaction. Pt species in Ptn@KL are identified as Pt1, and Pt4, Pt9, and Pt13 clusters, respectively; the corresponding Pt–Pt coordination number ranges from 0, 2, 3.3 to 4.5. When tested in n-HAM at 440 °C, Pt4@KL shows the highest benzene yield of 85.7 % with ∼ 100 % conversion and superior durability up to 600 h. In-situ characterizations and theoretical calculations demonstrate that the optimal Ptn@KL CTs towards n-HAM is a fully exposed Pt cluster with CNPt–Pt of 2.

Unactivated Pd-catalyzed oxidative cross-coupling reactions of arenes with benzene: a theoretical and experimental study

Oxidative C–H bond activated palladium-catalyzed aromatic cross-coupling reactions offer advantages of fewer required synthetic steps but disadvantages of loss of inherent regioselectivity and selectivity. In one proposed catalytic cycle, each arene adds to a palladium carboxylate catalyst according to a concerted metalation deprotonation mechanism, followed by reductive elimination to couple the arenes and the replenishment of the catalyst by an oxidant. Using this proposed mechanism, molecular structures and free energy profiles were calculated for coupling of benzene with a range of heteroarenes containing various substituents and with several Pd-carboxylate catalysts. Reaction kinetics were analysed using the energetic span model, predicting turnover frequencies (TOFs) of heterocoupling (HB and BH) and homocoupling (HH and BB) pathways and assessing degrees of turnover frequency control (XTOFs). More electron-withdrawing carboxylate ligands and more electron-donating heteroarene substituents decrease activation and reaction free energies of addition steps, with C-2 more favourable than C-3. When heteroarene and catalyst choice are particularly favourable, the first association can become exergonic, causing a significant change in catalytic kinetics. When not exergonic, free energy for addition of benzene is almost always higher, leading to large energetic spans and slower TOFs (BB &lt; HB &lt; BH &lt; HH). Non-exergonic pathways are also faster with more electron-withdrawing ligands and more electron-donating heteroarene substituents because of lower energy addition steps and a smaller energetic span. For exergonic associations, the low-energy arene–catalyst intermediate creates a larger energetic span, slowing down the HH and HB pathways. More electron-withdrawing ligands and more electron-donating substituents increase the relative TOF for BH, and the reaction requires only small excesses of benzene to induce heterocoupling.

Decoupling Aromatic Yield and Coke Formation in Methanol‐to‐Aromatic Reaction on Zn(II) Exchanged H‐ZSM‐5 Zeolite

AbstractMethanol to aromatic reaction is an alternative pathway to produce aromatics from non‐petroleum resources. Zn‐modified ZSM‐5 zeolite is the widespread catalyst for MTA due to its high activity and selectivity to aromatics. However, a desired high yield of aromatics is usually accompanied with undesired coke formation and fast deactivation of catalyst, because aromatic molecules also serve as the precursor for coke formation. To decouple the aromatic yield and coke formation rate, in this work we use Zn‐ZSM‐5 to investigate coke formation and catalyst deactivation. The coke distribution along the catalyst bed was analyzed and its correlation with the concentration gradient of methanol, olefins and aromatics along the bed was deciphered. Coke was found to form very fast at catalyst bed in the copresence of methanol and aromatics. On the contrary, much less coke was observed at the later layers of the catalyst bed where methanol had been fully converted and aromatics were present in the highest concentration. Based on this finding, we adjusted the reaction conditions to successfully improve the yield of aromatics without reducing catalyst lifetime in compromise, by applying a higher methanol partial pressure that enables a faster consumption of methanol and reduces the period of copresence of methanol and aromatics.

Cycloaddition and Skeleton Rearrangement of Heterocyclic Ketene Aminals (HKAs) with 1-Diazonaphthalen-2(1H)-ones for the Synthesis of Functionalized 1,2,3-Triazoles.

We developed a protocol for the synthesis of highly functionalized 5,6-dihydro-imidazo[1,2-c][1,2,3]triazole derivatives 4-5 (DHITs) from 1-diazonaphthalen-2(1H)-one derivatives with heterocyclic ketene aminals (HKAs). This strategy involved cycloaddition and skeletal rearrangement entailing the heating of a mixture of substrates 1 with HKAs 2-3 and THF without any catalyst. As a result, a series of DHITs 4-5 were produced by cleaving one bond (1 C═N bond) and forming three bonds (1 N-N and 2 C-N bonds) in a single step. This protocol achieved the dual functionalization of diazo building blocks involving both the aromatic nitrogen alkylation reaction to form an ArC-N bond without any metal catalyst and the intermolecular cycloaddition of the N═N bond. These strategies can be used to synthesize functionalized DHITs for combinatorial and parallel syntheses via one-pot reactions without any catalyst.

A novel molecular structure parameter determination method for biomass thermochemical conversion mechanism investigation

The low-grade energy properties and high O content of biomass limit its efficient energy utilization. Torrefaction is known to be one of the most promising thermochemical conversion methods for upgrading biomass. 250 °C Gas-pressurized (GP) torrefaction realizes deep decomposition of hemicellulose in biomass to as high as 99.7% by deoxygenation and aromatization. However, the above thermochemical conversion mechanism at molecular-level is currently scant. Here, a novel molecular structural parameter method and pure hemicellulose torrefaction were employed to investigate the thermochemical conversion mechanism. Results demonstrate that O content of 250 °C GP torrefied hemicellulose was as low as 28.8 wt%, which was considerably lower than 44.6 wt% of traditional torrefied hemicellulose. There are five deoxygenation mechanisms of hemicellulose during the GP torrefaction: deacetylation, decarbonylation, dehydroxylation, ring opening and cyclization reactions to produce CO2/CH3COOH, CO, H2O, ketones/aldehydes and furans. The deoxygenation and aromatization reactions cause the chemical structure of hemicellulose evolution significantly, these mechanisms are: active hemicellulose undergo aromatization reaction through cyclization and deoxidation to generate preliminary 2-ring furans polymer, followed by stepwise polymerization reactions to form 4-ring and 6-ring furans polymers. These polymerization reactions further greatly enhance deoxygenation reaction. A thermochemical conversion mechanism model is developed based on the above investigation. This work provides a novel method for determining the molecular structure and reaction mechanism of thermochemical converted biomass.

Multi-Substituted Phosphonated and Sulfonated Polymer Materials: Characterization and Blends with Basic Polymers

The growing demand for energy, limited resources, and climate warming call for alternative sustainable energy production. A promising candidate is the proton-exchange membrane fuel cell (PEMFC) using a proton conducting polymer as an electrolyte membrane. The most common proton-exchange membranes are based on sulfonated polymers, such as Nafion®. Since their proton conduction is driven by hydronium ions (H3O+) and hence require water, the operating temperature is limited to 100°C. Unlike in sulfonated polymer materials, the proton conduction in materials with phosphonic acid groups occurs via a hopping process and does not require water.1 This study introduces a highly substituted phosphonated and sulfonated polymer based on poly(pentafluorostyrene), which makes the material adaptable in anhydrous and hydrous operating conditions since the phosphonic acid and sulfonic acid units can conduct cooperatively. The phosphonic acid group is introduced via the nucleophilic aromatic substitution Michaelis-Arbuzov reaction. The Para-Fluoro-Thiol reaction was used to introduce sulfonic acid groups into the polymer backbone. In the past, both reaction steps were well investigated.2,3 The highly substituted polymer material was blended with a basic polymer to circumvent water solubility and investigated according to its proton conductivity, thermal stability, and mechanical properties.(1) Kumar, A. J. Mater. Chem. A 2020, 8 (43), 22632–22636. DOI: 10.1039/d0ta07732a.(2) Atanasov, V.; Oleynikov, A.; Xia, J.; Lyonnard, S.; Kerres, J. Journal of Power Sources 2017, 343, 364–372. DOI: 10.1016/j.jpowsour.2017.01.085.(3) Delaittre, G.; Barner, L. Polym. Chem. 2018, 9 (20), 2679–2684. DOI: 10.1039/c8py00287h.

Unlocking the Potential of Glutinol: Structural Diversification and Antifungal Activity against Phytopathogenic Fusarium Strains.

Unlike most common pentacyclic plant triterpenes, glutinol has a methyl group at position C-9 and a Δ5 double bond. At the same time, it lacks a methyl at C-10. These features significantly modify its chemical behavior compared to other triterpenes, particularly under oxidative conditions. Although the isolation of glutinol from various plant species has been documented, its chemistry remains largely unexplored. In this study, glutinol was isolated from the bark of Balfourodendron riedelianum as a starting material for top-down strategies of structural diversification, which included ring fusion, oxidation, aromatization, and ring cleavage reactions. Glutinol, together with a library of 22 derivatives, was evaluated for antifungal activity against three phytopathogenic Fusarium strains, F. solani, F. graminearum, and F. tucumaniae. Some of the derivatives displayed antifungal activity; in particular, compound 12, featuring a triazine ring, displayed the best fungicidal properties against F. solani and F. graminearum, while the ring B cleavage product 23 showed the best activity against F. tucumaniae. This study highlights the potential of glutinol as a scaffold for structural diversification, and these results may contribute to the design of novel fungicidal agents against phytopathogenic strains.

Divergent Aromatization of α-Halobenzyl γ-Butenolides Initiated by Selective Enol Protonation to Benzo[c]fluorenones and Naphthalenes.

An unprecedented divergent aromatization reaction of α-halobenzyl γ-butenolides has been described for the selective and concise synthesis of highly substituted benzo and higher π-extended fluorenones, and 1,3-disubstituted naphthalenes depending on the migration ability of the quaternary α-substituent. This aromatization switch from Ag+-mediated planarization to ylidenebutenolides likely originates from selective protonation on the enolic double bond rather than the benzyl halides by TfOH.

The effect of hydrothermal pretreatment on the catalytic performance of Zn/HZSM-5 catalysts for ethylene aromatization reaction

To address the issue of coking and deactivation of Zn/HZSM-5 catalysts used for lightolefins aromatization, a high-temperature hydrothermalmethod was employed for catalyst pretreatment. The catalysts were characterized using XRD, N2 physical adsorption-desorption, NH3-TPD, Py-FTIR, XPS, and TG techniques. The effect of high-temperaturehydrothermal pretreatment on the catalytic performance and stability of the catalyst was investigated using ethylene aromatization as a probe reaction. The results showed that the Zn/HZSM-5 catalyst exhibited excellent catalytic performance after48 h of high-temperature hydrothermal pretreatment. Although the conversion of ethylene slightly decreased, the catalyst lifetime was significantly extended, increasing from 72to 216 h, while the aromatics selectivity remained above 60%. It was suggested that the hydrothermal treatment enhanced the interaction between ZnO species and Brønsted acid sites, promoting the generation of ZnOH+ species. This not only suppressed the hydrogen transfer reaction but also significantly enhanced the dehydrogenation performance of the catalyst, improving the selectivity towards hydrogen. Additionally, the catalyst exhibited increased carbon capacity and reduced carbon deposition rate after hydrothermal treatment, demonstrating excellent anti-coking properties.

Pore evolution and reaction mechanism of coal under the combination of chemical activation and autothermal oxidation

Aiming at the limitation problems such as limited scope, high cost and energy consumption of coal bed penetration enhancement technology by traditional physical and chemical methods, a coal seam methane penetration enhancement method based on the combined action of chemical activation and auto thermal oxidation is proposed from the idea of utilizing the in-situ energy of the coal body. In this paper, N2 and CO2 adsorption, XPS and FTIR methods are used to study the pore structure evolution law and the change characteristics of the reactive structure of coal matrix under the effect of chemically activated autothermal oxidation. The synergistic microporous pore volume of chemical activation and auto thermal oxidation was 48.91 cm3/g−1 × 10-3, which was 28.96 % and 22.7 % higher than chemical activation and auto thermal oxidation respectively; The microporous specific surface area was 162.7 m2/g, which was 38 % and 26.6 % higher than chemical activation and auto thermal oxidation respectively. Activated coals expand and merge holes to a deeper degree after oxidative warming, and the complexity of the pore structure in the coal decreases; Highly reactive radicals in coal pores substantially promote the oxidation of coal structure, enhance the aromatic polymerization reaction of activated coal, and improve the maturity and aromaticity of activated coal, and the oxygen-containing functional groups in activated coal are negatively correlated with the oxidation temperature. The results of this study reveal the potential of the auto thermal oxidation-driven penetration enhancement method under chemical activation for coal seam gas penetration enhancement and extraction.

Accelerated multistep thermal stabilization of polyacrylonitrile fibers using an ethylenediamine pretreatment

The polyacrylonitrile multifilament yarn underwent a multistep heat treatment process including stabilization times ranging from 5 to 75 min following impregnation with a 30% ethylenediamine (EDA) aqueous solution. A series of measurements were employed to determine the structure and properties of thermally stabilized PAN samples. These included fiber thickness, fiber density, flame testing, tensile testing, X-ray diffraction, thermal analysis (differential scanning calorimetry and thermogravimetric analysis), and infrared spectroscopy. The results from XRD and IR spectroscopy indicated that the rate of aromatization reactions increased with longer stabilization times. A detailed examination of the XRD curves obtained through curve-fitting procedures suggested a rapid transformation of the original structure into a disordered amorphous phase containing pre-graphitic domains, evidenced by a gradual reduction in the degree of apparent crystallinity of the original PAN sample. The integration of EDA before the thermal stabilization stage significantly reduced the cyclization time of nitrile groups in the PAN polymer structure, thereby accelerating the stabilization reactions. This chemical pretreatment also improved the thermal stability of the samples by promoting oxidative cross-linking of the PAN polymer chains. After a 75 min multistep stabilization, the carbon yield at 1000 °C was 70.5%. Conversion index values, calculated using IR, XRD, and DSC methods, were 98.3%, 94.8%, and 89.5% respectively for the 75 min sample. These findings highlight the importance of EDA in accelerating the formation of an aromatic structure, which is critical for withstanding the high temperatures of subsequent carbonization stages.Graphical abstract