Carbon‐Nitride Popcorn—A Novel Catalyst Prepared by Self‐Propagating Combustion of Nitrogen‐Rich Triazenes

Small, Год журнала: 2023, Номер 19(12)

Опубликована: Янв. 13, 2023

The interest in development of non-graphitic polymeric carbon nitrides (PCNs), with various C-to-N ratios, having tunable electronic, optical, and chemical properties is rapidly increasing. Here the first self-propagating combustion synthesis methodology for facile preparation novel porous PCN materials (PCN3-PCN7) using new nitrogen-rich triazene-based precursors reported. This found to be highly precursor dependent, where variations terminal functional groups newly designed (compounds 3-7) lead different behaviors, morphologies resulted PCNs. foam-type PCN5, generated from 5 comprehensively characterized shows a ratio 0.67 (C3 N4.45 ). Thermal analyses PCN5 formulations ammonium perchlorate (AP) reveal that has an excellent catalytic activity thermal decomposition AP. further evaluated closer-to-application scenario, showing increase 18% burn rate AP-Al-HTPB (with 2 wt% PCN5) solid composite propellant. developed template- additive-free synthetic specially should provide platform PCNs variety building block chemistries, morphologies, suitable broad range technologies.

Язык: Английский

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Nonbonding Electron Delocalization Stabilizes the Flexible N₈ Molecular Assembly

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(5), С. 1507 - 1514

Опубликована: Фев. 1, 2024

Electron delocalization has an important impact on the physical properties of condensed materials. However, L-electron in inorganic, especially nitrogen, compounds needs exploitation to improve energy efficiency, safety, and environmental sustainability high-energy-density materials (HEDMs). This Letter presents intriguing N8 molecule, ingeniously utilizing nitrogen's delocalization. The exhibiting a unique lollipop-shaped conformation, can fold at various angles with very low barriers, self-assembling into environmentally stable, all-nitrogen crystals. These crystals demonstrate unparalleled stability, high density, mechanical sensitivity, optimal electronic thermal conductivity, outperforming existing HEDMs. remarkable these designed are attributed two distinct delocalized systems within L-shell: π- lone pair σ-electrons, which not only stabilize molecular structure but also facilitate interconnected 3D networks intermolecular nonbonding interactions. work might pave way experimental synthesis stable solids.

Язык: Английский

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A new sulfur-containing laser-sensitive primary explosive based on thiazole-4-carbohydrazide

Energetic Materials Frontiers, Год журнала: 2024, Номер 5(3), С. 191 - 198

Опубликована: Фев. 9, 2024

This study effectively synthesized thiazole-4-carbohydrazide (SZCA) and its ionic salt SZCA·HClO4 energetic complex Cu(SZCA)2(ClO4)2 (ECC-1). The new compound SZCA, ECC-1 were fully characterized through elemental analysis, infrared spectroscopy, 13C NMR spectroscopy thermal stability analysis. combustion heat of was measured by oxygen bomb calorimetry, detonation performance predicted Kamlet-Jacobs formula EXPLO5, respectively. mechanical sensitivity tested using BAM method. In particular, we comprehensively evaluated the initiation ability lead plate destruction experiment laser experiment. results show that have a decomposition temperature 236 °C, exhibits acceptable (impact sensitivity: 3.4 J, friction 4 N), decent properties (D: 6.6 km s−1, P: 21.3 GPa). And could be initiated single-pulse (λ: 808 nm, 20 W, t: 3 ms), successfully detonated next charge, such as RDX CL-20.

Язык: Английский

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Introducing Carborane Clusters into Crystalline Frameworks via Thiol‐Yne Click Chemistry for Energetic Materials

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 18, 2024

Abstract Crystalline frameworks represent a cutting‐edge frontier in material science, and recently, there has been surge of interest energetic crystalline frameworks. However, the well‐established porosity often leads to diminished output energy, necessitating novel approach for performance enhancement. Thiol‐yne coupling, versatile metal‐free click reaction, underutilized As proof concept, we herein demonstrate potential this by introducing energy‐rich, size‐matched, reductive 1,2‐dicarbadodecaborane‐1‐thiol (CB−SH) into an acetylene‐functionalized framework, Zn(AIm) 2 , via thiol‐yne reaction. This innovative decoration strategy resulted remarkable 46.6 % increase energy density, six‐fold reduction ignition delay time (4 ms) with red fuming nitric acid as oxidizer, impressive enhancement stability. Density functional theory calculations were employed elucidate mechanism which CB−SH promotes hypergolic ignition. The modification presented here permits engineering design advanced materials.

Язык: Английский

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Structure‐Induced Energetic Coordination Compounds as Additives for Laser Initiation Primary Explosives

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Дек. 9, 2024

Laser ignition of primary explosives presents more reliable alternative to traditional electrical initiation methods. However, the commercial initiator lead azide (LA) requires a high-power density laser detonate, with minimum energy (E

Язык: Английский

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Coordination Competition Strategy for Constructing High-Energy Photosensitive Complexes

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

High-dimensional energetic coordination compounds (ECCs) exhibit high stability and low sensitivity owing to their complex network structure, making them valuable in functional materials such as combustion catalysis insensitive detonating explosives. Four ECCs, [Co(DNBT)(H2O)4]n (ECC-1), [Ni(DNBT)(H2O)4] (ECC-2), [Cu2(DNBT)2(H2O)3MeOH] (ECC-3), [Zn(DNBT)(H2O)4] (ECC-4), were synthesized by modifying the metal centers using 5,5'-dinitro-4H,4'H-3,3'-bi(1,2,4-triazole) (DNBT) ligands. After changing solution environment adding auxiliary ligand 4H-1,2,4-triazol-4-amine (4-ATr), we obtained three ECCs with similar structures once again: [Co2(DNBT)2(4-ATr)3(H2O)2] (ECC-5), [Ni2(DNBT)2(4-ATr)3(H2O)2] (ECC-6), [Cu2(DNBT)2(4-ATr)3] (ECC-7). fewer water molecules chosen for laser ignition detonation tests evaluate laser-induced capabilities, indicating potential applications initiators. The response behavior differs between [Cu2(DNBT)2(4-ATr)3]. exhibits excellent response, a minimum initiation energy of 11 mJ short lengthy delay 2.31 ms, whereas is less sensitive under same conditions. Theoretical calculations at different power densities indicate that possesses more efficient photothermal conversion. This reduced may stem from presence water. charge transfer these thoroughly analyzed through theoretical structural studies.

Язык: Английский

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Employing Nitrogen–Sulfur Synergy: 1,2,3-Triazole-Thiadiazole-Based Energetic Materials

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 8, 2025

In this study, we synthesized energetic materials integrating thiadiazole and triazole moieties. The newly developed compounds were thoroughly characterized using NMR, IR, elemental analysis, TGA-DSC, single-crystal X-ray diffraction (for compound 3). These exhibited acceptable properties, including high densities (1.88–1.92 g cm–3), moderate to good detonation performance (VOD: 6383–8128 m s–1), thermal stability (143–238 °C), less sensitivity impact (>15 J) friction (360 N). Notably, 4 8 achieved superior velocities compared nearly all reported sulfur-based date. This work highlights the significance of triazole-thiadiazole frameworks in development fine-tuning materials.

Язык: Английский

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Role of -SF5 Groups in Modulating the Stability and Energy Characteristics of Fluorinated Molecules

Energies, Год журнала: 2025, Номер 18(7), С. 1841 - 1841

Опубликована: Апрель 5, 2025

In this paper, we present our investigations into the detonation performance and stability variations caused by replacing -CF3 or -OCF3 group with -SF5. The widely applied DFT B3LYP/cc-pVTZ approach was employed to evaluate HOMO–LUMO gap, cohesive energy, chemical hardness, electronegativity. Based on these parameters, predict changes in thermal resulting from inclusion of -SF5 instead -OCF3. Our results indicate that, some cases, density fluorine-containing nitro compounds decreases due presence pentafluorosulfanyl group. Additionally, machine learning techniques were used determine pressure velocity fluorine–sulfur-containing compounds. findings suggest that exhibit better than ones. Overall, groups aromatic polynitro improved neither nor properties such as groups.

Язык: Английский

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Shock Response in Cage-like Polynitrocubane High-Energy-Density Materials: Competition between Strain Energy and Structural Symmetry

Energetic Materials Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

Язык: Английский

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Construction of High-Performance Energetic MOFs: C₄N₈O₄^2– and C₃N₄O₄^2– with Their Derivatives, Compared with Their Energetic Salts

Crystal Growth & Design, Год журнала: 2023, Номер 23(2), С. 820 - 831

Опубликована: Янв. 19, 2023

A promising strategy for handling the inherent contradiction of energetic materials (EMs, energy vs stability) metal–organic frameworks and salts is proposed. series novel high-performance EMs, [(C4N8O42–)(K+)2(H2O)2], [(C3N4O42–)2(Cu2+)2(H2O)4], [(C4HN8O4–)(K+)(H2O)] [(C4HN8O4–) (K+)(H2O)] (2–3 5–6) 7–11, were synthesized, characterized, fully investigated. The detailed structures physiochemical properties 2–3 5–8 obtained by single-crystal X-ray diffraction (XRD). Differential scanning calorimetry, impact sensitivity, friction sensitivity measured followed simulation calculation ΔHf, noncovalent interaction, detonation velocity pressure, Hirshfeld surface to evaluate comprehensive synthesized substances. relationships between thermal stabilities, mechanical sensitivities, performance with molecular compounds discussed. Additionally, reaction transition states bond dissociation nitro simulated investigate mechanism preparation decomposition 2 future studies on EMs.

Язык: Английский

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