Accelerating the discovery of insensitive high-energy-density materials by a materials genome approach

Nature Communications, Год журнала: 2018, Номер 9(1)

Опубликована: Июнь 18, 2018

Finding new high-energy-density materials with desired properties has been intensely-pursued in recent decades. However, the contradictory relationship between high energy and low mechanical sensitivity makes innovation of insensitive an enormous challenge. Here, we show how a genome approach can be used to accelerate discovery high-energy explosives by identification "genetic" features, rapid molecular design, screening, as well experimental synthesis target molecule, 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide. This as-synthesized energetic compound exhibits graphite-like layered crystal structure measured density 1.95 g cm-3, thermal decomposition temperature 284 °C, detonation velocity 9169 m s-1, extremely sensitivities (impact sensitivity, >60 J friction >360 N). Besides considered system six-member aromatic hetero-aromatic rings, this also applicable development high-performing materials.

Язык: Английский

---

Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials

Accounts of Chemical Research, Год журнала: 2015, Номер 49(1), С. 4 - 16

Опубликована: Дек. 30, 2015

Nitrogen-rich heterocycles represent a unique class of energetic frameworks featuring high heats formation and nitrogen content, which have generated considerable research interest in the field energy density materials (HEDMs). Although traditional C-functionalization methodology aromatic hydrocarbons has been fully established, studies on N-functionalization strategies nitrogen-containing still great potential to be exploited by virtue forming diverse N-X bonds (X = C, N, O, B, halogen, etc.), are capable regulating performance stability resulting compounds. In this sense, versatile N-heterocyclic offers flexible strategy meet requirements developing new-generation HEDMs. Account, role strategic designing new frameworks, including N-C, N-N, N-O, N-B N-halogen bonds, is emphasized. family N-functionalized HEDMs, derivatives, N-C most widely used type due good nucleophilic capacity heterocyclic backbones. introduction carbon tends decrease performance, significant improvement material sensitivity makes attractive for safety concerns. More importantly, "explosophores" can readily introduced into linkage, thus providing promising route various Formation additional N-N typically gives rise higher formation, implying enhancement detonation performance. many cases, increased hydrogen bonding interactions within functionalized also improve thermal accordingly. Introduction single N,N'-azo bridge several azole moieties leads an extended chain, demonstrating high-nitrogen The N-O functionalization become increasingly efficient tool exploring HEDMs with both low sensitivity. As highly dense building block, oxygen not only improves significantly but better balance. Furthermore, suitable broad variety N-heterocycles five-membered azoles six-membered azines. Newly explored endowed some characteristics. Typical examples include N-halogenated fused triazole FOX-7 as hypergolic oxidizers very short ignition delay times. addition, exploratory expanded applications ionic liquids, green pyrotechnic colorants, high-oxygen carriers. Overall, methodologies involving different bond provided approach ingredients application scope materials. Discussion perspectives protocols given summarize possible structure-property correlations, guidelines future design

Язык: Английский

---

A promising high-energy-density material

Nature Communications, Год журнала: 2017, Номер 8(1)

Опубликована: Июль 27, 2017

High-energy density materials represent a significant class of advanced and have been the focus energetic community. The main challenge in this field is to design synthesize compounds with highest possible maximum chemical stability. Here we show an compound, [2,2'-bi(1,3,4-oxadiazole)]-5,5'-dinitramide, synthesized through two-step reaction from commercially available reagents. It exhibits surprisingly high (1.99 g cm-3 at 298 K), poor solubility water most organic solvents, decent thermal stability, positive heat formation excellent detonation properties. solid-state structural features compound are also investigated via X-ray diffraction several theoretical techniques. sensitivity properties explosive similar those 2, 4, 6, 8, 10, 12-(hexanitrohexaaza)cyclododecane (CL-20), developed shows great promise for potential applications as high-energy material.High energy interest, but limiting factor many compounds. authors between that exhibit good stability

Язык: Английский

---

Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-triazole Monoanion and Dianion: Controllable Preparation, Characterization, and High Performance

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(24), С. 7500 - 7503

Опубликована: Июнь 6, 2016

Molecular modification of known explosives is considered to be an efficient route design new energetic materials. A family salts based on the 3,5-bis(dinitromethyl)-1,2,4-triazole monoanion and dianion were controllably synthesized by using 1-diamino-2,2-dinitroethene as a precursor. X-ray structure determination monohydrazinium 3,5-bis(dinitromethyl)-1,2,4-triazolate (5) monoammonium (6) diammonium hydrate (8·H2O) further confirmed structures these anions. In addition, supported data, in system, roving proton ring nitrogen rather than gem-dinitro carbon results extensive hydrogen-bonding interactions higher packing coefficients. Interestingly, 5 6 possess highest calculated crystal densities, 1.965 1.957 g cm(-3) at 150 K, for hydrazinium ammonium salts, respectively. Energetic evaluation indicates that (detonation velocity vD = 9086 m s(-1); detonation pressure P 38.7 GPa) (vD, 9271 41.0 exhibit great properties, superior those current highly explosive benchmarks, such 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

Язык: Английский

---

Tribochemistry, Mechanical Alloying, Mechanochemistry: What is in a Name?

Frontiers in Chemistry, Год журнала: 2021, Номер 9

Опубликована: Май 26, 2021

Over the decades, application of mechanical force to influence chemical reactions has been called by various names: mechanochemistry, tribochemistry, alloying, name but a few. The evolution these terms largely mirrored understanding field. But what is meant terms, why have they evolved, and does it really matter how process called? Which parameters should be defined describe unambiguously experimental conditions such that others can reproduce results, or allow meaningful comparison between processes explored under different conditions? Can information on encoded in clear, concise, self-explanatory way? We address questions this Opinion contribution, which we hope will spark timely constructive discussion across international mechanochemical community.

Язык: Английский

---

1,2,5‐Oxadiazole‐Based High‐Energy‐Density Materials: Synthesis and Performance

ChemPlusChem, Год журнала: 2019, Номер 85(1), С. 13 - 42

Опубликована: Окт. 16, 2019

Abstract This Review covers the synthesis and performance of most promising 1,2,5‐oxadiazole‐based high‐energy density materials (HEDMs). These comprise a 1,2,5‐oxadiazole subunit as key structural motif linked to various acyclic explosophoric groups or nitrogen‐rich nitrogen‐oxygen azoles: 1,2,4‐triazole, tetrazole, 1,2,4‐ 1,3,4‐oxadiazoles. Energetic alliances two more rings directly through heteroatom spacers are also presented. Particular attention is devoted installation different explosophores: nitro, nitramino, azo, azoxy, dinitromethyl, trinitroethyl moieties their combination. Promising environmentally benign energetic with high detonation velocity pressure, outstanding insensitivity summarized. Overall, presented may be considered next‐generation high‐performance that superior commonly used traditional explosives (TNT, PETN, RDX, HMX).

Язык: Английский

---

Explosives in the Cage: Metal–Organic Frameworks for High‐Energy Materials Sensing and Desensitization

Advanced Materials, Год журнала: 2017, Номер 29(36)

Опубликована: Июль 21, 2017

An overview of the current status coordination polymers and metal-organic frameworks (MOFs) pertaining to field energetic materials is provided. The explosive applications MOFs are discussed from two aspects: one for detection explosives, other desensitization. By virtue their adjustable pore/cage sizes, high surface area, tunable functional sites, rich host-guest chemistry, have emerged as promising candidates both sensing challenges perspectives in these areas thoroughly discussed, processing methods practical also briefly.

Язык: Английский

---

Taming of 3,4-Di(nitramino)furazan

Journal of the American Chemical Society, Год журнала: 2015, Номер 137(51), С. 15984 - 15987

Опубликована: Дек. 15, 2015

Highly energetic 3,4-di(nitramino)furazan (1, DNAF) was synthesized and confirmed structurally by using single-crystal X-ray diffraction. Its highly sensitive nature can be attributed to the shortage of hydrogen-bonding interactions an interactive nitro chain in crystal structure. In order stabilize this structure, a series corresponding nitrogen-rich salts (3-10) has been prepared fully characterized. Among these materials, dihydrazinium 3,4-dinitraminofurazanate (5) exhibits very promising detonation performance (νD = 9849 m s(-1); P 40.9 GPa) is one most powerful explosives date. To ensure practical applications 5, rather than preparing 1 through acid-base reactions, alternative route nitration N-ethoxycarbonyl-protected 3,4-diaminofurazan aqueous alkaline workup developed.

Язык: Английский

---

Conjugated Energetic Salts Based on Fused Rings: Insensitive and Highly Dense Materials

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(44), С. 15001 - 15007

Опубликована: Окт. 17, 2018

Nitroamino-functionalized 1,2,4-triazolo[4,3- b][1,2,4,5]tetrazine (1), when combined with intermolecular hydrogen bonds (HBs) and strong noncovalent interactions between layers, results, for example, in an interlayer distance of 2.9 Å dihydroxylammonium 3,6-dinitramino-1,2,4-triazolo[4,3- (2c) a packing coefficient 0.805. For 6,6'-dinitramino-3,3'-azo-1,2,4-triazolo[4,3- (3b), two fused rings are linked by azo group, which expands the conjugated system resulting even shorter 2.7 higher 0.807. These values appear to be shortest distances highest coefficients reported tetrazine energetic materials. With high coefficients, both possess densities 1.92 g cm-3 1.99 at 293 K, respectively. Compared its precursor, hydroxylammonium moiety serves as buffer chain (H-N-O-H), connecting anion cation through bonds, giving rise more favorable stacking, density lower sensitivity. The sensitivities all salts than that their neutral precursors, such compound 2 (3 J, >5 N) 2c (25 360 N). detonation properties (detonation velocity vD = 9712 m s-1 pressure P 43 GPa) 3b (vD 10233 s-1; 49 exceed those present explosive benchmarks, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) hexanitrohexaazaisowurzitane (CL-20). molecular structures several these new materials confirmed single-crystal X-ray diffraction measurements. Using calculated experimental ring planar large π-conjugated results compromise desirable stabilities properties, thus enhancing future utilization design

Язык: Английский

---

Crystal Engineering for Creating Low Sensitivity and Highly Energetic Materials

Crystal Growth & Design, Год журнала: 2018, Номер 18(10), С. 5713 - 5726

Опубликована: Сен. 6, 2018

Energy and safety are the two most important concerns of energetic materials (EMs), while they usually contradict each other: high energy typically goes together with low safety. Low sensitivity highly (LSHEMs) balance well thus desired for extensive applications. Nevertheless, on whole, energy–safety contradiction, component limits, insufficient knowledge about relationships among components, structures, properties performances EMs have made development LSHEMs, or even entire group EMs, evolve slowly. This Perspective focuses upon current progress in clarifications contradiction crystal packing–impact relationship EMs. Also, we propose strategies creating new LSHEMs desensitized through engineering, covering traditional composed neutral single-component molecules, cocrystals, ionic salts. Two levels intrinsic molecule crystal, accounted constructing LSHEMs: at molecular level, it is proposed to store much chemical bonds avoiding any bond formation an that too weak intrinsically safety; level suggested intermolecular interactions be enhanced increase packing compactness density strengthen anisotropy facilitate ready shear slide mechanical sensitivity; overall, a big π-bonded oxygen close zero hydrogen bond-aided face-to-face π–π stacking preferred as LSHEM. Hopefully, this will set root establishing systematic theory LSHEMs.

Язык: Английский

---