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

Wang, Shan; Wang, Qianyou; Feng, Xiao; Wang, Bo; Yang, Li

doi:10.1002/adma.201701898

Cited by 153 publications

(87 citation statements)

References 249 publications

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“…Loading more nitro groups and higher structural tension into a single molecule does improve explosive performance, but usually leads to complicated and not cost-effective synthetic procedures. By a trade-off of detonation performance and cost, HMX is regarded as the best military high-energetic explosives nowadays [7], although it is neither the most powerful one nor the cheapest one.Parallel to the intensive studies on molecule engineering on the backbone of nitrogen-rich organic energetic molecules [8,9], the exploration of advanced energetic materials extends to the crystal engineering on their energetic co-crystals [10-13], energetic salts [14][15][16][17][18][19][20], as well as coordination polymers or metal-organic frameworks [21][22][23][24][25][26][27]. The essential strategy is to control the intermolecular packing/linkage of the energetic organic fuel and oxidizer components in crystals by non-covalent interactions to modify/enhance the explosive performance and/or to reduce the sensitivity to a practicable level.…”

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confidence: 99%

Molecular perovskite high-energetic materials

et al. 2018

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Since the black powder, the first known explosive, was discovered by ancient Chinese in the seventh century, people have been finding powerful, stable, reliable and low-cost energetic materials for military equipment and civil industry. To obtain a better explosive performance, an efficient strategy is to load unstable chemical bonds [1][2][3], as well as to combine fuel with oxidizer components in a proper ratio for achieving sufficient combustion and rapid detonation [4][5][6]. An effective way is to incorporate fuel and oxidizer properties into a single molecule [7], as demonstrated by a series of classical organic nitro group/nitrogen-rich molecules, such as trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (HMX), hexanitrohexaazaisowurtzitane (CL-20) and octanitrocubane (ONC) (Fig. S1). Loading more nitro groups and higher structural tension into a single molecule does improve explosive performance, but usually leads to complicated and not cost-effective synthetic procedures. By a trade-off of detonation performance and cost, HMX is regarded as the best military high-energetic explosives nowadays [7], although it is neither the most powerful one nor the cheapest one.Parallel to the intensive studies on molecule engineering on the backbone of nitrogen-rich organic energetic molecules [8,9], the exploration of advanced energetic materials extends to the crystal engineering on their energetic co-crystals [10-13], energetic salts [14][15][16][17][18][19][20], as well as coordination polymers or metal-organic frameworks [21][22][23][24][25][26][27]. The essential strategy is to control the intermolecular packing/linkage of the energetic organic fuel and oxidizer components in crystals by non-covalent interactions to modify/enhance the explosive performance and/or to reduce the sensitivity to a practicable level. However, for a specific energetic molecular component, it is highly challenging to predict/engineer the crystal structure of its co-crystals, salts, or metal-organic frameworks [10], and the examples with good detonation performance, high stability and low cost are still scarce.Here we present a promising solution, i.e., assembly of both low-cost organic fuel and oxidizer components into a closely packed, high-symmetry ternary compounds (vide infra), to achieve advanced energetic materials with a nice combination of high explosive power, high stability, and low cost. The presented materials belong to the so-called molecular perovskites [28] with a general formula of ABX 3 , which topologically mimic the cubic structure of the very well-known inorganic perovskites, the simplest high-symmetry structure for ternary compounds, but have at least one organic molecular component (usually A component). Recently, molecular perovskites have attracted growing attention, as illustrated by the extensive studies on methyl-ammonium lead iodide for high performance solar cells [29][30][31][32], and the phase transitions together with the ...

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“…Anal. calcd for C 45 under stirring for 10 min to give a clear violet solution. By the addition of 0.1 M NaOH, the pH value of the solution was adjusted to 3~4.…”

Section: 35-tris[(47-bis(2-carboxyethyl)-147-triazacyclonon-1mentioning

confidence: 99%

“…[27][28][29] Nitroaromatic compounds (NACs) are one family of commonly used explosives and also prominent organic contaminants, which have become a great threat to homeland security, anti-terrorism and natural environment. [30,31] The practical significance of their reliable and rapid identification has prompted chemists to develop the fluorescent probes based on conjugated polymers, [32,33] nanomaterials, [34,35] quantum dots, [36,37] metal-organic frameworks etc., [38][39][40][41][42][43][44][45] for use in detecting NACs. As an alternative for above materials, discrete luminescent metal-organic assemblies like metallacycles and metallacages are a suitable class of chemosensors for the detection of NACs in solution as well as thin film on account of their solubility and abundant photophysical properties.…”

Section: Introductionmentioning

confidence: 99%

Hexanuclear 3d − 4f metal–organic cages assembled from a carboxylic acid‐functionalized tris‐triazamacrocycle for highly selective fluorescent sensing of picric acid

Tang

Sun

et al. 2019

Applied Organom Chemis

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Two LnIII ions are sandwiched by dinuclear CoII building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H6L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co4Ln2(LH2.5)2(H2O)4]·(ClO4)6·NO3·nH2O [Ln = Dy, n = 12 (1); Ln = Yb, n = 9 (2)], whose internal cavity accommodates a guest NO3− anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency.

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“…9,10 These merits make them have extensive applications in catalysis, gas storage and separation, sensors, bio-medicine, and energy storage and conversion. [11][12][13] Especially, the unique structure and properties of MOFs are very suitable for high-performance supercapacitor electrode materials such as the extremely large specific surface area, easily adjustable pore size, and abundant pseudocapacitive redox centers. 10 The MOF-based supercapacitor electrode materials mainly include two categories.…”

Section: Introductionmentioning

confidence: 99%

Significantly Enhanced Ultrathin NiCo-based MOF Nanosheet Electrodes Hybrided with Ti3C2Tx MXene for High Performance Asymmetric Supercapacitors

Wang¹,

Liu²,

Wang³

et al. 2020

Eng. Sci.

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In situ synthesis of NiCo based metal-organic framework (MOF) nanosheets and the exfoliation of Ti 3 C 2 T x into isolated nanosheets (MXene), called, NiCo-MOF/Ti 3 C 2 T x hybrid nanosheets, are simultaneously achieved by a facile ultrasonic method. This method can effectively avoid the oxidation and restacking of Ti 3 C 2 T x nanosheets, and also make them uniformly disperse on the surface of NiCo-MOF. The formed NiCo-MOF/Ti 3 C 2 T x hybrid nanosheets achieve a high specific capacitance of 815.2 A g-1 at 1 A g-1. The practical asymmetric supercapacitor (ASC) is fabricated using activated carbon and NiCo-MOF/Ti 3 C 2 T x hybrid nanosheets. The ASC device achieves an energy density of 39.5 Wh kg-1 at a power density of 562.5 W kg-1 , and also demonstrates a suitable cycling stability with 82.3 % of capacitance retention after 10000 continuous cycles at 5 Ag-1. The enhanced electrochemical property of NiCo-MOF/Ti 3 C 2 T x is attributed to the nanosheet-like and mesoporous structure, high electronic conductivity, and synergistic effect of hybrid electroactive components.

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

Cited by 153 publications

References 249 publications

Molecular perovskite high-energetic materials

Molecular perovskite high-energetic materials

Hexanuclear 3d − 4f metal–organic cages assembled from a carboxylic acid‐functionalized tris‐triazamacrocycle for highly selective fluorescent sensing of picric acid

Significantly Enhanced Ultrathin NiCo-based MOF Nanosheet Electrodes Hybrided with Ti3C2Tx MXene for High Performance Asymmetric Supercapacitors

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