Modular Synthesis of High Performance Energetic Biocidal Bicyclic Compounds Derivated from Iodopyrazoles.

Modular synthesis can combine different functional module to flexibly regulate comprehensive properties and study the diversity of compounds. This study established a modular bicyclic synthesis strategy of combining polynitro energetic module with iodine-containing biocidal module. Compounds 1-6 with high iodine content (48.72-69.56%) and high thermal stability (Td: 172-304 ˚C) were synthesized and exhaustively identified. By modular synthesis, the detonation properties and gas-production of 3-6 improved greatly expanding their biocidal efficacy and maintained the iodine atomic utilization of iodine-containing module. Notably, 4,5-diiodo-3,4',5'-trinitro-1,3'-bipyrazole (5) and 3,5-diiodo-4,4',5'-trinitro-1,3'-bipyrazole (6) exhibit high detonation velocities (D: 5903 m s-1, 5769 m s-1, respectively) and highest gas production of 212.85 L mol-1 and 217.66 L mol-1 after decomposition. This study diversifies polyiodio-nitro compounds, and also inspire the implementation of similar synthesis strategies to provide family-level synthetic solutions to energetic biocidal materials.

An Intramolecular-Lock Facilitates Planar Tricyclic Fused Energetic Compounds.

Exploiting novel fused cyclic frameworks through simple and efficient methods has provided a blueprint for developing advanced explosives. In this study, six new [5,6,5]-tricyclic fused energetic compounds (I-VI) were synthesized through an intramolecular cyclization strategy involving a C-NH2 directed cyclization reaction. The work not only boosts the development of fused cyclic energetic compounds but also highlights their potential applications as secondary or heat-resistant explosives.

High-Performance Azo Cathodes Enabled by N-Heteroatomic Substitution for Zinc Batteries with a Self-Charging Capability.

Redox-active azo compounds are emerging as promising cathode materials due to their multi-electron redox capacity and fast redox response. However, their practical application is often limited by low output voltage and poor thermal stability. Herein, we use a heteroatomic substitution strategy to develop 4,4'-azopyridine. This modification results in a 350 mV increase in reduction potential compared to traditional azobenzene, increasing the energy density at the material level from 187 to 291 Wh kg-1. The introduced heteroatoms not only raise the melting point of azo compounds from 68 °C to 112 °C by forming an intermolecular hydrogen-bond network but also improves electrode kinetics by reducing energy band gaps. Moreover, 4,4'-azopyridine forms metal-ligand complexes with Zn2+ ions, which further self-assemble into a robust superstructure, acting as a molecular conductor to facilitate charge transfer. Consequently, the batteries display a good rate performance (192 mAh g-1 at 20 C) and an ultra-long lifespan of 60,000 cycles. Notably, we disclose that the depleted batteries spontaneously self-charge when exposed to air, marking a significant advancement in the development of self-powered aqueous systems.

Construction of Adaptive Deformation Block: Rational Molecular Editing of the N-Rich Host Molecule to Remove Water from the Energetic Hydrogen-Bonded Organic Frameworks.

Energetic hydrogen-bonded organic frameworks (E-HOFs), as a type of energetic material, spark fresh vitality to the creation of high energy density materials (HEDMs). However, E-HOFs containing cations and anions face challenges such as reduced energy density due to the inclusion of crystal water. In this work, the modification of amino groups in N-rich organic units could form a smart building block of hydrogen-bonded frameworks capable of changing the volume of the void space in the molecule through adaptive deformation of E-MOF blocks, thus enabling the replacement of water. Based on the above strategy, we report an interesting example of a series of hydrogen-bonded organic frameworks (E-HOF 2a and 3a) synthesized using a facile method. The crystal structure data of all of the compounds were also obtained in this work. Anhydrous 2a and 3a exhibit higher density, good thermal stability, and low mechanical sensitivity. The strategy of covalent bond modification for the host molecules of energetic frameworks shows enormous potential in eliminating the crystalline H2O of hydration and exploring high energy density materials.

Intramolecular Hydrogen Bonds Assisted Construction of Planar Tricyclic Structures for Insensitive and Highly Thermostable Energetic Materials.

Safety is fundamental for the practical development and application of energetic materials. Three tricyclic energetic compounds, namely, 1,3-di(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (ATDT), 5'-nitro-3-(1H-tetrazol-5-yl)-2'H-[1,3'-bi(1,2,4-triazol)]-5-amine (ATNT), and 1-(3,4-dinitro-1H-pyrazol-5-yl)-3-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (ATDNP), were effectively synthesized through a simple two-step synthetic route. The introduction of intramolecular hydrogen bonds resulted in excellent molecular planarity for the three new compounds. Additionally, they exhibit regular crystal packing, leading to numerous intermolecular hydrogen bonds and π-π interactions. Benefiting from planar tricyclic structural features, ATDT, ATNT, and ATDNP are insensitive (IS > 60 J, FS = 360 N) when exposed to external stimuli. Furthermore, ATNT (Td = 361.1 °C) and ATDNP (Td = 317.0 °C) exhibit high decomposition temperatures and satisfying detonation performance. The intermolecular hydrogen bonding that produced this planar tricyclic molecular structure serves as a model for the creation of innovative multiple heterocycle energetic materials with excellent stability.

Improvement of Thermal Stability and Sensitivity of Furazan/Furoxan via Ring Closure Generation of Vicinal Amino-Nitro Structure.

Energetic compounds that display high thermal stability and insensitivity properties are essential for applications in mining, gas drilling, etc. In this work, a novel 4-nitro-5-aminoisoxazole energetic moiety oriented to enhance thermal stability and decrease the sensitivity of furazan/furoxan analogues was constructed. The generation of a vicinal amino-nitro structure can be effectively realized in one step by a green and mild ring-closing reaction of nitroacetonitrile potassium salt with chloroxime in aqueous solution. Seven new energetic compounds with good thermal stability (Td: 155.8∼270.3 °C) and low sensitivity (IS: >40 J, FS: 96∼192 N) were synthesized. The nitro-furazan and isoxazole combined product exhibits the advantages of both skeletons, with energetic properties (Dv = 8350 m s-1, P = 30.1 GPa) that may find value in insensitive energetic materials. This strategy promises to achieve a balance between energy levels and stability of furazan/furoxan analogues and offers a new way for the design and synthesis of highly thermally stable compounds that meet special applications.

Nonbonding Electron Delocalization Stabilizes the Flexible N8 Molecular Assembly.

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

Host-Guest Technique for Designing Highly Energetic Compounds with the Nitroamino Group.

A new energetic material, 2-azido-4,7-nitroamino-1H-imidazo[4,5-d]pyridazine (ANIP) with a highly sensitive azido group and its host-guest compounds (ANIP/H2O and ANIP/H2O2), and energetic salts were obtained. With the guest and protons in host molecules, an abundant hydrogen bond system can be formed. This results in high crystal density and good sensitivity, which suggests that the host-guest strategy is a promising way to balance the contradiction between energy and sensitivity and provides a new path to obtain a new generation of high energetic materials.

Assembly of 1D Helical Energetic Coordination Polymers Using a Flexible Bridged Furazan-triazole Cation.

Two new energetic coordination compounds with 1D helical chain structures have been synthesized. First, the polyamine precursor 4,5-diamino-2-((4-amino-1,2,5-oxadiazole-3-yl)methyl)-2,4-dihydro-3H-1,2,4-triazole-3-imino chloride salt (TATAF-Cl) is obtained by incorporating 4-(chloromethyl)-1,2,5-oxadiazol-3-amine with 4H-1,2,4-triazole-3,4,5-triamine. Using a simple hydrothermal method, two energetic complexes, Ag(TATAF)(ClO4)2 (ECP-1) and Ag(TATAF)(NO3)2·H2O (ECP-2), with a helical 1D MOF structure of furazan and triazole were synthesized. Compounds ECP-1 and ECP-2 have relatively high nitrogen and oxygen content (N + O%: 52.04%, 61.04%), excellent crystal density (2.229 g cm-3, 2.116 g cm-3 at 298 K) and high heat of detonation (1.18 kcal g-1, 1.06 kcal g-1), good detonation performance (P: 35.34 GPa, 29.52 GPa; Dv: 8412 m s-1, 7794 m s-1), and moderate sensitivity (IS: 8 J, 13 J; FS: 72 N, 64 N). Structurally, the Ag+ of the two ECPs is coordinated with two energetic cations, two perchlorates, or one nitrate via tetragonal coordination to form a single helical structure that is interspersed up and down in two directions.

Exploring a Fused Triazole-Tetrazine Binary CN Material for a Promising Initiating Substance.

The pursuit of binary carbon-nitrogen (CN) materials with high density and good thermal stability presents a significant challenge due to the inherent trade-off between high-energy storage and low bond dissociation energy. In this study, we designed and synthesized (S)-1,2-bis(3-azido-1H-1,2,4-triazol-1-yl)diazene (BAzTD) and 2,9-diazidobis([1,2,4]-triazolo)[1,5-d:5',1'-f][1,2,3,4]tetrazine (DAzTT) through a straightforward reaction. Remarkably, DAzTT demonstrated a high density of 1.816 g·cm-3 (at 298 K) and a considerable thermal decomposition temperature of 216.86 °C. These properties outperform those of previously reported binary heterocyclic CN compounds and polyazido heterocyclic compounds. The quantum-chemical methods further substantiated the integral role of aromaticity as the driving force behind this difference. Additionally, the initiation capability of DAzTT was evaluated by a notably low minimum primary charge (MPC = 40 mg), surpassing conventional organic primary explosives, such as commercial 2-diazo-4,6-dinitrophenol (DDNP, MPC = 70 mg). The exceptional priming ability highlights the potential as an environmentally friendly replacement for toxic lead azide. DAzTT sets a new standard for binary CN compounds and provides a valuable precursor for high-nitrogen carbon nitride materials.

Backbone Isomerization to Enhance Thermal Stability and Decrease Mechanical Sensitivities of 10 Nitro-Substituted Bipyrazoles.

The development of novel, environmentally friendly, and high-energy oxidizers remains interesting and challenging for replacing halogen-containing ammonium perchloride (AP). The trinitromethyl moiety is one of the most promising substituents for designing high-energy density oxidizers. In this study, a backbone isomerization strategy was utilized to manipulate the properties of 10 nitro group-substituted bipyrazoles containing the largest number of nitro groups among the bis-azole backbones so far. Another advanced high-energy density oxidizer, 3,3',5,5'-tetranitro-1,1'-bis(trinitromethyl)-1H,1'H-4,4'-bipyrazole (3), was designed and synthesized. Compared to the isomer 4,4',5,5'-tetranitro-2,2'-bis(trinitromethyl)-2H,2'H-3,3'-bipyrazole (4) (Td = 125 °C), 3 possesses better thermostability (Td = 156 °C), which is close to that of ammonium dinitramide (ADN) (Td = 159 °C), and it possesses better mechanical sensitivity (impact sensitivity (IS) = 13 J and friction sensitivity (FS) = 240 N) than that of 4 (IS = 9 J and FS = 215 N), thereby demonstrating a promising perspective for practical applications.

Polyiodo Azole-Based Metal-Organic Framework Energetic Biocidal Material for Synergetic Sterilization Applications.

Biological hazards caused by bacteria, viruses, and toxins have become a major survival and development issue facing the international community. However, the traditional method of disinfection and sterilization is helpless in dealing with viruses that spread quickly and are highly infectious. Metal-organic framework (MOF) biocidal materials hold promise as superior alternatives to traditional sterilization materials because of their stable framework structures and unique properties. Now, we demonstrate for the first time the synthesis of a MOF (TIBT-Cu) containing Cu metal centers and tetraiodo-4,4'-bi-1,2,4-triazole as the main ligand. This novel MOF biocidal material has good thermal stability (Td = 278 °C), excellent mechanical sensitivity, and a high bacteriostatic efficiency (>99.90%). Additionally, the particles produced by the combustion of TIBT-Cu are composed of active iodine substances and CuO particles, which can act synergistically against harmful microorganisms such as bacteria and viruses. This study provides a new perspective for the preparation of highly effective bactericidal materials.

Enhancing the Photocatalytic Activity of Zirconium-Based Metal-Organic Frameworks Through the Formation of Mixed-Valence Centers.

Despite the desirability of metal-organic frameworks (MOFs) as heterogeneous photocatalysts, current strategies available to enhance the performance of MOF photocatalysts are complicated and expensive. Herein, a simple strategy is presented for improving the activity of MOF photocatalysts by regulating the atomic interface structure of the metal active sites on the MOF. In this study, MOF (PCN-222) is hybridized with cellulose acetate (CA@PCN-222) through an optimized atomic interface strategy, which lowers the average valence state of Zr ions. The electronic metal-support interaction mechanism of CA@PCN-222 is revealed by evaluating the photocatalytic CO2 reduction reaction (CO2 RR). The experimental results suggested that the electron migration efficiency at the atomic interface of the MOFs strongly coupled with cellulose is significantly improved. In particular, the CO2 RR to formate activity of CA@PCN-222 photocatalyst greatly increased from 778.2 to 2816.0 µmol g-1 compared with pristine PCN-222 without cellulose acetate. The findings suggest that the strongly coupled metal-ligand moiety at the atomic interface of MOFs may play a synergistic role in heterogeneous catalysts.

Can Catenated Nitrogen Compounds with Amine-like Structures Become Candidates for High-Energy-Density Compounds?

The worthwhile idea of whether amine-like catenated nitrogen compounds are stable enough to be used as high-energy materials was proposed and answered. Abstracting the NH3 structure into NR3 (R is the substituent) yields a new class of amine-like catenated nitrogen compounds. Most of the azole ring structures have a high nitrogen content and stability. Inspired by this idea, a series of new amine-like catenated nitrogen compounds (A1 to H5) were designed, and their basic energetic properties were calculated. The results showed that (1) amine-like molecular structures are often characterized by low density; however, the density of these compounds increases as the number of nitrogens in the azole ring increases; (2) these catenated nitrogen compounds generally have extremely high enthalpies of formation (882.91-2652.03 kJ/mol), and the detonation velocity of some compounds exceeds 9254.00 m/s; (3) the detonation performance of amine-like catenated nitrogen compounds designed based on imidazole and pyrazole rings is poor due to their low nitrogen content; and (4) the bond dissociation enthalpy of trigger bonds of most compounds is higher than 84 kJ/mol, indicating that these compounds have a certain thermodynamic stability. In summary, amine-like catenated nitrogen compounds have the potential to become energetic compounds with excellent detonation properties and should be considered to be synthesized by experimental chemists.

Regulation of stability and density of energetic materials via isomerism.

Selective regulation of stability and density via isomerism is a promising strategy for developing energetic materials. In this work, we selectively introduced dinitromethyl groups at different positions of 4-nitro-1,2,3-triazole. The regional heterogeneity endows a high crystal density by virtue of the dense packing; on the other hand, it changes the charge distribution in the molecule, and reinforces the hydrogen bonding interactions, all of which stabilize the material. The resulting compounds exhibit excellent detonation properties and impact sensitivity that are comparable to those of HMX (Dv = 9250 m s-1 and IS = 10 J).

Asymmetrical Methylene-Bridge Linked Fully Iodinated Azoles as Energetic Biocidal Materials with Improved Thermal Stability.

The instability and volatility of iodine is high, however, effective iodine biocidal species can be readily stored in iodinated azoles and then be released upon decomposition or detonation. Iodine azoles with high iodine content and high thermal stability are highly desired. In this work, the strategy of methylene bridging with asymmetric structures of 3,4,5-triiodo-1-H-pyrazole (TIP), 2,4,5-triiodo-1H-imidazol (TIM), and tetraiodo-1H-pyrrole (TIPL) are proposed. Two highly stable fully iodinated methylene-bridged azole compounds 3,4,5-triiodo-1-((2,4,5-triiodo-1H-imidazol-1-yl)methyl)-1H-pyrazole (3) and 3,4,5-triiodo-1-((tetraiodo-1H-pyrrol-1-yl)methyl)-1H-pyrazole (4) were obtained with high iodine content and excellent thermal stability (iodine content: 84.27% for compound 3 and 86.48% for compound 4; Td: 3: 285 °C, 4: 260 °C). Furthermore, their composites with high-energy oxidant ammonium perchlorate (AP) were designed. The combustion behavior and thermal decomposition properties of the formulations were tested and evaluated. This work may open a new avenue to develop advanced energetic biocidal materials with well-balanced energetic and biocidal properties and versatile functionality.

Thermal stability of azole-rich energetic compounds: their structure, density, enthalpy of formation and energetic properties.

Energetic compounds, as a type of special material, are widely used in the fields of national defense, aerospace and exploration. Their research and production have received growing attention. Thermal stability is a crucial factor for the safety of energetic materials. Azole-rich energetic compounds have emerged as a research hotspot in recent years owing to their excellent properties. Due to the aromaticity of unsaturated azoles, many azole-rich energetic compounds have significant thermal stability, which is one of the properties that researchers focus on. This review presents a comprehensive summary of the physicochemical and energetic properties of various energetic materials, highlighting the relationship between thermal stability and the structural, physicochemical, and energetic properties of azole-rich energetic compounds. To improve the thermal stability of compounds, five aspects can be considered, including functional group modification, bridging, preparation of energetic salts, energetic metal-organic frameworks (EMOFs) and co-crystals. It was demonstrated that increasing the strength and number of hydrogen bonds of azoles and expanding the π-π stacking area are the key factors to improve thermal stability, which provides a valuable way to develop energetic materials with higher energy and thermal stability.

New technology for preparing energetic materials by nanofiltration membrane (NF): rapid and efficient preparation of high-purity ammonium dinitramide (ADN).

The development of environment-friendly and non-toxic green energetic materials and their safe, environmentally friendly, and economical production is very important to the national economy and national security. As an innovative, efficient, and environmentally friendly energetic material, the preferred preparation method of ammonium dinitramide (ADN) is the nitro-sulfur mixed acid method, which has the advantages of high yield, simple method, and easy access to raw materials. However, the large number of inorganic salt ions introduced by this method limits the large-scale production of ADN. Nanofiltration (NF) has been widely used in various industrial processes as a separation method with high separation efficiency and simple operation. In this study, NF was used for the desalination and purification of ADN synthesized by the mixed acid method. The effects of NF types, operation process (pressure, temperature, and feed solution concentration) on desalination efficiency, and membrane flux during purification were examined. The results showed that 600D NF could achieve the efficient desalination and purification of ADN. It was verified that the highest desalination and purification efficiency was achieved at 2 MPa pressure, 25 °C, and 1 time dilution of the feed solution, and the membrane flux of the desalination and purification process was stable. Under the optimized process conditions, the removal rate of inorganic salts and other impurities reached 99% (which can be recycled), the purity of ADN reached 99.8%, and the recovery rate reached 99%. This process has the potential for the large-scale production of ADN and provides a new process for the safe, efficient, and cheap preparation of energetic materials.

Modulating the Conduction Band of MOFs by Introducing Tiny TiO2 Nanoparticles for Enhanced Photocatalytic Performance: Importance of the Loading Position.

The preparation of TiO2 and metal-organic framework (MOF) into composite photocatalysts has been proven to be a mature and effective strategy to achieve stronger catalytic activity. In this work, we focus on exploring the significant effects and mechanisms of the relative positions of decorated titanium oxide nanoparticles and MOFs on the final catalytic activity. We first used a simple in situ method to encapsulate tiny TiO2 nanoparticles into a Zr-MOF (PCN-222), where Zr-Ti bonds were created at the interface of the two components. Thanks to the strong interfacial interaction forces, band bending occurred in TiO2@PCN-222 and a more negative conduction band (Δ = 0.26 V) with better electron transport properties was obtained. The results of photocatalytic CO2 reduction experiments under visible light showed a 78% increase (142 µmol g-1 h-1) in the production rate of HCOO-. Surprisingly, the loading of TiO2 nanoparticles on the MOF surface (TiO2@PCN-222) resulted in a significant decrease of 56% in the catalyst yield activity due to poor adsorption and electron transfer properties. This work demonstrates the possibility of tuning the band structure and catalytic activity of MOFs with the help of changing the position of the dopant and shows the importance of the rational design of MOF-based composites.

Enhanced Energetic Performance via the Combination of Furoxan and Oxa-[5,5]bicyclic Structures.

Three new compounds based on the combination of furoxan (1,2,5-oxadiazole N-oxide) and oxa-[5,5]bicyclic ring were synthesized. Among them, the nitro compound showed satisfactory detonation properties (Dv, 8565 m s-1; P, 31.9 GPa), which is comparable to the performance of RDX (a classic high-energy secondary explosive). Additionally, the introduction of the N-oxide moiety and oxidation of the amino group more effectively improved the oxygen balance and density (d, 1.81 g cm-3; OB%, +2.8%) of the compounds compared to furazan analogues. Combined with good density and oxygen balance as well as moderate sensitivity, this type of furoxan and oxa-[5,5]bicyclic structure will open up a platform for the synthesis and design of new high-energy materials.