RSC Advances
·
2022
·Vol. 12
·期 13
·7712-7719
·
IF 4.036
Qi Xue,Fuqiang Bi,Yifen Luo,Jiarong Zhang,Kaidi Yang,Bozhou Wang,Ganglin Xue
Two energetic bicyclic scaffolds (furazan–isoxazole and furazan–1,3,4-oxadiazole) were constructed via different cyclization reactions. Based on the energetic bicyclic scaffolds, the energetic compounds, 3-(4-nitraminofurazan-3-ly)-isoxazole-5-methylnitrate 1c and 5-(4-nitraminofurazan-3-ly)-1,3,4-oxadiazole-2-methylnitrate 2c, were designed and synthesized in good yields. Because of the acidity of nitramine, the corresponding energetic ionic salts, ammonium 3-(4-nitraminofurazan-3-ly)isoxazole-5-methylnitrate 1d and ammonium 5-(4-nitraminofurazan-3-ly)-1,3,4-oxadiazole-2-methylnitrate 2e, were also obtained and well characterized, their structures were further determined by X-ray single crystal diffraction. To have a better understanding of the structure–property relationships of furazan-bicyclic scaffolds and nitrate groups, their thermal behaviors, detonation performances and the sensitivities were investigated via differential scanning calorimetry (DSC), ESP analysis, Hirshfeld surfaces calculation, EXPLO5 program and BAM standard techniques. Compared with those of ammonium 5-(4-nitraminofurazan-3-ly)-1,2,4-oxadiazole-2-methylnitrate 3e, the results show that all these methyl nitrate energetic compounds based on bicyclic scaffolds of furazan–isofurazan exhibit good detonation performances and extraordinary insensitivities. As supported by experimental and theoretical data, the formation of energetic ionic salts causes an increase of the weak interactions, significantly improving the thermal performance over 110 °C.
研究领域:
化学
·
材料科学
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DOI
PubMed
高影响因子
CATALYSIS LETTERS
·
2025
·Vol. 155
·期 8
·1-7
·
IF 2.4
He Huichao,Fu Xiaoxue,Guo Yujie,Ke Gaili
Since the traditional approaches for 3,3’-diamino-4,4’-azofurazan (DAAF) synthesis are not environment-friendly and economical enough, the development of green and low-cost approaches for the synthesis of DAAF is valuable and significant. Herein, the electrochemical synthesis of DAAF from the oxidation of 3 4-diaminofurazan (DAF) was studied in different electrode and electrolyte systems. It was found that the pH of alkaline aqueous electrolyte, the solvent of electrolyte and electrode play important role in DAF oxidation into DAAF. In an electrochemical cell with graphite sheet anode, Pt wire cathode and DAF/ n Bu 4 NBF 4 /acetonitrile electrolyte, the optimal DAAF yield of 63% and faradic efficiency above 60% (at 1.80 V vs. Ag/AgCl) were achieved. Mechanism investigations revealed that the electrochemical synthesis of DAAF in such an electrochemical cell is originated from the direct oxidation of DAF on graphite anode, not involving radical pathway. Graphical
研究领域:
电化学
·
有机合成
·
绿色化学
·
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2019
·Vol. 48
·期 39
·14705-14711
·
IF 4.052
Hualin Xiong,Hongwei Yang,Caijin Lei,Pengjiu Yang,Wei Hu,Guangbin Cheng
Several energetic materials, which are composed of furoxan and 1,2,4-oxadiazole backbones, were synthesized by nitrating 3,3′-bis(5-amino-1,2,4-oxadiazol-3-yl)-4,4′-azofuroxan (2) under 100 wt% HNO3 or 100 wt% HNO3/Ac2O followed by a cation metathesis. All synthesized compounds were fully characterized by multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis, while 3,3′-bis(1,2,4-oxadiazol-5(4H)-one-3-yl)-4,4′-azofuroxan (3) and diammonium 3,3′-bis(5-nitramino-1,2,4-oxadiazole-3-yl)-4,4′-azofuroxan (4a) were confirmed by single crystal X-ray diffraction. The physicochemical and energetic properties of these compounds including density, thermal stability and sensitivity were investigated. Compounds 3 and 4 have high densities (3: 1.90 g cm−3, 4: 1.92 g cm−3), which are comparable to that of HMX (1.91 g cm−3). All energetic compounds show relatively high calculated heat of formation in the range from 504.79 kJ mol−1 to 1405.62 kJ mol−1. Their detonation properties were evaluated by EXPLO5 code using the measured density and calculated heat of formation. Among them, compounds 3 and 4 have good detonation performance (3: D = 8891 m s−1, P = 34.7 GPa, 4: D = 9505 m s−1, P = 41.3 GPa) and acceptable sensitivities (3: IS = 10 J, 4: IS = 4 J), which indicate their potential applications as high-performance energetic materials.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FirePhysChem
·
2021
·
IF 0
Qi Xue,Fuqiang Bi,Junlin Zhang,Jiarong Zhang,Bozhou Wang,Minjie Wu
Two novel energetic compounds, 3-nitroxymethyl-5-(4-nitro-furazan-3-yl)-1,2,4-oxadiazole ( 4 ) and 3-nitroxymethyl-5-(4-azido-furazan-3-yl)-1,2,4-oxadiazole ( 5 ), were synthesized. Both of them were fully characterized, and the structure of 4 was further confirmed by X-ray single crystal diffraction. The thermal behaviors, detonation performances and the sensitivities of 4 and 5 were also investigated by differential scanning calorimetry (DSC), EXPLO5 program and BAM standard techniques. In addition, the electrostatic potential energy surface (ESP) was studied by Multiwfn program and density functional theory at B3LPY/6-31G (d, p). Both compounds have low melt-point, good energetic performance and mechanical sensitivity, which endow them with promising properties as plasticizing ingredients in propellant formulations.
研究领域:
有机化学
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含能材料
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晶体结构
·
热分析
✓ 已验证
DOI
CHEMICAL ENGINEERING JOURNAL
·
2014
·
IF 4.058
Deyong Kong,Bin Liang,Hui Yun,Jincai Ma,Zhiling Li,Aijie Wang,Nanqi Ren
Antibiotics existing in wastewaters must be degraded to eliminate its antibacterial activity before discharging into the environment. Electrochemical reduction by continuous electrons supply can degrade various refractory pollutants, however, the information about the feasibility and characterization of the cathodic degradation of nitrofurans antibiotic furazolidone (FZD) is scarce. Here, we investigated the degradation of FZD using a poised cathode electrochemical reactor. The cyclic voltammetry (CV) preliminarily proved the feasibility of FZD degradation on cathode. In contrast to the different buffer solutions concentrations, buffer types, and initial FZD concentrations which only had obvious impact on the FZD degradation efficiency, different cathode potentials had significant effects both on the FZD degradation efficiency and degradation products composition. Catholyte PBS could be replaced by Na 2 CO 3 –NaHCO 3 and NaCl buffer solution for the FZD degradation. The cathodic degradation pathway of FZD was proposed based on intermediate products analysis. When the cathode potential was lower than −0.75 V, both the furan ring and oxazole ring of FZD were destroyed to generate linear chain products after N–N bond disconnection, suggesting that the high toxic biological metabolite of FZD, 3-amino-2-oxazolidinone (AOZ) could be detoxified by cathodic degradation. This study suggests that the electrochemical reduction could serve as a potential strategy for the treatment of FZD and AOZ containing wastewater.
研究领域:
环境科学
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微生物学
·
毒理学
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产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2019
·Vol. 21
·期 41
·6136-6144
·
IF 3.382
Han Gao,Xiaolu Yao,Ming Huang,Jialin Cai,Zhirong Suo,Guan Luo
In this study, a self-assembled spherical shell and porous spherical structures of 3,3′-diamino-4,4′-azoxyfurazan (DAAF) were fabricated by a simple surfactant-induced and a solvent-induced method, respectively. Scanning electron microscopy (SEM) was employed to characterize their morphology. The results of X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy indicated that the crystal and molecular structures of both products remained unchanged when compared with the case of raw DAAF. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to characterize the thermal behavior of the as-prepared crystals, and the related thermodynamic parameters were calculated. Finally, the self-assembly mechanism has been discussed.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2022
·
IF 4.01
Qamar-un-Nisa Tariq,Yu-fan Bi,Saira Manzoor,Maher-un-Nisa Tariq,Wen-Li Cao,Wen-Shuai Dong,Jian-Guo Zhang
Due to the acidity and the limited applications of 3,4-dinitropyrazole (DNP), two types of nitrogen-rich energetic cocrystals (DD1 and DD2) based on DNP and 3,4-diaminofurazan (DAF) were synthesized. The magnificently grown cocrystals were thoroughly examined by Fourier transform infrared spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, elemental analysis, and nuclear magnetic resonance. A differential scanning calorimetry analysis revealed that both cocrystals have different endothermic peaks and remarkably similar exothermic peaks. Moreover, thermogravimetric analysis demonstrates that the thermal decomposition of DD1 and DD2 seems to be three mass loss stages. Hirshfeld surface analysis suggests that O···H (hydrogen bonding) close contacts contribute the most to the stabilization of DD1 and DD2. Subsequently, the pH values of DD1 and DD2 indicate that cocrystals reduce the acidity of DNP; additionally, the inclusion of hydrogen peroxide can improve the oxygen balance of the cocrystal to a certain degree. The obtained cocrystals have high nitrogen contents and acceptable sensitivities to external stimuli (friction and impact) that prove them as promising candidates for expanding the applications of DNP in the field of energetic materials after overcoming an acidity problem.
研究领域:
化学
·
材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF COORDINATION CHEMISTRY
·
2018
·
IF 1.703
Zi-Mei Ding,Wen-Li Cao,Xiao-Jing Hang,Xiao Ma,Hui Zheng,Kang-Zhen Xu,Jie Huang
The green nitrogen-rich coordination compound Cd(SCZ)2(AFT)2 (1) (AFT =4-amino-3-(5-tetrazolate)-furazan and SCZ = semicarbazide) was first synthesized and characterized by EA and Fourier Transform Infrared (FT-IR). The single crystal was cultivated and determined with X-ray diffraction. It revealed that 1 crystallizes in the monoclinic space group P21/c. A Cd2+ ion is coordinated by four N atoms and two O atoms to form a distorted octahedral structure. Among them, two nitrogen atoms are from the two AFT ions and the other four atoms are from two SCZ molecules. The thermal decomposition behavior of 1 was studied with DSC and TG-DTG methods. The apparent activation energy (E), thermal stability, and safety parameters (T
SADT, T
TIT, and T
b) were calculated for 1. Moreover, entropy of activation (ΔS
≠), enthalpy of activation (ΔH
≠), free energy of activation (ΔG
≠), specific heat capacity (C
p), and impact sensitivity were also discussed in detail.
研究领域:
化学
·
材料科学
✓ 已验证
DOI
高影响因子
Reaction Chemistry & Engineering
·
2023
·Vol. 8
·期 8
·1993-2000
·
IF 3.9
Shichun Weng,Wei Feng,Wenqian Wu,Zichao Guo,Junjie Li,Huanhuan Chen,Liping Chen,Wanghua Chen
3-Amino-4-amidoximinofurazan (AAOF) is an important precursor for the synthesis of high energy furazan energetic materials. The traditional batchwise synthesis approach has the shortcomings of low productivity and high possibility of thermal runaway. This article aims to develop a continuous-flow and safe synthesis approach for AAOF. To achieve this goal, the precipitation problems appearing in the oximation and cyclization reaction stages have been first tackled by diluting the hydroxylamine hydrochloride and sodium hydroxide solution with water, which also reduced the thermal risk of AAOF synthesis. The continuous-flow platform for AAOF synthesis has been established, and the continuous-flow operation parameters have been optimized. The optimal temperatures for the nitrosation–rearrangement coupling reaction, neutralization reaction, oximation and cyclization were 15 °C, 15 °C, 25 °C and 115 °C, respectively. The optimal set retention times for these four stages were 15 min, 5 min, 60 min and 10 min, respectively. The continuous-flow synthesis approach offered an optimal yield of AAOF (95%), which is comparable to the result of batch operation. The total flow rate of the whole process is 10.34 mL min−1, and the final productivity is calculated to be about 0.546 mol h−1 of AAOF. The main merits for the continuous-flow synthesis of AAOF include the following: (1) the reaction time is only one-third of that for batch operation and (2) continuous-flow operation is inherently safe due to the lower liquid holdup and stronger temperature control ability. This work is supposed to be beneficial to the continuous and safe synthesis of AAOF.
研究领域:
化学工程
·
能源材料科学
✓ 已验证
产品关联
DOI
高影响因子
ORGANIC PROCESS RESEARCH & DEVELOPMENT
·
2023
·
IF 3.4
Junjie Li,Wei Feng,Shichun Weng,Zichao Guo,Wanghua Chen
3,4-bis(4-Aminofurazano-3-yl) furoxan (DATF) is a key precursor for the high-energy explosive 3,4-bis(4-nitrofurazano-3-yl) furoxan (DNTF), and it is also a high-nitrogen content energetic material. In this paper, the synthesis process of DATF was characterized using the HPLC technique, and the effects of four reaction parameters have been thoroughly studied. The thermal risk analysis for DATF synthesis was conducted with a reaction calorimeter (RC1) and an accelerating rate calorimeter. It was found that extracting the intermediate 3-amino-4-oxycyanofurazan from the aqueous to organic phases was an important way to improve the yield of DATF. Therefore, hydrophobic ethyl acetate was selected as one reaction solvent. The higher yield of DTAF obtained was about 60%. In addition, HPLC monitoring and reaction calorimetry results indicated that the rate of diazotization and decomposition of diazonium salt was feeding-controlled, and the cycloaddition reaction was a slow process. Most of the reaction heat has been released by the diazotization and decomposition of diazonium salt, while the heat effect of cycloaddition was not significant. Thermal stability analysis supported the conclusion that the decomposition of the reaction mixture was hardly possible to be triggered by the reaction heat. The thermal risk of DATF synthesis was low.
研究领域:
化学工程
·
安全科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER RESEARCH
·
2024
·Vol. 31
·期 7
·1-11
·
IF 2.6
Zhang Jingxuan,Huang Yeming,Wang Xin,Wang Dunju
3,4-Dinitrofurazanfuroxan (DNTF) is widely used in fusion-cast-based explosive carriers owing to its low melting point, high energy, and excellent stability. To reduce the susceptibility of DNTF and improve the thermal properties, core–shell composites (DNTF@PDA@HTPB) were synthesized using the oxidative self-polymerization reaction of dopamine. The results showed that hydroxyl-terminated polybutadiene (HTPB) was tightly coated on the surface of DNTF@PDA crystals, and the crystal structure of the high-energy crystals did not experience any significant changes during the encapsulation process. Compared with the raw DNTF, the thermal decomposition of DNTF in the DNTF@PDA and DNTF@PDA are delayed by 13.3℃ and 17.1℃, respectively. This phenomenon indicates that the thermal stability of DNTF@PDA and DNTF@PDA@HTPB composites is improved. The ignition speed of DNTF@PDA@HTPB is faster, and the flame activity is more vigorous. Meanwhile, the friction susceptibility of DNTF@PDA@HTPB is reduced by 44% compared to DNTF, and the impact susceptibility is significantly reduced by 75%. This study provides a new idea to improve fused-cast explosives' structure and combustion performance.
研究领域:
材料科学
·
爆炸物化学
✓ 已验证
产品关联
DOI
高影响因子
MICROCHEMICAL JOURNAL
·
2021
·
IF 4.821
Jian-Bo Chen,Xueyan Zhao,Zhenqi Zhang,Ya Chen,Xiaolin Fu,Yu Liu
Recently, 3,3-diamino-4,4-azoxyfurazan (DAAF) as one of most promising energetic furazan compounds has been widely studied because of its excellent explosive performances. Nowadays, the Oxone oxidation method is regarded as a main pathway to synthesize DAAF. However, several unknown impurities are yielded when the Oxone method is used to prepare DAAF. The identification of DAAF’s impurities is beneficial to optimize synthetic route of DAAF and then improve its purity. In this study, chemical structures of DAAF and its main impurities were analyzed by developing an unknown analysis workflow based on ultrahigh-performance liquid chromatography-tandem diode array detector -tandem high resolution mass spectrometry (UHPLC-DAD-HRMS). They were fully separated by UHPLC after the optimization of chromatographic conditions. HRMS based on a Q-Orbitrap system was performed to elucidate chemical structure of the impurities by determining exact mass of the impurities and their MS/MS fragments. Besides DAAF, eight unknown impurities were detected under negative ion mode ([M-H] - ) of HRMS with a heated electrospray ionization. Comprehensive analysis of UHPLC-DAD-HRMS provided more information including the retention time, UV–Vis spectrum, elementary composition and MS/MS fragments, and then possible structures of the impurities were proposed in this work. Further, the ion at m / z 211.0328, impurity I and impurity V were confirmed to be DAAF, DAF and DAAzF, respectively, through 1 H NMR and 13 C NMR after synthesizing their reference materials. In addition, the source of these impurities during the synthesis of DAAF has been analyzed. The impurities were originated from the precursor, the intermediate and byproduct of preparing DAAF through the hydrazine, the isomerism and the nitrosation.
研究领域:
化学
·
材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）