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The exploiting electrocatalysts for water/seawater electrolysis with remarkable activity and outstanding durability at industrial grade current density remains a huge challenge. Herein, CoMoNx and Fe-doped CoMoNx nanosheet arrays are in-situ grown on Ni foam, which possess plentiful holes, multilevel heterostructure, and lavish Co5.47N/MoN@NF and Fe-Co5.47N/MoN@NF interfaces. They require low overpotentials of 213 and 296 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline media to achieve current density of 800 mA cm-2, respectively, and both possess low Tafel slopes (51.1 and 49.1 mV dec-1) and undiminished stability over 80 h. Moreover, the coupled Co5.47N/MoN@NF and Fe-Co5.47N/MoN@NF electrolyzer requires low voltages of 1.735 V to yield 500 mA cm-2 in alkaline water. Notably, they also exhibit exceptional electrocatalytic properties in alkaline seawater (1.833 V@500 mA cm-2). The experimental studies and theoretical calculations verify that Fe doping does reduce the energy barrier from OH* to O* intermediates during OER process after catalyst reconstruction, and the non-metallic N site from MoN exhibits the lowest theoretical overpotential. The splendid catalytic performance is attributed to the optimized local electron configuration and porous structure. This discovery provides a new design method toward low-cost and excellent catalysts for water/seawater splitting to produce hydrogen.
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The construction of yolk-shell composites with dielectric/magnetic multiple loss mechanisms has become a promising strategy to obtain high-efficiency microwave absorbing materials. An ideal microwave absorber should possess dielectric and magnetic loss abilities, thereby leading to the attenuation and absorption of incident electromagnetic radiation. Herein, the yolk-shell structured CoFe2O4@carbon (YS-CoFe2O4@C) and Co3Fe7/FeO@carbon (YS-Co3Fe7/FeO@C) composites were designed and synthesized through a series of processes, which include in-situ coating, heat-treating, etching and subsequent carbonization reduction reaction. The composite materials with specific structure, composition, and electromagnetic parameters could be effectively obtained by controlling the reaction conditions. The combination of alloy with high magnetic loss and carbon with advanced dielectric loss as well as the unique yolk-shell structure endow YS-Co3Fe7/FeO@C improved impendence matching and large attenuation constant. The YS-Co3Fe7/FeO@C composites show optimized microwave absorption behaviors, the minimum reflection loss is up to -57.6 dB at 12.30 GHz with the of 2.5 mm and the corresponding effective absorption bandwidth is 5.27 GHz (10.10-15.37 GHz). Moreover, the widest effective bandwidth could reach 7.0 GHz (11-18 GHz) with the thickness of 2.3 m. This design provides a novel concept for tuning microwave absorption efficiency of magnetic/dielectric composites to prepare high-performance microwave absorbers.
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As an efficient non-precious metal catalyst for the oxygen evolution reaction (OER), phosphides suffer from poor electrical conductivity, so it is still a challenge to reasonably design their structures to further improve their conductivity and OER performances. Here, we present a novel Ni5P4/N-doped carbon@CoFeP/N-doped carbon composite (Ni5P4/NC@CoFeP/NC) as electrocatalysts for OER. This elaborate structure consists of Ni5P4/NC derived from Ni-MOF and CoFeP/NC derived from CoFe-Prussian blue analog MOF (Co-Fe PBA). The cube-like CoFeP/NC are scattered and uniformly coated on the sheet of Ni5P4/NC flowers. Among them, NC can enhance the conductivity of phosphides, while CoFeP/NC can increase the electrochemical active area, which benefit the properties of Ni5P4/NC@CoFeP/NC. Notably, the Ni5P4/NC@CoFeP/NC catalyst possesses outstanding OER performances with a low overpotential of 260 and 303 mV at a current density of 10 and 100 mA·cm-2, an ultra-low Tafel slope of 31.1 mV·dec-1 and excellent stability in 1 M KOH. XPS analysis shows that proper chemical composition promotes the oxidation of transition metal species and the chemisorption of OH-, thus accelerating the OER kinetics. Therefore, this work provides a hopeful method for designing and preparing transition metal phosphide/carbon composite as OER electrocatalysts.
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It is highly challenging to design low-cost, efficient electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, a hierarchical heterostructure was constructed on three-dimensional (3D) Ni foam, which contains Ni3S2 nanorods decorated with both Co9S8 and amorphous MoSx nanosheets and Ni3S2 nanowires decorated with amorphous MoSx nanosheets, namely, MoSx@Co9S8@Ni3S2/NF. The synergistic effects from the strong interactions of the heterointerface and unique hierarchical heterostructure endow the MoSx@Co9S8@Ni3S2/NF with abundant active sites and effective mass and electron transport pathways, resulting in excellent activity toward both HER and OER in 1 M KOH. It only gives a low overpotential of 76.5 mV to achieve 10 mA cm-2 for HER and a low overpotential of 310 mV to achieve 100 mA cm-2 for OER. Based on the superior catalytic activity of MoSx@Co9S8@Ni3S2/NF for OER and HER, we demonstrated the activity of overall water splitting using MoSx@Co9S8@Ni3S2/NF as both the anode and cathode. It shows a higher catalytic activity for overall water splitting with a low cell voltage of 1.52 V at 10 mA cm-2 than commercial Pt/C/NF||IrO2/NF (1.61 V) and superior stability. This work provides a platform for the design and preparation of efficient electrocatalysts with various hierarchical heterostructures.
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Metal-organic-frameworks (MOFs) derived carbon or nitrogen-doped carbon (NC) materials are usually used as electromagnetic wave (EMW) absorbers. However, the effective control of the composition and structure of composites is still a major challenge for the development of high-performance EMW absorbing materials. In this work, core-shell structure and bimetallic composition Cu/nitrogen doped carbon @Co/ nitrogen doped carbon (Cu/NC@Co/NC) composites were designed and synthesized through the thermal decomposition of Cu-MOF@Co-MOF precursor. Cu/NC@Co/NC composites with different compositions were obtained by changing the ratio of Co-MOF and Cu-MOF. The composite (Cu/NC@Co/NC-3.75) prepared using 3.75 mmol of Co(NO3)2·6H2O exhibits outstanding EMW absorption properties due to the optimized impedance matching and strong attenuation ability, which is caused by enhanced interfacial and dipolar polarization as well as multiple reflection and scattering. With the filler loading in paraffin of 35 wt%, the minimum reflection loss (RLmin) is up to -54.13 dB at 9.84 GHz with a thin thickness of 3 mm, and the effective absorption bandwidth (EAB, RL≤ - 10 dB) reaches 5.19 GHz (10.18-15.37 GHz) with the corresponding thickness of 2.5 mm. Compared with the Cu/NC and Co/NC, the Cu/NC@Co/NC-3.75 composite exhibits much better EMW absorbing performances caused by the bimetallic composition and the unique core-shell structure. This work provides a rational design for MOF-derived lightweight and broadband EMW absorbing materials.
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The growth of wafer-scale single-crystal two-dimensional transition metal dichalcogenides (TMDs) on insulating substrates is critically important for a variety of high-end applications1-4. Although the epitaxial growth of wafer-scale graphene and hexagonal boron nitride on metal surfaces has been reported5-8, these techniques are not applicable for growing TMDs on insulating substrates because of substantial differences in growth kinetics. Thus, despite great efforts9-20, the direct growth of wafer-scale single-crystal TMDs on insulating substrates is yet to be realized. Here we report the successful epitaxial growth of two-inch single-crystal WS2 monolayer films on vicinal a-plane sapphire surfaces. In-depth characterizations and theoretical calculations reveal that the epitaxy is driven by a dual-coupling-guided mechanism, where the sapphire plane-WS2 interaction leads to two preferred antiparallel orientations of the WS2 crystal, and sapphire step edge-WS2 interaction breaks the symmetry of the antiparallel orientations. These two interactions result in the unidirectional alignment of nearly all the WS2 islands. The unidirectional alignment and seamless stitching of WS2 islands are illustrated via multiscale characterization techniques; the high quality of WS2 monolayers is further evidenced by a photoluminescent circular helicity of ~55%, comparable to that of exfoliated WS2 flakes. Our findings offer the opportunity to boost the production of wafer-scale single crystals of a broad range of two-dimensional materials on insulators, paving the way to applications in integrated devices.
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A novel pomegranate-like Ni-NSs@MSNSs nanocatalyst was successfully synthesized via a modified Stöber method, and its application in the hydrogenation of dicyclopentadiene (DCPD) was firstly reported. The Ni-NSs@MSNSs possessed a high specific area (658 m2/g) and mesoporous structure (1.7-3.3 nm). The reaction of hydrogenation of DCPD to endo-tetrahydrodicyclopentadiene (endo-THDCPD) was used to evaluate the catalytic performance of the prepared materials. The distinctive pomegranate-like Ni-NSs@MSNSs core-shell nanocomposite exhibited superior catalytic activity (TOF = 106.0 h-1 and STY = 112.7 g·L-1·h-1) and selectivity (98.9%) than conventional Ni-based catalysts (experimental conditions: Ni/DCPD/cyclohexane = 1/100/1000 (w/w), 150 °C, and 2.5 MPa). Moreover, the Ni-NSs@MSNSs nanocatalyst could be rapidly and conveniently recycled by magnetic separation without appreciable loss. The Ni-NSs@MSNSs also exhibited excellent thermal stability (≥750 °C) and good recycling performance (without an activity and selectivity decrease in four runs). The superior application performance of the Ni-NSs@MSNSs nanocatalyst was mainly owing to its unique pomegranate-like structure and core-shell synergistic confinement effect.
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Fluorinated polyurethane (FPU) with a different fluorine content was prepared using perfluoropolyether glycols, poly(propylene glycol), and isophorone diisocyanate as starting materials, and 1,4-butanediol as a chain extender. The structure and molecular weight of FPU were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography. A solution of FPU in xylene and cresol was then coated on copper wires using an enameled machine to prepare enameled wires. The friction coefficient and adhesion performance of the enameled wires were tested. The friction coefficient of the as-prepared enameled wires reached 0.095, which was much lower than 0.149 of the polyurethane without fluorine. FPU-based enameled wires also showed good mechanical performances and increased breakdown voltages. In addition, FPU exhibited good hydrophobic and oleophobic characterization.
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Surface-active heteropolyacid-based ionic liquids with varying alkyl carbon chains were synthesized, which were subsequently analyzed. The desulfurization of fuels was investigated utilizing various surface-active heteropolyacid-based ionic liquids, and acetonitrile was used as the extractant for the coupling of ODS and EDS. The influences of the alkyl group, surface activity, and hydrophobicity of ionic liquids on sulfur removal were studied. The results suggested that the ionic liquids were stable. Among these ionic liquids, [C4ImBS]3[PW12O40] exhibited the best catalytic performance. Using [C4ImBS]3[PW12O40] as the catalyst, the influences of the catalyst amount, aqueous hydrogen peroxide amount, and reaction temperature on the sulfur removal were explored. Under the optimum conditions, the sulfur removal could achieve 100% efficiency. The recycle experiments also proved that the ionic liquid could be reused.
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Transition-metal compounds/carbon hybrids with high electrocatalytic capability possess attractive potential as a counter electrode (CE) for dye-sensitized solar cells (DSSCs). However, the simple structure and agglomeration always result in poor performance. Herein, cobalt selenides confined in hollow N-doped porous carbon interconnected by carbon nanotubes (CNTs) with cobalt selenides encapsulated inside (denoted as CoSe@NPC/CoSe@CNTs) are formed through in situ pyrolysis and selenization process. In this strategy, ZIF-67 is used as the precursor, structure inducer, and carbon source for the orientated growth of CNTs. Such a rational architecture provides a stable interconnected conductive network and a hierarchically porous structure, with more available active sites and a shortened pathway for charge transport, synergistically enhancing the electrocatalytic activity. Specifically, the DSSCs based on CoSe@NPC/CoSe@CNTs demonstrate a high efficiency of 7.36%, even superior to that of Pt (7.16%). Furthermore, the CoSe@NPC/CoSe@CNT CE also demonstrates a good long-term stability in the iodine-based electrolyte.
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A novel ionic liquid immobilized on a magnetic polymer microsphere catalyst is reported in this paper. The obtained core-shell-shell catalyst consisted of magnetic nanoparticles (MNPs) as the core, catalytic inert St-co-DVB as the intermediate protective layer, and cross-linked polyaryl imidazole ionic liquids as the active catalytic layer located at the outermost [Im[OH]/MNPs@P(St-DVB)@P(VBC-DVB)]. This catalyst exhibited a high ion-exchange rate (64.65%), high saturation magnetic strength, and excellent acid and alkali corrosion resistance. In the catalyzed Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate, the conversion of benzaldehyde maintained at 92.1% during six times reuse. Optimizing the materials of the protective layer and regulating the thickness of the inert protective layer decreased the corrosion ratio of MNPs in acidic media from 44.82 to 0.44%. Adjusting the thickness of the catalytic layer realized excellent catalytic activity (97%) and high magnetic response performance. In summary, introducing an inert protective layer to the structure of ionic liquids immobilized on the magnetic polymer microsphere catalyst, regulating its thickness, and optimizing its structure achieved a catalyst with high activity, excellent stability, and easy magnetic separation.
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The design and development of low-cost, highly efficient, and stable electrocatalysts to take the place of noble-metal catalysts for the oxygen evolution reaction (OER) remain a significant challenge. Herein, the synthesis of yolk-shell-structured binary transition metal phosphide Cox Fe1-x P with different Co/Fe ratios by phosphidation of a cobalt ferrite precursor is reported. The as-synthesized Cox Fe1-x P catalysts were used for the OER. All yolk-shell Cox Fe1-x P catalysts with different Co/Fe ratios showed much better performance than the corresponding solid catalyst. The formation of Co oxides on the catalyst surface during OER and the optimal Co/Fe ratio were found to be critical to their activity. Among the as-prepared Cox Fe1-x P catalysts, that with a Co/Fe ratio of 0.47/0.53 (Co0.47 Fe0.53 P) exhibited the best performance. Co0.47 Fe0.53 P has an overpotential of 277â mV at a current density of 10â mA cm-2 , a Tafel slope of 37â mV dec-1 , and superior stability in alkaline medium. The outstanding performance is partly ascribed to the transfer of valence electrons from Co to P and Fe. The Co0.47 Fe0.53 P matrix with excellent conductivity and Fe phosphate that is stable on the surface of the catalyst are also helpful for the OER performance. In addition, the yolk-shell structure of Co0.47 Fe0.53 P increases the contact area between electrolyte and catalyst. These characteristics of Co0.47 Fe0.53 P greatly improve its OER performance. This optimized binary transition metal phosphide provides a new approach for the design of nonprecious-metal electrocatalysts.
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Quantitatively mapping and monitoring the strain distribution in 2D materials is essential for their physical understanding and function engineering. Optical characterization methods are always appealing due to unique noninvasion and high-throughput advantages. However, all currently available optical spectroscopic techniques have application limitation, e.g., photoluminescence spectroscopy is for direct-bandgap semiconducting materials, Raman spectroscopy is for ones with Raman-active and strain-sensitive phonon modes, and second-harmonic generation spectroscopy is only for noncentrosymmetric ones. Here, a universal methodology to measure the full strain tensor in any 2D crystalline material by polarization-dependent third-harmonic generation is reported. This technique utilizes the third-order nonlinear optical response being a universal property in 2D crystals and the nonlinear susceptibility has a one-to-one correspondence to strain tensor via a photoelastic tensor. The photoelastic tensor of both a noncentrosymmetric D3h WS2 monolayer and a centrosymmetric D3d WS2 bilayer is successfully determined, and the strain tensor distribution in homogenously strained and randomly strained monolayer WS2 is further mapped. In addition, an atlas of photoelastic tensors to monitor the strain distribution in 2D materials belonging to all 32 crystallographic point groups is provided. This universal characterization on strain tensor should facilitate new functionality designs and accelerate device applications in 2D-materials-based electronic, optoelectronic, and photovoltaic devices.
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Developing lightweight and broadband microwave absorbers for dealing with serious electromagnetic radiation pollution is a great challenge. Here, a novel Fe-Co/N-doped carbon/reduced graphene oxide (Fe-Co/NC/rGO) composite with hierarchically porous structure was designed and synthetized by in situ growth of Fe-doped Co-based metal organic frameworks (Co-MOF) on the sheets of porous cocoon-like rGO followed by calcination. The Fe-Co/NC composites are homogeneously distributed on the sheets of porous rGO. The Fe-Co/NC/rGO composite with multiple components (Fe/Co/NC/rGO) causes magnetic loss, dielectric loss, resistance loss, interfacial polarization, and good impedance matching. The hierarchically porous structure of the Fe-Co/NC/rGO enhances the multiple reflections and scattering of microwaves. Compared with the Co/NC and Fe-Co/NC, the hierarchically porous Fe-Co/NC/rGO composite exhibits much better microwave absorption performances due to the rational composition and porous structural design. Its minimum reflection loss (RLmin) reaches - 43.26 dB at 11.28 GHz with a thickness of 2.5 mm, and the effective absorption frequency (RL ≤ - 10 dB) is up to 9.12 GHz (8.88-18 GHz) with the same thickness of 2.5 mm. Moreover, the widest effective bandwidth of 9.29 GHz occurs at a thickness of 2.63 mm. This work provides a lightweight and broadband microwave absorbing material while offering a new idea to design excellent microwave absorbers with multicomponent and hierarchically porous structures.
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A novel porous cocoon-like reduced graphene oxide (rGO) with high porosity and low density was fabricated by a simple and green reduction reaction using ascorbic acid as the reductant in combination with a freeze-drying process without annealing. The bulk density of porous cocoon-like rGO is only 28.49 mg/cm3, and the porosity reaches 94.57%. The reaction times have an important influence on the formation of porous cocoon-like rGO and the reduction degree of rGO. The porous cocoon-like rGO exhibits an excellent microwave-absorbing property with a low mass filling ratio of 7.0 wt %; its minimum reflection loss (RL) is -29.05 dB at 15.96 GHz with a sample thickness of 2.0 mm and the effective absorption bandwidth (RL < -10 dB) is 5.27 GHz. The microwave-absorbing property of porous cocoon-like rGO is much better than that of GO and other porous rGO. The in-depth analyses of the reduction degree, porosity, and microwave-absorbing performance illustrate that the microwave-absorbing performance of rGO is significantly related to the reduction degree and porosity. In addition, the synthetic route for porous cocoon-like rGO is simple, has low energy consumption, and is environmentally friendly. Our work demonstrates that the porous cocoon-like rGO is a promising lightweight microwave absorber with high performance.
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The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are considered to be cornerstones of many energy conversion and storage technologies. It is difficult studying high-performance nonprecious materials as cost-effective bifunctional electrocatalysts for both the OER and ORR in future practical applications. In this study, NiCo2S4 hollow spheres (NiCo2S4 HSs) were fabricated via an effective and facile one-pot "green" approach in an N, N-dimethylformamide-ethylene glycol binary solution. The obtained NiCo2S4 HSs had a high specific surface area as well as numerous active sites and showed a remarkable catalytic performance and durability toward both the OER and ORR in an alkaline electrolyte. For the ORR, NiCo2S4 HSs exhibited a positive half-wave potential of 0.80 V and demonstrated outstanding stability and enhanced methanol tolerance. For the OER, NiCo2S4 HSs presented a low overpotential (400 mV) at a current density of 10 mA cm-2, small Tafel slope, and excellent stability in 0.1 M KOH. Moreover, regarding the overall electrocatalytic activity, the potential difference of NiCo2S4 HSs was 0.83 V, surpassing that of NiCo2S4 nanoparticles, binary counterparts (CoS, NiS), and most highly active bifunctional catalysts described in the literature. The superior catalytic performance of NiCo2S4 HSs is mainly ascribed to its unique hollow structure, which increases molecular diffusion and adsorption, as well as the synergistic effect of Ni and Co, which offers richer redox reaction sites. Importantly, this strategy may facilitate the design and preparation of excellent bifunctional nonprecious metal electrocatalysts in various domains.
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In the present work, a cell environment which mimicked the real body environment according to the concentration radio between serum albumin and hemoglobin was built, and the cell morphology, the membrane deformation capacity, and the structure of intracellular hemoglobin of single human living erythrocyte under the effect of pH and serum albumin were studied. It was found that at different suspension pH, the magnitude of variations in cell shape and membrane deformation capacity changes with the structural changes of the intracellular hemoglobin. At pH 4. 14, 4. 76 and 10. 18, the loss of helical structure for hemoglobin, exposing of the hydrophobic amino acid in the globin chains, and changing of the combination of heme and globin, would completely destroy the stability of hemoglobin's structure, which seriously changes RBC's morphology and membrane deformation capacity. While at pH 6. 51 and 7. 80, the Raman spectra of erythrocytes are found to have no such changes, indicating that the structure of intracellular hemoglobin was not varied, thus the cell morphology and membrane deformation capacity are quite close to the normal values. At pH 5. 49 and 8. 76, RBC's morphology and membrane deformation capacity have different degrees of variation, but the structure of intracellular hemoglobin has not changed, suggesting that the cell morphology and membrane deformation capacity may be reversible. The results suggest that in the suspension solution containing serum albumin, erythrocytes have better ability to regulate and control the variation of the extracellular pH. In summary, upon building an environment which contains the same concentration radio of serum albumin to hemoglobin in the blood, this work performed systematic studies on the effect of pH on human erythrocytes. It can not only help to solve the problems about the mechanism of the structural and functional changes of erythrocytes induced by environmental pH, but also elucidates the possible variation of the erythrocyte under different pathologic states. It is therefore significant for the prevention and treatment of some diseases.
Asunto(s)
Eritrocitos/citología , Albúmina Sérica , Forma de la Célula , Hemoglobinas , Humanos , Concentración de Iones de Hidrógeno , Análisis de la Célula Individual , Espectrometría RamanRESUMEN
The hollow Co(3)O(4) microspheres were prepared by a gas-liquid diffusion reaction in the presence of ionic liquid [Bmim][BF(4)] in combination with calcination at 300 °C. Their structures and morphologies were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectrometry, and X-ray photoelectron spectroscopy. The growth mechanism of hollow Co(3)O(4) microspheres was proposed. The ethanol sensing properties were measured using a WS-30A gas sensor measurement system. The influence of working temperatures, ethanol concentrations, and specific surface areas of Co(3)O(4) microspheres on the ethanol sensing properties was investigated. The hollow Co(3)O(4) microspheres showed excellent sensitivity to ethanol vapor at a lower operating temperature.
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Pentanitromonoformylhexaazaisowurtzitane (PNMFIW) was synthesized by the nitrolysis of tetraacetyldiformylhexaazaisowurtzitane (TADFIW) in mixed nitric and sulfuric acids and structurally characterized by element analysis, FT-IR, MS and (1)H NMR. Single crystals of PNMFIW were grown from aqueous solution employing the technique of controlled evaporation. PNMFIW belongs to the orthorhombic system having four molecules in the unit cell, with space group P2(1)2(1)2(1) and the lattice parameters a=8.8000(18)A, b=12.534(2)A, and c=12.829(3)A. The calculated density reaches 1.977 g/cm(3) at 93 K, while the experimental density is 1.946 g/cm(3) at 20 degrees C. The calculated detonation velocity and pressure of PNMFIW according to the experimental density are 9195.76 m/s and 39.68G Pa, respectively. PNMFIW is insensitive compared with epsilon-HNIW through drop hammer impact sensitivity test.