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.

Crossed Andreev reflection in normal-superconductor-normal junction based on Kekulé-Y patterned graphene.

We theoretically study the crossed Andreev reflection (CAR) of the normal metal-superconductor-normal metal (NSN) heterojunction based on Kekulé-Y patterned graphene with two doping types, i.e.nSnandnSpconfigurations. It is found that the enhanced CAR is more likely to occur in thenSpjunction rather than thenSnjunction. To be concrete, the almost perfect CAR occurs in a large range of incident angle in the single Dirac cone phase when the incident energy is inside the gap of the nonlinear band. Furthermore, the roles of the length of superconductor and pseudospin-valley coupling on conductance are also evaluated.

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.

Novel phosphate functionalized sodium alginate hydrogel for efficient adsorption and separation of Nd and Dy from Co.

The recovery of rare earth elements (REEs) including neodymium (Nd) and dysprosium (Dy) from NdFeB permanent magnets has become one of the main ways to solve the increased demand for rare earth. Herein, n-dodecyl phosphate (DPPA) was used for the first time as the adsorption functional group donor, sodium alginate as the substrate, and calcium chloride solution as the reactive solvent, a hybrid hydrogel adsorbent DPPA/CaALG was synthesized by sol-gel method for application in the adsorption and separation of Nd and Dy from the Co-Nd-Dy ternary system. SEM-EDS, and N2 adsorption-desorption analysis showed the successful preparation of DDPA/CaALG with mesoporous structure. Batch experiments showed the superiority of the hybrid hydrogel for the good selective adsorption of Nd and Dy, such as large adsorption capacity (Nd: 162.5 mg/g, Dy: 183.5 mg/g), and no adsorption for Co. FT-IR, XPS showed that PO and P-O groups are involved in the adsorption process of Nd and Dy as electron acceptors, where the ion exchange of P-OH is dominant. Furthermore, the chemical properties of ligands and complexes were analyzed by Density Functional Theory (DFT) calculations and revealed their adsorption behaviors as well as the competition between different metal ions.

Photocatalytic CO2 reduction of 2D/0D CoAl-LDH@Cu2O catalyst with p-n heterojunction.

Layered double hydroxides (LDHs) are widely used in catalytic field, especially in photocatalysis, benefiting from the ultrathin 2D structure and luxuriant surface functional groups. However, the wide band gap and low utilization rate of solar spectrum affect their photocatalytic performance. Herein, we integrated n-type CoAl-LDH with p-type Cu2O nanoparticles to construct a p-n heterojunction with a strong built-in electric field, which can prevent photoinduced electron-hole pairs from recombination as well as facilitate charge transfer. With the X-ray photoelectron spectroscope and in situ Fourier transform infrared spectroscopy, we confirmed the charge transfer under light illumination complying with the type II-scheme mechanism and analyzed the intermediates during photocatalytic CO2 reduction reaction (CO2RR). The highest yields reached 320.9 µmol h-1 g-1 for CoAl-LDH@Cu2O-60 (LC-60) under 1 h light irradiation, which was about 1.6 times than the pristine CoAl-LDH. The sample also exhibited excellent stability which maintained 84.1% of initial performance after 4 circulations.

Effects of elevated carbon dioxide on plant growth and leaf photosynthesis of annual ryegrass along a phosphorus deficiency gradient.

Introduction: Soil phosphorus (P) deficiency limits plant growth and productivity in grassland ecosystems and may moderate the growth-promoting effects of "carbon dioxide (CO2) fertilization effect". Methods: To evaluate the interactive effects of these two factors on the growth and physiology for annual ryegrass (Lolium multiflorum Lam.), plants were grown in controlled growth chambers with a range of P supply (0.004, 0.012, 0.02, 0.06, 0.1 and 0.5 mM) under two levels of CO2 (400 and 800 µmol mol-1, respectively). Results: Elevated [CO2] dramatically increased the aboveground biomass and net photosynthetic rates of annual ryegrass by 14.5% and 25.3% under sufficient P supply (0.5 mM), respectively, whereas decreased the belowground biomass and net photosynthetic rates under lower P supply of P0.004, P0.02, and P0.06. Two-way ANOVA results showed that CO2 × P (p < 0.001) significantly affected stomatal traits, leaf photosynthesis and biomass. The stimulation of growth and photosynthesis by elevated CO2 concentration (e[CO2]) was reduced or highly suppressed, indicating that the sensitivity of annual ryegrass to P deficiency was enhanced under e[CO2]. Discussion: These results indicated that P limitation may offset the positive effects of e[CO2] on plant growth by altering stomatal traits, leaf photochemical processes and biochemical composition in annual ryegrass.

The organism fate of inland freshwater system under micro-/nano-plastic pollution: A review of past decade.

Micro- and nano-plastics (MPs/NPs) are characterized by their small size and extensive surface area, making them global environmental pollutants with adverse effects on organisms at various levels, including organs, cells, and molecules. Freshwater organisms, such as microalgae, emerging plants, zooplankton, benthic species, and fish, experience varying impacts from MPs/NPs, which are prevalent in both terrestrial and aquatic inland environments. MPs/NPs significantly impact plant physiological processes, including photosynthesis, antioxidant response, energy metabolism, and nitrogen removal. Extended exposure and ingestion to MPs/NPs might cause metabolic and behavioral deviations in zooplankton, posing an extinction risk. Upon exposure to MPs/NPs, both benthic organisms and fish display behavioral and metabolic disturbances, due to oxidative stress, neural toxicity, intestinal damage, and metabolic changes. Results from laboratory and field investigations have confirmed that MPs/NPs can be transported across multiple trophic levels. Moreover, MPs/NPs-induced alterations in zooplankton populations can impede energy transfer, leading to food scarcity for filter-feeding fish, larvae of benthic organism and fish, thus jeopardizing aquatic ecosystems. Furthermore, MPs/NPs can harm the nervous systems of aquatic organisms, influencing their feeding patterns, circadian rhythms, and mobility. Such behavioral alterations might also introduce unforeseen ecological risks. This comprehensive review aims to explore the consequences of MPs/NPs on freshwater organisms and their interconnected food webs. The investigation encompasses various aspects, including behavioral changes, alterations in physiology, impacts on metabolism, transgenerational effects, and the disruption of energy transfer within the ecosystem. This review elucidated the physiological and biochemical toxicity of MPs/NPs on freshwater organisms, and the ensuing risks to inland aquatic ecosystems.

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.

Application of common industrial solid waste in water treatment: a review.

Industrial solid waste has a wide range of impacts, and it is directly or indirectly related to land, atmosphere, water, and other resources. Industrial solid waste has a large amount of production, complex and diverse components and contains a variety of harmful substances. However, as industrial by-products, it also has a lot of available value. Industrial solid waste has been continuously studied in water treatment due to its special composition and porous and loose structure. It is known that there are few reviews of various industrial solid wastes in the field of wastewater treatment, and most of them only discuss single industrial solid waste. This paper aims to sort out the different studies on various solid wastes such as fly ash, red mud, wastewater sludge, blast furnace slag and steel slag in dyeing, heavy metal, and phosphorus-containing wastewater. Based on the modification of industrial solid waste and the preparation of composite materials, adsorbents, coagulants, catalysts, filtration membranes, geological polymers, and other materials with high adsorption properties for pollutants in wastewater were formed; the prospect and development of these materials in the field of wastewater were discussed, which provides some ideas for the mutual balance of environment and society. Meanwhile, some limitations of solid waste applications for wastewater treatment have been put forward, such as a lack of further researches about environment-friendly modification methods, application costs, the heavy metal leaching, and toxicity assessment of industrial solid waste.

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.

Effect of Current Density on the Corrosion Resistance and Photocatalytic Properties of Cu-Ni-Zn0.96Ni0.02Cu0.02O Nanocomposite Coatings.

2 at.% Cu + 2 at.% Ni were co-doped in ZnO nanoparticles by a simple hydrothermal method, and then the modified nanoparticles were compounded into Cu-Ni alloy coatings using an electroplating technique. The effects of the current density (15-45 mA/cm2) on the phase structure, surface morphology, thickness, microhardness, corrosion resistance, and photocatalytic properties of the coatings were investigated. The results show that the Cu-Ni-Zn0.96Ni0.02Cu0.02O nanocomposite coatings had the highest compactness and the best overall performance at a current density of 35 mA/cm2. At this point, the co-deposition rate reached its maximum, resulting in the deposition of more Zn0.96Ni0.02Cu0.02O nanoparticles in the coating. More nanoparticles were dispersed in the coating with a better particle strengthening effect, which resulted in a minimum crystallite size of 15.21 nm and a maximum microhardness of 558 HV. Moreover, the surface structure of the coatings became finer and denser. Therefore, the corrosion resistance was significantly improved with a corrosion current density of 2.21 × 10-3 mA/cm2, and the charge transfer resistance was up to 20.98 kΩ·cm2. The maximum decolorization rate of the rhodamine B solution was 24.08% under ultraviolet light irradiation for 5 h. The improvement in the comprehensive performance was mainly attributed to the greater concentration of Zn0.96Ni0.02Cu0.02O nanoparticles in the coating, which played the role of the particle-reinforced phase and reduced the microstructure defects.

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.

Manganese-Titanium Mixed Ion Sieves for the Selective Adsorption of Lithium Ions from an Artificial Salt Lake Brine.

Lithium recovery is imperative to accommodate the increase in lithium demand. Salt lake brine contains a large amount of lithium and is one of the most important sources of lithium metal. In this study, Li2CO3, MnO2, and TiO2 particles were mixed, and the precursor of a manganese-titanium mixed ion sieve (M-T-LIS) was prepared by a high-temperature solid-phase method. M-T-LISs were obtained by DL-malic acid pickling. The adsorption experiment results noted single-layer chemical adsorption and maximum lithium adsorption of 32.32 mg/g. From the Brunauer-Emmett-Teller and scanning electron microscopy results, the M-T-LIS provided adsorption sites after DL-malic acid pickling. In addition, X-ray photoelectron spectroscopy and Fourier transform infrared results showed the ion exchange mechanism of the M-T-LIS adsorption. From the results of the Li+ desorption experiment and recoverability experiment, DL-malic acid was used to desorb Li+ from the M-T-LIS with a desorption rate of more than 90%. During the fifth cycle, the Li+ adsorption capacity of the M-T-LIS was more than 20 mg/g (25.90 mg/g), and the recovery efficiency was higher than 80% (81.42%). According to the selectivity experiment, the M-T-LIS had good selectivity for Li+ (adsorption capacity of 25.85 mg/g in the artificial salt lake brine), which indicates its good application potential.

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.

Preparation and Properties of (Cu, Ni) Co-Doped ZnO Nanoparticle-Reinforced Cu-Ni Nanocomposite Coatings.

Here, 2% Cu + 2% Ni co-doped ZnO nanoparticles were synthesized using the hydrothermal method and were used as particle reinforcements of Cu-Ni nanocomposite coatings prepared by electroplating technology. The effects of the added (Cu, Ni) co-doped ZnO nanoparticles (2-8 g/L) on the phase structure, surface morphology, thickness, microhardness, corrosion resistance, and photocatalytic properties of the coatings were investigated. The nanocomposite coatings have obvious diffraction peaks on the crystal planes of (111), (200), and (220), showing a wurtzite structure. The surface of the nanocomposite coatings is cauliflower-like, and becomes smoother and denser with the increase in the addition of nanoparticles. The grain size, thickness, microhardness, corrosion resistance, and photocatalytic properties of the nanocomposite coating reach a peak value when the added (Cu, Ni) co-doped ZnO nanoparticles are 6 g/L. At this concentration, the mean crystallite size of the coating reaches a minimum of 15.31 nm, and the deposition efficiency of the coating is the highest. The (Cu, Ni) co-doped ZnO nanoparticle reinforcement makes the microhardness reach up to 658 HV. The addition of nanoparticles significantly improves the corrosion resistance and photocatalytic properties of nanocomposite coatings. The minimum corrosion current density is 2.36 × 10-6 A/cm2, the maximum corrosion potential is -0.301 V, and the highest decolorization rate of Rhodamine B is 28.73% after UV irradiation for 5 h.

Nanobubble size distribution measurement by interactive force apparatus under an electric field.

Nanobubbles have been applied in many fields, such as environmental cleaning, material production, agriculture, and medicine. However, the measured nanobubble sizes differed among the measurement methods, such as dynamic light scattering, particle trajectory, and resonance mass methods. Additionally, the measurement methods were limited with respect to the bubble concentration, refractive index of liquid, and liquid color. Here, a novel interactive force measurement method for bulk nanobubble size measurement was developed by measuring the force between two electrodes filled with bulk nanobubble-containing liquid under an electric field when the electrode distance was changed in the nm scale with piezoelectric equipment. The nanobubble size was measured with a bubble gas diameter and also an effective water thin film layer covered with a gas bubble that was estimated to be approximately 10 nm based on the difference between the median diameter of the particle trajectory method and this method. This method could also be applied to the solid particle size distribution measurement in a solution.

Trinitromethyl Energetic Groups Enhance High Heats of Detonation.

The introduction of groups with high enthalpies of formation can effectively improve the detonation performance of the compounds. A series of novel energetic compounds (10-13) with high enthalpies of formation, high density, and high nitrogen-oxygen content were designed and synthesized by combining gem-polynitromethyl, 1,2,4-oxadiazole, furoxan, and azo groups. All the new compounds were thoroughly characterized by IR, NMR, elemental analysis, and differential scanning calorimetry. Compounds 10 and 11 were also further characterized with single-crystal X-ray diffraction. Compound 11 has high density (1.93 g cm-3), high enthalpy of formation (993.5 kJ mol-1), high detonation velocity (9411 m s-1), and high heat of detonation (6889 kJ kg-1) and is a potentially excellent secondary explosive.

Three-dimension titanium phosphate aerogel for selective removal of radioactive strontium(II) from contaminated waters.

The effective removal of radioactive strontium (especially 90Sr) from nuclear wastewater is crucial to environmental safety. Nevertheless, materials with excellent selectivity in Sr removal remain a challenge since the similarity with alkaline earth metal ions in the liquid phase. In this work, a novel titanium phosphate (TiP) aerogel was investigated for Sr(II) removal from the radioactive wastewater based on the sol-gel method and supercritical drying technique. The TiP aerogel has amorphous, three-dimensional and mesoporous structures with abundant phosphate groups, which was confirmed by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FT-IR). The adsorbent exhibited high efficiency and selectivity for the removal of Sr(II) with an extensive distribution coefficient up to 4740.03 mL/g. The adsorption equilibrium reached within 10 min and the maximum adsorption capacity was 373.6 mg/g at pH 5. And the kinetics and thermodynamics data fitted well with the pseudo-second-order model and Langmuir model respectively. It can be attributed to the rapid trapping and slow intraparticle diffusion of Sr(II) inside the mesoporous channels of the TiP aerogel. Furthermore, TiP aerogel exhibited over 80% removal for 50 mg/L Sr2+ in real water systems (seawater, lake water and tap water). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy revealed that strong ionic bonding formed during Sr(II) adsorption with the phosphate group on TiP aerogel. These results indicated that TiP aerogel is a promising high-capacity adsorbent for the effective and selective capture of Sr(II) from radioactive wastewater.

Different nanobubbles mitigate cadmium toxicity and accumulation of rice (Oryza sativa L.) seedlings in hydroponic cultures.

Cadmium (Cd) contamination can pose a severe threat to food production and human health. The accumulation of Cd in rice will decrease rice biomass, photosynthetic activity, and antioxidant capacity, affecting crop yield. The effects of different nanobubbles on the growth and Cd accumulation of rice seedlings under hydroponic conditions were investigated in this study. The results showed that the biomass, photosynthetic pigment content, and antioxidant enzyme activity of rice seedlings decreased when treated with Cd alone and that Cd induced lipid peroxidation in rice seedlings. However, when different types of nanobubbles were introduced into the nutrient solution, the bioavailability of Cd in the solution was reduced. As a result, the Cd content in rice was significantly decreased compared to treatment with Cd alone. Nanobubbles increased the biomass of rice, enhanced photosynthesis, and improved the antioxidant capacity of rice by increasing antioxidant enzyme activities to alleviate Cd-induced oxidative stress. At the same time, nanobubbles increased the Fe content in rice, which decreased the Cd content, as Cd is antagonistic to Fe. In conclusion, these results suggested that nanobubbles are a potential method of mitigating Cd stress that may help to improve rice yield and could be further explored in production.