α-Fe2O3-In2O3 mixed oxide nanoparticles synthesized under hydrothermal supercritical conditions

α-Fe₂O₃-In₂O₃ mixed oxide nanoparticles system has been synthesized by hydrothermal supercritical and postannealing route, starting with (1−x)Fe(NO₃)₃·9H₂O·xIn(NO₃)₃·5H₂O aqueous solution (x=0-1). X-ray diffraction and Mössbauer spectroscopy have been used to study the phase structure and substitutions in the nanosized samples. The concentration regions for the existence of the solid solutions in the α-Fe₂O₃-In₂O₃ nanoparticle system together with the solubility limits of In³⁺ ions in the hematite lattice and of Fe³⁺ ions in the cubic In₂O₃ structure have been evidenced. In general, the substitution level is considerably lower than the nominal concentration x. A justification of the processes leading to the formation of iron and indium phases in the investigated supercritical hydrothermal system has been given.     

Preparation of CeO2 by a simple microwave–hydrothermal method

Cerium carbonate hydroxide (orthorhombic Ce(OH)CO₃) hexagonal-shaped microplates were synthesized by a simple and fast microwave–hydrothermal method at 150 °C for 30 min. Cerium nitrate, urea and cetyltrimethylammonium bromide were used as precursors. Ceria (cubic CeO₂) rhombus-shape was obtained by a thermal decomposition oxidation process at 500 °C for 1 h using as- synthesized Ce(OH)CO₃. The products were characterized by X-ray powder diffraction, field-emission scanning electron microscopy, thermogravimetric analysis and Fourier transformed infrared spectroscopy. The use of microwave–hydrothermal method allowed to obtain cerium compounds at low temperature and shorter time compared to other synthesis methods.     

Stepwise synthesis of fine crystalline Ce-doped yttrium aluminum garnet in water medium in subcritical and supercritical conditions

In this paper the continuous stepwise method of a production of fine crystalline yttrium aluminum garnet doped with cerium (YAG: Ce³⁺) in supercritical water fluid (SCWF) are represented. The synthesis was carried out in water medium in two stages: first in subcritical conditions and then in an atmosphere of supercritical water fluid. The stoichiometric mixture of yttrium oxide and aluminum hydroxide in a water solution of cerium nitrate was maintained the certain time at 280°C and under vapor water pressure 6.3 MPa. Then temperature and pressure were risen up to a supercritical condition (T = 392–400°C, P_{H2 O}P_{H_2 O} = 22 MPa). The concentration of cerium ions in reaction medium was changed in the interval 0.012–0.706 wt %. The products, obtained on various stages of synthesis, were investigated by physical-chemical methods. During the first stage, the crystals of boehmite and yttrium hydroxide under hydrothermal conditions were arising, and eventually poorly formed YAG: Ce³⁺ were appearing. At this stage, the diffusion of cerium ions into intermediate products takes place. Because of this, at the second step of synthesis, in supercritical conditions, YAG: Ce³⁺, phosphor with high luminescence intensity at 530 nm, was obtained. In supercritical conditions well-faceted crystals of 0.5–3.0 μm with rhombododecahedral habitus were produced.     

Theoretical investigation on the reaction kinetics of NO2 with CH3OH and HCHO under combustion conditions

Methanol (CH₃OH) and formaldehyde (HCHO) reacting with nitrogen dioxide (NO₂) contribute to the largest uncertainty for the CH₃OH/NO_x low temperature combustion mechanism. CH₃OH and NO₂ only undergo H-abstraction reactions, while HCHO + NO₂ involves multiple reaction channels, among which H-abstraction dominates. In the present work, a high level quantum chemical method, CCSD(T)/aug-cc-pVQZ//M06–2X-D3/6-311++G(d,p), was employed to investigate the reaction pathways. The reaction kinetics were explored by RRKM/master equation simulations with multidimensional small-curvature tunneling (SCT) corrections and hindered rotor approximations. The H-abstraction reactions with barriers higher than 20 kcal/mol indicate a nonnegligible quantum tunneling effect even under combustion conditions. Our computations predict the tunneling factors to be 3–4 for the studied reactions at 500 K. A significant tunneling effect is also expected for H-abstraction of large alcohols and aldehydes by NO₂. The computed total rate coefficients show good agreement with previous experimental measurements over narrow ranges of temperature and pressure, ensuring the accuracy of the reported branching ratios covering a wide T, P range for the two reactions. The results of CH₃OH + NO₂ reveal the dominant role of HONO_cis + CH₂OH. It's also uncovered the dominance of HONO_cis + CHO pathway in HCHO + NO₂ under the studied conditions. The detailed reaction kinetics information reported in this work is useful for building rate rules for the mechanisms of other nitrogen-containing alcohol-based fuels.     

(TPP)NO3的合成、表征与分子识别NO

在氯仿与无水乙醇的混合溶剂(体积比为1:1)中,四苯基卟啉(TPP)与Ce(NO₃)·6H₂O混合反应后,得产物Ce(TPP)NO₃. 通过紫外-可见光谱、红外光谱、荧光光谱、质谱、核磁共振氢谱的分析与表征,四苯基卟啉与铈原子以四齿方式进行配位,在同一个铈原子上还有一个硝酸根配位. 向Ce(TPP)NO₃的二氯甲烷溶液中通入NO气体,NO可以配位在同一个铈原子上,得到新的配合物Ce(TPP)(NO)NO₃,向此溶液中通入N₂,金属卟啉配合物可以恢复为配合物Ce(TPP)NO₃.     

A molecular dynamics study of fuel droplet evaporation in sub- and supercritical conditions

Evaporation processes of a fuel droplet under sub- and supercritical ambient conditions have been studied using molecular dynamics (MD) simulations. Suspended n-dodecane droplets of various initial diameters evaporating into a nitrogen environment are considered. Both ambient pressure and temperature are varied from sub- to supercritical values, crossing the critical condition of the chosen fuel. Temporal variation in the droplet diameter is obtained and the droplet lifetime is recorded. The time at which supercritical transition happens is determined by calculating the temperature and concentration distributions of the system and comparing with the critical mixing point of the n-dodecane/nitrogen binary system. The dependence of evaporation characteristics on ambient conditions and droplet size is quantified. It is found that the droplet lifetime decreases with increasing ambient pressure and/or temperature. Supercritical transition time decreases with increasing ambient pressure and temperature as well. The droplet heat-up time as well as subcritical to supercritical transition time increases linearly with the initial droplet size d₀, while the droplet lifetime increases linearly with ${\mathrm{d}}_0^2$. A regime diagram is obtained, which indicates the subcritical and supercritical regions as a function of ambient temperature and pressure as well as the initial droplet size.     

Characteristics of LiFePO4 obtained through a one step continuous hydrothermal synthesis process working in supercritical water

The olivine-like material LiFePO₄ was prepared via a continuous hydrothermal synthesis process working from subcritical to supercritical water conditions. The influence of some processing parameters–temperature and reaction time–was investigated in terms of material purity, grain size and morphology. Supercritical conditions were found to be attractive to synthesize in one step a well-crystallized material without impurities. The primary particles size was in the nanometric range. They showed a natural tendency to form micron size agglomerates, which were supposed to be the cause of the limited capacity, as demonstrated through a cross study using laser particle size distribution analysis, electrochemical measurements and XRD at different Li contents.     

Hydrothermal growth and characterization of La(OH)3 nanorods and nanocables with Ni(OH)2 coating

La(OH)₃/Ni(OH)₂ nanocables and La(OH)₃ nanorods were synthesized by the reaction of KOH with La(NO₃)₃ and Ni(NO₃)₂ at 180 °C under a hydrothermal conditions. X-ray diffraction, transmission electron microscopy and thermal analyses indicated that the nanocable consists of La(OH)₃ core and Ni(OH)₂ outer shell. The diameters of the La(OH)₃ nanorods range from 20 to 30 nm and the lengths range from 150 to 1000 nm. The thickness of the Ni(OH)₂ coating ranges from 10 to 20 nm. The formation mechanism of the nanocables is discussed.     

Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO₂ radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO₂ + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO₂ + FOX-7 results in the formation of NO₃ radical, which has never been detected experimentally during the decomposition of FOX-7.     

Effect of ozone addition and ozonolysis reaction on the detonation properties of C2H4/O2/Ar mixtures

Ozone is one of the strongest oxidizers and can be used to enhance detonation. Detonation enhancement by ozone addition is usually attributed to the ozone decomposition reaction which produces reactive atomic oxygen and thereby accelerates the chain branching reaction. Recently, ozonolysis reaction has been found to be another mechanism to enhance combustion for unsaturated hydrocarbons at low temperatures. In this study, the effects of ozone addition and ozonolysis reaction on steady detonation structure and transient detonation initiation and propagation processes in C₂H₄/O₂/O₃/Ar mixtures are examined through simulations considering detailed chemistry. Specifically, the homogeneous ignition process, the ZND detonation structure, the transient direct detonation initiation, and pulsating instability of one-dimensional detonation propagation are investigated. It is found that the homogenous ignition process consists of two stages and the first stage is caused by ozonolysis reactions which consume O₃ and produces CH₂O as well as H and OH radicals. The ozonolysis reaction and ozone decomposition reaction can both reduce the induction length though they have little influence on the Chapman–Jouguet (CJ) detonation speed. The supercritical, critical and subcritical regimes for direct detonation initiation are identified by continuously decreasing the initiation energy or changing the amount of ozone addition. It is found that direct detonation initiation becomes easier at larger amount of ozone addition and/or larger reaction progress variable. This is interpreted based on the change of the induction length of the ZND detonation structure. Furthermore, it is demonstrated that the ozonolysis reaction can reduce pulsating instability and make the one-dimensional detonation propagation more stable. This is mainly due to the reduction in activation energy caused by ozone addition and/or ozonolysis reaction. This work shows that both ozone decomposition reaction and ozonolysis reaction can enhance detonation for unsaturated hydrocarbon fuels.     

Effect of Hydrolysis Conditions on the Direct Formation of Nanoparticles of Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

The effect of the cation concentration, hydrolysis temperature, and composition in the CeO₂–ZrO₂ system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO₂ were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm³ by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm³ at the starting composition of 50 mol% ZrO₂ under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH₄)₂Ce(NO₃)₆. Ceria–zirconia solid solutions containing large amount of ZrO₂ maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h.     

Organic-ligand-assisted supercritical hydrothermal synthesis of titanium oxide nanocrystals leading to perfectly dispersed titanium oxide nanoparticle in organic phase

Titanium oxide (TiO₂) nanocyrstals which are perfectly dispersed in organic solvents are synthesized by organic-ligand-assisted supercritical hydrothermal synthesis. The addition of hexaldehyde to the supercritical hydrothermal synthesis of TiO₂ leads to the in-situ surface modification, which enables the synthsized TiO₂ nanocrystals to be perfectly dispersed in iso-octane because of its hydrophobic nature. Further, the one-pot synthesis of hybrid materials results in the significant reduction of the particles size, probably due to the capping effect of hexaldehyde to suppress the particles growth.     

Exploring the chemistry behind low temperature auto-ignition of isopropyl nitrate in an RCM: An experimental and kinetic modeling study

The low-temperature auto-ignition chemistry of isopropyl nitrate (iPN) was experimentally and numerically investigated in the present study. The ignition delay times (IDTs) of iPN were measured stoichiometrically over a temperature range of 560–600 K at effective pressures of 5 and 10 bar in a rapid compression machine. A two-stage ignition phenomenon of iPN was observed. Both the first-stage IDTs and total IDTs vary rapidly within the narrow temperature range investigated (∼40 K). A recent iPN kinetic mechanism proposed by Fuller and Goldsmith for pyrolysis studies was extended. The reaction kinetics of CH₃CHO + NO₂ has been theoretically calculated at 500–1500 K and 0.01–100 atm. The rate information of CH₃ + NO₂ was updated based on previous theoretical results. The O₂-addition channel of acetyl radical (CH₃CO), which accounts for the first-stage IDT, was also considered in the present work. The extended iPN kinetic model predicts the two-stage IDTs well. Simulation results suggest that the IDTs are most sensitive to the following two reactions: (1) CH₃ + NO₂ = CH₃O + NO; (2) CH₃ + NO₂ = CH₃NO₂. The former promotes the overall reactivity by yielding the reactive methoxy radical, while the latter forms a relatively stable product (i.e., CH₃NO₂). The reaction of CH₃CHO + NO₂ = CH₃CO + HONO supplements the formation of CH₃CO. The different consumption channels of CH₃CO radicals (the O₂-addition reaction and the decomposition reaction) lead to different chain reactions yielding OH radicals with increasing temperature in the ignition process. The “NONO₂ loop” is the main route for OH formation in the studied conditions, which is mainly responsible for the iPN ignition.     

The effect of clustering of VO2+ ions in sub- and supercritical water. An in situ EPR study

Temperature variations of the EPR spectra of VO²⁺ ions in sub- and supercritical water under isothermal and temperature gradient conditions are investigated using an in situ EPR. Broadening of the hyperfine structure at increasing temperature and the appearance of an unresolved broad low-intensity line (ΔH _pp ≈ 300 Oe) in the supercritical state are observed in the absence of temperature gradients, indicating an increase of exchange interaction between VO²⁺ ions in supercritical water. An exchange-narrowed anisotropic absorption line is observed under the temperature-gradient conditions in the subcritical water near the transition to a supercritical state. The shape of this line is close to that observed in the solid salt VOSO₄ · 3H₂O. It is shown that in situ EPR allows us to investigate the effects of changing the local environment of paramagnetic ions, which precedes the well-known process of clustering and formation of amorphous oxide particles in sub- and supercritical conditions.     

Noncatalytic organic rearrangement using supercritical water

Abstract

Significant acceleration of Beckmam and pinacol rearrangements can be achieved by using supercritical water (scH₂O), especially just near the critical point even in the absence of any acid catalysts. A high-pressure, high-temperature flow reactor system with FTlR operable at 500°C and 50 MPa was suaxssfdy developed, wherein the non-catalytic Beckmam and pinacol rearrangements using scH₂O were carried out and monitored. It has been demonstrated that scH₂0 itself acts very effectively in the place of conventional acid catalysts for both the rearrangements. The rate of the pinacol rearrangement using scH₂O is 28,200-fold rate of that in 0.871 M HCl solution at 46.7 MPa under distillation conditions. The high rate of reaction may be attributed to a great increase in the local proton concentration around the organic reactants.     

Flower-like Ni3(NO3)2(OH)4@Zr-metal organic framework (UiO-66) composites as electrode materials for high performance pseudocapacitors

Zr-metal organic frameworks (Zr-MOFs, UIO-66) as a kind of crystalline porous material possess controllable porous structure and strong thermal stability up to 753 K. In this paper, we synthesized Ni₃(NO₃)₂(OH)₄, Zr-MOF with high specific surface area (1073 m² g⁻¹) and Ni₃(NO₃)₂(OH)₄@Zr-MOF composite for pseudocapacitor material. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were taken to characterize the structure and morphology of Ni₃(NO₃)₂(OH)₄, Zr-MOF, and Ni₃(NO₃)₂(OH)₄@Zr-MOF. The porous structure of Zr-MOF favors the utilization of the active material Ni₃(NO₃)₂(OH)₄ and interfacial charge transport and provides short diffusion paths for ions, which results in a high specific capacitance. Electrochemical properties are evaluated by cyclic voltammetry (CV) and galvanostatic charge/discharge measurement. A maximum specific capacitance (SC) of 992 F/g was obtained from CV at a scan rate of 5 mVs⁻¹, which is higher than Zr-MOF (∼134 F g⁻¹) and Ni₃(NO₃)₂(OH)₄ (∼753 F g⁻¹). Meanwhile, the Ni₃(NO₃)₂(OH)₄@Zr-MOF composite electrode exhibits a good cycling stability over 3000 cycles.

     

Synthesis of dimension-tunable ZnO nanostructures via the design of zinc hydroxide precursors

A facile synthesis route is presented to achieve dimension-tunable ZnO nanostructures by the design of zinc hydroxide precursors under the surfactant-free condition. From three types of zinc hydroxide precursors, namely, crystalline Zn(OH)(NO₃)(H₂O) nanobelts, amorphous zinc hydroxides microparticles and soluble Zn(OH)^2-₄\mathrm{Zn}(\mathrm{OH})^{2-}_{4} species, the porous ZnO nanosheets, ZnO nanoparticles and ZnO nanowires can be achieved, respectively. The porous ZnO nanosheets exhibit large polar surface area. Thermal analysis indicates that the crystalline Zn(OH)(NO₃)(H₂O) nanobelts were converted to the porous ZnO nanosheets by in situ lattice reconstruction, which was attributed to the unique fibrous structure of Zn(OH)(NO₃)(H₂O) nanobelts. The as-prepared dimension-tunable ZnO nanostructures have potential applications in solar cells, photocatalysis, novel chemical and biological sensors, etc.     

Nanoporous ZnO nanostructures for photocatalytic degradation of organic pollutants

ZnO porous bamboo-leave-like nanorods and nanoporous networks were prepared by thermal conversion from Zn₂CO₃(OH)₂?H₂O bamboo-leave-like nanorods, Zn(OH)₂ nanoparticle networks and Zn(OH)₂ long nanostrand networks, respectively. Among them, the ZnO nanoporous networks prepared from Zn(OH)₂ nanostrands had the highest surface area of 78.57 m²/g and presented the best photocatalytic decomposition of organics. The morphologies of the Zn(OH)₂ nanostructures significantly depended on the solvent used for the precursors of aminoethanol and Zn(NO₃)₂ and then determined the corresponding structures and properties of the final ZnO nanostructures. The ethanol/water mixture solvent dramatically increased the stability of Zn(OH)₂ nanostrands. This is very beneficial for the collection and application of Zn(OH)₂ nanostrands.     

Decomposition processes and structural transformations of cerium propionate into nanocrystalline ceria at different oxygen partial pressures

The structural transformations that occur when thermal treatments turn cerium propionate into nanocrystalline ceria have been analysed with thermoanalytical techniques (TG, DTA and MS) and with structural and magnetic characterization (HRTEM, SQUID and XRD) of the final and intermediate products. Attention has been paid to what occurs during the decomposition of propionate and how the process is affected by the furnace atmosphere (oxidizing or inert). In an oxidizing atmosphere, the decomposition of cerium propionate is triggered by the oxidation of Ce³⁺ to Ce⁴⁺. This reaction entails the loss of large unoxidized propionate fragments of the propionate ligands. As decomposition proceeds, the carbonaceous residue makes the oxygen transport inside the material more difficult and decomposition becomes diffusion limited. At this point, extensive oxidation of the residue begins until it is completely removed. Crystallization of CeO₂ occurs simultaneously with decomposition. In these conditions, crystalline nanoparticles (diameter of 3–5 nm) can be obtained at a temperature as low as 300 °C. In an inert atmosphere, decomposition occurs in three steps. During the first step, one of the three propionate ligands is lost, with little oxidation of Ce³⁺, and is substituted by a hydroxyl group. The second step entails the loss of the remaining ligands with a substantial oxidation of Ce³⁺ to Ce⁴⁺. After this step, the intermediate product is, proposed as, a mixture of amorphous Ce(OH)₃ and Ce(OH)₄. Finally, the third step leads to conversion of the Ce hydroxide into crystalline CeO₂. In an inert atmosphere, the process is less reproducible than in air and a carbonaceous residue remains in the product.     

Preparation and characterization of slice-like Cu2(OH)3NO3 superhydrophobic structure on copper foil

Superhydrophobic structure was prepared on copper foil via a facile solution-immersion method. Thus slice-like Cu₂(OH)₃NO₃ crystal was prepared on the surface of the copper foil by sequential immersing in an aqueous solution of sodium hydroxide and cupric nitrate. And the superhydrophobic structure was obtained by modifying the slice-like Cu₂(OH)₃NO₃ crystal with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS-17). The morphologies, chemical compositions and states, and hydrophobicity of the surface-modifying films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and water contact angle measurement. Moreover, the thermal stability of the slice-like structure was also evaluated using thermogravimetric analysis (TGA). It was found that roughening of the copper foil surface helped to increase the hydrophobicity to some extent, but no superhydrophobicity was obtained unless the slice-like Cu₂(OH)₃NO₃ crystal formed on the Cu substrate was modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. Besides, the superhydrophobicity of the FAS-17-modified slice-like Cu₂(OH)₃NO₃ structure was closely related to the surface morphology. And this hydrophobic structure retained good superhydrophobic stability at elevated temperature and in long-term storage as well, which should be critical to the application of Cu-matrix materials in engineering.