Direct gem-Difluoroalkenylation of X−H Bonds with Trifluoromethyl Ketone N-Triftosylhydrazones for Synthesis of Tetrasubstituted Heteroatomic gem-Difluoroalkenes

The direct gem-difluoroalkenylation of X−H bonds represents the most straightforward approach to access heteroatomic gem-difluoroalkenes that, as the isostere of the carbonyl group, have great potency in drug discovery. However, the construction of tetrasubstituted heteroatomic gem-difluoroalkenes by this strategy is still an unsolved problem. Here, we report the first direct X−H bond gem-difluoroalkenylation of amines and alcohols with trifluoromethyl ketone N-triftosylhydrazones under silver (for (hetero)aryl hydrazones) or rhodium (for alkyl hydrazones), thereby providing a most powerful method for the synthesis of tetrasubstituted heteroatomic gem-difluoroalkenes. This method features a broad substrate scope, high product yield, excellent functional group tolerance, and operational simplicity (open air conditions). Moreover, the site-specific replacement of the carbonyl group with a gem-difluorovinyl ether bioisostere in drug Trimebutine and the post-modification of bioactive molecules demonstrates potential use in medicinal research. Finally, the reaction mechanism was investigated by combining experiments and DFT calculations, and disclosed that the key step of HF elimination occurred via five-membered ring transition state, and the difference in the electrophilicity of Ag- and Rh-carbenes as well as the multiple intermolecular interactions rendered the effectiveness of Rh catalyst selectively for alkyl hydrazones.     

Regulating Phase Junction and Oxygen Vacancies of TiO2 Nanoarrays for Boosted Photoelectrochemical Water Oxidation

In this study, we have provided a facile solution to synthesize well-aligned titanium dioxide nanorods by using hydrothermal reaction. By calcining the materials under different atmospheres and temperatures, a batch of titanium dioxides with excellent oxygen evolution reaction(OER) catalytic efficiency were obtained. This new structured TiO₂ photoanode material yields a high photocurrent density of 5.69 mA/cm² at 1.23 V vs. reversible hydrogen electrode(RHE) under simulated solar light(100 mW/cm²). Surface photovoltage techniques and other measurements were carried out to confirm that the enhanced photoelectrochemical performances were attributed to the synergistic effect of the phase junction and a certain content of surface states, which accelerate the separation and transmission of the photogenerated charges. This material with phase junction and surface states promises a potential application in the field of photoelectric catalysis under solar light.     

基于平面度的燃料电池电化学性能模拟

 固体氧化物燃料电池的翘曲会影响电极-盖板界面的接触情况，从而影响电化学性能，对相关制造工艺提出了很大的挑战．为了分析燃料电池平面度对放电过程的影响，揭示其潜在的风险，我们建立了两个基于有限元法的仿真模型，对考虑平面度缺陷的燃料电池封装和放电进行分析．在对固体氧化物燃料电池进行平面度测量的基础上，首先建立了具有真实燃料电池翘曲特性的几何模型，分析封装过程中接触压力的分布情况．然后将接触电阻的仿真结果导入到三维多物理场耦合模型中，模拟具有平面度缺陷的燃料电池电化学性能．计算结果展示了燃料电池两侧封装过程中接触压力的分布情况．通过对比有接触电阻和无接触电阻的燃料电池电流密度，分析了电池与盖板的接触对放电过程的影响．结果表明，燃料电池的凹陷面较难达到满意的接触状态，需要比凸起面更大的封装压力．燃料电池表面接触电阻的变化将引起电流传导路径的变化，产生局部高电流或低电流．这项工作强调了在燃料电池中保持均匀分布的接触电阻的重要性，为今后的优化工作奠定了基础．     

Proton conductivity study on three CS/IL@fle-MOF membranes

The low-cost, high specific surface area and porosity, controlled pore size, and chemical properties of metal–organic framework (MOF) materials have attracted much attention in the exploration of proton conduction. The method of chemically modifying MOF structures or introducing conductive medium into the holes can effectively improve the proton conductivities of the materials. Here, the structural tunability of ionic liquid (IL) and flexible MOF (fle-MOF) materials are matched to give full play to the conductivity of IL, the framework support, and the microporous effect of MOFs, which achieves the synergistic effect of performance and expands the temperature range of proton transfer. Three kinds of CS/IL@fle-MOF membranes were prepared by combining three fle-MOFs with 1-carboxymethyl-3-methylimidazole (CMMIM) in different proportions to obtain 15 pieces of membranes. The comparative analyses show that CS/IL@fle-MOF membranes have excellent proton conduction performance at a wider temperature range (263–353 K) and lower relative humidity (75% RH). Among them, the proton conductivities of CS/CMMIM@MIL-88A-25% and CS/CMMIM@MIL-88B-125% are up to 1.33 and 1.42 S cm⁻¹ at 75% RH and 353 K, respectively; whereas those of CS/CMMIM@MIL-53(Fe)-75% and CS/CMMIM@MIL-88B-125% reach up to 2.1 × 10⁻³ and 1.28 × 10⁻³ S cm⁻¹ at 75% RH and 263 K, respectively. The E_a of CS/CMMIM@fle-MOFs is in the range of 0.1–0.5 eV, suggesting that the proton transport follows predominantly the typical Grotthuss transfer mechanism. The results of this study indicate that the CS/CMMIM@fle-MOF membranes combinations offer great potential for the design of composite porous proton-conducting materials.     

Development of efficient and accurate skeletal mechanisms for hydrocarbon fuels and kerosene surrogate

In this paper,the methodology of the directed relation graph with error propagation and sensitivity analysis(DRGEPSA),proposed by Niemeyer et al.(Combust Flame 157:1760-1770.2010).and its differences to the original directed relation graph method are described.Using DRGEPSA,the detailed mechanism of ethylene containing 71 species and 395 reaction steps is reduced to several skeletal mechanisms with different error thresholds.The 25-species and 131-step mechanism and the 24-species and115-step mechanism are found to be accurate for the predictions of ignition delay time and laminar flame speed.Although further reduction leads to a smaller skeletal mechanism with 19 species and 68 steps,it is no longer able to represent the correct reaction processes.With the DRGEPSA method,a detailed mechanism for n-dodecane considering low-temperature chemistry and containing 2115 species and8157 steps is reduced to a much smaller mechanism with249 species and 910 steps while retaining good accuracy.If considering only high-temperature(higher than 1000 K)applications,the detailed mechanism can be simplified to even smaller mechanisms with 65 species and 340 steps or48 species and 220 steps.Furthermore,a detailed mechanism for a kerosene surrogate having 207 species and 1592 steps is reduced with various error thresholds and the results show that the 72-species and 429-step mechanism and the66-species and 392-step mechanism are capable of predicting correct combustion properties compared to those of the detailed mechanism.It is well recognized that kinetic mechanisms can be effectively used in computations only after they are reduced to an acceptable size level for computation capacity and at the same time retaining accuracy.Thus,the skeletal mechanisms generated from the present work are expected to be useful for the application of kinetic mechanisms of hydrocarbons to numerical simulations of turbulent or supersonic combustion.     

Experimental and Numerical Investigation on Effects of the Steam Ingestion on the Aerodynamic Stability of an Axial Compressor

In order to investigate the influence of steam ingestion on the aerodynamic stability of a two-stage low-speed axial-flow compressor, multiphase flow numerical simulation and experiment were carried out. The total pressure ratio and stall margin of the compressor was decreased under steam ingestion. When the compressor worked at 40% and 53% of the nominal speed, the stall margin decreased, respectively, by 1.5% and 6.3%. The ingested steam reduced the inlet Mach number and increased the thickness of the boundary layer on the suction surface of the blade. The low-speed region around the trailing edge of the blade was increased, and the flow separation region of the boundary layer on the suction surface of the blade was expanded; thus, the compressor was more likely to enter the stall state. The higher the rotational speed, the more significant the negative influence of steam ingestion on the compressor stall margin. The entropy and temperature of air were increased by steam. The heat transfer between steam and air was continuous in compressor passages. The entropy of the air in the later stage was higher than that in the first stage; consequently, the flow loss in the second stage was more serious. Under the combined action of steam ingestion and counter-rotating bulk swirl distortion, the compressor stability margin loss was more obvious. When the rotor speed was 40% and 53% of the nominal speed, the stall margin decreased by 6.3% and 12.64%, respectively.     

Finite-time boundedness of uncertain Hamiltonian systems via sliding mode control approach

Nonlinear Dynamics - This paper seeks to address the problem of finite-time stabilization for a class of uncertain Hamiltonian systems via sliding mode control approach. A novel sliding function in...     

Spreading of Oil Droplets Containing Surfactants and Pesticides on Water Surface Based on the Marangoni Effect

Oil droplets containing surfactants and pesticides are expected to spread on a water surface, under the Marangoni effect, depending on the surfactant. Pesticides are transported into water through this phenomenon. A high-speed video camera was used to measure the movement of Marangoni ridges. Gas chromatography with an electron capture detector was used to analyze the concentration of the pesticide in water at different times. Oil droplets containing the surfactant and pesticide spread quickly on the water surface by Marangoni flow, forming an oil film and promoting emulsification of the oil–water interface, which enabled even transport of the pesticide into water, where it was then absorbed by weeds. Surfactants can decrease the surface tension of the water subphase after deposition, thereby enhancing the Marangoni effect in pesticide-containing oil droplets. The time and labor required for applying pesticides in rice fields can be greatly reduced by using the Marangoni effect to transport pesticides to the target.     

Characteristics of uranium sorption on illite in a ternary system: effect of phosphate on adsorption

Journal of Radioanalytical and Nuclear Chemistry - Na, Mg, Al and Cl in Roman glasses and pottery were analyzed by PIGE with 2.5 MeV protons and 2.0 MeV deuteron activation...