Thermal Activation of CH4 and H2 as Mediated by the Ruthenium Oxide Cluster Ions [RuOx]+ (x=1–3): On the Influence of Oxidation States

Thermal gas-phase reactions of the ruthenium-oxide clusters [RuO_x]⁺ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]⁺/CH₄ couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO₂]⁺ brings about the generations of [Ru,O,C,H₂]⁺/H₂O, [Ru,O,C]⁺/H₂/H₂O, and [Ru,O,H₂]⁺/CH₂O, whereas [RuO₃]⁺ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H₂). Regarding the reactions with H₂, as compared to CH₄, both [RuO]⁺ and [RuO₂]⁺ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO₃]⁺ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuO_x]⁺ (x=1–3) with CH₄ and H₂ have been compared with the previously reported results of Group 8 analogues [OsO_x]⁺/CH₄/H₂ (x=1–3) and the [FeO]⁺/H₂ system. The electronic origins for their distinctly different reaction behaviors have been addressed.     

Dynamics of laser-induced cavitation bubble during expansion over sharp-edge geometry submerged in liquid – an inside view by diffuse illumination

Laser ablation in liquids is growing in popularity for various applications including nanoparticle production, breakdown spectroscopy, and surface functionalization. When laser pulse ablates the solid target submerged in liquid, a cavitation bubble develops. In case of “finite” geometries of ablated solids, liquid dynamical phenomena can occur inside the bubble when the bubble overflows the surface edge. To observe this dynamics, we use diffuse illumination of a flashlamp in combination with a high-speed videography by exposure times down to 250 ns. The developed theoretical modelling and its comparison with the experimental observations clearly prove that this approach widens the observable area inside the bubble. We thereby use it to study the dynamics of laser-induced cavitation bubble during its expansion over a sharp-edge (“cliff-like” 90°) geometry submerged in water, ethanol, and polyethylene glycol 300. The samples are 17 mm wide stainless steel plates with thickness in the range of 0.025–2 mm. Bubbles are induced on the samples by 1064-nm laser pulses with pulse durations of 7–60 ns and pulse energies of 10–55 mJ. We observe formation of a fixed-type secondary cavity behind the edge where low-pressure area develops due to bubble-driven flow of the liquid. This occurs when the velocity of liquid overflow exceeds ~20 m s⁻¹. A re-entrant liquid injection with up to ~40 m s⁻¹ velocity may occur inside the bubble when the bubble overflows the edge of the sample. Formation and characteristics of the jet evidently depend on the relation between the breakdown-edge offset and the bubble energy, as well as the properties of the surrounding liquid. Higher viscosity of the liquid prevents the generation of the jet.     

Characteristic behaviour of plasma fluctuations inside a plasma bubble in presence of a magnetic field due to the formation of a potential well

Experiments were carried out to observe the effect of a magnetic field and grid biasing voltage in presence of a plasma bubble in a magnetized, filamentary discharge plasma system. A spherical mesh grid of 80% optical transparency was negatively biased and introduced into the plasma for creating a plasma bubble. Diagnostics via an electrical Langmuir probe and a hot emissive probe were extensively used for scanning the plasma bubble. Plasma floating potential fluctuations were measured at three different positions of the plasma bubble. The instability in the pattern showed the dynamic transition from periodic to chaotic for increasing magnetic fields. Time scale analysis using continuous wavelet transform was carried out to identify the presence of non‐linearity from the contour plots. The mechanisms of the low‐frequency instabilities along with the transition to chaos could be qualitatively explained. Non‐linear techniques such as fast Fourier transform, phase space plot, and recurrence plot were used to explore the dynamics of the system appearing during plasma fluctuations. In order to demonstrate the observed chaotic phenomena in this study, characteristics of chaos such as the Lyapunov exponent were obtained from experimental time series data. The experimentally observed potential structure is confirmed with numerical analysis based on fluid hydrodynamics.     

Motion of Enzyme‐Powered Microshell Motors

Microshells are attractive in constructing bubble‐propelled micromotors due to the lower energy consumption for bubbles forming on a concave surface. In this work, enzyme‐powered microshell motors were fabricated on multimetallic (Au/Ag/Au) microshells along with the modification of catalase on its concave surface. The catalase triggered the decomposition of hydrogen peroxide to oxygen gas, hence propelling the autonomous motion of microshell motors. A size‐dependent motion behaviour was observed for the microshell motors in the form of slow tremble and fast translation motion for a size smaller and larger than 5 μm, respectively, according to the size, generation efficiency and ejection mechanism of bubbles and the intensity of Brownian motion. In addition, the effect of fuel concentration on the motion speed of microshells was dependent on whether the bubble generation was affected by the limited mass transfer in the microshell space. These findings play an important role for the design of microshell motors.     

三氯一氟甲烷分子在辐射场中的光谱性质与解离特性研究

采用B3LYP/6-311++g(3df,3pd)方法和基组对氟利昂物质CFC-11 (CFCl_3)分子进行了一系列的理论研究.包括了该分子的基态结构、电偶极矩、总能量、最高占据分子轨道能级E_H和最低未占据分子轨道能级E_L、能隙、红外与拉曼光谱性质、C-F键解离,并探讨电场对该分子的影响.结果表明:基态结构优化后的理论计算值和实验值的最大误差低于2%,C-F键受电场强度的增大而被拉长,能隙E_g随E_H和E_L的变化出现先增大后减小;电场影响着CFC-11分子的红外与拉曼光谱吸收强度,红外与拉曼光谱随着电场变化出现红移或蓝移现象.电场可作为一种辅助手段对其重叠或准重叠谱线进行分离.势阱深度随反向电场逐渐增大而减小,直至消失,使得C-F键的束缚能力逐渐减弱.本文有望为实现CFC-11分子最终发生解离而降解提供一种可行有效的调控手段.     

超声处理对煤层气解吸效果的影响

煤岩吸附解吸性能评价对煤层气的开发十分重要。利用自行设计的煤岩吸附解吸性能评价装置,进行了CH4、CO2、N2等在煤岩中的吸附解吸性能评价。在此基础上,研究了不同参数超声波处理对煤层气解吸效果的影响,分析了超声波促进煤层气解吸的机理。研究表明,煤岩中的气体主要以吸附态和自由态存在,煤岩对不同气体吸附量从大到小依次为CO2、CH4、N2。经超声波处理后,煤层气的解吸速度可提高70%,同时煤层气的解吸量增加。解吸量增加幅度与超声波处理参数有关,随处理功率的增大,解吸量增加,增加幅度可达20%。分析认为超声波的"剥离"作用是超声波提高煤层气解吸效果的机理之一。     

Space-time finite element methods stabilized using bubble function spaces

ABSTRACT

In this paper, a stabilized space-time finite element method for solving linear parabolic evolution problems is analyzed. The proposed method is developed on a base of a space-time variational setting, that helps on the simultaneous and unified discretization in space and in time by finite element techniques. Stabilization terms are constructed by means of classical bubble spaces. Stability of the discrete problem with respect to an associated mesh dependent norm is proved, and a priori discretization error estimates are presented. Numerical examples confirm the theoretical estimates.     

石英砂粒径对水合物沉积物力学性质的影响

利用自主研发的水合物沉积物原位合成与力学性质测试的高压低温三轴仪,通过多级加荷的试验方法,以不同粒径的砂粒作为沉积物骨架进行三轴压缩试验,得到了剪切过程的应力-应变关系曲线,以及不同粒径尺寸沉积物的强度,还有剪切过程中的体积变化关系。结果表明:含水合物沉积物强度随着沉积物粒径尺寸的增大而增强;在降压剪切过程中,所有粒径的水合物沉积物式样均有明显的剪缩现象。     

Shape stability of a gas bubble in a soft solid

Predicting the onset of non-spherical oscillations of bubbles in soft matter is a fundamental cavitation problem with implications to sonoprocessing, polymeric materials synthesis, and biomedical ultrasound applications. The shape stability of a bubble in a Kelvin-Voigt viscoelastic medium with nonlinear elasticity, the simplest constitutive model for soft solids, is analytically investigated and compared to experiments. Using perturbation methods, we develop a model reducing the equations of motion to two sets of evolution equations: a Rayleigh-Plesset-type equation for the mean (volume-equivalent) bubble radius and an equation for the non-spherical mode amplitudes. Parametric instability is predicted by examining the natural frequency and the Mathieu equation for the non-spherical modes, which are obtained from our model. Our theoretical results show good agreement with published experiments of the shape oscillations of a bubble in a gelatin gel. We further examine the impact of viscoelasticity on the time evolution of non-spherical mode amplitudes. In particular, we find that viscosity increases the damping rate, thus suppressing the shape instability, while shear modulus increases the natural frequency, which changes the unstable mode. We also explain the contributions of rotational and irrotational fields to the viscoelastic stresses in the surroundings and at the bubble surface, as these contributions affect the damping rate and the unstable mode. Our analysis on the role of viscoelasticity is potentially useful to measure viscoelastic properties of soft materials by experimentally observing the shape oscillations of a bubble.