Low-Frequency Relaxation Oscillations in Capacitive Discharge Processes

Low-frequency （2.72-3.70 Hz） relaxation oscillations at 100 mTorr at higher absorbed power were observed from time-varying optical emission of the main discharge chamber and the periphery. We interpret the low frequency oscillations using an electromagnetic model of the slot impedance with parallel connection variational peripheral capacitance, coupled to a circuit analysis of the system including the matching network. The model results are in general agreement with the experimental observations, and indicate a variety of behaviours dependent on the matching conditions.     

High and low frequency relaxation oscillations in a capacitive discharge plasma

Both high and low frequency relaxation oscillations have been observed in an argon capacitive discharge connected to a peripheral grounded chamber through a slot with dielectric spacers. The oscillations, observed from time-varying optical emission of the main discharge chamber, show, for example, a high frequency （46 kHz） relaxation oscillation at 100 mTorr, with an absorbed power near the peripheral breakdown, and a low frequency （2.7-3.7 Hz） oscillation, at a higher absorbed power. The high frequency oscillation is found to ignite a plasma in the slot, but usually not in the periphery. The high frequency oscillation is interpreted by using an electromagnetic model of the slot impedance, combined with the circuit analysis of the system including a matching network. The model is further developed by using a parallel connection of variable peripheral capacitance to analyse the low frequency oscillation. The results obtained from the model are in agreement with the experimental observations and indicate that a variety of behaviours are dependent on the matching conditions.     

聚乙烯单链量子热输运的同位素效应

高分子导热材料的有效调控受到了日益广泛的关注.应用密度泛函理论(DFT)、中央插入延展(central insertion scheme,CIS)方法及非平衡格林函数(NEGF)理论,对包含432个原子、长18.533 nm的聚乙烯单链量子热输运的同位素效应进行了研究.计算结果表明,室温下长100 nm的纯12C聚乙烯单链的热导率理论上限高达314.1 W·m~(-1)·K~(-1);对于~(12)C聚乙烯单链,其他条件一定时,~(14)C掺杂引起的热导同位素效应比~(13)C更为显著;室温下纯~(12)C聚乙烯单链中~(14)C掺杂原子百分数为50%时同位素效应最显著,此时平均热导比未掺杂时下降了51%.这对探索聚乙烯材料热输运的同位素影响机理具有十分积极的意义.     

Normal and Abnormal Enhancement of IR Absorption of CO Adsorbed on Electrodes of Nanostructured Materials

A new phenomenon of enhanced IR absorption has been revealed recently and reported in the present paper. In referring to the surface enhanced IR absorption (SEIRS)^[l], which is limited to systems of particular molecules (PNBA, etc.) adsorbed on island films of Au, Ag metals, the newly discovered phenomenon is of significant importance in fundamental studies as well as in applications of electrocatalysis and surface analysis, since nanostructured transition metals or alloys were involved in this phenomenon.     

Tuning Redox Active Polyoxometalates for Efficient Electron-Coupled Proton-Buffer-Mediated Water Splitting

We present strategies to tune the redox properties of polyoxometalate clusters to enhance the electron-coupled proton-buffer-mediated water splitting process, in which the evolution of hydrogen and oxygen can occur in different forms and is separated in time and space. By substituting the heteroatom template in the Keggin-type polyoxometalate cluster, H₆ZnW₁₂O₄₀, it is possible to double the number of electrons and protonation in the redox reactions (from two to four). This increase can be achieved with better matching of the energy levels as indicated by the redox potentials, compared to the ones of well-studied H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀. This means that H₆ZnW₁₂O₄₀ can act as a high-performance redox mediator in an electrolytic cell for the on-demand generation of hydrogen with a high decoupling efficiency of 95.5 % and an electrochemical energy efficiency of 83.3 %. Furthermore, the H₆ZnW₁₂O₄₀ cluster also exhibits an excellent cycling behaviour and redox reversibility with almost 100 % H₂-mediated capacity retention during 200 cycles and a high coulombic efficiency >92 % each cycle at 30 mA cm⁻².     

Electronic properties of LiMn2?xTixO4

Ti-substituted LiMn₂O₄ (LiMn_2−x Ti _x O₄, x=0, 0.15, 0.30, 0.45, 0.60, and 0.75) has been synthesized using solid-state reactions. Their crystal and electronic structures were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). XRD data suggested that the lattice parameters of LiMn_2−x Ti _x O₄ increase due to the replacement of Mn by Ti ions. XPS results indicated that the substituted Ti ions were in +4 oxidation state; consequently, the normal oxidation state of Mn ions has been detected by measuring the binding energy splitting of Mn 3s states, which decreases with the content of substituted Ti. The valence band spectra suggested that the intensity of e _g level of Mn 3d orbitals increased due to the increase of the Mn³⁺/Mn⁴⁺ ratio.     

Sr2MgMoO6阳极材料制备与催化性能

通过溶胶-凝胶过程制备了固体氧化物燃料电池双钙钛矿阳极材料Sr₂MgMoO₆（SMMO）,研究了样品制备过程对材料的相态结构组成、传输性能、H₂氧化催化活性等方面的影响。结果表明,SMMO对制备过程的要求高,难以通过简单一步退火反应获得相态纯净的双钙钛矿结构,高纯度的SMMO需要经过反复混合及充分退火反应制取,同时样品中少量的杂质相SrMoO₄也很难彻底消除;样品中的杂质对材料的电导率有明显影响,纯度越高,材料的导电传输性能越好;SMMO的纯度对阳极材料的电化学性能影响很大,纯度越高,阳极的界面阻力越小,阳极催化氧化H₂的性能越好,对应单电池的输出功率越大;在800℃下,SMMO阳极的界面电阻低至1.07 Ω·cm²,对应单电池的输出功率可达710 mW·cm^-2。     

In situ FTIR spectroscopic studies of CO adsorption on electrodes with nanometer-scale thin films of ruthenium in sulfuric acid solutions

A nanometer-scale thin film of ruthenium supported on glassy carbon (nm-Ru/GC) was prepared by electrochemical deposition under cyclic voltammetric conditions. Scanning tunneling microscopy (STM) was used to investigate the structure and to measure the thickness of the thin film. It has been found that the Ru thin film is composed of layered Ru crystallites that appear in a hexagonal form with dimensions of about 250 nm and thickness around 30 nm. In situ FTIR spectroscopic studies demonstrated that such a nanostructured Ru thin film exhibits abnormal infrared effects (AIREs) for CO adsorption (G.Q. Lu et al., Langmuir 16 (2000) 778). In comparison with CO adsorbed on a massive Pt electrode, the IR absorption of CO_ad on nm-Ru/GC was significantly enhanced. Moreover, the direction of CO_ad bands is inverted and the full width at half maximum of CO_ad bands is increased. It has been revealed that the enhancement factor of IR absorption of CO adsorbed on nm-Ru/GC electrodes depends strongly on the thickness of the Ru film. An asymmetrical volcano relationship between the enhancement factor and the thickness of the Ru film has been obtained. The maximum value of the enhancement factor was measured as 25.5 on a nm-Ru/GC electrode of Ru film thickness around 86 nm. The present study has contributed to exploration of the particular properties of nanostructured Ru film material and to the origin of the abnormal infrared effects.     

Diffraction patterns for a transmission volume hologram under Bragg mismatch

We have presented simulations and experiments for 2-dimensional diffraction distributions of a transmission volume hologram. We sample the input pattern with a few elementary points and calculate the diffraction of the corresponding elementary grating. The simulations can describe well the diffraction pattern obtained in the experiment and can be used to predict the tolerance for angular deviation of the reading beam. The tolerance for angular deviation depends on its direction. It is affected by the Bragg degeneracy. The simulation results provide a clear picture of the spatial tolerance for reading a transmission volume hologram.     

氟化石墨的电化学性能研究

对系列氟化石墨及其作为碱性电池正极添加剂的电化学性能进行了研究,考察了氟化石墨作为电极活性材料及用作添加剂时电池的放电行为以及氟化石墨的氟化程度和电极中氟化石墨的含量对电池的放电性能的影响.研究了MnO₂中添加氟化石墨后对电极循环性能的影响,并用XRD比较了几种不同碳材料与氟化石墨的结构特点及MnO₂电极放电前后的状态变化,初步探讨了氟化石墨改善二氧化锰电化学性能的作用机制.