Methane conversion to C2 hydrocarbons in solid electrolyte membrane reactors

Solid electrolyte membrane reactors (SEMRs) have been used to both study and influence catalytic reaction rates. Methane coupling is the reaction most thoroughly and intensively studied in these membrane reactors. In the last 20 years, oxygen ion (O²⁻), proton (H⁺) and mixed (O²⁻-e⁻, H⁺-e⁻) conducting membranes have been tested in order to maximize the conversion of methane to C₂ compounds. The present review contains the fundamental operating principles of the various SEMR types and their applications in this reaction. The difficulties that should be overcome in order to promote this SEMR process to an industrial scale are discussed.     

Solar energy conversion from water photolysis by biological and chemical systems

The production of chemicals and fuels, or energy-rich compounds, from water by sunlight is described as a particularly attractive means for the conversion of solar energy to a valuable renewable resource. The redox properties of photoexcited molecules and the operating mechanism of light-driven systems are first considered. The mechanism of water oxidation carried out by higher plants and green algae-which is actually one of the most important biochemical reactions—as well as that of artificial photosystems, up-to-now designed trying to simulate the natural process with higher efficiency and simplicity, are likewise discussed. A number of biological and chemical light-driven systems are presented as practical ways to solar energy conversion.     

Plasma-Chemical Conversion of Lower Alkanes with Stimulated Condensation of Incomplete Oxidation Products

Oxidative conversion of a mixture of natural gas and oxygen in a barrier-discharge plasma-chemical reaction was investigated experimentally. The process was conducted at atmospheric pressure and room temperature. The discharge was initiated by high-voltage pulses of 50–100 s duration at a repetition frequency of up to 2 kHz. The principal feature of the process was that in the plasma-chemical reactor conditions were created which stimulated the condensation of the products of incomplete oxidation of methane that resulted in the formation of aerosol even from nonsaturated vapor. The removal of intermediate reagents from the gaseous phases into the aerosol prevented them from further oxidation. Depending on the experimental conditions, the mass percentage of the components of the condensate formed varied within the following limits: formic acid from 20 to 40%, methanol from 8 to 15%, methylformate from 4 to 8%, and water from 40 to 60%. The conversion process has been realized on a laboratory setup of average power up to 1 kW. In the single-pass mode, a 57% degree of conversion of the mixture has been achieved. The energy value of the condensate is 15–20 kWh/kg.     

阳离子改性HZSM-5沸石上低碳醇反应历程的TPSR-MS研究

用ＴＰＳＲ－ＭＳ技术研究了Ｃｕ，Ｚｎ和Ｇａ改性Ｈ－ＺＳＭ－５沸石的活性中心性质及Ｃ１～Ｃ４醇的反应历程。结果表明，Ｚｎ－和Ｇａ－ＺＳＭ－５有两种芳构化活性中心，即Ｂ酸和Ｚｎ，Ｇａ活性物种；甲醇在Ｃｕ－ＺＳＭ－５上只生成二甲醚、ＣＯ和ＣＯ２，而在Ｚｎ－ＺＳＭ－５上芳构化反应历程为：（１）醇经由醚脱水生成烯烃，Ｃ２～Ｃ４醇学可单分子脱水生成烯烃；（２）烯烃中间物齐聚，齐聚物通过氢转移和脱氢途径环化、芳     

Analysis of serotonin in brain microdialysates using capillary electrophoresis and native laser-induced fluorescence detection

Serotonin or 5-hydroxytryptamine (5-HT) is a major neurotransmitter in the central nervous system. In this work, a method for analyzing 5-HT in brain microdialysis samples using a commercially available capillary electrophoresis (CE) system has been developed. A pH-mediated in-capillary preconcentration of samples was performed, and after separation by capillary zone electrophoresis, native fluorescence of 5-HT was detected by a 266 nm solid-state laser. The separation conditions for the analysis of 5-HT in standard solutions and microdialysates have been optimized, and this method has been validated on both pharmacological and analytical bases. Separation of 5-HT was performed using a 80 mmol/L citrate buffer, pH 2.5, containing 20 mmol/L hydroxypropyl-beta-cyclodextrin (HP-beta-CD) and +30 kV voltage. The detection limit was 2.5 x 10(-10) mol/L. This method allows the in vivo brain monitoring of 5-HT using a simple, accurate CE measurement in underivatized microdialysis samples.     

Chemical mass shifts in resonance ejection experiments in the quadrupole ion trap

Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions.     

一种全光归零码到非归零码变换的新技术方案

报道了一种利用单只半导体光放大器和光滤波器实现全光归零码到非归零码变换的新技术方案.当探测（Probe）光和数据信号光同时输入到SOA时,基于SOA中的交叉增益调制和交叉相位调制现象,探测光光谱的后沿和前沿将分别产生红移和蓝移.通过调节光滤波器和探测光的中心波长之间的失调量,滤出光谱的特定部分,可以得到转换后的NRZ码光信号.这种新型的全光码型变换器具有结构简单、偏振不敏感、控制参量少和稳定性高的特点.分别采用仿真和实验的方式实现了20 Gbit/s光数据信号从RZ码到NRZ码的全光码型变换,并且仿真结果和实验结果相吻合.     

三电极共面介质阻挡放电的放电特性及诱导气流实验研究

等离子体流动控制激励器由于其响应速度快、激励频带宽、能量损耗低、可靠性强的优势,在航空航天领域的主动流动控制等方面得到了广泛应用.文章提出了一种新型的等离子体气动激励器——三电极共面介质阻挡放电激励器,研究了该激励器电极结构对放电特性和诱导气流速度的影响,并与传统共面介质阻挡放电和沿面介质阻挡放电激励器进行了比较.结果表明:（1）随着激励电压的提高,高压电极和地电极之间先出现了丝状放电并逐渐延伸到第三电极;（2）随着第三电极与高压电极之间的距离增大,诱导气流速率从2.4 m/s下降到0 m/s,而第三电极宽度的变动对诱导气流速度影响可忽略不计;（3）相同外部条件下,该激励器诱导的气流速度小于沿面介质阻挡放电激励器,但高于共面介质阻挡放电激励器.      

特定结构光催化剂的制备及其构效关系

高效光催化剂的设计是光催化研究的关键.本文介绍了超临界处理、醇解、溶剂蒸发诱导自组装(EISA)法和喷雾干燥技术在特定结构TiO2和非钛催化剂制备中的应用,并初步介绍了光催化剂的构效关系,说明具有特定组成和形貌结构的光催化剂的制备对提高光催化性能起到了关键的作用.     

Sensing the ortho Positions in C6Cl6 and C6H4Cl2 from Cl2− Formation upon Molecular Reduction

The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl₂⁻. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using ortho-, meta- and para-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl₂⁻ formation can only occur in 1,2-C₆H₄Cl₂, where the two closest C–Cl bonds are cleaved while the chlorine atoms are brought together within the ring framework due to excess energy dissipation. These results show that a strong coupling between electronic and C–Cl bending motion is responsible for a positional isomeric effect, where molecular recognition is a determining factor in chlorine anion formation.