Mass spectrometric monitoring of oxidation of aliphatic C6–C8 hydrocarbons and ethanol in low pressure oxygen and air plasmas

Experimental and theoretical studies on the oxidation of saturated hydrocarbons (n‐hexane, cyclohexane, n‐heptane, n‐octane and isooctane) and ethanol in 28 Torr O₂ or air plasma generated by a hollow cathode discharge ion source were made. Ions corresponding to [M + 15]⁺ and [M + 13]⁺ in addition to [M ? H]⁺ and [M ? 3H]⁺ were detected as major ions where M is the sample molecule. The ions [M + 15]⁺ and [M + 13]⁺ were assigned as oxidation products, [M ? H + O]⁺ and [M ? 3H + O]⁺, respectively. By the tandem mass spectrometry analysis of [M ? H + O]⁺ and [M ? 3H + O]⁺, H₂O, olefins (and/or cycloalkanes) and oxygen‐containing compounds were eliminated from these ions. Ozone as one of the terminal products in the O₂ plasma was postulated as the oxidizing reagent. As an example, the reactions of C₆H₁₄^+? with O₂ and of C₆H₁₃⁺ (CH₃CH₂CH⁺CH₂CH₂CH₃) with ozone were examined by density functional theory calculations. Nucleophilic interaction of ozone with C₆H₁₃⁺ leads to the formation of protonated ketone, CH₃CH₂C(=OH⁺)CH₂CH₂CH₃. In air plasma, [M ? H + O]⁺ became predominant over carbocations, [M ? H]⁺ and [M ? 3H]⁺. For ethanol, the protonated acetic acid CH₃C(OH)₂⁺ (m/z 61.03) was formed as the oxidation product. The peaks at m/z 75.04 and 75.08 are assigned as protonated ethyl formate and protonated diethyl ether, respectively, and that at m/z 89.06 as protonated ethyl acetate. Copyright © 2016 John Wiley & Sons, Ltd.     

Accelerating Oxygen‐Reduction Catalysts through Preventing Poisoning with Non‐Reactive Species by Using Hydrophobic Ionic Liquids

Developing cost‐effective electrocatalysts for the oxygen reduction reaction (ORR) is a prerequisite for broad market penetration of low‐temperature fuel cells. A major barrier stems from the poisoning of surface sites by nonreactive oxygenated species and the sluggish ORR kinetics on the Pt catalysts. Herein we report a facile approach to accelerating ORR kinetics by using a hydrophobic ionic liquid (IL), which protects Pt sites from surface oxidation, making the IL‐modified Pt intrinsically more active than its unmodified counterpart. The mass activity of the catalyst is increased by three times to 1.01 A mg^?1_Pt@0.9 V, representing a new record for pure Pt catalysts. The enhanced performance of the IL‐modified catalyst can be stabilized after 30 000 cycles. We anticipate these results will form the basis for an unprecedented perspective in the development of high‐performing electrocatalysts for fuel‐cell applications.     

A Versatile Iron–Tannin‐Framework Ink Coating Strategy to Fabricate Biomass‐Derived Iron Carbide/Fe‐N‐Carbon Catalysts for Efficient Oxygen Reduction

The conversion of biomass into valuable carbon composites as efficient non‐precious metal oxygen‐reduction electrocatalysts is attractive for the development of commercially viable polymer electrolyte membrane fuel‐cell technology. Herein, a versatile iron–tannin‐framework ink coating strategy is developed to fabricate cellulose‐derived Fe₃C/Fe‐N‐C catalysts using commercial filter paper, tissue, or cotton as a carbon source, an iron–tannin framework as an iron source, and dicyandiamide as a nitrogen source. The oxygen reduction performance of the resultant Fe₃C/Fe‐N‐C catalysts shows a high onset potential (i.e. 0.98 V vs the reversible hydrogen electrode (RHE)), and large kinetic current density normalized to both geometric electrode area and mass of catalysts (6.4 mA cm^?2 and 32 mA mg^?1 at 0.80 V vs RHE) in alkaline condition. This method can even be used to prepare efficient catalysts using waste carbon sources, such as used polyurethane foam.     

Effect of alumina thickness on Al_2O_3/InP interface with post deposition annealing in oxygen ambient

In this paper, the effect of alumina thickness on Al2O3/InP interface with post deposition annealing （PDA） in the oxygen ambient is studied. Atomic layer deposited （ALD） Al2O3 films with four different thickness values （5 nm, 7 nm, 9 nm, 11 rim） are deposited on InP substrates. The capacitance-voltage （C-V） measurement shows a negative correlation between the alumina thickness and the frequency dispersion. The X-ray photoelectronspectroscopy （XPS） data present significant growth of indium-phosphorus oxide near the Al2O3/InP interface, which indicates serious oxidation of InP during the oxygen annealing. The hysteresis curve shows an optimum thickness of 7 nm after PDA in an oxygen ambient at 500 ℃ for 10 min. It is demonstrated that both sides of the interface are impacted by oxygen during post deposition annealing. It is suggested that the final state of the interface is of reduced positively charged defects on Al2O3 side and oxidized InP, which degrades the interface.     

Oxygen–Nitrogen Switchable Copolymers of 2,2,2‐Trifluoroethyl Methacrylate and N,N‐Dimethylaminoethyl Methacrylate

In this work, a novel class of O₂/N₂ switchable polymers is reported, which is prepared by atom transfer radical copolymerization (ATRcoP) of commercially available 2,2,2‐trifluoroethyl methacrylate (FMA) and N,N‐dimethylaminoethyl methacrylate (DMA). The copolymer is random and contains 10 FMA units and 85 DMA units. Its aqueous solution becomes transparent with O₂ bubbling and turns to turbid with N₂ purging. This O₂/N₂‐responsive switchability between the transparent and turbid states is reversible. The FMA–DMA copolymer is thermosensitive and has a lower critical solution temperature (LCST) of 24.5 °C. O₂ molecules interact with fluorinated groups of the copolymer and increase the LCST to 55 °C. Purging N₂ removes O₂ and returns the polymer thermosensitivity back to its initial state. The switchability occurs in the whole temperature range (24.5–55 °C).

     

Synthesis on large area and uniform nanosheet morphology of polycrystalline cobalt oxide Co3O4 obtained from oxidation of Co films in a pure oxygen atmosphere

Large area and uniform nanosheets Co₃O₄ have been fabricated by thermal annealing of cobalt thin film under the DC magnetron sputtering method. The synthesis is based on controlling the simple thermal oxidative formation of precursor Co films. The Co films were heated at 300, 400, and 500 °C for two hours in a pure oxygen atmosphere. At 300 °C, CoO and Co₃O₄ phases appear to survive together. An amount of pure polycrystalline Co₃O₄ nanosheets were observed at 400 °C. The structural and morphological properties of the nanosheets Co₃O₄ were characterized by means of transmission electron microscopy (TEM) and Raman spectroscopy.     

Scanning transmission X‐ray microscopy probe for in situ mechanism study of graphene‐oxide‐based resistive random access memory

Here, an in situ probe for scanning transmission X‐ray microscopy (STXM) has been developed and applied to the study of the bipolar resistive switching (BRS) mechanism in an Al/graphene oxide (GO)/Al resistive random access memory (RRAM) device. To perform in situ STXM studies at the C K‐ and O K‐edges, both the RRAM junctions and the I₀ junction were fabricated on a single Si₃N₄ membrane to obtain local XANES spectra at these absorption edges with more delicate I₀ normalization. Using this probe combined with the synchrotron‐based STXM technique, it was possible to observe unique chemical changes involved in the BRS process of the Al/GO/Al RRAM device. Reversible oxidation and reduction of GO induced by the externally applied bias voltages were observed at the O K‐edge XANES feature located at 538.2 eV, which strongly supported the oxygen ion drift model that was recently proposed from ex situ transmission electron microscope studies.     

氧气A带吸收系数的温度依赖关系研究

氧气A带是理想的大气要素反演通道,吸收系数是重要的参数之一,它影响到反演结果的精度.结合HITRAN2012数据库和大气温度廓线图,分析氧气A带吸收系数的影响因素,推出各因素与温度的依赖关系,确定吸收系数随温度的变化.结果表明,氧气A带谱线半宽度受温度依赖系数影响较小,而受温度影响较大.线型因子随温度产生了两种变化,在谱线半宽度以外的谱线位置上,随温度的增大,函数值减小,而在中心频率到谱线半宽度的谱线位置上,随温度的升高而增大.谱线线强对温度具有强依赖关系.利用逐线积分算法计算氧气A带吸收系数,同时考虑了谱线半宽度的压力展宽效应和谱线线强及半宽度对温度的依赖关系,得出氧气A带吸收系数对温度的依赖关系主要来源于线强的温赖关系,尤其是中心频率处温度影响较大;而Lorentzian线型函数的温赖关系不明显.利用布鲁克光谱仪在1 cm-1下测量63 m处氧气A带的吸收光谱,与理论模型在同等条件下的透过率比较,误差小于0.83%,验证了温度校正模型的正确性.     

光激活磁共振脑功能成像的研究现状及前景

磁共振脑功能成像经过20年的发展已经成为大脑认知神经科学研究中最主要的技术.光激活磁共振脑功能成像是将它与新发展起来的光遗传学相结合的新兴技术,具有高时空选择性地分析特定神经回路或特定类型的神经元在整个功能网络中的作用的巨大潜力,为理解人类脑功能和揭示神经精神疾病机理可提供新的技术手段.