空气中电晕放电高能电子密度沿反应器分布的光谱研究(英)

利用目前在等离子体特性诊断方面较为先进实用的发射光谱法,在常温常压下测量了正脉冲电晕放电空气中的Ｎ２（Ｃ３ Πｕ →Ｂ３ Πｇ） 发射光谱相对强度沿线－ 筒式反应器的径向分布,由此得到了正脉冲电晕放电等离子体中高能电子（ ≥１１ ．０３ｅＶ） 的电子密度沿线－ 筒式反应器的径向分布．随径向距离增大高能电子密度呈非线性递减,对于不同放电电压这种递减规律相同．     

Bi‐Microporous Metal–Organic Frameworks with Cubane [M4(OH)4] (M=Ni,Co) Clusters and Pore‐Space Partition for Electrocatalytic Methanol Oxidation Reaction

Embedding cubane [M₄(OH)₄] (M=Ni, Co) clusters within the matrix of metal–organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material type based on the pore‐space partition of the cubic primitive minimal‐surface net (MOF‐14‐type) has been realized. CTGU‐15 made from the [Ni₄(OH)₄] cluster not only has very high BET surface area (3537 m² g^?1), but also exhibits bi‐microporous features with well‐defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU‐15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU‐15 (1:2) made from ketjen black (KB) and CTGU‐15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg^?1 and excellent peak current density (29.8 mA cm^?2) at low potential (0.6 V). The isostructural cobalt structure (CTGU‐16) has also been synthesized, further expanding the application potential of this material type.     

Rare earth‐doped calcium‐based magnetic catalysts for transesterification of glycerol to glycerol carbonate

Several rare earth‐doped, calcium‐based magnetic catalysts were prepared for the synthesis of glycerol carbonate. The basicity and basic strength analysis of the catalysts showed that the doping of rare earth improved the basicity of the catalysts, and the doping of lanthanum maximized it. In addition, with the doping of lanthanum, the particle size of the catalyst became smaller to promote the organic reactants near the active sites of catalysts, thereby effectively improving the performance. NiFe₂O₄@[CaO‐La₂O₃] shows better catalytic performance with 99.0% yield of glycerol carbonate compared to the other catalysts. The NiFe₂O₄@(CaO‐La₂O₃) could be reused in six cycles without significant loss in activity.     

综合有机化学实验:提取丁香花中的丁香酚多步合成香兰素

介绍了一个综合型有机化学实验，作为一个整体项目大约安排12周时间来完成。以不含香兰素的丁香花为原料，提取其中的丁香酚来多步合成香兰素，并进行物理和化学性质检验，整个实验技术路线包含了蒸馏、合成、重结晶等多种操作，同时在纯化和结构鉴定过程中还用到红外、紫外-可见和高效液相色谱等多种大型仪器分析技术。     

Asymmetric Synthesis of a Fused Tricyclic Hydronaphthofuran Scaffold by Desymmetric [2+2+2] Cycloaddition

A rhodium(I)‐BINAP‐catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily available materials with excellent chemo‐, regio‐, diastereo‐, and enantioselectivity. Notable features of these reactions include 100 % atom economy, very broad scope, and mild reaction conditions.     

An Ultra‐Long‐Life Lithium‐Rich Li1.2Mn0.6Ni0.2O2 Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries

Voltage decay and capacity fading are the main challenges for the commercialization of Li‐rich Mn‐based layered oxides (LLOs). Now, a three‐in‐one surface treatment is designed via the pyrolysis of urea to improve the voltage and capacity stability of Li_1.2Mn_0.6Ni_0.2O₂ (LMNO), by which oxygen vacancies, spinel phase integration, and N‐doped carbon nanolayers are synchronously built on the surface of LMNO microspheres. Oxygen vacancies and spinel phase integration suppress irreversible O₂ release and help lithium ion diffusion, while N‐doped carbon nanolayer mitigates the corrosion of electrolyte with excellent conductivity. The electrochemical performance of LMNO after the treatment improves significantly; the capacity retention rate after 500 cycles at 1 C is still as high as 89.9 % with a very small voltage fading rate of 1.09 mV cycle^?1. This three‐in‐one surface treatment strategy can suppress the voltage decay and capacity fading of LLOs.     

DNA‐Based Adaptive Plasmonic Logic Gates

Self‐assembled plasmonic logic gates that read DNA molecules as input and return plasmonic chiroptical signals as outputs are reported. Such logic gates are achieved on a DNA‐based platform that logically regulate the conformation of a chiral plasmonic nanostructure, upon specific input DNA strands and internal computing units. With systematical designs, a complete set of Boolean logical gates are realized. Intriguingly, the logic gates could be endowed with adaptiveness, so they can autonomously alter their logics when the environment changes. As a demonstration, a logic gate that performs AND function at body temperature while OR function at cold storage temperature is constructed. In addition, the plasmonic chiroptical output has three distinctive states, which makes a three‐state molecular logic gate readily achievable on this platform. Such DNA‐based plasmonic logic gates are envisioned to execute more complex tasks giving these unique characteristics.     

Enantioselective separation and dissipation of pydiflumetofen enantiomers in grape and soil by supercritical fluid chromatography–tandem mass spectrometry

Pydiflumetofen is registered in many countries and is widely used in crop production in the racemate form. However, the environmental behavior of the enantiomers has not been studied. An effective and sensitive chiral analytical method was first established for analyzing the pydiflumetofen enantiomers by supercritical fluid chromatography with tandem triple quadrupole mass spectrometry. The enantiomers could be separated and detected using the Chiralcel OD‐3 column in less than 3 min. The separation conditions were as follows: mobile phase, CO₂/methanol (80:20); flow rate, 1.0 mL/min; column temperature, 30°C, auto back‐pressure regulator pressure, 2000 psi with modified quick, easy, cheap, effective, rugged, and safe sample treatment method. The average recoveries of analytes from both matrices at three spiking levels were in the range of 84.1–103.0%. The limit of quantitation for each enantiomer was 0.005 mg/kg with a baseline resolution of approximately 1.64. The method was applied to monitor the enantioselective dissipation of pydiflumetofen in grape and soil. In grapes, (?)‐pydiflumetofen was degraded more rapidly than (+)‐pydiflumetofen. In soil, (+)‐pydiflumetofen was preferentially degraded. The data provided useful references for the risk assessment and rational use of pydiflumetofen in agriculture.     

Mo的引入方式对CeO2脱硝性能的影响

固定源排放的氮氧化物(NOx)导致了严重的环境污染问题,NH3选择性催化还原(NH3-SCR)被认为是目前控制NOx排放的最有效技术,已广泛应用于电力行业的烟气排放治理.然而,我国非电行业的NOx减排仍然面临着重大挑战,因为其排放的废气温度通常低于300oC,且含有一定量的SO2,传统的钒基SCR催化剂因活性温度(300～400oC)较高而无法有效发挥作用.因此,亟待开发新型的高效低温SCR催化剂.铈基催化剂由于氧化铈(CeO2)的优异储氧能力(OSC)和良好的氧化还原能力而显示出较好的低温(80～300oC)脱硝性能,如Mn-Ce,W-Ce,Ta-Ce,Cu-Ce和Nb-Ce等.但这些铈基催化剂易被烟气中的SO2毒化而导致催化活性降低.因此,提高铈基SCR催化剂抗硫中毒能力是其产业化应用的关键.已有研究发现,通过构筑结构保护层或添加另一种金属来保护活性组分是提高SCR催化剂抗硫性能的一种可行策略.氧化钼(MoO3)通常被用做传统V2O5/TiO2催化剂的促进剂以提高其水热稳定性和表面酸性.研究表明,在V/Ti催化剂中引入钼物种不仅可以提高其SCR活性,而且提高了V/Ti催化剂的抗SO2性能,这是由于VMo/Ti表面较少的V–O–V键削弱了对SO2的氧化作用.Tang等开发了一种Fe2O3/MoO3纳米片催化剂,显示出比纯Fe2O3更好的抗SO2能力,主要是由于层状结构的MoO3能阻止NH4+在硫酸氢铵中的沉积.目前关于Mo的引入方式即催化剂的制备方法对铈基催化剂物化性能和NH3-SCR催化性能(特别是抗SO2能力)的影响的研究还比较少.本文分别采用浸渍法和沉淀法在CeO2中引入钼物种,制备了Mo-CeO2和MoCe-cp催化剂来探究制备方法对MoCe催化剂的脱硝性能及抗SO2中毒能力的影响.结果表明,引入Mo可以显著地提高CeO2的低温脱硝性能,其中Mo-CeO2催化剂在150 oC即可达到80％以上的脱硝效率,同时抗SO2中毒性能也得到了显著提高.对催化剂结构、氧化还原能力、表面酸度和反应物分子的吸附脱附性质进行了表征,并与MoCe催化剂脱硝性能和抗硫性能相关联.结果表明,Mo-CeO2和MoCe-cp催化剂的物理化学性质和脱硝性能有明显区别.首先,Mo-CeO2中的钼物种主要存在于CeO2表面,而MoCe-cp中的钼物种主要存在于CeO2体相,其为Mo-CeO2表面带来大量的Br?nsted酸位并抑制了硝酸盐的吸附,促使NH3-SCR反应按照Eley-Rideal机理进行,进而表现出优于MoCe-cp的低温活性.其次,Mo-CeO2表面更多的Mo物种抑制了SO2的吸附,从而使Mo-CeO2表现出更好的抗SO2性能.本文为具有实际应用前景的铈基NH3-SCR催化剂的设计提供了参考.     

ZIF-8衍生的具有可控氧空位的ZnO对光催化去除NO的增强及毒性NO2形成的抑制

氧化锌作为一种半导体材料,具有合适的能带结构位置,高催化效率,低成本和环境可持续性,因而广泛用于光催化领域.然而,由于氧化锌的宽带隙,可见光吸收能力差以及光生电子-空穴对的快速复合,极大地影响了其光催化效率.通过引入氧空位调控光催化剂的结构被证明是一种可以改善光生载流子的分离,从而提高光催化性能的有效方法.本文以ZIF-8为前驱体,采用两步煅烧法合成了具有不同浓度氧空位分布的ZnO纳米光催化剂,通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、电子顺磁共振(EPR)、荧光光谱仪(PL)等手段系统地分析了合成的光催化剂的理化性质,并评价了它们在可见光下光催化氧化去除NO反应性能.EPR结果表明,样品中氧空位的浓度取决于温度处理的过程.通过两步煅烧法得到氧化锌中氧空位的含量高于一步直接煅烧法所得的样品.此外,随着煅烧温度升高,合成的氧化锌晶格越完好,其氧空位含量越少.UV-Vis DRS结果表明,两步煅烧法合成的ZnO与商业的ZnO及一步法直接煅烧合成的ZnO相比,其吸光范围从紫外光拓展到了可见光,表现出了更加优异的吸光性能.光催化反应结果表明,与商业氧化锌和一步直接煅烧法所得样品相比,两步煅烧法合成的样品表现出了更优异的光催化去除NO性能,并抑制了中间产物毒性NO2的产生,促进了NO的深度氧化.具体反应路径为:在光照过程中,光生电子很容易被氧空位俘获,与O2反应产生更多的超氧自由基(·O2^-),从而将NO氧化成最终的产物硝酸盐.尤其有趣的是,先在350 ℃煅烧2小时再400℃煅烧1小时的两步法样品Z 350-400的NO去除效率分别比一步法样品Z 400(400℃煅烧)和商用ZnO高出1.5和4.6倍.这表明以MOF材料衍生的具有适当量氧空位的金属氧化物为一种高效去除NO的光催化剂具有很好的应用前景.