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.     

Li adsorption on monolayer and bilayer MoS_2 as an ideal substrate for hydrogen storage

Based on the first-principles plane wave calculations, we show that Li adsorbed on monolayer and bilayer MoS_2 forming a uniform and stable coverage can serve as a high-capacity hydrogen storage medium, and Li-coated MoS_2 can be recycled by operations at room temperature due to Li having strength binding, big separation and is stable against clustering. The full Li coverage MoS_2 system(2 * 2 hexagonal MoS_2 supercell) can reach up to eight H_2 molecules on every side, corresponding to the gravimetric density of hydrogen storage up to 4.8 wt% and 2.5 wt% in monolayer and bilayer MoS_2, respectively. The adsorption energies of hydrogen molecules are in the range of 0.10 e V/H_2–0.25 e V/H_2,which are acceptable for reversible H_2 adsorption/desorption near ambient temperature. In addition, compared with light metals decorated low dimension carbon-based materials, the sandwiched structure of MoS_2 exhibits the greatly enhanced binding stability of Li atoms as well as slightly decreased Li-Li interaction and thus avoids the problem of metal clustering.It is interesting to note that the Li atom apart from the electrostatic interaction, acts as a bridge of hybridization between the S atoms of MoS_2 and adsorbed H_2 molecules. The encouraging results show that such light metals decorated with MoS_2 have great potential in developing high performance hydrogen storage materials.     

聚乙烯单链拉伸应变下的量子热输运

在室温下,聚乙烯纳米纤维拉伸后的热导率可比聚乙烯块体的热导率提高几十到数百倍.为了相对准确地考察该现象的微观机制,根据聚合物高分子链拉伸应变后系带分子形变的微观特征,从量子力学出发,在密度泛函理论(DFT)计算的基础上,用非平衡格林函数(NEGF)方法,对聚乙烯单链拉伸前、后的声子透射谱、热导及热导率进行了比较,讨论了聚乙烯单链拉伸应变下热输运性能变化的规律.计算表明:聚乙烯单链导热性能随拉伸应变的增加而单调减少.分析了先前分子动力学(MD)方法在计算模型上的不足之处,并对实验现象做出了合理解释.这对澄清高分子聚合物拉伸后热物理性能提升的微观机制有着积极的意义.     

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.     

钯纳米晶体在电催化甲酸氧化反应中的形貌效应

本文基于课题组前期工作,选用适当的金属前驱物、还原剂、稳定剂和保护剂,通过调控氧化刻蚀和反应动力学等,成功合成了形貌和尺寸均不相同的Pd纳米晶.经过认真的纳米粒子清洗和电极修饰组装,考察了它们在电催化甲酸氧化反应中的形貌与性能的关系.研究结果表明,Pd纳米晶样品的最大电流密度以纳米八面体（nanooctahedra）、纳米线（nanowires）、纳米立方体（nanocubes）、纳米瓜子（nanotapers）、凹面纳米立方体（concave nanocubes）的顺序递增,催化甲酸氧化反应的起始氧化电位均小于0.2V.研究结果印证了Pd纳米晶催化甲酸氧化反应的催化性能在尺寸效应上主要受活性表面积的影响,扣除表面积效应后的催化性能与其尺寸没有明确关系.该系列Pd纳米晶的催化性能主要取决于其表面结构,得出Pd纳米晶催化甲酸氧化反应遵循{111}晶面〈{100}晶面〈高指数晶面的性能活性顺序.综合最大电流密度和最小操作电位因素发现,Pd凹面纳米立方体和Pd纳米瓜子具有相对较好的商用价值.     

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。     

外电场作用下N2O分子的结构与光谱特性

采用密度泛函B3LYP方法,在6-311+g(d)基组水平上研究了不同外电场对直线型分子N₂O的基态结构、偶极矩、轨道能级、红外和拉曼光谱特性的影响,并采用杂化CIS方法研究了N₂O分子在外电场作用下前9个激发态的激发特性.结果表明:外电场导致分子键长变化,但并没有改变分子的直线特征,偶极矩和分子总能量随外电场的增加先减小后增大,而能隙随外电场的增加先增大后减小,外电场的增加使LUMO(lowest unoccupied molecular orbital)组成由π~*轨道变为σ~*轨道,外电场使红外光谱发生移动,峰的强度增强或减弱.外电场的增加显著影响了N₂O分子的激发特性.激发能、激发波长受外电场影响发生了变化,同时,振子强度受外电场影响明显,禁阻跃迁变为可允许的跃迁,允许的跃迁在电场作用下变为禁阻跃迁或者跃迁变弱.紫外光谱在电场的作用下吸收峰发生了明显的移动,而且有新的吸收峰产生.     

基于镍泡沫支撑的Co_3O_4纳米多孔结构的高性能超级电容器电极

在众多能量存储和转化器件中,超级电容器由于具有功率密度高、充放电迅速和优异的循环性能的优点而被广泛研究.然而,较低的比容量和能量密度,限制了超级电容作为大尺度能量存储和转化器件的广泛应用.为了提高超级电容器的比容量,需要增大电极材料和电解质的接触面积,进而促进电极材料俘获/释放电解质中的粒子(例如电子、离子或者小分子).在此,我们通过简单的水热法联合高温退火实验方案能够大规模制备出镍泡沫支撑的Co_3O_4多孔纳米结构.无需借助导电胶和粘合剂,在集流器镍泡沫上"生长"Co_3O_4多孔纳米结构直接作为超级电容的电极材料.这种多孔纳米结构和一体化设计思路不仅能够有效提高电极的导电性,而且能够有效缩短离子和电子的迁移路径.由于多孔的结构特征和优异的导电性能,Co_3O_4电极表现出超高比容量(在电流密度为2.5 m A·cm~(-2)和5.5 m A·cm~(-2)时,比容量分别为1.87 F·cm(-2)(936 F·g-1)和1.80 F·cm~(-2)(907 F·g-1))、较好的倍率性能(电流密度从2.5 m A·cm~(-2)增大到100 m A·cm~(-2)时,保留其48.37%的初始电容)和超高的循环稳定性(经历4000次电流密度为10 m A·cm~(-2)的循环充放电过程,保留其92.3%的比容量).这种多孔纳米结构和一体化设计思路对设计其他高性能储能器件具有重要的指导意义.     

聚噻吩单链量子热输运的第一性原理研究

聚噻吩块体通常被视为绝热材料,其热导率小于1W·m~(-1)·K~(-1).但近年发现对于室温下沿聚噻吩分子链方向排列的无定形聚噻吩纳米纤维,其热导率高于聚噻吩块体,可达4.4W·m~(-1)·K~(-1).为了相对准确地揭示纳米尺度聚噻吩单链热输运的微观特征,从量子力学出发,在密度泛函理论计算的基础上,应用中间插入延展方法结合非平衡格林函数方法,对长度为25.107nm、包含448个原子的聚噻吩单链的量子热输运及其同位素效应进行了研究,并与分子动力学方法模拟的结果进行了详细比较.结果表明:室温下32 nm长的纯聚噻吩单链热导率上限高达30.2 W·m~(-1)·K~(-1),与铅的热导率35 W·m~(-1).K~(-1)相近;相同掺杂比例(原子百分数)下C元素热导的同位素效应比S元素显著;室温下聚噻吩单链中~(12)C,~(13)C等比例随机掺杂时的同位素效应最为显著,此时聚噻吩单链的平均热导至少降低了30%;室温下纯聚噻吩单链的热导随C的相对原子质量增加近似呈反比例减小,随S的相对原子质量增加呈非线性单调增加.该研究对认识和调控聚噻吩这种新型功能材料的热输运特性具有积极的价值.