氮掺杂及水分子吸附碳纳米管电子场发射第一性原理研究

对闭口碳纳米管(CNT)顶端分层掺氮及吸附不同数目水分子体系,运用第一性原理研究了有电场存在时的电子场发射性能.结果表明：掺氮并吸附水分子的CNT结构稳定;外电场愈强、水分子数愈多,体系态密度(DOS)向低能端移动幅度愈大且最高分子占据轨道(HOMO)/最低分子空轨道(LUMO)能隙愈小.吸附能,DOS/LDOS,HOMO/LUMO及其能隙分析一致表明,第三层氮掺杂CNT吸附不同数目水分子体系的场发射性能最佳. 关键词： 氮掺杂 水吸附 密度泛函理论 电子场发射     

碳掺杂闭口硼氮纳米管场发射第一性原理研究

运用第一性原理研究了闭口硼氮纳米管（BNNT）顶层掺碳体系（C@BNNT）的电子场发射性能.结果表明：随外电场增强,C@BNNT电子结构变化显著,态密度（DOS）向低能方向移动;碳原子的局域态密度（LDOS）在费米能级附近明显增大;赝能隙、最高占据分子轨道（HOMO）/最低未占据分子轨道（LUMO）能隙减小;体系电荷移向帽端.DOS,HOMO/LUMO及Mulliken电荷分析一致表明,与BNNT相比,C@BNNT电子场发射性能显著改善,且C@BN_moreNT性能更优. 关键词： 碳掺杂 硼氮纳米管 电子场发射 第一性原理     

H2的自由扩散和吸附状态的对比研究

运用巨正则Monte Carlo方法, 模拟了H₂在自由扩散状态下及碳纳米管吸附状态下的分布, 对H₂的自由扩散和吸附状态进行了对比研究. 研究表明: 77 K和2 MPa下, (30, 30)扶手椅型碳纳米管质量储氢密度为3.74%, 77 K和10 MPa下, 质量储氢密度为7.4%. 吸附状态的H₂分子主要汇聚在碳纳米管内外两个壁面. 关键词： 储氢 碳纳米管 巨正则Monte Carlo     

H2O在SrTiO3-(001)TiO2表面上吸附和解离的密度泛函理论研究

利用密度泛函理论研究了0.25单层（ML）,0.5ML,0.75ML和1ML吸附率下H₂O在SrTiO₃-（001）TiO₂表面上的吸附行为.比较了不同吸附率下分子吸附和解离吸附的稳定性,利用微动弹性带（nudged elastic band）方法计算了H₂O的解离势垒.结果表明：在低吸附率（0.25ML和0.5ML）时,H₂O表现为解离吸附;在0.75ML吸附率下,分子吸附和解离吸附同时存在;而在全吸附（吸附率为1ML）时,分子吸附更稳定.基于对H₂O分子与表面之间以及H₂O分子之间的电荷转移和相互作用的分析,讨论了吸附率对H₂O吸附和解离的影响. 关键词： 2O')" href="#">H₂O 吸附 3-（001）TiO₂表面')" href="#">SrTiO₃-（001）TiO₂表面 密度泛函理论     

Li修饰的C$lt;sub$gt;6$lt;/sub$gt;分子对H$lt;sub$gt;2$lt;/sub$gt;O的吸附研究

采用密度泛函理论中的广义梯度近似研究C₆Li吸附H₂O分子并将之进行分解的催化过程. 几何优化发现：Li原子最稳定的吸附位置是位于C 原子顶位上方. 研究表明,第一个H₂O 分子吸附在C₆Li上需要克服1.77 eV的能量势垒,然后分解为H和OH且与Li原子成键. 当吸附第二个H₂O分子时,第二个H₂O分子需要克服1.2 eV的能量势垒分解为H和OH,其中H与Li原子上的H原子结合成H₂,OH则替代Li 原子上的H结合在Li原子上. 因此C₆Li 可以作为催化剂将H₂O分子进行分解得到H₂. 分析可知：C₆Li主要是通过Li原子与H₂O之间形成的偶极矩作用来吸附H₂O 分子,与C₆₀Li₁₂ 的储氢机制类似. 研究结果可为储氢材料的制备提供一个新的思路. 关键词： 6')" href="#">C₆ Li 2O')" href="#">H₂O 密度泛函理论     

碳掺杂硼氮纳米管电子场发射的第一性原理研究

对闭口硼氮纳米管（BNNT）顶层掺碳体系,运用第一性原理研究了电子场发射性能.结果表明,掺碳的BNNT体系电子结构变化显著;外电场愈强,体系态密度向低能端移动幅度愈大,且最高占据分子轨道（HOMO）/最低未占据分子轨道（LUMO）能隙愈小.体系态密度和局域态密度,HOMO和LUMO及其能隙分析一致表明,各种碳掺杂体系中C_eqBNNT的场发射性能最佳. 关键词： 硼氮纳米管 碳掺杂 第一性原理     

H2O分子在五边形BCN上的吸附与解离特性研究

基于密度泛函理论的第一性原理计算方法,研究了H₂O分子在五边形BCN上的吸附与解离过程.研究结果表明,五边形BCN结构的B原子是H₂O分子的最稳定的活性吸附位点. H₂O分子在该活性位点极易解离,其初步解离过程为放热反应且分解势垒仅为0.191 eV,并形成稳定的OH/H产物.深入研究发现,H₂O分子初步解离后的五边形BCN表面,可直接分解后续吸附的H₂O分子.该研究结果为五边形BCN对H₂O分子的吸附解离机制提供理论借鉴.     

碳纳米锥电子场发射的第一性原理研究

运用第一性原理研究了不同锥角和结构的碳纳米锥 （CNC） 电子场发射性能.结果表明：随外电场 （E_add） 增强,CNC电子结构变化显著,费米能级 （E_f） 处态密度 （DOS） 明显增大;赝能隙减小;体系电荷移向尖端.DOS,HOMO/LUMO及Mulliken电荷分析表明：CNC的电子场发射性能除依赖于尖端结构外,很大程度上还取决于锥角大小,特别顶层6个原子的CNC₃和CNC₄场发射性能 关键词： 碳纳米锥 电子场发射 第一性原理     

磷掺杂硼钒氧簇化合物的二维相关红外光谱研究

一个新颖的磷掺杂硼钒氧簇化合物[Li(H₂O)₂]₂[Cu(en)₂]₃[H₂en]₂[V₁₂P₁₂B₆O₆₈(OH)₄(H₂O)]·3(H₂O)1通过水热法合成,通过Li⁺连接成一维无限结构,再通过氢键连成三维立体结构。针对该化合物,通过二维红外相关光谱并作了详细分析,化合物1簇阴离子振动偶极矩对磁场和温度的变化均有响应峰,2D-IR COS提供了一种结构表征新方法。     

对碳纳米管阵列的场发射电场增强因子以及最佳阵列密度的研究

研究了外电场、碳纳米管自身线度、尤其管的阵列密度对碳纳米管的场发射性能的影响,从理论上深入探索碳纳米管阵列的电场增强因子并提出改善其场发射电子性能的有效途径.研究结果表明,碳纳米管阵列的电场增强因子的数量级一般为102—103,并对任何长径比的碳纳米管阵列,都对应着一个最佳阵列密度,当碳纳米管阵列密度取此最佳密度值时,其电场增强因子明显提高.这里的理论研究对弄清碳纳米管的场发射机理及实验合成高发射性能的碳纳米管阵列有一定的意义 关键词： 碳纳米管阵列 最佳阵列密度 电场增强因子 长径比     

分层掺B和吸附H2O碳纳米管的结构稳定性及电子场发射性能

运用基于第一性原理的密度泛函理论,系统研究了处于外电场中分层掺B并吸附不同数目H₂O碳纳米管体系的结构稳定性和电子场发射性能. 研究表明:第3层掺B并吸附5个H₂O的B₃CNT+5H₂O体系结构最稳定,管帽处Mulliken电荷最密集,尤其与单独掺B的B₃CNT和单独吸附H₂O的B₃CNT+5H₂O相比,其Fermi能级处态密度分别     

类富勒烯纳米晶CNx薄膜及其场致电子发射特性

利用微波等离子体增强化学气相沉积技术制备出了CN_x薄膜,并利用x射线光电子能谱、x射线衍射、扫描电子显微镜和Raman光谱等测试手段对所制备的CN_x薄膜的微结构和成分进行了分析.研究了其场致电子发射特性.发现薄膜的结构和场发射特性与反应系中的甲烷、氮气及氢气的流量比有关,当甲烷、氢气及氮气流量比为8/50/50 sccm时,制备的薄膜具有弯曲层状的纳米石墨晶体结构（类富勒烯结构）和很好的场发射特性.场发射阈值电场降低至1.1V/μm.当电场为5.9V/μm时,平 关键词： 类富勒烯 x薄膜')" href="#">CN_x薄膜 场致电子发射 微波等离子体增强化学气相沉积     

SIMS,EID and flash-filament investigation of O2, H2, (O2 + H2) and H2O interaction with vanadium

Comparative investigations of secondary ion emission, electron induced ion emission and flash filament signals from polycrystalline vanadium surfaces exposed to well-defined O₂, H₂, H₂O and (O₂ + H₂) doses (<500 L) have been carried out. The vanadium target could be heated and bombarded by either electrons (300 eV) or ions (3 keV) under ultra high vacuum conditions (<10^?10 Torr). The investigations were carried out with a computer controlled ultra high vacuum mass spectrometer. The experimental results establish exact reproducible spectra of well defined surface layers. They give detailed insight into the reactions between H₂, O₂ H₂O and vanadium, and some interactions between these species. They further indicate the importance of bulk and surface diffusion as well as the influence of the probing ion and electron bombardment. A clear distinction between bulk oxygen, surface oxides, and adsorbed oxygen for the vanadium-oxygen interaction at room temperature could be established. For the interaction of hydrogen with clean and oxygen covered vanadium surfaces the formation of adsorbed hydrogen, bulk solution of hydrogen, and the formation of OH groups and H₂O could be demonstrated. A detection limit below 10^?5 of one single monolayer for metal bonded hydrogen could be established.     

The electronic structure and magnetic properties of metallic antiferromagnetic Co[(CH3PO3)(H2O)] studied by first-principles calculations

The electronic structure, the metallic and magnetic properties of metal phosphonate Co[(CH₃PO₃)(H₂O)] have been studied by first-principles calculations, which were based on the density-functional theory (DFT) and the full potential linearized augmented plane wave (FPLAPW) method. The total energy, the spin magnetic moments and the density of the states (DOS) were all calculated. The calculations reveal that the compound Co[(CH₃PO₃)(H₂O)] has a stable metallic antiferromagnetic (AFM) ground state and a half-metallic ferromagnetic (FM) metastable state. Based on the spin distribution obtained from calculations, it is found that the spin magnetic moment of the compound is mainly from the Co²⁺, with some small contributions from the oxygen, carbon and phosphorus atoms, and the spin magnetic moment per molecule is 5.000μ_B, which is in good agreement with the experimental results.     

Spectroscopic evidence for the effect of the ortho H<Subscript>2</Subscript>O spin on the electron transfer in photosynthesis

A spin mechanism for electron transfer control in the reaction center of purple bacteria in photosynthesis is proposed. Rotation and conversion of the ortho/para spin isomers of two H₂O molecules located near the special pair of the reaction center are treated as the sources of the coherent modulations of transient kinetics. Modulation of the collective wave function of the reaction center electrons by the total proton spin of ortho H₂O is a key feature allowing the molecule to play the role of a gate controlling the electron transfer. The iron atom in the reaction center with the gradient magnetic field is treated as a catalyst removing the strict forbiddenness of H₂O ortho/para conversion. It is shown that the modulation of the reaction center stimulated emission kinetics observed in the field of femtosecond pulses coincides with the rotational transitions of ortho/para H₂O. Influence of the effect of the electric field (Stark effect) on the level displacement and ortho/para conversion rate is discussed.     

On the origin of electron stimulated desorption of H+ from metal surface

The emission of hydrogen ESD ions from polycrystalline Nb is studied experimentally. The results demonstrate clearly that no ESD emission of H⁺ occurs from a pure H adsorbate. However, adsorption of H₂O, present as an impurity in H₂, and H₂ adsorption on Nb preceded by O adsorption, produce strong H⁺ ESD emission. It is shown that Auger ionization of O can account for the increased H⁺ yield and it is postulated that similar effects also occur on other metal surfaces.     

Field electron emission images of multi-walled carbon nanotubes

Field electron emission microscope images from multi-walled carbon nanotubes can typically be characterized by the presence of five pentagons surrounding a sixth central pentagon. The observations of bright line centered interference patterns between adjacent pentagons in the field electron emission microscope images of multi-walled carbon nanotubes have been reported in the literature. We have observed a shift from bright to dark line centered interference patterns and associated this with the presence of surface adsorption. In order to identify the origin of the contaminant, multi-walled carbon nanotubes were dosed with H₂, H₂O, CO and O₂ and then imaged in the field electron emission microscope. Only the samples exposed to O₂ showed a shift from a bright line centered pattern between adjacent pentagons of a clean surface to a dark line centered pattern when one pentagon was contaminated or a bright line centered pattern when both adjacent pentagons become contaminated. The results of the experimental studies and the modeling of the changes in the field emission pattern as phase shifts in the wave function of the tunneling electrons due to modifications in the surface work function are presented.     

Preparation and electrochemical performance of spherical MnOx with high capacitance

A promising electrode material, MnO_x, was prepared by chemical precipitation method using MnSO₄?·?H₂O as manganese source and (NH₄)₂CO₃ as precipitant. The as-prepared manganese oxide was characterized by field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), and X-ray diffraction (XRD), respectively. The effects of reaction temperature and calcination temperature on the electrochemical properties of the electrode materials were investigated. The results show that MnO_x with a spherical morphology exhibits an excellent performance in the energy storage field. Under the optimal experimental conditions, the specific capacitance of pure MnO_x reaches up to 592 F g^?2 in the alkaline media when the current density is 5 mA cm^?2 over the potential window from ?0.3 to +0.4 V. The combination resistance and transfer resistance of MnO_x are 0.86 and 0.08 Ω, respectively. These findings make MnO_x a promising electrode material for electrochemical capacitors.