HL—1装置的金属杂质沉积实验

采用立体探针与二次离子质谱计（ＳＩＭＳ）分析相结合，对ＨＬ－１装置刮削层空间的杂质沉积特性和分布规律进行了实验研究。测量了在石墨活动孔栏条件下，立体针表面杂质沉积特性和分布规律进行了实验研究。测量了在石墨活动孔栏条件下，立体探针表面杂质沉积的径向分布，纵向分布，极向分布和Ｈ＾＋剖面分布。并讨论了实验结果。     

HL—1装置刮离层的金属杂质分布

HL-1装置运行期间,石墨收集探针收集了刮离层中的金属杂质沉积;利用俄歇电子谱仪(AES)和X射线光电子谱仪(XPS)分析了探针表面层的金属杂质组份分布及深度分布。给出了HL-1装置放电期间刮离层中总的金属重杂质流通量为5.3×10~(13)cm~(-2)·s~(-1)。     

用于接触式探测的多模光纤探针形状优化

对于进行接触式探测的多模光纤探针,信号光来自于附着于探针表面的待测物。基于几何光学,提出了一个物理模型,用以分析探头形状对所收集的信号光强度的影响。采用此模型,对抛物线型探头进行了仿真,给出了最优形状参数,并采用表面增强拉曼探针进行了初步实验验证。此分析可用于指导各种光纤传感器的设计,以确定其最佳的形状参数,适用于荧光传感器、表面等离子体共振传感器、表面增强拉曼传感器等。     

HL-2A装置偏滤器位形下氢和碳的粒子通量比

等离子体-壁相互作用通过各种机制释放粒子，主等离子体中杂质的数量限制了装置的性能。要深入认识杂质释放的机制，测量和分析粒子通量非常重要。文献[1]中详细描述了用光谱方法测量托卡马克等离子体中来自局部表面的向内的杂质通量，文献[2]报道了用这种方法测定ASDEX装置ICRF加热条件下向内的铬的通量。     

熔石英再沉积层结构的纳米级表征和杂质分析

利用原子力显微镜观察熔石英不同蚀刻时间的表面形貌,结合二次离子质谱分析,研究了熔石英的再沉积层结构和杂质分布。结果表明,熔石英表面深度10nm的再沉积层内存在大量微裂纹和杂质,经蚀刻展开形成nm级划痕和坑点,其分布随着深度增加呈指数衰减。根据nm级划痕密度、宽深比随蚀刻深度变化的规律,估算出再沉积层厚度,估算结果与二次离子质谱测得的杂质嵌入深度基本一致。杂质元素嵌入深度与抛光微裂纹分布特征的关联性表明,杂质很有可能藏匿在抛光微裂纹中。     

石墨炉内石墨探针表面上的原子化机理研究 Ⅳ钒的原子化机理

本文通过X-射线衍射分析(XRD),扫描电子显微镜分析(SEM),化学分析光电子能谱分析(ESCA),并结合原子吸收测量,研究了钒在普通石墨管中石磨探针表面上发生的固相化学反应。结果表明,钒化合物在灰化阶段即可转化为热稳定性较高的碳化物,原子化的最后步骤为碳化物的热分解。     

用四探针及阳极氧化方法测量硅中扩散层杂质分布

本文讨论了:(1)用阳极氧化法在硅片表面去层的技术;(2)用四探针测量扩散层面电导的方法;(3)用阳极氧化去层及四探针测量面电导方法求得扩散层精细杂质分布。文中着重讨论了实验技术中的实际问题,如如何在阳极氧化过程中取得精细而均匀的去层(300—1500?);如何控制及测量去层厚度;测量面电导及杂质分布时的误差来源及减小误差的措施。以典型的磷在硅中扩散的杂质分布测量为例:扩散深度为4.9μm,测量间距为400—1600?,面电导测量误差估计小于3％,杂质分布误差估计小于20％。简单地提出了一些测量中尚待进一步解决的问题。     

HL-1装置石墨孔栏杂质收集探针的俄歇电子能谱及孔栏表面分析

在HL-1装置的输样机构上安放了硅收集探针。经过55次高功率托卡马克放电辐照后,对于因石墨孔栏被腐蚀而溅射蒸发,并沉积在硅收集探针上的杂质涂层进行了俄歇电子能谱(AES)分析,获得无主动冷却石墨孔栏被腐蚀而溅射蒸发出来的碳杂质流通量约为8×10~(13)cm~(-2)·S~(-1),金属重杂质镍和铬较GH39高镍钢孔栏时降低44％左右。     

二次离子质谱在HL－1托卡马克研究中的应用

应用ＬＡＳ－２０００二次离子质谱表面分析系统作了如下测量：（１）测出ＨＬ－１装置的总出气量以及其主要出气组分的出气量百分比和出气峰值温度等参数；（２）对等离子体－表面相互作用进行了ＳＩＭＳ／蒙特卡洛互补分析，测出等离子体边界层中氢气量径向特征长度和氢粒子注入硅片的特征深度，估算出氢通量平均动力温度；（３）对硅收集探针的ＳＩＭＳ／ＡＥＳ分析表明，ＨＬ－１等离子体删削层中主要杂质组分为Ｏ、Ｃ、Ｎｉ、Ｍｏ和Ｃｒ，同时给出原子密度相对百分比；在ＨＬ－１装置中用原位蒸钛来吸氧、碳杂质，从而提高了等离子体纯度和品质；（４）定期检测表明，装置的器壁表面污染呈减弱趋势，这说明ＨＬ－１真空系统的设计研制及运行维护技术措施等是合适的。     

多层金属圆柱线中量子输运的表面和界面散射效应

考虑了量子尺寸效应以及来自杂质、粗糙表面和粗糙界面三方面的散射,运用量子统计的格林函数方法和久保公式,计算多层金属圆柱线中的各种散射电导率.计算结果表明,在杂质、表面和界面的弱散射极限下,系统总电导率等于各个子能级通道的电导率之和,而各子能级通道中杂质、表面和界面产生的散射率是可相加的. 关键词：     

1,2-环己二酮基态光解离反应的理论研究

通过密度泛函理论计算研究了1, 2-环己二酮(α-CHD)基态光解离反应的势能面. 通过IRC方法确定了5个主要的反应通道, 相应的产物分别为P₁(c-C₅H₈O+CO), P₂(2C₂H₄+2CO), P₃(CH₂CHCH₂CH₂CHO+CO), P₄(2CH₂CO+C₂H₄)和P₅(CH₃CHCO+CH₂CHCHO). 获得了反应过程中反应物、产物、中间体和过渡态的结构参数. 详细阐述了这些通道的反应过程, 分析了其反应机理, 总结出最优的反应路径为α-CHD→c-C₅H₈O+CO. 理论分析与实验结果相符. 获得的结果为进一步进行与1, 2-环己二酮相关的研究提供有价值的信息.     

Activation mechanisms of silver toward CO oxidation by tungsten carbide substrate: A density functional theory study

The development of efficient catalysts for low temperature CO oxidation is important to the application of fuel cells. In this work, we report that the Ag monolayer on WC (0001) surface (Ag_ML/WC) could effectively catalyze CO oxidation through the L-H mechanism (CO + O₂ → OOCO → CO₂ + O). The most sluggish reaction step is suggested to be CO + O → CO₂ with a barrier of 0.48 eV, which is 1.21 eV lower than the barrier of O₂ dissociation. The electronic structure and d-band center analyses demonstrate that the promoted activity may originate from the synergistic effect between Ag monolayer and WC. The present study is conducive to design new efficient and cost-effective catalysts for CO oxidation without using of the noble platinum.     

Nitric oxide reduction by CO ON Rh(111): Temperature programmed reaction

The reaction of NO with CO on Rh(111) has been studied with temperature programmed reaction (TPR). Comparisons are made with the reaction of O₂ with CO and the reaction of NO with H₂. The rate-determining step for both CO oxidation reactions is CO(a) + O(a) → CO₂(g). Repulsive interactions between adsorbed CO and adsorbed nitrogen atoms lead to desorption of CO in a peak at 415 K which is in the temperature range where the reaction between CO(a) and O(a) produces CO₂(g). Thus the extent of reaction of CO(a) with NO(a) is less than that between CO(a) and O(a) due to the lower coverage of CO caused by adsorbed N atoms and NO. A similar repulsive interaction between NO(a) and H(a) suppresses the NO + H₂ reaction. CO + NO reaction behavior on Rh(111) is compared to that observed on Pt(111).     

Mechanistic study on Mo(CO)6‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes

By means of density functional theory, the Mo(CO)₆‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes was investigated. All the intermediates and transition states were optimized completely at B3LYP/6‐311++G(d,p) level (LANL2DZ(f) for Mo). Calculations indicate that the complexation of 5‐allenyl‐1‐ynes with Mo(CO)₆ occurred preferentially at the triple bond to give the complex M1 and then the complexation with the distal double bond of the allenes generates the complex M5 . In this reaction, Mo(CO)₆‐catalyzed intramolecular [2 + 2] cycloaddition is more favorable than [2 + 2 + 1] cycloaddition. The reaction pathway Mo(CO)₆ + R → M5 → T7 → M12 → M13 → T11 → M18 → P4 is the most favorable one, and the most dominant product predicted theoretically is P4 . The solvation effect is remarkable, and it decreases the reaction energy barriers. Copyright © 2011 John Wiley & Sons, Ltd.     

Ni(111)表面一氧化碳和氢共吸附的密度泛函理论研究

本文用密度泛函理论(DFT)的总能计算研究了一氧化碳和氢原子在Ni(111)表面上p(2×2)共吸附系统的原子结构和电子态，结果表明CO和H原子分别被吸附于两个对角p(1×1)元胞的hcp和fcc位置.以氢分子和CO分子作为能量参考点，总吸附能为2.81 eV，相应的共吸附表面功函数φ为6.28 eV.计算得到的C—O，C—Ni和H—Ni的键长分别是1.19?, 1.96?和 1.71?，并且CO分子以C原子处于hcp的谷位与金属衬底原子结合.衬底Ni(111)的最外两层的晶面间距在吸附后的相对变化分别是 关键词： Fisher-Tropsch反应 催化作用 Ni(111) p(2×2)/(CO+H) 共吸附     

Vanadium oxide nanostructures on Rh(1 1 1): Promotion effect of CO adsorption and oxidation

The adsorption of CO and the reaction of CO with pre-adsorbed oxygen at room temperature has been studied on the (2 × 1)ORh(1 1 1) surface and on vanadium oxideRh(1 1 1) “inverse model catalyst” surfaces using scanning tunnelling microscopy (STM) and core-level photoemission with synchrotron radiation. Two types of structurally well-defined model catalyst V₃O₉Rh(1 1 1) surfaces have been prepared, which consist of large (mean size of 50 nm, type I model catalyst) and small (mean size <15 nm, type II model catalyst) two-dimensional oxide islands and bare Rh areas in between; the latter are covered by chemisorbed oxygen. Adsorption of CO on the oxygen pre-covered (2 × 1)ORh(1 1 1) surface leads to fast CO uptake in on-top sites and to the removal of half (0.25 ML) of the initial oxygen coverage by an oxidation clean-off reaction and as a result to the formation of a coadsorbed (2 × 2)O + CO phase. Further removal of the adsorbed O with CO is kinetically hindered at room temperature. A similar kinetic behaviour has been found also for the CO adsorption and oxidation reaction on the type I “inverse model catalyst” surface. In contrast, on the type II inverse catalyst surface, containing small V-oxide islands, the rate of removal of the chemisorbed oxygen is significantly enhanced. In addition, a reduction of the V-oxide islands at their perimeter by CO has been observed, which is suggested to be the reason for the promotion of the CO oxidation reaction near the metal-oxide phase boundary.     

一个简便快速测定CO的纳米金表面等离子体共振吸收光谱法

CO主要由火焰或烤炉等碳的不完全燃烧所产生,是一种常温下为无色、无臭的有毒气体,人们受一氧化碳的污染在慢性中毒时完全意识不到它,有时甚至有舒适的感觉,这些特性更增加了它的危害性。因此,探索简便快速灵敏的CO检测方法具有重要意义。研究表明,在pH 7.2 磷酸盐缓冲溶液中,一氧化碳还原HAuCl₄ 生成近似球形的金纳米粒子(NG),其平均粒径为45 nm,在1.70, 2.20和9.70 keV处产生3个金元素的能谱峰,在540 nm处产生一个表面等离子体共振(SPR) 吸收峰。采用分光光度法优化了分析条件,选择磷酸盐缓冲缓冲溶液的pH为7.2,磷酸盐缓冲浓度为40 mmoL·L-1,HAuCl₄浓度为40.0 μg·mL-1,反应时间为5 min。在选定条件下,CO浓度在0.2～8.75 μg·mL-1范围内与其SPR吸收峰峰值成线性关系,检出限为0.1 μg·mL-1 CO。考察了共存物质对测定1.0 μg·mL-1 CO的影响。结果表明, 当相对误差在±5%之内,200倍的SO2-₃, PO3-₄, SO2-₄、CO2-₃, NO-₃;100倍的Zn2+, K+, BrO-₃, Na₂S, 乙醇, 甲醇;80倍的Ni2+,Cr3+,Co2+,Ca2+, Mg2+, Fe3+, 葡萄糖, Pb2+, Al3+, SeO2-₃, Na₂S₂O₃,甲醛;50倍的Mn2+不干扰测定。这表明该SPR光度法具有较好的选择性。采用本法测定了空气样品中CO含量,结果与气相色谱法一致,相对误差在1.8%～4.2%之间。     

Pu(100)表面吸附CO2的密度泛函研究

采用广义梯度密度泛函理论的改进Perdew-Burke-Ernzerh方法结合周期性层晶模型,研究了CO₂分子在Pu（100）面上的吸附和解离.吸附能和几何构型的计算表明,CO₂以穴位C4O4构型吸附最为有利,吸附能为1.48 eV.布居分析和态密度分析表明,CO₂与Pu表面相互作用的本质主要是CO₂分子的杂化轨道2π_μ与Pu5f,Pu6d,Pu7s轨道通过强电子转移和弱重叠杂化的方式相互作用而生成了新的化学键.计算的CO₂→CO+O解离能垒为0.66 eV,解离吸附能为2.65 eV, 表明在一定热激活条件下CO₂分子倾向于发生解离性吸附.O₂,H₂,CO和CO₂在Pu （100）面吸附的比较分析表明,较低温度下的吸附强度顺序依次为O₂,CO,CO₂,H₂;较高温度下的吸附强度顺序依次为O₂,CO₂,CO,H₂. 关键词： 密度泛函理论 Pu （100） 2')" href="#">CO₂ 吸附和解离     

Quasiclassical dynamics of light + heavy-heavy atom reactions: the reaction X + F2 → XF + F (X = Mu,H, D,T)

Quasiclassical trajectory calculations have been carried out for the collinear reaction X + F₂(v = 0, 1) → XF + F (X = Mu, H, D, T) using the best extended LEPS surface No II of Jonathan et al.. The behaviour of individual trajectories has been used to find the regions of the potential surface that are important for determining the total reaction probability. The bottleneck close to the saddle point and repulsive wall of the exit valley are found to be the important dynamical regions of the surface. Comparison is made with other quasiclassical calculations for light + heavy-heavy atom reactions and with quantum calculations.     

FeO+催化N2O与CO反应的密度泛函理论研究

本文采用密度泛函理论DFT-B3LYP方法6-311+G(2d) 的基组, 计算研究了气相中六重态和四重态FeO+离子催化N2O和CO生成N2和 CO2反应的微观机理, 通过计算两种重态金属离子亲氧性（OA）, 从热力学方面说明了主题反应的可行性。分析反应过程的热力学性质和动力学因素得到FeO+与N2O复合生成反应复合物, 之后继续与CO复合成中间体是能量有利反应路径,所得结果与实验观测相符.