Au2Ag和AuAg2团簇对CO催化氧化反应的理论研究

本文采用密度泛函理论,对Au₂Ag和AuAg₂团簇催化CO的氧化反应机理进行了系统的研究.对CO+O₂→CO₂+O和CO+O→CO₂两个氧化反应,文中分别讨论了ER反应机理和LH反应机理,结果发现在CO+O₂反应中倾向于LH反应机理,而在CO+O反应中则倾向于ER反应机理.此外,在完整的CO氧化反应中,Au₂Ag团簇两个催化氧化反应过程中的势垒都很低,说明其有望成为良好的CO氧化催化剂.     

H2在Al12X (X=Al, Ni, Cu)团簇表面解离吸附的第一性原理研究

以Ni和Cu原子中心替换的二十面体Al12X(X=Ni、Cu)团簇为基体、采用密度泛函理论系统计算研究了H原子及H2分子在团簇表面的吸附,并对比了纯Al13团簇对H及H2的吸附,结果表明：相对于纯Al13中H原子的桥位吸附、掺杂团簇Al12X(X=Ni、Cu)中H原子均吸附于团簇顶位;无论是吸附H原子还是H2分子,Al12Ni的几何结构均发生大的畸变;相较H2在纯Al13团簇表面的解离吸附,H2在掺杂团簇Al12X(X=Ni、Cu)表面的解离反应过程中反应能均增大、势垒均降低,这表明掺杂团簇Al12X(X=Ni、Cu)相较纯Al13团簇更有利于H2解离吸附的发生。     

H_2在Al_(12)X(X=Al,Ni,Cu)团簇表面解离吸附的第一性原理研究

以Ni和Cu原子中心替换的二十面体Al_(12)X(X=Ni、Cu)团簇为基体、采用密度泛函理论系统计算研究了H原子及H_2分子在团簇表面的吸附,并对比了纯Al_(13)团簇对H及H2的吸附,结果表明:相对于纯Al_(13)中H原子的桥位吸附、掺杂团簇Al_(12)X(X=Ni、Cu)中H原子均吸附于团簇顶位;无论是吸附H原子还是H_2分子,Al_(12)Ni的几何结构均发生大的畸变;相较H_2在纯Al_(13)团簇表面的解离吸附,H_2在掺杂团簇Al_(12)X(X=Ni、Cu)表面的解离反应过程中反应能均增大、势垒均降低,这表明掺杂团簇Al_(12)X(X=Ni、Cu)相较纯Al_(13)团簇更有利于H_2解离吸附的发生.     

Cu/CeO2(110)界面特性的第一性原理研究

Cu-CeO₂体系因其特殊的催化能力而在固体氧化物燃料电池和水煤气转化反应等多个催化领域有重要应用. 采用基于密度泛函理论的第一性原理方法, 在原子和电子层面上系统地研究了单个Cu原子及Cu小团簇在CeO₂(110)面上的吸附构型, 价键特性和电子结构, 结果表明: 1) 单个Cu原子的最稳定吸附位是两个表面O的桥位; 2) Cu团簇的稳定吸附构型为扭曲的四面体结构; 3) Cu原子及Cu团簇的吸附在CeO₂(110)面的gap区域引入了间隙态, 这些间隙态主要来自于Cu及其近邻的O和表层还原形成的Ce³⁺, 间隙态的出现表明Cu的吸附增强了CeO₂(110)表面的活性; 4) 吸附的单个Cu原子及Cu团簇分别被CeO₂(110)面表层的Ce⁴⁺离子氧化形成了Cu^δ+和Cu₄^δ+, 并伴随着Ce³⁺离子的形成, 这个反应可归结为Cu_x/Ce⁴⁺→Cu_x^δ+/Ce³⁺; 5) Cu团簇的吸附比Cu单原子的吸附引入了更多的Ce³⁺离子, 进而形成了更多的Cu^δ+-Ce³⁺催化活性中心. 结合已报道的Cu/CeO₂(111)界面特性, 更加全面地探明了Cu与CeO₂(111)和(110)两个较稳定低指数表面的协同作用特性, 较为系统地揭示了Cu增强CeO₂催化特性的原因及Cu与CeO₂协同作用的内在机理. 关键词： 2')" href="#">Cu/CeO₂ U')" href="#">DFT+U 吸附 电子结构     

中性金-钒-氧团簇氧化一氧化碳研究

本文实验制备了中性AuVO_(2～4)团簇并研究了其与CO和O_2的反应.实验结果表明,团簇AuVO_4和AuVO_3与CO反应主要生成吸附产物,而团簇AuO_2可与O_2反应生成AuVO_4.密度泛函理论计算结果表明,团簇AuVO_4和AuVO_3可在较高温度条件下氧化CO生成CO_2,从而形成催化氧化循环:AuVO_4+CO■AuVO_3+CO_2,AuVO_3+CO■AuVO_2+CO_2,AuVO_2+O_2→AuVO_4.     

中性金-钒-氧团簇氧化一氧化碳研究（英文）

本文实验制备了中性AuVO_(2～4)团簇并研究了其与CO和O_2的反应.实验结果表明,团簇AuVO_4和AuVO_3与CO反应主要生成吸附产物,而团簇AuO_2可与O_2反应生成AuVO_4.密度泛函理论计算结果表明,团簇AuVO_4和AuVO_3可在较高温度条件下氧化CO生成CO_2,从而形成催化氧化循环:AuVO_4+CO■AuVO_3+CO_2,AuVO_3+CO■AuVO_2+CO_2,AuVO_2+O_2→AuVO_4.     

Au_7团簇吸附O_2和CO及其对CO的催化反应机理研究

本文采用密度泛函理论,研究了Au_7团簇催化CO的氧化反应机理.研究发现,二维平面结构的Au_7团簇更容易吸附CO和O_2分子. Au_7团簇吸附一个O_2分子的吸附能为0.64 eV,但在吸附多个O_2分子时,平均吸附能有了明显的下降,表明Au_7团簇进行多吸附O_2分子的可能性不大. Au_7团簇吸附一个CO分子的吸附能为1.26 eV,且在吸附多个CO分子时,平均吸附能虽有减少,但减小的幅度不大,说明Au_7团簇有可能吸附多个CO分子.此外,在Au_7团簇催化CO的氧化反应过程中,整个反应克服的最高势垒仅为0.34 eV,说明Au_7团簇有望成为良好的CO氧化催化剂.     

Au10催化CO氧化反应机理的密度泛函理论研究

采用密度泛函理论方法研究了Au10团簇催化CO氧化反应的详细机理. 对CO、O2、O、CO2四种主要吸附物及CO+O2、CO2+O、CO+O和CO+O+O四种共吸附物的吸附行为进行计算, 得到最佳活性吸附位. 模拟反应分别按照Langmuir-Hinshelwood(LH)机理和Eley-Rideal(ER)机理进行, 其中LH机理包括L1、L2两条路径, ER机理包括E1、E2两条路径. 通过对各路径活化能比较得到: 首先CO+O2→CO2+O反应按照LH机理进行的可能性较大, 并且相比较L1、L2两条路径, 由于反应按照L1路径进行时只需克服33.9和56.4 kJ•mol-1的能垒, 所以反应更易按照L1路径进行, 最佳反应路径为O2(gas)+CO(gas)→O2(ads)+CO(gas)→O2(ads)+CO(ads)→OCOO(ads)→O(ads)+ CO2(ads); 然后CO+O→CO2反应分别克服6.9和4.3 kJ•mol-1能垒, 放热352.1 kJ•mol-1, 说明低温下吸附态的O原子很容易与CO反应生成第二个CO2分子.     

低温等离子体催化水煤气变换反应:催化剂载体的影响

水煤气变换反应是工业上用于提纯H₂以及去除CO的重要化学反应。为克服水煤气变换反应低温下动力学的限制,本文建立一种低温等离子体协同铜基催化剂催化水煤气变换反应体系,使得反应能在120℃时进行。通过研究不同载体(Al₂O₃、CeO₂、TiO₂、SiO₂、SAPO-34)负载铜催化剂对等离子体催化的影响后发现,当CuO_x/CeO₂催化剂同等离子体耦合时,表现出最佳的催化活性,CO转化率57%,氢气产率42%。研究表明,更好的催化性能归因于CuOx/CeO₂催化剂表面的氧空位以及数量众多的Cu活性位点,有利于吸附反应物,促使反应的进行。但是载体的比表面积、颗粒尺寸、酸性位点数量,介电常数并不是影响本文实验条件下低温等离子体催化WGS反应的主要因素。     

团簇ConAgm (n +m =13)表面吸附C2H4的第一性原理研究

基于密度泛函理论的第一性原理计算方法,本文对ConAgm(n+m=13)团簇的几何结构进行优化后,研究了C2H4分子在这类团簇的表面吸附行为,讨论了团簇的平均结合能、二阶能量差分、稳定性、DOS以及吸附前后键长的变化情况。结果表明,C2H4在团簇top位的吸附主要为物理吸附,而在face位和bridge位的吸附主要为化学吸附。吸附后,C2H4@Ag13的稳定性高于C2H4@Co13,且在face位吸附时C2H4@Co2Ag11的结构最为稳定。随着Co原子数的增加,团簇中原子间成键能力减弱,而d电子轨道则呈现出较强的相互作用,并导致其向能量相对高处发生转移     

原子──分子离子反应N＋NH~＋（0，0）→N_2（V’，j’）＋H~＋的准经典轨线的研究

用准经典轨线法研究原子－原子离子反应Ｎ＋ＮＨ＋（０，０）→Ｈ＋＋Ｎ２（ｖ’，ｊ’）。这是一个放能的无阈能反应，且存在平均振动能随初始平动能升高而线性下降的特点。基于对势能面的分析，成功地解释了反应机理。     

Thermal Cross‐Linking of Poly(Vinyl Methyl Ether). III. Rheological Kinetics of Cross‐Linking Reaction

Abstract

The kinetics of the thermally activated cross‐linking reaction of poly(vinyl methyl ether) (PVME) were investigated rheologically by evaluating the viscoelastic material functions such as elastic storage modulus, G′, viscous loss modulus, G″ and complex dynamic viscosity, η*, during the curing process, both isothermally and nonisothermally. The isothermal kinetics reaction was described using a phenomenological equation based on the Malkin and Kulichikhin model, which was predicated originally for the isothermal curing kinetics of thermosetting polymers followed by differential scanning calorimetery (DSC) and was found to be applicable for rheokinetic reactions as well. An excellent representation of the data was obtained using this model; the rate of the reaction was found to be second order regardless of the temperature, which is in good agreement with literature data. The temperature dependence of the cross‐linking rate constant was described by an Arrhenius plot with an apparent activation energy equal to 60–62 kJ mol^?1, in reasonable agreement with the value obtained previously from the temperature dependence of gel time, t _gel. The nonisothermal kinetics reaction rate was described by a model that included the classical rate equation, the Arrhenius equation, and the time–temperature relationships. The apparent activation energy obtained nonisothermally was found to be frequency independent and equal to 72 kJ mol^?1, in very good agreement with the value obtained isothermally from the temperature dependence of t _gel in part II.     

金刚石单晶生长的声发射实时检测初探

采用声发射检测技术,对高温高压下人造金刚石单晶的生长过程进行了检测和分析。利用由PCI-8型声发射仪和LMD-800型铰链式六面顶压机组成的声发射检测系统,检测了金刚石单晶的生长过程。将金刚石单晶生长和不生长过程中检测到的声发射信号进行对比和频谱分析,结果表明:声发射信号与金刚石单晶生长过程存在对应关系;金刚石单晶生长对应的声发射信号是一种低频信号,可以利用声发射信号的变化规律研究金刚石单晶在高温高压条件下的原位反应机理。     

Parametrization of Barrier Characteristics for Spherical-Oblate Systems in any Configuration of Colliding Nuclei

The behaviors of barrier characteristics are analyzed for spherical-oblate systems over different configurations of colliding nuclei. For this purpose, we have extended our previous study [Phys. Rev. C 89(2014) 054607], it is devoted to optimum "cold" and "hot" configuration] to analyze the same reaction systems in various configurations.The investigation on some chosen systems reveals that the barrier height and its position can be parameterized in times of the different orientations.     

Energy transport in plasma etching of nanoporous dielectric materials

A Monte Carlo routine was developed to simulate the motion and energetics of ions in the pores of a xerogel material under plasma etching conditions. The simulation included the effects of an applied electric field and input conditions for the pore as a function of pressure and applied voltage in the plasma reactor. We were interested in the ion energy in a pore, the ion penetration depth and the effect of ion energy on etching.At low pressures the nanoporous material etches faster than dense silicon dioxide. This is to be expected given the decrease in density and increase in surface area that arises due to the porosity. However, as the pressure is increased, the etch rate decreases dramatically and, eventually, the dense oxide may etch faster than the porous material. CHF₃ was used as the etchant gas and, for this gas, we believe this behavior to be controlled by the ion energy and energy transport in the pores of the xerogel material. As the pressure in the plasma reactor is increased, the incoming ions switch over from etching activation to polymerisation activation. This agrees with the observed crossover in etch rate seen experimentally and with the cessation in etching as pressure is increased. The switch is affected by pore roughness and correlates with the average ion energy in the pore.     

Dynamic aggregation evolution of competitive societies of cooperative and noncooperative agents

We propose an evolution model of cooperative agent and noncooperative agent aggregates to investigate the dynamic evolution behaviors of the system and the effects of the competing microscopic reactions on the dynamic evolution. In this model, each cooperative agent and noncooperative agent are endowed with integer values of cooperative spirits and noncooperative spirits, respectively. The cooperative spirits of a cooperative agent aggregate and the noncooperative spirits of a noncooperative agent aggregate change via four competing microscopic reaction schemes: the win-win reaction between two cooperative agents, the lose-lose reaction between two noncooperative agents, the win-lose reaction between a cooperative agent and a noncooperative agent (equivalent to the migration of spirits from cooperative agents to noncooperative agents), and the cooperative agent catalyzed decline of noncooperative spirits. Based on the generalized Smoluchowski's rate equation approach, we investigate the dynamic evolution behaviors such as the total cooperative spirits of all cooperative agents and the total noncooperative spirits of all noncooperative agents. The effects of the three main groups of competition on the dynamic evolution are revealed. These include: (i) the competition between the lose-lose reaction and the win-lose reaction, which gives rise to respectively the decrease and increase in the noncooperative agent spirits; (ii) the competition between the win-win reaction and the win-lose reaction, which gives rise to respectively the increase and decrease in the cooperative agent spirits; (iii) the competition between the win-lose reaction and the catalyzed-decline reaction, which gives rise to respectively the increase and decrease in the noncooperative agent spirits.     

Synthesis and characterization of PbS nanorods and nanowires

 A surfactant assisted solvotermal approach for the controllable synthesis of PbS nanowires and nanorods is applied. The synthesis is based on decomposition of lead thiocyanate in boiling benzyl alcohol with Cetyl trimethyl ammonium bromide used as a surfactant. Nanowires of PbS (about 2–3 μm with an average diameter of 30–50 nm) and nanorods (200–300 nm in length with an axial ratio of 4–5) were synthesised. The nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED) and X-ray diffraction analysis. The experimental results indicate that the reaction duration and concentration of surfactant play key roles in determining the final morphologies of PbS blocks building and also in their crystallinity. A possible mechanism for creation of PbS nanowires and nanorods is discussed.     

Exactly Solvable Model of Reactions on a Random Catalytic Chain

In this paper we study a catalytically-activated A+A0 reaction taking place on a one-dimensional regular lattice which is brought in contact with a reservoir of A particles. The A particles have a hard-core and undergo continuous exchanges with the reservoir, adsorbing onto the lattice or desorbing back to the reservoir. Some lattice sites possess special, catalytic properties, which induce an immediate reaction between two neighboring A particles as soon as at least one of them lands onto a catalytic site. We consider three situations for the spatial placement of the catalytic sites: regular, annealed random, and quenched random. For all these cases we derive exact results for the partition function, and the disorder-averaged pressure per lattice site. We also present exact asymptotic results for the particles' mean density and the system's compressibility. The model studied here furnishes another example of a 1D Ising-type system with random multisite interactions which admits an exact solution.     

利用双折叠模型对弹核为α的熔合垒高度和位置的系统学分析

本文系统分析了α粒子与不同的靶核熔合时, 势垒高度和位置与相互作用核的电荷数和均方根半径的关系. 通过基于密度依赖的核子-核子相互作用(CDM3Y6)的双折叠模型来计算核势. 得到了当弹核为α时垒高度和位置的参数化公式. 通过分析质量数从16到238的原子核表明, 参数化公式可以精确地再现弹核为α的熔合反应的垒高度和位置, 其精确度在±1%以内. 此外, 其结果还能很好地和实验值, 经验值, Royer, KNS, AW和亲近势的结果相符合.     

Systematic analysis of fusion barrier heights and positions for proton projectiles using the single folding model

The nuclear potentials between protons and different target nuclei are calculated by using the single folding model with the density-dependent nucleon-nucleon interaction.The fusion barrier heights and positions for proton projectiles fusing with different target nuclei with masses from 51 amu to 139 amu are systematically shown,with charge numbers and root-mean-square radii of the interacting nuclei.The parameterized formulas for the fusion barrier height and position are obtained for proton projectile fusing with the different nuclei.The calculated results of parameterized formulas are compared to empirical values,as well as those of the proximity potential and AkyüzWinther(AW) potential.It is shown that the calculated results agree perfectly with theirs.The parameterized formulas can reproduce the exact barrier heights and positions for proton fusion systems.