立方铂纳米粒子的形状变化与熔化特性的分子动力学研究

采用分子动力学方法结合嵌入原子多体势,对立方铂纳米粒子的热稳定性进行了模拟研究.计算结果表明,立方纳米粒子在升温过程中首先转变为由{111}和{100}面所构成的十四面体,然后再转变为球形,最后熔化为液态.通过计算立方铂钠米粒子的统计半径,发现形状转变温度在1250 K左右.尽管形状不同,立方纳米粒子和球形纳米粒子的熔点是相同的. 关键词： 纳米粒子 热稳定性 分子动力学     

Pt-Au核-壳结构纳米粒子热稳定性的分子动力学研究

采用分子动力学方法结合嵌入原子势, 对Pt-Au核-壳纳米粒子的热稳定性进行了研究. 计算结果表明: Pt-Au纳米粒子的熔点明显高于Au纳米粒子而低于Pt纳米粒子. 通过计算Lindemann指数发现: 壳层中的Au首先熔化, 然后逐渐向内部扩展, 最终导致核中的Pt完全熔化; 熔化所经历的温度区间明显宽于单质纳米粒子, 而且该熔化过程呈现典型的两阶段熔化特征; 在两次熔化之间, 存在着固(核)液(壳)共存的结构. 关键词： 纳米粒子 熔化 分子动力学     

Synthesis and characterization of polyhedral and quasi-sphere non-polyhedral Pt nanoparticles: effects of their various surface morphologies and sizes on electrocatalytic activity for fuel cell applications

In this article, polyhedral and non-polyhedral Pt nanoparticles were prepared by modified polyol method using AgNO₃ as a good structure-modifying agent. Their TEM and HRTEM images showed the particle size in the range of 8–16 nm for both the above cases. The structures and properties of the surfaces of Pt nanoparticles were investigated through cyclic voltammetry in dilute perchloric acid (HClO₄) electrolyte solution. A comparison of the electrocatalytic property in methanol electrooxidation was made. Here, the effects of polyhedral and non-polyhedral morphologies on their catalytic properties were studied. The results revealed that the special catalytic activity of quasi-sphere non-polyhedral Pt nanoparticles is higher than that of polyhedral Pt nanoparticles. In addition, Pt nanoparticles of un-sharp and quasi-sphere morphologies exhibit the tolerance to poisoning species better than that of Pt nanoparticles of sharp and polyhedral morphologies due to the various morphologies of the catalyst surfaces in the chronoamperometric plots. Therefore, these experimental evidences showed the morphology-dependent catalytic property according to the various morphologies and complexity of their catalyst surfaces.     

Intensity-driven,laser induced transformation of Ag nanospheres to anisotropic shapes

The shapes of initially spherical Ag nanoparticles in soda-lime glass are persistently changed using fs laser irradiation. With linearly polarized pulses, this shape transformation of the nanoparticles causes optical dichroism of the material. The intensity dependence of this effect is studied comprehensively, addressing the whole intensity range of permanent modifications as well as the influence of the number of laser pulses applied to one spot on the sample. The results are used as basis to develop a complete scenario of the possible mechanisms leading to the laser-induced shape transformation of metallic nanoparticles in glass.     

Investigation of metal nanoparticles produced by laser ablation and their catalytic activity

Polydiphenylsilylenemethylene (PDPhSM) thin films, which are difficult to fabricate by conventional methods because of their insolubility and high melting point, have been synthesized by using laser-ablated metal nanoparticles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) in this paper. TPDC was first evaporated on silicon substrates and then exposed to metal (Pt, Cu and Ag) nanoparticles deposition by laser ablation prior to heat treatment. The catalytic activity of Pt, Cu and Ag nanoparticles has been studied. The results showed that the mean diameter of Pt nanoparticles was the smallest, Cu nanoparticles the moderate and Ag nanoparticles the biggest, while the polymerization efficiency for Pt nanoparticles was the highest, Cu nanoparticles the moderate and Ag nanoparticles the lowest. In addition, the penetration behaviours of Pt, Cu and Ag nanoparticles into the TPDC monomer films during laser ablation were different due to the particle size or the chemical interaction between metal nanoparticles and TPDC molecules.     

Direct observation of dynamic shape transformation and coalescence in platinum nanosheets on graphite surface at room temperature by time-resolved AFM

The shape transformation of platinum (Pt) nanosheets with a uniform thickness of as thin as 3.5 ± 1 nm supported on graphite was investigated by in situ atomic force microscopy (AFM). The AFM observations revealed the shape transformation and the coalescence in preferred directions for the Pt nanosheets at room temperature (25 °C), which is much lower than the melting point of bulk metallic platinum (1769 °C). The behavior may be attributed to the high surface energy for the edge parts of Pt nanosheets with the small curvature of the nanometer scale.     

Polyhedral carbon nanoparticles at high pressures

The solid-phase transformations of polyhedral nanoparticles at a pressure of 8.0 GPa and various temperatures have been investigated by X-ray diffraction, small-angle X-ray scattering, and transmission electron microscopy. It has been found that the graphene layers of the inner cavities of polyhedral particles are transformed into onion-like structures at temperatures above ～1000°C. This transformation gives rise to the formation of hybrid-type sp2 carbon nanoparticles, which combine the outer polyhedral shape with the quasispherical onion-like core. Polyhedral nanoparticles smaller than ～40 nm are completely transformed into onion-like particles at 1600°C.     

Synthesis and electro-catalytic activity of Pt-Co nanoflowers

The study of metallic nanoflowers has attracted more and more attention because of their larger surface areas and active sites, which could be applied for surface-sensitive areas. Despite these excellent characteristics, it is still very hard to synthesize noble metal nanoflowers as the flower-like structure is apt to change into some more stable shapes which are covered by lower energy surfaces. In this study, Pt-Co nanoflowers were successfully synthesized by a two-step method via the reaction between Co nanoparticles and Pt precursor. From the transmission electron microscopy (TEM) images, it could be seen clearly that the products possessed a flower-like nanostructure. The morphology of the final products depended on a number of parameters, such as the reaction time and the reaction temperature. Based on the experimental results and theoretical calculation, the formation of nanoflowers could be attributed to the galvanic replacement reaction between Co nanoparticles and Pt precursor. In addition, the electrochemical catalytic activity of Pt-Co nanoflowers toward methanol oxidation was also evaluated in comparison with that of commercial Pt black. Owing to the special structure, the electro-catalytic activity and stability of Pt-Co nanoflowers were much better than those of commercial Pt black.     

Molecular dynamic simulation of the size- and shape-dependent lattice parameter of small Platinum nanoparticles

The molecular dynamics simulation method has been used to study the size- and shape-dependent lattice parameter of unsupported small Pt nanoparticles, where the shapes concerned are sphere, cube, and cuboctahedron. It is shown that the lattice parameters decrease with decreasing the particle size in specific shape. The lattice variations of cubic shapes are higher than those of cuboctahedral shapes, and those of cuboctahedral shapes are higher than spherical ones. Furthermore, the shape effect on lattice parameter increases with decreasing the particle size. By linear fitting the simulated results, it is found that the particle shape can contribute to 7% of the total lattice parameter variation for cubic shape and to 5% for cuboctahedral shape. The present simulation results are qualitatively consistent with experimental values and the predictions by Continuous-Medium (CM) model.     

基于变换热力学的三维任意形状热斗篷设计

在变换热力学的基础上,通过坐标变换的方法,推导出三维任意形状热斗篷导热系数的通解表达式,并进行了全波仿真验证.结果表明:热流均能绕过保护区域流出,保护区域的温度保持不变,而且热斗篷外的温度场并没有破坏,具有很好的热保护和热隐身的效果.这一方法把变换热力学从二维拓展到三维,具有普遍的适用性.同时,这种技术为热流流动路径和目标温度场的控制奠定了理论基础,在微芯片、电动机的保护以及目标热隐身上有潜在应用.     

FEM for Blood-Based SWCNTs Flow Through a Circular Cylinder in a Porous Medium with Electromagnetic Radiation

This work aims to study magnetohydrodynamic flow through a circular cylinder in a horizontal position of SWCNTs in blood as a base fluid in the existence of non-linear thermal radiation and heat source/sink. Three kinds of nanoparticles shapes are considered. The study is employed the finite element technique to explore and enhance the influences of essential parameters on temperature profiles and is debated the heat transport within blood injects with SWCNTs and exposes to electromagnetic radiation. The treatment with thermal analysis and heat transfer rate being a better substitute more than surgery and chemotherapy for cancer therapy. Utilizing of nanoparticles thermal features is a mounting area of nanomedicine field because of the probable for purposeful demolition of cancer cells.This remedy is relied on many parameters, including nanofluid thermal conductivity, nanoparticles volume fraction,thermal radiation and power and heat source. The numerical solutions for flow and heat transfer features are assessed for diverse governing parameters values. The obtained results are substantiated against the relevant numerical results in the published researches. Results show that both flow velocity and temperature increase for larger values of thermal radiation, heat source and SWCNTs volume fraction with lamina and cylinder shapes. Also, spherical shape of SWCNTs occurs high disturbances in velocity and temperature distribution in the case of cooled cylinder.     

The effect of thermal treatment on the organization of copper and nickel nanoclusters synthesized from the gas phase

The condensation of 85000 Cu or Ni atoms from the high-temperature gas phase has been simulated by molecular dynamics with the tight binding potential. The efect of the subsequent thermal treatment on the shape and structure of synthesized particles was studied by simulating their gradual heating in a range of 100–1200 K. Some tendencies are revealed that are characteristic of the influence of heat treatment on the nanoparticles synthesized from the gas phase. It is concluded that short-term heating leads to significant ordering of the internal structure in 70% of agglomerated nanoparticles with the predominant formation of spherical shapes. In order to explain this result, the main mechanisms of cluster formation from the gas phase have been analyzed and it is found that the agglomeration temperature plays the main role in the formation of clusters with unified shape and structure. This opens the fundamental possibility of obtaining Cu and Ni nanoclusters with preset size, shape, and structure and, hence, predictable physical properties.     

A study on the optical and electrical properties of direct-patternable ZnO films incorporated various contents of Pt nanoparticles

Platinum nanoparticles were synthesized by the methanol reduction method, and their size was controlled to 3 nm on average using PVP [poly(N-vinyl-2-pyrrolidon)] as a protecting unit. Various contents of Pt nanoparticles were incorporated into ZnO solutions which were synthesized by a sol-gel process. ZnO films with Pt nanoparticles of various content were annealed at 500 °C and 600 °C for 1 h. The crystallinity increased with the annealing temperature and also slightly with the content of Pt nanoparticles. The sheet resistance of ZnO films decreased with the incorporation of Pt nanoparticles, however the decreasing behavior was not maintained with increasing content of Pt nanoparticles. A shift of valence band maximum energy of ZnO film with Pt nanoparticles to higher energy was also observed due to electron transfer from Pt nanoparticles to ZnO film. The optical transmittance was 88 ± 2% in the visible region for all the ZnO films. Well-defined 60 μm wide direct-patterned ZnO films containing Pt nanoparticles of 0.5 atomic percent could be formed without using dry etching process.     

铂纳米粒子热稳定性的原子级模拟研究

本文采用分子动力学结合嵌入原子多体势,模拟了铂纳米粒子在升温过程中的热稳定性和熔化机制,并利用共近邻分析方法分析了它的微结构演化过程。模拟的结果表明：铂纳米粒子的熔点明显低于体材料的熔点;由于表面层原子的结合力较弱,在升温过程中表面会首先出现预熔;纳米粒子的熔化是从表面层开始的,并随着温度的升高,熔化的表面层会逐渐向内部扩展,最终导致纳米粒子整体转变为液态结构;当温度低于表面预熔温度时,纳米粒子保持良好的晶态结构。     

阴极微凸起形状对热不稳定性的影响

为了研究阴极微凸起形状对其热不稳定性的影响,采用数值模拟方法研究了不同外加电场条件下,圆柱、圆台和圆锥形等不同形状微凸起的热不稳定性发展过程。结果显示:对于不同形状的微凸起,当微凸起顶部温度达到阴极材料的熔点时,微凸起内部温度分布差异显著,随着微凸起形状由圆柱-圆台-圆锥形变化,微凸起内部温度接近材料熔点的部位越来越少;外加电场相同时,微凸起形状越接近圆锥形,爆炸电子发射延迟时间越长;在阴极表面电场强度高于11 GV/m时,爆炸电子发射延迟时间随着微凸起顶底半径比值的减小或阴极表面电场强度的下降近似成指数规律增长。     

Thermal stability of Pt nanoclusters interacting to carbon sublattice

The catalytic activity of Pt clusters is dependent not only on the nanoparticle size and its composition, but also on its internal structure. To determine the real structure of the nanoparticles used in catalysis, the boundaries of the thermal structure stability of Pt clusters to 8.0 nm in diameter interacting with carbon substrates of two types: a fixed α-graphite plane and a mobile substrate with the diamond structure. The effect of a substrate on the processes melting of Pt nanoclusters is estimated. The role of the cooling rate in the formation of the internal structure of Pt clusters during crystallization is studied. The regularities obtained in the case of “free” Pt clusters and Pt clusters on a substrate are compared. It is concluded that platinum nanoparticles with diameter D ≤ 4.0 nm disposed on a carbon substrate conserve the initial fcc structure during cooling.

     

[110]Au纳米线在加温过程中结构与热稳定性的原子级模拟研究

采用分子动力学方法结合量子修正Sutton-Chen型多体力场,对[110]Au纳米线在升温过程中的结构与热稳定性进行了研究,并引入Lindemann指数和最小半径来研究它的熔化机理和形状演化.结果表明:纳米线在预熔之前,局部区域发生了由fcc到hcp的结构转变.纳米线的预熔首先出现表面上,然后向内部传播,最后才完全熔化为液态结构.纳米线在完全熔化后才开始出现径缩,并最终断裂成为球形纳米团簇.     

Influence of various shapes of nanoparticles on unsteady stagnation-point flow of Cu-H2O nanofluid on a flat surface in a porous medium: A stability analysis

The nanofluid and porous medium together are able to fulfill the requirement of high cooling rate in many engineering problems. So, here the impact of various shapes of nanoparticles on unsteady stagnation-point flow of Cu-H₂O nanofluid on a flat surface in a porous medium is examined. Moreover, the thermal radiation and viscous dissipation effects are considered. The problem governing partial differential equations are converted into self-similar coupled ordinary differential equations and those are numerically solved by the shooting method. The computed results can reveal many vital findings of practical importance. Firstly, dual solutions exist for decelerating unsteady flow and for accelerating unsteady and steady flows, the solution is unique. The presence of nanoparticles affects the existence of dual solution in decelerating unsteady flow only when the medium of the flow is a porous medium. But different shapes of nanoparticles are not disturbing the dual solution existence range, though it has a considerable impact on thermal conductivity of the mixture. Different shapes of nanoparticles act differently to enhance the heat transfer characteristics of the base fluid, i.e., the water here. On the other hand, the existence range of dual solutions becomes wider for a larger permeability parameter related to the porous medium. Regarding the cooling rate of the heated surface, it rises with the permeability parameter, shape factor (related to various shapes of Cu-nanoparticles), and radiation parameter. The surface drag force becomes stronger with the permeability parameter. Also, with growing values of nanoparticle volume fraction, the boundary layer thickness (BLT) increases and the thermal BLT becomes thicker with larger values of shape factor. For decelerating unsteady flow, the nanofluid velocity rises with permeability parameter in the case of upper branch solution and an opposite trend for the lower branch is witnessed. The thermal BLT is thicker with radiation parameter. Due to the existence of dual solutions, a linear stability analysis is made and it is concluded that the upper branch and unique solutions are stable solutions.     

Ion beam shaping of embedded metal nanoparticles by Si+ ion irradiation

Fine Co and Pt nanoparticles are nucleated when a silica sample is implanted with 400 keV Co⁺ and 1370 keV Pt⁺ ions. At the implanted range, Co and Pt react to form small Co _x Pt_(1?x) nanoparticles during Si⁺ ion irradiation at 300 °C. Thermal annealing of the pre-implanted silica substrate at 1000 °C results in the formation of spherical nanoparticles of various sizes. When irradiated with Si⁺ ions at 300 °C, particles in the size range of 5–17 nm undergo rod-like shape transformation with an elongation in the direction of the incident ion beam, while those particles in the size range of 17–26 nm turn into elliptical shape. Moreover, it is suspected that very big nanoparticles (size >26 nm) decrease in size, while small nanoparticles (size <5 nm) do not undergo any transformation. During Si⁺ ion irradiation, the crystalline nature of the nanoparticles is preserved. The results are discussed in the light of the thermal spike model.     

Effect of pressure on melting and solidification of metal nanoparticles

A thermodynamic model was developed to clarify the dependence of melting temperature on hydrostatic pressure in the nanoscopic scale. It is based on the classic Clausius-Clapeyron relation and the size dependence of the melting entropy. The melting of nanoparticles in matrix with coherent and incoherent boundaries was also under consideration. It was shown that external hydrostatic pressure leads to the appearance of extrema of the melting temperature that was considered as a function of the characteristic size of nanoparticles.