Oxygen Vacancies Enhancing Electrocatalysis Performance of Porous Copper Oxide

Porous CuO particles with oxygen vacancies are first synthetized by a simple calcination of Cu₂C₂O₄ particles. Oxygen vacancies are confirmed by high resolution transmission electron microscopy, electron paramagnetic resonance measurements, and X‐ray photoelectron spectroscopy. When porous CuO particles with oxygen vacancies are as‐assembled as nonenzymatic glucose sensors, they reveal high sensitivity and good anti‐interference ability. The existing oxygen vacancies can help to increase the rate that electron reaches to the surface and accelerate the kinetics of the surface redox reactions to enhance the electrochemical performances of materials. In this work, the response time of porous CuO particles with oxygen vacancies' modified electrode for the electrocatalysis reaction is less than 3 s. Meanwhile, the calibration plot is linear over the wide concentration range of 0.5 × 10^?6‐6.32 × 10^?3m and a detection limit of 50 × 10^?9m . The developed sensor displays high sensitivity of 10 490.45 µA mm ^?1 cm^?2 and good anti‐interference ability, which is prior than many previous noble metal‐based and Cu‐based electrocatalysts.     

Monte Carlo Simulation of the Concentration Dependence of Segregation at Vicinal Grain Boundaries

Using the Metropolis algorithm Monte Carlo technique solute-atom segregation is studied at two vicinal grain boundaries (GBs)—the = 5/(002)/ = 36.89° symmetrical twist and the = 5/(310)/ = 53.13° symmetrical tilt—at 850 K on the Ni-rich side of the Ni-Pt phase diagram, over the concentration range 0–10 at.% Pt. Unlike the Pt-rich side of the phase diagram the structures of both GBs remain stable in this concentration range. The dilute limit behavior for most GB sites extends to at least 0.1 at. %. At higher concentrations the effective segregation energies steadily decrease with increasing solute concentrations, due to solute-solute interactions between segregated atoms, until saturation occurs. It is argued that simple statistical mechanical models, e.g., the Fowler-Guggenheim model do not work well, even in the case of simple vicinal GBs.     

A Subnanoscale Investigation of Sb Segregation at MnO/Ag Ceramic/Metal Interfaces

We have studied Sb segregation at MnO/Ag(Sb) ceramic/metal heterophase interfaces employing three-dimensional atom-probe (3DAP) microscopy. Specimens are prepared by the internal oxidation of Ag(Mn) alloys, leading to the formation of nanometer-size MnO precipitates within a Ag(Mn) matrix. Sb is introduced into the internally oxidized specimens with a vapor diffusion treatment. Appreciable Sb segregation is observed only after a subsequent segregation anneal is performed, and the measured interfacial excess of Sb at the MnO/Ag(Sb) interfaces, _Sb ^MnO/Ag, is determined directly. The temporal evolution of the MnO precipitates is followed for the different processing steps employed. It is shown that the concentration of silver within the MnO precipitates decreases from an initial value of 45–50 at.% Ag to less than 5 at.% Ag with increasing annealing time at the different processing temperatures. Thus the MnO precipitates form under paraequilibrium conditions and the precipitates inherit Ag from the matrix. With increasing aging time orthoequilibrium conditions prevail and the MnO precipitates reject the silver atoms they inherited from the matrix.     

Effects of Metastable Diffusion Short-Circuits on Surface Segregation

The role of defects introduced by both quenching and plastic deformation on the acceleration of surface segregation kinetics in the nickel-sulphur system is discussed. An estimation of the diffusion coefficient of sulphur in as-quenched single-crystal of nickel is given.Regarding cold-worked structures, the annihilation of the vacancies produces very quick segregation of sulphur atoms on the dislocation network at the beginning of the annealing treatment. However, the diffusion acceleration becomes truly significant when the pipes inside sub-grain boundaries resulting from the deformation are rearranged properly to form a percolated network.These results demonstrate that the micro-structural evolution of diffusion short circuits should be taken into account when describing complex diffusion kinetics.     

On the Relationship Between Entropy and Enthalpy of Grain Boundary Segregation

An extensive study of anisotropy of grain boundary segregation in -iron, performed in the last decade, confirmed the existence of a linear relationship between entropy and enthalpy of solute segregation at individual grain boundaries. A thermodynamic analysis of this relationship is performed in the present work. It is shown that this dependence defines a compensation temperature and an entropy-like parameter. The compensation temperature is not necessarily connected with a phase transformation, but it represents exclusively a mean temperature at which all boundaries approach to a mean value of the Gibbs free energy of segregation. The most important consequences of this dependence are outlined: a reversed anisotropy of grain boundary segregation at temperatures above the compensation temperature, and a new method for the prediction of the enthalpy and entropy of solute segregation at individual grain boundaries.     

Influence of Oxygen Vacancies on the Luminescence Spectra of Y2O3 Thin Films

Luminescence spectra of Y₂O₃ thin films annealed in air and in vacuum are investigated. It is established that the presence of oxygen vacancies leads to a decrease in the intensity of the luminescence band with a maximum at 3.4 eV (related to emission of selflocalized Frenkel excitons describing the excited state of a molecular ion (YO₆)^9–) and of the luminescence band with a maximum at 2.9 eV (related to the anion sublattice). It is revealed that the oxygen vacancies also lead to a decrease in the luminescence intensity in the 2.60, 2.35, 2.10. 1.90, and 1.70 eV bands that are related to radiative recombination in the donor–acceptor Y³⁺–O^2– pairs. The donor–acceptor distances are calculated.     

Segregation of Aluminium at Nickel-Sapphire Interfaces

Sessile drop experiments of pure liquid Ni on the basal surface of pure sapphire were conducted under controlled atmosphere and temperature. This system has been traditionally considered as non-reactive, based on thermodynamic assessments. However, the results of this study demonstrate that a capillary driven interaction exists between the pure liquid Ni and the sapphire, which causes the dissolution of the sapphire substrate mainly at the triple junction. Oxygen and Al resulting from the dissolution process diffuse into Ni and segregate at its interfaces with the atmosphere and the sapphire (probably as Al _x O _y clusters), which reduces the interface energy. It is considered that this reduction is beneficial for the adhesion of both liquid and solid Ni on sapphire. The amount of Al introduced into the drop, and hence the segregation of Al that affects the interface energy (and adhesion), are related to the size of the sessile drop.     

稀土改性的氧化镍基低温乙烷氧化脱氢催化剂活性氧物种的Raman光谱研究

利用共沉淀法制备了几种稀土金属氧化物改性的氧化镍催化剂 ,考察了其乙烷氧化脱氢 (ODE)制乙烯的催化性能 ,讨论了不同稀土金属氧化物掺杂浓度对催化剂催化性能的影响 ,利用Raman光谱技术初步表征反应在该类催化剂上的活性氧物种为Raman谱带出现在 1 0 60cm- 1 的表面双原子超氧物种O-2 ,该谱峰的大小与催化剂的ODE性能有很好的对应关系。     

Segregation at the surface of an Au/Pd alloy exposed to CO

We use density functional theory (DFT) with the generalized gradient approximation (GGA) and the revised Perdew-Burke-Ernzerhoff (rPBE) functional, to study the surface composition of the (1 1 1) and (1 0 0) dilute Pd/Au alloy. We find that the energy of Pd atoms is lower when they substitute an Au atom in the bulk than when they substitute an Au atom in the surface layer, or when they are adsorbed on the surface. Whether they are in the surface layer or in the bulk, the Pd atoms interact very weakly with each other. CO adsorbs on the Pd atom in the surface layer and the energy of this complex is lower than that of CO in gas and Pd atom in the bulk. The interaction between the PdCO complexes formed when CO adsorbs on a Pd atom imbedded in the surface layer, is also negligible. We use these energies, equilibrium thermodynamics, and a simple lattice-gas model to examine the equilibrium composition of the surface layer, as a function of temperature, CO pressure and the Pd/Au ratio. We find that the surface Pd concentration for a nanoparticle of an Au/Pd alloy differs from that in a bulk sample. The difference is due mainly to the fact that in a nanoparticle the migration of Pd atoms to the surface depletes the bulk concentration while in a large sample; the bulk provides an infinite source of Pd atoms to populate the surface sites. This system is of interest because Pd/Au alloys are selective catalysts for vinyl acetate synthesis when the Pd concentration on the surface is very low.     

Atomic-Scale Structure and Chemistry of Segregation at Matrix/Precipitate Heterophase Interfaces

We study experimentally the local chemistry and atomic structure of heterophase interfaces on an atomic scale. In this work, the heterophase precipitate/matrix interfaces of small molybdenum nitride precipitates in an -iron matrix are investigated on a subnanometer scale by 1-dimensional atom-probe field-ion microscopy (1D-APFIM) and 3-dimensional atom-probe microscopy (3DAPM). Molybdenum nitride precipitates are generated by annealing Fe- 2 at.% Mo- X, where X = 0.4 at.% Sb or 0.5 at.% Sn, at 550°C, in an ammonia/hydrogen atmosphere. Internal nitridation at this temperature produces thin, coherent platelet-shaped molybdenum nitride precipitates. 1D-APFIM selected area analyses are efficient in determining the composition of the precipitates and it is found that a possible Sn or Sb segregation at coherent matrix/precipitate interfaces is either nonexistent or below the detection limit of 1D-APFIM. 3DAPM analyses, however, provide significantly better counting statistics and detect a small, but significant segregation of Sb at the matrix/precipitate interface with a Gibbsian interfacial excess of 0.30 ± 0.15 nm^–2. This is in distinct contrast to the segregation behavior of Sn or Sb at the interfaces of semicoherent coarse precipitates produced by internal nitridation at 600°C, for which much larger Gibbsian interfacial excesses of Sn or Sb, up to 7 ± 3 nm^–2, have been measured. In contrast, the thin platelets are either coherent or have significantly fewer misfit dislocations than is geometrically necessary for a full compensation of the lattice parameter misfit between precipitate and matrix. This demonstrates that Sn or Sb segregation with an appreciable Gibbsian interfacial excess is related to the presence of misfit dislocations at the interfaces of the coarse precipitates.     

B对Mo等元素在奥氏体钢/Cr2O3界面占位倾向影响的理论研究

超级奥氏体不锈钢中因含有更高铬、钼含量,具有极高的耐点蚀、晶间腐蚀性能,这与Mo等合金元素对钝化膜结构的影响密切相关,尤其含硼超奥钢钝化层表面Cr、Mo含量明显增加,但其原子层次的微观作用机制尚不清楚.本文采用第一性原理方法,研究了置换原子(Mo、Mn、Ni、Si),及间隙原子B在fcc-Fe/Cr₂O₃界面占位倾向,并分析了可稳定存在于界面B对这些元素偏析倾向的影响.结果表明:Mo、Mn、Ni、Si、B均可与fcc-Fe/Cr₂O₃界面结构体系形成稳定结构;Mo、Ni倾向分布于界面基体侧,Mo有向氧化层扩散的趋势,B处于fcc-Fe/Cr₂O₃界面基体侧更稳定,Mn、Si易分布于氧化层中;存在于界面B对四种元素在fcc-Fe/Cr₂O₃界面体系中的占位影响不同,有利于Mn、Mo偏析于界面基体侧,但抑制Mo向界面基体侧的偏析程度,使得Si、Ni更均匀的分布于基体. Mo等合金元素分布于界面时的态密度来看,界面处M...     

用离子辐照模拟研究反应堆结构材料中金属/金属界面原子扩散行为

介绍了利用载能离子辐照模拟研究反应堆结构材料中金属／金属界面原子扩散行为的实验进展,特别是辐照参数（如辐照剂量、辐照温度、核能损、电子能损以及膜结构等）对界面原子扩散行为的影响,并对可能的机理进行了简要的评述。 Atom diffusion at metal/metal interfaces is very important for property of reactor structural materials, which can be simulated by using energetic ion irradiations. The present situation of experimental studies on atom diffusion at metal/metal interfaces induced by energetic ion irradiations is reviewed. The influence of experimental parameters such as the irradiation dose, irradiation temperature, electronic energy loss, nuclear energy loss and the interface structure on the intermixing is emphatically introduced. In addition, the possible mechanisms of metal/ metal intermixing are also briefly described.     

紫外激光调控CoFe2O4表面氧空位以增强析氧反应催化活性

本文以尖晶石型材料CoFe₂O₄为模型催化剂,研究证实脉冲紫外激光辐照可以有效调控材料表面的氧空位含量,进而改变其析氧催化活性,得到了催化活性随辐照时间的火山型变化趋势. 这种激光辐照方法可用于定量研究过渡金属化合物的表面阳离子价态、阴离子空位和物化性质间的关联.     

Analysis of Gibbsian Segregation at Heterophase Cu-MnO Interfaces

An alternative methodology to analyze Gibbsian segregation at heterophase interfaces with transmission electron microscopy (TEM) is presented and discussed. In this approach the actual concentration of the segregating element in a monolayer at the interface is obtained. This is in contrast to line scans or maps where the concentrations determined are a convolution of the concentration profiles with the electron probe and where for general interfaces the deconvolution problem can not be solved accurately. This is possible because the present approach uses explicitly the information offered by hetero-interfaces. The method is tested on the possible segregation of indium and gallium dissolved in a Cu matrix to interfaces between MnO precipitates and the Cu matrix. The occurrence of indium segregation is clearly demonstrated and the In concentration in the terminating Cu monolayer at the parallel {111} Cu/MnO interface is determined to be 15 ± 3 at.%, whereas the average In concentration in the Cu matrix is 3.8 ± 0.4 at.%. Further it was found that indium effectively blocks gallium segregation towards the oxide side of the interface. On the other hand, the presence of gallium does not influence the segregation of indium. Explanation for the gallium segregation at the oxide side relies on a thin spinel type Ga _x Mn _y O₄, which reduces the misfit at the metal-oxide interface.     

The low-temperature diffusion of Hydrogen through annealed,quenched and aged gold

An electrolytic method has been used to measure the diffusivity of hydrogen through gold in the well-annealed state, as-quenched from 1248 K, and in foils formed by aging the quenched material at temperatures in the range 348–673 K. The resulting diffusivities are consistent with a simple statistical model in which a fraction of the H atoms saturate traps formed by quenched-in vacancies, but the mobility is primarily determined by the excess of nontrapped H atoms diffusing through “normal” sites in the fcc lattice.     

Oxygen vacancy dominant strong visible photoluminescence from BiFeO3 nanotubes

In this Letter, we report oxygen vacancy dominant strong visible photoluminescence (PL) from multiferroic BiFeO₃(BFO) nanotubes (NTs) prepared by sol–gel template method. Abundant oxygen vacancies present in BFO NTs provide alternate paths for the photo‐induced carrier generation and recombination thus affecting the PL and photoabsorption characteristics. This study not only assists in understanding the optoelectronic characteristics of BFO NTs at nanoscale but also suggests BFO nanostructures as potential candidates for future photonic and sensing applications. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

离子辐照引起的金属／绝缘体界面混合与相变研究

载能离子穿过固体界面引起界面原子迁移使界面原子混合和物质成分变化，从而导致界面发生材料相变。简要介绍了载能离子辐照引起金属／绝缘体界面混合效应及相变现象的主要实验研究进展、低能离子和高能离子辐照引起金属／绝缘体界面现象差异，并对离子辐照引起界面混合及相变的机制进行了初步探讨。When penetrating an interface between two kind of solids, energetic ions can induce atomic diffusion at both sides of the interface and then result in intermixing, atom re-distribution or composition change, as well as phase transformation. Main progress on the study of intermixing and phase change at metal/insulator interface induced by energetic ion irradiations, the difference of phenomena occurred at metal/insulator interfaces induced by high-and low-energy ions were briefly reviewed. Furthermore, the possible mechanisms related to intermixing and phase change at metal/insulator interface produced by energetic ion irradiations were also discussed in short words.     

Segregation Effects at a High-Angle Twist Boundary in ZnO

Ab initio density functional plane-wave pseudopotential calculations were performed for a = 7 ( = 21.79°) [0001] twist boundary in ZnO with and without the presence of Sb impurities. The segregation energies revealed a significant driving force for segregation and it was shown that the formation of an Sb monolayer was favoured. Decreased coordination in the boundary core suggested a trend towards the formation of an intergranular phase. The impurity states caused by the monolayer were located within the band gap and higher in energy relative to the state produced by a single impurity. Charge transfer to the Sb monolayer was observed indicating a possible enhancement of the grain boundary potential barrier.     

Hydrothermal Synthesis of Metal Oxide Nanoparticles at Supercritical Conditions

Hydrothermal synthesis of CeO₂ and AlO(OH) were conducted using a flow type apparatus over the range of temperature from 523 to 673 K at 30 MPa. Nanosize crystals were formed at supercritical conditions. The mechanism of nanoparticle formation at supercritical conditions was discussed based on the metal oxide solubility and kinetics of the hydrothermal synthesis reaction. The reaction rate of Ce(NO₃)₃ and Al(NO₃)₃ was evaluated using a flow type reactor. The Arrhenius plot of the first order rate constant fell on a straight line in the subcritical region, while it deviated from the straight line to the higher values above the critical point. The solubility of Ce(OH)₃ and AlO(OH) was estimated by using a modified HKF model in a wide range of pH and temperature. In acidic conditions, where hydrothermal synthesis reaction is concerned, solubility gradually decreased with increasing temperature and then drastically dropped above the critical point. The trend of the solubility and the kinetics around the critical point could be explained by taking account of the dielectric constant effect on the reactions. There are two reasons why nanoparticle are formed at supercritical conditions. Larger particles are produced at subcritical conditions due to Ostwald ripening; that could not be observed in supercritical water because of the extremely low solubility. Second reason is the faster nucleation rate in supercritical water because of the lower solubility and the extremely fast reaction rate.     

对当量为1的预混乙烯/氧气/氩气火焰的实验研究

利用可调谐同步辐射真空紫外光电离和分子束质谱技术研究了当量为1的低压、预混乙烯/氧气/氩气火焰．利用光电离效率谱和光电离质谱,探测了火焰中燃烧中间物,并鉴别了C3H4、C2H4O和C4H4等中间物的同分异构体．在近电离阈值光予能量下,通过扫描燃烧炉的位置测量了火焰中物质的摩尔分数曲线,并利用Pt/Pt-13％Rh热电偶测得了火焰的温度曲线．与以前的工作相比,观察到很多新的燃烧中间物,如C3H2、C3H3、C3H5、C2H6O、C4H2、C4H4、C4H6、C3H4O、C3H6O、C3H8O、C5H6、C4H8O和C7H8等．同时,在火焰中检测到了包括CH3、C2H3、C2H5、HCO、C3H3以及C3H5在内的一系列自由基．在实验工作的基础上,发展了一个包含40种火焰物质和223个基元反应的简化动力学模型来对火焰进行模拟．对主要物质和大部分中间产物的拟合结果与实验值相当吻合．