Surface morphological changes induced in catalysts by acoustic waves

An interdigital transducer device equipped with a metal catalyst sample that can be used to enhance catalytic activity by acoustic excitation is investigated. It was found that the propagation of 20 MHz surface acoustic waves of the Rayleigh type on Pt thin film single crystals causes drastic changes in surface morphology. The process of film breaking is observed and it is concluded that a phase shift in the acoustic wave induced by folds and cavities in the sample is responsible for the appearance of cracks. The influence of the change in morphology on catalytic activity and the acoustically induced rate enhancement effect is studied, and it is concluded that these changes are not a significant factor in the observed enhancement.     

Floating synthesis with enhanced catalytic performance via acoustic levitation processing

Acoustic levitation supplies a containerless state to eliminate natural convection and heterogeneous crystal nucleation and thus provides a highly uniform and ultra clean condition in the confined levitating area. Herein, we attempt to make full use of these advantages to fabricate well dispersed metal nanoparticles. The gold nanoparticles, synthesized in an acoustically levitated droplet, exhibited a smaller size and improved catalytic performance in 4-nitrophenol reduction were synthesized in an acoustically levitated droplet. The sound field was simulated to understand the impact of acoustic levitation on gold nanoparticle growth with the aid of crystal growth theory. Chemical reducing reactions in the acoustic levitated space trend to occur in a better dispersed state because the sound field supplies continuous vibration energy. The bubble movement and the cavitation effect accelerate the nucleation, decrease the size, and the internal flow inside levitated droplet probably inhibit the particle fusion in the growth stage. These factors lead to a reduction in particle size compared with the normal wet chemical synthetic condition. The resultant higher surface area and more numerous active catalytic sites contribute to the improvement of the catalytic performance.     

Studying acoustic-wave fields in langasite-family crystals using the BESSY II synchrotron radiation source

The process of the excitation and propagation of pseudosurface acoustic waves in crystals of the langasite family is studied via X-ray diffractometry for the first time. The investigations are carried out using the BESSY II synchrotron radiation source in the double-crystal X-ray diffractometer scheme. The process of pseudosurface acoustic wave propagation is studied based on an analysis of the diffraction spectra of acoustically modulated crystals. Both the velocities of the pseudosurface acoustic waves and the power flow angles of the acoustic energy are measured for the first time. The pseudosurface acoustic wave is shown to be flowing. Surface and pseudosurface acoustic waves generated by an interdigital transducer in the Z cut of a La₃Ga_5.5Ta_0.5O₁₄ crystal are compared.     

Model of electroless Ni deposition on SiCp/Al composites and study of the interfacial interaction of coatings with substrate surface

Metallization techniques based on electroless plating are used to coat SiC_p/Al composite materials. The directly palladium chloride (PdCl₂) solutions in HCl is used to render the surface of such non-conductive substrates catalytically active towards metal deposition in the electroless plating solution. The microstructures of Ni-coated composites provided by scanning electron microscope (SEM) bring light into the palladium activation and electroless coating process. Also, X-ray photoelectron spectroscopy (XPS) and Line-scan have allowed to monitor the chemical and compositional surface modifications of activated and coated SiC_p/Al composites, as well as to understand the mechanisms of the catalyst (palladium species) chemisorption on the composites surface and the interaction mechanisms of Ni layer with the SiC_p/Al composites. The experimental results show that a nickel-substrate bonding action takes place during plating. Ni atom existing on the surface of the composites can partially obtain electrons from metals Al of the SiC_p/Al composites when the substrate is embedded in the Ni layers, that is, the orbital interaction through the mutual overlap of the electronic orbits does exist in the interfacial regions between the coated Ni atoms and composites substrate instead of the mechanical-interlocked form. On the basis of the evidence, a model of electroless Ni deposition on SiC_p/Al composites is submitted including Pd activation and Ni deposition processes to describe the formation of catalytic centers and the growth of deposited layer. The deposition model reveals that metal-substrate bond plays an important role in the high adhesion strength between the Ni coatings and the composites.     

Insensitivity of sub-Kelvin electron-phonon coupling to substrate properties

We have examined the role of the substrate on electron-phonon coupling in normal-metal films of Mn-doped Al at temperatures below 1 K. Normal metal-insulator-superconductor junctions were used to measure the electron temperature in the films as a function of Joule heating power and phonon temperature. Theory suggests that the distribution of phonons available for interaction with electrons in metal films may depend on the acoustic properties of the substrate, namely, that the electron-phonon coupling constant Σ would be larger on the substrate with smaller sound speed. In contrast, our results indicate that within experimental error (typically ±10%), Σ is unchanged among the two acoustically distinct substrates used in our investigation.     

Cooperative activation effect on H2O adsorption in MnO–Co catalyzed steam methane reforming

Steam methane reforming is a very important chemical process in hydrogen production and solid oxide fuel cells (SOFCs). Cobalt (Co) is an important catalyst for dry and steam methane reforming. However, previous studies have confirmed that metal Co surfaces only have weak adsorption activity for H₂O, which is evidently unfavorable for steam reforming. In this work we used first-principles simulations to study the activity of MnO–Co catalysts for the adsorption of H₂O. Compared with the Co (111) surface and pristine Co clusters, the MnO–Co catalytic layer has a stronger adsorption capability for H₂O because of the introduction of the MnO substrate, which is crucial for improving the steam reforming reaction and inhibiting carbon disposition in SOFCs. The cooperation mechanism between MnO and Co is discussed based on the analysis of electronic structures. The conclusions from this work are universal for other metal-oxide composite catalyst layers.     

Novel catalysts: Indium implanted SiO2 thin films

Interactions of Indium (In) and silicon (Si) atoms are known to catalyze certain organic chemical reactions with high efficiency. In an attempt of creating a material that manifests the interactions, In implanted SiO₂ thin films were prepared by ion beam injection and their catalytic abilities for organic chemical reactions were examined. It has been found that, with an injection energy of approximately 0.5 keV, a thin In film is formed on a SiO₂ substrate surface and the In implanted SiO₂ thin film can catalyze an organic chemical reaction. It has been also shown that there is an optimal ion dose for the highest catalytic ability in the film preparation process. Thin-film-type catalyzing materials such as the one proposed here may open a new way to enhance surface chemical reaction rates.     

Ionization and excitation of some atomic targets and metal oxides by electron impact

We have calculated total inelastic and total ionization cross-sections for collisions of electrons on atomic targets oxygen (O), aluminium (Al) and copper (Cu) and metal oxides AlO and Al₂O, at impact energies from near excitation threshold to 2000 eV. A complex (optical) energy-dependent interaction potential is used to derive total inelastic cross-sections resulting from ionization as well as excitation processes. The inelastic cross-sections are bifurcated into discrete and continuum contributions and total ionization cross-sections have been deduced therefrom. Our calculation also provides information, hitherto sparse, on the excitation processes in the atomic targets O, Al, Cu and metal oxides AlO, Al₂O. Adequate comparisons are made with other theoretical and experimental data.     

Surface chemistry of hot electron and metal-oxide interfaces

Fundamental mechanisms for energy conversion and dissipation on surfaces and at interfaces have been significant issues in the community of surface science. Electronic excitation in exothermic chemical reactions or photon absorption involves the generation of energetic or hot electrons that are not in thermal equilibrium via non-adiabatic electronic excitation. A number of experimental and theoretical studies have demonstrated the influence of excited hot electrons on atomic and molecular processes, and it is a key moderator in the surface energy conversion process. The charge transfer through the metal-oxide interfaces has a significant impact on catalytic performance in mixed metal-oxide catalysts. In order to understand the influence of hot electrons and metal-oxide interfaces on the surface reactions, various detection schemes of exoelectron detection, including metal-insulator-metal and metal-semiconductor Schottky diodes, have been developed. Catalysts coupled with surface plasmons exhibit peculiar catalytic performance related to hot electron flow. In this review, we outline recent research efforts to relate hot electron flow with surface reactions occurring at metal-oxide interfaces. We report recent studies on the observation of hot electrons and the correlation between hot electrons and catalytic activity and selectivity on metallic surfaces. We show recent results from studies of surface reactions on nanocatalysts coupled with surface plasmons, where hot electron transport is the key process in energy dissipation and conversion processes.     

Full-wave modeling of piezoelectric transducers for SAW acousto-optical interactions

In this paper we present an accurate and efficient numerical method for a rigorous full-wave analysis of interdigital transducers (IDT) for the excitation of surface acoustic waves on the piezoelectric substrate of acousto-optical devices. The problem is formulated in terms of an integral equation that is solved by the method of moments. The transducer input admittance and the power coupling factors to both surface and bulk waves are computed. Numerical results for some configurations of X-Y LiNbO₃ IDT for acousto-optic applications are in very good agreement with measured data. It is pointed out that bulk wave excitation may be a serious limitation in the design of efficient, wide band transducers for acousto-optical devices.     

A finite difference analysis of the field present behind an acoustically impenetrable two-layer barrier

The interaction of an incident sound wave with an acoustically impenetrable two-layer barrier is considered. Of particular interest is the presence of several acoustic wave components in the shadow region of this barrier. A finite difference model capable of simulating this geometry is validated by comparison to the analytical solution for an idealized, hard-soft barrier. A panel comprising a high air-content closed cell foam backed with an elastic (metal) back plate is then examined. The insertion loss of this panel was found to exceed the dynamic range of the measurement system and was thus acoustically impenetrable. Experimental results from such a panel are shown to contain artifacts not present in the diffraction solution, when acoustic waves are incident upon the soft surface. A finite difference analysis of this experimental configuration replicates the presence of the additional field components. Furthermore, the simulated results allow the additional components to be identified as arising from the S(0) and A(0) Lamb modes traveling in the elastic plate. These Lamb mode artifacts are not found to be present in the shadow region when the acoustic waves are incident upon the elastic surface.     

X-ray and AFM studies of polydisperse TiO2 (anatase) particles

Titanium dioxide (TiO₂) materials of a high chemical purity, as-prepared by the thermal hydrolysis, as well as subsequently modified by adsorption of different metal cations (Fe³⁺, Co²⁺, Cu²⁺), have been investigated by the X-ray diffraction, X-ray fluorescence and AFM microscopy methods. All TiO₂ powders have a fine-dispersated anatase structure and consist of grown together nanocrystallites of ∼8-17 nm. TiO₂ particles, usually ranging from 100 to 600 nm, show the ability to form large agglomerates, up to 2 μm in size. Contrary to the pure anatase, metal-modified TiO₂ particles possess a positive charge on their surface and can be lifted away by the AFM tip from the substrate surface during the scanning. This effect is mostly pronounced for the Fe-modified TiO₂ sample, where particles up to 250 nm are removed. The possible interaction mechanisms between different TiO₂ particles and the silicon tip are discussed. The electrostatic force has been found to play an essential role in the sample-tip interaction processes, and its value depends on the type of metal cation used.     

ZnO薄膜/金刚石在不同激励条件下声表面波特性的计算与分析

本文首先以刚度矩阵法为基础, 给出了ZnO薄膜/金刚石在四种不同激励条件下的有效介电常数计算公式. 然后以此为工具, 分别计算了多晶ZnO(002) 薄膜/多晶金刚石和单晶ZnO(002) 薄膜/多晶金刚石的声表面波特性, 并根据计算结果及设计制作声表面波器件的要求, 对ZnO膜厚的选择进行了详细地分析. 最后讨论了ZnO/金刚石/Si复合晶片可以忽略Si衬底对声表面特性影响时对金刚石膜厚的要求. 关键词： 声表面波 压电多层结构 有效介电常数 刚度矩阵法     

The response of turbulent premixed flames to normal acoustic excitation

To model the thermo-acoustic excitation of flames in practical combustion systems, it is necessary to know how a turbulent flame front responds to an incident acoustic wave. This will depend partly on the way in which the burning velocity responds to the wave. In this investigation, the response of CH₄/air and CH₄/H₂/air mixtures has been observed in a novel flame stabilisation configuration, in which the premixture of fuel and air is made to decelerate under controlled conditions in a wide-angle diffuser. Control is provided by an annular wall-jet of air and by turbulence generators at the inlet. Ignition from the outlet of the diffuser allows an approximately flat flame to propagate downwards and stabilise at a height that depends on the turbulent burning velocity. When the flow is excited acoustically, the ensemble-averaged height oscillates. The fluctuations in flow velocity and flame height are monitored by phase-locked particle image velocimetry and OH-planar laser induced fluorescence, respectively. The flame stabilised against a lower incident velocity as the acoustic amplitude increased. In addition, at the lowest frequency of 52 Hz, the fluctuations in turbulent burning velocity (as represented by the displacement speed) were out-of-phase with the acoustic velocity. Thus, the rate of displacement of the flame front relative to the flow slowed as the flow accelerated, and so the flame movement was bigger than it would have been if the burning velocity had not responded to the acoustic fluctuation. With an increase in frequency to 119 Hz, the relative flame movement became even larger, although the phase-difference was reduced, so the effect on burning velocity was less dramatic. The addition of hydrogen to the methane, so as to maintain the laminar burning velocity at a lower equivalence ratio, suppressed the response at low amplitude, but at a higher amplitude, the effect was reversed.     

Epitaxially grown zinc oxide films for electro-optic and acousto-optic interactions

Measurements of acoustic surface waves (ASW) and optical guided waves (OGW) wave properties have been carried out on chemical vapor deposited (CVD) epitaxial zinc oxide (ZnO) films on sapphire (Al₂O₃) substrates of different orientations. Surface preparation and orientation effects have been studied. Untuned acoustic insertion loss of 40 dB at 160 MHz and optical propagation loss of better than 5 dB/cm at 6328Å for the TE₀ mode were obtained in a 2μm thick (11$\text{2}$4) ZnO film deposited on a (0001) sapphire substrate.     

Electronic excitations by chemical reactions on metal surfaces

Dissipation of chemical energy released in exothermic reactions at metal surfaces may happen adiabatically by creation of phonons or non-adiabatically by excitation of the electronic system of the metal or the reactants. In the past decades, the only direct experimental evidence for such non-adiabatic reactions has been exoelectron emission into vacuum and surface chemiluminescence which are observed in a special class of very exothermic reactions. The creation of e–h pairs in the metal has been discussed in many theoretical models but it was only recently that a novel experimental approach using Schottky diodes with ultrathin metal films makes direct measurement of reaction-induced hot electrons and holes possible. The chemical reaction creates hot charge carriers which travel ballistically from the metal film surface toward the Schottky interface and are detected as a chemicurrent in the diode. By now, such currents have been observed during adsorption of atomic hydrogen and deuterium on Ag, Cu and Fe surfaces as well as chemisorption of atomic and molecular oxygen, of NO and NO₂ molecules and of certain hydrocarbons on Ag. This paper reviews briefly exoelectron and chemiluminescence experiments and the concept of the Nørskov–Newns–Lundqvist model. The major part is devoted to the detection of chemically induced e–h pairs with thin metal film Si Schottky diodes by discussing the different influences on the chemicurrent magnitude and presenting experimental results predominantly with hydrogen and deuterium atoms. The experiments introduce a new method to investigate surface reaction kinetics and dynamics by use of an electronic device. In addition, the diodes may be used as selective reactive gas sensors.     

银纳米线表面等离激元波导的能量损耗

金属纳米结构的表面等离激元可以突破光学衍射极限,为光子器件的微型化和集成光学芯片的实现奠定基础.基于表面等离激元的各种基本光学元件已经研制出来.然而,由于金属结构的固有欧姆损耗以及向衬底的辐射损耗等,表面等离激元的传输能量损耗较大,极大地制约了其在纳米光子器件和回路中的应用.研究能量损耗的影响因素以及如何有效降低能量损耗对未来光子器件的实际应用具有重要意义.本文从纳米线表面等离激元的基本模式出发,介绍了它在不同条件下的场分布和传输特性,在此基础上着重讨论纳米线表面等离激元传输损耗的影响因素和测量方法以及目前常用的降低传输损耗的思路.最后给出总结以及如何进一步降低能量损耗方法的展望.表面等离激元能量损耗的相关研究对于纳米光子器件的设计和集成光子回路的构建有着重要作用.     

Time-resolved measurements of electron transfer processes at the PTCDA/Ag(111) interface

The electron transfer processes at the interface between 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) and Ag(111) have been studied using time- and angle-resolved two-photon photo-emission (2PPE). For this system a dispersing unoccupied interface state can be identified that is located 0.6 eV above the Fermi level with an effective electron mass of 0.39 m_e at the [`(G)]\overline{\Gamma}-point. The lifetime of 54 fs for the interface state is relatively short indicating a large penetration of the wavefunction into the metal. Supported by model calculations this interface state is interpreted as predominantly arising from an upshift of the occupied Shockley surface state of the clean metal substrate due to the interaction with the PTCDA overlayer. Coverage dependent measurements show a second long-lived component in the time-resolved measurements for higher PTCDA coverages that can be associated to charge transfer processes from the PTCDA multilayers into the metal substrate. Additionally the influence of the PTCDA adlayers on the image-potential states is studied indicating that the n = 1 image-potential state is localized in the first two monolayers of the PTCDA film.     

Phase equilibrium measurements of acoustically levitated squalane–CO2 mixtures by Raman spectroscopy

This work describes the phase equilibrium measurements of acoustically levitated binary mixtures with concentration measurements using Raman spectroscopy without sample extraction of the autoclave. The levitator design is implemented in a Single‐Droplet Optical Cell for levitation processes under varying atmospheres. The advantages of acoustic levitation of small droplets under increased temperatures and pressure combined with spectroscopic applications like Raman spectroscopy enable novel experiments possibly relevant to the fields of chemical engineering. To the author's knowledge, this is the first use of Raman spectroscopy for phase equilibria investigations on acoustically levitated droplets under high pressure and temperature. The results show very good agreements with literature data. Copyright © 2014 John Wiley & Sons, Ltd.     

Multi-modal particle manipulator to enhance bead-based bioassays

By sequentially pushing micro-beads towards and away from a sensing surface, we show that ultrasonic radiation forces can be used to enhance the interaction between a functionalised glass surface and polystyrene micro-beads, and identify those that bind to the surface by illuminating bound beads using an evanescent field generated by guided light.The movement towards and immobilisation of streptavidin coated beads onto a biotin functionalised waveguide surface is achieved by using a quarter-wavelength mode pushing beads onto the surface, while the removal of non-specifically bound beads uses a second quarter-wavelength mode which exhibits a kinetic energy maximum at the boundary between the carrier layer and fluid, drawing beads towards this surface. This has been achieved using a multi-modal acoustic device which exhibits both of these quarter-wavelength resonances. Both 1-D acoustic modelling and finite element analysis has been used to design this device and to investigate the spatial uniformity of the field.We demonstrate experimentally that 90% of specifically bound beads remain attached after applying ultrasound, with 80% of non-specifically bound control beads being successfully removed acoustically. This approach overcomes problems associated with lengthy sedimentation processes used for bead-based bioassays and surface (electrostatic) forces, which delay or prevent immobilisation. We explain the potential of this technique in the development of DNA and protein assays in terms of detection speed and multiplexing.