Characterization of Heterogeneous Catalysts by use of Test Reactions

The following report gives an overview on work done in the Catalysis Laboratory of the Department of Chemistry, National University of Singapore over the last 15 years (1989–2004). Much of this work can be described as “characterization of catalytically active surfaces through test reactions”. The methods, systems studied and the reactions that we evaluated will be described. The review will mostly concentrate on work from the authors’ laboratory, but other relevant work will also be cited.     

Component reconstruction in the primary space of spectra and concentrations. Alternating regression and related direct methods

A set of methods that extract the spectral components in a chromatographic run is considered. The methods do not need libraries of previously known spectra or retention times. The methods have been developed for two-dimensional spectra but they can also be used for chromatographic analyses with a single-channel detector. The methods are direct; they do not use principal components as the starting point. Alternating regression (AR) remains in the primary space of spectra and concentrations during the calculations. Random numbers are used as the starting spectra. Regression is used to solve first for the concentrations, then for the spectra. The method uses two kinds of constraints: all spectra and concentrations are forced to be positive; and all concentration profiles are forced to a unimodal shape with a single local maximum. It is assumed that all observations are a linear sum of components. Compact alternating regression (CAR) is a new variant of the basic AR. The idea is to replace multiplication of a large matrix by two multiplications of smaller matrices. This typically speeds up the iterations by a factor of ten. AR and CAR have been successfully used with combined techniques such as gas chromatography—mass spectrometry and liquid chromatography with UV—visible detection. The reliability of the solution is checked by repeatedly injecting noise and performing the analysis several times. This produces estimates of confidence intervals. AR and CAR have recently been extended to handle single-dimensional signals. Examples are single-channel detectors such as the flame ionization detector in gas or liquid chromatography with a fixed-wavelength UV detector. A batch of samples is used as the observation matrix. As a result, one obtains both the concentrations and the elution shapes of individual chromatographic peaks.     

Effect of surfactants on the stability of thin liquid film flow on a rotating disk

The effect of surfactants on surface instabilities of thin liquid film flow on a rotating disk was studied at different flow rates Q (0.5相似文献   

吸附O的Cu(110)c(2×1)表面原子结构和电子态

采用第一性原理的密度泛函理论方法计算了清洁Cu(110)表面和吸附O原子的Cu(110) c(2×1)表面的原子结构, 结构弛豫和电子结构, 得到了各种表面结构参数. 分别计算了O原子在Cu(110)表面三个可能吸附位置吸附后的能量, 并给出了能量最低的吸附位置上各层原子的弛豫特性和态密度. 结果表明O吸附后的Cu(110)表面有附加列(added-row)再构的特性, O原子吸附在最表层铜原子上方, 与衬底Cu原子的垂直距离为0.016 nm, 以氧分子为能量基准的吸附能为－1.94 eV; 同时由于Cu 3d- O 2p态的杂化作用使得低于费米能级5.5~6.0 eV的范围内出现了局域的表面态. 计算得到清洁的和氧吸附的Cu(110)表面的功函数分别为4.51 eV和4.68 eV. 电子态密度的结果表明：在Cu(110) c(2×1) 表面O吸附的结构下, 吸附O原子和金属衬底之间的结合主要是由于最表层Cu原子3d态和O原子2p态的相互作用.     

First principle calculations study of AlN surface terminal structure evolution under different conditions

The surface structure and properties of aluminum nitride (AlN) play an important role in many applications. Using the first principle calculations method, we analyzed the surface terminal structure of AlN and its evolution under different conditions by determining the surface energy, adsorption energy, and evaporation energy of the Al and N terminals on the AlN(0001) surface. Our results show that the reason why the N terminal is less stable than the Al terminal is not only because of its high surface energy but also because its adsorption performance is extremely sensitive to the adsorption position. The surface N atoms combine to form N₂ molecules that escape during the evaporation process at high temperature. After surface N atoms escape, the AlN surface structure reconstitutes to form a hexagonal closest packing (HCP)–like structure, and the energy barrier for the reconstructing process is 3.2 eV. This shows that the structure and form of the AlN(0001) terminals depend on the environmental conditions.     

Fourier transform Raman spectral measurements of powdered quaternary mixtures of organic compounds: Exceptional pure component spectral reconstruction using band-target entropy minimization (BTEM)

Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures.     

Wave chaos in quantum systems with point interaction

We study perturbations of the quantized version ₀ of integrable Hamiltonian systems by point interactions. We relate the eigenvalues of to the zeros of a certain meromorphic function . Assuming the eigenvalues of ₀ are Poisson distributed, we get detailed information on the joint distribution of the zeros of and give bounds on the probability density for the spacings of eigenvalues of . Our results confirm the wave chaos phenomenon, as different from the quantum chaos phenomenon predicted by random matrix theory.SFB 237 Essen-Bochum-Düsseldorf     

The intersection marker method for 3D interface tracking of deformable surfaces in finite volumes

Currently, the majority of computational fluid dynamics (CFD) codes use the finite volume method to spatially discretise the computational domain, sometimes as an array of cubic control volumes. The Finite volume method works well with single‐phase flow simulations, but two‐phase flow simulations are more challenging because of the need to track the surface interface traversing and deforming within the 3D grid. Surface area and volume fraction details of each interface cell must be accurately accounted for, in order to calculate for the momentum exchange and rates of heat and mass transfer across the interface. To attain a higher accuracy in two‐phase flow CFD calculations, the intersection marker (ISM) method is developed. The ISM method is a hybrid Lagrangian–Eulerian front‐tracking algorithm that can model an arbitrary 3D surface within an array of cubic control volumes. The ISM method has a cell‐by‐cell remeshing capability that is volume conservative and is suitable for the tracking of complex interface deformation in transient two‐phase CFD simulations. Copyright © 2015 John Wiley & Sons, Ltd.     

Distorted wave response of ultrasonic annular stator incorporating non-uniform geometry

The traveling wave ultrasonic stator is normally fabricated with teeth. The tooth geometry improves the driving speed, but it creates natural frequency splitting and mode contamination, especially a distorted traveling wave. A dynamic model of a stepped-plate periodic stator is developed to examine the distortion. The stator is treated as an annular supported by a thin mid plate, and the support stiffness is formulated by using equivalent energy principle. The effects of the tooth and mid plate on the natural frequency and vibration mode are examined by using the perturbation method. The rules governing the frequency splitting, frequency perturbation as well as mode contamination are also identified. The traveling wave response and elliptical trace on stator surface are obtained by using the mode superposition method and they are proved to be distorted due to the tooth geometry. The response at the repeated doublets becomes coupled forward and backward traveling waves, but that at the split doublets becomes coupled forward traveling, standing and backward traveling waves. The results indicate that the tooth mass instead of the stiffness decreases the vibration amplitude and driving speed of the dominant wave, but their effects are different at the repeated and split doublets. Inspection of the model implies that the distortion can be suppressed by using a suitable combination of the wavenumber, tooth count, tooth height and occupying fraction. Numerical calculations are carried out to demonstrate the tooth geometry effect on the transient waveform, driving speed and elliptical trace. The optimization of the tooth geometry that can help achieve a purer traveling wave is discussed.     

The polynomial reconstruction problem: The first 50 years

The problem of reconstructing the characteristic polynomial of a graph of order at least 3 from the collection of characteristic polynomials of its vertex-deleted subgraphs was posed by Cvetkovi? in 1973 as a spectral counter part to the well-known Ulam's reconstruction conjecture. Over the last 50 years, this problem has received notable attention, many positive results have been obtained, but in the general case the problem is still unresolved. In particular, no counter example is found in literature. In this expository paper we survey classical and some more recent results concerning the polynomial reconstruction problem, discuss some related problems, variations and generalizations.