Electrochemical cells with multilayer functional electrodes

Microstructural and chemical changes in a NiO-YSZ electrocatalytic electrode were studied. The microstructural changes in the NiO-YSZ electrocatalytic electrode after the cell operation was compared with the electrode quenched under the applied voltage to suppress the oxidation process. The reversible reduction of NiO into Ni and the formation of intergranular Ni layers at the NiO/YSZ interface were investigated. It was shown that in a compositional range of the NiO-YSZ electrodes from 1/3 to 2/3 the value of the ambipolar conductivity increased with increasing voltage applied to the electrochemical cell. The observed reversible increase in the value of ambipolar conductivity of the electrocatalytic electrode is described in frames of the model of reversible reduction of NiO into Ni under the conditions of cell operation.     

Multilayered electrochemical cell for NOx decomposition at moderate temperatures

A new multilayered electrochemical cell for NO_x decomposition was prepared. The cell demonstrated good characteristics at moderate temperatures (350–450 °C) and possessed much higher selectivity with respect to NO_x decomposition than previous one. It was found that the “crossover” process from high selective regime to the normal regime depends on the chemical composition of the catalytic electrode.     

第一性原理研究荷电状态对Pd_(13)团簇催化分解NO性能的影响

文章运用了第一性原理计算方法研究一氧化氮在中性和带电荷背景的Pd_(13)团簇上的吸附和分解.研究结果表明:NO在中性和带电荷的Pd_(13)团簇上均倾向于吸附在Pd_(13)团簇的空位.带负电的Pd_(13)团簇比中性、带正电的Pd_(13)团簇对于NO的催化分解更有利,体现在带负电的Pd_(13)团簇上有更强的吸附能和更低的反应能垒.     

NO在Ir(111)表面吸附与解离的第一性原理研究

本文系统研究了NO在Ir(111)表面的吸附,解离,以及可能的N_2生成机理.结果表明,顶位吸附的NO,其解离能垒较高(3.17 eV),不会发生解离,而三重Hcp和Fcc空位吸附的NO发生解离,能垒分别为1.23和1.28 eV.N_2是唯一的生成物,不会有副产物N_2O的产生.其最可能的反应路径为N和NO经过N_2O中间体而生成N_2,而不是直接N提取和N-N聚合产生N_2的机理.     

Boron and nitrogen co-doped graphene nanosheets for NO and NO2 gas sensing

Using dispersion-corrected density functional theory calculations, the adsorption behavior of NO and NO₂ molecules is studied over B-doped and BN co-doped graphene sheets (BC_mN_n-Gr; $m,n=0,1,2,3$ and $m+n=3$). To examine practical gas sensing application and selectivity, the adsorption of H₂O, CO and CO₂ molecules is also studied on the BC_mN_n-Gr surfaces. It is found that the preferred adsorption site for the adsorption of these molecules is above the B atom due to accumulation of a local positive charge. Meanwhile, the incorporation of nitrogen atoms in BC_mN_n-Gr makes a substantial increase in the adsorption energies of NO and NO₂, mainly due to the shift in the Fermi energy and electron (donor) concentration states of these surfaces. According to our results, the electronic structure of BC₃-Gr, BC₂N-Gr and BCN₂-Gr is sensitive to NO and NO₂ as evidenced by relatively large variation of the electronic structure as well as charge-transfer values. To address the curvature effect of BC_mN_n-Gr nanosheets on the adsorption and sensing properties of NO and NO₂, the adsorption of these molecules is also investigated over B-doped and BN-codoped ($6,6$) carbon nanotubes. The calculations also indicate that BN co-doped graphene sheets can be used as an efficient and promising gas sensing material for detecting NO and NO₂ molecules in the presence of H₂O, CO and CO₂.     

Stochastic generalization for a hyperbolic model of spinodal decomposition

A model for diffusion and phase separation which takes into account exponential relaxation of the solute diffusion flux and its fluctuations is developed. The model describes a system undergoing phase separation governed by a partial differential equation of hyperbolic type. The analysis is done for the evolution of patterns in spinodal decomposition for the system supercooled below critical temperature. Analytical results show that relaxation processes of the solute diffusion flux lead to the selection of patterns with different wavenumbers. Considering spatial-temporal correlations of the flux fluctuations, we have found that the temporal correlations promote selecting large-period patterns, whereas the corresponding spatial correlations accelerate such processes.     

A 3D shape retrieval method for orthogonal fringe projection based on a combination of variational image decomposition and variational mode decomposition

The orthogonal fringe projection technique has as wide as long practical application nowadays. In this paper, we propose a 3D shape retrieval method for orthogonal composite fringe projection based on a combination of variational image decomposition (VID) and variational mode decomposition (VMD). We propose a new image decomposition model to extract the orthogonal fringe. Then we introduce the VMD method to separate the horizontal and vertical fringe from the orthogonal fringe. Lastly, the 3D shape information is obtained by the differential 3D shape retrieval method (D3D). We test the proposed method on a simulated pattern and two actual objects with edges or abrupt changes in height, and compare with the recent, related and advanced differential 3D shape retrieval method (D3D) in terms of both quantitative evaluation and visual quality. The experimental results have demonstrated the validity of the proposed method.     

Ionic and Mixed Conductors for Electrochemical Devices

The contribution gives a brief overview on the use of ionic and mixed conductors for electrochemical devices such as fuel cells, batteries, sensors, permeation membranes or electrochemical windows. Special emphasis is laid on the understanding of thermodynamics and kinetics of charge carrier concentration and mobilities, in particular on the dependence of the properties on the control parameters. A second part of the contribution is devoted to the use of this knowledge to optimise electrochemical properties and devices. In this context the introduction of interfaces and the use of the spacing of interfaces as practical “degrees of freedom” are discussed with regard to future applications.     

A circle similarity algorithm for an automatic circular decomposition of blood cell images

This paper presents an iterative algorithm for circular decomposition which investigates the separation of overlapped circular particles of a binary image, in order to locate their center coordinates and to estimate their radii. Since this algorithm is based on the measure of a circle similarity of an object in an image to execute a search for concavities, object segmentation and circle recognition, its implementation is simpler than the algorithm based on polygonal approximation. In this work we compare the accuracy and robustness of the proposed circle similarity algorithm with a polygonal approximation based algorithm using synthetic images and real blood cell images. Both the algorithms are able to decompose connected blood cells. However, the input parameters of the polygonal approximation method shows high sensitivity to the shape or agglomeration of an object, while the proposed algorithm demonstrates more stable performance.     

ITO负载单原子钇吸附NO和CO的第一性原理研究

基于密度泛函理论,对氧化铟锡(Indium Tin Oxide,ITO)表面负载单原子Y模型的表面性能进行了第一性原理计算.根据表面能计算结果可知,单原子Y最稳定负载位置为空位(H),即确定了ITO负载单原子钇(Single-atom Y supported on ITO,Y/ITO)稳定模型.对ITO和Y/ITO表面吸附气体分子(NO和CO)模型的吸附性能进行了第一性原理计算.根据对比ITO和Y/ITO表面的吸附能和态密度计算结果可知,单原子钇负载提高了ITO表面的稳定性和吸附性能.根据对比Y/ITO表面吸附NO和CO气体分子的吸附能和态密度计算结果可知,NO和CO气体分子吸附均为自发行为,过程放热.且NO气体分子更容易吸附在Y/ITO表面,即Y/ITO对NO气体分子更敏感.     

(TPP)NO3的合成、表征与分子识别NO

在氯仿与无水乙醇的混合溶剂(体积比为1:1)中,四苯基卟啉(TPP)与Ce(NO₃)·6H₂O混合反应后,得产物Ce(TPP)NO₃. 通过紫外-可见光谱、红外光谱、荧光光谱、质谱、核磁共振氢谱的分析与表征,四苯基卟啉与铈原子以四齿方式进行配位,在同一个铈原子上还有一个硝酸根配位. 向Ce(TPP)NO₃的二氯甲烷溶液中通入NO气体,NO可以配位在同一个铈原子上,得到新的配合物Ce(TPP)(NO)NO₃,向此溶液中通入N₂,金属卟啉配合物可以恢复为配合物Ce(TPP)NO₃.     

Convergence characteristics of a domain decomposition scheme for approximation of quantum forces

We investigate the convergence characteristics of a domain decomposition scheme to approximately compute quantum forces in the context of semiclassical Bohmian mechanics. The study is empirical in nature. Errors in the approximate quantum forces are compiled while relevant parameters in the numerical scheme are systematically changed. The compiled errors are analyzed to extract underlying trends. Our analysis shows that the number of Bohmian particles used in discretization has relatively weak influence on the error, while the length scale of interaction among subdomains controls the error in most cases. More precisely, the overall numerical error decreases as the length scale of interaction among subdomains decreases, if the error due to the truncation of the tail of the probability density distribution is adequately controlled. Our results suggest that it may be necessary to develop an efficient method to effectively control the error due to the truncation of the tail. Further studies, especially rigorous mathematical ones, should follow to understand and improve the behavior of the scheme.     

The spectral decomposition for a class of linear transport operators

The spectral decomposition theorem is proved for linear transport operators with separable scattering kernels and energy-dependent collision frequency in both one- and three-dimensional geometries.     

Heterogeneous fixation of N2: Investigation of a novel mechanism for formation of NO

Formation of NO initiated by heterogeneous fixation of N₂ during pyrolysis is investigated experimentally and theoretically. The experiments were conducted with beech wood as well as with the pure biomass components cellulose, xylan, and lignin. The NO formation during char oxidation was recorded as function of pyrolysis atmosphere (N₂ or Ar), pyrolysis temperature (700–1050 °C), and oxidizing atmosphere (O₂ in N₂ or Ar). The results confirm earlier reports that biomass char may be enriched in N during pyrolysis at 900 °C and above. The N-uptake involves re-capture of N-volatiles as well as uptake of N₂. During char oxidation, the captured N is partly oxidized to NO, resulting in increased NO formation. The NO yield from oxidation of beech wood char made in N₂ increases with pyrolysis temperature, and is about a factor of two higher at 1050 °C than the corresponding yield from chars made in Ar. The experiments with pure materials show that the lignin char has the strongest ability to form NO from uptake of N₂, while xylan char forms only small amounts of NO from N₂. Density Functional Theory (DFT) calculations on model chars have revealed a number of chemisorption sites for N₂, many of which are weakly bound and therefore expected to have a short half-life at the higher pyrolysis temperatures. However, the chemisorption of N₂ across a single ring of the armchair surface was found to have an activation energy of 344 ± 30 kJ mol⁻¹ and form a stable, exothermic product with cyano groups. This demonstrates that at least one channel exists for the high-temperature incorporation of N₂ into a char which could give rise to the observed increase in NO release in subsequent char oxidation.     

在SQUID心磁测量中基于奇异值分解和自适应滤波的噪声消除法

采用矩阵奇异值分解(singular value decomposition, SVD)的方法，对高温射频超导量子干涉仪(HTc rf-SQUID)采集到的单通道心磁信号进行处理.证明了对于近似周期性的心磁信号，在无参考噪声的情况下矩阵奇异值分解的方法与自适应窄带陷波相结合有较好的消除广谱噪声的效果. 关键词： 高温射频超导量子干涉仪 心磁信号 奇异值分解 噪声消除     

心磁信号广义S变换域奇异值分解滤波方法

针对心磁信号工频及背景噪声干扰问题, 提出了广义S变换奇异值分解(singular value decomposition, SVD)滤波方法.在离散S变换基础上, 导出了广义矩阵S变换和逆变换公式. 通过对采样信号进行广义S变换, 调节时频分辨率, 利用SVD分解方法确定有效心磁信 号区域, 实现自适应时频滤波. 实验结果表明, 该方法能有效滤除工频及背景噪声干 扰, 且在较少奇异值个数情况下可获得更好的滤波性能. 关键词： 心磁信号 S变换 奇异值分解 时频滤波     

Effects of pressure on the structure and the thermal decomposition kinetics of RDX

Abstract

High pressure and temperature structural changes for RDX were investigated to 7.0 GPa and 570 K in a diamond anvil cell apparatus using FTIR absorption, optical microscopy, and energy-dispersive powder x-ray diffraction techniques. Three distinct solid phases were observed. The effects of pressure on the thermal decomposition kinetics as a function of RDX pressure were investigated using an infrared absorption technique. Solid phase I was found to have a pressure enhanced reaction rate with an energy and volume of activation of 51 Kcal/mole and -5.6 cc/mole respectively. Solid II was not observed to react and the observed reaction rate of Solid III decreased with increasing pressure.     

纳米碳管作为氧扩散电极催化层第二相碳载体的电极特性

以纳米碳管和活性碳二元碳材料为催化层碳载体制备了氧扩散电极,采用稳态极化和电化学阻抗技术对其在碱性介质中氧还原反应的电催化活性进行了研究.结果表明,双载体电极比单载体纳米碳管、活性炭电极具有更高的电催化活性,纳米碳管和活性炭质量比为50∶50时双载体电极的催化活性最好;电极动力学参数测试表明,催化层中引入第二相纳米碳管载体提高了电极比表面积、电子导电性和氧还原反应速度;采用浸渍还原法在第二相纳米碳管载体中负载纳米级Pt催化剂,即使在低Pt负载量下(45.7μg/cm2)也明显改善了双载体电极的催化活性.阻抗测试表明,载Pt与未载Pt催化剂的双载体电极均受氧在薄液膜中的扩散控制.     

圆柱腔低频声场的球谐函数分解及声场再现

针对圆柱腔低频声场的球谐函数分解,提出了基于移动式球形传声器阵列(简称球阵)测量的空间域直接求解法。利用空间域测量数据,在压缩感知(Compressive Sensing,CS)理论框架下通过一次线性方程组求解,获得整体坐标系下的声场展开系数。首先讨论了感知矩阵的列相关性,比较不同球阵形式及球面采样点数目,不同球谐函数截断阶数以及空间测量位置等的影响。随后在飞机舱室模型内利用文中提出的方法求解声场展开系数,再现腔内水平面的声压分布,并与传统球坐标变换方法做比较。实验结果表明,利用空间域直接求解法,通过球面随机挑选10个采样点的刚性球阵在声腔3个位置进行声场测量,不仅能够有效求解声场展开系数,而且声场再现精度更高,同时计算效率也显著提高。