Iron oxide-Palladium core-shell nanospheres for ferromagnetic resonance-based hydrogen gas sensing

Interfaces of ferromagnetic transition metals such as Iron, Cobalt, and Nickel with non-magnetic palladium are of interest due to their unique magnetic and spintronic properties. These interfaces enable ferromagnetic resonance (FMR) based sensing of hydrogen gas. In the present work, we synthesized Fe₃O₄–Pd core-shell nanospheres via a one-pot synthesis method using the thermal decomposition of Fe³⁺ acetylacetonate in the presence of a reducing agent to produce the Fe₃O₄ core, followed by the reduction of a Pd²⁺ precursor to form the pure Pd shell. We found that our in-situ synthesized core-shell nanostructure is magnetically active and shows excellent H₂ gas sensing properties. The effect of reversible hydrogen gas absorption on the magnetism of Fe₃O₄–Pd core-shell nanospheres was investigated. The hydrogen-induced ferromagnetic-resonance (FMR) peak shift amounted to 30% of the peak linewidth for the virgin state of the sample. In addition, in the presence of hydrogen gas, we observed a fully reversible decrease in the FMR peak linewidth by about two times. This was accompanied by a nearly doubling of the FMR peak height. Response and recovery times of about 2 and 50 s, respectively, were extracted from the measurements. All the data was collected using a mix of just 3% hydrogen in a nitrogen carrier gas.     

Fourier transform ion cyclotron resonance mass spectrometry at the true cyclotron frequency

Ion cyclotron resonance (ICR) cells provide stability and coherence of ion oscillations in crossed electric and magnetic fields over extended periods of time. Using the Fourier transform enables precise measurements of ion oscillation frequencies. These precisely measured frequencies are converted into highly accurate mass-to-charge ratios of the analyte ions by calibration procedures. In terms of resolution and mass accuracy, Fourier transform ICR mass spectrometry (FT-ICR MS) offers the highest performance of any MS technology. This is reflected in its wide range of applications. However, in the most challenging MS application, for example, imaging, enhancements in the mass accuracy of fluctuating ion fluxes are required to continue advancing the field. One approach is to shift the ion signal power into the peak corresponding to the true cyclotron frequency instead of the reduced cyclotron frequency peak. The benefits of measuring the true cyclotron frequency include increased tolerance to electric fields within the ICR cell, which enhances frequency measurement precision. As a result, many attempts to implement this mode of FT-ICR MS operation have occurred. Examples of true cyclotron frequency measurements include detection of magnetron inter-harmonics of the reduced cyclotron frequency (i.e., the sidebands), trapping field-free (i.e., screened) ICR cells, and hyperbolic ICR cells with quadrupolar ion detection. More recently, ICR cells with spatially distributed ion clouds have demonstrated attractive performance characteristics for true cyclotron frequency ion detection. Here, we review the corresponding developments in FT-ICR MS over the past 40 years.     

Theoretical analysis and experimental verification of thermal decomposition mechanism of CuSe

Experiments on the thermal decomposition of CuSe were carried out by using a thermogravimetric analyzer (TGA) at different heating rates. The kinetic parameters and mechanisms were discussed based on model-free and model-based analyses. The decomposition rate and decomposition behavior of CuSe were investigated by using a vacuum thermogravimetric furnace. The results showed that the R3 model was identified as the most probable mechanism function under the present experimental conditions. The average values of activation energy and the pre-exponential factor were 12.344 J/mol and 0.152 s^-1, respectively. The actual decomposition rate of CuSe was found to be 0.0030 g/(cm²·min).     

基于经验模态分解方法的拉曼光谱信号处理研究

经验模态分解(EMD)方法是一个以信号内在物理频率成分为对象的自适应时频分析方法,而常见的非平稳信号分析方法,比如小波分析,它需要选择小波基,不同小波基的分析结果不同;拉曼光谱信号是典型的非线性和非平稳信号,EMD方法充分地保留了信号本身的非线性和非平稳的特征,适应于拉曼光谱信号的分析。实验在自行研制的拉曼光谱测试平台上获得了原始的拉曼光谱信号,并通过经验模态分解将信号分解成不同频率的10个本征模式分量,信号能量集中在750cm^-1和1500cm^-1左右,最后进行了频率成分分析和去噪处理,并和小波分析方法进行了对比,验证了EMD方法的有效性和实用性,该方法在拉曼光谱信号分析中有较好的应用前景。     

Catalytic properties of dispersed iron oxides Fe2O3/MO2 (M = Zr,Ce, Ti and Si) for sulfuric acid decomposition reaction: Role of support

Supported iron oxides have been established as an important class of catalyst for high temperature sulfuric acid decomposition. With an objective to elucidate the role of support in modifying the overall catalytic properties of dispersed iron oxide catalysts, a series of supported iron oxide based catalysts, Fe₂O₃ (15 wt%)/MO₂ (M = Zr, Ce, Ti and Si), synthesized by adsorption-equilibrium method, is investigated for sulfuric acid decomposition reaction. The structure of dispersed iron oxide phases largely depended on the nature of the support oxide as revealed by the XRD and Mössbauer studies. α-Fe₂O₃ is found to be present as a major phase on ZrO₂ and CeO₂ support while ε-Fe₂O₃ was the major phase on silica supported iron oxide. On the other hand, presence of mixed oxide Fe₂TiO₅ was revealed over TiO₂ support. Strong dispersed metal oxide-support interactions inhibited the total reduction of the dispersed phase on SiO₂ and TiO₂ as compared to complete reduction of dispersed iron oxide on CeO₂ and ZrO₂ supports during temperature programmed reduction upto 1000 °C. The order of catalytic activity at a temperature of ～750 °C is observed as Fe₂O₃/SiO₂ > Fe₂TiO₅/TiO₂ > Fe₂O₃/ZrO₂ > Fe₂O₃/CeO₂, while at higher temperatures of ～900 °C the SO₂ yield is found to be comparable for all catalysts. A relationship between the rate of sulfate decomposition and catalytic activity is established through detailed TG-DTA investigations of sulfated catalyst and support. Considerable influence of the support oxide on the composition, structure, redox properties, morphology and catalytic activities of the active iron oxide dispersed phase has been observed. Thus, the support oxides operate as a critical component in the complex supported metal oxide catalysts and these findings might influence the design and development of future high temperature sulfuric acid decomposition catalysts.     

基于改进奇异值分解滤波和谱峭度的滚动轴承故障诊断

针对含噪信号的有效奇异值个数难以确定的问题，提出了一种改进的奇异值分解降噪方法--奇异值累积法。该方法通过计算奇异值的实际下降值与奇异值平均下降速度累积量的差值，并取该差值最大值点的位置作为有效奇异值的分界点来确定有效奇异值的个数。在此基础上，提出了一种基于奇异值累积法与快速谱峭度的滚动轴承故障诊断方法。采用奇异值累积法对原信号进行降噪处理，然后利用快速谱峭度确定滤波器中心频率及带宽，通过分析频段包络谱中明显的频率成分来诊断故障。该方法可以有效去除信号中的噪声，使得到的峭度值所反映的故障冲击更接近实际情况。对含内圈、外圈故障的滚动轴承实验数据进行分析，实验结果表明，相比快速谱峭度的故障诊断方法，该方法具有更好的故障识别效果。     

Experimental methods in chemical engineering: Electron paramagnetic resonance spectroscopy-EPR/ESR

Electron paramagnetic resonance (EPR) spectroscopy, also known as electron spin resonance spectroscopy (ESR), utilizes absorption of microwave radiation by unpaired electrons in a magnetic field. The interaction between the unpaired electron(s) and nearby magnetic nuclei helps identify paramagnetic species and can provide information about the motion of the molecule and the local polarity, pH, viscosity, concentration, and accessibility to other paramagnetic species. This mini-review discusses the fundamental underpinnings of EPR needed to correctly interpret EPR spectra. We describe various types of EPR spectra encountered by chemical engineers, and use application examples drawn from the chemical engineering literature to illustrate the information available from the technique. Few chemical engineering departments or even chemistry departments have EPR instruments, which contributes to the significant barrier that prevents this being adopted as a routine measurement technique. However, in 2016 and 2017, Web of Science indexed 7000 articles that applied EPR spectroscopy. A bibliometric map categorized the keywords in four categories based on co-occurrences: magnetic properties, films, and luminescence; crystal structure, complexes, and ligands; nanoparticles, oxidation, and degradation; and, systems, radicals, and H₂ O₂ .     

Relative vibration identification of cutter and workpiece based on improved bidimensional empirical mode decomposition

Frontiers of Mechanical Engineering - In the process of cutting, the relative vibration between the cutter and the workpiece has an important effect on the surface topography. In this study, the...     

High active and easily prepared cobalt encapsulated in carbon nanotubes for hydrogen evolution reaction

We prepared M/CeO₂ (M = Fe, Co or Ni) by coprecipitation method, and then fabricated M@CNT/CeO₂ electrocatalysts through ethanol decomposition on M/CeO₂. Experimental results showed that the activity of Co@CNT/CeO₂ for hydrogen evolution reaction (HER) was much higher than that of Fe@CNT/CeO₂ and Ni@CNT/CeO₂, these experimental results were consistent with the density functional theory (DFT) calculation results. The electrocatalysts from ethanol decomposition on Co/CeO₂ at 800 °C with different time were obtained, and their electrocatalytic activities for HER were discussed. Co@CNT-90 showed higher activity than others, when the reaction time exceeded 90 min, their HER activities declined gradually, because long-term ethanol decomposition caused decreased dispersion and thicker layers of carbon nanotube (CNT). To obtain a current density of 10 mA cm⁻², overpotential of 181 mV was required for Co@CNT-90, and its polarization curve after 8000 cycles retained a similar performance to the initial polarization curve. The high activity and durability of Co@CNT-90 could be explained from the carbon-encapsulated-metal structure, thus metal was protected by carbon layers and prevented metal from contacting with electrolyte directly. XRD patterns, TEM images and experimental results proved that Co was well encapsulated by CNT.     

基于小波分析的谐波在线监测系统

针对传统谐波在线监测系统存的结果不准确，无法描述谐波动态变化特点，设计了基于小波分析的谐波在线监测系统。首先设计了谐波在线监测系统的硬件模块，然后谐波在线监测系统的软件模块，依据小波变换分析谐波信号特征，得到的谐波变化率，从而谐波在线监测系统的监测结果，最后采用具体实验进行了谐波在线监测系统性能的仿真实验，由实验结果可知，该系统的谐波监测精度高，可以有效检测各种谐波分量，保证电力系统稳定运行。