乙酸丁酯反应精馏过程模拟设计

反应精馏偶合了反应和精馏两种单元操作,通过精馏促进反应,可以提高反应转化率和收率,为可逆反应的化工过程生产提供了新的设计途径。基于严格热力学分析计算,利用计算机模拟和优化手段。提出了乙酸丁酯反应精馏、分离纯化的生产流程。采用UNIQUAC方程表征乙酸-正丁醇-乙酸丁酯-水四元非理想体系的汽液平衡,首先,根据实验数据回归了热力学模型中的交互作用参数,并预测了体系中5个共沸物组成,模型的计算结果与实际数据吻合。基于平衡级模型,提出了由平衡反应器、反应精馏塔、倾析器和纯化塔构成的可行流程,对提出的设计流程进行了模拟、优化,得到了操作工艺参数。模拟结果对工业过程的设计和改造具有一定的指导意义。     

Observation of Multiple Gap Structures Using NdFeAsO<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>F<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>–GaAs Tunneling Junction

We have carried out point contact tunneling measurements by contacting degenerated GaAs semiconductor to polycrystalline samples of NdFeAsO_1−x F _x with T _c=44−51±1.2. The obtained conductance curves have plural structures included in energy region of the superconducting gap. These structures are seen at almost the same bias positions on every measurement. And as temperature increases, the structures are smeared out. Thus, the structures are attributed to multiple gap structures. The gap values are Δ _S=6.3±0.3 meV, Δ _L=12.5±0.5 meV and 2Δ _S/k _B T _c=3.1±0.3, 2Δ _L/k _B T _c=6.2±0.7. Separately from these multiple gap structures, some fine structures are seen in outer energy region of the gap structures. We have calculated d² I/dV ² and T _c from using conventional s-wave Eliashberg equations by appropriately assuming α ² F(ω). The phonon positions of the calculated d² I/dV ² curve are in quite good agreement with that of experimental result. Moreover, the calculated T _c reproduces the experimental one.     

Carbon Nitride Loaded with an Ultrafine,Monodisperse, Metallic Platinum-Cluster Cocatalyst for the Photocatalytic Hydrogen-Evolution Reaction

For the realization of a next-generation energy society, further improvement in the activity of water-splitting photocatalysts is essential. Platinum (Pt) is predicted to be the most effective cocatalyst for hydrogen evolution from water. However, when the number of active sites is increased by decreasing the particle size, the Pt cocatalyst is easily oxidized and thereby loses its activity. In this study, a method to load ultrafine, monodisperse, metallic Pt nanoclusters (NCs) on graphitic carbon nitride is developed, which is a promising visible-light-driven photocatalyst. In this photocatalyst, a part of the surface of the Pt NCs is protected by sulfur atoms, preventing oxidation. Consequently, the hydrogen-evolution activity per loading weight of Pt cocatalyst is significantly improved, 53 times, compared with that of a Pt-cocatalyst loaded photocatalyst by the conventional method. The developed method is also effective to enhance the overall water-splitting activity of other advanced photocatalysts such as SrTiO₃ and BaLa₄Ti₄O₁₅.     

Equilibrium and kinetic studies of selective adsorption and separation for strontium using DtBuCH18C6 loaded resin

A crown ether loaded resin was prepared by successive impregnation and fixing the 4′,4′(5″)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its molecule modifier, 1-dodecanol, onto the porous silica/polymer composite support (SiO₂-P particles). The characterization of DtBuCH18C6 loaded resin was examined by thermal gravimetry and differential thermal analysis and electron probe microanalysis. The adsorption behavior of Sr(II), Cs(I), Ru(III), Pd(II), La(III), Nd(III), Sm(III), Gd(III), Zr(IV), and Mo(VI) was investigated by the batch method. Furthermore, the column test for Sr (II) was performed. The batch experiments were carried out by varying the shaking times, HNO₃ concentration, and initial concentration of metal ions. A relatively large K _d value above 182 cm³/g for Sr(II) was obtained in the presence of 3 M HNO₃. In contrast, the K _d values of Cs(I), Ru(III), Pd(II), La(III), Nd(III), Sm(III), Gd(III), Zr(IV), and Mo(VI) were considerably lower than 10 cm³/g. The adsorption of Sr(II) was found to be controlled by chemisorption mechanism, and followed a Langmuir-type adsorption equation. The breakthrough curve of Sr(II) had S-shaped profile, and the elution percentage was estimated to be 99.9% by using the eluent of H₂O.     

Development of an energy-binned photon-counting detector for X-ray and gamma-ray imaging

The aim of this study is to develop an energy-binned photon-counting (EBPC) detector that enables us to provide energy information of x-rays with a reasonable count statistics. We used Al-pixel/CdTe/Pt semiconductor detectors, which had an active area of 8 mm×144 mm and consisted of 18 modules aligned linearly. The size of a CdTe detector module was 8 mm×8 mm and the thickness of the CdTe crystal was 1 mm. Each module consisted of 40×40 pixels and the pixel size was 200 μm×200 μm. We applied the bias voltage of −500 V to the Pt common electrode. The detector counted the number of x-ray photons with four different energy windows, and output four energy-binned images with pixel depths of 12, 12, 11 and 10 bits at a frame rate of 1200 Hz (300 Hz×4 energy bins). The basic performance of the detector was evaluated in several experiments. The results showed that the detector realized the photon counting rate of 0.4×10⁶ counts/sec/pixel (10⁷ counts/sec/mm²), energy resolution 4.4% FWHM at 122 keV. The integral uniformity of the detector was about 1% and the differential uniformity was about 1%. In addition, the image quality was examined with a resolution chart and step-wedge phantoms made of aluminum and polymethyl methacrylate. And we compared the quality of an acquired image with that acquired with an energy integration detector. The results of these experiments showed that the developed detector had desirable intrinsic characteristics for x-ray photon counting imaging.     

The temperature dependence of luminescence from a long-lasting phosphor exposed to ionizing radiation

The temperature dependence of luminescence from a long-lasting phosphor (LLP), SrAl₂O₄ : Eu²⁺,Dy³⁺, exposed to ionizing radiation has been measured to understand the LLP luminescence mechanism. Evaluation of the decay constants of the LLP exposed to -, β- or γ-rays at temperatures from 200 to 390 K showed that the decay constant is divided into four components ranging from 10⁻⁴ to 10⁻¹ s⁻¹ with activation energies of 0.02–0.35 eV.

Total luminous intensity from the LLP with changing irradiation temperature has its maximum value around the room temperature. Irradiation at elevated temperature (390 K) has the total luminescence pattern with monotonous decrease as temperature rises. As a result of evaluating the temperature dependence of luminescence, the luminescence mechanism is considered as follows:

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Determining surface orientations of transparent objects based on polarization degrees in visible and infrared wavelengths

Techniques for modeling an object through observation are very important in object recognition and virtual reality. A wide variety of techniques have been developed for modeling objects with opaque surfaces, whereas less attention has been paid to objects with transparent surfaces. A transparent surface has only surface reflection; it has little body reflection. We present a new method for obtaining surface orientations of transparent surfaces through analysis of the degree of polarization in surface reflection and emission in visible and far-infrared wavelengths, respectively. This parameter, the polarization degree of reflected light at the visible wavelengths, is used for determining the surface orientation at a surface point. The polarization degree at visible wavelengths provides two possible solutions, and the proposed method uses the polarization degree at far-infrared wavelengths to resolve this ambiguity.     

Chemically Tuned p‐ and n‐Type WSe2 Monolayers with High Carrier Mobility for Advanced Electronics

Monolayers of transition metal dichalcogenides (TMDCs) have attracted a great interest for post‐silicon electronics and photonics due to their high carrier mobility, tunable bandgap, and atom‐thick 2D structure. With the analogy to conventional silicon electronics, establishing a method to convert TMDC to p‐ and n‐type semiconductors is essential for various device applications, such as complementary metal‐oxide‐semiconductor (CMOS) circuits and photovoltaics. Here, a successful control of the electrical polarity of monolayer WSe₂ is demonstrated by chemical doping. Two different molecules, 4‐nitrobenzenediazonium tetrafluoroborate and diethylenetriamine, are utilized to convert ambipolar WSe₂ field‐effect transistors (FETs) to p‐ and n‐type, respectively. Moreover, the chemically doped WSe₂ show increased effective carrier mobilities of 82 and 25 cm² V^?1s^?1 for holes and electrons, respectively, which are much higher than those of the pristine WSe₂. The doping effects are studied by photoluminescence, Raman, X‐ray photoelectron spectroscopy, and density functional theory. Chemically tuned WSe₂ FETs are integrated into CMOS inverters, exhibiting extremely low power consumption ( ≈ 0.17 nW). Furthermore, a p‐n junction within single WSe₂ grain is realized via spatially controlled chemical doping. The chemical doping method for controlling the transport properties of WSe₂ will contribute to the development of TMDC‐based advanced electronics.     

Synthesis of Nanohole‐Structured Single‐Crystalline Platinum Nanosheets Using Surfactant‐Liquid‐Crystals and their Electrochemical Characterization

Nanohole‐structured single‐crystalline Pt nanosheets have been synthesized by the borohydride reduction of Na₂PtCl₆ confined to the lyotropic liquid crystals (LLCs) of polyoxyethylene (20) sorbitan monooleate (Tween 80) with or without nonaethylene‐glycol (C₁₂EO₉). The Pt nanosheets of around 4–10 nm in central thickness and up to 500 nm or above in diameter have a number of hexagonal‐shaped nanoholes ∼1.8 nm wide. High‐resolution electron microscope images of the nanosheets showed atomic fringes with a spacing of 0.22 nm indicating that the nanosheets are crystallographically continuous through the nanoholed and non‐holed areas. The inner‐angle distributions for the hexagonal nanoholes indicate that the six sides of the nanoholes are walled with each two Pt (111), Pt (1 1) and Pt (010) planes. The formation mechanism of nanoholed Pt nanosheets is discussed on the basis of structural and compositional data for the resulting solids and their precursory LLCs, with the aid of similar nanohole growth observed for a Tween 80 free but oleic acid‐incorporated system. It is also demonstrated that the nanoholed Pt nanostructures loaded on carbon exhibit fairly high electrocatalytic activity for oxygen reduction reaction and a high performance as a cathode material for polymer‐electrolyte fuel cells, along with their extremely high thermostability revealed through the effect of electron‐irradiation.