Enhanced Zintl anions by carbon doping in Al-Na clusters and new magic structure Al6Na4C

This article investigated the low-energy structures of Al₆Na _mC (m = 2, 4, 6, 8) clusters and their electronic structures by using genetic algorithm combined with density functional theory and configuration interaction methods. The computations show that the C atoms prefer sitting at the center, whereas the Na atoms tend to locate at the outside of the clusters. The valence molecular orbitals (MOs) agree well with the prediction of the jellium model. The stronger attraction of the central carbon to the valence electrons will depress the potential energies locally, which makes the 2S level go obviously lower and the 2P and 1D orbitals form a sub-band. The 26 valence electrons in Al₆Na₄C form closed 1S²1P⁶2S²1D¹⁰2P⁶ shells and correspond to a new magic structure. The MOs and electron localization function show that the sodium cores are exposed at the outside of the valence electrons and form naked cations. The contraction of the valence electrons because of the carbon doping enhances the charges on the Al₆C moieties, and the Na⁺ cores on the peripheries are ionically bonded to the Zintl anions (Al₆C)^q−. The Al₆Na₄C has a tetrahedral structure with symmetry T_d, and it may be used as building blocks to synthesize Zintl solid.     

Synthesis of Pd/Pt core/shell nanostructures with truncated-octahedral morphology toward formic acid oxidation

In this study, a simple one-pot method was adopted to synthetize Pd/Pt core/shell nanostructures with truncated-octahedral morphology. The morphology of the obtained Pd/Pt nanoparticles was characterized by transmission electron microscopy (TEM) and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). In addition, the composition was determined by energy-dispersive X-ray spectroscopy (EDS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the electric structures were studied by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Based on the above results, it could be noticed that Pd/Pt core/shell nanostructures with truncated-octahedral morphology were produced, where the core consisted of Pd atoms and the shell consisted of Pt atoms. In order to test the catalytic properties of the prepared Pd/Pt nanoparticles, cyclic voltammetry (CV) was carried out in 0.5 M H₂SO₄ and 0.5 M H₂SO₄ + 1 M HCOOH. Compared with commercial Pt black, the Pd/Pt core/shell nanostructures with truncated-octahedral morphology exhibited higher activity and stability toward formic acid oxidation.

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Graphical abstract Pd/Pt core/shell nanostructures which exhibit excellent activity and stability are synthesized by a simple one-pot method

     

菱体型消色差相位延迟器延迟相位的方位效应

菱体型相位延迟器是高度消色差的λ/4相位延迟器.由于材料折射率色散的影响,在可见光范围内,仍存在2°的延迟偏差.为满足精确应用和测量的需求,从相位延迟的全反射相变理论出发,阐述了斜入射相位延迟原理,以菲涅耳菱体为例,分析了菱体型相位延迟器相位延迟随其入射角变化的规律性,结果表明:当光线非严格准直时,光的入射角对相位延迟量有明显的影响,延迟量不但对入射角变化敏感,而且还与入射光线的入射方位密切相关,呈不对称形式.当入射光的波长改变时,只需改变菱体延迟器的方位,让光线在菱体的前端面上斜入射,适当选取入射角,就可以补偿相位延迟的色散偏差,使同一菱体达到对不同波长都满足λ/4相位延迟.当角度调整精度Δi=±0.01°时,引入的延迟偏差不超过±0.009°,这一精度是其它石英波片或云母波片所不能比的.     

超音速来流中爆轰波衍射和二次起爆过程研究

预爆管技术被广泛地应用在爆轰波发动机的起爆过程中,但是在超音速来流中基于预爆管技术起始爆轰波的研究并未被广泛地开展。基于此,本文中数值研究了横向超音速来流对半自由空间内爆轰波的衍射和自发二次起爆、及管道内的衍射和壁面反射二次起爆两种现象的影响。数值模拟的控制方程为二维欧拉方程,空间上使用五阶WENO格式进行数值离散,采用带有诱导步的两步链分支化学反应模型。所模拟的爆轰波具有规则的胞格结构,对应于用惰性气体高度稀释过的可爆混合物中形成的爆轰波。结果表明:在半自由空间内,在本文所模拟的几何尺寸下,爆轰波并未成功发生二次起爆现象,但是爆轰波的自持传播距离随着横向超音速来流强度的增强而增加。在核心的三角形流动区域外,波面诱导产生了更多的横波结构;在管道内,横向的超音速来流在逆流侧对出口气流产生了压缩作用,能有效提高波面压力,因此反射后的激波压力也比较高。在同样的几何尺寸下,爆轰波在静止和超音速(Ma=2.0)气流中分别出现了二次起爆失败和成功两种现象,这是由于在超音速来流中化学反应面的褶皱诱导产生了横波结构,横波与管壁以及其他横波之间的碰撞提高了前导激波的强度,并最终促进了爆轰波在超声速流主管道内的成功起始。     

多元醇及其二元混合物固-固相变的IR研究

固固相变储能物质多元醇类以其有适宜的转变温度、较高的转变焓、具有经济和技术潜力而受到人们的重视,已在热力学和动力学等方面对其进行广泛和深入的研究[1-3],并通过红外光谱法研究了几种纯多元醇固固转变的机理[1].本文对几种多元醇及其二元混合物进行变温红外光谱的测定,进一步探讨了变化的规律.1　实　验11　药品:新戊二醇(ＮＰＧ)为保证试剂(日本东京化成株式工业会社),三羟甲基乙烷(ＰＧ)超纯(日本东京化成株式工业会社),季戊四醇(ＰＥ)化学纯(北京化学试剂公司).12　仪器美国ＰＥ公司Ｍ1730型富里叶变换红外光谱仪;日本Ｅ012Ａ号Ｈ…     

铁卟啉轴向配位络合物在环己烷氧化反应中的催化作用

亚铁卟啉络合物因其可逆键合分子氧的性能而受到人们的重视。基于生物体中的亚铁卟啉络合物的轴向位置键合有一定的基团,因而对于铁卟啉及其轴向配位体的研究较为活跃,但有关其催化性能方面的研究报导甚少。     

新型草酰胺桥联Cu(Ⅱ),Ni(Ⅱ)均双核配合物的合成及表征

合成了一种新配体N ,N′ 二 (2 氨乙基 ) 草酰胺双缩邻氨基苯甲醛Schiff碱 (H4L)及其Cu(Ⅱ )、Ni(Ⅱ )均双核配合物。并用元素分析、红外光谱、电子光谱、室温磁化率等对其组成和结构进行表征。室温磁矩表明配合物中两金属离子间通过草酰胺桥存在着反铁磁性自旋偶合作用。     

C/N/O centred metal clusters: super valence bonding and magic structure with 26 valence electrons

By using genetic algorithm combined with B3LYP and QCISD methods, this paper investigates the stabilities and electronic structures of Al₆OM_m (M?=?Na, K; m?=?2,4,6) and a few other Al_nXNa_m (X?=?C, N, O) clusters. The results show that the nonmetal doped metal clusters with 26 valence electrons have enhanced stabilities and large energy gaps. This paper extends the Jellium model for the application to the nonmetal doped metal clusters and explains the electronic origin of this strong magic structure. The nonmetal X atom is situated in the centre of the magic clusters. The 2s/2p orbitals of the central atom interact strongly with the superatomic 1S/1P orbitals and form bonding and antibonding orbitals. The bonding orbitals make the C/N/O atoms form s²p⁶ shell closure, and the antibonding orbitals make the metal moieties form closed 2S²2P⁶ shells. The 26 valence electrons form closed s²p⁶S²P⁶D¹⁰ shells, and this electronic configuration can be taken as the combination of the octet rule and 18-electron rule. The octahedral Al₆O^2? core is a superatomic anion with great stability, and it can be used as building blocks to assemble Zintl phase materials by interaction with alkali metals.     

基于化学模式识别技术的枳实HPLC定量指纹图谱研究

建立了枳实的高效液相色谱(HPLC)指纹图谱分析方法.色谱柱为Tnature-ACCHROM C18色谱柱(4.6 mmx250 mm,5 μm);以乙腈-0.5％甲酸水溶液为流动相进行梯度洗脱,结合液相色谱-四极杆飞行时间质谱(HPLC-QTOF-MS)联用技术对枳实指纹图谱中的共有峰进行鉴定;采用相似度评价、聚类分...     

Preparation of vanadate-glass threshold switches

Methods are described for making reproducible and robust vanadate-glass threshold switches both by a bulk and a thick-film technique; the latter method lendsitself to the large-scale production of the devices. The electrical characteristics obtained using dc, sine-wave and square-wave inputs are described and the various electrical parameters such as: threshold voltage, holding current, delay time, etc. are given. The results of a statistical analysis involving 30 alumina substrates with 12 switches on each are described, the population being analysed in terms of the standard deviation and mean deviation of the dc threshold voltage and the resistance of the off-state. An attempt is made to correlate the variation in parameters from device to device with variables involved in the furnace-firing schedule as well as the printing.