Mo_2C/γ-Al_2O_3催化剂上苯加氢反应的原位红外光谱研究

采用程序升温反应法制备了钝化态、还原钝化态和新鲜态Mo2C/γ-Al2O3催化剂,结合原位红外光谱表征技术和反应性能评价,考察、比较了三种催化剂苯加氢反应活性.原位红外光谱结果表明,新鲜态Mo2C/γ-Al2O3催化剂在室温就显示了较好的苯加氢反应活性,表现了类贵金属的催化活性.CO吸附在反应前后新鲜态Mo2C/γ-Al2O3催化剂上的对比结果表明,低价态的Mo位(Moδ+(0δ2))是苯加氢反应活性中心.三种催化剂的反应活性结果表明,新鲜态Mo2C/γ-Al2O3催化剂反应活性最好,催化剂寿命最长,失活之后在500°C下H2处理即可恢复原有活性.     

对新时期分析测试中心定位的思考

就如何理解和看待新时期分析测试中心的定位和发展,如何解决分析测试中心在结构和管理上存在的固有问题提出了粗略的观点.希望对分析测试中心的发展起到抛砖引玉的作用.     

Co3O4纳米晶催化氧化甲烷的理论研究：C-H键活化的晶面效应及活性中心

甲烷是一种在自然界中大量存在的原材料,在取代原油和合成重要化工产品等许多领域具有潜在的应用价值. 然而,由于CH₄中C-H键的键能特别大（约~4.5 eV）,如何实现甲烷的绿色有效转化在化学化工领域仍然是一个挑战. 本文采用密度泛函理论对Co₃O₄（001）和（011）晶面活化甲烷C-H键的机理进行了理论研究,得到了如下结论：（1） CH₄的C-H键在Co₃O₄晶面的解离具有很高的活性,只需要克服大约1 eV的能垒;（2）与Co^2＋相连的Co-O离子对是CH₄活化的活性位点,其中两个带正负电荷的离子对C-H解离起着协同作用,帮助产生Co-CH₃和O-H物种;（3）（011）面的反应活性明显大于（001）面,与实验的观察一致. 本文的计算结果表明,Co₃O₄纳米晶面对CH₄中C-H键的活化表现出明显的晶面效应和结构敏感效应,Co-O离子对活性中心对于活化惰性的C-H键发挥了关键作用.     

A Conjugate Addition Approach to Diazo-Containing Scaffolds with β Quaternary Centers

Structurally complex diazo-containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α-diazonium-α,β-unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β-hydroxy-α-diazo carbonyls with Sc(OTf)₃. Conjugate addition occurs selectively at the 3-position of indole to give α-diazo-β-indole carbonyls, and enoxy silanes react to give 2-diazo-1,4-dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α-diazo ester indole addition product with Rh₂(OAc)₄ caused a rearrangement to occur to give a 2-(1H-indol-3-yl)-2-enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.     

气相传输平衡技术制备LiGaO2薄膜

为获得与GaN薄膜晶格失配小的衬底材料,报道了利用气相传输平衡技术(VTE)在(100)-βGa2O3单晶衬底上制备高度[001]取向LiGaO2薄膜的方法。经过X射线衍射分析表明得到的薄膜是由单相LiGaO2组成。利用扫描电镜(SEM)观察表面形貌,发现经气相传输平衡技术处理得到的薄膜表面形貌主要受温度的影响,表面晶粒尺寸随温度上升而增大。而X射线衍射测试表明随着温度上升,所得到的薄膜也从多晶向单晶化转变。在经过退火处理后,通过观察吸收谱发现LiGaO2薄膜中产生色心,并且色心的种类与温度有关。表明可以通过气相传输平衡技术技术,在远低于LiGaO2熔点的温度制备外延GaN用(001)LiGaO2∥(100)β-Ga2O3复合衬底。     

Nanoscale detection of faint machinery vibration using the NV center in diamond

We propose a novel method for detection of the faint machinery vibration at the nanometer resolution based on the spin magnetic resonant effect. A suspension magnet acts as a vibration sensor to transfer the vibration signals as the magnetic field fluctuation to excite the spin magnetic resonance. Due to the high sensitivity of the magnetic field of the nitrogen-vacancy center in diamond, the theoretical detection limit of mechanical vibration is as high as 5.7 nm, and the actual measurement resolution reached 12.8 nm, and proved the potential for further improvement to ∼pm resolution. The feasibility of this method is verified by dynamic tests. This method provides a novel approach for the detection of micro-mechanical vibrations.     

Nonlinear Measures to Evaluate Upright Postural Stability: A Systematic Review

Conventional biomechanical analyses of human movement have been generally derived from linear mathematics. While these methods can be useful in many situations, they fail to describe the behavior of the human body systems that are predominately nonlinear. For this reason, nonlinear analyses have become more prevalent in recent literature. These analytical techniques are typically investigated using concepts related to variability, stability, complexity, and adaptability. This review aims to investigate the application of nonlinear metrics to assess postural stability. A systematic review was conducted of papers published from 2009 to 2019. Databases searched were PubMed, Google Scholar, Science-Direct and EBSCO. The main inclusion consisted of: Sample entropy, fractal dimension, Lyapunov exponent used as nonlinear measures, and assessment of the variability of the center of pressure during standing using force plate. Following screening, 43 articles out of the initial 1100 were reviewed including 33 articles on sample entropy, 10 articles on fractal dimension, and 4 papers on the Lyapunov exponent. This systematic study shows the reductions in postural regularity related to aging and the disease or injures in the adaptive capabilities of the movement system and how the predictability changes with different task constraints.     

Upper Bound of the Number of Zeros for Abelian Integrals in a Kind of Quadratic Reversible Centers of Genus One

By using the methods of Picard-Fuchs equation and Riccati equation, we study the upper bound of the number of zeros for Abelian integrals in a kind of quadratic reversible centers of genus one under polynomial perturbations of degree $n$. We obtain that the upper bound is $7[(n-3)/2]+5$ when $n\ge 5$, $8$ when $n=4$, $5$ when $n=3$, $4$ when $n=2$, and $0$ when $n=1$ or $n=0$, which linearly depends on $n$.     

Synthesis and Crystal Structure of a 1D Chained Coordination Polymer Containing One-dimensional Egg-like Channels： {[Cu2（C2O4）2（inta）4]（inta）}n （inta = Isonicotinamide）

A new one-dimensional copper coordination polymer chain has been prepared and fully characterized by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy. The compound {[Cu2(C2O4)2(inta)4](inta)}n1 crystallizes in the triclinic system,space group P1,with a=8.4722(5),b=10.9825(6),c=11.6128(6),α=104.8050(10),β=102.5740(10),γ= 109.6890(10)o,V=927.18(9)3,Mr=929.79,Z=1,Dc=1.665 g/cm3,F(000)=475,μ=1.231 mm-1,R=0.0453 and wR=0.1185 for 3290 observed reflections (I > 2σ(I)). Of the compound,the Cu center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the copper atom and each inta serving as a terminal ligand by employing only one N-donor to coordinate with the Cu center. An infinite {Cu2(C2O4)2}∞ chain is formed along the c axis. Furthermore,the 1D chains are held together via extensive hydrogen-bonding interactions to generate a three-dimensional network with 1D channels (ca. 5.491×11.507) where inta molecules are filled.     

THE EFFECT AND FUNCTION OF AliBu_2OR'''' ON BUTADIENE-PROPYLENE ALTERNATING COPOLYMERIZATION CATALYZED BY VO(OR)_2Cl-AIiBu_3 SYSTEM

Four kinds of AliBu_2OB' with different R' were synthesized. The effect of AliBu_2OR'/AliBu_3 mole ratio on the conversion, the [η] of copolymer and catalytic efficiency were studied. The conversion was increased obviously and the catalytic efficiency was 2.7 times higher than before. The effect of the amount of AliBu_2OR' on the valence state of vanadium ion and the change of the valence state of vanadium ion with reaction temperature and time were studied. The VIS and IR spectra of the trinary-component catalyst system were measured. The model of active center including AliBu_2OR' was proposed. The function of AliBu_2OB was explained.