STUDY ON POLYMER—Ru-Co—BIMETALLIC COMPLEXES CATALYSTS Ⅰ. SYNTHESIS OF CATALYSTS AND THEIR USE FOR THE HYDROFORMYLATION

Six kinds of polymer ligands, supported on SiO_2, containing coordinating atoms P, S and N respectively, have been synthesized. The Ru(Ⅲ)-Co(Ⅱ) bimetallic complexes of these polymer ligands have been obtained and examined as catalysts for the hydroformylation of cyclohexene. The effects of reaction temperature, pressure and Co/Ru ratio etc. on the activities of catalysts were investigated in detail. The catalysts are all polymer-noncarbonyl-metal complexes, easily to be prepared, active and stable. From the experimental results it can be suggested that under reaction conditions such polymer-noncarbonyl-metal complexes convert "in situ" to polymer-carbonyl-metal complexes, thus become active catalysts. The course of this conversion is supposed as a preliminary approach.     

肼溶胶-凝胶法制备高比表面积纳米氮化钛粉体的研究

以无水肼作氮源, 采用肼溶胶-凝胶技术(HSG)成功地制备了TiN粉体, 研究了不同钛源、处理气氛及焙烧温度对TiN粉体晶化过程的影响, 并对其形成机理进行了讨论. 与氨气氮化法相比, 该方法所需温度低、TiN的粒径小、比表面积大, 并且分散均匀.     

Precise Design of Covalent Organic Frameworks for Electrocatalytic Hydrogen Peroxide Production

Electrochemical synthesis of H₂O₂ with high productivity is a significant challenge in electrocatalysis. Herein, we develop Mg-ion contained covalent organic frameworks (MgP-DHTA-COF), comprising stacked 2D layers, well-defined skeletons, and well-ordered monodispersed active sites, for the electrocatalytic production of H₂O₂ directly from O₂ and H₂O. The precise-designed MgP-DHTA-COF achieves H₂O₂ selectivity up to 96%, high Faradaic efficiency of 91% and reliable stability for H₂O₂ synthesis in 0.10 mol L⁻¹ KOH aqueous solution. Both experiments and simulations demonstrate that the pyrrolic-N fixed Mg ions in the knots promote the reactivity of COF and enhance the adsorption ability of OOH*. This work provides a valuable example for the design of an efficient electrocatalyst based on COFs for H₂O₂ production.     

Surfaced-modified TiO2 Nanofibers with Enhanced Photodegradation Under Visible Light

Asynchronized surface modification method based on coaxial electrospinning was developed to fabricate high-efficiency photodegradative nanofiber for water purification. TiO₂ nanoparticles assembled uniformly on the surface of polycaprolactone(PCL) nanofibers to form composite nanofibers through one step process. The maximal content of Ti element was 25.6%(mass fraction) in the PCL/TiO₂ composite nanofibrous membrane, which exhibited hydrophilicity and excellent photodegradation under visible light in water. The Rhodamine B dye degraded 96.17% in 120 min under visible light by the PCL/TiO₂ composite membrane. The adsorption behavior fitted Langmuir model well and indicated chemical related adsorption. This PCL/TiO₂ composite nanofibrous membrane has super degradation properties and displays great application potential to environmental protection.     

A local search using solution fragments for the 2-machine bicriteria scheduling problem

In this work, we introduce a local search strategy for combinatorial optimization problems which explores neighborhoods obtained using fragments of current solutions. We apply the approach to the well-known -hard 2-machine bicriteria flowshop scheduling problem. Computational experiments using benchmark data show the approach to be effective when compared to other algorithms available for the problem.     

含Eu(Ⅲ)和Gd(Ⅲ)共轭高分子配合物发光性质研究

线性共轭高分子P-1是由单体1,4-二溴-2,3-二正丁氧基萘(M-2)和5,5'-二乙烯-2,2'-联吡啶(M-3)通过Pd催化Heck偶合反应合成得到,高分子配合物P-2和P-3由高分子P-1和Eu(TTA)3·2H2O和Gd(TTA)3·2H2O反应生成.高分子P-1能发射强蓝绿色荧光.高分子配合物P-2和P-3发光性能测试表明,含有Eu(Ⅲ)的高分子配合物P-2不仅显示高分子荧光,而且还显示了Eu(Ⅲ)(5D0→7F2)特征荧光,含Gd(Ⅲ)的高分子配合物P-3仅发射高分子的荧光,其荧光波长相对P-1而言,呈现13 nm红移.     

氯化血红素催化氧化巯基形成二硫键

对氯化血红素催化氧化巯基形成二硫键的反应进行了研究,发现N,N-二异丙基乙胺(DIEA)的加入可以提高氯化血红素的催化活性,并降低其在氧化过程中的自聚现象.在室温及少量DIEA存在下,将氯化血红素和巯基乙酸甲酯按摩尔比1∶4混合于p H=8.0的水溶液中,敞口搅拌反应20 min,可以催化空气氧化90%的巯基乙酸甲酯形成相应的分子间二硫键产物.该催化氧化体系还可应用于多肽合成中,在相同条件下,只需2 h即可完成还原型催产素和利那洛肽的氧化环合,生成高产率的催产素和利那洛肽环肽.与传统的氧化方法相比,氯化血红素催化氧化的方法具有高效、环保的优点,为多肽合成中二硫键的形成提供了一种新方法.     

壳聚糖接枝共聚改性最新研究进展

壳聚糖是一种天然高分子,也是迄今为止唯一发现的阳离子碱性多糖。壳聚糖分子链中富含羟基和氨基等反应性官能团,具有生物相容性、生物可降解性、抗菌性、无细胞毒性等优良性能,在生化、医药、环保、农业等领域有广泛的应用前景。然而,由于其大分子具有较好的立构规整性和较强的氢键作用,除稀盐酸、稀醋酸外,壳聚糖不溶于水和其它有机溶剂,因而限制了它的应用范围。为了扩大其应用领域,常通过接枝共聚反应来改善壳聚糖的性能。本文介绍了壳聚糖接枝共聚改性的最新研究进展,包括自由基引发接枝法、偶联接枝法以及催化接枝法。     

磁控溅射淀积掺Er富Si氧化硅膜中Er3+ 1.54μm光致发光

用磁控溅射淀积不同富Si程度的掺Er富Si氧化硅薄膜.室温下测量其光致发光谱,观察到各谱中都含有1.54和1.38μm两个发光峰,其中1.54和1.38μm的光致发光峰分别来自Er³⁺和氧化硅中某种缺陷.系统研究了Er³⁺1.54μm光致发光峰强度对富Si程度及退火温度的依赖关系.还发现1.54μm发光峰强度与1.38μm发光峰强度相互关联,对此进行了讨论 关键词： Er 富Si氧化硅 光致发光 纳米硅     

Pion Susceptibilities of the Vacuum in a Modified Global Colour Symmetry Model

Based on a modified version of the global color symmetry model,the pion susceptibilities of vacuum needed in the QCD sum rule external-field method for the coupling of pseudoscalar current to hadron have bean calculated beyond the vacuum saturation approximation.Comparison with the previous estimations has been given.