聚酰亚胺对高性能树脂共混体系界面的反应增强

研究了以5-降冰片烯-2,3-二羧酸单甲酯为端基的PMR型聚酰亚胺(POI)作为界面介质对部分相容的聚醚砜/聚苯硫醚(PES/PPS)、聚醚醚酮/聚醚砜(PEEK/PES)共混体系的界面性质、形态结构及结晶行为的影响.结果表明,POI可以有效地增强两相间的界面粘结,显著降低PPS/PES共混物中PPS分散区的尺寸,改善两组分间的相容性.在熔融共混过程中,POI从本体向界面扩散并同PPS,PES产生交联和/或接枝,POI同PPS的反应活性远高于PES,但POI与PES发生反应.POI是PPS结晶的有效成核剂.     

溶胶-凝胶型陶瓷碳硫离子选择性电极的研制

将溶胶-凝胶技术与印制电极技术相结合制作了复合陶瓷碳硫离子选择性电极。对溶胶-凝胶形成条件和印刷浆液的组成进行了试验,电极制作过程包括电极膜基质制备、溶胶、凝胶型型陶瓷碳硫离子敏感膜制备、敏感膜在基质上的固定化三步。对电极的参数进行了测试。该电极稳定性、重现性好,响应快。应用于实际和模拟样品分析,取得满意效果。采用该法制备离子选择性电极具有简易、价廉、易集成化等特点,适合于制作一次性使用的离子选择性电极。     

Synthesis and structure of the polymeric cluster compound [Mn(H2O)4]3[W4S4(CN)12]·nH2O containing very large cavities

The compound [Mn(H₂O)₄]₃[W₄S₄(CN)₁₂]·nH₂O (1) was prepared by the reaction of an aqueous solution of MnSO₄ with a glycerol solution of KCs₅[W₄S₄(CN)₁₂]·4H₂O. Complex 1 was characterized by X-ray diffraction analysis and IR spectroscopy. According to the X-ray diffraction data, the three-dimensional polymeric framework of 1 comprises only 24.2% of the unit-cell volume. The volume of the cavities per formula unit is 1664 ³. The cavities are occupied by highly disordered water molecules.     

原位Raman光谱揭示中性条件下硫化钼结构变化对其电催化析氢反应的促进作用

硫化钼是析氢反应(HER)有前途的电催化剂. S-或Mo物种均被认为是形成吸附氢触发HER反应的活性位, 但Mo中心和S配体间相互作用的本质仍不清楚. 另外, 采用中性的水作为质子源用于产氢, 来开发低成本的水裂解催化剂体系为研究者高度关注, 但人们很少研究中性水条件下HER反应的机理. 本文采用原位电化学Raman光谱对所合成的硫化钼中Mo-Mo和S-S物种在中性条件下的结构变化进行了监测. 结果显示, 归属于端位S-S物种的谱带随着Mo-Mo, Mo3-μ3S和Mo-S振动谱带频率而同步变化, 表明Mo-Mo键与端位S-S键起着协同作用, 从而有利于氢气的生成. 这可能是通过三核Mo3-μ3S物种的内部重组而确认的. 本文所揭示的HER反应中金属-配体相互作用的本质与作用表明了一个不同的反应机理, 而以往的机理认为, S或Mo活性位独立起作用而促进HER反应的进行.     

Fluoroethylene Carbonate Enabling a Robust LiF‐rich Solid Electrolyte Interphase to Enhance the Stability of the MoS2 Anode for Lithium‐Ion Storage

As a high‐capacity anode for lithium‐ion batteries (LIBs), MoS₂ suffers from short lifespan that is due in part to its unstable solid electrolyte interphase (SEI). The cycle life of MoS₂ can be greatly extended by manipulating the SEI with a fluoroethylene carbonate (FEC) additive. The capacity of MoS₂ in the electrolyte with 10 wt % FEC stabilizes at about 770 mAh g^?1 for 200 cycles at 1 A g^?1, which far surpasses the FEC‐free counterpart (ca. 40 mAh g^?1 after 150 cycles). The presence of FEC enables a robust LiF‐rich SEI that can effectively inhibit the continual electrolyte decomposition. A full cell with a LiNi_0.5Co_0.3Mn_0.2O₂ cathode also gains improved performance in the FEC‐containing electrolyte. These findings reveal the importance of controlling SEI formation on MoS₂ toward promoted lithium storage, opening a new avenue for developing metal sulfides as high‐capacity electrodes for LIBs.     

Six‐coordinated vanadium(IV) complexes with tridentate task‐specific ionic liquid Schiff base ligands: Synthesis,characterization and effect of ionic nature on catalytic activity

By reaction of 5‐(chloromethyl)salicylaldehyde with triphenylphosphine and N‐methylimidazole in two separate reactions, salicylaldehydetriphenylphosphonium chloride (S²) and salicylaldehydemethylimidazolinium chloride (S³) were prepared. Reaction of 2‐(aminomethyl)pyridine with these aldehydes resulted in the task‐specific ionic liquid Schiff base ligands L¹ and L², respectively. Then six‐coordinated vanadium(IV) Schiff base complexes of VO(acac)L^1–4 were synthesized by reactions of these tridentate Schiff base ligands and VO(acac)₂ in 1:1 stoichiometry. The aldehydes, ligands and VO(acac)L^1–4 complexes were characterized using infrared, ¹H NMR, ¹³C NMR, ³¹P NMR, UV–visible and mass spectroscopies, as well as elemental analysis. Paramagnetic property of the complexes was also studied using magnetic susceptibility measurements. The complexes were used as catalysts in epoxidation of cyclooctene and oxidation of methylphenyl sulfide and the reaction parameters were optimized. The effect of the ionic nature of the complexes was investigated in these oxidation reactions. The catalytic activity of the complexes could be varied by changing the ionic (cationic or anionic) character of VO(acac)L^1–4 catalysts in which counter anion variation showed a greater effect than cationic moiety variation.     

Oxido‐peroxido W(VI)‐histidine–MgAl‐layered double hydroxide composite as an efficient catalyst in sulfide oxidation

Oxido‐peroxido W(VI)‐histidine–MgAl‐layered double hydroxide composite was prepared by using MgAl‐layered double hydroxide as a host and oxido‐peroxido W(VI)‐histidine complex as a guest. The composite was characterized by XRD, IR, EDX,SEM and TEM techniques. This composite is tested for catalytic selective sulfoxidation reactions using hydrogen peroxide as oxidant showing good to moderate conversion along with high selectivity.     

PEI溶液紫外吸收光谱检测油气田硫化氢气体

建立了一种基于聚乙烯亚胺(PEI)溶液的紫外(UV)吸收光谱检测油气田硫化氢(H2S)气体浓度的方法。利用PEI结构中的氨基可与H2S气体反应的特性,测定通入H2S气体前后PEI溶液的UV吸收光谱,并分析了UV光谱吸收峰在230、365 nm附近的吸光度变化与气体浓度的关系。采用标准浓度的H2S气体样品进行浓度标定实验,建立了H2S气体浓度与吸光度之间的关系模型。实验结果表明:通入高纯度H2S气体时,PEI溶液的UV光谱在230 nm和365 nm处均出现较强吸收峰;通入较低浓度H2S气体时,UV光谱只在230 nm处出现吸收峰,该吸收峰附近的吸光度与H2S气体浓度间存在线性关系(相关系数为0.970 6),系统对H2S气体浓度的检出限可达15.39 mg/m3。基于PEI溶液的UV吸收光谱检测法可为油气田H2S气体浓度的快速、准确测定提供参考。     

片层WC/C的原位合成及其在甲醇氧化中的应用

以片层二硫化钨(WS2)为前驱体,氯化钠(Na Cl)为介质,CO为气体碳源,采用程序升温法一步合成片层碳化钨/碳复合材料(WC/C)。通过X射线衍射(XRD),X射线近边吸收谱(XANES)和扫描电镜(SEM)等一系列手段对样品的化学组成、形貌、结构等进行表征。研究发现,在高温渗碳过程中,不仅利用WS2的片层结构和Na Cl的锚定作用合成了具有薄层孔洞的WC,而且Na Cl和WS2金属面对碳膜生长的催化作用使WC表面覆有原位生长的碳膜,为电子传输提供了有效通道。将该材料作为载体材料进行电化学性能测试,结果表明:负载少量Pt后制得的Pt/WC/C电催化剂,在甲醇氧化反应(MOR)中表现出良好的电催化活性、稳定性及优异的抗CO中毒能力。     

Rapid microwave promoted heterocyclization of primary amines with triethyl orthoformate and sodium azide using zinc sulfide nanoparticles as recyclable catalyst

Microwave assisted synthesis of 1-substituted-1H-tetrazoles was developed using zinc sulfide nanoparticles as heterogeneous catalyst under solvent free conditions. The tetrazole derivatives were easily prepared through hterocyclization of primary amines with triethyl orthoformate and sodium azide in the presence of ZnS NPs. The experimental results were shown that a series of 1-substituted tetrazoles were synthesized under microwave irradiation by ZnS NPs as an effective and reusable heterogeneous catalyst in excellent yields. This protocol has advantages rather than other reported methods such as non-acidic catalyst, solvent free conditions and greener process as well as a solid recyclable catalyst. The catalyst was recovered and reused for several cycles with consistent activity.