Electrooxidation Mechanism of Methanol at Pt-Ru Catalyst Modified GC Electrode in Electrolytes with Different pH Using Electrochemical and SERS Techniques

The electrochemical and in-situ surface-enhanced Raman spectroscopy （SERS） techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon （Pt-Ru/GC） electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable.     

应用新型立式逆流色谱制备分离南蛇藤中的南蛇藤素

A versatile countercurrent chromatography with upright multilayer coil planet centrifuge, named upright countercurrent chromatography (UCCC), was applied to the isolation and purification of celastrol from the roots of Celastrus orbiculatus Thunb. The crude celastrol was obtained by elution with petroleum ether from ethanol extracts using a 15 cm length and 5 cm I.D. of silica gel flash chromatography. Preparative UCCC (Fig. 1) with a two-phase system composed of petroleum ether (b. p. 60 ～ 90 ℃ )-ethyl acetate-tetrachloromethanemethanol-water ( 1:1:8:6: 1, v/v) was successfully performed, yielding 705 mg celastrol at 99.5 % purity from 1020 rng of the crude extract in one step separation.     

一种非晶硅膜改性弹性玻璃毛细管交联中等极性固定相色谱柱的制备

研究了非晶硅膜改性的弹性玻璃毛细管交联ＯＶ－１７０１中等极性固定相色谱柱。在适当温度下，采用过氧化二异丙苯（ＤＣＵＰ）游离基引发交联ＯＶ－１７０１固定液，成功地制备了交联ＯＶ－１７０１柱，该柱具有柱效高、惰性好、耐溶剂、抗腐蚀和耐高温等性能，是一种新型高性能的中等极性交联柱。     

无机玻璃Li2O·2SiO2的结构松弛(Ⅰ)——TNM唯象模型描述

简介了结构松弛的主要特点及其唯象Tool-Narayanaswamy-Moynihan(TNM)模型的建立,并用此模型对无机玻璃(Li2O·2SiO2)在不同老化时间及不同老化温度下的结构松弛行为进行了模拟.得到了4个可调参数X、β、△h* 和A,其中β、△h* 和A不随老化温度及老化时间而发生变化,X则随老化时间的增加而增大,随老化温度的降低而降低.     

聚合物微晶尺寸和晶格畸变

聚合物微晶尺寸和晶格畸变是对聚合物材料性能有着重要影响的结构参数。本文介绍了应用Ｘ射线衍射方法测定聚合物微晶尺寸和结构畸变的几种方法：近似函数、次晶模型法、方差法、矩法。     

不饱和硼烯HClN=B:重排反应的DFT研究

采用量子化学中的密度泛函方法, 在B3LYP/6-311G**水平上研究了不饱和硼烯HClN=B:的重排反应机理。结果表明, 无论是氢原子H迁移还是氯原子Cl迁移都经过1个三元环过渡态,生成直线型产物。但氢原子H迁移是在面内进行, 而氯原子Cl迁移是在面外进行。根据计算结果,详细研究了不饱和硼烯HClN=B:重排反应的热力学及动力学函数, 在此基础上讨论了不饱和硼烯HClN=B:的存在寿命问题。     

表面修饰二氧化锡纳米微晶的制备与表征

制备了硅烷偶联剂KH-570表面修饰的SnO2纳米微晶，通过FT-IR、XPS、TEM和TG-DTA对其结构和表面特性进行表征和研究. FT-IR和XPS分析结果确证了KH-570与SnO2表面是以化学键合或物理吸附方式相结合,粒子表面存在酯基等有机官能团的红外吸收特征；观测到KH-570中Si原子的Si2s和Si2p谱线. TEM分析表明，表面修饰反应增强了SnO2纳米微晶的疏水性和分散性.由XPS和TG的实测数据探讨了纳米粒子具有较低包覆量的可能原因.     

纳米微晶Y_2Sn_(2-x)FexO_(7-δ)的制备及其催化选择性能研究

采用共沉淀并加法制备了Ｂ位掺杂烧绿石型稀土复合氧化物纳米微晶Ｙ２Ｓｎ２－ｘＦｅｘＯ７－δ（ｘ＝００～１０）。制备的纳米微晶属于立方晶系，Ｆｄ３ｍ，晶胞参数与掺杂量呈线性关系。通过Ｍｓｂａｕｅｒ、ＴＧＤＴＡ，气相色谱和γ射线辐照等技术研究了纳米微晶对ＣＯ的催化选择性能。结果表明，纳米微晶对ＣＯ的催化选择性明显高于一般粉料对ＣＯ的选择性；纳米微晶对ＣＯ的选择性与掺杂量有关；未辐照的纳米微晶，当掺杂量ｘ＝０６时，其对ＣＯ的选择性为最高，辐照后的纳米微晶，当掺杂量ｘ＝０４时，其对ＣＯ的选择性为最高     

光谱电化学法研究亚甲基蓝的电还原反应

用极谱法研究亚甲基蓝(MB)的电极吸附过程早有报道.近几年,用光谱电化学法研究其电化学行为又引起了许多人的兴趣.但在光透薄层电极上,由于光程太短,测试溶液浓度较高,导致亚甲基蓝发生聚合,影响实验结果的准确测定.为此本文利用特制的比色皿型长光程薄层光谱电化学池,在低浓度条件下研究其在SnO_2镀膜玻璃电极上的电还原反应.