多尺度炭材料担载铂作为稳定的电催化剂用于氧还原反应

炭载体的稳定性对于燃料电池电催化剂是至关重要的. 本文中采用酚醛树脂作为前驱体,二氧化硅为模板剂,制备了多介孔且石墨化程度高的炭载体（HGMC）. 相比于商品Vulcan XC-72,HGMC具有中等的比表面积和高的石墨化程度,因此在电位循环扫描过程中具有较高的化学稳定性,然而HGMC碳层堆叠的结构不利于传质. 为克服这一劣势,多壁碳纳米管（MWCNTs）作为隔离物加入至HGMC中以构建具有三维多尺度结构的载体（MSGC）. 与HGMC为载体担载Pt以及商品催化剂Pt/C-JM相比,由于炭载体的具有高稳定性以及三维多尺度结构,MSGC担载Pt后不仅使电催化剂的电化学稳定性提高,且氧还原反应过程中传质得到显著改善.     

碳载体不同预处理方法对Pt/C电催化氧化甲醇性能的影响

本文分别用混酸水热法(HT)和混酸冷凝回流法(RF)对Vulcan XC-72R碳黑进行预处理,并进一步研究其作为Pt/C催化剂载体的性能。循环伏安实验发现,采用HT法、RF法和未预处理的碳黑作为载体的Pt/C催化剂电催化甲醇氧化的比质量活性(正扫峰电流)分别为1055、704和395 mA/mgpt,即采用HT法预处理碳载体的Pt/C催化剂具有最高的电催化活性,而且计时电流实验也表现出最好的稳定性。实验结果表明,碳载体的预处理方法对制得的Pt/C催化剂的性能具有关键性的影响,且水热法是一种效果较好的预处理碳载体的方法。     

石墨纳米纤维用作质子交换膜燃料电池催化剂载体

利用质子交换膜燃料电池用过的废旧碳纸,采用球磨法制备了石墨纳米纤维(GNF,BET比表面积为229·3m2/g),并以GNF作为载体制备了Pt/GNF催化剂(电化学比表面积为98m2/g).与传统的以VulcanXC-72碳黑为载体的Pt/XC-72催化剂相比,其电化学比表面积及Pt粒径大小相近.采用恒电位氧化法考察了GNF,XC-72,Pt/GNF和Pt/XC-72的电化学稳定性.结果表明,在相同条件下,XC-72的峰电流增加了60%,而GNF增加了2%;Pt/XC-72的腐蚀电流比Pt/GNF的大40%;恒电位氧化60h后,Pt/XC-72约有84·7%的电化学比表面积损失,Pt/GNF仅损失37·2%.这表明GNF的抗腐蚀性优于XC-72,有希望成为质子交换膜燃料电池抗腐蚀的催化剂载体.     

中空石墨碳材料作为电催化剂载体在直接乙醇燃料电池中的应用

以间苯二酚、苯酚与甲醛为前体,合成了一种中空石墨碳材料(hollow graphitic carbon,HGC).透射电镜(TEM)、N2吸附-脱附和Raman光谱测试结果表明,所制备的HGC为中孔结构,平均孔径为36nm.与商品Vulcan XC-72R相比,HGC中孔结构丰富,石墨化程度高.分别以HGC和XC-72R为载体制备了总金属载量为45%的PtSn/C电催化剂,X射线衍射和TEM结果表明这两个样品的平均粒径和晶格常数相近.单池性能测试表明,以45%PtSn/HGC为阳极催化剂的直接乙醇燃料电池的最大功率密度达到了62mW/cm2,与PtSn/XC-72R的54mW/cm2相比提高了近15%.     

碳黑预处理对Pt/C催化剂对甲醇氧化电催化活性的影响

直接甲醇燃料电池(DMFC)由于具有较多的优点而受到广泛的关注. 但是碳载Pt (Pt/C)阳极催化剂电催化活性低是限制其应用的一个主要问题. 为了提高Pt/C催化剂对甲醇氧化的电催化性能, 分别用CO₂, 空气, H₂O₂或HNO₃对常用作为载体的Vulcan XC-72碳黑进行预处理. 结果表明, 在用CO₂, 空气, HNO₃, H₂O₂处理的及未处理的碳黑作载体制得的Pt/C催化剂电极上, 甲醇氧化峰的峰电流密度顺序为39, 33, 32, 20和18 mA•cm^－2, 表明用CO₂处理的碳载体制备的Pt/C催化剂对甲醇氧化有最好的电催化活性和稳定性. 其主要原因是用CO₂处理能减少碳黑表面的含氧基团和增加石墨化程度, 而使碳黑的电阻降低及Pt粒子在碳黑上的分散性变好.     

碱性介质中铂/碳气凝胶电催化氧化甲醇

以间苯二酚和甲醛为原料,采用溶胶-凝胶法制备了碳气凝胶(CAs);以CAs为载体,利用乙二醇还原法制备了Pt/CAs催化剂;在碱性条件下,采用循环伏安法测定了Pt/CAs催化剂电催化氧化甲醇的活性,结果表明,Pt/CAs显示出高的甲醇氧化催化活性,在1.0mol.L-1 NaOH和1.0mol.L-1 CH3OH溶液中,其峰电流密度是商品Vulcan XC-72R负载Pt催化剂Pt/C的3.9倍,甲醇起始氧化电位比Pt/C的负移约100mV.     

层级多孔碳载铂催化剂的制备及可达性

层级多孔碳作为氧还原铂基催化剂载体的选择之一, 简单的旋转圆盘电极(RDE)验证此类催化剂具有较高的氧还原活性, 但几乎都缺少膜电极(MEA)性能验证, 实用性无法保证. 本文设计制备了基于聚苯胺的层级多孔碳（NHPC）载铂催化剂（Pt/NHPC850）, 研究了其氧还原活性、 MEA质子传输和氧传输特性. RDE测试研究表明, Pt/NHPC850催化剂在低I/C（离聚物与碳载体质量比）时的面积活性低于实心碳载铂催化剂（Pt/XC-72）, 但当I/C增大到与膜电极中一致时, 由于Nafion树脂对Pt催化剂的毒化作用增强, 其面积活性反而优于 Pt/XC-72. Pt/NHPC850催化剂的高Pt分散性及其优异的抗Nafion毒化性能, 使其在I/C为0.8时的质量活性为Pt/XC-72催化剂的1.34倍. MEA质子传输研究表明, 即使在高加湿条件下, Pt/NHPC850质子电阻率仍高达72.6 mΩ·cm², 为Pt/XC-72的3倍. Pt/NHPC850制备的膜电极极化曲线在500 mA/cm²电流密度下性能迅速下降, Pt/NHPC850的氧增益电压达到144.4 mV, 比Pt/XC-72高56.7 mV. 表明Pt/NHPC850膜电极的质子传输和氧传输性能较差. 对比Pt/NHPC850催化剂的RDE和MEA的测试结果, 说明以层级多孔碳为载体的铂碳催化剂虽然耐Nafion毒化能力提高, 但是质子和氧气的氧传输性较差, 此类层级多孔碳还需进一步优化其结构, 才有可能满足低铂质子交换膜燃料电池（PEMFC）的应用需求.     

PtCr合金的溶液制备及其电化学性质分析

催化剂性能的高低直接决定了燃料电池性能的好坏. 采用Pt基合金不仅能够降低催化剂Pt的载量, 而且往往能够提高催化剂的性能. 本工作用Cr作为合金化元素, 通过液相共沉淀的方式制备了不同比例的碳载PtCr合金催化剂. 采用高分辨透射电镜(HRTEM), 扫描电镜(SEM)等技术对合金催化剂的物理性质进行了测试. 结果表明, 获得的PtCr/C催化剂均匀地分散在Vulcan XC-72碳载体上, 粒度小于4 nm. 通过电化学测试, 研究了不同比例PtCr合金的电化学催化性能. 循环伏安测试表明, 本实验条件合成的合金催化剂在Pt/Cr原子比为2/1的时候, 对氧还原动力学有最佳的催化性能.     

碳载体的O3处理对直接甲醇燃料电池Pt-Ru/C催化剂性能的影响

为了提高直接甲醇燃料电池阳极催化剂的催化活性, 利用O₃处理的Vulcan XC-72碳黑为载体, 制备Pt-Ru/C催化剂, 并与未经处理的Vulcan XC-72为载体制备的Pt-Ru/C催化剂的性能进行比较. 采用XPS和BET测试了O₃处理后碳粉表面的含氧浓度和比表面积, 结果表明, 随处理时间延长, 碳表面含氧浓度先减少后增加, 比表面积减小; 而随着处理温度升高, 比表面积增加, 含氧浓度先减少后增加. XRD, TEM方法对催化剂的结构及形貌的表征结果表明: O₃处理的碳黑为载体制备的Pt-Ru/C催化剂粒径均匀、分散性好. 在0.5 mol/L CH₃OH和0.5 mol/L H₂SO₄溶液中, 利用粉末微电极测试了循环伏安和稳态极化曲线, 结果表明: O₃处理碳粉为载体的催化剂比未经处理的碳粉为载体的催化剂的活性高. 研究了O₃处理碳粉的时间和温度对催化剂性能的影响, 电化学测试表明: 140 ℃处理6 min的碳粉为载体制备的催化剂对甲醇的电催化氧化活性最佳.     

碳载体的O3处理对直接甲醇燃料电池Pt-Ru/C催化剂性能的影响

为了提高直接甲醇燃料电池阳极催化剂的催化活性, 利用O₃处理的Vulcan XC-72碳黑为载体, 制备Pt-Ru/C催化剂, 并与未经处理的Vulcan XC-72为载体制备的Pt-Ru/C催化剂的性能进行比较. 采用XPS和BET测试了O₃处理后碳粉表面的含氧浓度和比表面积, 结果表明, 随处理时间延长, 碳表面含氧浓度先减少后增加, 比表面积减小; 而随着处理温度升高, 比表面积增加, 含氧浓度先减少后增加. XRD, TEM方法对催化剂的结构及形貌的表征结果表明: O₃处理的碳黑为载体制备的Pt-Ru/C催化剂粒径均匀、分散性好. 在0.5 mol/L CH₃OH和0.5 mol/L H₂SO₄溶液中, 利用粉末微电极测试了循环伏安和稳态极化曲线, 结果表明: O₃处理碳粉为载体的催化剂比未经处理的碳粉为载体的催化剂的活性高. 研究了O₃处理碳粉的时间和温度对催化剂性能的影响, 电化学测试表明: 140 ℃处理6 min的碳粉为载体制备的催化剂对甲醇的电催化氧化活性最佳.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。