导电玻璃上室温沉积钛膜及TiO2纳米管阵列的制备与表征

在掺氟的杂nO2(FTO)导电玻璃衬底上采用射频磁控溅射的方法室温沉积纯Ti薄膜, 以NH4F/甘油为电解液, 经电化学阳极氧化得到结构有序、微米级的TiO2纳米管阵列/FTO复合结构, 并通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)以及光电化学的方法对纳米管阵列进行了表征. 研究表明, 在氩气气压为0.5 Pa, 功率为150 W, 时间为0.5 h条件下在导电玻璃上室温沉积获得钛膜的结构为晶带T型组织, 表面均匀性好且致密度较高; 在电压为30 V下, 随着阳极氧化时间从1 h延长至3 h, 纳米管的管径从50 nm增加到75 nm, 纳米管的长度从750 nm增至1100 nm后减至800 nm, 管壁由平滑变为波纹状; 随氧化电压的升高, 纳米管管径逐渐增大, 而表面覆盖物逐渐减少, 可通过在稀的HF溶液(0.05%(w, 质量分数))中超声清洗去除; 此外, 瞬态光电流测试表明结晶的电极表现出更好的光电转换性能, 紫外光照射下能促进TiO2光生载流子有效分离, 在热处理温度为450 ℃时, 具有较高的光电化学性能.     

透明TiO2纳米管/FTO电极制备及表征

采用射频磁控溅射方法在透明导电玻璃(FTO)上沉积纯钛薄膜, 室温条件下在H3PO4+HF电解液中通过恒压阳极氧化方法得到TiO2纳米管阵列, 并通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、UV-Vis透射光谱以及光电化学的方法对纳米管阵列进行了表征. 研究表明, 在电压为20 V、氧化时间为50 min时, 钛薄膜转化为TiO2纳米管阵列, 管长约为380 nm, 内径约为90 nm, 管壁约为15 nm; 再经过500 ℃空气热处理6 h之后得到锐钛矿型的TiO2纳米管/FTO透明电极, 在可见光区的平均透过率约为80%, TiO2禁带宽度为3.28 eV, 发生了蓝移, 带尾扩展到2.6 eV; 此外, 对结晶前后的复合电极分别在暗态和紫外光下进行线性扫描和瞬态光电流测试, 结果表明, 结晶的电极表现出更好的光电转换性能; 施加阳极电压和紫外光照射都能够促进TiO2光生载流子有效分离,使电子迅速传至导电玻璃表面通过外电路形成光电流.     

透明TiO2纳米管/FT0电极制备及表征

采用射频磁控溅射方法在透明导电玻璃(FTO)上沉积纯钛薄膜,室温条件下在H3PO4 HF电解液中通过恒压阳极氧化方法得到TiO2纳米管阵列,并通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、UV-Vis透射光谱以及光电化学的方法对纳米管阵列进行了表征.研究表明,在电压为20V、氧化时间为50min时,钛薄膜转化为TiO2纳米管阵列,管长约为380nm,内径约为90nm,管壁约为15nm;再经过500℃空气热处理6h之后得到锐钛矿型的TiO2纳米管/FTO透明电极,在可见光区的平均透过率约为80%,TiO2禁带宽度为3.28eV,发生了蓝移,带尾扩展到2.6eV;此外,对结晶前后的复合电极分别在暗态和紫外光下进行线性扫描和瞬态光电流测试,结果表明,结晶的电极表现出更好的光电转换性能;施加阳极电压和紫外光照射都能够促进TiO2光生载流子有效分离,使电子迅速传至导电玻璃表面通过外电路形成光电流.     

NH4F/H3PO4体系中阳极氧化法制备TiO2纳米管阵列

以价廉的Ni板代替常用的Pt片为阴极,纯钛为阳极,采用电化学阳极氧化法在NH4F-H3PO4体系中制备出TiO2纳米管阵列.详细研究了制备参数(溶液酸度、氟离子浓度、外加电压和氧化时间)对所获纳米管阵列形貌的影响.采用场发射扫描电镜(FE-SEM)和X射线衍射(XRD)对样品的形貌和晶相结构进行了表征.在最优化的条件下,可以获得形貌规整、表面干净、有序的TiO2纳米管阵列.纳米管阵列的平均管径为60 nm.管长约530 nm.采用阳极氧化法制备的纳米管阵列是非晶态的.经400℃热处理2 h后,可以转变为锐钛矿相.实验结果还发现,经过热处理后,纳米管阵列变得更为有序,管径扩大至约95 nm.     

微含水量电解液中高管径比TiO_2纳米管阵列的制备

通过阳极氧化法在微含水量为0.5wt%的NH4F/乙二醇/H2O酸性电解质体系中制备了管径大、高管径比的二氧化钛(TiO2)纳米管阵列。采用SEM、XRD等测试手段对TiO2纳米管阵列形貌及晶相进行表征,探讨了不同氧化时间、电压对纳米管阵列形貌的影响,微含水量下氧化电压可以适当增加,更容易得到规整的长纳米管阵列;通过测定样品的光电流和紫外-可见光漫反射吸收光谱,研究分析了含水量以及超声工艺对纳米管光吸收及光电流特性,微含水量下得到的纳米管阵列可见光吸收边红移至420nm,对480~700nm可见光有明显的光吸收,光电流显著增大;丙酮作为超声介质可有效去除纳米管阵列表面的集束,能进一步提高纳米管阵列的光电性能。     

阳极氧化法制备二氧化钛纳米管阵列的研究

采用电化学阳极氧化法,将纯钛浸入HF酸水溶液,在钛基体表面原位构建高度有序的二氧化钛纳米管阵列,探讨阳极氧化电压、电解液浓度和电解液温度等对二氧化钛纳米管阵列尺寸和形貌的影响。通过SEM、XRD对二氧化钛纳米管阵列的结构特征进行表征,结果表明,不同的阳极氧化电压、电解液浓度和温度都将影响TiO2纳米管阵列的尺寸和形貌,在阳极氧化电压为20V,HF电解液浓度为0.5%t条件下,可制备出结构规整有序的TiO2纳米管阵列。     

ZnO/TiO2纳米管复合材料的制备及光电化学性能研究

采用电化学阳极氧化法制备TiO2纳米管,然后用光化学沉积法在TiO2纳米管表面沉积ZnO纳米颗粒制备ZnO/TiO2纳米复合材料。对样品进行了Raman谱、XRD和SEM表征,通过测定光电流-时间(I-t)和开路电压-时间(OCPT)曲线对ZnO/TiO2纳米复合材料的光电化学性能进行研究。结果表明,沉积ZnO没有改变TiO2的相结构;复合ZnO提高了TiO2的光电性能;在Zn(NO3)2浓度为10-3 mol.L-1的条件下制得的ZnO/TiO2纳米复合材料具有较好的光电性能。     

TiO_2纳米管阵列的制备及其对316不锈钢光生阴极保护作用的研究

应用直接电化学阳极氧化法,于含氟电解液中,在纯钛表面制备一层整齐有序的TiO2纳米管阵列.扫描电子显微镜(SEM),X射线衍射(XRD)表征该纳米管阵列的形貌及晶体结构,光电化学联用系统研究其光电响应特性及对316L的光生阴极保护作用.结果表明:以TiO2纳米管阵列膜作为光生阳极时,在紫外光区(λ<387nm)有显著增强的光生电流响应,并对316不锈钢有较好的光生阴极保护作用.暗态下,光生电极电位仍可维持较长的一段时间,继续起到阴极保护作用.     

CuS/TiO2纳米管异质结阵列的制备及光电性能

利用水热反应制备了CuS/TiO2纳米管异质结阵列,采用场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)和X射线衍射谱(XRD)等手段表征了异质结阵列的表面形貌和晶体结构.电流-电压曲线结果表明,CuS/TiO2纳米管异质结阵列具有明显的整流效应.根据表面光电压谱和相位谱,在376～600 nm之间,CuS/TiO2纳米管异质结阵列表现为p型半导体特征,电子在表面聚集;在300～376 nm之间表现为n型半导体特征,空穴在表面聚集;在376 nm处异质结阵列的表面光伏响应为零.CuS/TiO2和CuS/ITO之间界面电场的不同导致异质结在不同波长范围内表面电荷聚集的差异.光电化学性能测试发现,以CuS/TiO2纳米管异质结阵列为光阳极组成的光化学太阳电池,在大气质量AM 1.5G,100 mW/cm2标准光强作用下具有0.4%的光电转换能力.     

TiO_2纳米管阵列薄膜制备及生长机理的研究

本论文采用阳极氧化的方法,在NH4HF2+NH4H2PO4的混合水溶液中于室温下以金属钛为基体原位合成氧化钛纳米管阵列薄膜。讨论了电解液成分、外加电压、溶液的pH值对氧化钛纳米管阵列薄膜微观结构及形貌的影响,并建立了阳极氧化钛纳米管阵列薄膜的生长模型。氧化钛纳米管的结构与外加电压有很大的关系,只有电压在5～35V范围内才能制备出二氧化钛纳米管阵列薄膜,其管径随着电压的升高而增加,且管径范围为30～160nm。而薄膜的厚度与电解液有关,通过控制电解液的成分及pH值,可获得厚度为6.5μm的氧化钛纳米管阵列薄膜。     

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。     

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.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

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.