蚀刻金属铝箔覆型制备Ni-P微阵列材料及析氢电催化性能研究

以蚀刻金属铝箔为模板,用化学镀制备了具有微米阵列结构的Ni-P合金材料,使用扫描电镜、能量散射谱及X-射线衍射等表征手段对所得材料的微观形貌与物质组成进行了分析,并通过电化学方法研究了化学镀温度、施镀时间对材料析氢催化活性的影响。结果表明,70℃制得的Ni-P微阵列材料作电极其析氢过电位最小,电流密度为15m A/cm2时比光面Ni-P镀层下降了约100m V;同时表现出最高的交换电流密度13.53×10-6A/cm2,高出光面Ni-P镀层近1个数量级;70℃施镀4h能够得到析氢过电位较低且结构完整的镀层,延长镀时没有继续提升其性能。为直观衡量材料的催化活性,在双室槽中进行了光解水析氢测试。Ni-P微阵列材料表现出良好的催化活性,析氢速率较光面电极上升约200%。     

电化学法制备Ni-W-P纳米线阵列电极及其催化析氢性能

采用二次氧化法制备了多孔阳极氧化铝(AAO)模板, 通过控制电位沉积技术在AAO模板内组装了Ni-W-P合金纳米线阵列. 在扫描电子显微镜(SEM)下观察到Ni-W-P纳米线表面光滑, 长约20 μm, 直径均匀(约为100 nm), 与AAO模板孔径基本一致. 阴极极化曲线和交流阻抗图谱(EIS)的测试结果表明, Ni-W-P合金纳米线阵列电极析氢反应(HER)电阻减小, 具有更高的催化析氢活性, 电流密度为10 mA·cm^-2时, 析氢极化电位较Ni-W-P合金电极正移约250 mV.     

镍钨磷合金电结晶机理及其镀层结构与显微硬度

应用循环伏安、恒电位阶跃和 X射线衍射（ XRD）等方法研究了 Ni-W-P合金电沉积特点和镀层结构与显微硬度 .结果表明,在以柠檬酸铵为配体的溶液中, Ni-W-P合金沉积层较 Ni-W合金有较低的电化学活性 .根据电位阶跃的 i～ t曲线分析表明,在玻碳电极上 Ni-W-P合金电结晶过程遵从扩散控制瞬时成核三维成长模式进行,随着过电位的增加,电极表面上晶核数增多 . XRD试验结果表明, Ni-W-P合金镀层呈现明显的非晶态特征 .所获得的 Ni-W-P合金电沉积层的显微硬度在 450 kg· mm－ 2左右 .     

Ni-Sn电极析氢性能研究

在Fe基底材料上电镀Ni_Sn合金制备低析氢过电位的阴极活性材料 .该材料适用于氯碱工业隔膜型电解槽 ,可达到降低槽压、节能降耗的目的 .在电解槽阴极溶液NaOH 12 0 g/L ,NaCl190 g/L ;温度 90℃ ,阴极极化电流密度i=15 0mA/cm2 的条件下 ,测得其析氢过电位为 88mV .X射线衍射分析表明 ,该种材料与传统装饰用Ni_Sn合金的结构状态有所不同 .采用循环伏安法对Fe电极和Ni_Sn合金电极进行分析 ,可初步判断Ni_Sn合金对氢的吸附较弱 ,有利于析氢反应的进行     

硝酸铈及热处理对化学镀Ni-W-P合金的性能影响

为提高化学镀Ni-W-P镀层的耐蚀性和耐磨性,拓宽其应用,采用电化学方法和热处理等手段,研究了镀液中添加剂硝酸铈(Ce(NO3)3)的质量分数和热处理对化学镀Ni-W-P镀层的沉积速度、孔隙率、失重腐蚀速度、腐蚀电位、腐蚀电流、交流阻抗、显微硬度、摩擦系数等性能的影响。结果表明:添加1.0 wt%Ce(NO3)3时,所得镀层的沉积速度最大(36.5 g/m2·h),孔隙率最低(0.8个/cm2),耐腐蚀性能最好。镀层的组织均匀、致密、无缺陷和非晶态结构是其耐蚀性能高的重要原因。100~600℃热处理后,镀层硬度和耐磨性有所提高,而400℃热处理之后,合金显微硬度高达1100 HV,是镀态的1.8倍。     

TiN基IrO2-Ta2O5涂层析氢电极的催化性能

 采用热分解法制备了以离子镀TiN膜为基体的IrO2-Ta2O5涂层电极,通过循环极化曲线并结合扫描电镜、 X射线能谱和X射线衍射研究了涂层的析氢电催化性能. 结果表明,涂层呈多孔多裂纹的结构,焙烧温度对涂层的表面形貌和电催化活性影响很大. 420 ℃下焙烧的涂层具有最优的电催化活性. 涂层电极的析氢反应电极电位为-0.26 V(vs SCE), 低析氢过电位下的Tafel斜率为-0.04 V, 而在高析氢过电位下,电极表面吸附的大量氢原子改变了氧化物电极的结构,从而抑制了氧的阴极还原反应.     

温度对贮氢合金MlNi3.75Co0.65Mn0.4Al0.2动力学性能的影响

在-20℃～85℃的范围内系统地研究了温度对贮氢合金MINi3.75Co0.65Mn0.4Al0.2动力学性能的影响.结果表明:该贮氢合金电极的电化学反应电阻Rt,欧姆内阻Ro,阴极极化过电位,阳极极化过电位,阳极极化过程中的电化学反应过电位ηa和浓差极化过电位ηa均随温度的升高而减小,该电极的交换电流密度i0,对称因子β和电极中氢的扩散系数D随温度的升高而增大.当放电电流密度较低时,电化学反应是整个电极过程的速度控制步骤;当放电电流密度较高时,氢的扩散是整个电极过程的速度控制步骤;在中等放电电流密度下,电极过程由电化学过程和氢的扩散过程混合控制.该电极中电化学反应过程和氢扩散过程的活化能分别为28.1 kJ·mol-1和19.9 kJ·mol-1.     

Mo对脱合金制备的Ni-Mo电极骨架结构与析氢性能的影响

采用快速凝固结合脱合金化方法制备了不同Mo含量的纳米多孔Ni-Mo合金,通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和N₂吸附-脱附分析等对多孔合金的物相、形貌结构及孔径分布进行了表征,并通过线性扫描伏安、Tafel斜率、交流阻抗和循环伏安等方法测试了多孔合金电极的电催化析氢性能.结果显示,多孔合金电极材料在50 mA/cm²电流密度下析氢过电位随着Mo含量的增加先降低后升高,Ni_2.5Mo_2.5合金析氢活性最强,过电位为218 mV,析氢过程由Volmer-Heyrovsky步骤控制,交换电流密度为0.29 mA/cm²,经1000周循环后的极化曲线基本保持原状,50 mA/cm²电流密度下过电位增加3.67%,表现出优良的析氢稳定性.     

纳米晶Ni—Mo—Co合金镀层的结构与析氢行为

用电沉积方法制备了纳米Ni-Mo-Co合金沉积层,用XRD、XPS方法对沉积层的结构进行了表征,结果表明,Ni-Mo-Co合金出现较大的晶格畸变,纳米合金各物种的结合能发生不同程度的位移。在30％的KOH溶液中的阴极极化曲线表明,Ni-Mo-Co合金电极具有良好的析氢电催化活性。电化学的交流阻抗谱表明,低过电位时该合金电极上析氢过程为Volmer-Tafel机理,即吸附态的氢经化学脱附形成氢气,速率决定步骤是Volmer反应;在较高过电位时析氢反应表现为Volmer-Heyrovsky机理,即吸附态的氢经电化学脱附形成氢气。     

电沉积纳米镍合金在模拟海水溶液中的析氢性能

采用电沉积法获得Ni、Ni-Fe和Ni-Fe-C合金镀层电极,在90℃模拟海水(0.5mol·L-1NaCl,pH=12)的稳态极化曲线表明Ni-Fe-C合金电极具有最好的析氢催化性能.通过扫描电子显微镜(SEM)观察电极表面形貌、X射线衍射(XRD)与高分辨透射电子显微镜(HRTEM)分析合金的成分和晶体结构,发现电极材料的晶粒尺寸影响析氢催化性能,晶粒尺寸越小析氢催化活性越好.用电化学阻抗方法(EIS)研究电极析氢催化性能的本质原因,结果表明电极表面活性点数目和电极的本质电催化活性对合金电极析氢催化活性有重要的影响.     

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。     

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.

     

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.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。