Optical properties of carbon-containing titanium oxide nanocomposites obtained by the pulsed plasma chemical method

This paper presents the results of an experimental investigation on the optical properties of the TiO₂ and Ti_xC_yO_z nanopowders, produced by the pulsed plasma chemical method. Pulsed plasma chemical synthesis is realized on the laboratory stand, including a plasma chemical reactor (6 l) and TEA-500 electron accelerator. The parameters of the electron beam are as follows: 400–450 keV electron energy, 60 ns half-amplitude pulse duration, up to 200 J pulse energy, and 5 cm beam diameter. In TiO₂ sample, obtained using the pulsed plasma chemical method, the particles can be divided into two groups: 100–500 nm large spherical particles and tiny complex particles (sized less than 100 nm). For TixCyOz sample, the morphology of the particles is mainly presented with irregular fragment shape. The average size of the particles is ranged from 200 to 300 nm. The band gap for all synthesized samples is within 2.94–3.35 eV.     

Engineering Bimetallic Ag–Cu Nanoalloys for Highly Efficient Oxygen Reduction Catalysts: A Guideline for Designing Ag‐Based Electrocatalysts with Activity Comparable to Pt/C‐20%

Development of highly active and stable Pt‐free oxygen reduction reaction catalysts from earth‐abundant elements remains a grand challenge for highly demanded metal–air batteries. Ag‐based alloys have many advantages over platinum group catalysts due to their low cost, high stability, and acceptable oxygen reduction reaction (ORR) performance in alkaline solutions. Nevertheless, compared to commercial Pt/C‐20%, their catalytic activity still cannot meet the demand of commercialization. In this study, a kind of catalysts screening strategy on Ag_x Cu_100?x nanoalloys is reported, containing the surface modification method, studies of activity enhancement mechanism, and applied research on zinc–air batteries. The results exhibit that the role of selective dealloying (DE) or galvanic displacement (GD) is limited by the “parting limitation”, and this “parting limitation” determines the surface topography, position of d‐band center, and ORR performance of Ag_x Cu_100?x alloys. The GD‐Ag₅₅Cu₄₅ and DE‐Ag₂₅Cu₇₅ catalysts alloys present excellent ORR performance that is comparable to Pt/C‐20%. The relationship between electronic perturbation and specific activity demonstrates that positive shift of the d‐band center (≈0.12 eV, relative to Ag) for GD‐Ag₅₅Cu₄₅ is beneficial for ORR, which is contrary to Pt‐based alloys (negative shift, ≈0.1 eV). Meanwhile, extensive electrochemical and electronic structure characterization indicates that the high work function of GD‐Ag₅₅Cu₄₅ (4.8 eV) is the reason behind their excellent durability for zinc–air batteries.     

Surface Energy and Surface Stability of Ag Nanocrystals at Elevated Temperatures and Their Dominance in Sublimation‐Induced Shape Evolution

The surface energy and surface stability of Ag nanocrystals (NCs) are under debate because the measurable values of the surface energy are very inconsistent, and the indices of the observed thermally stable surfaces are apparently in conflict. To clarify this issue, a transmission electron microscope is used to investigate these problems in situ with elaborately designed carbon‐shell‐capsulated Ag NCs. It is demonstrated that the {111} surfaces are still thermally stable at elevated temperatures, and the victory of the formation of {110} surfaces over {111} surfaces on the Ag NCs during sublimation is due to the special crystal geometry. It is found that the Ag NCs behave as quasiliquids during sublimation, and the cubic NCs represent a featured shape evolution, which is codetermined by both the wetting equilibrium at the Ag–C interface and the relaxation of the system surface energy. Small Ag NCs (≈10 nm) no longer maintain the wetting equilibrium observed in larger Ag NCs, and the crystal orientations of ultrafine Ag NCs (≈6 nm) can rotate to achieve further shape relaxation. Using sublimation kinetics, the mean surface energy of Ag NCs at 1073 K is calculated to be 1.1–1.3 J m^?2.     

L-半胱氨酸辅助反相微乳法制备Ag_2S纳米晶

选用TX-100/环己烷/正己醇/水反相微乳体系,以Ag NO_3为Ag源、Na_2S·9H2O为S源、L-半胱氨酸为结构导向剂,室温下制备了高晶化度、直径为10—50 nm的Ag_2S纳米晶,并考察了影响其粒径大小的因素。紫外-可见吸收光谱表明,Ag_2S纳米晶在290 nm处呈现强吸收,与体相Ag2S(1 240 nm)相比,其吸收边发生了明显的蓝移。通过调控微乳体系中ω0(水与表面活性剂物质的量比)、Ag+与L-半胱氨酸的物质的量比、反应物浓度等可以实现对产物尺寸和形貌的调控。     

脉冲激光沉积VN/Ag复合薄膜的组织及摩擦学性能研究

利用脉冲激光沉积技术制备了不同Ag含量的VN/Ag复合薄膜,利用扫描电子显微镜、X射线衍射仪、纳米力学测试系统等设备表征薄膜的组织结构、成分、表面形貌及力学性能,利用UMT-3摩擦试验机考察薄膜在室温至900℃下的摩擦学性能。结果表明,随着Ag含量的增多,薄膜的组织形貌变差,硬度及弹性模量降低。当Ag含量为16%(原子分数)时薄膜在试验温度范围内的摩擦学性能最佳。由于Ag在低温的润滑特性及高温摩擦化学反应生成了新的润滑相,如V2O5、V6O11、V6O13、Ag3VO4、AgVO3等,使得摩擦系数随温度的升高而逐渐降低,在900℃下取得最低值0.08,实现了宽温域内的连续润滑。     

银/氯化银电极用于监测混凝土中氯离子含量的研究

采用干湿循环渗透法,通过实验室制备的银/氯化银电极来监测混凝土中的氯离子含量,测试了电极的响应性能和长期稳定性,研究了总氯离子含量与自由氯离子含量之间、总氯离子含量与电位之间的关系。结果表明:银/氯化银电极电位能比较好地监测到混凝土中氯离子含量变化的过程,具有良好的长期稳定性能。总氯离子含量随自由氯离子含量的增加而增加,两者之间呈现幂函数的规律。总氯离子含量随电位上升而下降,两者之间呈指数函数的规律。     

不同合成过程对溶胶-凝胶法制备的ZnO/Ag纳米复合材料光催化性能的影响

以乙酸锌、硝酸银为前驱体,二乙醇胺作为稳定剂,利用溶胶-凝胶法分别采用一步法和两步法制备得到ZnO以及ZnO/Ag纳米复合粉体。所有ZnO/Ag复合物中Ag的含量均为3%(摩尔分数)。对所制备样品的结构和光学性质通过XRD、SEM、TEM、XPS、PL、UV-vis进行了表征,进而以甲基橙为模拟污染物进行了光催化测试。结果表明,不同方法制备得到的ZnO/Ag纳米粉体晶粒均匀,无明显团聚现象,面心立方结构的金属Ag吸附在纤锌矿结构的ZnO表面形成异质结。与纯ZnO相比,掺Ag极大地改善了样品在紫外光下的光催化活性。对不同合成工艺的比较表明,用溶胶-凝胶一步法制备的ZnO/Ag复合物的光催化活性最高,经紫外光照射70min可完全降解甲基橙。     

Ag纳米颗粒等离激元光散射增强对Si刻蚀形貌的影响机制

通过实验与有限元(FDTD)模拟系统研究了不同粒径尺寸的Ag纳米颗粒在P(100)Si表面刻蚀过程中等离激元光散射增强对刻蚀孔形貌的影响。SEM结果表明,刻蚀孔由与粒径尺寸接近的垂直孔演化为一种上大下小的火炬状形貌特征孔,该孔的直径与纳米颗粒尺寸散射半径相仿。模拟不同粒径的Ag纳米颗粒进入刻蚀孔后的光散射特征,证实了Ag纳米颗粒等离激元散射对刻蚀孔初期形成的重要作用。分析表明,基于光照条件下电子-空穴的激发特征,刻蚀孔的形貌主要依赖Ag纳米颗粒等离激元散射的光增强,即通过改变入射光频率以及Ag纳米颗粒粒径可以有效地调控Si表面形貌特征。Ag纳米颗粒等离激元光散射增强技术在Si基太阳能电池、发光二极管(LED)器件等领域有潜在应用前景。