Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodepo-sition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.     

通过赝反伽伐尼反应实现金纳米粒子模块替换

通过可控的方式精确调控纳米粒子的结构仍是一个富有挑战性和鼓舞人心的课题.尽管单原子或两、三个金属原子的精细调控已经在金纳米粒子中实现,涉及三个以上金属原子的取代（模块取代）还没有报道.本工作报道了环己硫醇配体保护的Au₄₈（CHT）₂₆的合成及其通过赝反伽伐尼过程的模块取代.单晶结构揭示模块取代的产物与母体团簇共用一个相似的Au₃₁（CHT）₁₂主体,但剩余部分不同（Au₆（CHT）₁₁ vs.Au₁₆（CHT）₁₄）.一个有趣的发现是模块取代抑制了Au₄₈（CHT）₂₆的光热过程,却增强了它的发射,赋予了所合成团簇更好的双（多）功能应用潜力.光热效应的减弱和发射的增强也暗示了这两种作用能够彼此至少部分转化,对于研究这两种效应之间的相互影响也具有重要的启示.     

方钢管型钢再生混凝土组合柱轴压性能试验研究

为研究方钢管型钢再生混凝土组合柱轴压性能,设置了长细比、再生骨料取代率、再生混凝土强度、型钢配钢率和方钢管宽厚比等参数,对13个试件进行单调静力加载试验,观察试件破坏过程及破坏形态,获取试件荷载-位移和荷载-应变曲线,分析设计参数对组合柱轴压受力性能的影响。结果表明:试件的破坏顺序均为型钢首先被压屈,随后再生混凝土被压碎,最后的破坏是因为钢管外表面发生鼓屈而丧失轴压承载力;提高长细比、钢管宽厚比和再生粗骨料取代率,组合柱轴压承载力的最大降幅分别为10.7%、24.8%和9.9%;相反,提高再生混凝土强度和型钢配钢率,组合柱的轴压承载力最大提高幅度分别为19.7%和14.3%;总体上看,试件均表现出较高的承载力和良好的变形能力。在此基础上,参考国内外相关规程,采用叠加原理,建立了方钢管型钢再生混凝土组合柱的轴压承载力公式,并验证了计算公式的有效性。     

In situ Deposition of ‘Naked’ Gold Nanoparticles Supported on Silica Spheres as Recyclable Catalysts in Styrene Epoxidation

Tlie rational designs of particle size, morphology and surface states of the Au nanoparticles(AuNPs) are crucial for Au nanocatalyst. We herein report a method to synthesize the silica microspheres supported AuNPs(ca.1 nm) and their application in controlling the reaction conversion and selectivity in styrene epoxidation. Surfactant-ftee AuNPs deposited on silica microspheres were in situ fabricated with aid of the Ag nanoparticles (AgNPs) as sacrificial template by galvanic replacement reaction, leading to AuNPs/SiO2 catalyst directly without any post-treatment to expose crystal facets.A high conversion of 46.7% and selectivity of 91.7% to styrene oxide was achieved with H2O2 as oxidant in ethanol. The solid catalyst could be reused at least 10 reaction cycles without significant decrease in activity and selectivity. This study not only supplies an active, recoverable catalyst for styrene oxidation with green oxidant and solvent, but also demonstrates that the silica microspheres functionalized with thiol groups have a superior ability in stabilizing noble metal nanoparticles even without any surfactant.     

三维多孔核壳结构PdNi@Au催化剂的制备及对甲酸的电催化氧化

以K₂PdCl₄/K₂Ni(CN)₄为前驱体制备了具有凝胶特性的氰胶(Cyanogels), 利用硼氢化钠还原氰胶得到三维多孔珊瑚状PdNi合金前驱体, 在此基础上通过原位Galvanic置换反应, 制备得到内核为PdNi合金、 表面具有不同厚度Au层的三维多孔PdNi@Au催化剂. X射线衍射(XRD)分析和透射电子显微镜(TEM)观测结果显示, 该三维网状结构由粒径约7 nm的纳米颗粒相互连接形成; 能量分散光谱(EDX)线性扫描和元素分布(Mapping)分析显示该催化剂具有典型的核壳结构. 电化学测试结果表明, 表面Au层的厚度影响PdNi@Au催化剂的性能, 当Au的含量(摩尔分数)为5.6%时, 催化剂显示出对甲酸最佳的电催化活性, 对甲酸电催化氧化的峰电流密度达到商业化铂黑催化剂的7.2倍.     

燃气管网置换过程动态仿真计算与研究

燃气置换过程难以监测,供气压力、置换时间等参数计算大都依赖人员经验,容易产生资源浪费和安全隐患。本文建立燃气管网置换过程动态仿真模型,在采用一维拓扑网络算法的基础上,对管网中的阻力系数进行精确求解。文章首先建立水平直管结构,结合Fluent仿真对算法进行验证,并对燃气置换过程的规律进行分析和总结。最后将模型应用于实际燃气管网置换工程中,与实测数据进行对比,结果表明所提出的模型精度可以满足工程需求,能为燃气管网置换方案的制定提供重要指导依据。