利用手持技术探究铁的电化学腐蚀实验*

借助手持技术,利用电压传感器和pH传感器测定不同酸碱性环境下金属铁发生电化学腐蚀的模拟原电池电压变化情况,探究金属铁发生析氢腐蚀和吸氧腐蚀对应的pH范围,帮助学生深入理解铁的电化学腐蚀原理,感受化学定量实验的魅力。     

物理化学教学中安全工程教育的融合与内化实例*

如何强化安全工程教育是化学化工类专业高等教育的一个重要课题。通过对蒸汽锅炉爆炸、火灾爆燃事故以及锈蚀危害等3个实例的详细讲述,指出在物理化学的教学中,若适时融入相关的安全工程教育,可以使学生深刻理解安全事故发生及防范所依赖的物理化学原理,从而起到安全意识的内化作用。教学中现代教育技术的引入可以增强这一效果。     

Surface characteristics and electrochemical behaviour of sputter-deposited NiTi thin film

Thin nanocrystalline amorphous NiTi film was deposited on Si substrate using DC magnetron sputtering. The as-deposited NiTi thin film was crystallized by heat treatment at 500 °C for 1 h. The crystal structure, surface morphology, microstructure and surface chemistry of the deposited films were studied using X-ray diffraction, atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy (XPS), respectively. Corrosion behaviour was assessed in Ringer’s solution at 37 °C by open circuit potential (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy as a function of exposure time. OCP values indicate that the tendency for the formation of a spontaneous oxide film is greater for the NiTi thin films than the bulk NiTi. Long time exposure to Ringer’s solution was found to have a great effect on the corrosion behaviour of the samples. Significantly low corrosion current density was obtained for the annealed NiTi film from the potentiodynamic polarization curves indicating a typical passive behaviour, but as-deposited film and bulk NiTi alloy exhibited breakdown of passivity at potentials approximately +1.4 V (vs. SCE). XPS showed that the oxide film formed on the annealed NiTi thin film mainly composed of Ti oxides, and no evidence of Ni was found up to 8.2 nm beneath the top surface, suggesting the excellent corrosion resistance of this sample in Ringer’s solution.     

Electropolymerized coatings of poly(o‐anisidine) and poly(o‐anisidine)‐TiO2 nanocomposite on aluminum alloy 3004 by using the galvanostatic method and their corrosion protection performance

Poly(o‐anisidine) (POA) and poly(o‐anisidine)‐TiO₂ (POA‐TiO₂) nanocomposite coatings on aluminum alloy 3004 (AA3004) have been investigated by using the galvanostatic method. The electrosynthesized coatings were characterized by FT ‐ IR spectroscopy, XRD, SEM ‐ EDX and SEM. The corrosion protection performance of POA and POA‐TiO₂ nanocomposite coatings was investigated in the 3.5% NaCl solution by using potentiodynamic polarization technique and electrochemical impedance spectroscopy. The results show that the corrosion rate of the nanocomposite coatings is about 900 times lower than the bare AA3004 under optimal conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

铝合金表面电偶腐蚀与电子功函数的关系

铝合金中经常会引入一些第二相来改善其性能,第二相由于和铝基体的电位差不同,将会对铝合金的局部腐蚀产生重大的影响.为了揭示铝合金腐蚀的物理本质,本文利用基于密度泛函理论第一性原理的计算方法,详细计算了铝合金中一些主要第二相(Al_2Cu、Al_3Ti和Al_7Cu_2Fe)的多种晶面的电子功函数,分析了电子从各个晶面逸出的难易,求得了第二相与Al基体的本征电势差,我们发现不同的晶面暴露在合金最外层,会显著地影响本征电势差;即便是同一晶面,暴露在最外层的原子种类和构型不同,对腐蚀的影响也不一样.从电子的层面解释了电偶腐蚀发生的原因.     

非晶Ce-Ti氧化物用于NH3选择性催化还原NO的原位红外研究

采用原位红外光谱研究了在具有短程有序Ce-O-Ti结构的非晶Ce-Ti氧化物上NH₃选择性催化还原（SCR） NO_x反应. 在反应条件下,催化剂表面主要被NH₃吸附物种覆盖,而检测不到NO_x吸附物种. 经测定,NO的反应级数为0.5-0.6,表明Langmuir-Hinshelwood机理和Eley-Rideal机理同时存在. 可能的机理是NH₃吸附物种和弱吸附的NO_x反应,生成NH_yNO₃ （y = 0-4）活性中间物种,并通过GAUSSIAN计算和原位红外结果证实了它们的存在. Ce-O-Ti结构中Ce与Ti之间表现出原子尺度的相互作用,所以在SCR反应的活性温度窗口下,催化剂的氧化还原活性提高.     

原位漫反射傅里叶变换红外光谱研究锰铁基催化剂上低温选择性催化还原反应机理简

采用自蔓延燃烧法制备了Ti_0.9Mn_0.05Fe_0.05O_2-δ催化剂,运用原位漫反射傅里叶变换红外光谱对该催化剂的NO和NH₃稳态吸附以及NO和NH₃瞬态反应进行了详细地分析与讨论. 结果表明,相比于Lewis酸性位,150℃时Brönsted酸性位吸附的NH₃更具有SCR活性;与双齿硝酸盐和桥式硝酸盐相比,NO吸附产生的单齿硝酸盐是主要的中间物种;该SCR反应遵循Eley-Rideal和Langmuir-Hinshelwood机理,但以后者为主. 另外,O₂的存在有利于NO的氧化和配位态NH₃的活化.     

Rb2[U(NH2)6], a Rubidium Hexaamidouranate(IV) obtained from the Reaction of UI3 with RbNH2 in Anhydrous Ammonia

The pyrophoric compound Rb₂[U(NH₂)₆] was obtained as a grey to black powder from the reaction of more than three equivalents of RbNH₂ with UI₃ in anhydrous liquid ammonia. During the process, U^III is oxidized to U^IV and ammonia is reduced under evolution of H₂. Rb₂[U(NH₂)₆] crystallizes in the cubic crystal system, space group Fm3 m, with the lattice parameter a = 9.7870(12) Å, V = 937.4(2) ų, Z = 4 at T = 293 K. It is isotypic to K₂PtCl₆. The compound contains the unprecedented hexaamidouranate(IV) anion [U(NH₂)₆]^2–.     

多孔金属有机框架材料作为锂金属负极保护层助力长寿命锂氧气电池

在众多能源储存系统中,锂氧气电池以其高达3500 Wh·kg^-1的理论能量密度有望在性能上超越商用锂离子电池.然而,在电池充放电过程中,金属锂不可控的枝晶生长和严重的腐蚀问题极大地阻碍了锂氧气电池的发展.为了解决以上问题,制备了一种具有高比表面积、丰富孔道结构的金属有机框架材料（MOF-801）,并将其设计成金属锂负极的保护层应用在锂氧气电池中.在本工作中,成功合成了具有高达762.9 m²·g^-1比表面积,边长约为800 nm的立方体状纯净MOF-801材料.并且这种材料表现出对于有机电解液体系（四乙二醇二甲醚1 mol·L^-1三氟甲基磺酸锂）和强还原性的金属锂都具有很好的稳定性.得益于该材料丰富的孔道结构以及高比表面积,锂离子得以更均匀地分布在电极表面促进金属锂均匀沉积,有效避免了由于枝晶刺破隔膜而导致的短路甚至火灾事故.此外,MOF-801保护层本身的阻隔作用和材料捕捉水的特性可以帮助减少污染物质（水、氧气、强氧化性物质等）的穿梭效应带来的副反应,缓解锂氧气电池中金属锂负极的腐蚀情况.因此,将经过保护的金属锂组装成的对称电池进行测试,循环寿命长达800 h,同时充/放电过电势仅为0.023 V（未经保护的电池寿命仅为254 h,最终充/放电过电势高达5 V）,且循环阻抗大大降低,证明了这种策略有效地稳定了金属锂/电解液界面.将经过MOF材料保护的电极实际应用在锂氧气电池中,在限容量1000 mAh·g^-1,限电流500 mA·g^-1条件下,可以实现长达170圈的稳定长寿命的循环（是未经保护的电池寿命的2.88倍）.使用MOF-801保护层的锂氧气电池还表现出了高达8935 mAh·g^-1的高比容量.因此,本工作所报道的保护层策略为未来的碱金属空气电池负极保护领域提供了新颖的视角.     

PEFC catalyst layers: Effect of support microstructure on both distributions of Pt and ionomer and cell performance and durability

In order to improve the performance and durability of polymer electrolyte fuel cells (PEFCs), various improvements in the microstructures of cathode catalyst layers (CLs) were initiated in the early 1990s. More recent advances in CL materials are highlighted, including carbon supports for improved accessibility of Pt nanoparticles (NPs), adsorption of ionomer on the Pt surface, high-oxygen-permeability ionomers, corrosion resistance of mesoporous and microporous carbons, and conductive ceramic supports with a fused-aggregate network structure. These approaches are summarized as stepwise improvements. The influences of the support structure on the distribution of Pt NPs and ionomer are reviewed, as well as their effects on performance and durability. These approaches for carbon supports are extended to conductive ceramic supports and the unique advantages are discussed.