Statistical thermodynamics of polynuclear linear complexes with mixed valence states by means of the correlated walk

Expressions for the equilibrium electrode potential of linear N-nuclear complexes with homoredox centers were derived by the theory of the correlated walk as a function of the molar fraction of the oxidized moiety, the nearest-neighbor interaction energies and N. When the interaction energy was large in two-, three- and four-nuclear complexes, the expressions predicted two, three and four voltammetric peaks respectively owing to the formation of mixed valence states. The intuitive extension that the N-nuclear complex might exhibit N peaks was invalid. There were three peaks for any odd number of N. In contrast, four peaks appeared for any even number of N more than 4. For a polynuclear complex with N → ∞, the number of the peaks was reduced to two, as if the complex might be a binucleus. The log plot for the fraction vs. potential curve at large values of N deviated from a straight line. The averaged inverse slope was ca. 90 mV at 25°C. From the concentration distribution of a predominant species varying with the potential, the deviation of the log plot was ascribed to the coexistence of various isomers with different interaction energies. The difference in the voltammetric peak potential was approximately linear with the interaction energy for any N. Approximate equations for the potential difference for N= 2, 3 and 4 were obtained, and were applied to the experimental data available for polyferrocenes.     

Surface Properties of Anatase TiO2 Nanowire Films Grown from a Fluoride‐Containing Solution

Controlling the surface chemistry of nucleating seeds during wet‐chemical synthesis allows for the preparation of morphologically well‐defined nanostructures. Synthesis conditions play a key role in the surface properties, which directly affect the functional properties of the material. Therefore, it is important to establish post‐synthesis treatments to facilitate the optimization of surface properties with respect to a specific application, without losing the morphological peculiarity of the nanostructure. We studied the surface properties of highly crystalline and porous anatase TiO₂ nanowire (NW) electrodes, grown by chemical‐bath deposition in fluoride‐containing solutions, using a combined electrochemical and spectroscopic approach. As‐deposited films showed low capacity for catechol adsorption and a poor photoelectrocatalytic activity for water oxidation. Mild thermal annealing at 200 °C resulted in a significant improvement of the electrode photoelectrocatalytic activity, whereas the bulk properties of the NWs (crystal structure, band‐gap energy) remained unchanged. Enhancement of the functional properties of the material is discussed on the basis of adsorption capacity and electronic properties. The temperature‐induced decrease of recombination centers, along with the concomitant increase of adsorption and reaction sites upon thermal annealing are called to be responsible for such improved performance.     

微波法合成一维结构Cd(OH)2螺旋形纳米线

通过微波辐照法一步合成了长1~3 μm, 直径30~100 nm的螺旋形纳米线, 实验结果表明它是由更细的纳米线组装成束的. 通过改变反应物浓度可以调控螺旋纳米线的直径和长度, 不同的镉盐对产物的结构与形貌有较大的影响. 讨论了螺旋形纳米线可能的形成机理.     

硅衬底上聚丙烯酰胺/氧化锌纳米线薄膜蓝色发光二极管

采用高分子络合软模板法利用高分子络合和低温氧化烧结反应,在硅衬底上自组装生长出顶面平滑具有六角柱形结构的ZnO纳米线,并基于此聚丙烯酰胺/ZnO纳米线体系构筑了聚合物基ZnO纳米线发光二极管器件,在相对低的阈值电压下实现了常温常压下电场驱动的蓝色发射光,并且其发光颜色可由其应用的激励电压方便地调控.几乎垂直排列的ZnO纳米线/高分子薄膜在器件中被作为发射层.该方法使用聚合物作为LED器件的粘结剂和发光层的分散介质,稳定了硅衬底上埋置在聚合物薄膜中的ZnO纳米线准阵列并对ZnO纳米晶的表面起钝化作用,防止发光猝灭.结果表明,新技术是一种低成本制备ZnO基紫外/蓝色发光材料的工艺,并且减少了以往工艺中要求ZnO薄膜p型掺杂的麻烦.     

非晶SiO2纳米灯笼的制备和表征

在1000 ℃用活性炭把二氧化锡粉末还原成单质锡, 锡作为催化剂, 硅片作为硅源同时作为收集衬底, 在硅片上制备出了非晶SiO2纳米灯笼. 灯笼的一端连在硅片上, 另一端为一个锡球, 中间是一些圆弧状的SiO2纳米线把两端相连. 纳米灯笼具有良好的对称性. 利用扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、选区电子衍射(SAED) 和HRTEM自带的能谱分析仪(EDS)对样品的表面形貌、微观结构和成分进行了分析研究. 结果表明, 灯笼中SiO2纳米线为非晶态, 结点是晶态锡, 结点表面覆盖一层非晶态的硅的氧化物. 结合实验条件对纳米灯笼的生长机理进行了讨论, 提出了纳米灯笼生长的一个模型.     

在确定的热力学状态下测量气体导热系数与黏度

气体的导热系数和黏度是重要的热物性参数,其数值大小取决于所处的热力学状态。在目前的导热系数和黏度主要测量方法中,待测工质在测量时需经历非定常的过程或处于具有物性梯度的非平衡态之下,使得待测工质的物性在时间或者空间上不处于一个确定的热力学状态。本文利用圆柱定程干涉法,通过分析气体导热系数和黏度导致的声波能量耗散,结合气体输运理论中对稀疏气体的描述,探索了在确定的热力学状态下同时测量气体导热系数和黏度的方法,并以氩(Ar)为例进行了实验验证。测量结果与已有文献一致性较好,初步证实了方法的可行性。     

铜纳米线的液相制备及其表面修饰研究进展

在现代纳米科学技术领域中,铜纳米线由于具有独特的光学、电学、力学和热学性质而成为制备透明柔性导电电极的优良材料。铜价格低廉,自然存储量较大,是实际应用中替代贵金属的理想材料。然而,将铜离子还原为单质铜比较困难,且单质铜非常容易被氧化,这成为应用中亟需解决的关键问题。如何制备单分散、稳定且具有抗氧化性的铜纳米线也成为该领域的研究热点。在各种制备铜纳米线的方法中,液相还原法不仅可以解决以上问题,且该方法具有制备条件限制少、成本低、简单易行等优点而被广泛应用于铜纳米线的大量合成。本文从铜纳米线的研究背景和研究价值入手,首先综述了不同（光滑或粗糙、单晶或孪晶）铜纳米线的液相制备方法及其生长机制。讨论了铜纳米线的氧化及其抗氧化表面包覆问题。最后对铜纳米线的研究意义和应用前景做出展望。     

Well-dispersed sulfur anchored on interconnected polypyrrole nanofiber network as high performance cathode for lithium-sulfur batteries

Preparation of novel sulfur/polypyrrole (S/PPy) composite consisting well-dispersed sulfur particles anchored on interconnected PPy nanowire network was demonstrated. In such hybrid structure, the as-prepared PPy clearly displays a three-dimensionally cross-linked and hierarchical porous structure, which was utilized in the composite cathode as a conductive network trapping soluble polysulfide intermediates and enhancing the overall electrochemical performance of the system. Benefiting from this unique structure, the S/PPy composite demonstrated excellent cycling stability, resulting in a discharge capacity of 931 mAh g⁻¹ at the second cycle and retained about 54% of this value over 100 cycles at 0.1 C. Furthermore, the S/PPy composite cathode exhibits a good rate capability with a discharge capacity of 584 mAh g⁻¹ at 1  C.     

Bounds for the fundamental solutions of elliptic and parabolic equations

It is shown that any elloptic or parabolic operator in nondivergence form with measurable coefficients has a global fundamental solution verifying certain pointwise bounds.