富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐※

二氧化碳转化已成为现今世界研究的热点. 本工作采用原位电化学转化的策略, 将简单溶剂热法合成的层状甲酸氧铋纳米花(BiOCOOH NFs)还原为带有大量晶格位错的多孔铋纳米花(p-Bi NFs). 研究结果表明, p-Bi NFs电催化二氧化碳转化为甲酸盐具有较小的过电位(436 mV). 在–1.8 V(相对饱和甘汞电极, vs. SCE)时, 甲酸盐的分电流密度(j_formate)高达24.4 mA•cm^-2, 法拉第效率(FE_formate)为96.7%, 且在超过500 mV的宽电位窗口内FE_formate超过90%, 并具有很好的稳定性. 该催化剂的高催化性能可归因于前驱体晶格坍塌和重构而形成特殊的多孔粗糙的微纳多级结构, 其表面富含晶格位错和缺陷等高本征活性位, 且具有较强的电子传递能力. 本研究为设计合成高性能的电催化二氧化碳还原产甲酸催化剂提供了新的思路.     

配合参数对单晶炉驱动系统的影响分析

光伏产业的发展使得对硅材料的需求日益增加,同时硅单晶生产行业竞争也日趋激烈。作为生产硅单晶的重要装备,单晶炉的稳定性和可靠性关系到硅单晶生产效率的提升和成本的下降,因此其驱动系统的设计和优化成为装备制造的关键环节。本文以NVT-HG2000-V1型硅单晶生长炉的驱动系统为研究对象,用SolidWorks三维建模实现虚拟装配,采用ADAMS建立其动力学仿真模型,并对驱动系统的运动过程进行仿真模拟。采用控制变量法定量分析了铜套与升降轴的配合间隙及丝杠参数对驱动力和驱动力矩的影响规律,进而在提高硅单晶生长炉装备稳定性和可靠性方面给出合理的技术建议。结果表明,铜套与升降轴的配合间隙达到0.071 mm后能有效降低驱动系统运行所需驱动力矩,丝杠倾斜度、螺纹螺距与螺纹间摩擦系数的增大均会导致驱动系统运行所需力矩大幅增加。     

Structured water chains in external electric fields

ABSTRACT

We study the structural, energetic and electronic properties of the structured water chain clusters within the density functional theory. We refer the structured water chains to those water clusters that have specific geometric patterns stretched along one direction. External electric field required to keep the structures open chain, thereby preventing them to form closed structures, is applied along the length of the chain. The structures are essentially periodic with basic repeating unit consisting of the corner- or edge-sharing 4-, 5- or 6-membered ring water clusters. Our calculations underscore the possible existence of such structured water clusters in the electrostatic environments, which we simulate in its simplicity employing a dipolar, uniform and static electric field. Analysis reveals that the 5-membered ring water chain clusters, i.e. the pentamer chain clusters have the lowest average dipole moment per water molecule while the threshold field, that marks the onset of the field-induced closure of the HOMO (highest occupied molecular orbital)-LUMO (lowest unoccupied molecular orbital) energy gap, is highest, followed by that for the tetramer and hexamer chains. The results suggest that the pentamer chains are the most stable clusters over a wide range of electric fields.     

Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes

Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C.     

消光式核壳二聚体传感器的设计与光谱特性分析

根据ITO/Au纳米核壳二聚体粒子在生物医学领域的应用合理性,设计了一种实时检测生物液体的核壳二聚体探针消光式传感器;由偶极子理论推导出输出波长与外界环境折射率关系;利用MATLAB设计ITO/Au纳米核壳二聚体粒子结构;采用软件DDSCAT7.3结合离散偶极近似法,利用二聚体有效半径模拟计算了300~950nm可见光到红外光波段不同核壳比、二聚体间距、以及不同介质折射率的消光光谱;根据传感芯片折射率与偶极共振、耦合八级共振的响应关系得出ITO/Au二聚体的折射率灵敏特性。与传统Ag/Au核壳纳米粒子相比,ITO/Au纳米核壳二聚体结构引入了可作为传感芯片灵敏性自参考参数的耦合八级共振峰,同时ITO/Au二聚体结构的折射率灵敏度可达到419nm/RIU。这些工作及其结果对制作消光式传感器具有重要的意义。     

Self-Assembly of C3 Symmetric Rigid Macrolactams into Very Polar and Porous Trigonal Crystals

Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C₃-symmetric rings incorporating conjugated alkenes and dienes. All three C₃-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals.     

Some preliminary observations on a defect Navier–Stokes system

Some implications of the simplest accounting of defects of compatibility in the velocity field on the structure of the classical Navier–Stokes equations are explored, leading to connections between classical elasticity, the elastic theory of defects, plasticity theory, and classical fluid mechanics.     

Surface charging behaviors of electrocatalytic interfaces with partially charged chemisorbates

The surface charge is a key concept in electrochemistry. Mathematically, the surface charge is obtained from a spatial integration of the volume charge along a particular direction. Ambiguities thus arise in choosing the starting and ending points of the integration. As for electrocatalytic interfaces, the presence of chemisorbates further complicates the situation. In this minireview, I adopt a definition of the surface charge within a continuum picture of the electric double layer. I will introduce surface charging behaviors of firstly ordinary electrochemical interfaces and then electrocatalytic interfaces featuring partially charged chemisorbates. Particularly, the origin of nonmonotonic surface charging behaviors of electrocatalytic interfaces is explained using a primitive model. Finally, a brief account of previous studies on the nonmonotonic surface charging behavior is presented, as a subline of the spectacular history of electric double layer.     

晶格畸变检测仪研究碳化硅晶片中位错缺陷分布

利用晶格畸变检测仪研究了SiC晶片位错分布情况,通过对熔融KOH腐蚀后的SiC晶片进行全片或局部扫描,从而得到完整SiC晶片或局部区域的位错分布。与LEXT OLS4000 3D激光共聚焦显微镜扫描腐蚀图进行比较,晶格畸变检测仪扫描腐蚀图可以将晶片上位错腐蚀坑信息完全呈现出来,且根据腐蚀坑呈现的颜色及尺寸大小,可以分辨出三种不同类型的穿透型位错,其中黑点腐蚀坑对应螺位错,小尺寸白点腐蚀坑对应刃位错,大尺寸白点腐蚀坑对应混合型位错。采用晶格畸变测试仪研究了4英寸(101.6 mm)N型4H-SiC晶体不同生长时期的位错密度及分布情况,结果表明随着晶体生长,位错密度呈现逐渐降低的趋势,生长后期晶片的总位错密度降为生长前期晶片总位错密度的近1/3,有利于反馈位错缺陷在SiC晶体生长过程中的延伸和转化特性信息,以指导SiC晶体生长工艺改进。     

6英寸低位错锗单晶生长热场设计

锗片作为衬底材料已在空间太阳电池领域得到广泛的应用,新型锗基空间太阳能电池对锗片的需求由4英寸(1英寸=2.54 cm)提高到6英寸后,低位错锗单晶的生长难度增大。本文设计开发了一种适用于直拉法生长大尺寸、低位错锗单晶的双加热器热场系统,模拟研究了不同形状主加热器的热场分布,从而得到最优的热场环境。研究发现:渐变长度为L/h=1/2、渐变率α为65°的渐变型主加热器热场结构能够获得最佳的热场分布,有利于低位错单晶的生长。经验证,生长的锗单晶热应力较低,位错密度在310～450 cm^-2范围内。