用密度泛函理论研究纳米级的硼簇Bn（n=13～20）的物理和化学性质

采用密度泛函理论B3LYP与6—311＋＋G方法研究了硼簇Bn（n=13～20）的电子和几何结构、总能量、结合能、谐波频率、点对称性、电荷分布、偶极矩、化学键以及最高分了占据轨道和最低分子占轨道能量差．此外,借助第一和第二能级差确定最稳定的硼簇尺寸．研究表明硼簇几乎所有的物理性质有尺寸依赖性,双环管状结构的B20具有最高平均结合能．内有一原子的二十面体结构的B13不具有稳定构型,这种结构转变为开放式笼状．B20出现二维到三维的结构转变．Mulliken分析表明电荷分布有x-z和y-z平面对称．硼簇的平面稳定性可以通过离域键（π键和σ键）以及多中心键来解释．     

硼团簇、硼烷及金属硼化物的研究现状

硼原子因其半径小、缺电子、配位数大、价电子sp²杂化和三中心键等特点引起了科学家的高度关注。其团簇的电子结构、稳定性、芳香性和成键方式等性质的研究成为化学领域的一大热点。由于硼化物多样性的特点,其在光学、能源和储存工业气体方面具有潜在的应用价值。本文简述了近几年全硼团簇、硼烷及金属硼化物的研究现状。其中,分别从中性、阴离子和阳离子三种形式对全硼团簇和硼烷进行概括;金属掺杂硼化物主要包括金属掺杂的纯硼团簇和硼烷、过渡金属掺杂的三明治形式复合物以及金属中心硼分子轮。     

DNA为模板的铂纳米团簇沉积

Platinum nanoclusters were deposited along the supercoiled DNA strands after incubation of cis-(trans-1R，2R-diaminocyclohexane)(dl-camphorato)platinum(Ⅱ) (Cdp)， an analogue of the anti-tumor drug-carboplatin， with DNA and K₂PtCl₄ for 600 min and then through reduction of dimethylaminoborane (DMAB). The decrease of absorption of DNA at 260 nm indicates the coordination of Cdp and DNA. TEM and AFM were employed to characterize the morphologies and structures of platinum nanoclusters.     

一维纳米结构材料制备方法的研究进展

本文综述了一维纳米结构材料的制备方法,总结了一维纳米材料的最新研究成果及发展趋势。参考文献80篇。     

从零维硅量子点到二维硅烯:纳米硅单质的发现历程

20世纪90年代,多孔硅发光现象的发现,掀起了硅的低维材料的研究热潮。从零维硅量子点,到一维硅纳米线、硅纳米管,再到二维硅烯,不同形态的纳米硅逐步被发现。这些发现从理论预测到实验合成,从宏观尺度到界观尺度,丰富发展了对于硅的原有认识。随着理论研究的深入和技术手段的进步,纳米硅的种类、性质、合成方法等在不断地更新完善。纳米硅作为重要的半导体纳米材料,其发现历程中所蕴涵的新理论、新方法,对纳米材料的研究具有启示作用。     

纳米金的制备及其在重金属离子检测中的应用——一个分析化学综合性研究型实验

具有可控粒径、形貌纳米金的制备是近年来的一大研究热点。本实验以铯盐硼簇(Cs₂B₁₂H₁₂)为还原剂和包覆剂,成功在水相中将氯金酸还原制备了纳米级别的单分散纳米金颗粒。并将制备得到的纳米金胶体应用于重金属离子(Cr₃₊和Pb₂₊)的比色法检测中,进一步利用紫外可见光谱可以对重金属离子实现定量检测。通过该实验,可以让学生学习制备纳米金的方法,掌握利用紫外等多种分析手段对纳米粒子结构及性能进行表征的技能。     

硅溶胶负载非晶态NiB纳米团簇的制备与催化加氢性能

以硅溶胶为载体,通过化学还原法制备了具有超小尺寸的非晶态NiB催化剂. 采用高倍透射电镜、选区电子衍射和能量色散谱对样品的形貌和结构进行了表征. 结果表明,以硅溶胶为载体负载的非晶态NiB催化剂,其活性组分的粒径在1～2 nm, 并且活性组分Ni均匀地分布于硅溶胶载体上. 与传统的Raney Ni催化剂相比, NiB/硅溶胶表现出更为优异的催化加氢性能并极大地提高了氢化效率. 催化剂的优良活性可归因于载体硅溶胶的大表面积及其硅烷醇对活性组分的锚定功能,这使活性组分Ni以超小尺寸均匀地分散于载体上,从而使纳米粒子的表面效应得到充分发挥.     

NH3在硼纳米管表面吸附的密度泛函理论研究

利用密度泛函理论研究了NH₃在完整和含有缺陷的硼纳米管上的吸附行为以及相关电子性质. 计算结果表明, 对于α硼纳米管, 在不同的直径和手性条件下, NH₃均倾向于吸附在配位数为6的顶位上. 电子结构计算结果表明, NH₃能够吸附在纳米管表面主要是由于N和B原子产生了较强的相互作用. 表明硼纳米管是一种潜在的NH₃气气敏材料.     

蛋膜仿生制备纳米硫化锌

以鸡蛋膜作为生物载体,利用蛋膜上周期性分布的大分子与无机前驱体离子之间的螫合作用和电荷作用,引导和控制无机微晶在蛋膜载体上的形成、聚集和分布,成功制备了分散度好、形貌规整的平均粒径为95nm的ZnS纳米团簇.     

硼原子簇和碳原子簇

本文在一般性地讨论多面体硼烷和碳烷骨架几何性质的基础上,探讨了以已知封闭型硼烷(碳烷)骨架为基础,在保持对称性下依次进行截角-戴帽,交替地得到多面体碳烷(硼烷)-硼烷(碳烷)骨架系列的方法,并以构造I_h和O_h对称性系列作为例子。在此基础上,讨论了可能存在的多面体硼烷和碳烷以及高硼和高碳裸体原子簇的结构和性质。     

Hollow and Threadlike Nanostructures of Boron Carbide

An original low-temperature method is proposed for the synthesis of boron carbide from simple materials. It made it possible to obtain a powdered product in the form of hollow and threadlike nanostructures. The boron carbide nanotubes are shorter than bundles of nanotubes. The boron carbide nanostructures are grown from vapor-phase reagents at a high-temperature nanocenter, the enhanced reactivity of which is maintained as a result of the exothermic effect of the reaction.     

Controllable Growth of Fullerene Nanostructures

One‐dimensional fullerene nanostructures with well‐defined morphology have been prepared by a controllable method. Fullerene molecules, such as C₆₀ derivatives and endohedral metallofullerenes, are introduced into the pores of anodic aluminum oxide (AAO) templates under a direct current (DC) electric field. Then several nanostructures such as porous‐wall and solid‐wall fullerene nanowires and nanotubes were fabricated in the pores. The morphology of the fullerene nanostructures is well controllable, and the fullerene nanotubes can be further fabricated through filling nickel atoms inside to form fullerene‐metal composite structures. The results provide, in principle, a step toward broader applications of fullerene‐related materials in nanoscience and nanotechnology.     

碳化硼纳米线的制备和结构

以碳纳米管为模板，通过加热碳纳米管与硼粉的混合物，获得了笔直的硼碳纳米线.对纳米线的结构和成分进行研究，结果表明纳米线主要为B4C纳米线.在部分B4C纳米线的端部存在Ni颗粒，这些端部具有Ni颗粒的纳米线构成了纳米磁针.讨论了B4C纳米线的生长机制，B4C纳米线的生长主要为硼原子在碳纳米管中扩散并发生化学反应，使得碳纳米管晶格结构发生重组，形成B4C纳米线.反应后，硼原子部分取代了碳纳米管中碳原子，修补了碳纳米管中的晶格缺陷，获得了形态笔直的B4C纳米线.     

Boron nanotubes.

A survey of novel classes of nanotubular materials based on boron is presented. Pure boron nanotubes are a consequence of a general Aufbau principle for boron clusters and solid boron phases, which postulates various novel boron materials besides the well-known bulk phases of boron based on boron icosahedra. Furthermore, several numerical studies suggest the existence of a large family of compound nanotubular materials derived from crystalline AlB2. We compare these novel boron-based nanotubular materials to standard nanotubular systems built from carbon, and point out a number of remarkable structural and electronic properties that make boron-based nanotubular materials an ideal component for composite nanodevices and extended nanotubular networks.     

Optical absorption and photoluminescence properties of the PPV nanotubes and nanowires

We measured optical absorption and time resolved photoluminescence decay properties of the PPV nanotubes and nanowires which were prepared by CVD polymerization using templates. When compared with bulk PPV films, their nano objects showed different optical properties, long photoluminescence decay time and higher photoluminescence efficiencies.     

Bandgap Engineering of Hydroxy-Functionalized Borophene for Superior Photo-Electrochemical Performance

Two-dimensional (2D) semiconducting boron nanosheets (few-layer borophene) have been theoretically predicted, but their band gap tunability has not been experimentally confirmed. In this study, hydroxy-functionalized borophene (borophene-OH) with tunable band gap was fabricated by liquid-phase exfoliation using 2-butanol solvent. Surface-energy matching between boron and 2-butanol produced smooth borophene, and the exposed unsaturated B sites generated by B−B bond breaking during exfoliation coordinated with OH groups to form semiconducting borophene-OH, enabling a tunable band gap of 0.65–2.10 eV by varying its thickness. Photoelectrochemical (PEC) measurements demonstrated that the use of borophene-OH to fabricate working electrodes for PEC-type photodetectors significantly enhanced the photocurrent density (5.0 μA cm⁻²) and photoresponsivity (58.5 μA W⁻¹) compared with other 2D monoelemental materials. Thus, borophene-OH is a promising semiconductor with great optoelectronic potential.     

Structure of χ3-Borophene Studied by Total-Reflection High-Energy Positron Diffraction (TRHEPD)

We have investigated the structure of χ₃-borophene on Ag(111), a monolayer material of boron atoms, via total-reflection high-energy positron diffraction (TRHEPD). By comparing the experimental rocking-curves with ones for several structures calculated by using dynamical diffraction theory, we confirmed that the χ₃-borophene layer has a flat structure. The distance from the topmost layer of the metal crystal is 2.4 Å, which is consistent with results reported by X-ray standing wave-excited X-ray photoelectron spectroscopy. We also demonstrated that the in-plane structure of χ₃-borophene is compatible with the theoretical predictions. These structural properties indicate that χ₃-borophene belongs to a group of epitaxial monolayer sheets, such as graphene, which have weak interactions with the substrates.     

纳米材料的自组装研究进展

本文主要评述了近年来纳米材料自组装的研究进展，即对以纳米材料(包括零维的纳米粒子和一维的纳米管/线)为单元而开展的自组装方面的工作进行了介绍。将纳米材料自组装为各种尺度的有序结构会产生更优异的整体的协同性质，这对于以纳米材料为基础而构筑的微纳米器件有着重要的意义。由于目前纳米材料的研究主要集中在零维和一维体系，因此，本文分别就此两种体系的自组装行为进行了评述。具体内容包括：单分子层薄膜修饰的无机纳米粒子的自组装、大分子修饰的无机纳米粒子的自组装、未被修饰的无机纳米粒子的自组装；表面张力及毛细管力诱导的一维纳米材料的自组装、模板诱导的一维纳米材料的自组装、静电力诱导的一维纳米材料的自组装。     

硼氮掺杂的碳纳米管对硫化氢气敏性能的理论研究

应用密度泛函理论研究了纯(8, 0)单壁碳纳米管(SWCNT)和B原子、N原子以及BN原子对掺杂的(8, 0) SWCNTs对硫化氢气体分子的传感性质. 计算结果表明, 与纯碳纳米管相比, B原子掺杂的SWCNT显示了对H₂S分子的敏感性, 其几何结构和电子性质在吸附H₂S分子后发生了显著变化; 而N原子和BN原子对的掺杂没有改善SWCNT对H₂S分子的吸附性能, 因此我们建议B原子掺杂的SWCNT作为检测H₂S分子的新型气相传感器.