硼化氮-石墨烯杂化单原子层电学性质的第一原理

利用基于密度泛函理论的第一原理方法研究二维六方硼化氮片（h-BN） 石墨烯杂化单原子层的电学性质. 结果表明: 三角形h-BN嵌入石墨烯中或三角形石墨烯片嵌入二维h-BN中均会在能带结构导带和价带中间引入带间态, 带间态的形态与杂化方式有关; 半导体性与导体性质可相互转变, 即该杂化结构的电子结构可通过不同杂化形式调制.     

硼富勒烯及其相关结构研究进展

本文对硼富勒烯等硼纳米结构及其相关材料的研究进展进行了简要评述. 首先对硼和碳元素及其成键性质的区别与联系进行了讨论, 并简要介绍了碳富勒烯、纳米管和石墨烯的发现及其结构与性质. 接下来系统回顾了过去几十年来人们对硼团簇、硼纳米管和硼纳米线等纳米结构在理论和实验研究方面取得的进展.特别是最近几年来, 针对硼富勒烯、硼纳米管、硼单层平面、硼富勒烯固体等结构的研究取得了一些重要进展, 本文在结合我们自己研究工作的基础上, 对上述研究进展做了系统地介绍. 最后对硼富勒烯及其相关材料的研究前景进行了展望.     

Unique synthesis of graphene-based materials for clean energy and biological sensing applications

Graphene has unique physical properties,and a variety of proof-of-concept devices based on graphene have been demonstated.A prerequisite for the application of graphene is its production in a controlled manner because the number of graphene layers and the defects in these layers significantly influence transport properties.In this paper,we briefly review our recent work on the controlled synthesis of graphene and graphene-based composites,the development of methods to characterize graphene layers,and the use of graphene in clean energy applications and for rapid DNA sequencing.For example,we have used Auger electron spectroscopy to characterize the number and structure of graphene layers,produced single-layer graphene over a whole Ni film substrate,synthesized well-dispersed reduced graphene oxide that was uniformly grafted with unique gold nanodots,and fabricated graphene nanoscrolls.We have also explored applications of graphene in organic solar cells and direct,ultrafast DNA sequencing.Finally,we address the challenges that graphene still face in its synthesis and clean energy and biological sensing applications.     

低维硼碳纳米材料第一原理研究

介绍了近年来关于低维硼碳纳米材料结构和电子性质的研究工作.通过第一原理计算,从理论上预言了稳定的低维硼纳米结构,并系统研究了以稳定硼平面为基础的硼纳米管和硼纳米带的电子性质.对于硼碳复合纳米材料,以BC3,BC5和BC7有序结构的平面为基础,发现对其剪裁、氢化修饰之后,硼碳纳米结构具有丰富的电磁学性质,可能在未来电子学器件中得到广泛的应用.     

Imaging and dynamics of light atoms and molecules on graphene

Observing the individual building blocks of matter is one of the primary goals of microscopy. The invention of the scanning tunnelling microscope revolutionized experimental surface science in that atomic-scale features on a solid-state surface could finally be readily imaged. However, scanning tunnelling microscopy has limited applicability due to restrictions in, for example, sample conductivity, cleanliness, and data acquisition rate. An older microscopy technique, that of transmission electron microscopy (TEM), has benefited tremendously in recent years from subtle instrumentation advances, and individual heavy (high-atomic-number) atoms can now be detected by TEM even when embedded within a semiconductor material. But detecting an individual low-atomic-number atom, for example carbon or even hydrogen, is still extremely challenging, if not impossible, via conventional TEM owing to the very low contrast of light elements. Here we demonstrate a means to observe, by conventional TEM, even the smallest atoms and molecules: on a clean single-layer graphene membrane, adsorbates such as atomic hydrogen and carbon can be seen as if they were suspended in free space. We directly image such individual adatoms, along with carbon chains and vacancies, and investigate their dynamics in real time. These techniques open a way to reveal dynamics of more complex chemical reactions or identify the atomic-scale structure of unknown adsorbates. In addition, the study of atomic-scale defects in graphene may provide insights for nanoelectronic applications of this interesting material.     

特殊形貌纳米氧化锌的吸波性能研究

纳米ZnO作为一种新型吸波材料受到广泛关注,但对非c轴生长的ZnO纳米结构材料的吸波性能还缺乏系统研究.为了探讨ZnO纳米晶体的形貌对其吸波性能的影响,在熔盐、类离子液体等强极性介质中,合成了枝晶状、片状、锥状等非c轴生长的ZnO纳米结构材料,用XRD、SEM、TEM等对其物相、形貌进行了表征,对不同形貌的ZnO纳米结构材料的电磁性能与吸波性能进行了系统的分析,并与商品ZnO微粉的吸波性能进行了比较.结果表明,ZnO纳米片的吸波效果较好.复合了磁性材料后,ZnO的吸波性能有明显提高.     

Atom-by-atom spectroscopy at graphene edge

The properties of many nanoscale devices are sensitive to local atomic configurations, and so elemental identification and electronic state analysis at the scale of individual atoms is becoming increasingly important. For example, graphene is regarded as a promising candidate for future devices, and the electronic properties of nanodevices constructed from this material are in large part governed by the edge structures. The atomic configurations at graphene boundaries have been investigated by transmission electron microscopy and scanning tunnelling microscopy, but the electronic properties of these edge states have not yet been determined with atomic resolution. Whereas simple elemental analysis at the level of single atoms can now be achieved by means of annular dark field imaging or electron energy-loss spectroscopy, obtaining fine-structure spectroscopic information about individual light atoms such as those of carbon has been hampered by a combination of extremely weak signals and specimen damage by the electron beam. Here we overcome these difficulties to demonstrate site-specific single-atom spectroscopy at a graphene boundary, enabling direct investigation of the electronic and bonding structures of the edge atoms-in particular, discrimination of single-, double- and triple-coordinated carbon atoms is achieved with atomic resolution. By demonstrating how rich chemical information can be obtained from single atoms through energy-loss near-edge fine-structure analysis, our results should open the way to exploring the local electronic structures of various nanodevices and individual molecules.     

单层边缘功能化石墨烯的制备和表征

为探讨石墨烯的氧化过程,以浓硫酸、高锰酸钾和双氧水作为氧化剂,通过部分边缘氧化剥离石墨得到了单层边缘氧化石墨烯(SLMGO),用定量硼氢化钠还原得到了单层边缘功能化石墨烯(SLMFG).使用FT-IR、SEM、TEM、XRD和XPS等手段表征了SLMGO和SLMFG结构和形貌.结果表明:边缘功能化的单层石墨烯较深度氧化的多层石墨烯,能更好地保持层状平面结构.基于好的共轭程度,边缘功能化的石墨烯光电性能将更好.     

Graphene-based composite materials

Graphene sheets--one-atom-thick two-dimensional layers of sp2-bonded carbon--are predicted to have a range of unusual properties. Their thermal conductivity and mechanical stiffness may rival the remarkable in-plane values for graphite (approximately 3,000 W m(-1) K(-1) and 1,060 GPa, respectively); their fracture strength should be comparable to that of carbon nanotubes for similar types of defects; and recent studies have shown that individual graphene sheets have extraordinary electronic transport properties. One possible route to harnessing these properties for applications would be to incorporate graphene sheets in a composite material. The manufacturing of such composites requires not only that graphene sheets be produced on a sufficient scale but that they also be incorporated, and homogeneously distributed, into various matrices. Graphite, inexpensive and available in large quantity, unfortunately does not readily exfoliate to yield individual graphene sheets. Here we present a general approach for the preparation of graphene-polymer composites via complete exfoliation of graphite and molecular-level dispersion of individual, chemically modified graphene sheets within polymer hosts. A polystyrene-graphene composite formed by this route exhibits a percolation threshold of approximately 0.1 volume per cent for room-temperature electrical conductivity, the lowest reported value for any carbon-based composite except for those involving carbon nanotubes; at only 1 volume per cent, this composite has a conductivity of approximately 0.1 S m(-1), sufficient for many electrical applications. Our bottom-up chemical approach of tuning the graphene sheet properties provides a path to a broad new class of graphene-based materials and their use in a variety of applications.     

Research progress on the characterization and repair of graphene defects

Graphene has excellent theoretical properties and a wide range of applications in metal-based composites. However, because of defects on the graphene surface, the actual performance of the material is far below theoretical expectations. In addition, graphene containing defects could easily react with a matrix alloy, such as Al, to generate brittle and hydrolyzed phases that could further reduce the performance of the resulting composite. Therefore, defect repair is an important area of graphene research. The repair methods reported in the present paper include chemical vapor deposition, doping, liquid-phase repair, external energy graphitization, and alloying. Detailed analyses and comparisons of these methods are carried out, and the characterization methods of graphene are introduced. The mechanism, research value, and future outlook of graphene repair are also discussed at length. Graphene defect repair mainly relies on the spontaneous movement of C atoms or heteroatoms to the pore defects under the condition of applied energy. The repair degree and mechanism of graphene repair are also different according to different preparations. The current research on graphene defect repair is still in its infancy, and it is believed that the problem of defect evolution will be explained in more depth in the future.     

功能化石墨烯在生物医学研究中的应用

石墨烯以其独特的二维结构和优良的电学、光学、热学和机械性能,自2004年来倍受研究人员的高度关注,迅速成为材料、化学、物理和医学领域的热点研究课题.在简要介绍石墨烯基本情况的基础上,重点阐述了石墨烯在生物传感器、靶向给药中的应用.     

基于分子动力学模拟的含缺陷石墨烯力学性能的研究

基于分子动力学模拟的方法,研究了空位缺陷的位置、形状以及原子缺失率对石墨烯杨氏模量的影响。研究结果表明,单空位缺陷的位置对石墨烯杨氏模量有一定的影响,当施加应力方向与边缘缺陷的截面方向相同时,边缘缺陷比中间缺陷使得石墨烯的杨氏模量下降更少。研究结果还发现,映射横向长条状缺陷、映射纵向长条状缺陷、映射圆孔状缺陷和随机缺陷都使得石墨烯杨氏模量随着原子缺失率的增大而减小。对于映射圆孔状缺陷和随机缺陷,锯齿型石墨烯杨氏模量减小的幅度与扶手型的减小幅度相差不大。对于映射横向长条状缺陷和映射纵向长条状缺陷,锯齿型和扶手型石墨烯杨氏模量的减小幅度相差较大,这与石墨烯的手性矢量方向和条状缺陷方向是否一致有关。     

Preparation and characterization of graphene oxide paper

Free-standing paper-like or foil-like materials are an integral part of our technological society. Their uses include protective layers, chemical filters, components of electrical batteries or supercapacitors, adhesive layers, electronic or optoelectronic components, and molecular storage. Inorganic 'paper-like' materials based on nanoscale components such as exfoliated vermiculite or mica platelets have been intensively studied and commercialized as protective coatings, high-temperature binders, dielectric barriers and gas-impermeable membranes. Carbon-based flexible graphite foils composed of stacked platelets of expanded graphite have long been used in packing and gasketing applications because of their chemical resistivity against most media, superior sealability over a wide temperature range, and impermeability to fluids. The discovery of carbon nanotubes brought about bucky paper, which displays excellent mechanical and electrical properties that make it potentially suitable for fuel cell and structural composite applications. Here we report the preparation and characterization of graphene oxide paper, a free-standing carbon-based membrane material made by flow-directed assembly of individual graphene oxide sheets. This new material outperforms many other paper-like materials in stiffness and strength. Its combination of macroscopic flexibility and stiffness is a result of a unique interlocking-tile arrangement of the nanoscale graphene oxide sheets.     

KOH活化法制备活性碳及其应用研究

以滇朴为碳源,通过化学活化法成功制备出高性能的活性碳材料.并对其结构、形貌及性能进行了表征.SEM照片结果表明,利用KOH活化而得到的活性碳材料仍然保留了滇朴的纤维结构.通过KOH活化处理,活性碳材料中存在大量的芳香环,石墨微晶结构变多.BET结果证明活化后的活性碳材料含有丰富的微孔结构,孔径约为3.5 nm.利用此类活性碳材料对卷烟主流烟气成分进行吸附实验,KOH活化的活性碳对烟气中有害成分表现出更好的吸附性能.     

Bi,Se和Te吸附n/p型石墨烯电子结构研究

本文采用基于密度泛函理论的第一性原理方法研究了Bi,Se,Te在缺陷(单空位,B掺杂和N掺杂)石墨烯上的吸附结构及电子和磁性质.研究表明:在能量稳定的Bi(Se)/石墨烯吸附体系中,Bi吸附诱导产生磁性;在空位缺陷石墨烯上的吸附会改变费米能级处态密度分布,影响体系的导电性质;在B(N)掺杂吸附体系中,B比N对吸附原子的影响大;除Se在B掺杂石墨烯上吸附外,Bi,Se,Te在其它n/p型掺杂吸附体系中均显示磁性.缺陷增强了Bi,Se,Te与石墨烯之间的相互作用,对吸附体系的电子结构和电荷分布有较大的影响.     

Grains and grain boundaries in single-layer graphene atomic patchwork quilts

The properties of polycrystalline materials are often dominated by the size of their grains and by the atomic structure of their grain boundaries. These effects should be especially pronounced in two-dimensional materials, where even a line defect can divide and disrupt a crystal. These issues take on practical significance in graphene, which is a hexagonal, two-dimensional crystal of carbon atoms. Single-atom-thick graphene sheets can now be produced by chemical vapour deposition on scales of up to metres, making their polycrystallinity almost unavoidable. Theoretically, graphene grain boundaries are predicted to have distinct electronic, magnetic, chemical and mechanical properties that strongly depend on their atomic arrangement. Yet because of the five-order-of-magnitude size difference between grains and the atoms at grain boundaries, few experiments have fully explored the graphene grain structure. Here we use a combination of old and new transmission electron microscopy techniques to bridge these length scales. Using atomic-resolution imaging, we determine the location and identity of every atom at a grain boundary and find that different grains stitch together predominantly through pentagon-heptagon pairs. Rather than individually imaging the several billion atoms in each grain, we use diffraction-filtered imaging to rapidly map the location, orientation and shape of several hundred grains and boundaries, where only a handful have been previously reported. The resulting images reveal an unexpectedly small and intricate patchwork of grains connected by tilt boundaries. By correlating grain imaging with scanning probe and transport measurements, we show that these grain boundaries severely weaken the mechanical strength of graphene membranes but do not as drastically alter their electrical properties. These techniques open a new window for studies on the structure, properties and control of grains and grain boundaries in graphene and other two-dimensional materials.     

纳米钨酸锌的制备及其光催化性质的研究

旨在探索利用水热法合成钨酸锌材料的纳米结构,并对其所合成的材料的结构和形貌进行表征,测试了合成材料的光催化性质,以硝酸锌和钨酸钠作起始物,用PVP和SDBS作为修饰剂利用水热法合成不同形貌的纳米钨酸锌。利用X射线粉末衍射（XRD）、透射电子显微镜（TEM）等对产物进行表征。测试了合成钨酸锌纳米材料的紫外光催化性质,表明合成的钨酸锌具有较高的紫外光催化活性,说明钨酸锌具有潜在的应用价值。     

Fabrication of carbon nanotube/graphene core/shell nanostructures on SiO2 substrates using organic solvents: A molecular dynamics study

Using molecular mechanics and molecular dynamics simulations,we demonstrate that it is difficult to fabricate single-walled carbon nanotube (SWNT)/carbon nanoscroll (CNS) core/shell nanostructures on solid substrates because of the strong interaction between the graphene (GN) and the substrate.We propose an effective way to reduce the interaction between the GN and the substrate;SWNT/CNS core/shell nanostructures can be fabricated easily on SiO2 substrates by exploiting the volatilization of organic solvents,and inducement with SWNTs.These SWNT/CNS core/shell nanostructures on SiO2 substrates have the potential to be applied in telecom network transmission,or as electronic components in apparatuses such as microcircuit interconnects,nanoelectronics devices,heterojunctions,or sensors.     

非气态原料制备垂直石墨烯

垂直石墨烯是由石墨烯片垂直于基底生长而形成的一种新型3维碳材料结构,由于其独特的生长取向,可以有效减轻石墨烯层与层之间的堆叠,使石墨烯充分发挥其优异的特性.等离子体增强化学气相沉积技术作为合成垂直石墨烯的主要手段常需引入化工合成气为碳源,原料灵活性低.该文综述了非气态碳源用于垂直石墨烯的制备,介绍了所合成的垂直石墨烯在多种领域中的应用,并讨论了其生长机理.     

Half-metallic graphene nanoribbons

Electrical current can be completely spin polarized in a class of materials known as half-metals, as a result of the coexistence of metallic nature for electrons with one spin orientation and insulating nature for electrons with the other. Such asymmetric electronic states for the different spins have been predicted for some ferromagnetic metals--for example, the Heusler compounds--and were first observed in a manganese perovskite. In view of the potential for use of this property in realizing spin-based electronics, substantial efforts have been made to search for half-metallic materials. However, organic materials have hardly been investigated in this context even though carbon-based nanostructures hold significant promise for future electronic devices. Here we predict half-metallicity in nanometre-scale graphene ribbons by using first-principles calculations. We show that this phenomenon is realizable if in-plane homogeneous electric fields are applied across the zigzag-shaped edges of the graphene nanoribbons, and that their magnetic properties can be controlled by the external electric fields. The results are not only of scientific interest in the interplay between electric fields and electronic spin degree of freedom in solids but may also open a new path to explore spintronics at the nanometre scale, based on graphene.