2018年4期电子期刊

稀土有机配合物具有优异的发光性能,但其内在缺陷如较低的稳定性和较差的加工性等则限制了它们的实际应用。离子液体稳定性和溶解性能均较好,将稀土配合物和离子液体结合可以有效地弥补上述不足,同时可以赋予材料更多奇特和优异的性能,从而增强它们的实用性。本文主要介绍了一些典型的含离子液体和稀土配合物的发光材料体系,阐明了离子液体在这些体系中的地位及作用,并对这类材料未来的应用及发展前景作了展望。     

Illusion optics

The technique of “transformation optics” establishes a correspondence between coordinate transformation and material constitutive parameters. Most of the transformation optics mappings give metamaterials that have graded positive refractive indices that can steer light in curves defined by the coordinate transformation. We will focus on those “folded-geometry mappings” that give negative refractive index materials that have special wave scattering properties. One interesting example is a kind of remote illusion device that can transform the stereoscopic image of an object into the illusion of some other object of our choice. The conceptual device can create the illusion without touching or encircling the object. For any incident wave, the device transforms the scattered waves of the original object into that of the object chosen for illusion outside a virtual boundary. We will illustrate some possible applications of this type of metamaterial remote device, including “cloaking at a distance,” partial cloaking, cloaking from an embedded device, revealing a hidden object inside a container, turning the image of one object into that of another object, and seeing through a wall. The feasibility of building this remote illusion device by metamaterials will also be discussed.     

Structure search of two-dimensional systems using CALYPSO methodology

The dimensionality of structures allows materials to be classified into zero-, one-, two-, and threedimensional systems. Two-dimensional (2D) systems have attracted a great deal of attention and typically include surfaces, interfaces, and layered materials. Due to their varied properties, 2D systems hold promise for applications such as electronics, optoelectronics, magnetronics, and valleytronics. The design of 2D systems is an area of intensive research because of the rapid development of ab initiostructure-searching methods. In this paper, we highlight recent research progress on accelerating the design of 2D systems using the CALYPSO methodology. Challenges and perspectives for future developments in 2D structure prediction methods are also presented.     

Solvent effect in sonochemical synthesis of metal-alloy nanoparticles for use as electrocatalysts

Nanomaterials are now widely used in the fabrication of electrodes and electrocatalysts. Herein, we report a sonochemical study of the synthesis of molybdenum and palladium alloy nanomaterials supported on functionalized carbon material in various solvents: hexadecane, ethanol, ethylene glycol, polyethylene glycol (PEG 400) and Ionic liquids (ILs). The objective was to identify simple and more environmentally friendly design and fabrication methods for nanomaterial synthesis that are suitable as electrocatalysts in electrochemical applications. The particles size and distribution of nanomaterials were compared on two different carbons as supports: activated carbon and multiwall carbon nanotubes (MWCNTs). The results show that carbon materials functionalized with ILs in ethanol/deionized water mixture solvent produced smaller particles sizes (3.00 ± 0.05 nm) with uniform distribution while in PEG 400, functionalized materials produced 4.00 ± 1 nm sized particles with uneven distribution (range). In hexadecane solvents with Polyvinylpyrrolidone (PVP) as capping ligands, large particle sizes (14.00 ± 1 nm) were produced with wide particle size distribution. The metal alloy nanoparticles produced in ILs without any external reducing agent have potential to exhibit a higher catalytic activity due to smaller particle size and uniform distribution.     

Longitudinal oscillations in a classical Yang-Mills plasma

An analytical approach to the non linear system describing classical 1D longitudinal oscillations in an SU(2) plasma is proposed. A physical interpretation is given for two distinct “Abelian” and “non-Abelian” phases of the non-linear oscillations. Numerical estimates of meaningful physical quantities are made. Analytical results are extended to the physically more relevant SU(3) case, for which numerical simulations have been also carried out.     

Hybridization effect in coupled metamaterials

Although the invention of the metamaterials has stimulated the interest of many researchers and possesses many important applications, the basic design idea is very simple: composing effective media from many small structured elements and controlling its artificial EM properties. According to the effective-media model, the coupling interactions between the elements in metamaterials are somewhat ignored; therefore, the effective properties of metamaterials can be viewed as the “averaged effect” of the resonance property of the individual elements. However, the coupling interaction between elements should always exist when they are arranged into metamaterials. Sometimes, especially when the elements are very close, this coupling effect is not negligible and will have a substantial effect on the metamaterials’ properties. In recent years, it has been shown that the interaction between resonance elements in metamaterials could lead to some novel phenomena and interesting applications that do not exist in conventional uncoupled metamaterials. In this paper, we will give a review of these recent developments in coupled metamaterials. For the “metamolecule” composed of several identical resonators, the coupling between these units produces multiple discrete resonance modes due to hybridization. In the case of a “metacrystal” comprising an infinite number of resonators, these multiple discrete resonances can be extended to form a continuous frequency band by strong coupling. This kind of broadband and tunable coupled metamaterial may have interesting applications. Many novel metamaterials and nanophotonic devices could be developed from coupled resonator systems in the future.     

An informal partial overview of information mechanics

This article is concerned with the conceptual background of information mechanics (IM) and some of the consequences of axiomatization of IM, and touches on some examples as to instances in which IM might seem to have offered, within a single conceptual picture, interesting approaches to some questions which have variously been regarded as quite different. In IM, representation of information in physical systems is treated as a conceptual, computation, and design tool. Some examples touched on are an IM approximate relation among,h, c, m _e, G, and ∼α; particle masses and mass-charge relation; cosmological red shift without assuming that distant light sources are rapidly receding; gravity; and knowability of prediction. IM is then used as a tool for looking into making information processing “hardware” out of “software”, with information representations formed within extended region(s) of nearly homogeneous “medium(s)”. All or part of this material may be or become the subject of U.S. or foreign patents pending or issued. Inclusion of any material herein shall not be construed as implying any license under any patent.     

Non-conventional solid state fuel cells: Materials & technology

Investigation of “Non-conventional material” for fuel cells, such as oxide-salt-ceramic composites and ceria based or perovskite oxides with different dopants, leads to a much lower fuel cell operating temperature compared to conventional high temperature, ∼1000 °C, solid oxide fuel cells (SOFCs), which provides the new possibilities for facilitating SOFC commercialisation. This work is essentially an effort to develop new types of solid oxide ion and proton fuel cells (SOFC and SPFC) at fairly low temperatures, <800 °C, or intermediate temperature, 400 to 800 °C. The conventional high temperature SOFCs using yttria-stabilised zirconia (YSZ) materials, and low temperature SPFCs (<200 °C) using polymer membrane electrolytes have complex material and system problems from either special high temperature requests or expensive technology and reforming systems. This research is intended to provide materials and technology along new routes for so-called non-conventional fuel cell systems, to facilitate solid state fuel cell cmmercialisation. The fuel cell research on these non-conventional systems is promising. This paper, based on recent achievements in research on materials and technology, summaries the developnt of material systems and new fuel cell devices regarding their potential marketability in the near future. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Investigation of cation–anion interaction in 1‐(2‐hydroxyethyl)‐3‐methylimidazolium‐based ion pairs by density functional theory calculations and experiments

Gas‐phase structure, hydrogen bonding, and cation–anion interactions of a series of 1‐(2‐hydroxyethyl)‐3‐methylimidazolium ([HOEMIm]⁺)‐based ionic liquids (hereafter called hydroxyl ILs) with different anions (X = [NTf₂]^–, [PF₆]^–, [ClO₄]^–, [BF₄]^–, [DCA]^–, [NO₃]^–, [AC]^– and [Cl]^–), as well as 1‐ethyl‐3‐methylimizolium ([EMIm]⁺)‐based ionic liquids (hereafter called nonhydroxyl ILs), were investigated by density functional theory calculations and experiments. Electrostatic potential surfaces and optimized structures of isolated ions, and ion pairs of all ILs have been obtained through calculations at the Becke, three‐parameter, Lee–Yang–Parr/6‐31 + G(d,p) level and their hydrogen bonding behavior was further studied by the polarity and Kamlet–Taft Parameters, and ¹H‐NMR analysis. In [EMIm]⁺‐based nonhydroxyl ILs, hydrogen bonding preferred to be formed between anions and C2–H on the imidazolium ring, while in [HOEMIm]⁺‐based hydroxyl ILs, it was replaced by a much stronger one that preferably formed between anions and OH. The O–H···X hydrogen bonding is much more anion‐dependent than the C2–H···X, and it is weakened when the anion is changed from [AC]^– to [NTf₂]^–. The different interaction between [HOEMIm]⁺ and variable anion involving O–H···X hydrogen bonding resulted in significant effect on their bulk phase properties such as ¹H‐NMR shift, polarity and hydrogen‐bond donor ability (acidity, α). Copyright © 2011 John Wiley & Sons, Ltd.     

新型机械解理方法在二维材料研究中的应用

自从石墨烯被发现以来,机械解理技术已经成为制备高质量二维材料的重要方法之一,在二维材料本征物性的研究方面展现出了独特的优势.然而传统机械解理方法存在明显的不足,如制备效率低、样品尺寸小等,阻碍了二维材料领域的研究进展.近些年我们在机械解理技术方面取得了一系列的突破,独立发展了一套具有普适性的新型机械解理方法.这种新型机械解理方法的核心在于通过改变解理过程中的多个参数,增强层状材料与基底之间的范德瓦耳斯相互作用,从而提高单层样品的产率和面积.本文着重以石墨烯为例,介绍了该技术的过程和机理.相比于传统机械解理方法,石墨烯的尺寸从微米量级提高到毫米量级,面积提高了十万倍以上,产率大于95%,同时石墨烯依然保持着非常高的质量.这种新型机械解理方法具有良好的普适性,目前已经在包括MoS₂,WSe₂,MoTe₂,Bi2212等几十种材料体系中得到了毫米量级以上的高质量单层样品.更重要的是,在解理过程中,通过调控不同的参数,可以在层状材料中实现一些特殊结构的制备,如气泡、褶皱结构等,为研究这些特殊材料体系提供了重要的物质保障.未来机械解理技术还有很多值得深入研究的科学问题,该技术的突破将会极大地推动二维材料领域的研究进展.     

In situ synthesis of cobalt nanocrystal hierarchies in a transmission electron microscope

We report a versatile electron beam (e-beam) synthesis method for the local fabrication of ferromagnetic nanocrystals “on demand”. A localized irradiation in a transmission electron microscope (TEM) is used to convert a raw cobalt fluoride material into ferromagnetic metal by means of formation of a short-range ordered distribution of well-defined faceted three-dimensional (3D) cobalt nanocrystals on the carbon substrate. A range of sizes and morphologies can be obtained, depending on the size, intensity, and acceleration voltage of the e-beam and on the initial size/thickness of the 3D raw fluoride materials, with 300 kV acceleration voltage and thermionic LaB₆ emission found most favorable. The nanofabrication of locally quasi-monodispersed, small sized, and well-distributed 3D nanocrystals opens up the possibility to generate particle arrays on demand with desirable magnetic properties.     

二维原子晶体的低电压扫描透射电子显微学研究

二维原子晶体材料,如石墨烯和过渡金属硫族化合物等,具有不同于其块体的独特性能,有望在二维半导体器件中得到广泛应用.晶体中的结构缺陷对材料的物理化学性能有直接的影响,因此研究结构缺陷和局域物性之间的关联是当前二维原子晶体研究中的重要内容,需要高空间分辨率的结构研究手段.由于绝大部分二维原子晶体在高能量高剂量的电子束辐照下容易发生结构损伤,利用电子显微方法对二维原子晶体缺陷的研究面临诸多挑战.低电压球差校正扫描透射电子显微(STEM)技术的发展,一个主要目标就是希望在不损伤结构的前提下对二维原子晶体的本征结构缺陷进行研究.在STEM下,多种不同的信号能够被同步采集,包括原子序数衬度高分辨像和电子能量损失谱等,是表征二维原子晶体缺陷的有力工具,不但能对材料的本征结构进行单原子尺度的成像和能谱分析,还能记录材料结构的动态变化.通过调节电子束加速电压和电子辐照剂量,扫描透射电子显微镜也可以作为电子刻蚀二维原子晶体材料的平台,用于加工新型纳米结构以及探索新型二维原子晶体的原位制备.本综述主要以本课题组在石墨烯和二维过渡金属硫族化合物体系的研究为例,介绍低电压扫描透射电子显微学在二维原子晶体材料研究中的实际应用.     

Negative index materials with gain media for fast modulation

Negative index materials (NIM) enable subwavelength resolution and are promising for applications in integrated optical systems, since the mode volume is small. Most promising NIM systems essentially use noble metals (Ag, Au) with material losses much lower than in other metals, but still rather hefty, like in metal–dielectric–metal “fishnets”. Therefore, we perform extensive finite-difference time-domain modeling of NIM “fishnets” in combination with gain medium, InGaAsP multiple quantum wells in the present work. The signal recovery is weak, which is related to weak overlap between the radiation field and the gain medium. The signal modulation speed may be very large, in a picosecond range.     

Theory,preparation, properties and catalysis application in 2D graphynes-based materials

Carbon has three hybridization forms of sp⁻, sp²⁻ and sp³⁻, and the combination of different forms can obtain different kinds of carbon allotropes, such as diamond, carbon nanotubes, fullerene, graphynes (GYs) and graphdiyne (GDY). Among them, the GDY molecule is a single-layer two-dimensional (2D) planar structure material with highly π-conjugation formed by sp⁻ and sp²⁻ hybridization. GDY has a carbon atom ring composed of benzene ring and acetylene, which makes GDY have a uniformly distributed pore structure. In addition, GDY planar material have some slight wrinkles, which makes GDY have better self-stability than other 2D planar materials. The excellent properties of GDY make it attract the attention of researchers. Therefore, GDY is widely used in chemical catalysis, electronics, communications, clean energy and composite materials. This paper summarizes the recent progress of GDY research, including structure, preparation, properties and application of GDY in the field of catalysts.     

Geometry, topology, and physics of non-Abelian lattices

Conclusion  After reviewing in some detail the notion of non-Euclidean lattices, whose domain of physical realization lies mostly in the novel carbon structures of the family offullerenes, we have discussed a number of physical problems denned over such lattices. We have shown that the group-theoretical definition of these lattices leads to “designing” new tubular regular structures, endowed with symmetries unheard of in the frame of customary crystallography, which combine features of extreme complexity and, at the same time, of great regularity. We have compared the role of the non-Abelian symmetries which these super-lattices are characterized by, with that of (discrete) harmonic (Fourier) lattice symmetry typical of customary crystallographic lattices. Many novel features enter into play, due to thenon-flatness of the related lattice geometry, which led us to a novel—sometimes unexpected—insight into the dynamical and/or thermodynamical properties of various physical systems which have these lattices as ambient space. We have analyzed how lattice topology bears on the complex combinatorics (related to loop-counting) of the classical Ising model. These lattices, even though finite, are, of course, much closer to being three-dimensional than regular 2D lattices simply equipped with periodic boundary conditions. We have shown, on the other hand, how the relation between the lattice symmetry (for example, in the case of fullerene, the discrete subgroup ofSU(2) that we have denotedg ₆₀ and the symmetry proper to the Hamiltonian of quantum systems of many itinerant interacting electrons (Hubbard-like models) allows us to reduce the calculation of the system spectral properties to a “size” that can be dealt with numerically with present-day numerical exact diagonalization techniques much more easily than a regular 3D cluster with a quite smaller number of sites.     

Structure,thermodynamic and transport properties of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids from molecular dynamics simulations

Molecular dynamics (MD) simulations have been performed in order to investigate the properties of [C _n mim⁺][Tf₂N^?] (n?=?4,?8,?12) ionic liquids (ILs) in a wide temperature range (298.15?498.15?K) and at atmospheric pressure (1 bar). A previously developed methodology for the calculation of the charge distribution that incorporates ab initio quantum mechanical calculations based on density functional theory (DFT) was used to calculate the partial charges for the classical molecular simulations. The wide range of time scales that characterize the segmental dynamics of these ILs, especially at low temperatures, required very long MD simulations, on the order of several tens of nanoseconds, to calculate the thermodynamic (density, thermal expansion, isothermal compressibility), structural (radial distribution functions between the centers of mass of ions and between individual sites, radial-angular distribution functions) and dynamic (relaxation times of the reorientation of the bonds and the torsion angles, self-diffusion coefficients, shear viscosity) properties. The influence of the temperature and the cation's alkyl chain length on the above-mentioned properties was thoroughly investigated. The calculated thermodynamic (primary and derivative) and structural properties are in good agreement with the experimental data, while the extremely sluggish dynamics of the ILs under study renders the calculation of their transport properties a very complicated and challenging task, especially at low temperatures.     

Ultrabroad near-infrared photoluminescence from ionic liquids containing subvalent bismuth

We have shown that Lewis-acidic halogenoaluminate ionic liquid (IL) containing subvalent bismuth can be used as a near-IR (NIR) luminescent material. Raman and absorption spectra evidence the coexistence of Bi(5)(3+) and Bi(+) in the liquid. The Bi(5)(3+) and Bi(+) emitters, stabilized by this Lewis-acidic liquid, demonstrate ultrabroad NIR photoluminescence with a lifetime of around 1 μs. We envisage that the bismuth activated ILs would not only enrich the well-established spectrum of soft luminescent materials but also might promote the design of novel photonic materials activated by other p-block elements.