Post-modified Strategies of Graphdiyne for Electrochemical Applications

The new carbon material graphdiyne (GDY) has been verified to have a great application prospect in electrochemical field. In order to study its properties and expand its scope of application, various experiments including structural control tests are imposed on GDY. Among them, as one of the most commonly used methods to modify the structure, heteroatom doping is favored for its advantages in synthesis methods and the control of mechanical, electrical and even magnetic properties of carbon materials. According to the published studies, the top-down methods of doping heteroatoms for GDY only need cheap raw materials, simple synthetic route and strong controllability, which is conducive to rapid performance breakthroughs in electrochemical applications. This review selects the typical cases in the development of that post-modification method from the application of GDY in the electrochemical field. Here, based on the existed reports, the commonly used non-metal elements (such as nitrogen, sulfur) and metal elements (such as iron) have been introduced to post-modify GDY. Then, a detailed analysis is made for corresponding electrochemical applications, such as energy storage and electrocatalysis. Finally, the challenges and prospects of post-modified GDY in synthesis and electrochemical applications are proposed. This review provides us a useful guidance for the development of high-quality GDY suitable for electrochemical applications.     

Heteroatom Doped Graphdiyne and Analogues:Synthesis,Structures and Applications

As a new carbon allotrope,graphdiyne(GDY)has shown intensive practical application prospects in the energy field,catalysis,gas separation,etc.,due to its unique 2D π-conjugated structure,rich sp-hybridized carbon atoms and semiconductor characteristics.Considerable efforts have been made to the development of well-defined GDY materials in recent years.The doping heteroatoms can further tune the structures,semiconductor properties of GDY,and expand the promising applications.This review summarized a comprehensive development of heteroatom doped GDYs,including their synthesis,structures,properties,applications in nanotechnology,as well as the forecast in the future.     

石墨炔结构表征及在光电催化反应中的应用

石墨炔是一种新型碳材料,自2010年实验室成功制备后受到广泛关注。石墨炔是一种由sp和sp²杂化碳组成的高度共轭结构。随着石墨炔合成化学的发展,多种不同构型的石墨炔被制备和表征。石墨炔特殊的电子和孔结构,使其在催化领域中具有广泛的应用。本文总结了近年来石墨炔材料在表征方法和光电催化反应方面的研究进展,并探讨了石墨炔未来发展的机遇和挑战。     

石墨炔衍生物的合成与应用

石墨炔是由sp和sp²两种杂化碳构成的新型二维碳同素异形体。基于石墨炔化学合成规律和独特优势,利用其他芳炔前体替代六乙炔基苯,可以获得结构特异、尺寸可控的石墨炔基衍生物,而局域碳骨架的改变可以实现石墨炔衍生物性能调控,包括电导率、带隙、迁移率、空腔尺寸和电荷分离等。这类具有优良半导体性能的石墨炔基衍生物可以广泛应用于电化学储能、电催化、光电转换器件、非线性光学等诸多领域。本文主要综述了近年来石墨炔衍生物的优化设计、结构表征和光电性能,并对其代表性应用进行了总结和展望。     

2D graphdiyne materials: challenges and opportunities in energy field

Graphdiyne(GDY),a novel two-dimensional(2D)carbon allotrope featuring one-atom-thick planar layers of sp andhybridized carbon network,is a rapidly rising star on the horizon of materials science.Because of its unparalleled structural,electronic,chemical and physical properties,it has been receiving unprecedented increases from fundamental studies to practical applications,particularly the field of energetic materials.In this review,we aim at providing an up-to-date comprehensive overview on the state-of-the-art research into GDY,from theoretical studies to the key achievements in the development of new GDY-based energetic materials for energy storage and conversion.By reviewing the state-of-the-art achievements,we aim to address the benefits and issues of GDY-based materials,as well as highlighting the existing key challenges and future opportunities in this exciting field.     

Graphdiyne:A Versatile Material in Electrochemical Energy Conversion and Storage

Graphdiyne(GDY),which is composed of sp2-/sp-hybridized carbon atoms,has attracted increasing attention.In the structure of GDY,the existence of large triangular-like pores,well dispersed electron-rich cavities as well as a large π-conjugated structure endows GDY with a natural bandgap,fast electron/ion transport,and tunable electronic properties.These unique features make GDY competitive in areas of gas separation and capture,electronics,detectors,catalysts,biomedicine and therapy,and energy-related fields.Benefiting from the facile synthesis method,various GDY structures and GDY-based composites have been successfully prepared and show great potential in the practical application of energy storage and catalysis areas.Here,this review aims at providing a timely and comprehensive update on the preparation and application of GDY materials.The current development of GDY materials in various electrochemical fields especially in energy conversion,energy storage,and catalysis is mainly summarized.Moreover,the potential development prospects are also discussed.     

Electronic and magnetic properties of the two-dimensional C4H-type polymer with strain effects, intrinsic defects and foreign atom substitutions

Following the two-dimensional periodic single-layer sheet successful synthesized experimentally very recently [Adv. Mater., 2011, 23, 4497], we present systematically the electronic and magnetic properties of this novel polymer (referred to as C(4)H) without and with strain-modifying, vacancy-doping, and nonmetal element (B, N, and P) doping by means of first-principles calculations. It was found that: (a) the C(4)H sheet is a nonmagnetic semiconductor with a wide indirect band gap. (b) The atomic structure, binding energies and electronic properties of the C(4)H sheet could be significantly modified by applying strain. (c) Vacancy defects can lead to intrinsic magnetism in C(4)H and, surprisingly, the induced spin polarization has large spatial extension; especially, room-temperature ferromagnetism in H vacancies-doped case is quite feasible. (d) Substitution of B, P and N at the unhydrogenated C site could form a local magnetic moment, whereas no spin-polarization could be induced for that with N at the hydrogenated C site. The present study provides theoretical insight leading to a better understanding of novel 2D structures, and further experimental studies are expected to confirm the attractive predictions.     

Research on the Preparation of Graphdiyne and Its Derivatives

As a new 2D carbon material allotrope composed of sp and sp² carbon atoms, graphdiyne (GDY) possesses a highly conjugated porous structure, easily tunable intrinsic bandgap, and various excellent properties. Such properties allowed researchers to develop methods to prepare GDY, so that it can be applied for energy storage and conversion, environmental protection, various electronic devices and so on. In this review, the authors systematically discuss the methods and strategies developed for preparing GDY and its derivatives, including the synthesis of GDY by using liquid-, solid-, and gas-phase methods, the synthesis of heteroatom-doped GDY, the preparation of GDY-based composites, and the synthesis of GDY analogues. All these preparation methods can provide the way to obtain GDY for specific studies and applications.     

One-dimensional Intrinsic Ferromagnetic Semiconductor CuCl_2: a First-principles Study

One-dimensional nanowires with robust magnetism are desirable for spintronic applications. Herein, on the basis of the first-principles calculations, systematic investigations on the electronic and magnetic properties of the CuCl2 nanowire were performed, which can be potentially tailored from its bulk form. The CuCl2 nanowire exhibits a ferromagnetic ground state. The band structures indicate that the CuCl2 nanowire is a ferromagnetic semiconductor. The spin flip gap is large enough for avoiding spin flip. Phonon dispersion and Born-Oppenheimer molecular dynamics simulation manifest that the CuCl2 nanowire is stable. In addition, distinct magnetic properties of the CuCl2 nanowires inside two types of carbon nanotubes were obtained. The study broadens the family of the existing one-dimensional materials with promising applications for spintronics.     

Supercritical CO2-induced New Chemical Bond of C−O−Si in Graphdiyne to Achieve Robust Room-Temperature Ferromagnetism

The realization of ferromagnetic ordering of two-dimensional (2D) carbon material graphdiyne (GDY) has attracted great attention due to its promising application in spin semiconductor devices. However, the absence of localized spins makes the pristine GDY intrinsically nonferromagnetic. Herein, we report the realization of robust room-temperature (RT) ferromagnetism (FM) with Curie temperature (T_C) up to 325 K for GDY Nanosheets (GDYNs) by supercritical CO₂ (SC CO₂). Experimental and theoretical calculations reveal that the new chemical bond of C−O−Si can be formed because of the unique effect of SC CO₂, which help to enhance the charge transfer and generates long-range ferromagnetic order. The RT saturation magnetization (M_S) reaches 1.125 emu/g, which is much higher than that of carbon-based materials reported up to now. Meanwhile, by changing the conditions of SC CO₂ such as pressure, ferromagnetic responses can be manipulated, which is great for potential spintronics applications of GDY.     

石墨炔-有机共轭分子复合材料的制备及其储锂性能

发展了基于超分子化学的新方法实现了对石墨炔的原位氮掺杂,通过利用石墨炔与有机共轭分子间强的π–π作用,原位制备了石墨炔/卟吩复合材料薄膜,并用作锂离子电池的负极材料,其比容量增加到了1000 mAh∙g⁻¹,该复合材料表现出优良的倍率性能和循环稳定性,为可控制备掺氮石墨炔复合材料提供了新的思路。     

Graphdiyne:from Preparation to Biomedical Applications

Graphdiyne(GDY)is a kind of two-dimensional carbon nanomaterial with specific configurations of sp and sp2 carbon atoms.The key progress in the preparation and application of GDY is bringing carbon materials to a brand-new level.Here,the various properties and structures of GDY are introduced,including the existing strategies for the preparation and modification of GDY.In particular,GDY has gradually emerged in the field of life sciences with its unique properties and performance,therefore,the development of biomedical applications of GDY is further summarized.Finally,the challenges of GDY toward future biomedical applications are discussed.     

基于碳基磁性材料的磁固相萃取技术在食品分析应用中的研究进展

食品中残留的痕量有毒物质严重威胁人体健康,对其进行分析十分必要。然而,食品中有毒物质种类多、量少、基质复杂,需选择适当的样品预处理技术进行提取和净化。磁固相萃取(MSPE)因具有操作简单、省时快速、无需离心过滤、环境友好等优点,被认为是一种高效的样品预处理技术并应用于食品分析中。MSPE中使用的磁性吸附剂的吸附容量和选择性是影响MSPE萃取效率和选择性高低的关键,对所建立分析方法的准确度起着关键作用。碳基磁性材料是具有价格低廉、来源丰富、比表面积大、化学稳定性好、吸附容量高、绿色环保等优点的一类新型功能性磁性材料,可以富集不同性质的有机、无机分析物,在环境分析、生物检测、污染治理等多个领域取得了较大进展。近年来,基于碳基磁性材料的MSPE技术在食品分析预处理领域逐渐得到应用,但尚处于起步阶段,存在巨大的应用潜力。该文以碳基类别(碳纳米管、石墨烯、金属有机骨架衍生碳、活性炭等)为主线,综述了采用MSPE技术,以碳基磁性材料为吸附剂,对食品样品中酯类、真菌毒素、多环芳烃、抗生素、生物碱、酚类、维生素、抗菌药等物质进行萃取,进而采用液相色谱法等进行分析的应用实例,同时阐述了该技术存在的问题,并对其发展方向做出了展望。该综述将为基于碳基磁性材料的MSPE技术在食品分析中的广泛应用提供理论依据和技术支撑。     

石墨炔孔结构:设计、合成和应用

石墨炔作为一种新兴碳材料, 由于具有特殊的电子特性、 丰富的纳米级孔隙以及能在相对低温下合成的特点, 在催化、 能源及生物等领域受到广泛关注. 石墨炔自下而上的合成特点使其在结构上具有可设计性, 而其显著特征在于具有拓扑有序的规则孔道结构. 在过去的10年间, 研究人员在石墨炔孔结构设计方面进行了大量的实验和理论研究. 孔结构设计所带来的独特性能为其提供了良好的应用前景. 本文从石墨炔的合成特点出发, 总结了单体、 催化剂、 模板及溶液4个因素对石墨炔结构的影响, 并从孔结构出发讨论了其应用. 为研究者以应用为导向, 设计合成具有特殊孔结构的石墨炔提供了思路. 最后还探讨了孔结构设计给石墨炔带来的机遇与挑战, 并对三维多孔结构石墨炔的设计进行了展望.     

Fabrication and Application of Graphdiyne-based Heterogeneous Compositions:from the View of Interaction

Graphdiyne(GDY)has the unique feature in the topological ordered arranged sp-and sp2-hybridized carbon atoms,thus deriving a series of 2D allotropes.Due to inhomogeneous π-bonding and carbon orbital overlap between different hybrid carbon atoms,GDY possesses a natural band gap with a Dirac cones structure.And GDY exhibits semiconductor property with a conductivity of 2.516×10-4 S/m at room temperature.The topological distribution of alkyne and benzene bonds of GDY makes its surface charge distribution extremely uneven,which produces high intrinsic activity for further modification.Its unique molecular structure endows the specific interaction with various species,such as ions,atoms,molecules and nanoparticles,showing excellent charge transport capability and unique advantages in mass transfer and energy conversion.From the view of the interaction principle between GDY and different compositions,we summarized the application of GDY-based materials in the fields of catalysis,energy conversion and storage,biological detection and so on.     

2D Graphdiyne: A Rising Star on the Horizon of Energy Conversion

Two-dimensional (2D) graphdiyne (GDY), a rapidly rising star on the horizon of carbon materials, is a new carbon allotrope featuring sp- and sp²-cohybridized carbon atoms and 2D one-atom-thick network. Since the first successful synthesis of GDY by Professor Li's group in 2010, GDY has attached great interests from both scientific and industrial viewpoints based on its unique structure and physicochemical properties, which provides a fertile ground for applications in various fields including electrocatalysis, energy conversion, energy storage and optoelectronic devices. In this work, various potential properties of the GDY-based electrocatalysts and their recent advances in energy conversion are reviewed, including atomic catalysts, heterogeneous catalysts, and metal-free catalysts. The critical role of GDY in improving catalytic activity and stability is analyzed. The perspectives of the challenges and opportunities faced by GDY-based materials for energy conversion are also outlined.     

Synergistic Effect of Graphdiyne-based Electrocatalysts

The synergistic effect can help improve the electrocatalyst performances by combining the advantages of individual components. In particular, such an effect has been more important in the atomic catalysts. In this review, we have summarized the synergistic effect of N, X co-doping graphdiyne[X=B, S, F or transition metal(TM)] electrocatalysts and graphdiyne-based dual-atom catalyst(GDY-DAC). In general, the synergistic cooperation between two different dopants in co-doped GDY and adjacent active sites in GDY-DAC not only promotes their catalytic activity but also greatly enhances the thermodynamic stability of the catalysts. For the N, X co-doping GDY electrocatalysts, doping the heteroatoms like boron, sulphur, phosphorus, and fluorine with nitrogen can further tune the charge density distribution and electronic structure. Meanwhile, the electron exchange between two doping atoms and GDY substrate has been discussed, where the TM-based GDY-DAC is a very promising catalyst for electrocatalysis. More importantly, electronic interactions between different elements on GDY have been carefully discussed. In the end, we have also supplied perspectives to the future developments of the GDY-based electrocatalysts.     

二维碳石墨炔的结构及其在能源领域的应用

从二维碳材料石墨炔(GDY)的分子和电子结构出发,重点论述石墨炔在能源存储和转换两个领域的应用,包括最新的理论和实验进展。石墨炔独特的三维孔隙结构,使得石墨炔在锂存储和氢气存储应用中具备天然的优势,既可以用作锂离子相关的储能器件,包括锂离子电池、锂离子电容器等;也可作为储氢材料,用于燃料电池等。通过掺杂的方法,还能进一步提高石墨炔储锂和储氢的性能。由于sp炔键和sp²苯环的存在,使石墨炔具有多重共轭的电子结构,在具备狄拉克锥的同时,其带隙也可通过多种途径调控,使得石墨炔不仅可以作为非金属高活性催化剂替代贵金属在光催化等方面应用,还可以在太阳能电池的空穴传输层和电子传输层方面获得应用,展现了石墨炔在能源方面独特的应用价值。我们将从理论预测和实验研究两方面介绍该领域目前的研究现状和发展趋势。     

Dual Manipulation of Ferromagnetism in Co-Doped ZnO Thin Films by Surfactant and n-Type Carriers

We present a conceptually-new approach “dual manipulation effect” using the surfactant passivation and the electron carrier doping for mediating intrinsic ferromagnetism in Codoped ZnO dilute magnetic semiconductor (DMS) thin films. The first-principles calculations show that the surface passivation by hydrogen serves as a magnetism switch for the Co-O-Co magnetic coupling at the surface of the thin film, and thus can control the spin polarization of the doped Co atoms. Meanwhile, the electron carrier doping can further function as an effective layerlike ferromagnetism mediator for the underneath layer. The dual manipulation effect sheds light on the essential magnetism origin of n-type Co:ZnO DMS thin films, and may be used as an alternative strategy for enhancing the ferromagnetism in other n-type DMS oxides thin films.     

有机磁体--新世纪的新材料

有机磁性材料是最近二十多年发展起来的新型的功能材料 ,因为其结构的多样性 ,可用化学方法合成 ,可得到磁性能与机械、光、电等方面结合的综合性能等特点 ,在超高频装置、高密度存贮材料、吸波材料、微电子工业和宇航等需要轻质磁性材料的领域有很大的应用前景。本文综述了有机磁性化合物的发展和研究近况。