化学课堂新知识：新型碳材料——石墨炔

Since the first successful chemical synthesis of graphdiyne by the group of Prof. Yuliang Li, this material is attracting much attention and becoming a new research focus and field. As a new carbon allotrope, graphdiyne has a unique three-dimensional pore structure and electronic structure, thus, can be applied in energy storage devices and the fields of catalyst. This article briefly describes theoretical calculation prediction and development of the new material, in particular, its electrochemical property and catalytic property. Introducing this new carbon material into the related teaching of chemistry knowledge of university can expand the academic vision of scientific research and improve the learning interest and scientific research literacy of the undergraduates.     

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.     

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。     

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.     

石墨炔零价金属原子催化剂的合成及应用

原子催化剂是零价金属原子锚定于载体上的一种新型催化剂, 具有原子利用率高、 选择性高以及反应活性和稳定性高等优点, 一直是催化领域的研究前沿, 在催化和能量转换领域具有广阔的发展前景. 石墨炔与金属原子之间独特的不完全电荷转移性质实现了零价过渡金属原子的稳定锚定, 解决了传统单原子催化剂易迁移和聚集的问题, 被认为是新一代催化剂. 本综述从石墨炔原子催化剂的结构性质、 表征以及应用等方面出发, 综合评述了相关领域的最新研究成果, 介绍了石墨炔原子催化剂在电催化固氮制氨、 产氢、 全水解和CO₂固定等方面的应用和发展前景, 为实现新概念高性能催化材料的设计合成提供了研究思路.     

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.     

Application of Graphdiyne and Its Analogues in Photocatalysis and Photoelectrochemistry

Graphdiyne(GDY),a new carbon allotrope composed of sp-sp2 carbon atoms,has attracted increased attention in recent years.It has a direct band gap of 0.46-1.22 eV,high charge carrier mobility and lower work function compared to most of the typical semiconductors,which ensure successful hybridization with other semiconductors(e.g.,TiO2,g-C3N4).This review aims at discussing recent achievements of GDY and its analogues applied in photocatalytic and photoelectrochemical(PEC)reactions.Meanwhile,some challenges and new perspectives of opportunities in developing catalysts and electrodes based on GDY and its analogues are also discussed.     

Graphdiyne Hybrid Nanowall Arrays for High-capacity Aqueous Rechargeable Zinc Ion Battery

Development of aqueous rechargeable zinc ion battery is an important direction towards grid energy storage sought in various applications.At present,the efficient utilization of aqueous rechargeable zinc ion batteries has been seriously affected due to the defects nature of the cathode materials,such as poor capacity,limited rate performance,and limited cycle stability.Therefore,the search for high-performance cathode materials is a main challenge in this field.Herein,we in-situ prepared graphdiyne-wrapped K0.25·MnO2(K0.25·MnO2@GDY)hybrid nanowall arrays as the cathode of aqueous rechargeable zinc ion battery.The hybridnanowall arrays have obviously alleviated the pulverization and sluggish kinetic process of MnO2 cathode materials and shown high specific capacity(520 mA·h/g at a current density of 55 mA/g),which is near-full two-electron capacity.The high specific capacity was resulted from more than one Zn2+(de)intercalation process occurring per formula unit,in which we observed a structural evolution that partially stemmed from ion exchange between the intercalated K+and Zn2+ions during the discharge process.The present investigation not only provides a new material for the aqueous rechargeable Zn ion batteries,also contributes a novel route for the development of next generation aqueous rechargeable Zn ion batteries with high capacity.     

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.     

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。     

Metal/Graphitic Carbon Nitride Composites: Synthesis,Structures, and Applications

Graphitic carbon nitride (g‐C₃N₄) has been widely used in fields related to energy and materials science. However, nanostructured g‐C₃N₄ photocatalysts synthesized by traditional thermal polycondensation methods have the disadvantage of small specific surface areas and wide band gaps; these limit the catalytic activity and application range of g‐C₃N₄. Based on the unique nanostructure of g‐C₃N₄, it is a feasible method to modify g‐C₃N₄ with metals to design novel metal–semiconductor composites. Metals alter the photochemical properties of g‐C₃N₄, in particular, narrow the band gap and expand photoabsorption into the visible range, which improves the photocatalytic performance. This review covers recent progress in metal/g‐C₃N₄ nanocomposites for photocatalysts, organic systems, biosensors, and so on. The aim is to summarize the synthetic methods, nanostructures, and applications of metal/g‐C₃N₄ nanocomposite materials, as well as discuss future research directions in these areas.     

Nitrogen‐Doped Carbon Nanomaterials: Synthesis,Characteristics and Applications

Nonmetallic carbon‐based nanomaterials (CNMs) are important in various potential applications, especially after the emergence of graphene and carbon nanotubes, which demonstrate outstanding properties arising from their unique nanostructures. The pristine graphitic structure of CNMs consists of sp² hybrid C?C bonds and is considered to be neutral in nature with low wettability and poor reactivity. To improve its compatibility with other materials and, hence, for greater applicability, CNMs are generally required to be functionalized effectively and/or doped with heteroatoms in their graphitic frameworks for feasible interfacial interactions. Among the various possible functional/doping elements, nitrogen (N) atoms have received much attention given their potential to fine tune the intrinsic properties, such as the work‐function, charge carrier concentration, surface energy, and polarization, of CNMs. N‐doping improves the surface energy and reactivity with enhanced charge polarization and minimal damage to carbon frameworks. The modified surface energy and chemical activity of N‐doped carbon nanomaterials (NCNMs) can be useful for a broad range of applications, including fuel cells, solar cells, Li‐ion batteries, supercapacitors, chemical catalysts, catalyst supports, and so forth.     

Graphdiyne:a Highly Sensitive Material for ppb-Level NO2 Gas Sensing at Room Temperature

Detection of a trace amount of NO2 at room temperature has very important applications in air quality monitoring,protection of human health and medical diagnose.However,the existing NO2 sensors often suffer from low sensitivity when the concentration at the ppb-level.Here,we report a new kind of materials based on graphdiyne(GDY)for highly sensitive detection of ppb-level(ppb:part per billion)NO2 at room temperature.After thermal treatment of the as-prepared GDY at 600℃under argon atmosphere for 2 h(the obtained sample denoted as GDY-600),the prepared sensor with GDY-600 displays excellent sensitivity with a response value of 6.2％towards 250 ppb NO2 at room temperature,which is better than most of reported sensing materials.In addition,the sensor exhibits significantly high selectivity to NO2 against typical interfering gases including CO,CO2,NH3,H2,H2S and toluene.Moreover,the sensor shows remarkable stability after repetitive measurements.The superior sensing performance of GDY-600 can be ascribed to the highly π-conjugated structure with special acetylenic bonds and abundant oxygen-containing functional groups,which are all beneficial for the gas adsorption and redox reaction on the surface.     

含杂原子富勒烯C_(58)X_2(X=B、N、P)电子结构的量子化学研究

用CNDO／2方法在586微机上计算了C60，C59X1和C58X2（X=B、N、P）的23种位置异构体共73个分子的电子结构。在C58X2的23种位置异构体中C58B2（1，9），C58N2（1，9）和C58P2（1，2）分别是最稳定的。C59X1和的稳定性都比C60差，氧化或还原都比C60容易。在C59X1和分子中与杂原子相距1个、2个或3个键的C原子的电荷密度比C60分子的增加或减少较多，其亲电或亲核反应能力增强；与杂原子直接相连的键或挪巨1个、2个、3个键的2个C原子间WibergOrder比C60分子增加或减少较多，其键的强度增强或减弱。     

石墨烯的制备、功能化及在化学中的应用

石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.     

石墨烯的制备、功能化及在化学中的应用

石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.     

石墨烯的制备、功能化及在化学中的应用

石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.     

石墨烯的制备、功能化及在化学中的应用

石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.     

石墨烯的制备、功能化及在化学中的应用

石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.     

石墨烯的制备、功能化及在化学中的应用

石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.