石墨炔:从合成到应用

正石墨炔是一种新型碳的同素异形体,是由sp和sp~2两种杂化形式的碳原子组成的二维层状材料~1。具有中国自主知识产权的石墨炔自2010年被首次成功合成以来,吸引了全世界来自化学、物理、材料、生物和电子等学科的科学家对其进行探索~2。石墨炔独特的纳米级孔隙、二维层状共轭骨架结构及半导体性质等特性,使之在能源、电化     

少层石墨双炔薄膜的液相范德华外延生长法

<正>新型低维碳材料的探索与制备是纳米碳材料领域的重要挑战。石墨炔(Graphyne)是一种二维(2D)碳的同素异形体材料1,由sp和sp2两种杂化态的碳原子共同构成,在二维平面内具有均一分布的孔洞结构,因此具有与富勒烯(0D),碳纳米管(1D)和石墨烯(2D)完全不同的电子结构和骨架结     

层状稀土氢氧化物杂化发光材料研究进展

层状稀土氢氧化物(LRHs)是一类具有二维层状结构的新型无机层状功能材料.由于LRHs具有可变的组成、丰富的插层化学行为以及稀土离子特有的荧光性质等优点,因此是一种很有发展潜力的新型发光功能材料.本文综述了层状稀土氢氧化物杂化发光材料的研究进展,探讨了主客体间相互作用对其光物理性质及稳定性的影响,为实现层状稀土氢氧化物杂化发光材料在光学器件领域(LED照明和光纤维等)及生命分析领域的应用提供了重要的理论依据.     

基于二维层状黑磷的高性能柔性固态超级电容器

正近年来,二维纳米材料以其特殊层状结构与优良性能作为柔性储能器件电极材料,人们已进行了广泛探索研究,期望发现性能优异的柔性二维电极材料。黑磷作为一种p型直接带隙层状单元素半导体上世纪60年代已被发现~1,但对二维层状黑磷的广泛兴趣始于2014年其在场效应管中的成功应用~2,近两年相关研究激增。研究发现,二维黑磷维持     

介孔氮化碳的合成及其在环境卫生领域中的应用

石墨相氮化碳是一种新兴的二维蜂窝状纳米材料,其结构中C原子和N原子以sp2方式杂化,通过PZ轨道上的孤对电子相互作用形成类似于苯环的π键,构成高度离域的共轭体系。这一独特结构使其可与一些离子或分子产生疏水、π－π键、氢键和静电力等相互作用,进而成为一种颇具潜力的吸附剂。但同时石墨相氮化碳本身紧密堆叠的层状结构导致其比表面积较小（< 10 m2/g）。介孔氮化碳应运而生,其具有孔尺寸为2～50 nm的典型介孔结构,与石墨相氮化碳相比,比表面积和孔体积获得有效提高且吸附位点更加丰富。该文总结了介孔氮化碳的合成方法及其在环境卫生领域的应用,并展望了其发展方向。     

石墨双炔的合成方法

石墨炔是一种新型碳的同素异形体,是由sp和sp²两种杂化形式的碳原子组成的二维层状材料。其中,石墨双炔是石墨炔家族中重要的一员,其独特的纳米级孔隙、二维层状共轭骨架结构及半导体性质等特性,使之在电化学、光催化、非线性光学、电子学等诸多领域优势显著,因此,发展石墨双炔的制备方法有着重要的意义。本文将首先介绍石墨双炔的结构,随后主要介绍石墨双炔合成方法的研究进展,包括有机全合成、表面在位化学反应和溶液相聚合反应等几个方面,其中溶液相聚合的方法取得了较为突出的进展。在本文的最后,主要探讨了石墨双炔合成方法中的挑战与机遇,并对合成方法的未来进行了展望。     

新型二维功能材料及衍生物的设计和制备

二维功能材料的制备方法常见的有以下几种:(1)机械剥离或液相剥离具有面间弱相互作用、面内强共价键合作用的层状材料生成单层或少数层的二维材料;(2)化学合成方法;(3)Langmuir-Blodgett单分子膜技术法;(4)层层自组装法;(5)化学气相沉积法;(6)分子束外延法和(7)原子层沉积技术法。这些材料及其有机-高分子衍生物具有独特的结构特征和优异的性质,在场效应晶体管、光调制器、锁模和Q开关激光、光限幅、信息和能源存储、射频器件、化学传感器等领域具有重要的潜在应用价值。近年来,除了众所周知的石墨烯外,其他诸如类石墨烯的无机纳米材料(六方氮化硼、过渡金属卤化物、石墨化氮化碳、层状金属氧化物等)、二维聚合物、金属-有机框架、钙钛矿、黑磷等二维材料也被广泛研究或探索。开发或探索更多二维材料应用的关键是设计和制备新颖的二维材料和它们的有机-高分子衍生物。在不久的将来,兼具规模经济和功能行为的二维材料化学的突破将极大地驱动新型二维材料应用领域的拓展。本文综述了二维材料的基本概念、研究进展、亟待解决的关键问题和未来的发展趋势。     

二维材料及其量子点在分离科学领域的研究进展

二维材料是一种新型的分离材料,具有原子尺寸、机械强度优异、比表面积大、表面化学丰富以及 物理、化学稳定性良好等特性,引起了分离科学领域研究人员的广泛关注,其中以石墨烯为典型代表。随着 对石墨烯材料的广泛研究,相继发展了二维过渡金属硫化物（TMDs）、层状双氢氧化物（LDHs）、金属有机框 架（MOFs）、共价有机骨架（COFs）、二维过渡金属碳化物或碳氮化物（MXene）、六方氮化硼（h-BN）等多种新 兴二维材料。该文介绍并讨论了二维材料及其量子点的特点及应用,重点介绍了二维材料及其量子点在膜分 离、固相萃取/固相微萃取、液相色谱、气相色谱、毛细管电色谱等分离科学领域中的应用。此外,还探讨了 二维材料在分离科学领域中面临的挑战及应用前景。     

MXene及其复合材料在钠/钾离子电池中的应用

MXene作为一种新型的二维层状结构材料而备受关注, MXene具有高电子传导率、较大的比面积、较好的机械性能以及独特的层状结构, 已广泛应用于储能、催化、吸附等领域。近年来, MXene及其复合材料应用于二次电池领域引起了人们的广泛关注。氧化物、硫化物等材料具有高容量, 但存在电导率低、反应过程中体积膨胀、循环稳定性差等问题, 构建与MXene的复合材料既能提高容量又可以增强材料的电子导电率, 有效缓解反应过程中体积膨胀, 实现最佳的电化学性能。本文主要对MXene及其复合材料在钠离子电池和钾离子电池中的最新研究进展进行总结, 简要介绍了钠离子电池、钾离子电池和MXene的研究背景, 重点介绍了MXene复合材料在钠离子电池中的应用研究, 主要按照硫化物、氧化物、碳材料进行分类, 对其合成方法与电化学性能进行综述, 同时总结了MXene复合材料在钾离子电池中的研究进展。最后本文对MXene及其复合材料的发展及其应用前景进行了总结与展望。     

新型二维功能材料及衍生物的设计和制备

二维功能材料的制备方法常见的有以下几种:机械剥离或液相剥离具有面间弱相互作用、面内强共价键合作用的层状材料生成单层或少数层的二维材料;化学合成法;LangmuirBlodgett单分子膜技术法;层层自组装法;化学气相沉积法;分子束外延法和原子层沉积技术法。这些材料及其有机-高分子衍生物具有独特的结构特征和优异的性质,在场效应晶体管、光调制器、锁模和Q开关激光、光限幅、信息和能源存储、射频器件、化学传感器等领域具有重要的潜在应用价值。近年来,除了众所周知的石墨烯外,其他诸如类石墨烯的无机纳米材料(六方氮化硼、过渡金属卤化物、石墨化氮化碳、层状金属氧化物等)、二维聚合物、金属-有机框架、钙钛矿、黑磷等二维材料也被广泛研究或探索。开发或探索更多二维材料应用的关键是设计和制备新颖的二维材料及其有机-高分子衍生物。在不久的将来,兼具规模经济和功能行为的二维材料化学的突破将极大地驱动新型二维材料应用领域的拓展。本文综述了二维材料的基本概念、研究进展、亟待解决的关键问题和未来的发展趋势。     

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.     

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.     

Regulating Efficient and Selective Single-atom Catalysts for Electrocatalytic CO2 Reduction

Anchoring transition metal (TM) atoms on suitable substrates to form single-atom catalysts (SACs) is a novel approach to constructing electrocatalysts. Graphdiyne with sp−sp² hybridized carbon atoms and uniformly distributed pores have been considered as a potential carbon material for supporting metal atoms in a variety of catalytic processes. Herein, density functional theory (DFT) calculations were performed to study the single TM atom anchoring on graphdiyne (TM₁−GDY, TM=Sc, Ti, V, Cr, Mn, Co and Cu) as the catalysts for CO₂ reduction. After anchoring metal atoms on GDY, the catalytic activity of TM₁−GDY (TM=Mn, Co and Cu) for CO₂ reduction reaction (CO₂RR) are significantly improved comparing with the pristine GDY. Among the studied TM₁−GDY, Cu₁−GDY shows excellent electrocatalytic activity for CO₂ reduction for which the product is HCOOH and the limiting potential (U_L) is −0.16 V. Mn₁−GDY and Co₁−GDY exhibit superior catalytic selectivity for CO₂ reduction to CH₄ with U_L of −0.62 and −0.34 V, respectively. The hydrogen evolution reaction (HER) by TM₁−GDY (TM=Mn, Co and Cu) occurs on carbon atoms, while the active sites of CO₂RR are the transition metal atoms . The present work is expected to provide a solid theoretical basis for CO₂ conversion into valuable hydrocarbons.     

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.     

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。     

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.     

N,P-co-Doped Graphdiyne as Efficient Metal-free Catalysts for Oxygen Reduction Reaction

The carbon-based metal-free catalyst is one of the ideal alternatives to Pt as electrocatalysts for oxygen reduction reaction,which can reduce the cost of fuel cells and zinc-air batteries.Here,graphdiyne(GDY),a carbon material with uneven charge distribution,was used as substrate.By doping nitrogen and phosphorus,a N-P-GDY catalyst was prepared,which further regulated the electron structure of GDY.The sheet-like morphology of GDY was preserved in N-P-GDY.The N and P were distributed uniformly in the catalyst,whereas defects and active sites were created by doping N and P,as demonstrated by the element mapping images and Raman spectra.X-Ray photoelectron spectroscopy results indicated N and P existed in many forms in N-P-GDY.The N-P-GDY exhibited higher activity for ORR than only N or P doped GDY,due to the synergistic effect of N and P in N-P-GDY.Moreover,the activity of N-P-GDY changed little after a long time cyclic voltammetry test or injecting methanol in the electrolyte.Besides,the four electrons transfer reaction to produce water was the main process for ORR on N-P-GDY catalysts.     

High‐Yield and Damage‐free Exfoliation of Layered Graphdiyne in Aqueous Phase

The two‐dimensional carbon material graphdiyne (GDY) holds great promise as a semiconductor and porous material, however, exfoliation of bulk GDY into single‐ or few‐layered GDY in the aqueous phase remains a challenge. We report an efficient method for the damage‐free exfoliation of bulk GDY into single‐ or few‐layered GDY with high yield in an aqueous solution of inorganic salts (e.g., Li₂SiF₆). This was confirmed by spherical‐aberration‐corrected scanning transmission electron microscopy, scanning/transmission electron microscopy, atomic force microscopy, Fourier transform infrared/Raman spectroscopy, X‐ray photoelectron spectroscopy. The method gives high exfoliation efficiency (75 wt %) without creating additional structural defects or oxides in the exfoliated GDY. Theoretical calculations suggest that non‐covalent adsorption of the anion, diffusion of the cation, and subsequent repulsive forces between adjacent flakes are the main driving force for the efficient exfoliation.     

Template Based Synthesis of Porous Graphdiyne Nanosheet for Reversible and Fast NO2 Detection by UV Irradiation

Two-dimensional graphdiyne (GDY) formed by sp and sp² hybridized carbon has been found to be an efficient toxic gas sensing material by density functional theory (DFT). However, little experimental research concerning its gas sensing capability has been reported owing to the complex preparation process and harsh experimental conditions. Herein, porous GDY nanosheets are successfully synthesized through a facile solvothermal synthesis technique by using CuO microspheres (MSs) as both template and source of catalyst. The porous GDY nanosheets exhibit a broadband optical absorption, rendering it suitable for the light-driven optoelectronic gas sensing applications. The GDY-based gas sensor was demonstrated to have excellent reversible to NO₂ behaviors at 25 °C for the first time. More importantly, higher response value and faster response-recovery time once exposed to NO₂ gas molecules are achieved by the illumination of UV light. In this way, our work paves the way for the exploration of GDY-based gas detection experimentally.     

Graphdiyne:Structure of Fluorescent Quantum Dots

Graphdiyne (GDY) as an emerging two‐dimensional carbon allotrope exhibits excellent performance in energy chemistry, catalytic chemistry, optoelectronics, electronics, etc. because of the unique structure combining an sp‐ and sp²‐hybrid carbon network. However, the poor solubility of pristine GDY is a major obstacle to its applications in many fields. Proposed here is a facile strategy to control the preparation of GDY quantum dots (GDY‐Py QDs), in which pyrene groups are covalently linked to GDY by using a Sonogashira cross‐coupling reaction. The as‐prepared GDY‐Py QDs, with an average diameter of about 3±0.1 nm, show superior dispersibility in many organic solvents and water. The GDY‐Py QDs display not only bright fluorescent with a high relative quantum yield (QY) of 42.82 %, but they are also well‐behaved as contrast agents in cell imaging. The GDY‐Py QDs are bestowed with high stability and non‐cytotoxicity, and exhibit long fluorescent times, and have potential for optical imaging and biomedical applications.