Graphdiyne-Based Single-Atom Catalysts with Different Coordination Environments

As a special carbon material, graphdiyne (GDY) features the superiorities of incomplete charge transfer effect on the atomic level, tunable electronic structure and anchoring metal atoms directly with organometallic coordination bonds M (metal)-C (alkynyl carbon in GDY), providing it an ideal platform to construct single-atom catalysts (ACs). The coordination environment of single atoms anchored on GDY plays a key role in their catalytic performance. The mini-review highlights state-of-the-art progress in the rational design of GDY-based ACs and their applications, and mainly reveals the relationship between the coordination engineering of the GDY-based ACs and corresponding catalytic performance. Finally, some prospects concerning the future development of GDY-based ACs in energy conversion are also discussed.     

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.     

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.     

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.     

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.     

Engineering Graphdiyne for Solar Photocatalysis

Graphdiyne (GDY) with a direct band gap, excellent carrier mobility and uniform pores, is regarded as a promising photocatalytic material for solar energy conversion, while the research on GDY in photocatalysis is a less developed field. Herein, the distinctive structure, adjustable band gap, and electronic properties of GDY for photocatalysis is firstly summarized. The construction and progress of GDY-based photocatalysts for solar energy conversion, including H₂ evolution reaction (HER), CO₂ reduction reaction (CO₂RR) and N₂ reduction reaction (NRR) are then elaborated. At last, the challenges and perspectives in developing GDY-based photocatalysts for solar fuel production are discussed. It is anticipated that a timely Minireview will be helpful for rapid progress of GDY in solar energy conversion.     

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.     

Diffusion Kinetics Study of Lithium Ion in the Graphdiyne Based Electrode

Herein,we report a comparative investigation of the electrochemical lithium diffusion within graphidyne(GDY)based electrodes.The transfer kinetic behaviors of lithium ions during the insertion/extraction process are analyzed through different methods including the galvanostatic intermittent titration technique(GITT)and the electrochemical impedance spectroscopy(EIS).GDY with the morphology of nanosheets(GDY NS)shows lithium diffusion coefficients in the orders range of 10-12-10-13 cm2/s through the GITT method.Meanwhile,EIS indicates quite a lower value of lithium diffusion coefficients between 10-13 and 10-15 cm2/s,which indicates that the analysis technique has an influence on the evaluation of GDY-based electrodes.In addition,under the same measurement condition of GITT,GDY nanoparticles(GDY NP)exhibit a lower value of Li+diffusion coefficient(10-14-10-16 cm2/s)during the charge-discharge process compared to those of GDY NS,which can be ascribed to the wide distributing range of particle size in GDY NP based electrodes.The analysis results in this work reveal that the aggregating forms of GDY electrode material have an important effect on the diffusion process of lithium ions,which provides a pathway to optimize the performance of GDY-based energy storage devices.     

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: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.     

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.     

Fabrication and Excellent Antibacterial Activity of Well-defined CuO/Graphdiyne Nanostructure

Copper oxide(CuO),due to its low cost,good chemical and physical stability,has recently been given special attention as a potential candidate for antibacterial agents.However,developing novel CuO nanocomposites with improved antibacterial property and unraveling the interface promotion mechanism has been a fundamental challenge for decades.Herein,well-defined CuO/graphdiyne(CuO/GDY)nanostructures with uniformly anchored CuO nanoparticles(ca.4.5 nm)have been fabricated.The CuO/GDY nanostructure exhibited superior E.coli inactivation efficiency,which is nearly 19 times and 7.9 times higher than the bare GDY and commercial CuO,respectively.The improved E.coli inactivation performance was mainly due to the increased reactive O2-species generated by the activation of molecular O2 over CuO/GDY surface.These findings demonstrate the efficient antibacterial activity of well-defined CuO/GDY nanostructures and provide insights on the development of efficient GDY-based antibacterial materials.     

Journey from Small-Molecule Diyne Structures to 2D Graphdiyne: Synthetic Strategies

Graphdiyne (GDY) exhibits unique characteristics of a highly conjugated π system, evenly distributed nanopores, and a direct band gap. This has encouraged multidisciplinary research groups to investigate its application in energy conversion and storage, catalysts, electronic devices, sensing, and separation. Herein, the achievements of synthetic strategies for preparing small-molecule diyne structures (GDY substructure), 1D nanoribbons, and 2D GDY are presented. These studies may help future investigations into the basic structure-related properties of GDY and synthetic methodology for the future developments of GDY-related 2D carbon materials.     

石墨炔在电化学储能器件中的应用

当今社会,电化学储能器件在人类的社会活动中变得越来越重要。电极材料作为电化学储能器件的核心部分,一直是人们研究的焦点。石墨炔是一种新型的二维平面结构的全碳材料,它宽的层间距、大的比表面积、独特的三维孔隙结构和好的导电性使其在能源存储器件电极材料应用中具有巨大的潜力。基于石墨炔温和的制备方法与独特的结构特征,本文详细介绍了近年来石墨炔在储能方面的理论分析和实验进展。通过研究锂/钠在单层、多层石墨炔上的迁移率和存储,理论分析石墨炔基电池具有很好的储锂储钠性能。实验方面,石墨炔作为电极材料在储钠储锂方面的容量与理论值相近。此外石墨炔作为电极材料成功应用于超级电容器和金属-硫电池,并表现出了优异的容量存储性能。石墨炔纳米形貌的调控、石墨炔的热处理,以及异原子的掺杂等均可以有效地提高石墨炔在这些储能器件中的性能。     

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.     

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.     

Study of Graphdiyne-based Magnetic Materials

Carbon-based magnetic semiconductors are easy to be modified with low cost and low power consumption.While they can demonstrate robust long-range magnetic ordering and show great potential for application after introducing magnetic moments.Graphdiyne(GDY),as an allotrope of carbon,exhibits intrinsic semiconductor properties and paramagnetic properties due to its unique structure and the presence of sp carbon.To improve the magnetic properties of GDY and prepare excellent magnetic semiconductor materials,scientists have done a lot of related research work.The most direct and effective method to introduce magnetism is heteroatom doping.In this review,we have entirely described the latest GDY magnetism introduction methods,effects,and theoretical calculations,etc.Doping methods include post-doping and molecular design doping.The doping elements have covered non-metallic elements(N,H,F,Cl,S),metallic elements(Fe),and functional groups.The magnetic properties of the modified GDY materials were studied by experimental analysis and theoretical calculations.This review provides a sufficient basis and direction for related researches.     

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.     

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-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。