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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2025 , Vol. 37 >Issue 12: 1917 - 1930

DOI: https://doi.org/10.7536/PC20250520

Review

Synthesis of Graphynes and Their Applications in Third-Order Nonlinear Optics

  • Juemin Zhao 1 ,
  • Bin Liang 1 ,
  • Yaxing Tang 1 ,
  • Jie Li , 1, * ,
  • Zheng Xie , 2, *
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  • 1 Ministry of Education Key Laboratory of Interface Science and Engineering in Advanced Materials， Taiyuan University of Technology， Taiyuan 030024， China
  • 2 College of Chemistry and Chemical Engineering， University of Jinan， Jinan 250022， China
* （Jie Li）；
（Zheng Xie）

Received date: 2025-05-26

  Revised date: 2025-07-02

  Online published: 2025-12-10

Supported by

National Natural Science Foundation of China(22275202)

Natural Science Foundation of Shanxi Province(20210302123144)

National Natural Science Foundation of China(21875267)

Shanxi Scholarship Council of China(2021-057)

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Abstract

Graphynes are a kind of low-dimensional carbon material composed of sp- and sp²-hybridized carbon atoms with unique electronic conjugation topologies and tunable chemical properties. Recently， significant progress has been made in the synthesis methods of graphynes. Various derivative structures as well as different morphologies from nanosheets to macroscopic films have been achieved through dry or wet chemical methods， which provide important theoretical and experimental supports for designing new carbon materials. Due to the high specific surface areas， abundant chemically active sites， and adjustable bandgap structures， graphyne derivatives exhibit high nonlinear optical coefficients and ultra-fast carrier migration rates， revealing great application potential in nonlinear optics. In this paper， the structural classification， synthesis strategies， and third-order nonlinear optical properties of graphynes are systematically reviewed， aiming to provide references for practical applications of graphynes in optical and optoelectronic fields.

Contents

1 Introduction

2 Structure of Graphyne

2.1 Structure of intrinsic Graphyne

2.2 Structure of Graphyne derivatives

3 Preparation of graphyne carbon materials

3.1 Preparation of graphdiynes

3.2 Preparation of graphynes

4 Applications of graphynes in third‑order nonlinear optics

4.1 Optical Kerr effect

4.2 Saturable absorption

4.3 Reverse saturable absorption

5 Conclusion and outlook

Key words： graphyne; graphyne derivatives; nonlinear optics; optoelectionic devices

Cite this article

Juemin Zhao , Bin Liang , Yaxing Tang , Jie Li , Zheng Xie . Synthesis of Graphynes and Their Applications in Third-Order Nonlinear Optics[J]. Progress in Chemistry, 2025 , 37(12) : 1917 -1930 . DOI: 10.7536/PC20250520

1 Introduction

With the continuous advancement of laser technology, pulsed lasers are widely used in fields such as material processing, signal detection, and optical communication. The damage caused by high-energy lasers to human ocular tissues and optical components has also become an increasingly pressing concern. Therefore, the development of advanced materials with efficient protective capabilities is of great significance[1-4]. In recent years, low-dimensional carbon materials such as carbon nanotubes and graphene have exhibited strong light-matter interaction, high nonlinear optical coefficients, and broad-bandwidth optical response characteristics, demonstrating promising application prospects in areas such as laser Q-switching, optical modulators, and optical limiting for laser protection[5]. However, the electronic structural limitations of traditional single-hybridized carbon networks (such as zero bandgap and limited carrier mobility) constrain their development in areas such as fast optical response, high optical damage thresholds, and dynamic tunability. Consequently, the development of novel carbon materials with multiple hybridization states and tunable structures has become a focal point of research.
Carbon exists in three distinct hybridization states: sp, sp2, and sp3. Different hybridization combinations give rise to carbon allotropes. Traditional carbon materials are predominantly composed of sp2 or sp3 hybridized carbon atoms[6-8], all of which exhibit locally planar structures. In contrast, the carbon–carbon triple bond formed by sp-hybridized carbon atoms adopts a linear structure, featuring high conjugation and structural advantages such as the absence of cis–trans isomerism. Therefore, developing carbon materials with mixed hybridization states involving sp-hybridized carbon atoms holds profound significance. In 1987, theoretical chemist Baughman et al.[9] predicted through theoretical calculations a structure in which adjacent six-membered carbon rings are linked via acetylene bonds, naming it graphyne (GY); subsequently, Haley et al.[10] proposed a structure in which adjacent six-membered rings are connected via butadiyne bonds, naming it graphdiyne (GDY). In 2010, Li Yuliang’s team[11] successfully synthesized, for the first time, a uniform, continuous, large-area graphdiyne film on copper foil. With breakthroughs in the synthetic methodologies for graphyne, research on the structure, properties, and applications of graphyne and its derivatives has deepened steadily. Its unique optical, electrical, thermal, and mechanical properties endow it with tremendous application potential across multiple fields[11-16]. In particular, due to its rapid nonlinear optical response, high third-order nonlinear refractive index, and excellent stability, graphyne is regarded as a promising candidate to surpass graphene as a nonlinear optical material[17-19]. This article reviews and discusses the structure, synthesis, and research progress of graphyne and its derivatives in the field of nonlinear optics, with the aim of providing a reference for the development of graphyne materials in this domain.

2 The structure of graphdiyne

2.1 Intrinsic graphdiyne structure

Graphyne is a carbon material that contains both sp and sp 2hybridized carbon atoms. As shown in Scheme 1, it can be classified into mono-yne, di-yne, and poly-yne (graphyne-n) based on the number of acetylene linkages; based on the number of carbon atoms in the carbon network, graphyne can also be divided into α-GYs, β-GYs, 6,6,12-GYs, γ-GYs (divided into GY and GDY), and others[20]. The percentages of acetylene linkages in α-GYs, β-GYs, GY, 6,6,12-GY, and GDY are 100%, 66.67%, 33.33%, 41.67%, and 50%, respectively[21]. With the exception of 6,6,12-GYs, which exhibit rectangular symmetry, most graphynes possess hexagonal symmetry similar to that of graphite (GR)[22-24].
图式1 （a）石墨烯；（b）GDY；（c）GY；（d）α‐GY；（e）β‐GY和（f）6，6，12‐GY的结构示意图[20]

Scheme 1 Schematic structures of （a） graphene； （b） GDY； （c） GY； （d） α-GY； （e） β-GY and （f） 6，6，12-GY[20]

Both GY and GDY are planar, wrinkled network structures, with layers stacked via van der Waals forces and π–π interactions, and a layer spacing d ≈ 0.33 nm. The presence of sp and sp2 hybridized carbon atoms gives graphdiyne molecules three distinct types of C–C bonding: in GY, the theoretical bond lengths for C(sp2)–C(sp), C(sp)≡C(sp), and C(sp 2) $\stackrel{\mathrm{ }\mathrm{ }\mathrm{ }\mathrm{ }}{=}$C(sp2) bonds are 0.141, 0.122, and 0.142 nm, respectively[25]; in GDY, the theoretical bond lengths for C(sp 2)–C(sp), C(sp)≡C(sp), and C(sp2) $\stackrel{\mathrm{ }\mathrm{ }\mathrm{ }\mathrm{ }}{=}$C(sp2) bonds are 0.140, 0.123, and 0.143 nm, respectively. The introduction of C≡C bonds endows graphdiyne with larger in-plane pores than graphene, and the pore size can be tuned by varying the number of acetylene linkages; furthermore, the introduction of C≡C bonds reduces the number of carbon atoms per unit area, resulting in a lower density for graphdiyne compared to graphene. Graphdiyne is, to date, the most stable sp–sp2 hybridized carbon material, with a calculated heat of formation of 12.4 kJ/mol[26–27], a binding energy of 7.78 eV/atom, an in-plane lattice constant of 0.944 nm, and it belongs to the class of high-binding-energy materials[28].
The unique molecular structure of graphdiyne endows it with a special electronic structure. Simulations of the electronic band structure of monolayer graphdiyne indicate that it exhibits a direct band gap at the M point of the hexagonal Brillouin zone and possesses “self-doping” characteristics[25], with a band gap of approximately 0.44–2.23 eV[29-31]. The exceptionally high carrier mobility and tunable band gap make graphdiyne an excellent semiconductor material[29-31]. Similar to graphene, graphdiyne nanoribbons have both zigzag and armchair edges (Fig. 1a). The armchair edges are flat and straight, while the zigzag edges are corrugated and can be further classified into alternating and symmetric zigzag configurations. As shown in Fig. 1b, the band gap of graphdiyne with these two edge configurations decreases as the width of the nanoribbon increases[32]. All zigzag graphdiyne is a magnetic semiconductor[33], whereas the armchair configuration is a non-magnetic semiconductor; however, the magnetic moment in armchair graphdiyne can be induced by single-atom vacancies[34].
图1 （a） 石墨炔扶手椅构型和锯齿形构型；（b） 扶手椅/锯齿形GDY/GY纳米带的带隙与宽度的关系曲线[32]

Fig.1 （a） Armchair and sawtooth configuration of GDY/GY； （b） band gap versus width curves for armchair/sawtooth GDY/GY nanoribbons[32]

2.2 Graphdiyne Derivative Structures

Based on a bottom-up synthesis strategy, researchers have used other arynes to replace hexaethynylbenzene, for example, by introducing heteroatoms or metal atoms between sp-hybridized acetylenic carbon atoms[35-38],or by using other aromatic rings (carbon-based aromatic rings or heterocycles containing N, B, S, Cl, etc.) to replace the benzene ring[37,39-45],to obtain structurally tunable graphdiyne derivatives (Scheme 2),greatly expanding the structural diversity of graphdiyne.
First, the derivatization of graphdiyne affects the material's chemical properties. After introducing functional groups or dopant elements, the number of surface active sites increases, and the chemical activity is enhanced. Cao et al.[46]incorporated anthraquinone-modified graphdiyne quantum dots (GDY-AQ QDs) as additives into perovskite films, using the anthraquinone functional groups to passivate trap states and slow down charge carrier recombination, thereby accelerating charge transport. Bai et al.[47]inserted functionalized triazine-based graphdiyne (Tz-GDY) nanospheres between the SnO2electron transport layer and the perovskite layer, passivating interfacial defects and improving power conversion efficiency.
Second, the derivatization of graphdiyne alters its electronic properties, enabling bandgap tuning, enhanced conductivity, and improved charge separation efficiency. Mohajeri et al.[48]used first-principles DFT calculations to systematically investigate the electronic structure and optical properties of modified GDY/GY. The results indicate that modification with —O, —CO, and —COOH functional groups induces a sharp change in the density of states near the Fermi level due to charge transfer between edge oxygen atoms and the carbon surface, thereby forming p/n-type semiconductor materials. Additionally, the absorption spectrum shifts toward the near-infrared region, effectively broadening its application scope in optoelectronic devices.
图式2 石墨炔衍生物结构类型

Scheme 2 Structures of graphyne derivatives

3 Synthesis of Graphdiyne Carbon Materials

Following the Li Yuliang team’s successful synthesis of large-area GDY films on copper foil surfaces, researchers have successively developed a series of dry and wet chemical methods for preparing graphdiyne, with the associated processes becoming increasingly mature.

3.1 Preparation of Graphdiyne

3.1.1 Dry chemistry method

Dry chemistry typically refers to chemical reactions conducted under solid- or gas-phase conditions. The dry chemistry methods for graphdiyne primarily include mechanical ball milling, explosion synthesis, and chemical vapor deposition.
In the mechanical ball milling method, mechanical force drives the breaking and recombination of chemical bonds in the precursors to synthesize graphdiyne. As shown in Fig. 2a, under the action of high mechanical force, the C—Si bond in trimethylsilylacetylene breaks and reacts with halogenated benzene in the presence of CuCl catalyst to form phenylethyne. The acetylene bonds then undergo self-coupling to form butadiyne bonds, yielding graphdiyne[49].Liu et al.[43] used 1,3,6,8-tetrabromopyrene and CaC2 to prepare pyrene-based graphdiyne derivatives via mechanical ball milling (Fig. 2b). This method is simple to operate, but process parameters need to be optimized to improve the quality and uniformity of graphdiyne.
图2 （a） 机械球磨法制备GDY [49]；（b） 机械球磨法制备芘基石墨炔[43]；（c） 爆炸法合成GDY示意图[50]

Fig.2 （a） Schematic diagram of GDY synthesized by mechanical ball milling[49]； （b） schematic diagram of pyrene-GDY synthesized by mechanical ball milling[43]； （c） schematic diagram of GDY synthesized by explosive method[50]

The explosion method involves using certain conditions (such as high temperature, high pressure, or plasma) to complete a reaction process akin to an “explosion” in an extremely short time. The energy released instantaneously during the explosion breaks the C≡C bonds in carbon sources (such as acetylene), generating highly reactive carbon radicals. The high-pressure environment enables these carbon radicals to rearrange via sp²/sp hybridization, ultimately forming graphdiyne. Zuo et al.[50]obtained GDY via ultrafast dehydrogenation and cross-coupling of hexaethynylbenzene at 120 °C. By controlling the reaction atmosphere, it is also possible to tune the structure from a three-dimensional framework to ultrafine nanochains (Fig. 2c). This method does not require metal catalysts or organic solvents, effectively avoiding extraneous contamination and is of great significance for producing high-purity GDY.
Chemical vapor deposition is a method for depositing high-quality thin films or nanomaterials on a substrate surface through gas-phase chemical reactions, and it is suitable for growing various materials such as graphene, boron nitride, and graphdiyne. Liu et al.[51]used hexaethynylbenzene as a precursor, triggering a self-coupling reaction of terminal alkynes on the Ag(111) substrate surface to successfully synthesize GDY and its derivative thin films (Fig. 3a). This method addresses the issue of low molecular mobility on Cu surfaces, thereby reducing the difficulty of carbon network growth on the substrate. Tran et al.[52]employed chemical vapor deposition to synthesize hydrogen-substituted (H-GDY) and fluorine-substituted (F-GDY) graphdiyne thin films on copper foil (Fig. 3b). HRTEM reveals (Fig. 3c) that the interlayer spacing of F-GDY is 0.34 nm, and AFM measurements indicate a film thickness of approximately 3.5 nm. The ultrathin nature endows F-GDY with the ability to regulate charge transport, making it suitable for use as an artificial synaptic sensor[53]. Qian et al.[54]developed a novel strategy for synthesizing GDY thin films via vapor-phase deposition on ZnO nanorod arrays (ZnO NR). The orientation-controlled ZnO NR can induce ordered growth of the thin film, ultimately forming large-area, transparent GDY films. TEM confirms the continuity of the film, with an interlayer spacing (0.365 nm) larger than that of graphene (Figs. 3d and e).
图3 （a） 化学气相沉积法制备GDY[51]；（b） 化学气相沉积法制备F-GDY/H-GDY[52]；（c） F-GDY的AFM和HRTEM图像[53]；（d） ZnO纳米阵列上沉积GDY薄膜示意图和（e） TEM和HRTEM图像[54]

Fig.3 （a） Schematic diagram of GDY synthesized by CVD method[51]； （b） schematic diagram of F-GDY/H-GDY synthesized by CVD method[52]； （c） AFM and HRTEM images of F-GDY[53]； （d） schematic diagram of GDY thin films deposited on ZnO nano-arrays； （e） TEM and HRTEM images of GDY thin films[54]

Therefore, dry chemistry methods offer advantages such as being environmentally friendly and easy to operate, but they are limited by complex equipment and difficulties in achieving structural uniformity and defect control.

3.1.2 Wet chemical method

To address the above-mentioned issues, wet chemical synthesis methods have been developed, in which coupling reactions between monomer molecules occur in solution to generate graphdiyne, offering advantages such as mild reaction conditions and easy controllability. Commonly used synthesis reactions include the Glaser coupling, Glaser-Hay coupling, and Eglinton coupling. Based on these reactions, specific methods such as the copper foil template method, interfacial synthesis, hydrothermal synthesis, and solution-phase van der Waals epitaxy have been developed.
The copper foil templating method is an important laboratory technique for preparing high-quality GDY films, yielding products with advantages such as high crystallinity, large-area uniformity, and controllable layer numbers. In the reaction, copper foil serves dual roles as both a catalyst and a growth substrate, reducing the activation energy and enabling the reaction to proceed under mild conditions. In 2010, Li et al.[11]successfully synthesized large-area multilayer GDY films on copper foil via the Glaser–Hay cross-coupling reaction of hexaethynylbenzene. SEM images revealed the continuity of the film, and HRTEM images clearly showed lattice fringes with a spacing of 4.1913 Å (Fig. 4a). Zhao et al.[55]prepared GDY nanowall structures on copper foil by adjusting the ratio of pyridine, N, N, N, N-tetramethylethylenediamine, and acetone in the mixed solvent, as well as the monomer concentration. Liu et al.[39]utilized the aggregation-induced emission properties of tetraphenylethylene units to synthesize fluorescent graphdiyne derivative (TPE-GDY) films (Fig. 4b). He et al.[56]synthesized methoxy-functionalized graphdiyne (OMe-GDY) on copper foil using 1,3,5-triethynyl-2,4,6-trimethoxybenzene, enhancing the material’s ion affinity and transport capability while reducing its susceptibility to oxidation (Fig. 4c). Kong et al.[57]synthesized triazole-substituted graphdiyne (TzlGDY) using a top-down approach, and HRTEM and SAED confirmed the in-plane periodicity and ABC-type stacking structure of multilayer TzlGDY (Fig. 4d).
图4 （a） 铜箔生长法合成GDY反应流程图及SEM和TEM图像[11]；（b） 四苯乙烯单元的荧光石墨炔衍生物薄膜的合成示意图[39]；（c） OMe-GDY合成路线图[56]；（d） TzlGDY合成路线、HRTEM和SAED图像[57]

Fig.4 （a） Synthetic route， SEM and TEM images of GDY based on copper foil method[11]； （b） schematic diagram of the synthesis of fluorescent TPE-GDY[39]； （c） synthetic route to OMe-GDY[56]； （d） synthetic route， HRTEM and SAED images of TzlGDY[57]

Interface synthesis is a strategy for synthesizing two-dimensional thin films at phase interfaces through molecular self-assembly or directed reactions, with the core advantage being that it does not require a metal substrate as a catalyst. Matsuoka et al.[58]successfully prepared crystalline graphdiyne films (Fig. 5a)under ambient conditions by exploiting the self-coupling reaction of hexaethynylbenzene (HEB) at liquid/liquid or gas/liquid interfaces. Compared to the liquid/liquid interface method, the gas/liquid interface method is superior and can be used to prepare high-quality few-layer GDY nanosheets (about 3.0 nm thick) with a regular hexagonal morphology. This method is also applicable to the preparation of nitrogen-doped GDYs (such as pyrazine-GDY and triazine-GDY). Xu et al.[59]achieved control over the topological structure of TPE-GDY by modifying the solvent in the liquid-liquid interface method (Fig. 5b). Yang et al.[60]successfully synthesized ultra-thin GDY nanowires (UNWs) with diameters less than 3 nm at room temperature using the liquid-liquid interface, which exhibit high crystallinity, a wide bandgap (about 1.82 eV), and strong photoelectric properties (Fig. 5c). Yin et al.[61]developed a solid/liquid interface synthesis method driven by a microwave-induced temperature gradient, using HEB as the precursor, and successfully prepared GDY films with an average thickness of less than 2 nm (Fig. 5d). Compared with the copper foil method, the interface method is not limited by substrate size and is suitable for large-area synthesis; however, the crystallinity of the product is inferior to that achieved by the template method.
图5 （a） GDY液-液/气-液界面法示意图及电镜表征结果[58]；（b） 两种拓扑结构TPE-GDY的液/液界面法示意图[59]；（c） GDY纳米线合成示意图及电镜表征结果[60]；（d） 固/液界面温度梯度驱动合成GDY[61]

Fig.5 （a） Schematic diagram and electron microscope characterization of GDY by liquid-liquid/gas-liquid interfacial method[58]； （b） schematic diagram of liquid/liquid interface method for two topologies of TPE-GDY[59]； （c） schematic diagram and electron microscopy characterization of GDY nanowires[60]； （d） temperature gradient-driven synthesis of GDY at solid/liquid interfaces[61]

The van der Waals epitaxy strategy leverages van der Waals forces to achieve controlled growth of two-dimensional materials on specific substrates (such as graphene). Gao et al.[62]reported a method for synthesizing ultrathin single-crystal GDY films on graphene surfaces using HEB as a monomer via a liquid-phase van der Waals epitaxy strategy (Figure 6).The resulting product has a size of 50 μm and a thickness of only 1.74 nm. This method significantly reduces lattice-matching requirements and can yield high-quality films; however, it faces the challenge of difficulty in separating the film from the graphene.
图6 液相范德华外延合成GDY[62]

Fig.6 Liquid-phase van der Waals epitaxial synthesis of GDY[62]

In summary, wet chemical methods enable the precise construction of GDY two-dimensional networks through molecular self-assembly and controlled coupling in solution, offering the advantage of structural tunability. However, solvent toxicity, sluggish reaction kinetics, and insufficient defect control hinder their large-scale application. In the future, efforts should focus on developing green solvent systems, optimizing reaction pathways, and refining defect engineering to produce high-quality, high-yield GDY materials.

3.2 Preparation of Graphene Monacetylene

Graphdiyne can be obtained through the self-coupling of hexa-ynes, whereas graphyne, with its benzene rings connected by acetylene linkages, requires cross-coupling of monomers and is subject to steric hindrance, making its synthesis more challenging.

3.2.1 Dry chemistry method

Dry chemical methods for synthesizing graphyne mainly include ball milling and chemical vapor deposition. Li et al.[63-64]used CaC2as an sp-hybridized carbon source and 1,3,5-tribromobenzene or hexabromobenzene as an sp 2-hybridized carbon source, and carried out cross-coupling reactions under vacuum via ball milling to obtain hydrogen-substituted graphyne (H-GY, light yellow powder, Fig. 7a)and graphyne (black powder, Fig. 7b). The peaks at 1928 and 2221 cm-1in the Raman spectrum shown in Fig. 7cconfirmed the structure of GY. Yang et al.[65]used hexabromobenzene and calcium carbide as raw materials and prepared γ-GY via ball milling, with its structure verified by Raman spectroscopy and X-ray photoelectron spectroscopy. Choi et al.[66]developed a low-temperature CVD method that uses 1,3,5-tribromo-2,4,6-triethynylbenzene (TBTEB) to undergo cross-coupling on a copper foil surface, enabling controlled large-area growth of GY without the need for a co-catalyst (Fig. 7d). The SAED pattern reveals its (220) and (222) crystal planes (interplanar spacing 0.25 nm, interlayer spacing 0.39 nm) and ABC stacking structure (Fig. 7e).
图7 （a） 机械球磨法合成H-GY[63]；（b） 机械球磨法合成GY[64]；（c） GY的拉曼光谱和粉末照片[64]；（d） CVD法合成GY反应示意图及（e）HRTEM图谱（插图为SAED图谱）[66]

Fig.7 （a） Synthesis of H-GY by mechanical ball milling[63]； （b） synthesis of GY by mechanical ball milling[64]； （c） Raman spectrum and powder photographs of GY[64]； （d） schematic illustration of the synthesis of GY by CVD method and （e） HRTEM images （inset are SAED images）[66]

3.2.2 Wet chemical method

Wet chemical methods mainly include the interface method, the one-pot method, and the ultrasonic method. Song et al.[67]proposed a general interface synthesis method for graphyne monoyne derivatives, in which two monomer precursors are dissolved separately in two immiscible solvents, successfully preparing three types of graphyne monoyne derivatives: H-GY, methyl-substituted graphyne (Me-GY), and fluorine-substituted graphyne (F-GY). As shown in Figure 8a,using H-GY as an example, two different monomers, 1,3,5-triynylbenzene (TEB) and 1,3,5-tribromobenzene (TBB), are dissolved in the organic phase and aqueous phase, respectively, and a cross-coupling reaction occurs at the interface to produce H-GY. Yang et al.[68]improved this method by slowly adding TEB dropwise into a triethylamine solution containing TBB within the same phase, thereby preparing a porous H-GY. Liang et al.[69]used 1,3,5-tris(tribromomethyl)benzene (tTBP) and carried out dehalogenative coupling on a copper foil surface under ultra-high vacuum, synthesizing H-GY with a micrometer-scale porous network structure (Figure 8b)).
图8 （a） 界面法合成石墨单炔衍生物示意图[67]；（b）脱卤均偶联反应合成H-GY示意图[69]

Fig.8 （a） Schematic diagram of the synthesis of GY derivatives by interfacial method[67]； （b） schematic representation of the synthesis of H-GY by dehalogenation homocoupling reaction[69]

Desyatkin et al.[70]used Pd(PPh3)4 and CuI as catalysts, with TBTEB as the starting material. By varying the reaction conditions, they prepared graphyne monoyne ranging from amorphous and nanocrystalline to large-sized crystalline forms via a one-pot method, thereby achieving control over the aggregation state structure of the product (Fig. 9a). Barua et al.[71]prepared GY with a wrinkled nanosheet morphology from hexabromobenzene and CaC2 via a one-pot method (Fig. 9b). He et al.[72]used hexabromobenzene and dicarboxyacetylene, employing Pd-catalyzed decarboxylative coupling in a one-pot process to synthesize graphyne monoyne. Song et al.[73]used 1,3,5-trifluoro-2,4,6-tris[2-(trimethylsilyl)ethynyl]benzene (TFTEB) as a precursor and employed a metal-free nucleophilic aromatic substitution (SNAr) one-pot reaction to synthesize gram-scale GY and its derivatives. This method avoids metal residues, significantly enhances the optical stability of the material, and lays the foundation for the scalable fabrication of NLO devices (Fig. 9c).
图9 （a） 以TBTEB为单体合成GY示意图[70]；（b）以六溴苯和电石反应合成GY示意图[71]；（c） 一锅法交叉偶联反应合成GY衍生物示意图[73]

Fig.9 Schematic of the synthesis of GY using （a） TBTEB monomer[70]； （b） HEB and CaC2 monomers[71]； （c） schematic diagram of the synthesis of GY derivatives[73]

Ultrasonic methods utilize the cavitation effect (the collapse of bubbles generating high temperature and pressure) to drive the chemical process of synthesizing GY. Ding et al.[74]used ultrasonic treatment of a mixture of CaC2and hexabromobenzene in anhydrous ethanol to synthesize GY in high yield (Figure 10). This process is intermediate-free, green, and safe.
图10 超声法合成GY示意图[74]

Fig.10 Schematic diagram of GY synthesized by ultrasonic method[74]

In summary, compared to dry chemistry methods, wet chemistry methods for synthesizing graphdiyne allow for precise control over the preparation process, yielding relatively pure products with diverse nanostructures, thereby greatly advancing the development of application research on graphdiyne. However, due to the low coupling efficiency of terminal alkynyl groups in precursors such as hexaethynylbenzene and unavoidable side reactions like oxidative addition during the reaction, it remains challenging to control the thickness and defects of the resulting graphdiyne. As a result, the perfect theoretical structure has yet to be achieved, and further development of additional graphdiyne synthesis methods is still needed.

4 Applications of Graphdiyne in the Field of Third-Order Nonlinear Optics

Third-order nonlinear optical (NLO) effects refer to the third-order susceptibility generated by a material in response to intense light illumination. Common third-order NLO effects include self-focusing and self-defocusing[75],the optical Kerr effect[76],two-photon absorption[77],saturable absorption[18],and reverse saturable absorption[78],among others. These effects hold great promise for applications in fields such as optical communications, ultrafast optics, and imaging technologies[79]. A large conjugated system is one of the key factors responsible for generating third-order NLO effects; consequently, conjugated molecules with delocalized π-electron systems have become a research hotspot for third-order NLO materials[80-81]. As early as 1997, Haley et al.[10] predicted that graphdiyne possesses a high nonlinear optical susceptibility, and in 2006 they experimentally confirmed that the graphdiyne monomer (diphenylbutadiyne, DPB) is an excellent two-photon absorbing material[82].

4.1 Optical Kerr Effect

The Kerr effect refers to the phenomenon where the refractive index of a material along a particular polarization direction changes under the influence of a polarized electric field (light field). Materials with high nonlinear optical refractive indices hold great potential for use in optical devices. Wu et al.[83]designed a novel photonic diode using a GDY/SnS2composite structure, as shown in Fig. 11a. When the sample is illuminated by a laser, unidirectional diffraction ring excitation is achieved during forward propagation (GDY/SnS2), indicating that graphdiyne possesses a very high nonlinear refractive index (≈10-5 cm2/W), making it suitable for use in photonic devices such as detectors and optical information converters. Dong et al.[17]experimentally investigated the third-order nonlinear optical response of GDY dispersed in several common alcohol solvents using femtosecond closed-aperture Z-scan techniques. As shown in Fig. 11b, graphdiyne exhibits a pronounced self-defocusing effect, and GDY dispersed in 1-PrOH solution displays the highest NLO refractive index (1.1×10-8 cm2/W), which is about one order of magnitude higher than that of most two-dimensional materials, demonstrating significant potential in next-generation NLO devices based on the Kerr effect.
图11 （a） GDY/SnS2光子二极管示意图[83]；（b） GDY在不同溶剂中归一化透射率的Z扫描曲线和理论拟合[17]

Fig.11 （a） Schematic diagram of non-reciprocal light propagation phenomena in GDY/SnS2 photodiode[83]； （b） experimental results and theoretical fits of short aperture Z-scan curves of normalized transmittance of GDY dispersions in different solvents[17]

4.2 O saturated absorption

Saturated absorption refers to the phenomenon where, as light intensity increases upon incidence into a medium, absorption gradually saturates, allowing light exceeding the saturation value to pass through the medium. Saturable absorber (SA) materials can be used in photonic devices such as pulsed lasers, optical modulators, and optical switches.

4.2.1 Pulsed lasers

Optical fiber lasers and solid-state lasers are two widely used types of pulsed lasers, extensively applied in industrial processing, optical fiber communication, and medical and military fields[84-87].Graphdiyne exhibits good application potential in both types of lasers.
In the field of fiber lasers, in 2019, Zhao et al.[88]used graphdiyne as a saturable absorber (SA) to realize a femtosecond mode-locked fiber laser, achieving a modulation depth of 11% and a saturation intensity of 60.1 MW/cm2, and generating mode-locked pulses with a central wavelength of 1564.70 nm and a pulse width of 734 fs (Fig. 12a–c). Compared with other two-dimensional materials, lasers based on GDY SAs exhibit broader spectral bandwidth and shorter pulse durations. Guo et al.[89]explored the application of graphdiyne in mid-infrared ultrafast photonics; the samples demonstrated a large nonlinear absorption coefficient (β > 10-1 cm·GW-1) and a low saturation intensity (Is < 10 GW·cm-2). Using it as an SA, they successfully constructed 1.5 µm (erbium-doped) and 2 µm (thulium-doped) mode-locked fiber lasers, generating trains of ultrashort pulses (Fig. 12d, e). Nie et al.[90]investigated the nonlinear optical response of GDY-PMMA thin films in the near-infrared region; hybrid mode-locked fiber lasers based on these films achieved bound-state soliton pulses with a temporal spacing of 13.31 ps and a spectral modulation period of 0.58 nm (Fig. 12f). The excellent stability (> 4.5 h) and near-infrared NLO performance of these materials highlight their potential for use in ultrafast lasers. Tu et al.[91]synthesized GDY nanosheets using a copper foil templating method and used them as an SA to fabricate a 2.8 µm fiber pulsed laser. The laser successfully achieved stable Q-switched pulse output, exhibiting advantages such as narrow pulse width (570 ns), high signal-to-noise ratio (37 dB), and high repetition rate (101 kHz), and realized a tunable wavelength range of 2779–2835 nm (Fig. 12g, h).
图12 （a） GDY非线性传输和拟合曲线；GDY锁模光纤激光器的（b）输出脉冲串和（c）光谱学[88]；GDY SA光纤器件在（d）1.5 µm，（e） 2 µm处的非线性能量依赖传输曲线[89]；（f） GDY-PMMA混合锁模光纤激光器的自相关轨迹[90]；（g， h） GDY SA光纤激光器的输出频谱及可调谐脉冲激光器的输出光谱[91]

Fig.12 （a） Nonlinear transmission and fitting curves of GDY； （b） output pulse train and （c） spectroscopy of a GDY based mode-locked fiber laser[88]； nonlinear energy-dependent transmission curves of a GDY SA fiber device （d） at 1.5 µm； （e） at 2 µm[89]； （f） autocorrelation trajectories of a GDY-PMMA hybrid mode-locked fiber laser[90]； （g， h） output spectrum， single-pulse curves and tunable-pulse laser output spectra of a GDY output spectra of SA fiber laser and tunable pulse laser[91]

In addition to fiber lasers, graphdiyne materials also exhibit excellent performance in solid-state laser applications. Zhang et al.[92]studied the NLO properties of GY-PMMA thin films and used them as an SA in a Q-switched solid-state laser at a wavelength of 1.06 µm, achieving a minimum pulse width of 241 ns, a maximum pulse energy of 0.76 µJ, and a peak power of 3.15 W (Fig. 13a, b). The pulse width was superior to that of graphene-based SA lasers, indicating that GY is an excellent near-infrared laser material. Zong et al.[93]prepared two-dimensional GDY films via a liquid–liquid interface reaction. A passively Q-switched laser based on this film achieved a minimum pulse width of 593.6 ns at 2.8 µm, demonstrating that GDY is a potential mid-infrared saturable absorber and an excellent broadband nonlinear optical modulator material. Xu et al.[37]prepared mercury-centered graphdiyne nanosheets HgL1 and HgL2 using an interfacial synthesis method. By leveraging the charge-transfer effect between the Hg d orbitals and the acetylene π system, they enhanced the third-order nonlinear polarization susceptibility. In a 2.8 µm mid-infrared pulsed laser, compared with HgL1, which uses triphenylamine as a building block, HgL2, which uses benzene rings as building blocks, exhibited a higher single-pulse energy (0.541 µJ) and peak power (1.23 W), outperforming traditional two-dimensional materials (Fig. 13c, d).
图13 （a） GY SA的CW和Q开关激光脉冲的光谱；（b）GY SA的自相关轨迹[92]；（c） HgL1为SA的Q开关单脉冲能量和峰值功率；（d） HgL2为SA的Q开关单脉冲能量和峰值功率[37]

Fig.13 （a） Spectra of CW and Q-switched laser pulses of GY SA； （b） autocorrelation trajectory of GY SA[92]； （c） HgL1 is the Q-switched single pulse energy and peak power of the saturable absorber； （d） HgL2 is the Q-switched single pulse energy and peak power of the saturable absorber[37]

4.2.2 All-Optical Modulation

All-optical modulation is a phenomenon in which light is controlled by light through the nonlinear optical effects of materials, and it finds extensive applications in fields such as optical communications. Zhang et al.[92]fabricated a GY-based optical switch that exhibits excellent on/off stability and fast response, revealing its ultrafast saturable absorption and all-optical switching performance in the near-infrared region (Fig. 14a–c). Wu et al.[94]synthesized graphene diacetylene oxide (GDYO) nanosheets (Fig. 14d), which retain the nonlinear properties of GDY while exhibiting improved dispersion stability. Using GDYO NSs as an intermediate modulating medium, spatial self-phase modulation (SSPM) (Fig. 14e) and cross-phase modulation (SXPM) were generated, successfully achieving all-optical switching from high to low levels (Fig. 14f).
图14 （a） GY光学开关设备示意图；（b） GY光学开关的长期输出波形；（c） 信号输入与GY光学开关结果的比较图[92]；（d） GDYO的化学结构式；（e） 基于SSPM的GDYO NS的非线性行为；（f） 基于SXPM的GDYO NS的非线性行为[94]

Fig.14 （a） Schematic of the GY optical switch； （b） long-term output waveform of the GY optical switch； （c） plot comparing the signal input with the GY optical switching results[92]； （d） synthesis of GDYO； （e） Nonlinear behavior of the GDYO NS based on the SSPM； and （f） nonlinear behavior of the GDYO NS based on the SXPM[94]

4.3 Anti-saturation absorption

In reverse saturable absorption (RSA), the absorption cross section of the excited state of a medium is larger than that of the ground state, resulting in an increase in the absorption coefficient with increasing light intensity. Zhang et al.[19]used Z-scan techniques to investigate the reverse saturable absorption effect of GDY nanosheets in the ultraviolet and infrared spectral regions (Figure 15).When the energy density exceeds a threshold, GDY exhibits optical limiting behavior, characterized by a low excitation threshold and a large modulation depth in the ultraviolet region. At the same time, since the excitation intensity of a ps laser is much lower than that of an ns laser, GDY achieves a greater modulation depth under ps excitation, highlighting its potential as an optical limiting material.
图15 GDY纳米片在纳秒（a）532 nm和（b）1064 nm激发波长下的开孔Z扫描曲线；GDY纳米片在皮秒（c） 532 nm和（d）1064 nm激发波长下的开孔Z扫描曲线[19]

Fig.15 Open-aperture Z-scan curves of GDY nanosheets at （a） 532 and （b） 1064 nm upon nanosecond excitation； （c） 532 and （d） 1064 nm upon picosecond excitation[19]

In addition to intrinsic graphdiyne materials, graphdiyne derivatives constructed through molecular structure design, heteroatom doping (such as B/N, S/P), and heterostructure engineering also exhibit excellent properties in the field of nonlinear optics[37,95]. For example, compared to phenyl units, TPE-GDY, which uses tetraethynylphenylethylene as a building block, can suppress rotation-induced excitation energy dissipation, enhance π-electron conjugation, and improve the material’s third-order nonlinear optical performance[59]. By introducing boron/nitrogen atoms to tune the electronic structure of GDY, the bandgap of B/N-GDY can be tuned over a wide range from 0.5 to 2.2 eV, and its nonlinear absorption coefficient is enhanced to 10-1 cm/GW, demonstrating application potential in broadband optical limiting and protection from ultraviolet to infrared wavelengths. By combining graphdiyne and porphyrin via π–π interactions to construct the composite material GDY/Por, or by synthesizing the hybrid material Por@GDY through alkyne self-coupling between hexaethynylbenzene and porphyrin, both materials integrate the structural advantages of graphdiyne and porphyrin, featuring efficient charge transfer pathways and a large number of active sites, and are predicted to exhibit outstanding reverse saturable absorption properties[96]. Graphdiyne/graphene van der Waals heterostructures obtained via liquid-phase epitaxial growth exhibit strong broadband absorption in the wavelength range of 400–1500 nm, with a modulation depth ΔR of 30.4%, showing promising application prospects in the field of third-order nonlinear optics[97].

5 Conclusion and Outlook

In summary, as a novel two-dimensional carbon allotrope, graphyne, with its unique sp-sp² hybridization structure and tunable electronic properties, exhibits a high nonlinear refractive index, a large nonlinear absorption coefficient, low saturation intensity, and an ultrafast relaxation time, thereby offering new opportunities for the development of nonlinear optical materials and devices. Currently, the controllable synthesis, efficient purification, and scale-up of graphyne remain the core bottlenecks limiting its practical applications. Future research directions include developing copper-free catalytic alkynyl coupling systems, introducing sterically hindered groups to suppress non-selective coupling, reducing metal contamination, and enhancing product purity. In terms of structural regulation, strategies such as introducing π-conjugated molecules to modulate the sp/sp² hybridization ratio, incorporating defects or dopant atoms to create intermediate energy levels within the band gap, and constructing composite systems with other materials can be employed to tune the band gap of graphyne and optimize its nonlinear optical response. As research continues to advance, innovative synthesis routes, controlled modulation of material structural properties, and expanded applications will continue to drive the development of graphyne science.

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