阅读说明：本技术 一种二维金属有机炔纳米片及其制备方法和应用 (Two-dimensional metal organic alkyne nanosheet and preparation method and application thereof ) 是由 黄维扬 许林利 张红阳 于 2019-11-25 设计创作，主要内容包括：本发明提供了一种二维金属有机炔纳米片,所述二维金属有机炔纳米片的结构通式如下：其中,所述R为至少含有三个炔基及一个苯环的有机炔配体；M为含有二价及以上金属离子的金属配体；3≤m≤6；n≥3；所述有机炔配体中的炔基都能与金属配体反应,发生键合连接,形成稳定的交联的网状结构,进而形成具有规律重复的具有交联结构的平面状二维金属有机炔纳米片。由于添加的有机炔配体结构单一、与特定的金属配体键合反应位点固定,形成的网状结构厚度大小可控,因此制备得到的平面状二维金属有机炔纳米片厚度可控,性能稳定,有利于后续使用。(The invention provides a two-dimensional metal organic alkyne nanosheet, which has the following structural general formula: wherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent or higher metal ions; m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3; alkynes in the organoalkyne ligandsThe group can react with a metal ligand to generate bonding connection to form a stable cross-linked network structure, and further form a regularly repeated planar two-dimensional metal organic alkyne nanosheet with a cross-linked structure. The added organic alkyne ligand has a single structure, is fixed with a specific metal ligand bonding reaction site, and forms a network structure with controllable thickness, so that the prepared planar two-dimensional metal organic alkyne nanosheet has controllable thickness and stable performance, and is beneficial to subsequent use.)

1. A two-dimensional metal organic alkyne nanosheet is characterized in that the structural general formula of the two-dimensional metal organic alkyne nanosheet is as follows:

wherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent or higher metal ions; m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3.

2. Two-dimensional metal-organic alkyne nanoplatelets according to claim 1 wherein R comprises a porphyrin group.

3. A two-dimensional metal organic alkyne nanosheet of any one of claims 1 to 2, wherein in the structural formula, the molar ratio of the organic alkyne ligand to the metal ligand is 1: (1.2-2.2).

4. A two-dimensional metalorganic alkyne nanosheet of any one of claims 1 to 2, wherein R is selected from any one of 1,3, 5-triacetylbenzene, tris (4-ethynylbenzene) amine, 4 "-divinyl-5 '- (4-ethynylphenyl) -1, 1', 1" -triphenyl, (9E,19E) -5,10,15, 20-tetrakis (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin, and transition metal- (9E,19E) -5,10,15, 20-tetrakis (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin except for an organic ligand formed by an alkyne-terminal H atom.

5. A two-dimensional metal organic alkyne nanosheet of any one of claims 1 to 2, wherein M is selected from any one of a mercury metal ligand, a platinum metal ligand, a nickel metal ligand, an iron metal ligand, a cobalt metal ligand, a zinc metal ligand and a copper metal ligand.

6. A two-dimensional metal organic alkyne nanosheet as recited in any one of claims 1 to 2, wherein the two-dimensional metal organic alkyne nanosheet has a thickness of 50 to 1200 nm.

7. A preparation method of a two-dimensional metal organic alkyne nanosheet is characterized by comprising the following steps:

providing a substrate, and placing the substrate in a container;

preparing a mixed solution of an organic alkyne ligand, a metal compound and a catalyst, adding the mixed solution into the container, standing for reaction, and growing a two-dimensional metal organic alkyne nanosheet on the surface of the substrate;

wherein the organic alkyne ligand at least contains three alkynyl groups and a benzene ring; the metal compound contains divalent and higher metal ions; the structural general formula of the two-dimensional metal organic alkyne nanosheet is as follows:

wherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent or higher metal ions; m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3.

8. A method of making two-dimensional metal-organic alkyne nanoplatelets as recited in claim 7 wherein the molar ratio of the organic alkyne ligand, the metal compound, the catalyst is 100: (120-220): (0.01-2).

9. A preparation method of a two-dimensional metal organic alkyne nanosheet according to any one of claims 7 to 8, wherein the catalyst is selected from at least one of cuprous iodide, triethylamine, and diisopropylamine; and/or the presence of a gas in the gas,

the substrate material is selected from any one of metal, silicon wafer, quartz wafer, glass wafer, silicon dioxide, silicon carbide, sapphire, aluminum arsenide and calcium fluoride.

10. A saturable absorber device, wherein the saturable absorber device is made of the two-dimensional metal organic alkyne nanosheet of any one of claims 1 to 6 or the two-dimensional metal organic alkyne nanosheet prepared by the preparation method of the two-dimensional metal organic alkyne nanosheet of any one of claims 7 to 9.

Technical Field

The invention relates to the field of nonlinear optical materials, in particular to a two-dimensional metal organic alkyne nanosheet and a preparation method and application thereof.

Background

In recent decades, two-dimensional nanomaterials represented by graphene have become the focus of attention of researchers. In the aspect of optics, the two-dimensional nano material and the bulk material have the characteristics of wide absorption wavelength, short response time, low optical loss and the like, so that the two-dimensional nano material has excellent saturable absorption performance and has wide application prospect in the field of laser modulation. Meanwhile, with the continuous development of short pulse laser technology in recent years, the all-solid-state laser passive Q-switching and mode-locking technology based on saturable absorbers is becoming an important means for studying the micro-world, information communication and material fine processing.

The performance of saturable absorbing materials as Q-switching or mode-locking elements has a very important influence on the laser output characteristics of lasers. The novel saturable absorption two-dimensional nano material with short response time, wide absorption wavelength, low optical loss and strong nonlinear effect continuously appears, is widely concerned and valued by people and becomes a research hotspot of passive Q-switching and mode-locking technologies. Graphene and derivatives thereof, black phosphorus, and two-dimensional transition metal sulfides (e.g., MoS)₂、WS₂And ReS₂Etc.) have been confirmed to have excellent passive Q-switching or mode-locking propertiesHowever, these two-dimensional nanomaterials are obtained by peeling from bulk materials, the thickness, size and structural order of the nanomaterials are difficult to control, and the problems of few varieties, uneven structures and the like further affect the universality of the nanomaterials and the stability of the properties during the use process.

Disclosure of Invention

The invention aims to provide a two-dimensional metal organic alkyne nanosheet and a preparation method and application thereof, and aims to solve the problems that the two-dimensional nanosheet in the prior art is uneven in structure and uncontrollable in thickness.

In order to achieve the purpose, the invention adopts the following technical scheme:

a two-dimensional metal organic alkyne nanosheet is provided, and the structural general formula of the two-dimensional metal organic alkyne nanosheet is as follows:

wherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent or higher metal ions; m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3.

And a preparation method of the two-dimensional metal organic alkyne nanosheet, which comprises the following steps:

providing a substrate, and placing the substrate in a container;

preparing a mixed solution of an organic alkyne ligand, a metal compound and a catalyst, adding the mixed solution into the container, standing for reaction, and growing a two-dimensional metal organic alkyne nanosheet on the surface of the substrate;

wherein the organic alkyne ligand at least contains three alkynyl groups and a benzene ring; the metal compound contains divalent and higher metal ions; the structural general formula of the two-dimensional metal organic alkyne nanosheet is as follows:

wherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent or higher metal ions; m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3.

And the saturated absorption device is made of the two-dimensional metal organic alkyne nanosheet or the two-dimensional metal organic alkyne nanosheet prepared by the preparation method of the two-dimensional metal organic alkyne nanosheet.

Compared with the prior art, the two-dimensional metal organic alkyne nanosheet provided by the invention has the structural general formulaWherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent and above metal ions, and M is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3; because one alkynyl can only react to generate small molecules, three alkynyls can only generate linear polymers, and the R at least contains three alkynyls, the reaction product forms a substance with a net structure; the organic alkyne ligand R at least contains three alkynyl groups and one benzene ring, the M is a metal ligand containing divalent and above metal ions, in the reaction process, the metal ligand reacts with the organic alkyne ligand, the alkynyl groups in the organic alkyne ligand can react with the metal ligand to be bonded and connected, a stable cross-linked network structure is formed, and the regularly repeated planar two-dimensional metal organic alkyne nanosheet with the cross-linked structure is further formed. The added organic alkyne ligand has a single structure, is fixed with a specific metal ligand bonding reaction site, and forms a network structure with controllable thickness, so that the prepared planar two-dimensional metal organic alkyne nanosheet has controllable thickness and stable performance, and is beneficial to subsequent use.

The preparation method of the two-dimensional metal organic alkyne nanosheet provided by the invention has the advantages that the raw materials are simple and easy to obtain, the method is simple, the two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate material can be prepared only by mixing the raw materials and placing the raw materials on the substrate material for reaction, the preparation method is simple, convenient and fast, and the mass production can be realized.

According to the saturable absorption device provided by the invention, the two-dimensional metal organic alkyne nanosheet or the two-dimensional metal organic alkyne nanosheet prepared by the preparation method of the two-dimensional metal organic alkyne nanosheet is used as a material of the saturable absorption device, and the two-dimensional metal organic alkyne nanosheet is controllable and uniform in thickness, controllable in microstructure, strong in optical saturable absorption performance and simple in preparation method, so that the laser regulation performance for the saturable absorption device is stable and excellent.

Drawings

Fig. 1 is a structure for preparing a two-dimensional metal organic alkyne nanosheet organic alkyne ligand according to an embodiment of the present invention.

Fig. 2 is a saturated nonlinear absorption theoretical fitting curve of a two-dimensional mercury organic nanosheet obtained by performing laser Z-scanning on a two-dimensional metal organic alkyne nanosheet prepared in embodiments 1 and 3 of the present invention.

FIG. 3 shows the output power of the two-dimensional metal organic alkyne nanosheet passively Q-switched (Nd: YAG) prepared in example 1 of the present invention.

FIG. 4 shows the single pulse energy and peak power of the two-dimensional metal organic alkyne nanosheet passively Q-switched (Nd: YAG) prepared in example 1 of the present invention.

FIG. 5 shows the pulse width and the repetition frequency of the two-dimensional metal organic alkyne nanosheet passively Q-switched (Nd: YAG) prepared in example 1 of the present invention.

FIG. 6 is a pulse sequence and a single pulse diagram of a two-dimensional metal organic alkyne nanosheet passively Q-switched (Nd: YAG) prepared in example 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.

In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

The embodiment of the invention provides a two-dimensional metal organic alkyne nanosheet, which has the following structural general formula:

specifically, in the structural general formula, m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3.

Specifically, R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; because one alkynyl can only react to generate small molecules, two alkynyls can only generate linear polymers, and the R at least contains three alkynyls, the reaction product forms a substance with a net structure; and meanwhile, the organic alkyne ligand R at least contains three alkynyl groups and one benzene ring, the two-dimensional nanosheet obtained by the reaction is further ensured to be a planar two-dimensional nanosheet by adding the benzene ring, and a relatively planar polymer can be obtained by adopting the organic alkyne ligand R at least containing three alkynyl groups and one benzene ring to carry out the reaction. If the selected organic alkyne ligands are less than three alkynyl groups, substances with a net structure are not easy to form; if no benzene ring is added, a three-dimensional structure is easily formed, and therefore, the reaction of the organic alkyne ligand containing at least three alkynyl groups and one benzene ring is favorable for forming a planar two-dimensional nanosheet.

Preferably, the structure of the two-dimensional metal organic alkyne nanosheet further comprises porphyrin. Porphyrins are a class of macromolecular heterocyclic compounds formed by the interconnection of the α -carbon atoms of four pyrrolyl subunits via methine bridges (═ CH-). Porphyrin is a planar structure, and the porphyrin group is added, so that the prepared product is further planar and cannot form a three-dimensional structure.

Preferably, the organic alkyne ligand comprises any one of 1,3, 5-triacetylbenzene (formula I in figure 1), tris (4-ethynylbenzene) amine (formula II in figure 1), 4 ' -divinyl-5 ' - (4-ethynylphenyl) -1,1 ', 3 ', 1 ' -triphenyl (formula III in figure 1), (9E,19E) -5,10,15, 20-tetrakis (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin (formula IV in figure 1), transition metal- (9E,19E) -5,10,15, 20-tetrakis (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin (formula V in figure 1) with the alkyne H atom removed from the base end, wherein, the transition metal in the transition metal- (9E,19E) -5,10,15, 20-tetra (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin is selected from any one of nickel, iron, cobalt, zinc, copper and platinum.

Specifically, in the structural general formula of the two-dimensional metal organic alkyne nanosheet, M is a metal ligand containing divalent or more metal ions, and a metal element with more than divalent can chemically react with alkynyl groups in two organic alkyne ligands, so that the organic alkyne ligands and the metal ligands are crosslinked through bonding reaction to form the two-dimensional metal organic alkyne nanosheet which has a crosslinked network structure and regularly repeated structures. Preferably, M is selected from any one of mercury metal ligand, platinum metal ligand, nickel metal ligand, iron metal ligand, cobalt metal ligand, zinc metal ligand and copper metal ligand.

Preferably, in the structural general formula of the two-dimensional metal organic alkyne nanosheet, the molar ratio of the organic alkyne ligand to the metal ligand is 1: (1.2-2.2). The addition amount of the organic alkyne ligand and the metal element is controlled, and the finally formed two-dimensional metal organic alkyne nanosheet is uniform in structure, controllable and uniform in thickness, stable in performance and beneficial to subsequent use.

Preferably, the thickness of the two-dimensional metal organic alkyne nanosheet is 50-1200 nm. The two-dimensional metal organic alkyne nanosheet with the thickness can have a controllable microstructure, ensures strong optical saturation absorption performance and stable and excellent performance, and can be used for laser regulation and control of a saturation absorption device. In a preferred embodiment of the invention, the thickness of the two-dimensional metal organic alkyne nanosheet is 300-400 nm.

The structural general formula of the two-dimensional metal organic alkyne nanosheet provided by the invention isWherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent and above metal ions, and M is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3; because one alkynyl can only react to generate small molecules, two alkynyls can only generate linear polymers, and the R at least contains three alkynyls, the reaction product forms a substance with a net structure; the organic alkyne ligand R at least contains three alkynyl groups and one benzene ring, the M is a metal ligand containing divalent and above metal ions, in the reaction process, the metal ligand reacts with the organic alkyne ligand, each alkynyl group in the organic alkyne ligand can react with the metal ligand to generate bonding connection, a stable cross-linked reticular structure is formed, and the planar two-dimensional metal organic alkyne nanosheet with a regularly repeated cross-linked structure is further formed. The added organic alkyne ligand has a single structure, is fixed with a specific metal ligand bonding reaction site, and forms a network structure with controllable thickness, so that the prepared planar two-dimensional metal organic alkyne nanosheet has controllable thickness and stable performance, and is beneficial to subsequent use.

The two-dimensional metal organic alkyne nanosheet is prepared by the following preparation method of the two-dimensional metal organic alkyne nanosheet.

Correspondingly, the embodiment of the invention also provides a preparation method of the two-dimensional metal organic alkyne nanosheet.

The method comprises the following steps:

s01, providing a substrate, and placing the substrate in a container;

s02, preparing a mixed solution of an organic alkyne ligand, a metal compound and a catalyst, adding the mixed solution into the container, standing for reaction, and growing a two-dimensional metal organic alkyne nanosheet on the surface of the substrate;

wherein the organic alkyne ligand at least contains three alkynyl groups and a benzene ring; the metal compound contains divalent and higher metal ions; the structural general formula of the two-dimensional metal organic alkyne nanosheet is as follows:

wherein R is an organic alkyne ligand at least containing three alkynyl groups and a benzene ring; m is a metal ligand containing divalent or higher metal ions; m is more than or equal to 3 and less than or equal to 6; n is more than or equal to 3.

Specifically, in step S01, a substrate is provided and placed in the container, and preferably, the substrate material is selected from any one of metal, silicon wafer, quartz wafer, glass wafer, silicon dioxide, silicon carbide, sapphire, aluminum arsenide, and calcium fluoride. The substrate material is provided, and the two-dimensional metal organic alkyne nanosheets can be attached to the surface of the substrate material for growth, so that the two-dimensional metal organic alkyne nanosheets can be collected. Preferably, the base material is cleaned and dried before use.

Specifically, in step S02, a mixed solution of an organoalkyne ligand, a metal compound, and a catalyst is prepared, the mixed solution is added to the container, and a standing reaction is performed to grow a two-dimensional metal-organoalkyne nanosheet on the surface of the substrate, preferably, the molar ratio of the organoalkyne ligand, the metal compound, and the catalyst is 100: (120-220): (0.01-2). The two-dimensional porous structure with a regular and repeated structure can be obtained by reacting according to the molar ratio, and the polymer with a symmetrical structure shows excellent optical saturation absorption and is favorable for being used for optical limiting devices. The thickness of the obtained two-dimensional metal organic alkyne nanosheet is further adjusted by adjusting the molar ratio of each substance, and the obtained two-dimensional metal organic alkyne nanosheet is uniform and controllable in thickness, stable in performance and beneficial to subsequent use. If the addition amount of the metal compound is too large or too small, the addition amount of the organic alkyne ligand is influenced, and the molecular weight of the two-dimensional metal organic alkyne nanosheet is further influenced. If the addition amount of the catalyst is too small, the catalytic effect is poor, the rate and the reaction degree of the chemical reaction can be reduced, and the generation of two-dimensional metal organic alkyne nanosheets is not facilitated; if the addition amount of the catalyst is too large, the reaction degree is also influenced, and the generation of the two-dimensional metal organic alkyne nanosheet is not facilitated. Preferably, the molar ratio of the organic alkyne ligand to the metal compound to the catalyst is 100: (140-210): (0.05-1). The two-dimensional porous structure with regular structure and better repeatability can be obtained by carrying out the reaction according to the molar ratio, and the polymer with symmetrical structure shows excellent optical saturation absorption and is more favorable for being used in an optical limiting device.

Preferably, the catalyst comprises at least one of cuprous iodide, triethylamine, and diisopropylamine, and is added to promote the reaction of the metal compound and the organic alkyne ligand to form the polymer.

Preferably, the metal compound is selected from mercuric chloride or trans-bis (trialkylphosphine) platinum dichloride. Mercury chloride or trans-bis (trialkylphosphine) platinum dichloride is used as a raw material of a metal compound to react with organic alkyne, the metal compound can remove chloride ions under the catalysis of an alkaline catalyst, and the metal and a terminal alkyne bond are subjected to a chemical reaction to generate a polymer.

In an embodiment of the present invention, the preparation method of the two-dimensional metal organic alkyne nanosheet includes the following steps:

s11, providing a substrate, and placing the substrate in a container;

s12, dissolving the organic alkyne ligand in a first organic solution to obtain a first mixture; dissolving the metal compound in deionized water to obtain a second mixture, measuring the first mixture and the second mixture with the same volume, adding the first mixture and the second mixture into the container, and adding the catalyst to obtain a third mixture; and cleaning the third mixture after standing reaction to obtain the two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate material.

Specifically, in step S11, a substrate is provided and placed in the container; the specific operation steps are as described in step S01 above, and are not described herein again.

Specifically, in step S12, the organic alkyne ligand is dissolved in a first organic solution to obtain a first mixture; dissolving the metal compound in deionized water to obtain a second mixture, measuring the first mixture and the second mixture with the same volume, adding the first mixture and the second mixture into the container, and adding the catalyst to obtain a third mixture.

Preferably, the first organic solvent is selected from one of hexane, cyclohexane, toluene, xylene, dichlorobenzene. Dissolving the organic alkyne ligand in a first organic solution to obtain a first mixture, and preferably, in the first mixture, the concentration of the organic alkyne ligand is 0.20-5.0 mM. Preferably, the concentration of the metal compound in the second mixture is 0.50 to 5.0 mM. The target product with good appearance and correct components can be obtained only by ensuring that the concentration of the organic alkyne ligand and the concentration of the metal compound are within the concentration range. If the concentration is too high, some nanoparticles with different components can be generated on the surface of the obtained nanosheet, or the transparency of the nanosheet is low; if the concentration is too low, the generation of the nanosheets is not visible to the naked eye, or the nanosheets are too thin to be visible to the naked eye. The first mixture and the second mixture are measured in the same volume and added to the container, and the catalyst is added to obtain a third mixture.

Specifically, the third mixture is washed after standing reaction to obtain a two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate material.

Preferably, the reaction time of the third mixture standing reaction is 2-200 hours. And cleaning after reaction to obtain the two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate material. Preferably, the two-dimensional metal organic alkyne nanosheet grows on a two-phase interface of the first mixture and the second mixture, after the two-dimensional metal organic alkyne nanosheet grows completely, a water phase below the nanosheet and an organic phase above the nanosheet are respectively pumped out by a needle cylinder, deionized water and an organic solvent are added for cleaning for 3-5 times, the metal compound or complex and an organic alkyne ligand in a clean water phase are respectively cleaned out by pumping out after cleaning; and after the deionized water and the organic solvent are pumped out, attaching the two-dimensional metal organic alkyne nanosheet to the surface of a substrate, and transferring the nanosheet by using the substrate.

In another embodiment of the present invention, the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

s21, providing a substrate, and placing the substrate in a container;

s22, dissolving the organic alkyne ligand and the metal compound in a first organic solvent to obtain a first organic mixture, dissolving the catalyst in a second organic solvent incompatible with the first organic solvent to obtain a second organic mixture, weighing the first organic mixture and the second organic mixture with the same volume, adding the first organic mixture and the second organic mixture into the container, standing, reacting, and then cleaning to obtain the two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate.

Specifically, the step S21 is the same as the step S01, and is not repeated here for brevity.

Specifically, in the step S22, the organoalkyne ligand and the metal compound are dissolved in a first organic solvent to obtain a first organic mixture, and the catalyst is dissolved in a second organic solvent incompatible with the first organic solvent to obtain a second organic mixture; preferably, the first organic solvent is selected from chlorobenzene or dichlorobenzene, and the organic phase can dissolve both the organoalkyne ligand and the metal compound. Preferably, the second organic solvent is an organic solvent incompatible with the first organic solvent, and is selected from ethylene glycol or isopropanol; preferably, the concentration of the catalyst in the second organic mixture is 0.001 to 0.05 mM.

Specifically, the first organic mixture and the second organic mixture with the same volume are measured and added into the container, and the container is kept still for reaction and then cleaned, so that the two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate is obtained. Preferably, the standing reaction time is 2-200 hours. Preferably, the two-dimensional metal organic alkyne nanosheet grows on a two-phase interface of a first organic mixture and a second organic mixture, after the nanosheet grows completely, the first organic mixture and the second organic mixture of the nanosheet are respectively pumped out by a needle cylinder, deionized water and an organic solvent are added for cleaning for 3-5 times, the metal compound or complex and an organic alkyne ligand in a clean water phase are respectively cleaned out by pumping out after cleaning; and after the deionized water and the organic solvent are pumped out, attaching the two-dimensional metal organic alkyne nanosheet to the surface of a substrate, and transferring the nanosheet by using the substrate.

The preparation method of the two-dimensional metal organic alkyne nanosheet provided by the invention has the advantages that the raw materials are simple and easy to obtain, the method is simple, the two-dimensional metal organic alkyne nanosheet can be prepared only by dissolving and then mixing the raw materials, the preparation method is simple and convenient, the speed is high, and the mass production can be realized.

Correspondingly, the embodiment of the invention also provides a saturated absorption device, and the saturated absorption device is made of the two-dimensional metal organic alkyne nanosheet or the two-dimensional metal organic alkyne nanosheet prepared by the preparation method of the two-dimensional metal organic alkyne nanosheet.

Preferably, the two-dimensional metal organic alkyne nanosheet obtained by post-treating the two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate and prepared as described above can be directly used as a saturable absorption device.

Further preferably, the method for post-treating the prepared two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate comprises the following steps: annealing the two-dimensional metal organic alkyne nanosheets growing on the surface of the substrate in a vacuum oven at 120-200 ℃ for 0.5-5 h, and then directly using the two-dimensional metal organic alkyne nanosheets as a saturable absorber device. The purpose of annealing is to improve the morphology of the material and improve the crystallinity of the material, so that the prepared two-dimensional metal organic alkyne nanosheet can be directly used as a saturable absorber device. The temperature is determined by thermogravimetric analysis, and the annealing temperature cannot be higher than the initial decomposition temperature of the material, but cannot be lower than the glass transition temperature of the material. If the annealing temperature is too high, the two-dimensional metal organic alkyne nanosheet material can be decomposed; if the annealing temperature is too low, the function of perfecting the shape of the two-dimensional metal organic alkyne nanosheet material is not achieved.

Preferably, the saturable absorption device can be applied to a laser passive Q-switching or mode-locking element.

According to the saturable absorption device provided by the invention, the two-dimensional metal organic alkyne nanosheet or the two-dimensional metal organic alkyne nanosheet prepared by the preparation method of the two-dimensional metal organic alkyne nanosheet is used as a material of the saturable absorption device, and the two-dimensional metal organic alkyne nanosheet is controllable and uniform in thickness, controllable in microstructure, strong in optical saturable absorption performance and simple in preparation method, so that the laser regulation performance for the saturable absorption device is stable and excellent.

The invention will now be described in further detail by taking the two-dimensional metal organic alkyne nanosheet and the preparation method thereof as examples.

Example 1

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is tris (4-ethynyl benzene) amine, a metal compound is mercuric chloride, and a catalyst is triethylamine; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

dissolving 3.0mg of said tris (4-ethynylbenzene) amine in 5ml of hexane to obtain a first mixture; dissolving 6.0mg of mercuric chloride in 10mL of deionized water to obtain a second mixture, measuring the first mixture and the second mixture with the same volume, adding the first mixture and the second mixture into the container, and adding one drop of triethylamine to obtain a third mixture;

standing the third mixture for 2-200 hours, cleaning, and generating a light yellow two-dimensional mercury organic alkyne nanosheet at a two-phase interface to obtain a two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate, wherein the structure of the prepared two-dimensional metal organic alkyne nanosheet isThe thickness is about 1220 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 150 ℃ for 1.5 hours to obtain the material directly used as a saturable absorber device.

Example 2

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is 1,3, 5-triacetylbenzene, a metal compound is mercuric chloride, and a catalyst is triethylamine; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

dissolving 1.4mg of the 1,3, 5-triacetylbenzene in 10ml of hexane to obtain a first mixture; dissolving 5.5mg of mercuric chloride in 10mL of deionized water to obtain a second mixture, measuring the first mixture and the second mixture with the same volume, adding the first mixture and the second mixture into the container, and adding one drop of triethylamine to obtain a third mixture;

standing the third mixture for 2-200 hours, cleaning, generating a transparent two-dimensional mercury organic alkyne nanosheet at a two-phase interface to obtain a two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate, wherein the prepared two-dimensional metal organic alkyne nanosheet has a structureThe thickness is about 380 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 140 ℃ for 0.5 hour to obtain the material directly used as a saturable absorber device.

Example 3

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is 1,3, 5-triacetylbenzene, a metal compound is mercuric chloride, and a catalyst is triethylamine; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

dissolving 1.1mg of the 1,3, 5-triacetylbenzene in 5ml of hexane to obtain a first mixture; dissolving 2.5mg of mercuric chloride in 5mL of deionized water to obtain a second mixture, measuring the first mixture and the second mixture with the same volume, adding the first mixture and the second mixture into the container, and adding one drop of triethylamine to obtain a third mixture;

standing the third mixture for 2-200 hours, cleaning, generating a transparent two-dimensional mercury organic alkyne nanosheet at a two-phase interface to obtain a two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate, wherein the prepared two-dimensional metal organic alkyne nanosheet has a structureThe thickness is about 310 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 140 ℃ for 1 hour to obtain the material directly used as a saturable absorber device.

Example 4

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is tris (4-ethynylbenzene) amine, a metal compound is trans-dichlorobis (trivinylphosphine) platinum, and a catalyst is cuprous iodide; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

dissolving 2.5mg of the tris (4-ethynylbenzene) amine, 5.2mg of trans-dichlorobis (trivinylphosphine) platinum in 10mL of dichlorobenzene; 0.005mg of catalyst cuprous iodide is dispersed in 10ml of ethylene glycol, the two phases are placed in the container to form two phases, a drop of triethylamine is added into the ethylene glycol on the upper layer by a dropper for standing reaction, a faint yellow platinum-containing two-dimensional nanosheet is generated on the interface of the two phases, a two-dimensional metal organic alkyne nanosheet growing on the surface of a substrate is obtained, and the structure of the prepared two-dimensional metal organic alkyne nanosheet is thatIn the structure of R₃is-CH₂CH₂CH₂CH₃-; the thickness is about 220 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 160 ℃ for 2 hours to obtain the material directly used as a saturable absorber device.

Example 5

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is (9E,19E) -5,10,15, 20-tetra (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin, a metal compound is mercuric chloride, and a catalyst is triethylamine; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

dissolving 3.8mg of the (9E,19E) -5,10,15, 20-tetrakis (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin in 6mL of toluene to obtain a first mixture; dissolving 2.0mg of mercuric chloride in 6mL of deionized water to obtain a second mixture, measuring the first mixture and the second mixture with the same volume, adding the first mixture and the second mixture into the container, and adding one drop of triethylamine to obtain a third mixture;

standing the third mixture for 2-200 hours, cleaning, and generating a deep purple two-dimensional mercury organic alkyne nanosheet at a two-phase interface to obtain a two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate, wherein the prepared two-dimensional metal organic alkyne nanosheet has a structure ofThe thickness is about 540 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 150 ℃ for 1.5 hours to obtain the material directly used as a saturable absorber device.

Example 6

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is 4,4 ' -divinyl-5 ' - (4-ethynylphenyl) -1,1 ', 3 ', 1 ' -triphenyl, a metal compound is trans-dichlorobis (tributylene phosphine) platinum, and a catalyst is cuprous iodide; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

1.5mg of the 4,4 "-divinyl-5 ' - (4-ethynylphenyl) -1,1 ', 3 ', 1" -triphenyl, 4.5mg of trans-dichlorobis (tributylenephosphine) platinum were dissolved in 8mL of dichlorobenzene; 0.004mg of cuprous iodide catalyst is dispersed in 8ml of ethylene glycol, two phases are placed in the container to form two phases, a drop of triethylamine is added into the ethylene glycol on the upper layer by a dropper for standing reaction, two-phase interfaces are obtained to generate yellow platinum-containing two-dimensional nanosheets, two-dimensional metal organic alkyne nanosheets growing on the surface of the substrate are obtained, and the prepared two-dimensional metal organic alkyne nanosheets have the structure thatIn the structure of R₃is-CH₂CH₂CH₂CH₃-; the thickness is about 380 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 180 ℃ for 1.2 hours to obtain the material directly used as a saturable absorber device.

Example 7

Preparing a two-dimensional metal organic alkyne nanosheet, wherein an organic alkyne ligand is (9E,19E) -5,10,15, 20-tetra (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin cobalt, a metal compound is trans-dichlorobis (trimethylphosphine) platinum, and a catalyst is cuprous iodide; the preparation method of the two-dimensional metal organic alkyne nanosheet comprises the following steps:

providing a quartz plate and placing the quartz plate in a container;

dissolving 2.0mg of the (9E,19E) -5,10,15, 20-tetrakis (4-ethynylphenyl) -5H,6H,10H,15H,20H porphyrin cobalt, 5.5mg of trans-dichlorobis (trimethylphosphine) platinum in 10mL of dichlorobenzene; 0.006mg of catalyst cuprous iodide is dispersed in 10ml of ethylene glycol, the two phases are placed in the container to form two phases, a drop of triethylamine is added into the ethylene glycol on the upper layer by a dropper for standing reaction to obtain a platinum-containing two-dimensional nanosheet with a dark reddish brown interface, and a two-dimensional metal organic alkyne nanosheet growing on the surface of the substrate is obtained, wherein the structure of the prepared two-dimensional metal organic alkyne nanosheet is thatIn the structure, M is selected from any one of nickel metal, iron metal, cobalt metal, zinc metal, copper metal and platinum metal, and R is₃is-CH₂CH₂CH₂CH₃-; the thickness is about 180 nm.

The preparation method of the material which can be directly used as the saturable absorption device comprises the following steps: and (3) placing the prepared two-dimensional metal organic alkyne nanosheet in a vacuum oven for annealing treatment at 165 ℃ for 1.8 hours to obtain the material directly used as a saturable absorber device.

Laser Z-scan analysis is performed on the two-dimensional metal organic alkyne nanosheets prepared in the above examples 1 and 3, and the analysis result is shown in fig. 2, where HgL1 in the figure is the two-dimensional metal organic alkyne nanosheet prepared in the above example 1, and HgL2 is the two-dimensional metal organic alkyne nanosheet prepared in the above example 3, and the saturated nonlinear absorption theory fitting curve of the two-dimensional mercury organic nanosheet obtained by the laser Z-scan technology is shown in the figure. As can be seen from the curves, HgL1 nanosheets and HgL2 nanosheets initially have a nearly linear curve with increasing input flux, and the input flux reaches 0.5J/cm²After that, a sharp bend appears, showing saturated nonlinear absorption properties. The two-dimensional metal organic nano sheet with the performance can be used for devices of saturable absorbers.

The passive Q-switched (Nd: YAG) performance of the two-dimensional metal organic alkyne nanosheet prepared in example 1 was analyzed, and the analysis results are as follows, and as shown in FIG. 3, the maximum continuous wave and Q-switched output power were 1.39W and 50mW, respectively, when the absorption pump power was 3.33W. The output spectrum was recorded with a central wavelength of 1064nm, which coincides with the maximum emission peak of Nd: YAG. As shown in FIGS. 4 and 5, stable passive Q-switched laser operation is realized in a pumping region of 2.01-3.33W, the pulse width is reduced along with the increase of the absorbed pumping power, and the repetition frequency, the pulse energy and the peak power basically rise. The pulse sequence and single pulse waveform are shown in FIG. 6, with a repetition frequency of 380kHz pulse train, a shortest pulse width of 145.1ns, a maximum pulse energy of 0.132 muJ, and a maximum peak power of 0.91W.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.