阅读说明：本技术 一种三元金属原子晶体氢化制备二维材料的方法 (Method for preparing two-dimensional material by hydrogenation of ternary metal atom crystal ) 是由 封伟 张鑫 王宇 赵付来 冯奕钰 李瑀 于 2018-07-12 设计创作，主要内容包括：本发明公开一种三元金属原子晶体氢化制备二维材料的方法,将Ga粉、Ge粉和Li片封装于真空石英管中,于充满氩气的真空管式炉中退火得到LiGaGe晶体前驱体,取出前驱体置于管式炉中暴露在H<Sub>2</Sub>环境中,再次退火得到二维材料前驱体LiGaGeH,用四氟胶带反复撕粘,即可得到二维材料2D-LiGaGeH。其体相材料具有0.06eV光学带隙,随材料层数的逐渐减少,带隙逐渐增大,在光电器件、光催化等方面具有较大应用前景。(The invention discloses a method for preparing a two-dimensional material by hydrogenation of a ternary metal atomic crystal, which comprises the steps of packaging Ga powder, Ge powder and a Li sheet in a vacuum quartz tube, annealing in a vacuum tube furnace filled with argon to obtain a LiGaGe crystal precursor, taking out the precursor, placing the precursor in the tube furnace, and exposing the precursor in a H atmosphere 2 And in the environment, annealing again to obtain a two-dimensional material precursor LiGaGeH, and repeatedly tearing and adhering by using a tetrafluoro adhesive tape to obtain the two-dimensional material 2D-LiGaGeH. The bulk phase material has an optical band gap of 0.06eV, and the band gap gradually increases with the gradual reduction of the number of layers of the material, so that the bulk phase material has a wide application prospect in the aspects of photoelectric devices, photocatalysis and the like.)

1. A method for preparing a two-dimensional material by hydrogenating a ternary metal atomic crystal is characterized in that three metals of Ga, Ge and Li are subjected to vacuum packaging and treatment according to an equal molar ratio to obtain a GaGeLi crystal, the temperature is increased to 1000-1100 ℃ within 350-450 min from 20-25 ℃ and is maintained for 1000-1200 min, and then the temperature is reduced to 20-25 ℃ at 0.5-3 ℃/min to obtain a precursor of the ternary metal atomic crystal; placing a ternary metal atom crystal precursor GaGeLi in a hydrogen atmosphere for processing to obtain a two-dimensional material precursor GaGeLiH, heating to 200-600 ℃ from 20-25 ℃ at a heating rate of 1-5 ℃ per minute, preserving heat for 20-80 hours, and naturally cooling to room temperature of 20-25 ℃; and repeatedly tearing and sticking by using a tetrafluoro adhesive tape to obtain the 2D-LiGaGeH layered material.

2. The method for preparing a two-dimensional material by hydrogenating the ternary metal atom crystal as in claim 1, wherein the vacuum degree of the three metals of Ga, Ge and Li is below 0.1MPa when the three metals are subjected to vacuum packaging and processing.

3. The method for preparing two-dimensional material by hydrogenating ternary metal atom crystal as claimed in claim 1, wherein the three metals Ge, Ge and Li are vacuum packed and treated, and the temperature is raised to 1000-1050 ℃ from 20-25 ℃ within 380-400 min, maintained for 1100-1200 min and then lowered to 20-25 ℃ at 0.5-1 ℃/min.

4. The method for preparing the two-dimensional material by hydrogenating the ternary metal atomic crystal according to claim 1, wherein the precursor GaGeLi of the ternary metal atomic crystal is placed in a hydrogen atmosphere to be processed to obtain the precursor GaGeLiH of the two-dimensional material, the temperature is raised to 400-600 ℃ from 20-25 ℃ at the temperature rising speed of 1-3 ℃ per minute, the temperature is kept for 24-72 hours, and then the two-dimensional material is naturally cooled to the room temperature of 20-25 ℃.

5. The method for preparing a two-dimensional material by hydrogenating the ternary metal atom crystal according to claim 1, wherein the ternary metal atom crystal precursor GaGeLi is treated in a hydrogen atmosphere at a vacuum degree of 50 to 100bar, preferably 60 to 80 bar.

Technical Field

The invention belongs to a method for preparing a two-dimensional material by hydrogenating a novel two-dimensional material precursor, and particularly relates to a simple method for preparing a two-dimensional layered material by hydrogenating a ternary atomic crystal LiGaGe to obtain LiGaGeH.

Background

Following graphene, there is a transition metal known as "inorganic grapheneChalcogenide compounds (2DLMCs) have great application potential in the aspects of photoelectron, catalysis, energy and the like based on excellent optical properties and slightly lower carrier mobility than graphene, and are widely concerned by researchers. Two-dimensional layered transition metal sulfur compounds (TMDCs: MoSe) having a graphene-like structure and a controllable band gap have been widely studied in recent years₂、WS₂Etc.), group iii-iv compounds (GeS, GeSe, etc.) and their associated heterojunctions. Compared with binary metal crystals, the preparation of ternary crystals is relatively more difficult, the problems of difficult uniform eutectic melting, difficult determination of eutectic point and the like, and the problems of subsequent further modification treatment and the like exist, so that related reports are less. In 1974, W Bockelmann et al first studied the LiGaGe crystal structure, then in 2008 Ulrich Hausssermann et al prepared a ternary metal precursor by arc remelting, hydrogenated to give a quaternary crystal AeGaEH (Ae: Ca, Sr, Ba; E: Si, Ge, Sn), and performed a series of studies. However, most of these preparation methods are complicated and most of the equipment involved is expensive.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a method for preparing a two-dimensional material by hydrogenating a ternary metal atomic crystal, which is used for hydrogenating a ternary metal precursor and starting from the ternary crystal precursor to simply prepare a novel two-dimensional material, namely starting from a two-dimensional material preparation path, and preparing a two-dimensional material with better performance by adopting the ternary crystal.

The technical purpose of the invention is realized by the following technical scheme:

a method for preparing two-dimensional material by hydrogenation of ternary metal atom crystal, vacuum packaging and processing Ga, Ge, Li three metals according to equal molar ratio to obtain GaGeLi crystal, raising the temperature from 20-25 ℃ to 1000-1100 ℃ within 350-450 min, maintaining the temperature for 1000-1200 min, and then cooling to 20-25 ℃ at 0.5-3 ℃/min to obtain ternary metal atom crystal precursor; placing a ternary metal atom crystal precursor GaGeLi in a hydrogen atmosphere for processing to obtain a two-dimensional material precursor GaGeLiH, heating to 200-600 ℃ from 20-25 ℃ at a heating rate of 1-5 ℃ per minute, preserving heat for 20-80 hours, and naturally cooling to room temperature of 20-25 ℃; and repeatedly tearing and sticking by using a tetrafluoro adhesive tape to obtain the 2D-LiGaGeH layered material.

In the technical scheme, when the three metals of Ga, Ge and Li are subjected to vacuum packaging and processing, the vacuum degree is below 0.1 MPa.

In the technical scheme, when three metals of Ge, Ge and Li are subjected to vacuum packaging and treatment, the temperature is increased to 1000-1050 ℃ within 380-400 min from 20-25 ℃, maintained for 1100-1200 min and then reduced to 20-25 ℃ at the speed of 0.5-1 ℃/min.

In the technical scheme, a ternary metal atom crystal precursor GaGeLi is placed in a hydrogen atmosphere to be processed to obtain a two-dimensional material precursor GaGeLiH, the temperature is raised to 400-600 ℃ from 20-25 ℃ at the temperature rise rate of 1-3 ℃ per minute, the temperature is kept for 24-72 hours, and then the temperature is naturally cooled to 20-25 ℃.

In the technical scheme, when the precursor GaGeLi of the ternary metal atom crystal is placed in a hydrogen atmosphere for treatment, the vacuum degree is 50-100 bar, and preferably 60-80 bar.

The technical scheme of the invention is that Ga, Ge and Li metals are packaged in a quartz tube in proportion, the quartz tube is placed in a vacuum tube furnace, the program temperature is set, a ternary metal precursor LiGaGe crystal is obtained by annealing, the precursor is taken out and placed in the tube furnace to be exposed to H₂And in the environment, setting the program temperature, annealing again to obtain a two-dimensional material precursor LiGaGeH, and repeatedly tearing and bonding by using a tetrafluoro adhesive tape to obtain the two-dimensional material 2D-LiGaGeH. Compared with the prior art, the LiGaGe ternary atomic crystal is subjected to hydrogenation treatment to obtain a LiGaGeH quaternary precursor, the LiGaGeH quaternary precursor is repeatedly torn and adhered through the tetrafluoro adhesive tape to obtain a novel two-dimensional material, and the LiGaGe ternary atomic crystal is subjected to hydrogenation treatment to prepare a new path of the two-dimensional material.

Drawings

Fig. 1 is a schematic diagram of a crystal structure of LiGaGe obtained by the technical scheme of the present invention.

Fig. 2 is an XRD spectrum of LiGaGe obtained by the technical scheme of the present invention.

FIG. 3 is an infrared spectrogram of LiGaGeH obtained by the technical scheme of the invention.

Fig. 4 is a scanning electron microscope image of the LiGaGeH bulk material according to the technical solution of the present invention.

Fig. 5 is an ultraviolet-visible absorption spectrum diagram of LiGaGeH with different numbers of layers according to the technical scheme of the present invention.

Detailed Description

The present invention will be further described with reference to the following embodiments. The following examples of the present invention are given to further illustrate the present invention, but not to limit the scope of the present invention.

Example 1

Weighing 10mmol of Ga (powder), 10mmol of Ge (powder) and 10mmol of Li (sheet material) in a glove box in sequence, adding the materials into a quartz tube in sequence, carrying out melt sealing by using a vacuum melt packaging device, sintering in a vacuum tube furnace, raising the temperature from normal temperature (20-25 ℃) to 1000 ℃ for 400min, maintaining the temperature for 1200min, and then cooling to the normal temperature (20-25 ℃) at the temperature of 0.5 ℃/min to obtain the ternary metal atomic crystal precursor. Taking out the precursor, placing the precursor in a tube furnace, and exposing the precursor to H₂In the environment, the temperature is increased from the normal temperature (20-25 ℃) to 200 ℃ at the temperature of 1-5 ℃ per minute and is maintained for 24 hours, then the temperature is reduced to the normal temperature (20-25 ℃), and the polytetrafluoroethylene tape is used for repeatedly tearing and sticking, so that the 2D-LiGaGeH layered material is obtained.

Example 2

Weighing 10mmol Ga, 10mmol Ge and 10mmol Li in a glove box in sequence, adding into a quartz tube in sequence, sealing by using a vacuum sealing device, sintering in a vacuum tube furnace, raising the temperature from normal temperature to 1100 ℃ for 400min, maintaining for 1000min, and then cooling to normal temperature at 0.5 ℃/min. Placing the precursor in a tube furnace, and exposing the precursor to H₂And in the environment, heating to 500 ℃ from the normal temperature at 60bar, maintaining for 20h, cooling to the normal temperature, and repeatedly tearing and adhering by using a tetrafluoro adhesive tape to obtain the 2D-LiGaGeH layered material.

Example 3

Weighing 10mmol Ga, 10mmol Ge and 10mmol Li in a glove box in sequence, adding into a quartz tube in sequence, sealing by vacuum sealing device, sintering in a vacuum tube furnace, heating from room temperature to 1000 deg.C for 400min, maintaining for 1150min, cooling to normal temperature at 0.5 deg.C/minAnd (4) warming. Taking out the precursor, placing the precursor in a tube furnace, and exposing the precursor to H₂In the environment, the temperature is increased to 550 ℃ from the normal temperature at 80bar, the temperature is reduced to the normal temperature after the temperature is maintained for 80h, and the 2D-LiGaGeH layered material is obtained by repeatedly tearing and sticking the layered material by using a tetrafluoro adhesive tape.

Example 4

Weighing 10mmol Ga, 10mmol Ge and 10mmol Li in a glove box in sequence, adding into a quartz tube in sequence, sealing by using a vacuum sealing device, sintering in a vacuum tube furnace, heating from normal temperature to 1100 ℃ for 350min, maintaining for 1200min, and cooling to normal temperature at 3 ℃/min. Taking out the precursor, placing the precursor in a tube furnace, and exposing the precursor to H₂In the environment, heating to 500 ℃ from the normal temperature at 100bar, maintaining for 24h, cooling to the normal temperature, and repeatedly tearing and adhering by using a tetrafluoro adhesive tape to obtain the 2D-LiGaGeH layered material.

Example 5

Weighing 10mmol Ga, 10mmol Ge and 10mmol Li in a glove box in sequence, adding into a quartz tube in sequence, sealing by using a vacuum sealing device, sintering in a vacuum tube furnace, heating from normal temperature to 1100 ℃ for 450min, maintaining for 1000min, and cooling to normal temperature at 1 ℃/min. Taking out the precursor, placing the precursor in a tube furnace, and exposing the precursor to H₂And (3) in the environment, heating to 400 ℃ from normal temperature at 50bar, maintaining for 72h, cooling to normal temperature, and repeatedly tearing and adhering by using a tetrafluoro adhesive tape to obtain the 2D-LiGaGeH layered material.

Example 6

Weighing 10mmol Ga, 10mmol Ge and 10mmol Li in a glove box in sequence, adding into a quartz tube in sequence, sealing by using a vacuum sealing device, sintering in a vacuum tube furnace, heating from room temperature to 1050 ℃ for 380min, maintaining for 1100min, and cooling to room temperature at 1 ℃/min. Taking out the precursor, placing the precursor in a tube furnace, and exposing the precursor to H₂And (3) in the environment, increasing the temperature to 600 ℃ from normal temperature, maintaining the temperature for 48 hours, then reducing the temperature to normal temperature, and repeatedly tearing and adhering by using a tetrafluoro adhesive tape to obtain the 2D-LiGaGeH layered material.

Taking the preparation of the material in example 6 as an example, as shown in the attached figures 1-5, the technical scheme of the invention is adopted to successfully prepare the 2D-LiGaGeH layered material, the product obtained after hydrogenation is connected with H on LiGaGe, and an infrared spectrogram is measured, wherein the infrared spectrogram is 1900cm_-1Near the Ge-H stretching vibration, 500cm_-1There is a rocking vibration nearby. Using violetOptical band gap measurement is carried out on different layers in the external-visible absorption spectrum, and the band gap of the bulk phase material is far lower than 1eV, and gradually decreases and gradually increases with the number of layers to obtain a single layer GeTeH, wherein the band gap reaches 0.98eV (already reaches 1 eV).

The preparation of the 2D-LiGaGeH layered material can be realized by adjusting the process parameters according to the content of the invention, and the 2D-LiGaGeH layered material has the performance basically consistent with that of the embodiment. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.