CN109019586B

CN109019586B - Preparation method of graphite-like alkyne

Info

Publication number: CN109019586B
Application number: CN201811054314.4A
Authority: CN
Inventors: 靳治良; 王国荣; 马秉正
Original assignee: North Minzu University
Current assignee: North Minzu University
Priority date: 2018-09-11
Filing date: 2018-09-11
Publication date: 2021-07-27
Anticipated expiration: 2038-09-11
Also published as: CN109019586A

Abstract

The invention relates to a method for preparing graphite-like alkyne, which comprises the following steps: taking cuprous iodide as a substrate, and carrying out coupling reaction on hexaalkynyl benzene in a solvent under the catalytic action of the cuprous iodide: and corroding by ammonia water to remove cuprous iodide, centrifugally separating, drying and grinding to obtain the graphite-like alkyne powder product. The preparation method of the graphite alkyne-like substance can prepare a large amount of graphite alkyne-like substances, shortens the research period of the graphite alkyne in other fields, and makes the application of the graphite alkyne in other fields possible.

Description

Preparation method of graphite-like alkyne

Technical Field

The invention belongs to the field of semiconductors, and particularly relates to a preparation method of graphite-like alkyne.

Background

Carbon element is widely present on the earth and is gradually discovered, recognized and utilized by people due to its unique physicochemical properties. Carbon has previously been considered to have only two allotropic isomers of graphite and diamond. The fullerene family was discovered in 1985 (H.W.Kroto, J.R.Heath, S.C.O' Brien, C/sub 60/: Buckminsterfullerene, nature,1985,318: 162-; carbon nanotubes were found in 1991 (Iijima S. structural microtubes of graphical carbon, Nature,1991, 354.); in 2004, two-dimensional carbon-based material graphene is discovered, and the family of carbon materials is greatly enriched. With the rapid development of synthetic chemistry, scientists have proposed methods for preparing different carbon allotropes while also producing some unnatural carbon allotropes. Since the first time that graphdiynes were proposed (a.t. balaban, c.c Rentia, e.ciupitu, Rev, roum. chim.,1968,13, 231-. In 2010, the institute of science and technology, li-liang, grows a graphite thin film (g.li, y.li, h.liu, Architecture of graphyne nanoscales, Chemical Communications,2010,46, 3256-3258) consisting of sp and sp2 hybridized carbon atoms on a copper foil substrate, and further, the research on carbon materials is pushed to a new high tide. Theoretical calculations predict that it has excellent physical and chemical properties. However, the graphite alkyne film prepared by the method has small mass, and is difficult to popularize and study in other aspects.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of the graphite-like alkyne, which has the advantages of simple process, large-scale preparation and stable existence in air.

The technical problem to be solved by the invention is realized by the following technical scheme:

a preparation method of a graphite-like alkyne comprises the following steps:

1) taking cuprous iodide as a substrate, and carrying out coupling reaction on hexaalkynyl benzene in a solvent under the catalytic action of the cuprous iodide:

2) and corroding by ammonia water to remove cuprous iodide, centrifugally separating, drying and grinding to obtain the graphite-like alkyne powder product.

And the mass ratio of the hexaalkynyl benzene to the cuprous iodide is as follows: 1:8-10.

And the solvent is pyridine, and the mass ratio of the solvent to cuprous iodide is as follows: 70-90:1.

Moreover, the coupling reaction is carried out under the protection of inert gas.

Further, the inert gas is nitrogen.

Moreover, the reaction temperature of the coupling reaction is 50-70 ℃ and the time is 1-3 days.

The invention has the advantages and beneficial effects that:

1. the preparation method of the graphite-like alkyne is simple in process, can be prepared on a cuprous iodide substrate in a large scale, stably exists in the air, and is a semiconductor similar to graphite.

2. According to the preparation method of the graphite-like alkyne, the prepared graphite-like alkyne only consists of carbon elements, and the carbon is sp²Sp hybridization, unique nano-pore, two-dimensional layered conjugated framework structure, semiconductor property and other characteristics, and has obvious advantages in the fields of energy, electrochemistry, photocatalysis, optics, electronics and the like.

3. Compared with the prior art, the preparation method of the graphite alkyne-like compound has the advantages of easy acquisition of hexa-alkynyl benzene, simple process route, short process period and high yield.

4. According to the preparation method of the graphite alkyne-like substance, the hydrogen production rate of the Pt/graphite alkyne-like cuprous iodide is improved by 2 times compared with the Pt/cuprous iodide in the hydrogen production by photocatalytic water decomposition of the prepared graphite alkyne-like substance.

5. The preparation method of the graphite alkyne-like substance can prepare a large amount of graphite alkyne-like substances, shortens the research period of the graphite alkyne in other fields, and makes the application of the graphite alkyne in other fields possible.

Drawings

FIG. 1 shows the chemical reaction equation for the preparation of hexaynylbenzenes.

FIG. 2 is a chemical structural formula of graphdiyne.

FIG. 3 is a process scheme for preparing a graphite-like alkyne in example 1.

FIG. 4 is a Transmission Electron Micrograph (TEM) of the graphoyne-like obtained in example 1.

Figure 5 is an XRD pattern of the graphoyne obtained from example 1.

Fig. 6 is a raman spectrum of the graphoyne-like obtained in example 1.

FIG. 7 is an infrared spectrum (FTIR) of the graphdine-like material prepared in example 1.

FIG. 8 is an X-ray photoelectron spectroscopy (XPS) of the graphdiyne prepared in example 1.

FIG. 9 is a comparison of hydrogen production for a graphite-like alkyne/cuprous iodide/Pt system.

FIG. 10 is a comparison of hydrogen production rate enhancement rates in different examples.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.

A novel method for preparing graphite-like alkyne comprises the following steps:

1) taking cuprous iodide as a substrate, and carrying out coupling reaction on hexaalkynyl benzene in a solvent under the catalytic action of the cuprous iodide;

2) and corroding by ammonia water to remove cuprous iodide to obtain the graphite-like alkyne. The mass ratio of the hexaalkynyl benzene to the cuprous iodide is as follows: 1:8-10. The solvent is pyridine, and the mass ratio of the solvent to cuprous iodide is as follows: 70-90:1. The coupling reaction is carried out under the protection of inert gas. The inert gas is nitrogen. The reaction temperature of the coupling reaction is 50-70 ℃ and the time is 1-3 days.

Hexaynylbenzenes, the reactants used in the following examples to prepare graphyne, were prepared from hexabromobenzene, trimethylsilyne and tetrabutylammonium fluoride according to the methods provided in the following references: li, Y.Li, H.Liu, Architecture of graphdiyne nanoscales, Chemical Communications,2010,46,3256-3258. the Chemical equations of the reaction are shown in FIG. 1.

Example 1

10mg of hexaynylbenzene was dissolved in 25ml of pyridine solution, and slowly added dropwise under nitrogen protection to a round-neck flask containing 50ml of pyridine and 900mg of cuprous iodide, the temperature of the reaction solution was 60 ℃ and the addition time was 24 hours. The reaction was then stirred for an additional 2 days at 60 ℃. After the reaction, the reaction mixture was washed with ammonia (AR grade) for three times, centrifuged, dried, and ground to obtain a black powder as a graphite-like alkyne substance. The structural formula is shown in figure 2, and the preparation process route is shown in figure 3.

Example 2

10mg of hexaynylbenzene was dissolved in 25ml of pyridine solution, and slowly dropped under nitrogen atmosphere into a round-neck flask containing 50ml of pyridine and 800mg of cuprous iodide (reaction solution temperature: 60 ℃ C.), and the dropping time was 24 hours. The reaction was then stirred for an additional 2 days at 60 ℃. After the reaction, the reaction mixture was washed with ammonia (AR grade) for three times, centrifuged, dried, and ground to obtain a black powder as a graphite-like alkyne substance.

Example 3

10mg of hexaynylbenzene was dissolved in 25ml of pyridine solution, and slowly dropped under nitrogen atmosphere into a round-neck flask containing 50ml of pyridine and 1000mg of cuprous iodide (reaction solution temperature: 60 ℃ C.), and the dropping time was 24 hours. The reaction was then stirred for an additional 2 days at 60 ℃. After the reaction, the reaction mixture was washed with ammonia (AR grade) for three times, centrifuged, dried, and ground to obtain a black powder as a graphite-like alkyne substance.

Example 4

10mg of hexaynylbenzene was dissolved in 25ml of pyridine solution, and slowly dropped under nitrogen atmosphere into a round-neck flask containing 50ml of pyridine and 900mg of cuprous iodide (reaction solution temperature: 60 ℃ C.), and the dropping time was 24 hours. The reaction was then stirred at 60 ℃ for 1 day. After the reaction, the reaction mixture was washed with ammonia (AR grade) for three times, centrifuged, dried, and ground to obtain a black powder as a graphite-like alkyne substance.

Example 5

10mg of hexaynylbenzene was dissolved in 25ml of pyridine solution, and slowly dropped under nitrogen atmosphere into a round-neck flask containing 50ml of pyridine and 900mg of cuprous iodide (reaction solution temperature: 60 ℃ C.), and the dropping time was 24 hours. The reaction was then stirred at 60 ℃ for a further 3 days. After the reaction, the reaction mixture was washed with ammonia (AR grade) for three times, centrifuged, dried, and ground to obtain a black powder as a graphite-like alkyne substance.

And (3) analyzing test results:

FIG. 4 is a Transmission Electron Microscope (TEM) image of the graphdine-like substance prepared in example 1, and as shown in FIG. 4, the Transmission Electron Microscope (TEM) test result shows that the graphdine-like substance prepared by the method uniformly grows on the surface of cuprous iodide, and the thickness is about 50-100 nm.

Fig. 5 is an XRD pattern of the graphyne-like powder, as shown in fig. 5, where only a strong peak appears around 25 °, indicating that the cuprous iodide substrate was completely removed, leaving only the graphyne-like.

FIG. 6 is a Raman spectrum of a graphdine-like compound prepared in example 1, as shown in FIG. 6, which shows 2 strong absorption peaks at 1375.8cm^-1、1571.3cm^-1Each being sp of an aromatic ring²Atomic respiratory vibrational mode generation and aromatic ring all sp²The stretching vibration mode of the atom pair is generated. The weaker two peaks are at 1925.8cm^-1And 2185.6cm^-1Generated by the stretching vibration of the conjugated diyne.

FIG. 7 is a graphdine-like infrared absorption Spectroscopy (FTIR), 1570cm^-1And 1711cm^-1A skeleton of an aromatic ring vibrates. 2198cm^-1Is the stretching vibration of carbon-carbon triple bond.

FIG. 8 is an X-ray photoelectron Spectroscopy (XPS) of the graphoyne obtained in example 1, showing that the graphoyne consists only of carbon elements and that carbon is sp²And sp hybridization.

FIG. 9 is a comparison of hydrogen production of a graphite alkyne-like/cuprous iodide/Pt system, and it can be seen from the figure that after the graphite alkyne-like substance is doped in the system, the hydrogen production rate in the system is obviously improved and is about 3 times that of the cuprous iodide/Pt system.

Fig. 10 is a comparison of the hydrogen production rate increase ratios in different embodiments, which shows that in the application process of photocatalytic decomposition of hydrogen in water, the substance obtained in example 1 has the best hydrogen production rate, the graphdiyne grown under other conditions has a certain increase in hydrogen production, and the substance obtained in example 1 has the highest increase of 2 times, as shown in fig. 10.

The graphite-like alkyne substance prepared by the method can grow on a cuprous iodide substrate in a large amount, can be centrifugally separated through ammonia water treatment to directly obtain graphite-like alkyne powder, only consists of carbon elements, has the characteristics of unique nanoscale pores, two-dimensional layered conjugated skeleton structure, semiconductor properties and the like due to sp2 and sp hybridization of carbon, and has obvious advantages in the fields of energy, electrochemistry, photocatalysis, optics, electronics and the like. The preparation of a large amount of the graphene has a great prospect for the subsequent application research of the graphdiyne, and particularly has great potential in the fields of photocatalysis, electrocatalysis and the like.

Although the present invention has been disclosed in connection with the embodiments and drawings, it will be understood by those skilled in the art that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.

Claims

1. A preparation method of a graphite-like alkyne comprises the following steps:

2) corroding by ammonia water to remove cuprous iodide, centrifugally separating, drying and grinding to obtain a graphite-like alkyne powder product;

the mass ratio of the hexaalkynyl benzene to the cuprous iodide is as follows: 1:8-10.

2. The method of preparing a graphdiyne according to claim 1, wherein: the solvent is pyridine, and the mass ratio of the solvent to cuprous iodide is as follows: 70-90:1.

3. The method of preparing a graphdiyne according to claim 1, wherein: the coupling reaction is carried out under the protection of inert gas.

4. A process for preparing a graphdiyne according to claim 3, wherein: the inert gas is nitrogen.

5. The method for preparing a graphdiyne according to claim 1,3 or 4, wherein: the reaction temperature of the coupling reaction is 50-70 ℃ and the time is 1-3 days.