CN115010126A - Method for preparing graphite diyne by using alkynyl negative ions - Google Patents
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Abstract
The invention discloses a method for preparing graphite diyne by using alkynyl negative ions, which comprises the following steps: weighing a proper amount of calcium carbide, hexabromobenzene, tribromobenzene and ball-milling beads, placing the mixture in a sealed ball-milling tank, replacing air in the ball-milling tank with nitrogen, and carrying out ball-milling to obtain graphite diacetylene intermediate powder. Then putting the graphite diyne intermediate powder into a reactor, adding tetrakis (triphenylphosphine) palladium and copper acetate as catalysts, adding anhydrous toluene as a solvent, heating the reactor for reaction, and performing nitrogen replacement for many times in the process. After the reaction is finished, evaporating the solution in the reactor to be dry, calcining at high temperature in a nitrogen atmosphere, and treating by nitrohydrochloric acid to obtain the final graphite diyne product. The invention uses calcium carbide (Ca) 2+ C, C:] 2‑ ) Common and easily-obtained raw materials are adopted for synthesizing the graphite diyne by using an alkyne source, the synthesis operation process is simplified, the yield of the graphite diyne is increased, the content of byproducts is reduced, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a method for preparing graphite diyne by utilizing alkynyl negative ions.
Background
Carbon is not only a major component of the biological existence in nature, but also a promising engineering material. Carbon materials are widely used as solar energy absorbing materials due to their natural black color, adjustable band gap, wide light absorption band and good electrical conductivity. Such as graphite, graphene oxide, reduced graphene oxide, and carbon nanotubes, have been developed and utilized. Meanwhile, the carbon material has the advantages of low cost, large specific surface area, good heat conductivity and high light conversion efficiency. Carbon materials are often combined with semiconductors and metals to increase their light absorption and solar energy conversion properties.
The Graphitic Diyne (GDY) is a compound containing both sp and sp 2 Carbon allotropes of hybridized carbon atoms. The structure of the carbon material is formed by splicing an infinite number of 18-C hexagonal shapes consisting of aromatic rings and acetylene bonds, so that the carbon material is called the most stable synthetic carbon material containing a diacetylene structure. GDY the unique pi conjugated network structure has homogeneous pore distribution and adjustable chemical and photoelectric characteristics, and may be used widely in catalysis, energy source, electronic device, biomedicine and other fields.
The first method for organically synthesizing graphite diyne is proposed by Liyuelian subject group. Subsequently, dawn, li chunxi, etc. prepared the grapyne by a ball milling method. In the process of preparing graphite diyne by the existing full-organic synthesis method, the used raw materials comprise trimethylsilyne, n-butyllithium, tetrahydrofuran, hexabromobenzene, palladium, triphenylphosphine, tetrahydrofuran, toluene, tetrabutylammonium fluoride, pyridine and the like, and the problems of complex synthesis process, complex required raw materials, low yield, high byproduct content and the like exist, so that the industrial production is difficult to form.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing graphite diyne by using alkynyl negative ions, which takes calcium carbide as an alkyne source (Ca) 2+ C, C:] 2- ) The method for synthesizing the graphite diyne has the advantages of easily available raw materials, simple operation, high yield, low content of byproducts and the like, adopts common easily available raw materials, simplifies the synthesis operation process, improves the yield of the graphite diyne, reduces the content of the byproducts, and is favorable for industrial production.
The invention provides a method for preparing graphite diyne by using alkynyl negative ions, which comprises the following steps:
(1) calcium carbide according to the mass ratio: hexabromobenzene: tribromobenzene ═ 2-3): 1: adding calcium carbide, hexabromobenzene, tribromobenzene and ball-milling beads into a sealed ball-milling tank, introducing nitrogen into the ball-milling tank, setting a planetary ball mill at 400-600 r/min, and carrying out ball-milling on a sample in the ball-milling tank for 6-10 h to obtain graphite diacetylene intermediate products 1,3, 5-triacetylbenzene and hexaynylbenzene;
(2) putting the intermediate product obtained in the step (1) into a reaction container, and mixing the intermediate product with tetrakis (triphenylphosphine) palladium in a mass ratio of: copper acetate: tribromobenzene ═ 0.2-0.3): (0.2-0.3): adding palladium tetrakis (triphenylphosphine) and copper acetate as catalysts into a reactor, injecting anhydrous toluene for dissolving, heating to 70-80 ℃ under the protection of nitrogen, reacting for 48-96 h, performing nitrogen replacement for many times in the reaction process, and removing gas impurity 2-butyne generated by the reaction;
(3) and after the reaction is finished, evaporating the solvent in the reactor to dryness, then placing the reactor in a tubular furnace, calcining for 1-3 h at 450-850 ℃ to remove the residual tribromobenzene and hexabromobenzene, soaking in aqua regia to remove the catalyst and other impurities, and performing suction filtration and drying to obtain the final product graphite diyne powder.
Preferably, the amount of the anhydrous toluene used in the step (2) is anhydrous toluene: tribromobenzene ═ 100-150 mL: 1g of the total weight of the composition.
Preferably, the temperature rise rate of the tube furnace in the step (3) is 3 ℃/min -1 The calcination temperature is 450 ℃, and the calcination time is 3 h.
Preferably, the rotating speed of the planetary ball mill in the step (1) is 500r/min, and the ball milling time is 10 h.
Preferably, the amount of the ball milling beads used in the step (1) is calculated according to the mass ratio as follows: tribromobenzene (20-50): 1.
preferably, the number of times of nitrogen replacement in the step (2) is 5.
The working principle of the invention is as follows:
in the step (1), in addition to uniformly mixing the raw materials in the ball milling process of calcium carbide, hexabromobenzene and tribromobenzene, the breakage of chemical bonds and the generation of new bonds also occur, the calcium carbide provides acetylene bond sources for the reaction process, and the obtained intermediate product mainly comprises 1,3, 5-triacetylbenzene, hexaalkynyl benzene and diacetylene bonds, namely alkynyl negative ions [: C tri C:] 2- and so on.
And (3) the coupling of benzene ring and acetylene bond can be catalyzed by tetrakis (triphenylphosphine) palladium, under the action of the tetrakis (triphenylphosphine) palladium, the substitution of-Br by alkynyl is further completed, and hexabromobenzene and tribromobenzene are converted into hexaalkynyl benzene and 1,3, 5-tri-acetylene benzene. The copper salt powder can be used for alkyne coupling reaction, and a plurality of benzene rings are coupled into a network structure through diyne bonds. When the hexabromobenzene and the tribromobenzene are used as main raw materials, in the organic cross-coupling reaction, as the 1,3, 5-triethylalkynylbenzene and the hexaalkynylbenzene form a network structure with less bonding and the required activation energy is lower, partial alkynyl groups of the 1,3, 5-triethylalkynylbenzene and the hexaalkynylbenzene can be firstly coupled to initially form the network structure, and then the partial double alkynyl groups lacking in the network are supplemented by diyne bonds to form a complete network structure. And nitrogen is introduced in the preparation process, so that a reaction byproduct, namely 2-butyne is effectively removed in time, and meanwhile, the hexaalkynyl benzene is protected from oxidative deterioration so as to avoid self cross coupling.
The invention has the beneficial effects that:
(1) according to the invention, a simple mechanochemical method and an organic cross-coupling method are combined and applied, firstly, mechanical ball milling is utilized to preliminarily complete the substitution of alkynyl on-Br and generate a diacetylene bond, then, organic cross-coupling is carried out, under the catalytic action of a catalyst, the benzene rings are connected through the diacetylene bond, the formation of the diacetylene bond between the benzene rings is effectively promoted, and the process is simplified;
(2) the preparation method has the advantages of easily available raw materials, simple operation of the preparation process, short preparation time, industrial application and high yield;
(3) the preparation method has the advantages that nitrogen replacement is carried out in the reaction process, so that reaction byproducts can be effectively removed in time;
(4) the graphite diyne product obtained by the method only consists of carbon elements, and is essentially characterized by being a good semiconductor and having a natural band gap.
Drawings
FIG. 1 is a schematic preparation scheme for the synthesis of graphitic diyne in example 1;
FIG. 2 is a scanning electron micrograph of the graphitic diyne from example 1;
FIGS. 3a and 3b are transmission electron micrographs of the graphite diyne in example 1;
FIG. 4 is an X-ray diffraction pattern of the graphitic diyne in examples 1-3;
FIG. 5 is a Raman spectrum of graphdine of example 1;
FIG. 6 is an infrared spectrum of graphdine diyne from example 1;
FIGS. 7a and 7b are X-ray photoelectron spectra of the graphite diyne in example 1;
FIG. 8 is a valence band spectrum of graphite diyne from example 1;
FIG. 9 is the Mott Schottky curve for the graphitic diyne from example 1;
FIG. 10 is a diagram showing the band structure of graphite diyne in example 1.
Detailed Description
In order to make the technical scheme of the invention easier to understand, the technical scheme of the invention is clearly and completely described by adopting a mode of a specific embodiment in combination with the attached drawings.
Example 1:
the method for preparing graphite diyne by using alkynyl negative ions comprises the following steps:
(1) calcium carbide according to the mass ratio: hexabromobenzene: tribromobenzene ═ 2.94: 1.03: 1.03, adding calcium carbide, hexabromobenzene and tribromobenzene into a sealed ball milling tank, and ball milling beads according to the mass ratio: tribromobenzene ═ 50: adding ball milling beads in an amount of 1.03, and introducing nitrogen into a ball milling tank;
(2) setting a planetary ball mill at 500r/min, and carrying out ball milling on the sample in the ball milling tank in the step (1) for 10h to obtain graphite diacetylene intermediate products 1,3, 5-triacetylbenzene and hexaynylbenzene;
(3) putting the intermediate product obtained in the step (2) into a reaction container, and mixing the intermediate product with tetrakis (triphenylphosphine) palladium in a mass ratio of: copper acetate: tribromobenzene ═ 0.25: 0.25: 1, adding tetrakis (triphenylphosphine) palladium and copper acetate as catalysts into a reactor, and reacting according to the weight ratio of anhydrous toluene: tribromobenzene 100 mL: injecting anhydrous toluene in an amount of 1g for dissolving, heating to 75 ℃ under the protection of nitrogen for reaction for 72 hours, performing nitrogen replacement for 5 times in the reaction process, and removing gas impurity 2-butyne generated by the reaction;
(4) after the reaction is finished, the solvent in the reactor is evaporated to dryness, and then the reactor is placed in a tubular furnace at the speed of 3 ℃/min -1 Rate ofHeating to 450 ℃, keeping the temperature and calcining for 3h to remove the residual tribromobenzene and hexabromobenzene, soaking in aqua regia to remove the catalyst and other impurities, and performing suction filtration and drying to obtain the final product graphite diyne powder.
Example 2:
the method for preparing graphite diyne by using alkynyl negative ions comprises the following steps:
(1) calcium carbide according to the mass ratio: hexabromobenzene: tribromobenzene ═ 2: 1: 1, adding calcium carbide, hexabromobenzene and tribromobenzene into a sealed ball-milling tank, and ball-milling beads according to the mass ratio: tribromobenzene ═ 20: 1, adding ball milling beads, and introducing nitrogen into a ball milling tank;
(2) setting a planetary ball mill at 400r/min, and carrying out ball milling on the sample in the ball milling tank in the step (1) for 8 hours to obtain graphite diacetylene intermediate products 1,3, 5-triacetylbenzene and hexaynylbenzene;
(3) putting the intermediate product obtained in the step (2) into a reaction container, and mixing the intermediate product with tetrakis (triphenylphosphine) palladium in a mass ratio of: copper acetate: tribromobenzene ═ 0.2: 0.2: 1, adding tetrakis (triphenylphosphine) palladium and copper acetate as catalysts into a reactor, and reacting according to the following ratio of anhydrous toluene: tribromobenzene 120 mL: injecting anhydrous toluene in an amount of 1g for dissolving, heating to 75 ℃ under the protection of nitrogen for reacting for 48-96 h, performing nitrogen replacement for 3-5 times in the reaction process, and removing gas impurity 2-butyne generated by the reaction;
(4) after the reaction is finished, the solvent in the reactor is evaporated to dryness, and then the reactor is placed in a tubular furnace at the speed of 3 ℃/min -1 Heating to 650 ℃, keeping the temperature and calcining for 3h to remove the residual tribromobenzene and hexabromobenzene, soaking in aqua regia to remove the catalyst and other impurities, filtering, and drying to obtain the final product graphite diyne powder.
Example 3:
the method for preparing graphite diyne by using alkynyl negative ions comprises the following steps:
(1) calcium carbide according to the mass ratio: hexabromobenzene: tribromobenzene ═ 2.5: 1: 1, adding calcium carbide, hexabromobenzene and tribromobenzene into a sealed ball-milling tank, and ball-milling beads according to the mass ratio: tribromobenzene ═ 30: 1, adding ball milling beads, and introducing nitrogen into a ball milling tank;
(2) setting a planetary ball mill at 550r/min, and carrying out ball milling on the sample in the ball milling tank in the step (1) for 6h to obtain graphite diacetylene intermediate products 1,3, 5-triacetylbenzene and hexaynylbenzene;
(3) putting the intermediate product obtained in the step (2) into a reaction container, and mixing the intermediate product with tetrakis (triphenylphosphine) palladium in a mass ratio of: copper acetate: tribromobenzene ═ 0.2: 0.3: 1, adding tetrakis (triphenylphosphine) palladium and copper acetate as catalysts into a reactor, and reacting according to the weight ratio of anhydrous toluene: tribromobenzene 135 mL: injecting anhydrous toluene in an amount of 1g for dissolving, heating to 70 ℃ under the protection of nitrogen for reacting for 48-96 h, performing nitrogen replacement for 3-5 times in the reaction process, and removing gas impurity 2-butyne generated by the reaction;
(4) after the reaction is finished, the solvent in the reactor is evaporated to dryness, and then the reactor is placed in a tubular furnace at the speed of 3 ℃/min -1 Heating to 500 ℃, keeping the temperature and calcining for 3h to remove the residual tribromobenzene and hexabromobenzene, soaking in aqua regia to remove the catalyst and other impurities, filtering, and drying to obtain the final product graphite diyne powder.
Example 4:
the method for preparing graphite diyne by using alkynyl negative ions comprises the following steps:
(1) calcium carbide according to the mass ratio: hexabromobenzene: tribromobenzene ═ 3: 1: 1, adding calcium carbide, hexabromobenzene and tribromobenzene into a sealed ball-milling tank, and ball-milling beads according to the mass ratio: tribromobenzene ═ 40: 1, adding ball milling beads, and introducing nitrogen into a ball milling tank;
(2) setting a planetary ball mill at 600r/min, and carrying out ball milling on the sample in the ball milling tank in the step (1) for 7h to obtain graphite diacetylene intermediate products 1,3, 5-triacetylbenzene and hexaynylbenzene;
(3) putting the intermediate product obtained in the step (2) into a reaction container, and mixing the intermediate product with tetrakis (triphenylphosphine) palladium in a mass ratio of: copper acetate: tribromobenzene ═ 0.3: 0.2: 1, adding tetrakis (triphenylphosphine) palladium and copper acetate as catalysts into a reactor, and reacting according to the following ratio of anhydrous toluene: tribromobenzene 150 mL: injecting anhydrous toluene in an amount of 1g for dissolving, heating to 80 ℃ under the protection of nitrogen for reacting for 48-96 h, performing nitrogen replacement for 3-5 times in the reaction process, and removing gas impurity 2-butyne generated by the reaction;
(4) after the reaction is finished, the solvent in the reactor is evaporated to dryness, and then the reactor is placed in a tubular furnace at the speed of 3 ℃/min -1 Heating to 850 ℃, keeping the temperature and calcining for 1h to remove the residual tribromobenzene and hexabromobenzene, soaking in aqua regia to remove the catalyst and other impurities, filtering, and drying to obtain the final product graphite diyne powder.
Structural part characterization analysis:
fig. 2 is a scanning electron micrograph of the graphite diyne in example 1, and the result shows that the prepared graphite diyne has a continuous sheet-like porous membrane structure.
Fig. 3a and 3b are transmission electron microscope images of the graphite diyne in example 1, and the results are consistent with the scanning electron microscope image in fig. 2, and the high resolution transmission electron microscope image of the graphite diyne does not show the existence of lattice fringes.
Fig. 4 is an X-ray diffraction pattern of the graphite diyne of examples 1 to 3, each having a strong peak at 23 °, consistent with the high resolution transmission electron micrograph of fig. 3b, showing an amorphous structure.
FIG. 5 shows the Raman spectrum at 2135cm for graphite diyne from example 1 -1 And 2255cm -1 The vibrational modes of the two alkyne triple bonds possessed by graphitic diyne are shown: full symmetry synchronous stretch/contraction and 1/3 extension, 2/3 contraction, respectively.
FIG. 6 is an IR spectrum of 1613cm of graphdine diyne obtained in example 1 -1 The signal peak is caused by the vibration of the aromatic ring C ═ C skeleton, and 2134cm -1 The signal peak at (A) is the stretching vibration of the acetylene bond.
FIGS. 7a and 7b are X-ray photoelectron spectra of the graphyne diyne in example 1, which shows that the graphyne diyne is an all-carbon material and has sp and sp 2 Hybrid characteristics.
FIG. 8 is a valence band spectrum of graphdine diyne from example 1, showing that the valence band value of graphdine diyne is 1.31V.
FIG. 9 is a Mott Schottky curve of the graphitic diyne of example 1, showing that at different frequencies, the flat band potentials are all-0.6V and are n-type semiconductors.
FIG. 10 is a diagram showing the band structure of graphite diyne in example 1, and the results are in accordance with those in FIGS. 8 and 9.
It should be noted that the embodiments described herein are only some embodiments of the present invention, and not all implementations of the present invention, and the embodiments are only examples, which are only used to provide a more intuitive and clear understanding of the present invention, and are not intended to limit the technical solutions of the present invention. Other embodiments, as well as other simple alternatives and variations to the embodiments of the present invention, which will occur to persons skilled in the art without inventive faculty, are within the scope of the invention.
Claims (6)
1. A method for preparing graphite diyne by using alkynyl negative ions is characterized by comprising the following steps:
(1) calcium carbide according to the mass ratio: hexabromobenzene: tribromobenzene (2-3): 1: adding calcium carbide, hexabromobenzene, tribromobenzene and ball-milling beads into a sealed ball-milling tank, introducing nitrogen into the ball-milling tank, setting a planetary ball mill at 400-600 r/min, and carrying out ball-milling on a sample in the ball-milling tank for 6-10 h to obtain graphite diacetylene intermediate products 1,3, 5-triacetylbenzene and hexaynylbenzene;
(2) putting the intermediate product obtained in the step (1) into a reaction container, and mixing the intermediate product with tetrakis (triphenylphosphine) palladium in a mass ratio of: and (3) copper acetate: tribromobenzene ═ 0.2-0.3): (0.2-0.3): adding palladium tetrakis (triphenylphosphine) and copper acetate as catalysts into a reactor, injecting anhydrous toluene for dissolving, heating to 70-80 ℃ under the protection of nitrogen, reacting for 48-96 h, performing nitrogen replacement for many times in the reaction process, and removing gas impurity 2-butyne generated by the reaction;
(3) and after the reaction is finished, evaporating the solvent in the reactor to dryness, then placing the reactor in a tubular furnace, calcining the reactor for 1 to 3 hours at the temperature of 450 to 850 ℃ to remove the residual tribromobenzene and hexabromobenzene, soaking the reactor in aqua regia to remove the catalyst and other impurities, and performing suction filtration and drying to obtain the final product graphite diyne powder.
2. The method for preparing graphite diyne by using alkynyl negative ions, wherein the amount of the anhydrous toluene used in the step (2) is as follows: tribromobenzene ═ 100-150 mL: 1g of the total weight of the composition.
3. The method for preparing graphite diyne by using alkynyl negative ions, wherein the temperature rise rate of the tube furnace in the step (3) is 3 ℃/min -1 The calcination temperature is 450 ℃, and the calcination time is 3 h.
4. The method for preparing graphite diyne by using alkynyl negative ions, according to claim 1, wherein the planetary ball mill in the step (1) rotates at a speed of 500r/min for a ball milling time of 10 h.
5. The method for preparing graphite diyne by using alkynyl anions according to claim 1, wherein the amount of the ball milling beads used in the step (1) is calculated by mass ratio as follows: tribromobenzene (20-50): 1.
6. the method for preparing graphitic diyne using alkynyl negative ions according to claim 1, wherein the number of nitrogen replacements in step (2) is 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116715232A (en) * | 2023-04-06 | 2023-09-08 | 浙江大学 | Preparation method of independently-supportable three-dimensional graphite alkyne foam and product thereof |
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