CN111484004A - Preparation method of graphene quantum dots - Google Patents
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Abstract
The invention provides a preparation method of graphene quantum dots, which comprises the following steps: providing an initial carbon nano tube, and carrying out oxidation treatment on the initial carbon nano tube to obtain a first carbon nano tube; calcining the first carbon nano tube to obtain a second carbon nano tube; and carrying out inert gas plasma treatment on the second carbon nano tube to obtain the graphene quantum dot. According to the preparation method, the graphene quantum dot material with stable photoelectric property and high quantum efficiency is prepared through the processes of oxidation, cutting and the like. The graphene quantum dots prepared by the method are stable in batch, high in production efficiency, suitable for industrial production and wide in application prospect in the fields of photoelectric display devices, photovoltaic devices and biomedicine.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method of graphene quantum dots.
Background
Graphene (Graphene) is a planar two-dimensional nanomaterial composed of a monolayer of carbon atoms. All carbon atoms in the graphene are represented by sp2The method performs orbital hybridization, so that the graphene has the characteristics of high heat conductivity coefficient, high electric conductivity coefficient, high structural strength and the like.
In recent years, graphene quantum dots have attracted attention as a novel fluorescent material. When two-dimensional graphene sheets are broken down to the nanoscale (typically less than 10 nm), graphene exhibits the characteristics of a semiconductor; under photon excitation, fluorescence is emitted. Graphene quantum dots have attracted extensive research interest since their discovery. Similar to semiconductor quantum dots, graphene quantum dots have the advantages of adjustable fluorescence emission, high light stability, wide excitation spectrum, small size and the like. In addition, the graphene quantum dots have the advantages of good biocompatibility, low toxicity, easy surface functionalization and the like. The advantages make up the defects of semiconductor quantum dots and traditional organic dyes, and have wide application prospects in the fields of photoelectric display devices, photovoltaic devices, biomedicine and the like.
At present, researchers have developed a plurality of methods for synthesizing graphene quantum dots, but these methods all have certain problems, such as low synthesis efficiency, poor fluorescence performance of the obtained graphene quantum dots, concentration of fluorescence emission wavelength in a blue light region, low fluorescence quantum efficiency, and the like. Therefore, how to efficiently prepare graphene quantum dots with excellent quantum efficiency is a focus of attention of researchers at present.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a preparation method of graphene quantum dots.
A preparation method of graphene quantum dots comprises the following steps:
providing an initial carbon nano tube, and carrying out oxidation treatment on the initial carbon nano tube to obtain a first carbon nano tube; calcining the first carbon nano tube to obtain a second carbon nano tube; and carrying out inert gas plasma treatment on the second carbon nano tube to obtain the graphene quantum dot.
According to the preparation method, the graphene quantum dot material with stable photoelectric performance and high quantum efficiency is prepared through the processes of oxidation, calcination (cutting of the carbon nano tube), argon plasma treatment (cutting of the carbon nano tube) and the like. The graphene quantum dots prepared by the method meet the actual size requirement of the quantum dots, are stable in batch, uniform in size distribution and high in production efficiency, are suitable for industrial production, and have wide application prospects in the fields of photoelectric display devices, photovoltaic devices and biomedicine.
Drawings
Fig. 1 is a flow chart of a process for preparing graphene quantum dots in some embodiments of the present invention.
Detailed Description
The invention provides a preparation method of graphene quantum dots, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, some embodiments of the present invention provide a method for preparing graphene quantum dots, which includes the following steps:
s10, providing an initial carbon nano tube, and carrying out oxidation treatment on the initial carbon nano tube to obtain a first carbon nano tube;
s20, calcining the first carbon nanotube to obtain a second nanotube;
and S30, performing inert gas plasma treatment on the second carbon nanotube to obtain the graphene quantum dot.
According to the preparation method, the graphene quantum dot material with stable photoelectric performance and high quantum efficiency is prepared through the processes of oxidation, calcination (cutting of the carbon nano tube), argon plasma treatment (cutting of the carbon nano tube) and the like. The graphene quantum dots prepared by the method meet the actual size requirement of the quantum dots, are stable in batch, uniform in size distribution and high in production efficiency, are suitable for industrial production, and have wide application prospects in the fields of photoelectric display devices, photovoltaic devices and biomedicine.
Specifically, in some embodiments, in the step S10, the initial carbon nanotube is a single-walled carbon nanotube, and graphene quantum dots with appropriate size (3-10 nm) and uniform distribution are easier to be realized through subsequent oxidation, cutting and cutting processes compared to multi-walled nanotubes. Therefore, the obtained graphene quantum dots are more stable in photoelectric performance and higher in quantum efficiency.
In some embodiments, in step S10, the initial nanotube may be oxidized by a conventional method to attach an oxidized group (e.g., a carboxyl group) to the surface of the carbon nanotube, and during the subsequent calcination process in step S02, the group may escape as a small molecule and form a defect on the surface of the carbon nanotube.
In some embodiments, in step S10, a certain amount of the initial carbon nanotube powder, deionized water, and concentrated nitric acid are added into a three-necked flask, stirred uniformly, and heated in a water bath. And then, after the water-bath heating is finished, transferring the obtained initial carbon nano tube treatment liquid into a centrifugal tube, carrying out centrifugal treatment at the rotating speed of 8000 rpm, pouring out the supernatant, dispersing the precipitate into deionized water again, and repeatedly centrifuging until the pH value of the supernatant is 6-7. And drying the treated initial carbon nano tube in vacuum to obtain oxidized initial carbon nano tube powder. In this process, the concentrated nitric acid water bath treatment of the initial carbon nanotube has the effect of oxidizing part of carbon atoms, so that the surface of the initial carbon nanotube is introduced with oxidized groups (such as carboxyl groups) to improve the dispersibility of the initial carbon nanotube, and the groups can escape in the form of small molecules and form defects on the surface of the carbon nanotube during the subsequent calcination process of step S02.
In some specific embodiments, in step S10, the concentrated nitric acid may be replaced by a strongly oxidizing water-soluble substance such as potassium permanganate, a mixed solution of concentrated nitric acid and potassium permanganate, and the like.
In some specific embodiments, in step S10, the ratio of the initial carbon nanotubes to the deionized water is in the range of 1: 50-500, the ratio of the initial carbon nanotubes to the deionized water is too small, the initial carbon nanotube concentration is low, the treatment efficiency is slow, the ratio of the initial carbon nanotubes to the deionized water is too large, and the initial carbon nanotubes cannot be completely immersed in the deionized water, thereby affecting the initial carbon nanotube carboxylation process; the proportion range of the deionized water to the concentrated nitric acid is 1: 1-5, the proportion of the deionized water to the concentrated nitric acid is too small, the content of the nitric acid is too high, nitrogen dioxide is generated in a solution in the reaction process, the influence on the environment is large, the proportion of the deionized water to the concentrated nitric acid is too large, the oxidability of a reaction solution is too small, and the initial carbon nano tube cannot be effectively oxidized.
In some specific embodiments, in step S10, the water bath temperature is 70 to 90 ℃, the temperature is too low, the time for carboxylation of the initial carbon nanotubes is long, the production efficiency is reduced, the temperature is too high, a large amount of nitric acid is decomposed, the oxidability of the reaction solution is reduced, and the initial carbon nanotubes cannot be carboxylated effectively; the carboxylation time of the initial carbon nano tube is 2-6 h, the time is too short, the initial carbon nano tube cannot be effectively oxidized, the time is too long, the production period is prolonged, and the industrial production is not facilitated.
In some specific embodiments, in step S10, the centrifugation rotation speed is 5000 rpm, the time is 3-5 min, the centrifugation rotation speed is too low, the initial carbon nanotubes cannot be completely settled if the centrifugation time is too short, the yield is reduced, the centrifugation rotation speed is too high, and the energy consumption and the production cost are increased if the centrifugation time is too long.
In some embodiments, in step S20, a certain amount of the first carbon nanotube powder is placed in a quartz boat, the quartz boat is transferred to a tubular muffle furnace, an inert gas is introduced, air in the tubular muffle furnace is removed, the temperature is rapidly raised to 800 to 1500 ℃ for a first calcination treatment, after 15 to 60 min of treatment, water vapor is introduced, a second calcination treatment is performed at 800 to 1000 ℃ for 10 to 30min, and then the second carbon nanotube after cutting is obtained.
In some embodiments, the first calcination treatment is performed at a temperature of 800 to 1500 ℃ in order to allow the organic functional groups on the surface of the first carbon nanotube to escape in the form of small molecules and to form defects on the surface of the carbon nanotube. The subsequent introduction of water vapor is to further etch and break the carbon nanotube by means of the reaction of water molecule and carbon atom at high temperature to cut carbon nanotube. Since the carbon atoms at the defect site have high reactivity and water molecules react preferentially with the carbon atoms, the defect gradually grows under the action of the water molecules and finally leads to the breakage of the carbon nanotube.
In some embodiments, the moving speed of the inert gas in the tubular muffle furnace is 20 cm-50 cm/min, the moving speed is too high, the gas is wasted, the cost is increased, the certain speed is too low, the risk of air infiltration into the muffle furnace is increased, and the inert environment of a reaction system cannot be effectively ensured;
in some embodiments, the first calcination treatment temperature is 800-1500 ℃, the temperature is too high, energy is wasted, the cost is increased, the temperature is too low, organic functional groups cannot effectively escape, the etching effect of the carbon nano tube is poor, and the subsequent reaction is influenced; the first calcination treatment time is 15-60 min, the time is too short, organic functional groups cannot effectively escape, the etching effect of the carbon nano tube is poor, subsequent reactions are affected, the time is too long, the preparation period is long, and the production is not facilitated.
In some embodiments, the second calcination treatment is performed in a mixed atmosphere with a volume ratio of water vapor to inert gas of 100: 5-20, the water vapor content is too high, a large amount of carbon nanotubes react with water molecules, the production efficiency is reduced, the water vapor content is too low, the amount of etched carbon nanotubes is small, the carbon nanotubes cannot be cut into carbon nanotube short tubes smaller than 10 nm, and quantum dots with proper sizes are difficult to prepare.
In some embodiments, the temperature of the second calcination treatment is 800-1000 ℃, the temperature is too high, energy is wasted, the cost is increased, the temperature is too low, the reaction of the carbon nanotubes and water molecules is slow, the preparation period is long, and the production is not facilitated; the time of the second calcination treatment is 10-30 min, the time is too short, the amount of the etched carbon nanotubes is less, the carbon nanotubes cannot be cut into carbon nanotube short tubes smaller than 10 nm, the subsequent reaction is influenced, the time is too long, the preparation period is prolonged, and the production is not facilitated.
In some embodiments, in step S30, the second carbon nanotube stub is placed in a fluidized bed reactor equipped with a plasma generating device (i.e., a pair of parallel electrodes is connected in a fluidized bed reaction chamber, and after a power supply is turned on, a high-energy electric arc is generated between the parallel electrodes, and the inert gas passes through the parallel electrodes and is ionized into an inert gas plasma), and the inert gas flow rate is adjusted to a certain range, so that the second carbon nanotube forms a stable fluidized state. At the same time, the positions of the parallel electrodes in the fluidized bed are adjusted, and the second carbon nanotubes in the fluidized state are positioned between the parallel electrodes. After the air in the fluidized bed is completely exhausted, the power supply is turned on, electric arcs are generated between the positive electrode and the negative electrode, and when inert gas passes through the area between the positive electrode and the negative electrode, ionization occurs under the action of the electric arcs, and inert gas plasma is generated. And after the carbon nano tube is bombarded by the inert gas plasma for 30-60 min, turning off the power supply, continuously introducing the inert gas until the temperature of the reactor is reduced to room temperature, and taking out the product in the reactor to obtain the graphene quantum dot powder.
In some embodiments, the second carbon nanotubes are subjected to an inert gas plasma treatment selected from an argon plasma treatment, a helium plasma treatment, a neon plasma treatment, a krypton plasma treatment, or a xenon plasma treatment.
In some embodiments, the moving speed of the inert gas in the fluidized bed reactor is 50-100 cm/min, the moving speed of the inert gas is too low, the carbon nano tube is deposited at the bottom of the reactor and cannot form a fluidized state, the energy utilization rate is low, the prepared product is not uniform, the moving speed of the inert gas is too high, the carbon nano tube is easily taken out of the reactor by airflow, and the production efficiency of the graphene quantum dot is obviously reduced;
in some embodiments, the second carbon nanotube in a fluidized state needs to be located between the parallel electrodes as much as possible, otherwise, the inert gas plasma generated between the electrodes cannot completely and effectively act on the carbon nanotube, so that the carbon nanotube stub cannot be cut into graphene quantum dots with uniform size.
In some embodiments, the air venting operation is due to the fact that during the plasma generation, if air is present in the reactor, various plasmas may be generated, which affect the purity and yield of the reaction products.
In some embodiments, the power supply of the plasma generator discharges at frequencies of 40 KHz, 13.56 MHz, 2.45GHz, other frequencies not allowed for use due to interference with wireless communications.
In some embodiments, the practical voltage of the plasma generator is 380V, the discharge current is 5-20A, the current is too small, the ionization efficiency of the inert gas is low, the production period is prolonged, the industrial production is not facilitated, the current is too large, the damage to positive and negative electrodes is large, parallel electrodes need to be frequently replaced, and the production cost is increased.
In some embodiments, the distance between the parallel electrodes (positive and negative electrodes) ranges from 2 mm to 20 mm, the distance is too short, the inert gas plasma generation efficiency is slow, the synthesis efficiency becomes low, the production period is prolonged, the distance is too long, and the condition for generating electric arcs between the electrodes becomes harsh and difficult to realize.
In some embodiments, the reaction time of the carbon nano short tube in the fluidized bed is 30-60 min, the reaction time is too short, the bombardment time of the carbon nano short tube by the inert gas plasma is insufficient, the carbon nano short tube cannot be completely opened, the graphene quantum dot material is obtained, the purity of the material is affected, the reaction time is too long, the production period is prolonged, energy is wasted, and the production cost is increased.
According to the preparation method provided by the embodiment of the invention, the graphene quantum dot material with stable photoelectric property and high quantum efficiency is prepared through the processes of oxidation, calcination (cutting of the carbon nano tube), argon plasma treatment (cutting of the carbon nano tube) and the like. The graphene quantum dots prepared by the method meet the actual size requirement of the quantum dots, are stable in batch, uniform in size distribution and high in production efficiency, are suitable for industrial production, and have wide application prospects in the fields of photoelectric display devices, photovoltaic devices and biomedicine.
The present invention will be described in detail below with reference to examples.
Example 1
(1) Single wall carbon nanotube oxidation
2 g of single-walled carbon nanotube powder, 200 ml of deionized water and 400 ml of concentrated nitric acid are respectively added into a 1000 ml three-necked flask, stirred uniformly and heated in a water bath at 80 ℃ for 3 hours. And after the water bath heating is finished, transferring the obtained single-walled carbon nanotube treatment liquid into 8 50 ml centrifuge tubes, carrying out centrifugal treatment at the rotating speed of 8000 rpm, pouring out the supernatant, re-dispersing the precipitate in deionized water, and repeatedly centrifuging until the pH value of the supernatant is 6-7. And (3) drying the treated single-walled carbon nanotube in vacuum to obtain carboxylated single-walled carbon nanotube powder.
(2) Single-walled carbon nanotube tailoring
And placing the oxidized single-walled carbon nanotube powder in a quartz boat, transferring the quartz boat into a tubular muffle furnace, introducing inert gas (argon) at the flow rate of 50 cm/min, exhausting for 30min, removing air in the tubular muffle furnace, regulating the flow rate of the inert gas (argon) to 20 cm/min, rapidly heating to 1000 ℃, and carrying out constant-temperature treatment for 30 min. Then, after the temperature is reduced to 800 ℃, water vapor with the amount of 10% of inert gas (argon) is introduced, the constant temperature reaction is carried out for 15 min, then, the muffle furnace is closed, the temperature is reduced to the room temperature, and the cut single-wall carbon nano short tube is taken out.
(3) Single-walled carbon nanotube cutting
And placing the cut carbon nano tube short tube into a fluidized bed reactor provided with a plasma generating device, exhausting for 30min at the flow rate of 100cm/min inert gas (argon), adjusting the flow rate of the inert gas (argon) to 60 cm/min after air in the fluidized bed is completely removed, adjusting the position of a parallel electrode to enable the parallel electrode to be in the fluidized state range of the carbon nano tube short tube, starting a power supply, discharging at the frequency of 40 KHz at the current of 5A to generate electric arc, ionizing the flow of the inert gas (argon), turning off the power supply after the inert gas (argon) plasma bombards the carbon nano tube short tube for 30min, continuing to introduce the inert gas (argon) to the reactor, cooling to the room temperature, taking out a product in the reactor, and obtaining graphene quantum dot powder.
Example 2
(1) Single wall carbon nanotube oxidation
2 g of single-walled carbon nanotube powder, 200 ml of deionized water and 400 ml of concentrated nitric acid are respectively added into a 1000 ml three-necked flask, stirred uniformly and heated in a water bath at 80 ℃ for 3 hours. And after the water bath heating is finished, transferring the obtained single-walled carbon nanotube treatment liquid into 8 50 ml centrifuge tubes, carrying out centrifugal treatment at the rotating speed of 8000 rpm, pouring out the supernatant, re-dispersing the precipitate in deionized water, and repeatedly centrifuging until the pH value of the supernatant is 6-7. And (3) drying the treated single-walled carbon nanotube in vacuum to obtain carboxylated single-walled carbon nanotube powder.
(2) Single-walled carbon nanotube tailoring
And placing the oxidized single-walled carbon nanotube powder in a quartz boat, transferring the quartz boat into a tubular muffle furnace, introducing inert gas (argon) at the flow rate of 50 cm/min, exhausting for 30min, removing air in the tubular muffle furnace, regulating the flow rate of the inert gas (argon) to 20 cm/min, rapidly heating to 1000 ℃, and carrying out constant-temperature treatment for 30 min. Then, after the temperature is reduced to 800 ℃, water vapor with the amount of 10% of inert gas (argon) is introduced, the constant temperature reaction is carried out for 15 min, then, the muffle furnace is closed, the temperature is reduced to the room temperature, and the cut single-wall carbon nano short tube is taken out.
(3) Single-walled carbon nanotube cutting
And placing the cut carbon nanotube short tube in a fluidized bed reactor provided with a plasma generating device, exhausting for 30min at the flow rate of 100cm/min inert gas (argon), adjusting the flow rate of the inert gas (argon) to 60 cm/min after air in the fluidized bed is completely removed, adjusting the position of a parallel electrode to enable the parallel electrode to be in the fluidized state range of the carbon nanotube short tube, starting a power supply, discharging at the frequency of 13.56 MHz at the current of 5A to generate electric arc, ionizing the flow of the inert gas (argon), turning off the power supply after the inert gas (argon) plasma bombards the carbon nanotube short tube for 30min, continuing introducing the inert gas (argon) to the reactor, cooling to the room temperature, taking out a product in the reactor, and obtaining graphene quantum dot powder.
Example 3
(1) Single wall carbon nanotube oxidation
2 g of single-walled carbon nanotube powder, 200 ml of deionized water and 400 ml of concentrated nitric acid are respectively added into a 1000 ml three-necked flask, stirred uniformly and heated in a water bath at 80 ℃ for 3 hours. And after the water bath heating is finished, transferring the obtained single-walled carbon nanotube treatment liquid into 8 50 ml centrifuge tubes, carrying out centrifugal treatment at the rotating speed of 8000 rpm, pouring out the supernatant, re-dispersing the precipitate in deionized water, and repeatedly centrifuging until the pH value of the supernatant is 6-7. And (3) drying the treated single-walled carbon nanotube in vacuum to obtain carboxylated single-walled carbon nanotube powder.
(2) Single-walled carbon nanotube tailoring
And placing the oxidized single-walled carbon nanotube powder in a quartz boat, transferring the quartz boat into a tubular muffle furnace, introducing inert gas (argon) at the flow rate of 50 cm/min, exhausting for 30min, removing air in the tubular muffle furnace, regulating the flow rate of the inert gas (argon) to 20 cm/min, rapidly heating to 1000 ℃, and carrying out constant-temperature treatment for 30 min. Then, after the temperature is reduced to 800 ℃, water vapor with the amount of 10% of inert gas (argon) is introduced, the constant temperature reaction is carried out for 15 min, then, the muffle furnace is closed, the temperature is reduced to the room temperature, and the cut single-wall carbon nano short tube is taken out.
(3) Single-walled carbon nanotube cutting
And placing the cut carbon nano tube short tube into a fluidized bed reactor provided with a plasma generating device, exhausting for 30min at the flow rate of 100cm/min inert gas (argon), adjusting the flow rate of the inert gas (argon) to 60 cm/min after air in the fluidized bed is completely removed, adjusting the position of a parallel electrode to enable the parallel electrode to be in the fluidized state range of the carbon nano tube short tube, starting a power supply, discharging at the frequency of 40 KHz at the current of 15A to generate electric arc, ionizing the flow of the inert gas (argon), turning off the power supply after the inert gas (argon) plasma bombards the carbon nano tube short tube for 30min, continuing to introduce the inert gas (argon) to the reactor, cooling to the room temperature, taking out a product in the reactor, and obtaining graphene quantum dot powder.
Claims (10)
1. A preparation method of graphene quantum dots is characterized by comprising the following steps:
providing an initial carbon nano tube, and carrying out oxidation treatment on the initial carbon nano tube to obtain a first carbon nano tube;
calcining the first carbon nano tube to obtain a second carbon nano tube;
and carrying out inert gas plasma treatment on the second carbon nano tube to obtain the graphene quantum dot.
2. The method of claim 1, wherein the initial carbon nanotubes are single-walled carbon nanotubes.
3. The preparation method of claim 1, wherein the size of the graphene quantum dot is 3-10 nm.
4. The method according to claim 1, wherein the graphene quantum dot is obtained by subjecting the calcined carbon nanotube to an inert gas plasma treatment under a condition that the second carbon nanotube is in a fluidized state.
5. The method according to claim 4, wherein the second carbon nanotube is placed in a fluidized bed reactor equipped with a plasma generator, the calcined carbon nanotube is converted into a fluidized state by introducing a flowing inert gas, the second carbon nanotube in the fluidized state is placed between a pair of electrodes of the plasma generator, and the inert gas plasma treatment is performed by applying a current.
6. The production method according to claim 5, wherein the inert gas plasma treatment is performed by energizing under the condition that a power discharge frequency of the plasma generation device is 40 KHz, 13.56 MHz, or 2.45 GHz; and/or the presence of a gas in the gas,
under the conditions that the practical voltage of the plasma generating device is 380V and the discharge current is 5-20A, electrifying to perform inert gas plasma treatment; and/or the presence of a gas in the gas,
the flow velocity of the flowing inert gas is 50-100 cm/min; and/or the presence of a gas in the gas,
the inert gas plasma treatment time is 30-60 min; and/or the presence of a gas in the gas,
the pair of electrodes are parallel electrodes, and the distance between the two electrodes is 2-20 mm.
7. The method according to claim 1, wherein the second carbon nanotube is subjected to an inert gas plasma treatment selected from an argon plasma treatment, a helium plasma treatment, a neon plasma treatment, a krypton plasma treatment, or a xenon plasma treatment.
8. The method according to claim 1, wherein the step of subjecting the first carbon nanotube to a calcination treatment comprises: carrying out primary calcination treatment on the first carbon nano tube under the condition of inert gas; and carrying out secondary calcination treatment under the condition of mixed atmosphere containing water vapor and inert gas.
9. The preparation method of claim 8, wherein the first carbon nanotube is subjected to a first calcination treatment under an inert gas condition, then an inert gas and water vapor are continuously introduced, and a second calcination treatment is performed under a mixed atmosphere condition containing the water vapor and the inert gas, wherein the volume of the water vapor and the inert gas is 100: 5-20.
10. The preparation method according to claim 8, wherein the temperature of the first calcination treatment is 800 to 1500 ℃; and/or the presence of a gas in the gas,
the time of the first calcination treatment is 15-60 min; and/or the presence of a gas in the gas,
the temperature of the second calcination treatment is 800-1000 ℃; and/or the presence of a gas in the gas,
the time of the second calcination treatment is 10-30 min.
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