CN102849724B - Preparation method of water-soluble carbon quantum dots - Google Patents
Preparation method of water-soluble carbon quantum dots Download PDFInfo
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- CN102849724B CN102849724B CN201210388668.9A CN201210388668A CN102849724B CN 102849724 B CN102849724 B CN 102849724B CN 201210388668 A CN201210388668 A CN 201210388668A CN 102849724 B CN102849724 B CN 102849724B
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Abstract
The invention discloses a new method for preparing water-soluble carbon quantum dots by taking graphite impurities as a raw material, and the graphite impurities are generated when a single-walled carbon nanotube is prepared by an arc process. The method comprises the steps of: adding the graphite impurities into a water solution containing a surface active agent, dispersing and centrifuging to obtain graphite particles with narrower size distribution; then, carrying out reaction between the graphite particles and a strong oxidant; adjusting the sizes of the carbon quantum dots by changing the reaction time and temperature; and finally, obtaining the water-soluble carbon quantum dots by alkali neutralization and dialysis bag separation. Compared with the prior art, the method for obtaining the carbon quantum dots by treating the graphite particles by the strong oxidant is simple in technology, and the quantum dots with different particle sizes can be obtained by controlling the size of the raw material, the experimental temperature and the reaction time; and the method is low in cost, thus being suitable for commercial production.
Description
Technical field
The invention belongs to nano material preparing technical field, specifically a kind of graphite impurities producing while utilizing arc process to prepare Single Walled Carbon Nanotube is prepared the method for water-soluble carbon quantum dot for raw material.
Background technology
From the beginning of the eighties in last century, the AlexanderEfros of doctor LoniSBrus of Bell Laboratory and USSR (Union of Soviet Socialist Republics) Yoffe institute and doctor A.I.Ekimov begin one's study after quantum dot (Quantum Dot), the optical property that it is remarkable, good electric property has caused the extensive concern of scientific circles, and be widely used in biomarker, disease detection, the fields such as semiconducter device and solar cell.Quantum dot has wide and continuous excitation spectrum, and emmission spectrum is narrow and symmetrical, and emmission spectrum can be controlled according to changing quantum dot size size, good biocompatibility, and fluorescence lifetime is long.Quantum dot has extremely wide application prospect on single-electron device, memory and various opto-electronic device.
Carbon quantum dot comprises carbon granule, Nano diamond and graphene quantum dot.With respect to other metal quantum points, carbon quantum dot is with low cost, and toxicity is little, environmentally safe, good biocompatibility, has good optical property and mechanical property, superior physics and chemistry stability, be widely used in photoelectric material biomarker, photodiode and sensor.
Oxidation style synthesizing water-solubility quantum dot is a kind of simple synthetic method efficiently, the graphite impurities producing for Single Walled Carbon Nanotube by electric arc legal system is raw material synthesizing water-solubility carbon quantum dot, with low cost, simple to operate and to reach quantum dot size controlled by controlling experiment parameter.Through existing literature search is found, X.Y. the people such as Xu delivered " Electrophoretic analysis andpurification of fluorescent single-walled carbon nanotube fragments; J.Am.Chem.Soc.2004; 126; 12736-12737 " on JAC S in 2004, and research can produce the carbon pipe fragment with fluorescent effect while finding purification Single Walled Carbon Nanotube.The people such as J.Xu delivered " Carbon nanoparticles as chromophores for photon harvesting andphotoeonversion; ChemPhysChem2011; 12; 3604-3608 " on ChemPhysChem in 2011, this paper carries out arc-over to prepare carbon granule raw material with pure Graphite Electrodes, then adopt strong acid oxidation style to prepare carbon quantum dot, but need to use and carry out centrifugation up to the centrifugal speed of 80000rpm, higher to equipment requirements, cost costliness, inconvenient operation.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, provide a kind of arc process that uses to prepare the method that graphite impurities raw material that Single Walled Carbon Nanotube produces is prepared water-soluble carbon quantum dot.
Object of the present invention can be achieved through the following technical solutions: a kind of preparation method of water-soluble carbon quantum dot, it is characterized in that, and the method comprises the following steps:
(1) raw materials pretreatment
The graphite impurities producing in the time that arc process is prepared Single Walled Carbon Nanotube is raw material, this raw material is added and in the deionized water that contains tensio-active agent, mix and be uniformly dispersed, then carry out centrifugation, by regulating segregation rate control raw materials size, then suction filtration is removed tensio-active agent, obtains graphite granule raw material;
(2) preparation of water-soluble quantum dot
Gained graphite granule raw material is put into strong oxidizer solvent and carry out oxidizing reaction, after finishing, reaction add alkaline reactant neutralization solution to neutral, then dialyse by dialysis tubing, the interception of controlling oxidizing reaction temperature, reaction times and dialysis tubing obtains the controlled water-soluble carbon quantum dot of size.
Described segregation rate is 3000～20000rpm.
Described oxidizing reaction temperature is 80～200 DEG C, and the reaction times is 5～50h, and the molecular retention amount of dialysis tubing is 1000～3000, dialyses 3 days.
The particle size range of described water-soluble carbon quantum dot is 1～20nm.
Described tensio-active agent is sodium lauryl sulphate, Sodium cholic acid or Triton X-100.
In the described deionized water that contains tensio-active agent, the concentration of tensio-active agent is 1wt%, and the mass ratio of graphite raw material and water phase surfactant mixture is (0.05～0.5): 100.
Described strong oxidizer is one or more the mixing solutions in the vitriol oil, concentrated nitric acid, potassium permanganate.
The add-on of described strong oxidizer is every milligram of raw material 0.01～0.5mmol.
Described alkaline reactant NaCO
3, NaOH or KOH.
Compared with prior art, the present invention, by controlling size, temperature of reaction and time, the dialysis tubing interception of graphite impurities raw material, obtains the controlled water-soluble carbon quantum dot of size, simple to operate, is applicable to commercially producing.
Brief description of the drawings
Fig. 1 is preparation technology's schema of water-soluble carbon quantum dot of the present invention
Fig. 2 is the prepared water-soluble carbon quantum dot uv absorption spectra of embodiment 1;
Fig. 3 is the prepared water-soluble carbon quantum dot fluorescence utilizing emitted light spectrogram of embodiment 1;
Fig. 4 is the AFM figure of the water-soluble carbon quantum dot prepared of embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Arc process is prepared to the graphite impurities that Single Walled Carbon Nanotube produces and be dissolved in (mass ratio of the aqueous solution of graphite impurities and sodium lauryl sulphate is 0.5: 100) in the aqueous solution that contains 1wt% sodium lauryl sulphate, and ultrasonic dispersion 1h, then adopt 3000rpm rotating speed centrifugal, by gained supernatant liquor again with the centrifugation of 6000rpm rotating speed, take out throw out, remove tensio-active agent by suction filtration.By the graphite granule of gained and sulfuric acid/nitric acid (v/v=3: 1) mix in 0.5ml/mg (being roughly equal to 0.01mmol/mg) ratio, be heated to 150 DEG C with oil bath and be oxidized back flow reaction, reaction is carried out 30 hours, take out solution and with 10 times of deionized water dilutions, then add NaCO
3neutralization is 7 to pH, and the dialysis tubing that is finally 2000 by gained solution with interception dialysis 3 days, obtains water-soluble carbon quantum dot, and its particle size range is 15～20nm, and its abosrption spectrogram, fluorescence emission spectrogram are respectively as shown in Figures 2 and 3.
Embodiment 2
The graphite impurities producing when arc process is prepared to Single Walled Carbon Nanotube is dissolved in (mass ratio of the aqueous solution of graphite impurities and sodium lauryl sulphate is 0.05: 100) in the aqueous solution that contains 1wt% sodium lauryl sulphate, ultrasonic dispersion 1h, then centrifugal under 17000rpm rotating speed, gained supernatant liquor, again with the centrifugation of 20000rpm rotating speed, takes out throw out and removes sodium lauryl sulphate by suction filtration.By gained graphite granule and sulfuric acid/nitric acid (v/v=3: 1) mix in 0.5ml/mg (being roughly equal to 0.01mmol/mg) ratio, be heated to 200 DEG C with oil bath and be oxidized back flow reaction, reaction is carried out 40 hours, take out solution and with 10 times of deionized water dilutions, adding NaOH to neutralize pH is 7 again, and the dialysis tubing that is 2000 with interception by gained solution dialysis 3 days, obtains water-soluble carbon quantum dot, its particle size range is 1～5nm, and its AFM shape appearance figure as shown in Figure 4.
Embodiment 3
Arc process is prepared to the graphite impurities that Single Walled Carbon Nanotube produces to be dissolved in the aqueous solution that contains 1wt% sodium lauryl sulphate, ultrasonic dispersion 1h, then centrifugal under 12000rpm rotating speed, gained supernatant liquor carries out the centrifugation of 15000rpm rotating speed again, takes out throw out and removes sodium lauryl sulphate by suction filtration.The graphite granule of gained is mixed in 0.5ml/mg (being roughly equal to 0.01mmol/mg) ratio with concentrated nitric acid, be heated to 150 DEG C with oil bath and be oxidized back flow reaction, reaction is carried out 5 hours, take out solution and with 10 times of deionized water dilutions, adding NaOH to neutralize pH is 7 again, the dialysis tubing that is 3000 with interception by gained solution, obtains water-soluble carbon quantum dot, and its particle size range is 10～15nm.
Embodiment 4
The graphite impurities producing when arc process is prepared to Single Walled Carbon Nanotube is dissolved in the aqueous solution that contains 1wt% Sodium cholic acid, ultrasonic dispersion 1h, then centrifugal under 6000rpm rotating speed, gained supernatant liquor carries out the centrifugation of 9000rpm rotating speed again, takes out throw out and removes Sodium cholic acid by suction filtration.Gained graphite granule is mixed in 0.5ml/mg (being roughly equal to 0.01mmol/mg) ratio with the vitriol oil, be heated to 120 DEG C be oxidized back flow reaction with oil bath, the reaction times is 50 hours, takes out solution and with 10 times of deionized water dilutions, then adds NaCO
3neutralization is 7 to pH, and finally to adopt interception be 2000 dialysis tubing to the gained solution desalination of dialysing, and obtains water-soluble carbon quantum dot, and its particle size range is 510mn.
Embodiment 5
Arc process is prepared to the graphite impurities that Single Walled Carbon Nanotube produces to be dissolved in the aqueous solution that contains 1wt%TritonX-100, and ultrasonic dispersion 1h, then the centrifugal precipitation of going under 3000rpm rotating speed, gained supernatant liquor, again with the centrifugation of 6000rpm rotating speed, takes out throw out and removes Triton X-100 by suction filtration.The graphite granule of gained is mixed in 0.5mmol/mg ratio with potassium permanganate solution, be heated to 120 DEG C with oil bath and be oxidized back flow reaction, reaction is carried out 30 hours, take out solution and with 10 times of deionized water dilutions, then adding KOH to neutralize pH is 7, the dialysis tubing that is finally 1000 by gained solution with interception dialysis 3 days, obtains water-soluble carbon quantum dot, and its particle size range is 15～20nm.
Claims (6)
1. a preparation method for water-soluble carbon quantum dot, is characterized in that, the method comprises the following steps:
(1) raw materials pretreatment
The graphite impurities producing in the time that arc process is prepared Single Walled Carbon Nanotube is raw material, this raw material is added and in the deionized water that contains tensio-active agent, mix and be uniformly dispersed, then carry out centrifugation, by regulating segregation rate control raw materials size, then suction filtration is removed tensio-active agent, obtains graphite granule raw material;
(2) preparation of water-soluble quantum dot
Gained graphite granule raw material is put into strong oxidizer solvent and carry out oxidizing reaction, after finishing, reaction add alkaline reactant neutralization solution to neutral, then dialyse by dialysis tubing, the interception of controlling oxidizing reaction temperature, reaction times and dialysis tubing obtains the controlled water-soluble carbon quantum dot of size;
The particle size range of described water-soluble carbon quantum dot is 1～20nm;
Described segregation rate is 3000～20000rpm; Described oxidizing reaction temperature is 80～200 DEG C, and the reaction times is 5～50h, and the molecular retention amount of dialysis tubing is 1000～3000, dialyses 3 days.
2. the preparation method of water-soluble carbon quantum dot according to claim 1, is characterized in that, described tensio-active agent is sodium lauryl sulphate, Sodium cholic acid or Triton X-100.
3. the preparation method of water-soluble carbon quantum dot according to claim 1, it is characterized in that, in the described deionized water that contains tensio-active agent, the concentration of tensio-active agent is 1wt%, and the mass ratio of graphite raw material and water phase surfactant mixture is (0.05～0.5): 100.
4. the preparation method of water-soluble carbon quantum dot according to claim 1, is characterized in that, described strong oxidizer is one or more the mixing solutions in the vitriol oil, concentrated nitric acid, potassium permanganate.
5. the preparation method of water-soluble carbon quantum dot according to claim 1, is characterized in that, the add-on of described strong oxidizer is every milligram of raw material 0.01～0.5mmol.
6. the preparation method of water-soluble carbon quantum dot according to claim 1, is characterized in that, described alkaline reactant NaCO
3, NaOH or KOH.
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| CN111490170B (en) * | 2019-01-25 | 2021-08-10 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN113788479A (en) * | 2021-10-29 | 2021-12-14 | 凯盛石墨碳材料有限公司 | Preparation method of graphite-based quantum dots |
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| Electrophoretic Analysis and Purification of Fluorescent Single-Walled Carbon Nanotube Fragments;Xiaoyou Xu et al.;《J.AM.CHEM.SOC.》;20041231;第126卷(第40期);第12736-12737页 * |
| Xiaoyou Xu et al..Electrophoretic Analysis and Purification of Fluorescent Single-Walled Carbon Nanotube Fragments.《J.AM.CHEM.SOC.》.2004,第126卷(第40期),第12736-12737页. |
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