CN110642241A - Preparation method of semiconductor carbon material - Google Patents
Preparation method of semiconductor carbon material Download PDFInfo
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- CN110642241A CN110642241A CN201910518920.5A CN201910518920A CN110642241A CN 110642241 A CN110642241 A CN 110642241A CN 201910518920 A CN201910518920 A CN 201910518920A CN 110642241 A CN110642241 A CN 110642241A
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Abstract
The invention discloses a preparation method of a semiconductor carbon material, which comprises the following steps: (1) diluting hydrogen peroxide with deionized water; (2) adding a carbon material into deionized water, stirring until the carbon material is uniformly dispersed, adjusting the pH of the system by using a 0.1mol/L dilute hydrochloric acid solution, stirring and heating; (3) weighing FeCl2Adding the mixture into the step (2), and stirring the mixture until the mixture is dissolved; (4) adding the hydrogen peroxide solution diluted in the step (1) into the step (3); (5) respectively and sequentially passing the product obtained in the step (4) through 0.1mol/L HCl and H2O, filtering and washing; the preparation method disclosed by the invention is green and environment-friendly, the carbon material is semiconductorized on the basis of retaining a ring structure, and the industrial production of the semiconductive carbon material is easy to realize.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a preparation method of a semiconducting carbon material.
Background
The carbon material is developed from zero-dimensional fullerene and one-dimensional carbon nanotube to two-dimensional graphene so far, and has excellent properties in the aspects of physics, chemistry, electricity, mechanics and the like due to the special structural characteristics of the carbon material. The excellent performances lead to potential application prospects in the fields of electronic devices, optical devices, chemical sensors, composite materials and the like.
Both the carbon nanotube and the graphene have excellent electrical properties, but the on/off current ratio is low because the on/off of the prepared field effect transistor cannot be controlled by a gate due to zero band gap width, and the field effect transistor cannot be applied to the electronic industry. Therefore, the method has important practical application value in opening a considerable band gap without destroying the excellent electrical properties of the carbon nanotube and the graphene. At present, the methods for opening the band gap mainly include: (1) destroying the crystal or chemical structure of the carbon nanotube or graphene; (2) the symmetry of graphene is broken by applying stress or the like, thereby opening the band gap. However, the band gap of the graphene prepared by the methods is narrow and difficult to control, and meanwhile, the required equipment is expensive and complicated in steps, so that the large-scale production of the graphene is difficult to realize.
Fullerene molecules have a very weak dispersion due to discrete energy levels in the solid, resulting in a narrow band gap width of only 0.5 eV. Thus, the use of fullerenes in the field of electronic devices is limited. The common method for broadening the band gap width of fullerene is mainly changed by doping boron and phosphorus with different contents, and the research on the treatment by chemical modification is less.
Disclosure of Invention
The present invention is directed to a method for producing a semiconducting carbon material, which solves the problems of the background art described above. In order to achieve the purpose, the invention provides the following technical scheme:
a method of preparing a semiconducting carbon material, the method comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:1 ~ 1:10 to obtain a hydrogen peroxide solution;
(2) adding 100mg of carbon material into 100mL of deionized water, stirring until the carbon material is uniformly dispersed, adjusting the pH of the system by using 0.1mol/L dilute hydrochloric acid solution, and stirring and heating to 25 ℃ of ~ 50 ℃;
(3) 0.98g of FeCl is taken2Adding the mixture into the solution obtained in the step (2), and stirringStirring until dissolving;
(4) dropwise adding a certain amount of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3);
(5) removing iron ions in the product obtained in the step (4) through a 0.1mol/L dilute hydrochloric acid solution;
(6) and (5) removing hydrogen ions and chloride ions in the product obtained in the step (5) through deionized water, and drying to obtain the semiconducting carbon material.
Preferably, the volume ratio of the hydrogen peroxide to the deionized water in the step (1) is 1: 3.
Preferably, the carbon material in step (2) includes fullerene or carbon nanotube or graphene, wherein the graphene is prepared by a mechanical exfoliation method or a vapor deposition method.
Preferably, the system pH =3 ~ 4 is adjusted in step (2).
Preferably, the amount of the hydrogen peroxide solution injected in the step (4) is 10mL ~ 200 mL.
Preferably, in the step (4), the hydrogen peroxide solution is dropwise added into the solution obtained in the step (3) through a micro syringe at an injection speed of 50 mL/h.
Preferably, the step (5) includes the steps of:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
Preferably, the step (6) comprises the steps of:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
Compared with the prior art, the invention has the beneficial effects that:
the invention is carried out by using hydrogen peroxide solution (H)2O2) With ferrous chloride (FeCl)2) The reaction generates hydroxyl free radical (. OH) with high activity, thereby being green and environment-friendly; OH is bonded with carbon atoms on the surface of the carbon material, so that the carbon material is hydroxylated, and the hydroxylated carbon material enables the carbon material to be semi-conductive on the basis of retaining a ring structure.
The invention also adjusts the band gap width of the semiconductor carbon material by controlling the injection amount of the hydrogen peroxide solution, and has strong controllability.
Drawings
Fig. 1 is a schematic structural diagram of a graphene semiconductor prepared in the first embodiment of the present invention.
Fig. 2 is an X-ray photoelectron spectrum of a graphene semiconductor prepared from graphene and hydrogen peroxide solutions with different amounts.
Fig. 3 is a raman spectrum of a graphene semiconductor prepared from graphene and hydrogen peroxide solutions with different amounts.
Fig. 4 is an X-ray photoelectron valence band spectrum of graphene semiconductors prepared from different amounts of hydrogen peroxide solutions.
Fig. 5 is a Mott-Schottky curve of graphene semiconductors prepared with different amounts of hydrogen peroxide solution.
Fig. 6 is a peak-off fit of the C1s spectrum of the graphene semiconductor prepared at 75mL for the injection of the hydrogen peroxide solution in fig. 3.
FIG. 7 is an X-ray photoelectron valence band spectrum of a fullerene semiconductor prepared at 75mL of injection of a hydrogen peroxide solution.
FIG. 8 is a Mott-Schottky curve of a fullerene semiconductor prepared at 75mL of injection of a hydrogen peroxide solution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a method for producing a semiconducting carbon material, comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:3 to obtain a hydrogen peroxide solution;
(2) adding 100mg of graphene into 100mL of deionized water, stirring until the graphene is uniformly dispersed, adjusting the pH of the system to be =3 by using 0.1mol/L of dilute hydrochloric acid solution, and stirring and heating to 35 ℃;
and (3) preparing the graphene in the step (2) by a mechanical stripping method.
The graphene is prepared by a mechanical stripping method, and specifically, 1.5g of polypropylene-polyethylene copolymer is weighed and added into 300mL of deionized water, and the mixture is stirred until the mixture is dissolved; then adding 0.3g of graphite powder, stirring until the graphite powder is uniformly dispersed, carrying out ultrasonic treatment for 2 hours, centrifuging the ultrasonic product for 5 minutes at the speed of 5000rpm, collecting 65% of dispersion liquid at the top, and drying to obtain solid graphene; the graphene prepared by the mechanical stripping method has high quality and few defects.
In the step (2), the graphene is uniformly dispersed in the deionized water by stirring for at least 5 min.
(3) Adding 0.98g of FeCl2 into the solution obtained in the step (2), and stirring until the FeCl2 is dissolved;
(4) dropwise adding 75mL of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3) through a micro-syringe at an injection speed of 50 mL/h;
according to the invention, the hydrogen peroxide solution and the solution obtained in the step (3) are slowly reacted by controlling the injection speed of the micro-injector, so that the solution obtained in the step (3) is prevented from overflowing in a large amount due to the activity of hydroxyl, and the operation is unsafe.
(5) Removing iron ions in the product obtained in the step (4) by using 0.1mol/L dilute hydrochloric acid solution.
The step (5) comprises the following steps:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
(6) And (5) removing hydrogen ions and chloride ions in the product obtained in the step (5) through deionized water, and drying to obtain the graphene semiconductor with the band gap width.
The step (6) comprises the following steps:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
The finally obtained graphene semiconductor is shown in fig. 1; with reference to fig. 3 to 4, the band gap width of the graphene semiconductor is 1.44eV as measured by a valence band spectrum of an X-ray photoelectron spectrum and a Mott-Schottky curve.
As can be seen from fig. 6, the graphene semiconductor has only one oxygen-containing group, i.e., hydroxyl group, and it is further verified that the degree of hydroxylation of graphene is high and the bonding of carbon and oxygen atoms is not changed.
Example 2:
a method for producing a semiconducting carbon material, comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:1 to obtain a hydrogen peroxide solution;
(2) adding 100mg of graphene into 100mL of deionized water, stirring until the graphene is uniformly dispersed, adjusting the pH of the system to be =4 by using 0.1mol/L of dilute hydrochloric acid solution, and stirring and heating to 25 ℃;
the graphene in the step (2) is prepared by a chemical vapor deposition method, and is specifically CH4、H2And Ar mixed gas reacts for 20min at 1000 ℃, and graphene is formed on the polycrystalline Ni foil.
(3) Adding 0.98g of FeCl2 into the solution obtained in the step (2), and stirring until the FeCl2 is dissolved;
(4) dropwise adding 75mL of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3) through a micro-syringe at an injection speed of 50 mL/h;
(5) removing iron ions in the product obtained in the step (4) through a 0.1mol/L dilute hydrochloric acid solution;
the step (5) comprises the following steps:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
(6) And (4) removing hydrogen ions and chloride ions in the product obtained in the step (5) through deionized water, and drying to obtain the graphene semiconductor with the band gap width of 1.23 eV.
The step (6) comprises the following steps:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
Example 3:
a method for producing a semiconducting carbon material, comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:10 to obtain a hydrogen peroxide solution;
(2) adding 100mg of graphene into 100mL of deionized water, stirring until the graphene is uniformly dispersed, adjusting the pH of the system to be =4 by using 0.1mol/L of dilute hydrochloric acid solution, and stirring and heating to 50 ℃;
and (3) preparing the graphene in the step (2) by a chemical vapor deposition method.
(3) Adding 0.98g of FeCl2 into the solution obtained in the step (2), and stirring until the FeCl2 is dissolved;
(4) dropwise adding 75mL of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3) through a micro-syringe at an injection speed of 50 mL/h;
(5) removing iron ions in the product obtained in the step (4) through a 0.1mol/L dilute hydrochloric acid solution;
the step (5) comprises the following steps:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
(6) And (4) removing hydrogen ions and chloride ions in the product obtained in the step (5) through deionized water, and drying to obtain the graphene semiconductor with the band gap width of 1.37 eV.
The step (6) comprises the following steps:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
Example 4:
this example was the same as the preparation method of example 1 except that the injection amount of the hydrogen peroxide solution in step (4) was reduced to 25 ml; finally, a graphene semiconductor with a band gap width of 0.86eV was obtained.
Example 5:
this example was the same as the preparation method of example 1 except that the injection amount of the hydrogen peroxide solution in step (4) was reduced to 50 ml; finally, a graphene semiconductor with a band gap width of 1.03eV was obtained.
Example 6:
this example was the same as the preparation method of example 1, only increasing the injection amount of the hydrogen peroxide solution in step (4) to 100 ml; finally, a graphene semiconductor having a band gap width of 1.57eV was obtained.
Example 7:
this example was the same as the preparation method of example 1, only increasing the injection amount of the hydrogen peroxide solution in step (4) to 150 ml; finally, a graphene semiconductor with a band gap width of 1.65eV was obtained.
As can be seen from fig. 2, as the hydrogen peroxide solution is increased, the intensity of the C1s spectrum is gradually decreased, and the intensity of the O1s spectrum is gradually increased, which further verifies the increase of the hydroxylation degree of graphene.
As can be seen from FIG. 5, the injection amount of graphene and graphene semiconductor injected by different hydrogen peroxide solutions was 1580 cm-1And 1350 cm-1Two scattering peaks are present near the position as a G peak and a D peak. The appearance of the D peak indicates that the hydroxyl groups are bonded with carbon atoms on the graphene sheet to destroy the stoneThe perfect structure of graphene reduces the structural symmetry of graphene, and the red shift phenomenon with small moving wave number of a D peak is generated along with the gradual increase of the hydroxylation degree. The larger the amount of hydrogen peroxide solution injected, the ratio of the D peak intensity to the G peak intensity (I)D/IG) The larger, so ID/IGThe change in value is related to the degree of hydroxylation.
As is clear from FIG. 3, the injection amounts of the hydrogen peroxide solution were 25mL, 50mL, 75mL, 100mL, and 150mL, respectively, and the valence band values (E) of the graphene semiconductorVB) Comprises the following steps: 0.66eV, 0.71eV, 1.09eV, 1.16eV, and 1.19eV, and the valence band value of the graphene electric conductor gradually increases with the increase of the hydroxylation degree; as can be seen from fig. 4, the injection amounts of the hydrogen peroxide solution were 25mL, 50mL, 75mL, 100mL, and 150mL, respectively, and the conduction band values (E) of the graphene semiconductorCB) The band gaps (E) of the graphene semiconductor were 25mL, 50mL, 75mL, 100mL, and 150mL, respectively, as shown by-0.20 eV, -0.32eV, -0.35eV, -0.41eV, and-0.46 eV, respectively, and the injection amounts of the hydrogen peroxide solution were 25mL, 50mL, 75mL, 100mL, and 150mL, respectivelyg) The molecular weight is respectively 0.86eV, 1.03eV, 1.44eV, 1.57eV and 1.65eV, which shows that the forbidden bandwidth of graphene can be opened by hydroxyl groups, and the forbidden bandwidth of graphene can be obviously regulated and controlled; the band gap width increases with increasing degree of hydroxylation.
Example 8:
a method for producing a semiconducting carbon material, comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:3 to obtain a hydrogen peroxide solution;
(2) adding 100mg of carbon nano tube into 100mL of deionized water, stirring until the carbon nano tube is uniformly dispersed, adjusting the pH of the system to be =4 by using 0.1mol/L of dilute hydrochloric acid solution, and stirring and heating to 35 ℃;
(3) adding 0.98g of FeCl2 into the solution obtained in the step (2), and stirring until the FeCl2 is dissolved;
(4) dropwise adding 75mL of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3) through a micro-syringe at an injection speed of 50 mL/h;
(5) removing iron ions in the product obtained in the step (4) through a 0.1mol/L dilute hydrochloric acid solution;
the step (5) comprises the following steps:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
(6) And (5) removing hydrogen ions and chloride ions in the product obtained in the step (5) through deionized water, and drying to obtain the semiconductor carbon nanotube with the band gap width.
The step (6) comprises the following steps:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
Example 9:
a method for producing a semiconducting carbon material, comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:3 to obtain a hydrogen peroxide solution;
(2) adding 100mg of fullerene into 100mL of deionized water, stirring until the fullerene is uniformly dispersed, adjusting the pH of the system to be =4 by using 0.1mol/L of dilute hydrochloric acid solution, and stirring and heating to 35 ℃;
(3) 0.98g of FeCl is taken2Adding the mixture into the solution obtained in the step (2), and stirring the mixture until the mixture is dissolved;
(4) dropwise adding 75mL of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3) through a micro-syringe at an injection speed of 50 mL/h;
(5) removing iron ions in the product obtained in the step (4) through a 0.1mol/L dilute hydrochloric acid solution;
the step (5) comprises the following steps:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
(6) And (3) removing hydrogen ions and chloride ions in the product obtained in the step (5) by deionized water, and drying to obtain the semiconducting fullerene with the band gap width of 1.62 eV.
The step (6) comprises the following steps:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
With reference to FIGS. 7 to 8, the fullerene semiconductor had a band gap width of 1.62eV as measured by a valence band spectrum of an X-ray photoelectron spectrum and a Mott-Schottky curve.
The present invention utilizes hydrogen peroxide (H)2O2) With ferrous chloride (FeCl)2) The reaction generates hydroxyl free radical (. OH) with high reaction activity; OH bonds to carbon atoms on carbon nanotubes, graphene and fullerenes, and changes the symmetry of their crystals and the hybridization pattern of the carbon atoms to yield carbon materials with semiconducting properties.
Claims (8)
1. A method for producing a semiconducting carbon material, comprising the steps of:
(1) preparing hydrogen peroxide and deionized water according to the volume ratio of 1:1 ~ 1:10 to obtain a hydrogen peroxide solution;
(2) adding 100mg of carbon material into 100mL of deionized water, stirring until the carbon material is uniformly dispersed, adjusting the pH of the system by using 0.1mol/L dilute hydrochloric acid solution, and stirring and heating to 25 ℃ of ~ 50 ℃;
(3) 0.98g of FeCl is taken2Adding the mixture into the solution obtained in the step (2), and stirring the mixture until the mixture is dissolved;
(4) dropwise adding a certain amount of the hydrogen peroxide solution obtained in the step (1) into the solution obtained in the step (3);
(5) removing iron ions in the product obtained in the step (4) through a 0.1mol/L dilute hydrochloric acid solution;
(6) and (5) removing hydrogen ions and chloride ions in the product obtained in the step (5) through deionized water, and drying to obtain the semiconducting carbon material.
2. The method of claim 1, wherein the volume ratio of hydrogen peroxide to deionized water in step (1) is 1: 3.
3. The method of claim 1, wherein the carbon material in the step (2) comprises fullerene or carbon nanotube or graphene, and wherein the graphene is prepared by a mechanical exfoliation method or a vapor deposition method.
4. The method for producing a semiconducting carbon material according to claim 1, wherein the system pH =3 ~ 4 is adjusted in step (2).
5. The method for producing a semiconductive carbon material according to claim 1, wherein the amount of the hydrogen peroxide solution injected in step (4) is 10mL ~ 200 mL.
6. The method for producing a semiconductive carbon material according to claim 5, wherein in the step (4), the hydrogen peroxide solution is added dropwise to the solution obtained in the step (3) by means of a micro syringe at an injection rate of 50 mL/h.
7. The method for producing a semiconducting carbon material according to claim 1, wherein: the step (5) comprises the following steps:
(5.1) washing the product obtained in the step (4) by using 0.1mol/L diluted hydrochloric acid solution, and filtering to obtain filtrate;
(5.2) dropwise adding hydrogen peroxide into 1-2 drops of the filtrate, adding the hydrogen peroxide into the potassium thiocyanate solution, judging whether the potassium thiocyanate solution turns into a blood red color, if so, returning to the step (5.1), otherwise, completely removing iron ions.
8. The method for producing a semiconducting carbon material according to claim 7, wherein: the step (6) comprises the following steps:
(6.1) washing the product obtained in the step (5) by using deionized water, and filtering;
(6.2) adding 1-2 drops of filtrate into the silver nitrate solution, if the silver nitrate solution generates white precipitates, returning to the step (6.1), otherwise, executing the step (6.3);
(6.3) dipping the filtrate by using a clean glass rod, dripping the filtrate into the middle part of pH test paper, if the pH test paper does not show red, executing the step (6.4), otherwise, returning to the step (6.1);
(6.4) placing the product obtained in the step (6.3) in a vacuum oven for drying for 24 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112850A (en) * | 2013-03-13 | 2013-05-22 | 上海第二工业大学 | Method for preparing high-quality graphene through catalytic oxidation multiple-intercalation |
| KR20160119882A (en) * | 2014-12-01 | 2016-10-17 | 주식회사 씨케이바이오텍 | Graphene oxide with higher amounts of oxygen group and method for preparing the same |
| CN106892425A (en) * | 2017-04-27 | 2017-06-27 | 山东金城石墨烯科技有限公司 | A kind of preparation method of nitration Graphene |
| CN108203088A (en) * | 2016-12-16 | 2018-06-26 | 北京福纳康生物技术有限公司 | A kind of high water solubility fullerol and preparation method thereof |
-
2019
- 2019-06-16 CN CN201910518920.5A patent/CN110642241A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112850A (en) * | 2013-03-13 | 2013-05-22 | 上海第二工业大学 | Method for preparing high-quality graphene through catalytic oxidation multiple-intercalation |
| KR20160119882A (en) * | 2014-12-01 | 2016-10-17 | 주식회사 씨케이바이오텍 | Graphene oxide with higher amounts of oxygen group and method for preparing the same |
| CN108203088A (en) * | 2016-12-16 | 2018-06-26 | 北京福纳康生物技术有限公司 | A kind of high water solubility fullerol and preparation method thereof |
| CN106892425A (en) * | 2017-04-27 | 2017-06-27 | 山东金城石墨烯科技有限公司 | A kind of preparation method of nitration Graphene |
Non-Patent Citations (1)
| Title |
|---|
| 李伟 等: "羟基自由基对多壁碳纳米管表面和结构的影响", 《无机化学学报》 * |
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