CN108529598B - Preparation method of carbon nano onion - Google Patents
Preparation method of carbon nano onion Download PDFInfo
- Publication number
- CN108529598B CN108529598B CN201810637580.3A CN201810637580A CN108529598B CN 108529598 B CN108529598 B CN 108529598B CN 201810637580 A CN201810637580 A CN 201810637580A CN 108529598 B CN108529598 B CN 108529598B
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- hydrothermal reaction
- aqueous solution
- citrate
- metal ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/154—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The embodiment of the invention provides a preparation method of carbon nano onions, which comprises the following steps: obtaining a reactant aqueous solution, wherein the reactant aqueous solution contains citrate; and carrying out hydrothermal reaction on the reactant aqueous solution, wherein the temperature of the hydrothermal reaction is more than or equal to 140 ℃. The preparation method of the carbon nano onion provided by the invention can realize the preparation of the carbon nano onion at the temperature of more than or equal to 140 ℃, and the reaction condition is milder; furthermore, the carbon nano-onion is prepared by hydrothermal reaction, and the method is simple in process flow and easy to operate, regulate and control. In addition, the preparation method of the carbon nano onion takes water as a reaction medium, and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a preparation method of carbon nano onions.
Background
Carbon nano-onions (CNOs), another novel carbon nanomaterial following fullerenes and carbon nanotubes, are onion-like spherical carbon simple substance structures, also called onion-like fullerenes, in the form of onion-like or polyhedral particle carbon atom clusters formed by several concentric spherical graphite shell layers, with sizes on the order of nanometers. The structure may be classified into only graphitic carbon layers, hollow CNOs, and non-hollow CNOs.
Since the first discovery of CNOs by Ugarte in 1992, various synthetic methods have been reported in succession. The production methods mainly include arc discharge method, plasma method, electron beam irradiation method, heat treatment method (which refers to high temperature treatment of carbon allotrope, such as diamond annealing method), pyrolysis method (which uses organic metal compound, organic metal polymer, etc. as metal source, and pyrolyzes with proper carbon source in inert gas to obtain composite material with nano metal uniformly dispersed in carbon aggregate), CVD method, laser irradiation method, and carbon dissociationThe sub-injection method, the liquid phase impregnation carbonization method, the metal-containing carbon-based xerogel explosion method, etc., but most of the methods need higher energy, for example, when the CNOs is prepared by calcining the nano-diamond powder at high temperature, high temperature conditions exceeding 1700 ℃ and certain gas atmosphere protection are often needed. The catalytic action of Ni/Al can realize CH in hydrogen atmosphere at 600 DEG C4Conversion of gases to CNOs.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of carbon nano onions, which aims to realize the preparation of the carbon nano onions by adopting milder reaction conditions. The specific technical scheme is as follows:
a method for preparing carbon nano onion comprises the following steps:
obtaining a reactant aqueous solution, wherein the reactant aqueous solution contains citrate;
and carrying out hydrothermal reaction on the reactant aqueous solution, wherein the temperature of the hydrothermal reaction is more than or equal to 140 ℃.
In some embodiments of the present invention, the reactant aqueous solution further comprises a metal ion, wherein the metal ion is a monovalent, divalent and/or trivalent metal ion; preferably, the metal ion is selected from Li+、Na+、K+、Ca2+、Mg2+、Ba2 +、Al3+Or any combination thereof.
In some embodiments of the invention, the reactant aqueous solution is obtained by:
citric acid and a metal ion source containing the metal ions are dissolved in water.
In some embodiments of the invention, the source of metal ions is selected from a water-soluble base and/or a water-soluble salt.
In some embodiments of the invention, the metal ion source is selected from one of sodium hydroxide, sodium chloride, sodium nitrate, potassium hydroxide, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, or any combination thereof.
In some embodiments of the invention, the reactant aqueous solution is obtained by:
dissolving citrate in water; the citrate salt contains the metal ion.
In some embodiments of the invention, the molar ratio of the citrate to the metal ion is 1: (0.1-10); preferably 1: (1-8).
In some embodiments of the present invention, the temperature of the hydrothermal reaction is 140-; preferably 160-200 ℃; more preferably 170 ℃ and 190 ℃ and most preferably 180 ℃.
In some embodiments of the present invention, the hydrothermal reaction is carried out for a period of time ranging from 2 to 48 hours, preferably from 4 to 24 hours, and more preferably from 4 to 12 hours.
The preparation method of the carbon nano onion provided by the invention can realize the preparation of the carbon nano onion at the temperature of more than or equal to 140 ℃, and the reaction condition is milder;
furthermore, the carbon nano-onion is prepared by hydrothermal reaction, and the method is simple in process flow and easy to operate, regulate and control.
In addition, the preparation method of the carbon nano onion takes water as a reaction medium, and is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an HRTEM of carbon nano-onions prepared in examples 1, 3, 5, wherein (a) is an HRTEM of carbon nano-onions prepared in example 1; (b) HRTEM for carbon nano-onions prepared in example 3; (c) is an HRTEM image of the carbon nano-onions prepared in example 5.
Fig. 2 is HRTEM of carbon nano-onions prepared in examples 2 and 4, wherein (a), (c) in fig. 2 are HRTEM of carbon nano-onions prepared in example 2, and (b), (d) in fig. 2 are HRTEM of carbon nano-onions prepared in example 4;
FIG. 3 is an HRTEM image of carbon nano-onions prepared in examples 6-19, wherein (a) is an HRTEM image of carbon nano-onions prepared in example 6; (b) HRTEM for carbon nano-onions prepared in example 7; (c) HRTEM for carbon nano-onions prepared in example 8; (d) HRTEM for carbon nano-onions prepared in example 9; (e) HRTEM for carbon nano-onions prepared in example 10; (f) HRTEM for carbon nano-onions prepared in example 11; (g) HRTEM for carbon nano-onions prepared in example 12; (h) HRTEM for carbon nano-onions prepared in example 13; (i) HRTEM for carbon nano-onions prepared in example 14; (j) HRTEM for carbon nano-onions prepared in example 15; (k) HRTEM for carbon nano-onions prepared in example 16; (l) HRTEM for carbon nano-onions prepared in example 17; (m) is an HRTEM of carbon nano-onions prepared in example 18;
fig. 4 is an HRTEM of carbon nano-onions prepared in example 23.
Detailed Description
The inventor unexpectedly finds out in the experimental process that the water solution containing citrate can prepare the carbon nano onion through hydrothermal reaction when monovalent, divalent and/or trivalent metal ions exist in the water solution; based on the above, the invention provides a preparation method of carbon nano-onion, which comprises the following steps:
step (1), obtaining a reactant aqueous solution, wherein the reactant aqueous solution contains citrate;
and (2) carrying out hydrothermal reaction on the reactant aqueous solution, wherein the temperature of the hydrothermal reaction is more than or equal to 140 ℃.
In a specific embodiment, in the step (2), the reactant aqueous solution may be transferred to a hydrothermal reaction kettle to perform a hydrothermal reaction; more specifically, a heating apparatus, such as an air-blast drying oven or a muffle furnace, may be heated to the temperature of the hydrothermal reaction in advance, and the hydrothermal reaction kettle to which the reactant aqueous solution is added may be placed in the heating apparatus to perform the hydrothermal reaction. The hydrothermal reaction kettle, the heating equipment and the like are all conventional equipment, and the invention is not limited herein.
After the hydrothermal reaction is finished, the obtained carbon nano onion is dispersed in water, and the solution is transparent.
In the specific implementation process, the carbon nano onion can be prepared by using a larger concentration or a smaller concentration of citrate, in some embodiments of the invention, the concentration of citrate in the obtained reactant aqueous solution can be 0.1-10M, or 0.1-1M, or 0.2M (1M ═ 1mol/L), and experiments prove that the carbon nano onion can be prepared in the concentration ranges. In particular embodiments, the citrate may be derived from citric acid dissolved in water.
In the practice of the present invention, the inventors have unexpectedly found that when the reactant aqueous solution further contains metal ions, the formation of carbon nano-onions can be accelerated; in some embodiments of the present invention, the reactant aqueous solution further comprises a metal ion, wherein the metal ion is a monovalent, divalent and/or trivalent metal ion.
In some embodiments of the invention, the metal ion is selected from Li+、Na+、K+、Ca2+、Mg2+、Ba2+、Al3+Or any combination thereof.
In some embodiments of the invention, the reactant aqueous solution is obtained by:
and dissolving citric acid and a metal ion source containing the metal ions in water to obtain the reactant mixed solution. In some embodiments of the invention, the source of metal ions is selected from a water-soluble base and/or a water-soluble salt containing the metal ions. As used herein, the term "water-soluble base" or "water-soluble salt" refers to a base or a salt having a solubility in 100g of water of 0.01g or more, preferably 1g or more, at 20 ℃. More specifically, the metal ion source may be selected from one of sodium hydroxide, sodium chloride, sodium nitrate, potassium hydroxide, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, or any combination thereof. The citric acid and citric acid used in the present inventionThe source of metal ions may contain some water of crystallization. For example, citric acid monohydrate, Mg (NO)3)2·6H2O、Ca(NO3)2·4H2O、Al(NO3)3·9H2O, and the like.
In some embodiments of the invention, the reactant aqueous solution is obtained by:
dissolving citrate in water; the citrate salt contains the metal ion; the citric acid salt used may be any commercially available common citric acid salt such as sodium citrate, monosodium citrate, disodium citrate, potassium citrate, monopotassium citrate, dipotassium citrate, calcium citrate, etc.; if desired, citrate may also be dissolved in water in combination with an amount of a metal ion source to adjust the ratio of citrate to metal ion.
In the practice of the present invention, the inventors have found that the amount of metal ions in the reactant aqueous solution has some influence on the reaction rate, and specifically, the more the amount of metal ions, the faster the reaction rate; in some embodiments of the invention, the molar ratio of citrate to the metal ion is 1: (0.1-10); preferably 1: (1-8). More specifically, it may be 1: 1. 1: (1-2), 1: (1-3), 1: (1-4), 1: (1-5), 1: (1-6) or 1: (1-7).
In some embodiments of the present invention, the temperature of the hydrothermal reaction is 140-; further preferably 160-200 ℃; more preferably 170 ℃ and 190 ℃ and most preferably 180 ℃.
In the specific implementation process of the invention, the inventor finds that the carbon nano onion can be formed when the temperature of the hydrothermal reaction is more than or equal to 140 ℃. The higher the reaction temperature, the higher the reaction rate, but considering the actual equipment situation, the temperature of the hydrothermal reaction can be 140-; for example, when a polytetrafluoroethylene-lined hydrothermal kettle is used, the hydrothermal reaction temperature may be 140-. Meanwhile, the lower the reaction temperature, the slower the reaction rate, and the poorer the time economy.
In each of the above hydrothermal reaction temperature ranges, the hydrothermal reaction time may be 2 to 48 hours, 4 to 24 hours, 4 to 12 hours, or 5 hours, 6 hours, 7 hours, 8 hours, or the like.
During the course of the experiments, the inventors further found that when the metal ions were selected from Li+、Ca2+、Mg2+、Ba2+、Al3+In the above formula, the prepared carbon nano onion is non-hollow carbon nano onion; when the metal ion is selected from Na+、K+In the case of the carbon nano onions, the prepared carbon nano onions may include hollow carbon nano onions, non-hollow carbon nano onions, and hollow or non-hollow carbon nano onions. For example, when citrate is reacted with Na+In a molar ratio of 1: 1, the prepared carbon nano onion is a hollow carbon nano onion; when citrate radical is reacted with Na+Or K+In a molar ratio of 1: 2, the prepared product can simultaneously contain hollow or non-hollow carbon nano onions.
Therefore, the preparation method of the carbon nano onion provided by the invention not only can prepare the carbon nano onion, but also can obtain carbon nano onions with different structures, such as hollow or non-hollow carbon nano onions, by adjusting the type of metal ions and the ratio of citrate to the metal ions.
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.
Preparation example containing Metal ions
Example 1
According to containing Na+The molar weight of the citric acid is 2:1, 2.7318g (0.013mol) of citric acid monohydrate and 1.0400g (0.026mol) of NaOH are respectively dissolved in 65mL of water, and the mixture is magnetically stirredStirring to prepare a reactant aqueous solution with the citric acid concentration of 0.2M, transferring the reactant aqueous solution into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle into an electrothermal blowing dry box at 180 ℃ for heat preservation for 8 hours, and cooling to room temperature after the reaction is finished.
Examples 2 to 13
Carbon nano onions were prepared according to the preparation method of example 1, using the process parameters in table 1.
TABLE 1 Process parameters for the preparation of carbon nano-onions in examples 2-13
Preparation examples not containing Metal ions
Example 23
2.7318g (0.013mol) of citric acid monohydrate is dissolved in 65mL of water, reactant aqueous solution with the citric acid concentration of 0.2M is prepared by magnetic stirring, the reactant aqueous solution is transferred to a 100mL of polytetrafluoroethylene-lined hydrothermal reaction kettle and is placed in an electrothermal blowing dry box at 180 ℃ for heat preservation for 8 hours, and the reaction is cooled to room temperature after the reaction is finished.
Transmission Electron Microscope (TEM) analysis
The carbon nano-onions prepared in examples 1 to 18 and 23 were subjected to High Resolution Transmission Electron Microscopy (HRTEM) tests under the following conditions: the acceleration voltage was 200kV and the samples were prepared on a standard copper grid carrying a carbon film.
HRTEM images of examples 1, 3, 5 are shown in FIG. 1;
it can be observed from the graphs in fig. 1 that the CNOs obtained by the reaction under the conditions of examples 1, 3 and 5 are all hollow structures and contain quasi-spherical CNOs, polyhedral CNOs and other intermediate transition forms, a few graphitized shell layers are formed on the outer edge, the size is about 10-20nm, the size distribution is uniform, regular and very clear concentric circle-shaped lattice fringes are formed, the lattice spacing is close to the (002) crystal face spacing of graphite and is about 0.34nm, and the carbon nano onion is high in crystallinity.
The inventors further found that when HRTEM testing was performed on the carbon nano oceans prepared in examples 2 and 4, hollow carbon nano onions and non-hollow carbon nano onions were simultaneously found; the results are shown in FIG. 2; FIGS. 2 (a), (b) show that the carbon nano-onions prepared in examples 2 and 4 have concentric ring-shaped hollow structures formed by curved graphitized shells, have clear and continuous lattice stripes with a spacing of about 0.34nm, are close to the (002) interplanar spacing of graphite, have a polyhedral overall morphology and have a size of about 10-20 nm; in FIG. 2, (c) and (d) show that the carbon nano-onions prepared in examples 2 and 4 comprise non-hollow carbon nano-onions, which are in the form of solid quasi-spheres and composed of graphitized shell layers, have relatively clear lattice fringes, but have a reduced continuity and have a diameter of about 20-30 nm.
HRTEM images of examples 6-18 are shown in FIG. 3;
as can be observed from fig. 3, the CNOs obtained by the reaction under the conditions of examples 6 to 18 have more distinct graphitized concentric circle-shaped lattice stripes, the outer graphitized shell layer is obviously increased compared with fig. 1, the overall structure is spherical, the structure is no longer similar to the hollow structure in fig. 1, the lattice stripes continue from the outer part of the sphere to the center, and the adjacent CNOs gradually start to aggregate and grow together.
The HRTEM of example 23 is shown in fig. 4, from which it can be seen that carbon nano-onions were produced even without the addition of metal ions.
The embodiments show that the preparation method of the carbon nano onion provided by the invention not only successfully prepares the carbon nano onion, but also can prepare two carbon nano onions with different structures.
Effect of Metal ions on reaction Rate
Citric acid is an organic acid, and each molecule contains three carboxyl groups, so the citric acid is acidic in an aqueous solution, the pH is related to the concentration of the citric acid in the solution, the pH is gradually reduced along with the increase of the concentration of the citric acid, on the contrary, if the concentration of the citric acid in the solution is reduced, the pH is gradually increased, so the consumption condition of the citric acid can be reflected by the change of the pH before and after the reaction of the solution, and under the condition of the same reaction time, the reaction rate is faster as the change of the pH is larger.
Inventors compared example 15(n (KNO)3) N (ca) 2: 1) and example 23 (no metal ion) were examined on the change of pH with reaction time during hydrothermal reaction, and the results are shown in Table 2 below.
TABLE 2 Change of reactant aqueous solutions of example 15 and example 23
h represents "hour" and d represents "day".
As can be seen from the data in table 2, in example 23, although carbon nano onions can be produced without adding metal ions, the pH changes very slowly, indicating that the reaction rate is very slow, and after adding metal ions, as shown in example 15, the pH changes more rapidly, indicating that the reaction rate is significantly accelerated, from which it can be seen that metal ions have an accelerating effect on the entire reaction.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (12)
1. A preparation method of carbon nano onion is characterized by comprising the following steps:
obtaining a reactant aqueous solution, wherein the reactant aqueous solution contains citrate and metal ions;
the concentration of the citrate is 0.1-10 mol/L;
the metal ion is selected from Li+、Na+、K+、Ca2+、Mg2+、Ba2+、Al3+One or any combination thereof;
the molar ratio of the citrate to the metal ion is 1: (0.1-10);
and carrying out hydrothermal reaction on the reactant aqueous solution, wherein the temperature of the hydrothermal reaction is 140-400 ℃, and the reaction time is 2-48 hours.
2. The method of claim 1, wherein the reactant aqueous solution is obtained by:
citric acid and a metal ion source containing the metal ions are dissolved in water.
3. The method of claim 2, wherein the source of metal ions is selected from the group consisting of water soluble bases and/or water soluble salts.
4. The method of claim 3, wherein the metal ion source is selected from the group consisting of sodium hydroxide, sodium chloride, sodium nitrate, potassium hydroxide, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, and any combination thereof.
5. The method of claim 1, wherein the reactant aqueous solution is obtained by:
dissolving citrate in water; the citrate salt contains the metal ion.
6. The method of claim 1, wherein the molar ratio of citrate to metal ion is from 1: (1-8).
7. The method as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 140-220 ℃.
8. The method as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 160-200 ℃.
9. The method as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 170-190 ℃.
10. The method of claim 1, wherein the hydrothermal reaction is at a temperature of 180 ℃.
11. The method of claim 1, wherein the hydrothermal reaction is carried out for a time of 4 to 24 hours.
12. The method of claim 1, wherein the hydrothermal reaction is carried out for a time of 4 to 12 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810637580.3A CN108529598B (en) | 2018-06-20 | 2018-06-20 | Preparation method of carbon nano onion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810637580.3A CN108529598B (en) | 2018-06-20 | 2018-06-20 | Preparation method of carbon nano onion |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108529598A CN108529598A (en) | 2018-09-14 |
CN108529598B true CN108529598B (en) | 2020-10-16 |
Family
ID=63469973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810637580.3A Expired - Fee Related CN108529598B (en) | 2018-06-20 | 2018-06-20 | Preparation method of carbon nano onion |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108529598B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109286018B (en) * | 2018-12-06 | 2021-12-31 | 中国科学院兰州化学物理研究所 | Preparation method of ultrathin two-dimensional carbon sheet |
CN109650380B (en) * | 2019-01-21 | 2022-04-19 | 中国科学院兰州化学物理研究所 | Method for preparing carbon nano onion by dry friction in vacuum environment |
CN112028062B (en) * | 2020-01-17 | 2022-03-15 | 南通大学 | Method for preparing onion-shaped nano graphite nodules by hydrothermal method |
CN115283667B (en) * | 2022-06-29 | 2024-02-23 | 燕山大学 | Preparation method for synthesizing onion carbon in situ by laser |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101885481A (en) * | 2009-05-11 | 2010-11-17 | 中国海洋石油总公司 | Method for preparing carbon nano onions |
CN101856614B (en) * | 2010-06-10 | 2012-05-23 | 天津大学 | Chemical vaporous deposition method for preparing carbon nano-onions by using Ni-Fe alloy as catalyst |
CN106276857B (en) * | 2016-08-12 | 2018-06-26 | 上海交通大学 | A kind of method for preparing functional carbon material |
CN106449996B (en) * | 2016-10-25 | 2018-11-27 | 吉林大学 | One kind being based on onion carbon nano-particles/Ag combination electrode organic solar batteries and preparation method thereof |
CN106882791B (en) * | 2017-02-20 | 2019-05-31 | 东南大学 | The preparation method and applications of water dispersible carbon nano-onions |
-
2018
- 2018-06-20 CN CN201810637580.3A patent/CN108529598B/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
Hydrothermal synthesis of highly fluorescent carbonnanoparticles from sodium citrate and their use for the detection of mercury ions;Yongming Guo et al;《carbon》;20121023;第52卷;2.2 Synthesis of F-CNPs * |
Also Published As
Publication number | Publication date |
---|---|
CN108529598A (en) | 2018-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108529598B (en) | Preparation method of carbon nano onion | |
JP5981049B2 (en) | Method for preparing nickel-cobalt-manganese hydroxide | |
CN110492090B (en) | Preparation and application of biomass carbon-coated cobalt sulfide-cobalt octasulfide composite material | |
JP2018531871A5 (en) | ||
Zhao et al. | Microwave-assisted hydrothermal rapid synthesis of amorphous calcium phosphate nanoparticles and hydroxyapatite microspheres using cytidine 5′-triphosphate disodium salt as a phosphate source | |
Li et al. | Effect of different carbon sources on the electrochemical properties of rod-like LiMnPO 4–C nanocomposites | |
CN113023727B (en) | Preparation method of nano onion carbon | |
Torres et al. | Unzipping of multi-wall carbon nanotubes with different diameter distributions: Effect on few-layer graphene oxide obtention | |
Zhang et al. | Hydrothermal synthesis of well crystallized C 8 and diamond nanocrystals and pH-controlled C 8↔ diamond phase transition | |
Gong et al. | Striking influence of NiO catalyst diameter on the carbonization of polypropylene into carbon nanomaterials and their high performance in the adsorption of oils | |
Wang et al. | Controlled growth of nickel nanocrystal arrays and their field electron emission performance enhancement via removing adsorbed gas molecules | |
US20210164114A1 (en) | Precursor materials and methods for the preparation of nanostructured carbon materials | |
Alessandro et al. | Selective synthesis of turbostratic polyhedral carbon nano-onions by arc discharge in water | |
CN114308049A (en) | Growth catalyst for preparing carbon nano tube with high specific surface area | |
US9278162B2 (en) | Single-crystal apatite nanowires sheathed in graphitic shells and synthesis method thereof | |
KR20130139452A (en) | Method of forming graphene and graphene using the method | |
CN102745665B (en) | A kind of method for preparing helical structure CNT | |
RU2681630C1 (en) | Arc method for graphene production | |
Zhang et al. | Hollow graphitic carbon nanospheres: synthesis and properties | |
US20230357014A1 (en) | Systems and methods for making carbon nanostructures | |
Sun et al. | Influence of surfactants on the microstructure and electrochemical performance of the tin oxide anode in lithium ion batteries | |
CN108003873B (en) | FePS3Preparation method and application of quantum dots | |
CN110759327B (en) | Preparation method of metal carbon crystal | |
BR112020019217A2 (en) | COMPOSITE CARBON MATERIAL | |
KR101325911B1 (en) | Method for controling morphology of LiFePO4 by using ethylene glycol with hydrothermal route and method for manufacturing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201016 Termination date: 20210620 |
|
CF01 | Termination of patent right due to non-payment of annual fee |