CN111943166A - Preparation of solvent-free hydrothermal carbon material - Google Patents
Preparation of solvent-free hydrothermal carbon material Download PDFInfo
- Publication number
- CN111943166A CN111943166A CN202010689628.2A CN202010689628A CN111943166A CN 111943166 A CN111943166 A CN 111943166A CN 202010689628 A CN202010689628 A CN 202010689628A CN 111943166 A CN111943166 A CN 111943166A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- hours
- drying
- solvent
- sample
- 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.)
- Granted
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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the field of preparation of porous materials, and mainly relates to preparation of a solvent-free hydrothermal carbon material, wherein tannic acid, vanillin and nano calcium carbonate are mixed, and a small amount of dilute sulfuric acid is dripped into the mixture and ground until the surface is wet; placing the ground sample in a vacuum drying oven for reaction; carbonizing the carbon material precursor in a nitrogen atmosphere, grinding and crushing, treating with dilute hydrochloric acid, drying, treating with distilled water, and drying to obtain the solvent-free hydrothermal carbon material. According to the invention, solid-solid mixing is adopted for carrying out hydrothermal reaction, and no solvent is added when the hydrothermal reaction is used for preparing the carbon material, so that the experiment risk is reduced; and directly obtaining the carbon material precursor after experimental reaction. The carbon material prepared by the method has good specific surface area and uniform pore size distribution, and can be further used for loading other metal materials.
Description
Technical Field
The invention belongs to the field of preparation of porous materials, and mainly relates to preparation of a solvent-free hydrothermal carbon material.
Technical Field
Most of the carbon materials are prepared by a solvent method, and ethylene glycol, isopropyl ketone or absolute ethyl alcohol is used as a solvent to react at high temperature. The solvents used in such methods cannot be recovered, causing pollution; the process of collecting the carbon material after the experimental reaction is complex, and multiple times of centrifugal filtration are needed; and there is a certain risk that such organic solvents operate at high temperatures.
At present, most of methods for preparing carbon materials by a hydrothermal method need to stir and mix an organic carbon source and a solvent, then place the mixture in a hydrothermal kettle, and react at a high temperature in a drying oven to generate the carbon materials.
However, when the carbon material is prepared by the method, the carbon material obtained by the experiment can be separated from the solvent only by the work of centrifugal filtration, drying and the like, so that a sample is obtained. The experimental operation is complicated and time-consuming.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a solvent-free hydrothermal carbon material, and the method adopts a solid-solid mixing hydrothermal reaction method to prepare the carbon material, so that no solvent is added, and the experimental risk is reduced; and the carbon material precursor is directly obtained after the experimental reaction, so that various complex works such as centrifugal suction filtration drying and the like after the solvent method hydrothermal reaction are saved, time and labor are saved, and the method is environment-friendly and efficient.
The preparation method of the solvent-free hydrothermal carbon material comprises the following specific steps:
(1) mixing tannic acid, vanillin and nano calcium carbonate, fully grinding and mixing, then dripping a small amount of dilute sulfuric acid for continuous grinding, and grinding a sample until the surface is wet;
(2) placing the ground sample in the step (1) in a vacuum drying box for reaction at the temperature of 160 ℃ and 200 ℃ for 10-14 hours;
(3) taking out the carbon material precursor in the step (2), placing the carbon material precursor in a tubular furnace, carbonizing the carbon material precursor in the tubular furnace in a nitrogen atmosphere at the carbonization temperature of 800-1000 ℃ for 1-5 hours, and then cooling;
(4) grinding and crushing the sample obtained in the step (3), magnetically stirring with dilute hydrochloric acid, performing ultrasonic treatment, performing suction filtration, and drying the sample in an air-blast drying oven;
(5) and (4) carrying out ultrasonic treatment on the sample obtained in the step (4) by using distilled water, carrying out suction filtration, and drying the sample in an air-blast drying oven to obtain the carbon material prepared by the solvent-free hydrothermal method.
Further, the concentration of the dilute hydrochloric acid in the step (1) is 0.5 m; the mass ratio of the tannic acid to the vanillin to the nano calcium carbonate is 1:1: 2-5.
Further, the reaction temperature in the step (2) is 180 ℃, and the reaction time is 12 hours.
Further, the carbonization temperature in the step (3) is 900 ℃, the heating rate is 2 ℃/min, and the carbonization time is 1.5 hours.
Further, the concentration of the dilute hydrochloric acid in the step (4) is 0.5 m; the magnetic stirring time is 6 hours, and the ultrasonic treatment time is 2 hours; the drying temperature is 60 ℃, and the drying time is 8 hours.
Further, the ultrasonic treatment time in the step (5) is 4 hours; the drying temperature is 60 ℃ and the drying time is 8 hours.
The invention has the beneficial effects that: according to the invention, solid-solid mixing is adopted for carrying out hydrothermal reaction, and no solvent is added when the hydrothermal reaction is used for preparing the carbon material, so that the experiment risk is reduced; and the carbon material precursor is directly obtained after the experimental reaction, so that various complex works such as centrifugal suction filtration drying and the like after the solvent method hydrothermal reaction are saved, time and labor are saved, and the method is environment-friendly and efficient.
The carbon material prepared by the method has good specific surface area and uniform pore size distribution, and can be further used for loading other metal materials.
Drawings
FIG. 1 is a photograph of a sample of a solvent-free hydrothermal carbon material obtained in example 1;
FIG. 2 is an electron microscope image of a solvent-free hydrothermal prepared carbon material obtained in example 1;
FIG. 3 is a photograph of a sample of a solvent-free hydrothermal-prepared carbon material obtained in comparative example 1;
FIG. 4 is an electron microscope image of a carbon material prepared by a solvent-free hydrothermal method according to comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
(1) Mixing 1g of tannic acid, 1g of vanillin and 2g of nano calcium carbonate, fully grinding and mixing, dripping 4-5 drops of 0.5m dilute sulfuric acid, continuously grinding, and grinding the sample until the surface is wet.
(2) And (3) transferring the ground sample obtained in the step (1) into a 50ml hydrothermal kettle, placing the kettle in a vacuum drying oven, and reacting for 12 hours at 180 ℃.
(3) And (3) taking out the carbon material precursor in the step (2), transferring the carbon material precursor into a quartz boat, placing the quartz boat in a tubular furnace, carbonizing the carbon material precursor in the atmosphere of 100 ml/min of nitrogen flow, raising the temperature to 900 ℃ at the rate of 2 ℃/min, preserving the heat for 1.5 hours, and then cooling.
(4) And (4) grinding and crushing the sample obtained in the step (3), magnetically stirring for 6 hours by using 0.5m dilute hydrochloric acid, performing ultrasonic treatment for 2 hours, performing suction filtration, and drying the sample in an air-blast drying oven at 60 ℃ for 8 hours.
(5) And (4) carrying out ultrasonic treatment on the sample obtained in the step (4) for 4 hours by using distilled water, then carrying out suction filtration, and drying the sample in an air-blast drying oven for 8 hours at the temperature of 60 ℃.
Example 2
(1) Mixing 1g of tannic acid, 1g of vanillin and 3g of nano calcium carbonate, fully grinding and mixing in a mortar, dripping 4-5 drops of 0.5m dilute sulfuric acid, continuously grinding, and grinding a sample until the surface is wet.
(2) And (3) transferring the ground sample in the step (1) into a 50ml hydrothermal kettle, placing the kettle in a vacuum drying oven, and reacting for 11 hours at 180 ℃.
(3) And (3) taking out the carbon material precursor in the step (2), transferring the carbon material precursor into a quartz boat, placing the quartz boat in a tubular furnace, carbonizing the carbon material precursor in the atmosphere of 100 ml/min of nitrogen flow, raising the temperature to 900 ℃ at the rate of 2 ℃/min, preserving the heat for 1.5 hours, and then cooling.
(4) And (4) grinding and crushing the sample obtained in the step (3), magnetically stirring for 6 hours by using 0.5m dilute hydrochloric acid, performing ultrasonic treatment for 2 hours, performing suction filtration, and drying the sample in an air-blast drying oven at 60 ℃ for 8 hours.
(5) And (4) carrying out ultrasonic treatment on the sample obtained in the step (4) for 4 hours by using distilled water, then carrying out suction filtration, and drying the sample in an air-blast drying oven for 8 hours at the temperature of 60 ℃.
Example 3
(1) Mixing 1g of tannic acid, 1g of vanillin and 4g of nano calcium carbonate, fully grinding and mixing, dripping 4-5 drops of 0.5m dilute sulfuric acid, continuously grinding, and grinding the sample until the surface is wet.
(2) And (3) transferring the ground sample in the step (1) into a 50ml hydrothermal kettle, placing the kettle in a vacuum drying oven, and reacting for 10 hours at 180 ℃.
(3) And (3) taking out the carbon material precursor in the step (2), transferring the carbon material precursor into a quartz boat, placing the quartz boat in a tubular furnace, carbonizing the carbon material precursor in the atmosphere of 100 ml/min of nitrogen flow, raising the temperature to 900 ℃ at the rate of 2 ℃/min, preserving the heat for 1.5 hours, and then cooling.
(4) And (4) grinding and crushing the sample obtained in the step (3), magnetically stirring for 6 hours by using 0.5m dilute hydrochloric acid, performing ultrasonic treatment for 2 hours, performing suction filtration, and drying the sample in an air-blast drying oven at 60 ℃ for 8 hours.
(5) And (4) carrying out ultrasonic treatment on the sample obtained in the step (4) for 4 hours by using distilled water, then carrying out suction filtration, and drying the sample in an air-blast drying oven for 8 hours at the temperature of 60 ℃.
Example 4
(1) Mixing 1g of tannic acid, 1g of vanillin and 5g of nano calcium carbonate, fully grinding and mixing, dripping 4-5 drops of 0.5m dilute sulfuric acid, continuously grinding, and grinding the sample until the surface is wet.
(2) And (3) transferring the ground sample obtained in the step (1) into a 50ml hydrothermal kettle, placing the kettle in a vacuum drying oven, and reacting for 12 hours at 180 ℃.
(3) And (3) taking out the carbon material precursor in the step (2), transferring the carbon material precursor into a quartz boat, placing the quartz boat in a tubular furnace, carbonizing the carbon material precursor in the atmosphere of 100 ml/min of nitrogen flow, raising the temperature to 900 ℃ at the rate of 2 ℃/min, preserving the heat for 1.5 hours, and then cooling.
Comparative example 1
(1) Mixing 1g of tannic acid, 1g of vanillin and 2g of nano calcium carbonate, fully grinding and mixing, dripping 4-5 drops of 0.5m dilute sulfuric acid, continuously grinding, and grinding the sample until the surface is wet.
(2) And (2) moving the ground sample in the step (1) into a quartz boat, placing the quartz boat in a vacuum drying box, placing the quartz boat in a tubular furnace, carbonizing the quartz boat in the atmosphere of 100 ml/min of nitrogen flow, raising the temperature to 900 ℃ at the rate of 2 ℃/min, preserving the heat for 1.5 hours, and then cooling.
The carbon materials prepared in examples 1 to 4 and comparative example 1 were analyzed for total pore volume, specific surface area, and average pore diameter using a scanning electron microscope to measure the particle diameter and specific surface area of the sample by nitrogen adsorption, and the analysis results are shown in table 1.
TABLE 1 Total pore volume, specific surface area and average pore diameter of the examples and comparative examples
As can be seen from the data in Table 1, the carbon material prepared by the method has good specific surface area and uniform pore size distribution, and can be further used for loading other metal materials.
The carbon material prepared by the method has uniform pore size distribution, has stronger adsorption capacity for subsequent loading of other metal oxides, can be better combined with the carbon material, and can better exert the performance of the carbon material.
The above embodiments are provided for illustrative purposes to enable persons skilled in the art to understand the present invention and implement the present invention, and the protection scope of the present invention is not limited thereby. The invention is within the scope of the claims, unless otherwise indicated herein or clearly indicated by the context of the claims.
Claims (6)
1. A preparation method of a solvent-free hydrothermal carbon material is characterized by comprising the following specific preparation steps:
(1) mixing tannic acid, vanillin and nano calcium carbonate, fully grinding and mixing, then dripping a small amount of dilute sulfuric acid for continuous grinding, and grinding a sample until the surface is wet;
(2) placing the ground sample in the step (1) in a vacuum drying box for reaction at the temperature of 160 ℃ and 200 ℃ for 10-14 hours;
(3) taking out the carbon material precursor in the step (2), placing the carbon material precursor in a tubular furnace, carbonizing the carbon material precursor in the tubular furnace in a nitrogen atmosphere at the carbonization temperature of 800-1000 ℃ for 1-5 hours, and then cooling;
(4) grinding and crushing the sample obtained in the step (3), magnetically stirring with dilute hydrochloric acid, performing ultrasonic treatment, performing suction filtration, and drying the sample in an air-blast drying oven;
(5) and (4) carrying out ultrasonic treatment on the sample obtained in the step (4) by using distilled water, carrying out suction filtration, and drying the sample in an air-blast drying oven to obtain the carbon material prepared by the solvent-free hydrothermal method.
2. The process for preparing a solventless hydrothermal carbon material as claimed in claim 1, wherein the dilute hydrochloric acid in the step (1) has a concentration of 0.5 m; the mass ratio of the tannic acid to the vanillin to the nano calcium carbonate is 1:1: 2-5.
3. The method of claim 1, wherein the reaction temperature in step (2) is 180 ℃ and the reaction time is 12 hours.
4. The method of claim 1, wherein the carbonization temperature in step (3) is 900 ℃, the heating rate is 2 ℃/min, and the carbonization time is 1.5 hours.
5. The process according to claim 1, wherein the dilute hydrochloric acid in step (4) has a concentration of 0.5 m; the magnetic stirring time is 6 hours, and the ultrasonic treatment time is 2 hours; the drying temperature is 60 ℃, and the drying time is 8 hours.
6. The method of claim 1, wherein the sonication in step (5) is carried out for a period of 4 hours; the drying temperature is 60 ℃ and the drying time is 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010689628.2A CN111943166B (en) | 2020-07-17 | 2020-07-17 | Preparation of solvent-free hydrothermal carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010689628.2A CN111943166B (en) | 2020-07-17 | 2020-07-17 | Preparation of solvent-free hydrothermal carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111943166A true CN111943166A (en) | 2020-11-17 |
| CN111943166B CN111943166B (en) | 2023-01-20 |
Family
ID=73340003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010689628.2A Active CN111943166B (en) | 2020-07-17 | 2020-07-17 | Preparation of solvent-free hydrothermal carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111943166B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113130866A (en) * | 2021-04-02 | 2021-07-16 | 中北大学 | Preparation method of boron-carbon thin-wall hollow sphere |
| CN115215337A (en) * | 2022-05-24 | 2022-10-21 | 中国科学院兰州化学物理研究所 | Method for synthesizing phenolic resin and preparing carbon material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964414A (en) * | 2014-04-30 | 2014-08-06 | 中国科学院上海高等研究院 | Solid-phase synthetic method of highly ordered mesoporous carbon material |
| CN104411628A (en) * | 2012-06-15 | 2015-03-11 | 陶氏环球技术有限责任公司 | Porous carbon compositiions |
| CN105645374A (en) * | 2014-12-06 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of mesoporous carbon material |
| CN106684357A (en) * | 2017-01-16 | 2017-05-17 | 南京师范大学 | Porous cobalt sulfide and nitrogen-doped carbon composite material and preparation method and application thereof |
| CN106794990A (en) * | 2014-09-30 | 2017-05-31 | 株式会社Lg化学 | The preparation method of hollow carbon capsule |
| CN107311142A (en) * | 2017-07-31 | 2017-11-03 | 中南大学 | A kind of method of the solvent-free quick high-specific surface area graphitized carbon for preparing Heteroatom doping |
| CN110116000A (en) * | 2019-04-04 | 2019-08-13 | 杭州师范大学 | A kind of sludge carbon-supported catalysts and its preparation method and application |
-
2020
- 2020-07-17 CN CN202010689628.2A patent/CN111943166B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104411628A (en) * | 2012-06-15 | 2015-03-11 | 陶氏环球技术有限责任公司 | Porous carbon compositiions |
| US20150336797A1 (en) * | 2012-06-15 | 2015-11-26 | Dow Global Technologies Llc | Porous carbon compositions |
| CN103964414A (en) * | 2014-04-30 | 2014-08-06 | 中国科学院上海高等研究院 | Solid-phase synthetic method of highly ordered mesoporous carbon material |
| CN106794990A (en) * | 2014-09-30 | 2017-05-31 | 株式会社Lg化学 | The preparation method of hollow carbon capsule |
| JP2017530076A (en) * | 2014-09-30 | 2017-10-12 | エルジー・ケム・リミテッド | Method for producing hollow carbon capsule |
| CN105645374A (en) * | 2014-12-06 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of mesoporous carbon material |
| CN106684357A (en) * | 2017-01-16 | 2017-05-17 | 南京师范大学 | Porous cobalt sulfide and nitrogen-doped carbon composite material and preparation method and application thereof |
| CN107311142A (en) * | 2017-07-31 | 2017-11-03 | 中南大学 | A kind of method of the solvent-free quick high-specific surface area graphitized carbon for preparing Heteroatom doping |
| CN110116000A (en) * | 2019-04-04 | 2019-08-13 | 杭州师范大学 | A kind of sludge carbon-supported catalysts and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113130866A (en) * | 2021-04-02 | 2021-07-16 | 中北大学 | Preparation method of boron-carbon thin-wall hollow sphere |
| CN113130866B (en) * | 2021-04-02 | 2022-02-22 | 中北大学 | Preparation method of boron-carbon thin-wall hollow sphere |
| CN115215337A (en) * | 2022-05-24 | 2022-10-21 | 中国科学院兰州化学物理研究所 | Method for synthesizing phenolic resin and preparing carbon material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111943166B (en) | 2023-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111943166B (en) | Preparation of solvent-free hydrothermal carbon material | |
| CN108722433B (en) | Preparation and application of shape-adjustable hollow cage-shaped Mn/Fe oxide nano material | |
| CN110002414B (en) | Preparation method of porous carbon nitride nanotube | |
| CN108328635B (en) | Method for preparing alumina aerogel | |
| CN108483502A (en) | A kind of preparation method and application of rhenium disulfide nanometer sheet | |
| CN109437203A (en) | A kind of preparation method of high-purity one dimension SiC nano material | |
| CN108996557B (en) | Hollow sphere structured nickel oxide/copper oxide composite nano material and preparation method thereof | |
| CN108178146A (en) | A kind of method for efficiently preparing high-energy density graphene aerogel | |
| CN115196605A (en) | Preparation method and application of graphite phase carbon nitride nanosheet | |
| CN110655056A (en) | Preparation method of porous nano silicon-carbon composite material | |
| KR100740633B1 (en) | Method for preparing graphite coated with silica | |
| CN104071760B (en) | The preparation method of the bar-shaped hexagonal boron nitride stupalith of a kind of porous | |
| CN113247940A (en) | Method for preparing neodymium oxide nanoparticles with small size by solid-phase sintering | |
| CN111215092B (en) | MOFs-derived yolk-shell type copper-manganese composite bimetallic oxide and preparation method thereof | |
| CN108500282A (en) | A kind of preparation method of carbon-supported metal tungsten nano particle | |
| CN116692790A (en) | Preparation method of high-purity hexagonal boron nitride with efficient cyclic utilization of boron source | |
| CN108383531B (en) | MgB doped with topological luminophores in heterogeneous phase2Base superconductor and method for producing same | |
| CN110015655A (en) | A kind of ultra-high throughput stripping means of graphene | |
| GB2617006A (en) | Expanded graphite and preparation method therefor | |
| JPH0653564B2 (en) | Method for purifying hexagonal boron nitride | |
| CN107021520A (en) | A kind of yttrium oxide powder and preparation method thereof | |
| RU2681860C1 (en) | Method of obtaining high-temperature thermoelectric material based on calcium cobaltite | |
| CN105984891A (en) | Method for preparing nano aluminum oxide at low temperature | |
| CN111908464B (en) | Method for preparing foam carbon material by using tannic acid | |
| CN114620757B (en) | Green synthesis method of perovskite lanthanum cuprate nanosheet |
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 |