CN110422840A - A kind of method of solid organic acid synthesis azepine graphene - Google Patents
A kind of method of solid organic acid synthesis azepine graphene Download PDFInfo
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- CN110422840A CN110422840A CN201910831066.8A CN201910831066A CN110422840A CN 110422840 A CN110422840 A CN 110422840A CN 201910831066 A CN201910831066 A CN 201910831066A CN 110422840 A CN110422840 A CN 110422840A
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- organic acid
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- 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
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Abstract
The invention discloses a kind of methods of solid organic acid synthesis azepine graphene, belong to synthesis azepine technical field of graphene.This method mixes solid organic acid, nitrogenous small molecule and its catalyst；Mixture is placed in and is reacted in inertia or the reactor of reducibility gas protection, room temperature is cooled under identical atmosphere protection after reaction, obtains solid product；Above-mentioned solid product is washed, is filtered, is dried to obtain azepine graphene product.The present invention has the characteristics that pollution-free, inexpensive, simple process, can be prepared on a large scale.
Description
Technical field
The invention belongs to synthesize azepine technical field of graphene, and in particular to a kind of solid organic acid synthesis azepine graphene
Method.
Background technique
Graphene is successfully obtained for the first time within 2004 by single layer sp2The two-dimentional carbonaceous crystal that hydridization carbon is constituted has and opens
The Surface Physical Chemistry property of the surface put, excellent carrier transport ability and easy modulation, in energy storage and conversion, electricity
Sub-information and its biomedicine field have great application potential.Nitrogen-doping graphene can effectively adjust graphene
Level structure and surface chemical property, widen it in the application in the fields such as catalysis, battery and bio-sensing.
Can the application of azepine graphene be realized, realize large-scale production depending on it.Azepine graphene can be by changing
Learn vapour deposition process preparation；Arc discharge method can also prepare azepine graphene；In addition, by graphene oxide and nitrogen-containing molecules heat
Solution can also prepare azepine graphene.Although chemical vapour deposition technique and arc discharge method etc. may be implemented in the face of nitrogen-atoms
Doping, but reaction condition is complicated and more demanding, is difficult to realize large-scale production.Graphite oxide is carried out using nitrogen substance
Although electrothermal treatment can prepare azepine graphene, nitrogen is in graphene edge and does not enter in graphene film.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of pollution-free, inexpensive, simple process, can extensive synthetic nitrogen
The method of miscellaneous graphene.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of method of solid organic acid synthesis azepine graphene comprising following steps:
Solid organic acid, catalyst are mixed with nitrogenous small molecule；
Mixture is placed in and is reacted in inertia or the reactor of reducing gas protection, in identical atmosphere after reaction
It is cooled to room temperature under protection, obtains solid product；
Above-mentioned solid product is washed, is filtered, is dried to obtain azepine graphene product.
Optionally, the solid organic acid includes malonic acid, succinic acid, adipic acid and butene dioic acid.
Optionally, the catalyst is sodium carbonate or sodium chloride.
Optionally, the nitrogenous small molecule is melamine or urea.
Optionally, the molar ratio of the solid organic acid, nitrogenous small molecule and catalyst is 1:0.1-5:0.1-20.
Optionally, the gas in the reactor is inert gas, which is argon gas or nitrogen.
Optionally, the gas in the reactor is reducing gas, which is hydrogen.
Optionally, the hybrid mode that solid organic acid, catalyst are mixed with nitrogenous small molecule is mixed for mechanical lapping
It closes or solution mixes.
Optionally, the concrete mode that solid organic acid, catalyst are mixed with nitrogenous small molecule is, by SOLID ORGANIC
After solution mixing is respectively prepared in acid, nitrogenous compound and catalyst, removal solvent obtains solid mixture.
Optionally, the reaction temperature of the reaction is 600-1500 DEG C, reaction time 0.1-100min.
The present invention has the following advantages compared with the prior art:
(1) raw materials such as solid organic acid, urea or the melamine used in the present invention, sodium carbonate or sodium chloride are inexpensively easy
, without pretreatment, advantageously reduce cost.
(2) synthesis technology process of the invention is simple, and easy to operate, influence factor is few, reproducible convenient for control.
(3) the azepine graphene that the present invention synthesizes can keep its pattern without reuniting.
(4) it is recycled after the sodium carbonate (sodium chloride) used in the present invention is recyclable.
(5) present invention largely synthesizes azepine graphene convenient for scale.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of 1 azepine graphene of the embodiment of the present invention.
Fig. 2 is scanning electron microscope (SEM) photo of 5 azepine graphene of the embodiment of the present invention.
Fig. 3 is scanning electron microscope (SEM) photo of 7 azepine graphene of the embodiment of the present invention.
Specific embodiment
The following further describes the technical solution of the present invention with reference to the accompanying drawings and detailed description.
A kind of method of solid organic acid synthesis azepine graphene, includes the following steps:
(1) by the mixing of solid organic acid, nitrogenous small molecule and its catalyst, (three's molar ratio can be 1:0.1-5:0.1-
20)；
(2) mixture is placed in and is reacted in inertia or the reactor of reducibility gas protection, identical after reaction
It is cooled to room temperature under atmosphere protection, obtains solid product；
(3) above-mentioned solid product washed, filtered, being dried to obtain azepine graphene product
The solid organic acid includes malonic acid, succinic acid, adipic acid and butene dioic acid.
The catalyst is sodium carbonate or sodium chloride.
The nitrogenous small molecule is melamine or urea.
The inert atmosphere is argon gas or nitrogen.
The reducing atmosphere is hydrogen.
The mixing includes mechanical lapping mixing or solution mixing (by solid organic acid, nitrogenous compound and catalyst
After solution mixing is respectively prepared, removal solvent obtains solid mixture).
The reaction temperature is 600-1500 DEG C,
The reaction time is 0.1-100min.
This method for raw material, is not necessarily to solid organic acid, nitrogenous small molecule and its inorganic sodium (sodium carbonate or sodium chloride)
Raw material is pre-processed, one-step synthesis azepine graphene, gained azepine graphene has three-dimensional net structure, can effectively press down
π-the π of graphene processed is stacked, and maintains its excellent characteristic, has big advantage in terms of large scale preparation.
Below it is some specific embodiments of this method:
Embodiment 1
Using mechanical lapping mode, by butene dioic acid, sodium carbonate and urea, 1:4:0.5 is mixed in molar ratio, and 1.5g is taken to place
In the reactor of argon atmospher protection.In 1000 DEG C of reaction 2min.After product is cooling, product is taken out, is washed with deionized water
It washs, filter, dry, collect product.XPS analysis shows that nitrogen content is 3.0% (atomic percent), scanning electron microscope sample as the result is shown
The network-like structure of product, lamellar spacing are about 2.3nm.
Embodiment 2
Using mechanical lapping mode, by butene dioic acid, sodium carbonate and urea, 1:1:0.5 is mixed in molar ratio, and 1.5g is taken to place
In the reactor of nitrogen atmosphere protection.In 800 DEG C of reaction 30min.After product is cooling, product is taken out, is washed with deionized water
It washs, filter, dry, collect product.XPS analysis shows that nitrogen content is 3.2% (atomic percent), scanning electron microscope sample as the result is shown
The network-like structure of product, lamellar spacing are about 3nm.
Embodiment 3
Using mechanical lapping mode, by succinic acid, sodium carbonate and urea, 1:0.5:0.5 is mixed in molar ratio, and 1.5g is taken to place
In the reactor of nitrogen atmosphere protection.In 1200 DEG C of reaction 5min.After product is cooling, product is taken out, is washed with deionized water
It washs, filter, dry, collect product.XPS analysis shows that nitrogen content is 2% (atomic percent), scanning electron microscope sample as the result is shown
Network-like structure, lamellar spacing are about 2.1nm.
Embodiment 4
Using mechanical lapping mode, by butene dioic acid, sodium carbonate and melamine, 1:1:0.5 is mixed in molar ratio, takes 1.5g
It is placed in the reactor of nitrogen atmosphere protection.In 900 DEG C of reaction 20min.After product is cooling, product is taken out, deionization is used
Product is collected in water washing, filtering, drying.XPS analysis shows that nitrogen content is 2.2% (atomic percent), and scanning electron microscope result is aobvious
The network-like structure of sample product, lamellar spacing are about 4nm.
Embodiment 5
Using mechanical lapping mode, by butene dioic acid, sodium carbonate and urea, 1:8:0.5 is mixed in molar ratio, and 1.5g is taken to place
In the reactor of nitrogen atmosphere protection.In 800 DEG C of reaction 10min.After product is cooling, product is taken out, is washed with deionized water
It washs, filter, dry, collect product.XPS analysis shows that nitrogen content is 2.8% (atomic percent), scanning electron microscope sample as the result is shown
The network-like structure of product, lamellar spacing are about 3.6nm.
Embodiment 6
Using mechanical lapping mode, by malonic acid, sodium carbonate and urea, 1:8:0.5 is mixed in molar ratio, and 1.5g is taken to be placed in
In the reactor of nitrogen atmosphere protection.In 900 DEG C of reaction 5min.After product is cooling, product is taken out, be washed with deionized,
Filtering, dry, collection product.XPS analysis shows that nitrogen content is 2.8% (atomic percent), scanning electron microscope sample as the result is shown
Network-like structure, lamellar spacing are about 4.1nm.
Embodiment 7
Using mechanical lapping mode, by butene dioic acid, sodium carbonate and urea, 1:20:5 is mixed in molar ratio, and 1.5g is taken to place
In the reactor of nitrogen atmosphere protection.In 1200 DEG C of reaction 3min.After product is cooling, product is taken out, is washed with deionized water
It washs, filter, dry, collect product.XPS analysis shows that nitrogen content is 3.3% (atomic percent), scanning electron microscope sample as the result is shown
The network-like structure of product, lamellar spacing are about 4.1nm.
Claims (10)
1. a kind of method of solid organic acid synthesis azepine graphene, which comprises the steps of:
Solid organic acid, catalyst are mixed with nitrogenous small molecule；
Mixture is placed in and is reacted in inertia or the reactor of reducing gas protection, in identical atmosphere protection after reaction
Under be cooled to room temperature, obtain solid product；
Above-mentioned solid product is washed, is filtered, is dried to obtain azepine graphene product.
2. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described consolidates
Body organic acid includes malonic acid, succinic acid, adipic acid and butene dioic acid.
3. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described urges
Agent is sodium carbonate or sodium chloride.
4. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described contains
Nitrogen small molecule is melamine or urea.
5. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described consolidates
The molar ratio of body organic acid, nitrogenous small molecule and catalyst is 1:0.1-5:0.1-20.
6. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that the reaction
Gas in device is inert gas, which is argon gas or nitrogen.
7. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that the reaction
Gas in device is reducing gas, which is hydrogen.
8. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described to consolidate
The hybrid mode that body organic acid, catalyst are mixed with nitrogenous small molecule is that mechanical lapping mixing or solution mix.
9. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described to consolidate
The concrete mode that body organic acid, catalyst are mixed with nitrogenous small molecule is, by solid organic acid, nitrogenous compound and catalyst point
After solution mixing is not made, removal solvent obtains solid mixture.
10. a kind of method of solid organic acid synthesis azepine graphene as described in claim 1, which is characterized in that described anti-
The reaction temperature answered is 600-1500 DEG C, reaction time 0.1-100min.
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| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
| CN103601178A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene from solid organic acid |
| CN104925795A (en) * | 2015-06-16 | 2015-09-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aza-graphene through solid nitrogenous organic acid |
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2019
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| WO2009106507A2 (en) * | 2008-02-28 | 2009-09-03 | Basf Se | Graphite nanoplatelets and compositions |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| GB201314084D0 (en) * | 2013-08-06 | 2013-09-18 | Univ Manchester | Production of graphene |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
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