CN105236382A - Nitrogen-doped carbon nano-sphere preparation method - Google Patents
Nitrogen-doped carbon nano-sphere preparation method Download PDFInfo
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- CN105236382A CN105236382A CN201510577236.6A CN201510577236A CN105236382A CN 105236382 A CN105236382 A CN 105236382A CN 201510577236 A CN201510577236 A CN 201510577236A CN 105236382 A CN105236382 A CN 105236382A
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Abstract
The present invention provides a nitrogen-doped carbon nano-sphere preparation method, wherein calcium carbide (CaC2) and glutamic acid are adopted as raw materials, a molar ratio of the calcium carbide to the glutamic acid is 2:1-4:1, a ratio of the total substance amount of the reactant to the reaction kettle volume is 2.5-5 mol/L, the heating temperature in the closed pressure resistance reactor is 130-150 DEG C, natural cooling is performed to achieve a room temperature after completing the reaction, and washing, suction filtration and drying are performed to obtain the nitrogen-doped carbon nano-spheres, wherein the diameter is 50-80 nm. According to the present invention, the advantages of single reactant, simple operation, less operation steps, low reaction temperature, less energy consumption, short cycle and low cost are provided, the obtained nitrogen-doped carbon nano-spheres have characteristics of easy separation, high nitrogen content, uniform size and high purity, and the method is suitable for large scale production.
Description
Technical field
The present invention relates to a kind of preparation method of Nano carbon balls, belong to ceramic chemosynthesis preparing technical field.
Background technology
The features such as density is low owing to having for Nano carbon balls, physicochemical property are stable, structure is special, specific surface area is large, electromagnetic performance and biocompatibility excellence, therefore in electrode materials, support of the catalyst, composite material reinforcement body, medicine parcel etc., there is potential using value, be expected to the advanced material becoming high-tech area.Nano carbon balls is the novel nano carbon material after soccerballene and CNT (carbon nano-tube), has caused the attention of various countries researchist, and prospect is very wide.
Many investigators study discovery, carbon nanomaterial is after some heterocyclic atoms of doping are as nitrogen-atoms, conduction type can be adjusted, change the electronic structure of carbon material, improve the carrier density of carbon material, thus improve electroconductibility and the stability of carbon material, lithium ion battery and ultracapacitor can be applied to; The carbon material surface that is introduced as of nitrogen-atoms provides more avtive spot simultaneously, changes the surface chemistry performance of carbon material, makes it have stronger absorption property, can better for support of the catalyst.
The method of usual synthetic nitrogen doping carbon nano material can be roughly divided into two classes: in-situ doped method and aftertreatment doping method.Namely in-situ doped method adulterates in the process of synthesis carbon material, as arc discharge, laser sintered method, chemical Vapor deposition process or heat treating process etc., synthesizes nitrating carbon nanomaterial by decomposing nitrogenous hydrocarbon polymer.But these processes all need higher energy expenditure, expensive hardware facility and loaded down with trivial details operating process, and impurity is difficult to remove completely, prepares nitrogen-doped carbon nano material and has higher cost, limit its practical application.Hydrothermal method is that reactor is put in Carbon and nitrogen sources mixing, and in addition ambient conditions assists (as microwave), but the reaction times is oversize, often needs tens hours, is unfavorable for suitability for industrialized production.Aftertreatment doping method obtains nitrogen-containing functional group by the carbon nanomaterial synthesized is carried out doping treatment, as ammonia reduction method, nitrogen precursor pyrolysis method etc., but these methods can only form surface functional group, can not adulterate and enter carbon material inside, therefore be difficult to the overall performance changing material.
L-glutamic acid (HOOCCH
2cH
2cH (NH
2) COOH) be a kind of acidic amino acid, containing two carboxyls and an amino in molecule, one-level dissociation constant pK (COOH) is 2.19, has slightly acidic; And carbide of calcium (CaC
2) be a kind of ionic compound, wherein negatively charged ion (C ≡ C)
2-show the characteristic of Lewis base, there is very strong reductibility.Therefore passing through heated sealed L-glutamic acid and carbide of calcium in a kettle. can make it that chemical reaction occurs, and produces acetylene gas, and generation nitrogen-doped carbon nanometer ball of can reuniting rapidly under hyperbaric environment, be placed in reactor upper strata.Wherein, L-glutamic acid not only as nitrogenous source, also as the organic acid of second carbon source and initiation reaction.
Summary of the invention
The invention provides a kind of industrial chemicals carbide of calcium (CaC be easy to get easy to use
2) as carbon source, L-glutamic acid as nitrogenous source, the method for synthetic nitrogen doping carbon nanometer ball under cryogenic.
The technical solution adopted in the present invention is:
(1) take carbide of calcium as carbon source, L-glutamic acid is nitrogenous source, and the mol ratio of carbide of calcium and L-glutamic acid is 2:1-4:1, is crushed to 1-2mm by carbide of calcium, puts into reactor, then add L-glutamic acid and be uniformly mixed, sealed reactor;
(2) by reactor heat temperature raising, react to 130-150 DEG C of carbide of calcium and L-glutamic acid, stop heating subsequently, allow reactor naturally cool to room temperature;
(3) open reactor, product layering in still, upper strata is cotton-shaped black solid product, gets reaction product layer respectively through 10%-20% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, after 60-80 DEG C of dry 6-10 hour, obtains Nitrogen in Products doping carbon nanometer ball.
In step (1), the volume ratio that total amount of substance of reactant accounts for reactor is 2.5-5mol/L.
In step (3), the diameter of the nitrogen-doped carbon nanometer ball of gained is 50-80nm.
Advantage of the present invention:
1. the present invention utilizes vapour deposition principle, adopts the in-situ doped method of reactor, utilizes heating L-glutamic acid to produce H
+react with carbide of calcium and produce acetylene gas and produce high pressure, under reactor environment, high pressure low temperature polymerization produces nitrogen-doped carbon nanometer ball.
2. the present invention is different from traditional hydro-thermal or solution thermal response method, and reactant used is all solid, and generated reactive gas reunion generates fluffy solid can invest reactor upper strata, is easy to the separation of realization response product.
3. the present invention is by controlling the amount of carbide of calcium and L-glutamic acid, can realize the regulation and control of the doping content of nitrogen element in Nano carbon balls.
4. the present invention does not need to introduce complicated experimental installation and loaded down with trivial details experimental procedure, raw material is from industrial chemicals carbide of calcium cheap and easy to get and modal foodstuff additive L-glutamic acid, and power consumption is few, and the reaction times is short, the Nano carbon balls of synthesis is easy to be doped into material internal, and itrogen content of getter with nitrogen doped is high.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of nitrogen-doped carbon nanometer ball;
Fig. 2 is the scanning electron microscope (SEM) photograph of nitrogen-doped carbon nanometer ball;
Fig. 3 is the EDS energy spectrogram of nitrogen-doped carbon nanometer ball;
Fig. 4 is the XPS figure of nitrogen-doped carbon nanometer ball;
Fig. 5 is the XPSN1s peak figure of nitrogen-doped carbon nanometer ball.
Below in conjunction with accompanying drawing and specific implementation method, the present invention is described in further detail.
Embodiment
Embodiment 1: take 19.20g (0.30mol) CaC
2crushing is the particle of 1-2mm to diameter, puts into 120ml stainless steel cauldron, then adds 22.05g (0.15mol) L-glutamic acid and be uniformly mixed, sealed reactor.Use heating devices heat reactor, when temperature rises to about 140 DEG C, temperature in the kettle starts sharply to rise to about 260 DEG C, now closes heating unit power supply, makes reactor naturally cool to room temperature in stove.After opening reaction kettle cover, reaction product is obviously divided into two-layer; Upper strata is cotton-shaped black solid, and lower floor is dark gray powder.Get upper strata black product respectively through 10% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, cleaning after product after dry 8 hours, obtains black powder product in about 70 DEG C baking ovens.Get upper strata product and identify carbon containing through Raman spectrum, as shown in Figure 1; Main containing carbon oxygen nitrogen through the qualification of EDS power spectrum, mass percent is respectively 83.14%, 5.37% and 11.42%, and impurity calcium eliminates substantially, as shown in Figure 3; Identify that the ratio of carbon oxygen nitrogen is respectively 90.75%, 5.31% and 3.94% through XPS, as shown in Figure 4; Wherein as shown in Figure 5,1 represents pyridine nitrogen, and 2 represent pyrroles's nitrogen, and the ratio of pyridine nitrogen and pyrroles's nitrogen is respectively 17.03% and 82.97%; Identify that its product is Nano carbon balls through scanning electronic microscope, diameter at about 50nm, as shown in Figure 2.
Embodiment 2: take 12.80g (0.20mol) CaC
2crushing is the particle of 1-2mm to diameter, puts into 120ml stainless steel cauldron, then adds 14.70g (0.10mol) L-glutamic acid and be uniformly mixed, sealed reactor.Use heating devices heat reactor, when temperature reaches about 130 DEG C, temperature in the kettle starts sharply to rise to about 260 DEG C, now closes heating unit power supply, makes reactor naturally cool to room temperature in stove.After opening reaction kettle cover, reaction product is obviously divided into two-layer; Upper strata is cotton-shaped black solid, and lower floor is dark gray powder.Get upper strata black product respectively through 15% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, cleaning after product after dry 6 hours, obtains black powder product in about 60 DEG C baking ovens.Get upper strata product and identify carbon containing through Raman spectrum; Main containing carbon oxygen nitrogen through the qualification of EDS power spectrum, mass percent is respectively 84.63%, 4.86% and 10.51%, and impurity calcium eliminates substantially; Identify that the ratio of carbon oxygen nitrogen is respectively 90.63%, 5.90% and 3.47% through XPS, wherein the ratio of pyridine nitrogen and pyrroles's nitrogen is respectively 15.47% and 84.53%; Identify that its product is Nano carbon balls through scanning electronic microscope, diameter is at about 50nm.
Embodiment 3: take 25.60g (0.40mol) CaC
2crushing is the particle of 1-2mm to diameter, puts into 120ml stainless steel cauldron, then adds 29.40g (0.20mol) L-glutamic acid and be uniformly mixed, sealed reactor.Use heating devices heat reactor, when temperature reaches about 150 DEG C, temperature in the kettle starts sharply to rise to about 260 DEG C, now closes heating unit power supply, makes reactor naturally cool to room temperature in stove.After opening reaction kettle cover, reaction product is obviously divided into two-layer; Upper strata is cotton-shaped black solid, and lower floor is dark gray powder.Get upper strata black product respectively through 20% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, cleaning after product after dry 10 hours, obtains black powder product in about 80 DEG C baking ovens.Get upper strata product and identify carbon containing through Raman spectrum; Main containing carbon oxygen nitrogen through the qualification of EDS power spectrum, mass percent is respectively 83.51%, 5.64% and 10.84%, and impurity calcium eliminates substantially; Identify that the ratio of carbon oxygen nitrogen is respectively 91.05%, 5.21% and 3.74% through XPS, wherein the ratio of pyridine nitrogen and pyrroles's nitrogen is respectively 15.13% and 84.87%; Identify that its product is Nano carbon balls through scanning electronic microscope, diameter is at about 50nm.
Embodiment 4: take 23.04g (0.36mol) CaC
2crushing is the particle of 1-2mm to diameter, puts into 120ml stainless steel cauldron, then adds 13.23g (0.09mol) L-glutamic acid and be uniformly mixed, sealed reactor.Use heating devices heat reactor, when temperature reaches about 140 DEG C, temperature in the kettle starts sharply to rise to about 260 DEG C, now closes heating unit power supply, makes reactor naturally cool to room temperature in stove.After opening reaction kettle cover, reaction product is obviously divided into two-layer; Upper strata is cotton-shaped black solid, and lower floor is dark gray powder.Get upper strata black product respectively through 10% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, cleaning after product after dry 8 hours, obtains black powder product in about 70 DEG C baking ovens.Get upper strata product and identify carbon containing through Raman spectrum; Main containing carbon oxygen nitrogen through the qualification of EDS power spectrum, mass percent is respectively 85.41%, 4.96% and 9.64%, and impurity calcium eliminates substantially; Identify that the ratio of carbon oxygen nitrogen is respectively 90.67%, 5.87% and 3.46% through XPS, wherein the ratio of pyridine nitrogen and pyrroles's nitrogen is respectively 14.24% and 85.76%; Identify that its product is Nano carbon balls through scanning electronic microscope, diameter is at about 50nm.
Embodiment 5: take 21.12g (0.33mol) CaC
2crushing is the particle of 1-2mm to diameter, puts into 120ml stainless steel cauldron, then adds 16.17g (0.11mol) L-glutamic acid and be uniformly mixed, sealed reactor.Use heating devices heat reactor, when temperature reaches about 140 DEG C, temperature in the kettle starts sharply to rise to about 260 DEG C, now closes heating unit power supply, makes reactor naturally cool to room temperature in stove.After opening reaction kettle cover, reaction product is obviously divided into two-layer; Upper strata is cotton-shaped black solid, and lower floor is dark gray powder.Get upper strata black product respectively through 10% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, cleaning after product after dry 8 hours, obtains black powder product in about 70 DEG C baking ovens.Get upper strata product and identify carbon containing through Raman spectrum; Main containing carbon oxygen nitrogen through the qualification of EDS power spectrum, mass percent is respectively 86.72%, 4.33% and 8.94%, and impurity calcium eliminates substantially; Identify that the ratio of carbon oxygen nitrogen is respectively 92.51%, 4.58% and 2.91% through XPS, wherein the ratio of pyridine nitrogen and pyrroles's nitrogen is respectively 15.11% and 84.89%; Identify that its product is Nano carbon balls through scanning electronic microscope, diameter is at about 50nm.
Claims (3)
1. prepare a method for nitrogen-doped carbon nanometer ball, it is characterized in that comprising following step:
(1) take carbide of calcium as carbon source, L-glutamic acid is nitrogenous source, and the mol ratio of carbide of calcium and L-glutamic acid is 2:1-4:1, is crushed to 1-2mm by carbide of calcium, puts into reactor, then add L-glutamic acid and be uniformly mixed, sealed reactor;
(2) by reactor heat temperature raising, react to 130-150 DEG C of carbide of calcium and L-glutamic acid, stop heating subsequently, allow reactor naturally cool to room temperature;
(3) open reactor, product layering in still, upper strata is cotton-shaped black solid product, gets reaction product layer respectively through 10%-20% dilute hydrochloric acid, distilled water and washing with alcohol suction filtration, after 60-80 DEG C of dry 6-10 hour, obtains Nitrogen in Products doping carbon nanometer ball.
2. the method preparing nitrogen-doped carbon nanometer ball according to claim 1, is characterized in that: in step (1), and the volume ratio that total amount of substance of reactant accounts for reactor is 2.5-5mol/L.
3. the method preparing nitrogen-doped carbon nanometer ball according to claim 1, is characterized in that: in step (3), and the diameter of the nitrogen-doped carbon nanometer ball of gained is 50-80nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244816A (en) * | 2008-03-24 | 2008-08-20 | 中南大学 | Method for synthesizing high purity carbon nano-ball and carbon microsphere |
| CN103288075A (en) * | 2013-05-24 | 2013-09-11 | 大连理工大学 | Nitrogen-doped graphene nanoribbon and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244816A (en) * | 2008-03-24 | 2008-08-20 | 中南大学 | Method for synthesizing high purity carbon nano-ball and carbon microsphere |
| CN103288075A (en) * | 2013-05-24 | 2013-09-11 | 大连理工大学 | Nitrogen-doped graphene nanoribbon and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JINGJING NIU等: "Facile synthesis and optical properties of nitrogen-doped carbon dots", 《NEW JOURNAL OF CHEMISTRY》 * |
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