CN102689896B - Method for preparing nitrogen doping functionalized oxide graphene simultaneously performing reduction - Google Patents
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Abstract
The invention discloses a method for preparing graphene oxide through simultaneously performing reduction and nitrogen doping functionalization, comprising the following steps of: grinding graphite oxide to be fine powder of 1-100 micrometers; mixing the fine powder with a solvent; stirring the mixture for 0.5-10 hours to prepare suspension liquid with the concentration of 0.25-5mg/mL; carrying out ultrasonic treatment on the suspension liquid for 0.5-2 hours with the power of 40-100W; performing centrifugal treatment on the system for 0.5-3 hours in the rotation speed of more than or equal to 3,000 rpm, and performing dialysis treatment on the system after bottom deposits are removed to prepare graphene oxide sol; mixing the graphene oxide sol with ammonia water with the concentration of 25-28 wt percent, sealing and reacting for 0.5-10 hours under the temperature of between 40 and 180 DEG C to obtain a functionalization graphene system; and drying the functionalization graphene system under the temperature of between 20 and 180 DEG C to prepare graphene oxide subjected to nitrogen doping functionalization. The method has the advantages of being simple in operation, mild in condition and low in energy consumption.
Description
Technical field
The invention belongs to a kind of preparation method of Graphene, the preparation method of a kind of reduction simultaneously specifically nitrogen doping functionalization graphene oxide.
Background technology
Graphene (Graphene) is SP
2the carbon atom of hydridization is piled up formed single thin film in six-ring mode, it is a kind of perfect two dimensional crystal, process is curling or assembling can form the soccerballene (fullerene) of zero dimension, the carbon nanotube (CNTs) of one dimension and three-dimensional graphite (graphite), is therefore counted as the parent of graphite form material.Graphene has unique two-dirnentional structure, unusual carrier type and excellent over-all properties, as: theoretical specific surface area is about 2600m
2g
-1, Young's modulus is about 1100GPa, and breaking tenacity is 125GPa, and thermal conductivity is 5000Wm
-1k
-1, carrier mobility is 200 000cm
2v
-1s
-1, and thering is room temperature quantum hall effect and dual polarization field-effect, Graphene also has good optical stability and chemical stability in addition.In fields such as electron device, matrix material, battery, field emission device, gas sensor, catalysis, energy storage materials, there is research widely, embodied the advantage of grapheme material uniqueness and huge development prospect.
Existing graphene preparation method is numerous, comprises the direct stripping method of micromechanics partition method, graphite and derivative thereof, SiC epitaxial growth method, redox graphene method, chemical Vapor deposition process, arc process, organic synthesis method, opens carbon Guan Fa etc.Wherein, redox graphene method because it is with low cost, simple to operate, mild condition, the advantage such as can prepare in a large number and get more and more people's extensive concerning.The reduction system of graphene oxide has reductive agent reduction (hydrazine hydrate, NaBH at present
4, xitix, HI, Zn, Fe etc.), the method such as thermal reduction, photo catalytic reduction, electrochemical reduction.Thermal reduction Graphene C/O is than high, but energy consumption is large, and graphene-structured is destroyed; Reductive agent redox graphene is not only introduced impurity, and often causes irreversible reunion, therefore develops new, efficient, green graphene oxide reduction system significant.
For grapheme material being applied to different fields, need to carry out modulation to performances such as the electricity of Graphene, optics, machineries.Heteroatom doping can change the character of material significantly, and wherein, N is atom doped is a kind of important modulation approach, generally adopts chemical doping and functional method.Yet, in the situation that nitrogen presoma exists, no matter be through processes such as Overheating Treatment (800 ℃ of ≈) or chemical vapor deposition (CVD)s, all there is the shortcomings such as energy consumption is high, N content low (≈ 5%), condition harshness.
Summary of the invention
The object of the invention is to overcome the deficiency in prior art, the preparation method of reduction nitrogen doping functionalization graphene oxide when providing a kind of simple to operate, mild condition, energy consumption low.
Preparation method of the present invention comprises following process:
(1) preparation of graphene oxide colloidal sol: first, graphite oxide is ground to form to the fine powder of 1-100 micron, by after itself and solvent, stirring 0.5-10h, to be mixed with concentration be 0.25-5mg/mL suspension; Then, suspension is carried out to 0.5-2h supersound process, power is 40-100W; Then, above-mentioned system is carried out to the centrifugal treating of 0.5-3h, rotating speed is >=3000rpm, removes bottom settlings thing, then passes through dialysis treatment, makes graphene oxide colloidal sol;
(2) preparation of functionalization graphene: by step (1) prepared graphene oxide colloidal sol be that 25-28wt% ammoniacal liquor mixes with concentration, sealing is reacted 0.5-10h at 40-180 ℃, obtains functionalization graphene system; Then at 20-80 ℃, be dried, can prepare the Graphene of nitrogen doping functionalization;
Graphene oxide colloidal sol wherein: concentration is that the volume ratio of 25-28wt% ammoniacal liquor is 5-50:1.
Described graphite oxide is that to take natural graphite, crystalline flake graphite, compact crystal shape graphite or synthetic graphite be raw material, adopts Hummers method, Staudenmaier method or Brodie legal system standby.
Described solvent is water, ethanol or the mixed solution of the two.
Described dialysis treatment is that graphene oxide colloidal sol is placed in to molecular weight cut-off is 3500 dialysis tubing, carries out the processing of 4-7 days in mobile deionized water, can make pure graphene oxide colloidal sol.
Principle of the present invention be ammoniacal liquor can with carboxyl, epoxy group(ing) and the carbonyl reaction of graphene oxide, generate amido, hydroxyl generates hydrogen bond with ammonia, completes the nitrogen doping functionalization process of graphene oxide, as shown in following; Meanwhile, under the alkalescence and heat effect of ammoniacal liquor,, there is the reduction process of graphene oxide in removing of graphene oxide generation oxy radical.
In prepared graphene oxide colloidal sol, graphene oxide almost all exists with monolithic, has realized effectively and having peeled off; Size wider distribution, shape is various; Under low temperature, (≤100 ℃) prepared functionalization graphene is black film like, have metalluster and certain physical strength, and toughness is better.
Compared with prior art, the method that the present invention prepares nitrogen doping functionalization graphene has the following advantages:
(1) reagent involved in the present invention is environmental friendliness reagent, has avoided danger such as environment, personal injuries;
(2) the present invention is simple to operate, and to equipment, without particular requirement, security and reproducible, can amplify by simple technique, realizes scale operation;
(3) in the present invention, excessive reductive agent is removed very simply, by heating, can remove excess of ammonia gas;
(4) the functionalization degree of the prepared nitrogen of the present invention doping functionalization graphene can be simply add-on by control ammoniacal liquor, reaction times, temperature of reaction etc. regulate, realize controllable function;
Accompanying drawing explanation:
Fig. 1 is the experimental phenomena electronic pictures that the embodiment of the present invention 1 is prepared nitrogen doping functionalization graphene; A-graphene oxide colloidal sol; B-graphene oxide colloidal sol and strong aqua by volume 10:1 mix, heating; C, d, e, f, g-be respectively graphene oxide colloidal sol and strong aqua by volume 10:1 react respectively 1,2,3,4,5 hour after mixing at 80 ℃;
Fig. 2 is that the embodiment of the present invention 1 is prepared the XPS(X photoelectron spectrum before and after the reaction of nitrogen doping functionalization graphene) contrast of spectrogram;
Fig. 3 is that the embodiment of the present invention 1 is prepared XPS(X photoelectron spectrum before and after the reaction of nitrogen doping functionalization graphene) variation of spectrogram: the C1s spectrum of a-graphene oxide; B) the C1s spectrum of nitrogen doping functionalization graphene;
Fig. 4 is the N1s spectrum that the embodiment of the present invention 1 is prepared nitrogen doping functionalization graphene;
Specific implementation method:
Embodiment 1:
Take natural graphite as raw material, adopt Hummers legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 1-100 micron, magnetic agitation 5h and water are mixed with the suspension that dark concentration is 1.5mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension is carried out the centrifugal treating of 0.5h, rotating speed is 3000rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 4 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 10:1, the ammoniacal liquor to adding 25% in graphene oxide colloidal sol, mixes, sealing; Then be placed in the oil bath of 80 ℃, reaction 5h, obtains Graphene system black, that homogeneous disperses, then dry at 50 ℃, can prepare the Graphene of nitrogen doping functionalization.
As shown in Figure 1, a is brown graphene oxide colloidal sol; When by graphene oxide colloidal sol and strong aqua by volume 10:1 mix, system darkens, as shown in b; Along with the prolongation in reaction times, c-g has reflected that system color finally becomes black, illustrates the reduction process that graphene oxide has occurred.As shown in Figure 2, in the obtained product of embodiment 1, O content reduces, and N content increases.By the matching of Fig. 3, a has confirmed that graphene oxide contains the groups such as hydroxyl, carboxyl, epoxy group(ing); After b has shown reaction, epoxide group disappears, and the reduction of part has occurred graphite oxide.By Fig. 4, can be found, the N element in product exists with three kinds of forms: pyridine type, amino-type and graphite mould; Wherein, amino-type nitrogen is main component.N:C=10%(mol ratio in the prepared nitrogen of embodiment 1 doping functionalization graphene), C:O=3.9(mol ratio).
Embodiment 2:
Take crystalline flake graphite as raw material, adopt Staudenmaier legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 1-100 micron, magnetic agitation 3h and water are mixed with the suspension of 2mg/mL; Under 40KHz, carry out the supersound process of 1h, ultrasonic power is 80W; Then suspension is carried out the centrifugal treating of 0.5h, rotating speed is 3000rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 4 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 20:1, the ammoniacal liquor to adding 25% in graphene oxide colloidal sol, mixes, sealing; Then be placed in the oil bath of 90 ℃, reaction 5h, obtains Graphene system black, that homogeneous disperses, then dry at 50 ℃, can prepare the Graphene of nitrogen doping functionalization.N:C=7%(mol ratio in prepared nitrogen doping functionalization graphene), C:O=4.7(mol ratio).
Embodiment 3:
Take synthetic graphite as raw material, adopt Brodie legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 1-100 micron, magnetic agitation 3h and ethanol are mixed with the suspension of 1mg/mL; Under 40KHz, carry out the supersound process of 1h, ultrasonic power is 70W; Then suspension is carried out the centrifugal treating of 0.5h, rotating speed is 4000rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 4 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 50:1, the ammoniacal liquor to adding 25% in graphene oxide colloidal sol, mixes, sealing; Then be placed in the water-bath of 70 ℃, reaction 5h, obtains Graphene system black, that homogeneous disperses, then dry at 40 ℃, can prepare the Graphene of nitrogen doping functionalization.N:C=5%(mol ratio in prepared nitrogen doping functionalization graphene), C:O=5.8(mol ratio).
Embodiment 4:
The fine and close crystalloid graphite of take is raw material, adopts Hummers legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 10-90 micron, magnetic agitation 4h and water/alcohol mixeding liquid (volume ratio 1:1) are mixed with the suspension of 5mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension is carried out the centrifugal treating of 0.5h, rotating speed is 4000rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 4 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 10:1, the ammoniacal liquor to adding 25% in graphene oxide colloidal sol, mixes, sealing; Then be placed in the oil bath of 70 ℃, reaction 4h, obtains Graphene system black, that homogeneous disperses, then dry at 50 ℃, can prepare the Graphene of nitrogen doping functionalization.N:C=4.5%(mol ratio in prepared nitrogen doping functionalization graphene), C:O=5.4(mol ratio).
Embodiment 5:
Take synthetic graphite as raw material, adopt Hummers legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 1-100 micron, magnetic agitation 1h and water are mixed with the suspension of 4mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension is carried out the centrifugal treating of 15min, rotating speed is 5000rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 7 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 25:1, to the ammoniacal liquor that adds 25% in graphene oxide colloidal sol, mix, be placed in hydrothermal reaction kettle, then reactor is placed in to 100 ℃, reaction 8h, obtains Graphene system thickness, black, that homogeneous disperses, then at 80 ℃, be dried, can prepare the Graphene of nitrogen doping functionalization.N:C=3%(mol ratio in prepared nitrogen doping functionalization graphene), C:O=6.2(mol ratio).
Embodiment 6:
Similar to embodiment 5, difference is that graphene oxide and 25% ammonia soln volume ratio are 5:1, N:C=16%(mol ratio in prepared prepared nitrogen doping functionalization graphene), C:O=6.3(mol ratio).
Embodiment 7:
The fine and close crystalloid graphite of take is raw material, adopts Staudenmaier legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 1-100 micron, magnetic agitation 4h and water are mixed with the suspension of 2mg/mL; Under 40KHz, carry out the supersound process of 1.5h, ultrasonic power is 90W; Then suspension is carried out the centrifugal treating of 0.5h, rotating speed is 3000rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 7 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 20:1, to the ammoniacal liquor that adds 25% in graphene oxide colloidal sol, mix, be placed in hydrothermal reaction kettle, at 140 ℃, react 1h, obtain Graphene system black, that homogeneous disperses, then at 50 ℃, be dried, can prepare the Graphene of nitrogen doping functionalization.N:C=8%(mol ratio in prepared nitrogen doping functionalization graphene), C:O=8.5(mol ratio).
Embodiment 8:
The fine and close crystalloid graphite of take is raw material, adopts Hummers legal system for graphite oxide; The graphite oxide of making is ground to form to the fine powder of 1-100 micron, magnetic agitation 12h and water are mixed with the suspension of 1.5mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension is carried out the centrifugal treating of 0.5h, rotating speed is 3500rpm, removes bottom settlings thing, and to be then placed in molecular weight cut-off be 3500 dialysis tubing to supernatant liquor, in mobile deionized water, again through the dialysis treatment process of 6 days, can make graphene oxide colloidal sol.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio, be 10:1, to the ammoniacal liquor that adds 25% in graphene oxide colloidal sol, mix, be placed in hydrothermal reaction kettle, at 180 ℃, react 3h, obtain the Graphene system of black bulk, then at 70 ℃, be dried, can prepare the Graphene of nitrogen doping functionalization.N:C=14%(mol ratio in prepared nitrogen doping functionalization graphene), C:O=9.7(mol ratio).
Claims (4)
1. a preparation method for reduction simultaneously nitrogen doping functionalization graphene oxide, is characterized in that comprising the following steps:
(1) preparation of graphene oxide colloidal sol: first, graphite oxide is ground to form to the fine powder of 1-100 micron, by after itself and solvent, stirring 0.5-10h, to be mixed with concentration be 0.25-5mg/mL suspension; Then, suspension is carried out to 0.5-2h supersound process, power is 40-100W; Then, above-mentioned system is carried out to the centrifugal treating of 0.5-3h, rotating speed is >=3000rpm, removes bottom settlings thing, then passes through dialysis treatment, makes graphene oxide colloidal sol;
(2) preparation of functionalization graphene: by step (1) prepared graphene oxide colloidal sol be that 25-28wt% ammoniacal liquor mixes with concentration, sealing is reacted 0.5-10h at 40-180 ℃, obtains functionalization graphene system; Then at 20-80 ℃, be dried, can prepare the Graphene of nitrogen doping functionalization;
Graphene oxide colloidal sol wherein: concentration is that the volume ratio of 25-28wt% ammoniacal liquor is 5-50:1.
2. the preparation method of a kind of reduction simultaneously as claimed in claim 1 nitrogen doping functionalization graphene oxide, it is characterized in that described graphite oxide is that to take natural graphite, crystalline flake graphite, compact crystal shape graphite or synthetic graphite be raw material, adopts Hummers method, Staudenmaier method or Brodie legal system standby.
3. the preparation method of a kind of reduction simultaneously as claimed in claim 1 nitrogen doping functionalization graphene oxide, is characterized in that described solvent is water, ethanol or the mixed solution of the two.
4. the preparation method of a kind of reduction simultaneously as claimed in claim 1 nitrogen doping functionalization graphene oxide, it is characterized in that described dialysis treatment is that graphene oxide colloidal sol is placed in to molecular weight cut-off is 3500 dialysis tubing, in mobile deionized water, carry out the processing of 4-7 days, can make pure graphene oxide colloidal sol.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102030325A (en) * | 2010-11-03 | 2011-04-27 | 中国科学院电工研究所 | Method for preparing biocompatible graphene |
CN102120572A (en) * | 2011-01-24 | 2011-07-13 | 南京大学 | Method for preparing nitrogen-doped graphene |
CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
-
2012
- 2012-03-15 CN CN201210067653.2A patent/CN102689896B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102030325A (en) * | 2010-11-03 | 2011-04-27 | 中国科学院电工研究所 | Method for preparing biocompatible graphene |
CN102120572A (en) * | 2011-01-24 | 2011-07-13 | 南京大学 | Method for preparing nitrogen-doped graphene |
CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
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