CN102689896A - Method for preparing graphene oxide through simultaneously performing reduction and nitrogen doping functionalization - Google Patents
Method for preparing graphene oxide through simultaneously performing reduction and nitrogen doping functionalization Download PDFInfo
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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 specifically reduction simultaneously and nitrogen doping functionalization graphene oxide.
Background technology
Graphene (Graphene) is SP
2The carbon atom of hydridization is piled up formed single thin film with the six-ring mode; It is a kind of perfect two dimensional crystal; Through curling or assembling soccerballene (fullerene), unidimensional carbon nanotube (CNTs) and the three-dimensional graphite (graphite) that can form zero dimension, therefore be counted as the parent of graphite form material.Graphene has unique two-dirnentional structure, unusual carrier type and excellent comprehensive performance, 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 having room temperature quantum hall effect and dual polarization field-effect, Graphene also has good optical stability and chemicalstability in addition.In fields such as electron device, matrix material, battery, field emission device, gas sensor, catalysis, energy storage materials extensive studies is arranged, embodied grapheme material special advantages and huge development prospect.
Existing graphene preparation method is numerous, comprises that micromechanics partition method, graphite and verivate thereof directly peel off method, SiC epitaxial growth method, redox graphene method, chemical Vapor deposition process, arc process, organic synthesis method, open carbon Guan Fa etc.Wherein, the redox graphene method is because of it is with low cost, simple to operate, mild condition, 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 80, NaBH at present
4, xitix, HI, Zn, Fe etc.), method such as thermal reduction, photo catalytic reduction, electrochemical reduction.Thermal reduction Graphene C/O is than high, but energy consumption is big, and graphene-structured is destroyed; The reductive agent redox graphene is not only introduced impurity, and often causes irreversible reunion, therefore develop new, efficiently, green graphene oxide reduction system is significant.
In order grapheme material to be applied to different fields, need carry out modulation to performances such as the electricity of Graphene, optics, machineries.Heteroatoms mixes and can change the character of material significantly, and wherein, N is atom doped to be a kind of important modulation approach, generally adopts chemical doping and functional method.Yet, under the situation that the nitrogen presoma exists, no matter be through processes such as bakingout process (800 ℃ of ≈) or chemical vapor deposition (CVD)s, all there are shortcomings such as energy consumption height, N content low (≈ 5%), condition harshness.
Summary of the invention
The objective of the invention is to overcome the deficiency in the prior art, a kind of simple to operate, mild condition is provided, the preparation method of reduction and nitrogen doping functionalization graphene oxide when energy consumption is low.
Preparing method of the present invention comprises following process:
(1) preparation of graphene oxide colloidal sol: at first, graphite oxide is ground to form the fine powder of 1-100 micron, with after itself and the solvent, stirring 0.5-10h, to be mixed with concentration be 0.25-5mg/mL suspension-s; Then, suspension-s is carried out the 0.5-2h supersound process, power is 40-100W; Then, above-mentioned system is carried out the centrifugal treating of 0.5-3h, rotating speed is >=3000rpm, removes the bottom settlings thing, passes through dialysis treatment again, makes graphene oxide colloidal sol;
(2) preparation of functionalization graphene: the graphene oxide colloidal sol that step ⑴ is prepared mixes for 25-28wt% ammoniacal liquor with concentration, and sealing is reacted 0.5-10h down at 40-180 ℃, obtains the functionalization graphene system; 20-80 ℃ of following drying, can prepare the Graphene of nitrogen doping functionalization then;
Graphene oxide colloidal sol wherein: concentration is that the volume ratio of 25-28wt% ammoniacal liquor is 5-50:1.
Said graphite oxide is to be raw material with natural graphite, crystalline flake graphite, compact crystal shape graphite or synthetic graphite, adopts Hummers method, Staudenmaier method or the preparation of Brodie method.
Said solvent is water, ethanol or the mixed solution of the two.
Described dialysis treatment is that graphene oxide colloidal sol is placed molecular weight cut-off is 3500 dialysis tubing, in the mobile deionized water, carries out 4-7 days processing, can make purified 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 then generates hydrogen bond with ammonia, accomplishes the nitrogen doping functionalization process of graphene oxide, shown in following; Simultaneously, under the alkalescence and heat effect of ammoniacal liquor, the reduction process of graphene oxide takes place in removing of graphene oxide generation oxy radical.
In the prepared graphene oxide colloidal sol, graphene oxide almost all exists with monolithic, has realized effectively peeling off; The size wider distribution, shape is various; (≤100 ℃) prepared functionalization graphene black in color film like metalluster and certain mechanical strength are arranged, and toughness is better under the low temperature.
Compared with prior art, the present invention's method of preparing 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 equipment is not had particular requirement, and security and good reproducibility can amplify through simple technology, realize scale operation;
(3) excessive reductive agent is removed very simply among the present invention, can remove excess of ammonia gas through heating;
(4) the functionalization degree of the prepared nitrogen doping functionalization graphene of the present invention can be simply add-on, reaction times, temperature of reaction through control ammoniacal liquor wait and regulate, realize controllable functionization;
Description of drawings:
Fig. 1 is the experimental phenomena electronic pictures of the embodiment of the invention 1 preparation nitrogen doping functionalization graphene; A-graphene oxide colloidal sol; B-graphene oxide colloidal sol and strong aqua 10:1 by volume mix, heating; C, d, e, f, g-be respectively graphene oxide colloidal sol and strong aqua 10:1 by volume reacted respectively under 80 ℃ 1,2,3,4,5 hour after mixing;
Fig. 2 is the contrast of XPS (x-ray photoelectron spectroscopy) spectrogram before and after the embodiment of the invention 1 preparation nitrogen doping functionalization graphene reaction;
Fig. 3 is the variation of XPS (x-ray photoelectron spectroscopy) spectrogram before and after the embodiment of the invention 1 preparation nitrogen doping functionalization graphene reaction: the C1s spectrum of a-graphene oxide; B) C1s of nitrogen doping functionalization graphene spectrum;
Fig. 4 is the N1s spectrum of the embodiment of the invention 1 preparation nitrogen doping functionalization graphene;
The practical implementation method:
Embodiment 1:
With the natural graphite is raw material, adopts the Hummers legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 1-100 micron, and magnetic agitation 5h and water are mixed with the suspension-s that dark concentration is 1.5mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension-s is carried out the centrifugal treating of 0.5h; Rotating speed is 3000rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 4 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 10:1, in graphene oxide colloidal sol, adds 25% ammoniacal liquor, mixes sealing; Place 80 ℃ oil bath then, reaction 5h, obtain black, homogeneous dispersive Graphene system, then 50 ℃ down dry, can prepare the Graphene of nitrogen doping functionalization.
As shown in Figure 1, a is brown graphene oxide colloidal sol; When with graphene oxide colloidal sol and strong aqua by volume 10:1 mix, system darkens, shown in b; Along with the prolongation in reaction times, c-g has reflected that the system color finally becomes black, explains the reduction process that graphene oxide has taken place.As shown in Figure 2, in the embodiment 1 obtained product, O content reduces, and N content increases.Through the match of Fig. 3, a has confirmed that graphene oxide contains groups such as hydroxyl, carboxyl, epoxy group(ing); B has shown that reaction back epoxide group disappears, and the reduction of part has taken place graphite oxide.Can find that by Fig. 4 the N element in the product exists with three kinds of forms: pyridine type, amino-type and graphite mould; Wherein, amino-type nitrogen is staple.N:C=10% (mol ratio) in the prepared nitrogen doping functionalization graphene of embodiment 1, C:O=3.9 (mol ratio).
Embodiment 2:
With the crystalline flake graphite is raw material, adopts the Staudenmaier legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 1-100 micron, and magnetic agitation 3h and water are mixed with the suspension-s of 2mg/mL; Under 40KHz, carry out the supersound process of 1h, ultrasonic power is 80W; Then suspension-s is carried out the centrifugal treating of 0.5h; Rotating speed is 3000rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 4 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 20:1, in graphene oxide colloidal sol, adds 25% ammoniacal liquor, mixes sealing; Place 90 ℃ oil bath then, reaction 5h, obtain black, homogeneous dispersive Graphene system, then 50 ℃ down dry, can prepare the Graphene of nitrogen doping functionalization.N:C=7% (mol ratio) in the prepared nitrogen doping functionalization graphene, C:O=4.7 (mol ratio).
Embodiment 3:
With the synthetic graphite is raw material, adopts the Brodie legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 1-100 micron, and magnetic agitation 3h and ethanol are mixed with the suspension-s of 1mg/mL; Under 40KHz, carry out the supersound process of 1h, ultrasonic power is 70W; Then suspension-s is carried out the centrifugal treating of 0.5h; Rotating speed is 4000rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 4 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 50:1, in graphene oxide colloidal sol, adds 25% ammoniacal liquor, mixes sealing; Place 70 ℃ water-bath then, reaction 5h, obtain black, homogeneous dispersive Graphene system, then 40 ℃ down dry, can prepare the Graphene of nitrogen doping functionalization.N:C=5% (mol ratio) in the prepared nitrogen doping functionalization graphene, C:O=5.8 (mol ratio).
Embodiment 4:
With fine and close crystalloid graphite is raw material, adopts the Hummers legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 10-90 micron, and magnetic agitation 4h and water/alcohol mixeding liquid (volume ratio 1:1) are mixed with the suspension-s of 5mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension-s is carried out the centrifugal treating of 0.5h; Rotating speed is 4000rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 4 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 10:1, in graphene oxide colloidal sol, adds 25% ammoniacal liquor, mixes sealing; Place 70 ℃ oil bath then, reaction 4h, obtain black, homogeneous dispersive Graphene system, then 50 ℃ down dry, can prepare the Graphene of nitrogen doping functionalization.N:C=4.5% (mol ratio) in the prepared nitrogen doping functionalization graphene, C:O=5.4 (mol ratio).
Embodiment 5:
With the synthetic graphite is raw material, adopts the Hummers legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 1-100 micron, and magnetic agitation 1h and water are mixed with the suspension-s of 4mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension-s is carried out the centrifugal treating of 15min; Rotating speed is 5000rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 7 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 25:1, in graphene oxide colloidal sol, adds 25% ammoniacal liquor, mixes; Place hydrothermal reaction kettle; Then reaction kettle is placed 100 ℃, the reaction 8h, obtain heavy-gravity, black, homogeneous dispersive Graphene system; 80 ℃ of following dryings, can prepare the Graphene of nitrogen doping functionalization then.N:C=3% (mol ratio) in the prepared nitrogen doping functionalization graphene, C:O=6.2 (mol ratio).
Embodiment 6:
Similar with embodiment 5, difference is that graphene oxide and 25% ammonia soln volume ratio are 5:1, N:C=16% (mol ratio) in the prepared prepared nitrogen doping functionalization graphene, C:O=6.3 (mol ratio).
Embodiment 7:
With fine and close crystalloid graphite is raw material, adopts the Staudenmaier legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 1-100 micron, and magnetic agitation 4h and water are mixed with the suspension-s of 2mg/mL; Under 40KHz, carry out the supersound process of 1.5h, ultrasonic power is 90W; Then suspension-s is carried out the centrifugal treating of 0.5h; Rotating speed is 3000rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 7 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 20:1; The ammoniacal liquor of adding 25% mixes in graphene oxide colloidal sol, places hydrothermal reaction kettle; 140 ℃ are reacted 1h down; Obtain black, homogeneous dispersive Graphene system, then 50 ℃ down dry, can prepare the Graphene of nitrogen doping functionalization.N:C=8% (mol ratio) in the prepared nitrogen doping functionalization graphene, C:O=8.5 (mol ratio).
Embodiment 8:
With fine and close crystalloid graphite is raw material, adopts the Hummers legal system to be equipped with graphite oxide; The graphite oxide of processing is ground to form the fine powder of 1-100 micron, and magnetic agitation 12h and water are mixed with the suspension-s of 1.5mg/mL; Under 40KHz, carry out the supersound process of 0.5h, ultrasonic power is 100W; Then suspension-s is carried out the centrifugal treating of 0.5h; Rotating speed is 3500rpm, removes the bottom settlings thing, and to place molecular weight cut-off be 3500 dialysis tubing to supernatant then; In the mobile deionized water,, can make graphene oxide colloidal sol again through 6 days dialysis treatment process.
According to graphene oxide colloidal sol and 25% ammonia soln volume ratio is 10:1; The ammoniacal liquor of adding 25% mixes in graphene oxide colloidal sol, places hydrothermal reaction kettle; React 3h down in 180 ℃; Obtain the Graphene system of black bulk,, can prepare the Graphene of nitrogen doping functionalization then 70 ℃ of following dryings.N:C=14% (mol ratio) in the prepared nitrogen doping functionalization graphene, C:O=9.7 (mol ratio).
Claims (4)
1. the reduction and the preparation method of nitrogen doping functionalization graphene oxide simultaneously is characterized in that may further comprise the steps:
(1) preparation of graphene oxide colloidal sol: at first, graphite oxide is ground to form the fine powder of 1-100 micron, with after itself and the solvent, stirring 0.5-10h, to be mixed with concentration be 0.25-5mg/mL suspension-s; Then, suspension-s is carried out the 0.5-2h supersound process, power is 40-100W; Then, above-mentioned system is carried out the centrifugal treating of 0.5-3h, rotating speed is >=3000rpm, removes the bottom settlings thing, passes through dialysis treatment again, makes graphene oxide colloidal sol;
(2) preparation of functionalization graphene: the graphene oxide colloidal sol that step ⑴ is prepared mixes for 25-28wt% ammoniacal liquor with concentration, and sealing is reacted 0.5-10h down at 40-180 ℃, obtains the functionalization graphene system; 20-80 ℃ of following drying, can prepare the Graphene of nitrogen doping functionalization then;
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 and nitrogen doping functionalization graphene oxide; It is characterized in that described graphite oxide is is raw material with natural graphite, crystalline flake graphite, compact crystal shape graphite or synthetic graphite, adopt Hummers method, Staudenmaier method or the preparation of Brodie method.
3. the preparation method of a kind of reduction simultaneously as claimed in claim 1 and 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 and nitrogen doping functionalization graphene oxide; It is characterized in that described dialysis treatment is that graphene oxide colloidal sol is placed molecular weight cut-off is 3500 dialysis tubing; In the mobile deionized water, carry out 4-7 days processing, can make purified graphene oxide colloidal sol.
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| CN110323443A (en) * | 2019-05-27 | 2019-10-11 | 北京理工大学 | A kind of spherical N doping redox graphene material and its application |
| CN110548530A (en) * | 2019-08-27 | 2019-12-10 | 生态环境部南京环境科学研究所 | modified graphene oxide ultraviolet photocatalytic film and preparation method thereof |
| CN110548530B (en) * | 2019-08-27 | 2022-07-22 | 生态环境部南京环境科学研究所 | Modified graphene oxide ultraviolet photocatalytic film and preparation method thereof |
| CN110498408A (en) * | 2019-09-02 | 2019-11-26 | 燕山大学 | Graphene self assembly powder and preparation method thereof |
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