CN105060279A - Grafting method for preparing three-dimensional porous nitrogen-doped graphene - Google Patents
Grafting method for preparing three-dimensional porous nitrogen-doped graphene Download PDFInfo
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Abstract
The invention discloses a grafting method for preparing three-dimensional porous nitrogen-doped graphene. Reduction products of thioamide compounds and zinc powder in a Zn-Hg/HCl reducing agent are utilized simultaneously and regulated and synthesized with the grafting method, and then 3D G-N (three-dimensional nitrogen-doped graphene) is formed. Carbon and sulfur bonds of the thioamide compounds are reduced on the presence of the Zn-Hg/HCl reducing agent; one reduction product of amino can have a grafting reaction with the surface of oxidized graphene and is decomposed at a high temperature, and accordingly, nitrogen doping of graphene is realized; the other reduction product of ZnS (zinc sulfide) precipitates and is deposited in nitrogen-doped sheet layers, and the aggregation effect of graphene can be effectively prevented; ZnS precipitates are dissolved with high-concentration hydrochloric acid later, and the porous three-dimensional nitrogen-doped graphene can be obtained.
Description
Technical field
The invention belongs to carbon material preparing technical field, be specifically related to a kind of method that Graft Method prepares three-dimensional porous nitrogen-doped graphene.
Background technology
Graphene (G), due to its impayable specific surface area and electroconductibility, has led the carbon nanomaterial research boom of a new round.But graphene sheet layer is easy to reunite under the effect of Van der Waals force, thus reduces its active surface sum application stability.And the three-dimensional grapheme of porous is due to its special space structure, greatly reduce the reuniting effect of Graphene, thus it is long-pending to maintain higher catalytically active surface.But based on current research, the controlled synthesis of high performance three-dimensional graphene composite material is still challenging problem.Theoretical investigation shows, Graphene energy band structure after N doping has adjustment, thus greatly can expand the application of Graphene in fields such as optics, electricity and magnetics.
Granted patent 201110204957.4 provides a kind of method adopting chemical Vapor deposition process to prepare nitrating Graphene: organic carbon source compound is mixed with solution or suspension liquid; The solution or suspension liquid that contain organic carbon-source cpd are coated in substrate surface; Under oxygen-free environment, vacuum condition, be warming up to 500 ~ 1300 DEG C by being coated with containing the solution of organic carbon-source cpd or the substrate of suspension liquid, then the nitrogen source compound passing into gaseous state reacts, and obtains nitrating Graphene.A kind of preparation method of nitrating Graphene of granted patent 201110371566.1 invention: liquid carbon source and itrogenous organic substance are mixed with mixing solutions or suspension liquid, and described mixing solutions or suspension liquid are coated in metal substrate surface; Under shielding gas atmosphere, the metal substrate being coated with mixing solutions or suspension liquid is heated to 750 DEG C ~ 1100 DEG C, keeps 1min ~ 300min, after cooling, obtain nitrating Graphene; The preparation method of this nitrating Graphene utilizes liquid carbon source and itrogenous organic substance to carry out thermal response and obtains nitrating Graphene, and relative to traditional explosion method, danger coefficient is lower.A kind of method utilizing plasma sputtering to make nitrating Graphene of granted patent 201210240521.5 invention, mainly utilizes plasma spraying techniques accurately to be adulterated by nitrogen element embedding graphene-structured.Chemical deposition top layer at the bottom of reactive group is utilized to grow single or multiple lift graphene film, then putting into plasma sputtering apparatus at the bottom of the reactive group having grown Graphene and the nitrogen element utilizing high pressure ionization to go out enters graphene-structured in vacuum environment doping, finally totally can obtain doped graphene by corroding completely at the bottom of reactive group.
At present, preparation method's mainly chemical Vapor deposition process and electrochemical process etc. of disclosed nitrating Graphene.In chemical Vapor deposition process, depositing time is the key controlling synthesizing graphite alkene, and prepared Graphene product is film graphene film.The nitrating Graphene of electrochemical production, nitrogen element is all present in the edge of graphene sheet layer, does not enter in graphene sheet layer, and the method preparation process is comparatively complicated in addition.
Summary of the invention
For the preparation method providing a kind of environmental protection simple, the present invention utilizes the amino in the reduzate benzene methanamine of Zn-Hg/HCl reductive agent and thiobenzoyl aminated compounds simultaneously, the three-dimensional porous nitrating Graphene (3DG-N) that utilized Graft Method to synthesize.Thiobenzoyl aminated compounds carbon sulphur double bond under reductive agent Zn-Hg/HCl exists is reduced, aminocompound benzene methanamine can be produced in this process, its amino can with surface of graphene oxide generation graft reaction, simultaneously high temperature issues solution estranged, to realize the N doping of Graphene; Another reduzate zinc sulphide (ZnS) precipitates, and is deposited in N doping lamella, effectively can prevents the reuniting effect of Graphene; Follow-up use high salt concentration acid dissolve ZnS precipitates, and can obtain poroid three-dimensional nitrating Graphene.
The object of the invention is to the above-mentioned deficiency overcoming prior art, provide that a kind of technique is simple, productive rate is high, production cost is low, environmental protection, the preparation method of the three-dimensional nitrating Graphene be easy to operate and control.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
The present invention adopts following technical scheme:
A kind of Graft Method prepares the method for three-dimensional porous nitrating Graphene, it is characterized in that, thioamide analog compound reduces carbon sulphur double bond under zinc system reductive agent exists, the aminocompound of generation and surface of graphene oxide generation graft reaction, and at high temperature decompose, complete the N doping of Graphene; Meanwhile, another reduzate zinc sulphide (ZnS) is deposited in N doping lamella, after above-mentioned reaction completes, dissolves ZnS precipitation in acid condition, namely obtains poroid three-dimensional nitrating Graphene.
Based on the above-mentioned amino utilized in the reduzate benzene methanamine of Zn-Hg/HCl reductive agent and thiobenzoyl aminated compounds, Graft Method is utilized to synthesize the principle of three-dimensional porous nitrating Graphene (3DG-N), the present invention carries out preferably to multiple thiobenzoyl aminated compounds, experiment finds, when adopting thiobenzamide, thioacetamide, thiopropionamide, Thionicotinamide, 2-cyano-thioacetamide, 4-chlorophenylthio ethanamide or 4-methyl thiobenzamide, can obtain that nitrogen content is high, the nitrating grapheme material of electrochemical performance.
Preferably, described zinc system reductive agent is Zn-Hg/HCl.In this reduction system, electronics is transferred to from Zn surface and is reduced group formation negative ion, and the proton then provided with reaction medium is combined, thus undersaturated carbon sulphur double bond is reduced.
Preferably, the concrete steps of above-mentioned preparation method are as follows:
1) adopt zinc system reductive agent reduction thioamide analog compound, reduzate and graphene oxide carried out graft copolymerization, obtains the nitrating grapheme material ZnS/G-N that interlayer deposits ZnS particle,
2) in acid condition, dissolve ZnS in sputtering ZnS/G-N, obtain three-dimensional nitrating grapheme material.
Preferably, step 1) in, the concrete steps of described doped ZnS and nitrogen-atoms are: thioamide analog compound and graphene oxide dispersion are placed in reductive agent, and reflux at 95-98 DEG C 3 ~ 6h in ethanol medium; React after washing and lyophilize 24-36h, obtain the graphene oxide of amino functional; Then be placed in microwave oven, in argon atmosphere, under 1200-1500W power, react 5-10min, obtain three-dimensional porous nitrogen-doped graphene.
Preferably, step 1) in, the concrete preparation method of described Zn-Hg/HCl is: be 1:1:1:20 mixing by zinc powder or zinc granule, mercury chloride, concentrated hydrochloric acid and water according to mass ratio, stir 5-10min, leave standstill, incline the liquid that anhydrates, use hydrochloric acid soln immersion treatment, exist side by side and namely use.
Thioamide analog compound consumption is very few, cannot provide enough amino, to cause in Graphene N doping not enough, but after its consumption reaches 10:1, continues to add the impact of thioamide analog compound on Graphene nitrogen content little.Therefore, the mass ratio of preferred thioamide analog compound and graphene oxide is 5-10:1.
Preferably, step 1) in, the preparation method of graphene oxide dispersion is scattered in the aqueous solution for getting graphene oxide, adds thioamide analog compound, then stir 10-15min, supersound process 1-1.5h after stirring 10-15min.Ultrasound cavitation effect can be produced when ultrasonic wave is propagated in a liquid.Liquid produces countless microbubbles under the effect of ultrasonic field, microbubble shakes, grows, collapses in ultrasonic field, discharge huge energy from generation to sharply collapsing, thus the Graphene particle suspended in aqueous can be broken up by the microjet with powerful surging force produced; Churned mechanically shearing force is large, can improve uniformity coefficient and the Graphene dispersion of particles of solute mixing.
Preferably, step 2) in, in described dissolving sputtering ZnS/G-N, the concrete steps of ZnS are: the hydrochloric acid added to ZnS/G-N, ultrasonic 1-2h, and intermediate water washing, to neutral, oven dry, obtains three-dimensional porous nitrogen-doped graphene.By the hole effect of supersound process, ZnS/G-N is broken up, accelerate the speed of reaction of hydrochloric acid and ZnS, Reaction time shorten.
The compounding design thinking of this material is as follows
First thiobenzamide is reduced in Zn-Hg/HCl reductive agent, generates ZnS and benzene methanamine; Utilize a large amount of oxy radical generation ring-opening reactions of the amino of benzene methanamine and surface of graphene oxide, make benzene methanamine be grafted to the surface of graphene oxide; Dried functionalization graphene, owing to depositing a large amount of non-complete oxidation region, also can produce high temperature instantaneously by strong absorption microwave, thus make oxy radical depart from surface of graphene oxide; Decompose under being grafted to the benzene methanamine high temperature on surface simultaneously and be doped in Graphene lattice, successfully realizing the doping to Graphene; The ZnS particle meanwhile generated can enter into nitrating graphene film interlayer, thus adds the sheet interlayer spacing of Graphene, saboteur's intermolecular forces.Finally by adjustment pH to acid, dissolve ZnS, poroid three-dimensional nitrogen-doped graphene can be obtained.Reduction reaction equation is as shown in Figure 1:
It is characterized in that, by Hummers method, common graphite is oxidized to graphite oxide, then to be mixed with weight percent concentration with graphite oxide be ultrasonic, centrifugal after the graphite oxide aqueous dispersion of 0.1%, obtain homodisperse graphite oxide aqueous dispersion; In graphite oxide aqueous dispersion, add the thiobenzamide that weight percent concentration is 20%, 95 DEG C of back flow reaction 3-6h in the Zn-Hg/HCl reductive agent of ethanol medium, after lyophilize, obtain graphene oxide and the ZnS particle of benzene methanamine functionalization; Product is placed in electromagnetic oven, in argon atmosphere, under 1200W power, reacts 5-10min, the material (ZnS/G-N) between obtained ZnS/ nitrating graphene layer; 3molL is added again in ZnS/G-N
-1aqueous hydrochloric acid, ultrasonic 1-2h, intermediate water washs neutrality, dry obtain three-dimensional porous nitrating Graphene.
The present invention has following beneficial effect relative to prior art:
1. in same reaction, utilize the reduzate of zinc powder and thioamide analog compound in Zn-Hg/HCl reductive agent simultaneously, utilize Graft Method to regulate and control to have synthesized three-dimensional porous nitrogen-doped graphene.
2. utilize a large amount of non-complete oxidation regions of dried functionalization graphene, make its strong absorption microwave and produce high temperature instantaneously, thus make oxy radical depart from surface of graphene oxide, realize the reduction of graphene oxide.
3. ammonia nitrating different from the past, the present invention is by Graft Method, and the decomposition reaction namely under amino ring-opening reaction with graphene oxide and high temperature realizes nitrating, thus obtains three-dimensional nitrating Graphene, and its nitrogen content is up to 7.2-9.2%.
4. zinc powder, was both used for reducing thiobenzamide as reductive agent, and generated ZnS in the reaction simultaneously and be deposited in graphene sheet layer, be conducive to follow-up formation vesicular structure.
5. the three-dimensional nitrating Graphene that prepared by the present invention shows excellent chemical property.During electrode materials as ultracapacitor, have high ratio capacitance, superior high rate performance, after discharge and recharge 10000 times, capability retention is up to 97.6%.
6. adopt ZnS deposit seeds to be deposited between nitrating graphene layer, then through removing the particle of precipitation, we can the loose three-dimensional porous structure of nitrating Graphene as seen from Figure 2, and this is conducive to promoting its catalytically active surface and amasss, and strengthens its catalytic efficiency.
Accompanying drawing explanation
Fig. 1 is reduction reaction equation of the present invention;
Fig. 2 is the SEM figure of three-dimensional nitrating Graphene prepared by the embodiment of the present invention 1.
Embodiment
Mode by the following examples further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition.
The preparation of the three-dimensional nitrating Graphene of embodiment 1
In the beaker of 1000mL, add the 130mL vitriol oil and 5g crystalline flake graphite, and under condition of ice bath mechanical stirring 2h.In above-mentioned system, slowly add 15g potassium permanganate, and continue under maintaining condition of ice bath to stir 2h, this one-phase is the low-temp reaction stage.Remove ice bath.Continue to stir the oxidation that lh. promotes graphite further under 35 DEG C of water-baths.This stage is middle temperature step of reaction.230mL deionized water is dripped lentamente in beaker. and be warming up to 980 DEG C of continuation reaction 30min, this stage is the pyroreaction stage.400mL deionized water is wherein added after pyroreaction terminates. and centrifuge washing obtains graphite oxide dispersion to neutrality.
Graphite oxide dispersion is diluted to the concentration of 0.1mg/mL, measures this dispersion liquid of 120mL and be added to 250mL single port flask at 95 DEG C after back flow reaction 3h with 10mL thiobenzamide and 5mlZn-Hg/HCl reductive agent; By products therefrom with intermediate water washing for several times, filter, lyophilize 24h, by obtain ZnS particle deposition functionalization nitrating graphene layer between material (ZnS/G-N);
3molL is added again in ZnS/G-N
-1aqueous hydrochloric acid, ultrasonic 1.5h, intermediate water washs neutrality, dry obtain three-dimensional porous nitrating Graphene.
Compare test and analysis to super capacitor performance: respectively 3DG-N and G-N and appropriate dehydrated alcohol are mixed, be prepared into strong solution, propose after nickel foam collector (2cm × 1cm) immerses the several seconds, active substance is made to be attached to inner hole wall and the outside surface of collector, vacuum-drying, 10MPa lower sheeting 30s, on each working electrode, the quality of active substance is about 2mg, tests by three electrode test systems.Found that, at 0.5Ag
-1under current density, the specific storage of ultracapacitor prepared by 3DG-N and G-N nitrating grapheme material is respectively 365Fg
-1, 255Fg
-1, energy density is respectively 47.2Whkg
-1, 33.5Whkg
-1, show that three-dimensional nitrating Graphene (3DG-N) prepared by the present invention has high rate performance better, more excellent super capacitor performance; Electrochemical analysis: the ultracapacitor prepared of G-N nitrating grapheme material at the diameter of high frequency region semi arch apparently higher than the situation of 3DG-N, the three-dimensional nitrating Graphene of 3DG-N prepared by display the present invention has the three-dimensional porous structure being more conducive to electric transmission, and larger catalytically active surface amasss.Its nitrogen content is up to 7.7%, and after discharge and recharge 10000 times, capability retention is up to 94.5%.
Embodiment 2
The preparation method of graphite oxide dispersion is with embodiment 1.
Graphite oxide dispersion is diluted to the concentration of 0.3mg/mL, measures this dispersion liquid of 120mL and be added to 250mL single port flask at 95 DEG C after back flow reaction 3h with 20mL Thionicotinamide and 5mlZn-Hg/HCl reductive agent; By products therefrom with intermediate water washing for several times, filter, lyophilize 24h, by obtain ZnS particle deposition functionalization nitrating graphene layer between material (ZnS/G-N);
3molL is added again in ZnS/G-N
-1aqueous hydrochloric acid, ultrasonic 1.5h, intermediate water washs neutrality, dry obtain three-dimensional porous nitrating Graphene.To the compare test of super capacitor performance and the method for analysis with embodiment 1.The specific storage of ultracapacitor prepared by 3DG-N and G-N nitrating grapheme material is respectively 325Fg
-1, 215Fg
-1, energy density is respectively 40.2Whkg
-1, 31.5Whkg
-1.Its nitrogen content is up to 7.2%, and after discharge and recharge 10000 times, capability retention is up to 95.2%.
Embodiment 3
The preparation method of graphite oxide dispersion is with embodiment 1.
Graphite oxide dispersion is diluted to the concentration of 0.5mg/mL, measures this dispersion liquid of 120mL and be added to 250mL single port flask at 95 DEG C after back flow reaction 3h with 25mL4-chlorophenylthio ethanamide and 5mlZn-Hg/HCl reductive agent; By products therefrom with intermediate water washing for several times, filter, lyophilize 24h, by obtain ZnS particle deposition functionalization nitrating graphene layer between material (ZnS/G-N);
3molL is added again in ZnS/G-N
-1aqueous hydrochloric acid, ultrasonic 1.5h, intermediate water washs neutrality, dry obtain three-dimensional porous nitrating Graphene.To the compare test of super capacitor performance and the method for analysis with embodiment 1.The specific storage of ultracapacitor prepared by 3DG-N and G-N nitrating grapheme material is respectively 335Fg
-1, 227Fg
-1, energy density is respectively 42.5Whkg
-1, 32.2Whkg
-1.Its nitrogen content is up to 9.2%, and after discharge and recharge 10000 times, capability retention is up to 97.6%.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. a Graft Method prepares the method for three-dimensional porous nitrogen-doped graphene, it is characterized in that, thioamide analog compound reduces carbon sulphur double bond under zinc system reductive agent exists, the aminocompound produced is by Graft Method and surface of graphene oxide generation ring-opening reaction, and at high temperature decompose, complete the N doping of Graphene; Meanwhile, another reduzate zinc sulphide ZnS is deposited in N doping lamella, after above-mentioned reaction completes, dissolves ZnS precipitation in acid condition, namely obtains poroid three-dimensional nitrating Graphene.
2. the method for claim 1, it is characterized in that, described thioamide analog compound is thiobenzamide, thioacetamide, thiopropionamide, Thionicotinamide, 2-cyano-thioacetamide, 4-chlorophenylthio ethanamide or 4-methyl thiobenzamide.
3. the method for claim 1, is characterized in that, described zinc system reductive agent is Zn-Hg/HCl.
4. the method for claim 1, is characterized in that, concrete steps are as follows:
1) adopt zinc system reductive agent reduction thioamide analog compound, reduzate and graphene oxide carried out graft copolymerization, obtains the nitrating grapheme material ZnS/G-N that interlayer deposits ZnS particle,
2) in acid condition, dissolve ZnS in sputtering ZnS/G-N, obtain three-dimensional nitrating grapheme material.
5. method as claimed in claim 4, it is characterized in that, step 1) in, the concrete steps of described doped ZnS and nitrogen-atoms are: thioamide analog compound and graphene oxide dispersion are placed in reductive agent, and reflux at 95-98 DEG C 3 ~ 6h in ethanol medium; React after washing and lyophilize 24-36h, obtain the graphene oxide of amino functional; Then be placed in microwave oven, in argon atmosphere, under 1200-1500W power, react 5-10min, obtain three-dimensional porous nitrogen-doped graphene.
6. method as claimed in claim 4, it is characterized in that, step 1) in, the concrete preparation method of described Zn-Hg/HCl is: be 1:1:1:20 mixing by zinc powder or zinc granule, mercury chloride, concentrated hydrochloric acid and water according to mass ratio, stir 5-10min, leave standstill, incline the liquid that anhydrates, use hydrochloric acid soln immersion treatment, exist side by side and namely use.
7. method as claimed in claim 4, is characterized in that, step 1) in, the mass ratio of described thioamide analog compound and graphene oxide is 5-10:1.
8. method as claimed in claim 5, is characterized in that, step 1) in, the preparation method of described graphene oxide dispersion is scattered in the aqueous solution for getting graphene oxide, add thioamide analog compound after stirring 10-15min, then stir 10-15min, supersound process 1-1.5h.
9. method as claimed in claim 4, is characterized in that, step 2) in, in described dissolving sputtering ZnS/G-N, the concrete steps of ZnS are: the hydrochloric acid added to ZnS/G-N, ultrasonic 1-2h, intermediate water washing, to neutral, oven dry, obtains three-dimensional porous nitrogen-doped graphene.
10. the three-dimensional porous nitrogen-doped graphene prepared of the arbitrary described method of claim 1-9, it is characterized in that, the nitrogen content of described three-dimensional porous nitrogen-doped graphene is 7.2-9.2%, and after discharge and recharge 10000 times, capability retention is 94.5-97.6%.
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| CN111825078A (en) * | 2019-04-22 | 2020-10-27 | 南京大学 | Method for preparing three-dimensional graphene foam material |
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