CN102167310A - Method for preparing nitrogen-doped graphene material with hydrothermal process - Google Patents
Method for preparing nitrogen-doped graphene material with hydrothermal process Download PDFInfo
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Abstract
The invention discloses a method for preparing a nitrogen-doped graphene material with a hydrothermal process, relating to a method for preparing the nitrogen-doped graphene material. The technical problems of lower nitrogen content, difficulty in control of nitrogen content, high production cost, complex structure of equipment required by reaction, rigorous reaction conditions, low yield, difficulty in industrialized production and the like in the traditional method for preparing the nitrogen-doped graphene material are solved in the invention. The method comprises the steps of: 1, dissolving graphite oxide in a solvent, adding a surfactant and uniformly mixing; 2, adding a nitrogen-containing compound, and uniformly mixing; and 3, after a hydro-thermal reaction, washing and drying to obtain the nitrogen-doped graphene material. The nitrogen-doped graphene material prepared in the invention has the advantages of higher nitrogen content, controllable nitrogen content, low production cost, simple structure of required equipment, high yield and easiness in realizing industrialized production.
Description
Technical field
The present invention relates to a kind of nitrogen-doped graphene preparation methods.
Background technology
The Graphene of two-dirnentional structure has the excellent physical chemical property, and fields such as ballistic transistor on the scene, ultracapacitor, lithium ion battery have important use to be worth.Yet it is very important that nitrogen mixes for the electronic structure of regulating Graphene.Nitrogen-doped graphene has important use in fields such as ultracapacitor, fuel cells.Therefore, in order to satisfy the demand of different field, synthetic to the adulterated design of this two-dimensional material nitrogen is very necessary.Traditional method for preparing nitrogen-doped graphene mainly contains: (1) feeds ammonia simultaneously and carries out nitrogen and mix in the process of chemical Vapor deposition process (CVD) preparation Graphene, and high nitrogen content is 5%; (2) prepare in the process of Graphene at arc discharge method, feed nitrogenous compounds such as pyridine or ammonia, preparation nitrogen-doped graphene material, high nitrogen content is 1%.Nitrogen content is lower and wayward in the nitrogen-doped graphene of this two kinds of methods preparation, production security is relatively poor, reaction process is complicated, severe reaction conditions, productive rate are low.
In sum, the nitrogen content lower (between 0.1%～5%) that existing nitrogen-doped graphene material preparation method exists, nitrogen content is wayward, production cost is high, reaction required equipment complexity, severe reaction conditions, problem such as yield poorly, thereby is difficult to suitability for industrialized production.
Summary of the invention
The present invention will solve that the nitrogen content that existing nitrogen-doped graphene material preparation method exists is lower, nitrogen content is wayward, production cost is high, reaction required equipment complexity, severe reaction conditions, yield poorly, be difficult to technical problem such as suitability for industrialized production; Thereby provide the method for Hydrothermal Preparation nitrogen-doped graphene material.
The method of Hydrothermal Preparation nitrogen-doped graphene material is finished by following step among the present invention:
One, graphite oxide is added in the solvent, add tensio-active agent again, use ultrasonic method or heated and stirred method to mix then, obtain mixture A, wherein, described solvent is water, methyl alcohol, ethanol, ethylene glycol, N, a kind of or wherein several mixing in the dinethylformamide, the mass ratio of described graphite oxide and solvent is 1: 100～2000, and the mass ratio of described tensio-active agent and graphite oxide is 0.01～50: 1;
Two, add nitrogenous compound then in mixture A, the mass ratio that adds nitrogenous compound and graphite oxide is 10～500: 1, adopts ultrasonic method or heated and stirred method to mix again and obtains mixture B;
Three, mixture B is carried out hydro-thermal reaction, hydrothermal temperature is 100～190 ℃, and the hydro-thermal reaction time is 4～48h, uses distilled water, ethanol or washing with acetone then, is drying under 60～110 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions again; Promptly obtain the nitrogen-doped graphene material.
The nitrogen content of the nitrogen-doped graphene material of the present invention's preparation is between 8%～19%, and kind, consumption and temperature of reaction and the time of passing through change adding nitrogenous compound, just can control the nitrogen content in the product.The productive rate of the nitrogen-doped graphene material of the present invention preparation is more than 98.9%, applied range; Can be applicable to aspects such as fuel cell, super-capacitor.The nitrogen content of the nitrogen-doped graphene material of the inventive method preparation is higher, nitrogen content is controlled, production cost is low, required equipment is simple, the output height, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 be embodiment 15 preparation the nitrogen-doped graphene material electron scanning micrograph; Fig. 2 is the XPS spectrum figure of nitrogen element of the nitrogen-doped graphene material of embodiment 15 preparation.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for Hydrothermal Preparation nitrogen-doped graphene material is finished by following step in the present embodiment: one, graphite oxide is added in the solvent, add tensio-active agent again, use ultrasonic method or heated and stirred method to mix then, obtain mixture A, wherein, described solvent is a water, methyl alcohol, ethanol, ethylene glycol, N, a kind of or wherein several mixing in the dinethylformamide, the mass ratio of described graphite oxide and solvent is 1: 100～2000, and the mass ratio of described tensio-active agent and graphite oxide is 0.01～50: 1; Two, add nitrogenous compound then in mixture A, wherein the mass ratio of nitrogenous compound and graphite oxide is 10～500: 1,, adopt ultrasonic method or heated and stirred method to mix again and obtain mixture B; Three, mixture B is carried out hydro-thermal reaction, hydrothermal temperature is 100～190 ℃, and the hydro-thermal reaction time is 4～48h, uses distilled water, ethanol or washing with acetone then, is drying under 60～110 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions again; Promptly obtain the nitrogen-doped graphene material.
The described solvent of present embodiment is a mixture, presses between each solvent arbitrarily than mixing.
The nitrogen content of the nitrogen-doped graphene material of present embodiment preparation and can be controlled nitrogen content in the product by changing the kind that adds nitrogenous compound and consumption between 10%～19%.The productive rate of the nitrogen-doped graphene material of the present invention's preparation is more than 98.9%.
Embodiment two: what present embodiment and embodiment one were different is: the described tensio-active agent of step 1 is a kind of in cationic surfactant, aniorfic surfactant, nonionogenic tenside and the amphoterics.Other step is identical with embodiment one with parameter.
Embodiment three: what present embodiment and embodiment two were different is: described cationic surfactant is a cetyl trimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide, hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride, lauryl alcohol polyoxyethylene ether dimethyl methyl ammonium chloride, polyoxyethylene octylphenol ether base dimethyl decyl brometo de amonio, polyoxyethylene octylphenol ether base dimethyl decyl ammonium chloride or hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride.Other step is identical with embodiment two with parameter.
Embodiment four: what present embodiment and embodiment two were different is: described aniorfic surfactant is sodium lauryl sulphate, sodium laurylsulfonate, hexadecyl benzene sulfonic acid sodium salt, sodium stearyl sulfate, N-oleoyl contract amino acid sodium, polyoxyethylenated alcohol sodium sulfate or fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium more.Other step is identical with embodiment two with parameter.
Embodiment five: what present embodiment and embodiment two were different is: described nonionic surface active agent is Polyvinylpyrolidone (PVP), propanediol polyoxypropylene Soxylat A 25-7, structure alcohol polyoxyethylene poly-oxygen propylene aether, polyurethane polyureas oxypropylene polyethenoxy ether, polyethylene glycol monooleate or octadecyl ethylene urea.Other step is identical with embodiment two with parameter.
Embodiment six: what present embodiment and embodiment two were different is: described amphoterics is EO
20PO
70EO
20(P123), EO
106PO
70EO
106(F127), lauryl dimethyl amine oxide, cocounut oil alkyl dimethyl amine oxide, dimethyl dodecyl amine oxide, dodecyl dihydroxy ethyl amine oxide, tetradecyl dihydroxy ethyl amine oxide, hexadecyl dihydroxy ethyl amine oxide, octadecyl dimethyl amine oxide or octadecyl dihydroxy ethyl amine oxide.Other step is identical with embodiment two with parameter.
Embodiment seven: what present embodiment and embodiment two were different is: the nitrogenous compound described in the step 2 is ammoniacal liquor, urea, pyridine, pyrroles, hydrazine, dimethylamine, thyl methyl amine, second two ammoniums, triethylamine, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, n-Butyl Amine 99, trimeric cyanamide, aniline, N-methyl-N-ethylbenzene, N, a kind of or wherein several mixing in N-Diethyl Aniline, tetraethyl-ammonium bromide, the hydroxide trimethylammonium ethyl ammonium.Other step is identical with embodiment two with parameter.
The described solvent of present embodiment is a mixture, presses between each solvent arbitrarily than mixing.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: ultrasonic method described in the step 1 is to be that 20～40KHz, ultrasonic power are under 200～700W condition in ultrasonic frequency, and ultrasonic time is 10min～1h.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: ultrasonic method described in the step 2 is to be that 20～40KHz, ultrasonic power are under 200～700W condition in ultrasonic frequency, and ultrasonic time is 10min～1h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what present embodiment was different with one of embodiment one to nine is: the method for heated and stirred described in the step 1 is to be that 35～70 ℃, stirring velocity are under 100～350r/min condition in temperature, and churning time is 10min～3h.Other step is identical with one of embodiment one to nine with parameter.
Embodiment 11: what embodiment was different with one of embodiment one to ten is: the method for heated and stirred described in the step 2 is to be that 35～70 ℃, stirring velocity are under 100～350r/min condition in temperature, and churning time is 10min～3h.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 12: what embodiment was different with one of embodiment one to 11 is: the hydrothermal method described in the step 3 is under 130～180 ℃ of conditions, and the hydro-thermal time is 5～20h.Other step is identical with one of embodiment one to 11 with parameter.
Embodiment 13: what embodiment was different with one of embodiment one to 11 is: the described hydrothermal method of step 3 is under 110～150 ℃ of conditions, hydrothermal treatment consists 8～14h.Other step is identical with one of embodiment one to 11 with parameter.
Embodiment 14: what embodiment was different with one of embodiment one to 11 is: the described hydrothermal method of step 3 is under 140～170 ℃ of conditions, hydrothermal treatment consists 5～12h.Other step is identical with one of embodiment one to 11 with parameter.
Embodiment 15: present embodiment nitrogen-doped graphene preparation methods is finished by following step: one, the 0.1g graphite oxide is added in the 35g ethanol, add the 0.05g Polyvinylpyrolidone (PVP) again, in ultrasonic frequency is that 30KHz, ultrasonic power are under the 400W condition, ultrasonic time is 30min, obtains mixture A; Two, adding the 1.5g pyridine then in mixture A, is that 35 ℃, stirring velocity are under the 300r/min condition in temperature, stirs 25min, obtains mixture B; Three, under 175 ℃ of conditions, mixture B is carried out hydro-thermal reaction 16h, use washing with alcohol again, then vacuum-drying 6h under 70 ℃ of conditions; Obtain the nitrogen-doped graphene material.
The electron scanning micrograph that present embodiment obtains the nitrogen-doped graphene material as shown in Figure 1, as can be seen from the figure, the microscopic appearance of product is a two-dimensional layered structure, thickness is about 5nm.The XPS spectrum figure of the nitrogen element of present embodiment acquisition nitrogen-doped graphene material as can be seen from the figure mainly contains pyridine nitrogen (N1), pyrroles's nitrogen (N2) and three types of nitrogen of quaternary nitrogen (N3) as shown in Figure 2 in the sample, total nitrogen content is 10.8%.Proved the generation of nitrogen-doped graphene material.Productive rate is more than 99.1%.
Embodiment 16: what present embodiment and embodiment 15 were different is: the described nitrogenous compound of step 2 is an ammoniacal liquor.
Present embodiment makes nitrogen-doped graphene material productive rate more than 99.2%, and total nitrogen content is 12.3%.
Embodiment 16: what present embodiment and embodiment 15 were different is: the described nitrogenous compound of step 2 is diethylamine and triethylamine, and the mass ratio of diethylamine and triethylamine is 1: 1.
Present embodiment makes nitrogen-doped graphene material productive rate more than 99.1%, and total nitrogen content is 11.5%.
Embodiment 17: what present embodiment and embodiment 15 were different is: the described nitrogenous compound of step 2 is urea, n-Butyl Amine 99 and hydroxide trimethylammonium ethyl ammonium, and the mass ratio of urea, n-Butyl Amine 99 and hydroxide trimethylammonium ethyl ammonium is 1: 3: 5.
Present embodiment makes nitrogen-doped graphene material productive rate more than 99.0%, and total nitrogen content is 16.2%.
Embodiment 18: what present embodiment and embodiment 15 were different is: the described nitrogenous compound of step 2 is hydrazine and urea, and the mass ratio of hydrazine and urea is 2: 3.
Present embodiment makes nitrogen-doped graphene material productive rate more than 99.3%, and total nitrogen content is 14.3%.
Claims (10)
1. the method for Hydrothermal Preparation nitrogen-doped graphene material is characterized in that the method for Hydrothermal Preparation nitrogen-doped graphene material is finished by following step:
One, graphite oxide is added in the solvent, add tensio-active agent again, use ultrasonic method or heated and stirred method to mix then, obtain mixture A, wherein, described solvent is water, methyl alcohol, ethanol, ethylene glycol, N, a kind of or wherein several mixing in the dinethylformamide, the mass ratio of described graphite oxide and solvent is 1: 100～2000, and the mass ratio of described tensio-active agent and graphite oxide is 0.01～50: 1;
Two, add nitrogenous compound then in mixture A, wherein the mass ratio of nitrogenous compound and graphite oxide is 10～500: 1, adopts ultrasonic method or heated and stirred method to mix again and obtains mixture B;
Three, mixture B is carried out hydro-thermal reaction, hydrothermal temperature is 100～190 ℃, and the hydro-thermal reaction time is 4～48h, uses distilled water, ethanol or washing with acetone then, is drying under 60～110 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions again; Promptly obtain the nitrogen-doped graphene material.
2. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 1 is characterized in that the described tensio-active agent of step 1 is a kind of in cationic surfactant, aniorfic surfactant, nonionogenic tenside and the amphoterics.
3. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 2 is characterized in that described cationic surfactant is cetyl trimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide, hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride, lauryl alcohol polyoxyethylene ether dimethyl methyl ammonium chloride, polyoxyethylene octylphenol ether base dimethyl decyl brometo de amonio, polyoxyethylene octylphenol ether base dimethyl decyl ammonium chloride or hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride.
4. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 2 is characterized in that described aniorfic surfactant is sodium lauryl sulphate, sodium laurylsulfonate, hexadecyl benzene sulfonic acid sodium salt, sodium stearyl sulfate, N-oleoyl contract amino acid sodium, polyoxyethylenated alcohol sodium sulfate or fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium more.
5. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 2 is characterized in that described nonionic surface active agent is Polyvinylpyrolidone (PVP), propanediol polyoxypropylene Soxylat A 25-7, structure alcohol polyoxyethylene poly-oxygen propylene aether, polyurethane polyureas oxypropylene polyethenoxy ether, polyethylene glycol monooleate or octadecyl ethylene urea.
6. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 2 is characterized in that described amphoterics is EO
20PO
70EO
20(P123), EO
106PO
70EO
106(F127), lauryl dimethyl amine oxide, cocounut oil alkyl dimethyl amine oxide, dimethyl dodecyl amine oxide, dodecyl dihydroxy ethyl amine oxide, tetradecyl dihydroxy ethyl amine oxide, hexadecyl dihydroxy ethyl amine oxide, octadecyl dimethyl amine oxide or octadecyl dihydroxy ethyl amine oxide.
7. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 2, it is characterized in that the nitrogenous compound described in the step 2 is ammoniacal liquor, urea, pyridine, pyrroles, hydrazine, dimethylamine, thyl methyl amine, second two ammoniums, triethylamine, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, n-Butyl Amine 99, trimeric cyanamide, aniline, N-methyl-N-ethylbenzene, N, a kind of or wherein several mixing in N-Diethyl Aniline, tetraethyl-ammonium bromide, the hydroxide trimethylammonium ethyl ammonium.
8. according to the method for the described Hydrothermal Preparation nitrogen-doped graphene of each claim material among the claim 2-7, it is characterized in that ultrasonic method described in the step 1 is is that 20～40KHz, ultrasonic power are under 200～700W condition in ultrasonic frequency, ultrasonic time is 10min～1h; Ultrasonic method described in the step 2 is to be that 20～40KHz, ultrasonic power are under 200～700W condition in ultrasonic frequency, and ultrasonic time is 10min～1.
9. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 8 is characterized in that the method for heated and stirred described in the step 1 is is that 35～70 ℃, stirring velocity are under 100～350r/min condition in temperature, and churning time is 10min～3h.
10. the method for Hydrothermal Preparation nitrogen-doped graphene material according to claim 9 is characterized in that the method for heated and stirred described in the step 2 is is that 35～70 ℃, stirring velocity are under 100～350r/min condition in temperature, and churning time is 10min～3h.
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