CN105752973A - Method for preparing nitrogen-doped graphene material in electrochemical stripping mode - Google Patents
Method for preparing nitrogen-doped graphene material in electrochemical stripping mode Download PDFInfo
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Abstract
The invention relates to a method for preparing a nitrogen-doped graphene material in an electrochemical stripping mode.The method includes the following specific steps that firstly, graphite is subjected to electrochemical stripping in a nitrogen-containing precursor; then, nitrogen-doped expanded graphite is prepared through thermal processing; finally, the nitrogen-doped expanded graphite is subjected to electrochemical stripping in inorganic electrolyte.The method has the advantages that the nitrogen-doped graphene prepared through the method is good in electrical conductivity and water dispersion performance; the preparation process is simple, convenient, easy to implement and free of pollution; when an electrode modified by the material is used as an electrocatalyst for a fuel cell cathode oxygen reduction reaction, the initial electric potential is low, current density is large, methanol resistance is good, and the electro-catalytic property of the material is close to that of a commercial Pt/C catalyst.
Description
Technical field
The present invention relates to a kind of method preparing nitrogen-doped graphene, belong to field of material preparation.
Background technology
Oxygen reduction reaction is the reaction that fuel battery negative pole occurs, and current fuel battery cathod catalyst mainly uses Pt or Pt based alloy catalyst, and due to Pt scarcity of resources, price is high, causes battery high cost, seriously hampers the commercialization of fuel cell.It is very significant for substituting Pt as fuel battery cathod catalyst with By Non-precious Metal Catalysts material and carbon nano-structured (CNT, graphite the are rare) material containing doped chemical (S, N, B).
Graphene is played the part of in oxygen reduction reaction is studied key player, but simple Graphene inertia is higher, and oxygen reduction activity is poor, but the method that can pass through doping nitrogen-atoms improves the Graphene catalysis activity to oxygen reduction reaction.The mode of current N doping is mainly heat treating process, but nitrogen-doped graphene prepared by this method exists the problem such as the presoma poisonous (such as NH3, pyridine) of nitrogen, the dispersive property difference in water.
Summary of the invention
The present invention is directed to the problems referred to above, utilize electrochemical method nitrating and stripping, prepare N doping graphene oxide water dispersible and good conductivity, when being used as oxygen reduction reaction eelctro-catalyst, the take-off potential of oxygen reduction reaction can be reduced, improve electric current density simultaneously.
The method that a kind of electrochemical stripping of the present invention prepares nitrogen-doped graphene, comprises the following steps:
A, with graphite for positive pole, stainless steel substrates is negative pole, in electrolyte, nitrogenous precursor and formaldehyde mixed solution, electrochemical stripping under certain pH, dry；Then with argon shield, calcine under uniform temperature, obtain N doping expanded graphite；
Above-mentioned electrolyte is sodium sulfate or ammonium sulfate, and concentration is 0.1～1mol/L；
Above-mentioned nitrogenous precursor is cyanamide, cdicynanmide or tripolycyanamide, and is 1:2～1:7 with the mol ratio of formaldehyde；
The pH of above-mentioned solution is 6.0～9.0；
The DC voltage that above-mentioned expansion applies is 2～10V；Calcining heat is 550～750 DEG C, and the time is 2～6h；
B, the step a N doping expanded graphite prepared electricity in electrolyte solution is peeled off, sucking filtration, washing, dry, obtain electric stripping nitrogen-doped graphene.
Above-mentioned electrolyte is ammonium sulfate or metabisulfite solution, and concentration is 0.5～1.5mol/L；
It is 5～15V that above-mentioned electricity peels off the unidirectional current applied.
The invention has the beneficial effects as follows: electrochemical stripping prepares nitrogen-doped graphene electric conductivity, water dispersible can be good；Preparation process is simple and easy to do, pollution-free；When the electrode modified with this material is used as the eelctro-catalyst of fuel battery negative pole oxygen reduction reaction, take-off potential is low, electric current density is big, methanol tolerance performance is good, and the electrocatalysis characteristic of material is close to business Pt/C catalyst.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1: electricity prepared by the present invention peels off nitrogen-doped graphene XRD figure；
Fig. 2: electricity prepared by the present invention peels off nitrogen-doped graphene SEM figure；
Fig. 3: in the present invention, the electricity of preparation peels off nitrogen-doped graphene TEM figure；
Fig. 4: electricity prepared by the present invention peels off nitrogen-doped graphene with business Pt-C catalyst linear sweep voltammetry figure comparing result in KOH solution；
Fig. 5: electricity prepared by the present invention peels off the nitrogen-doped graphene methanol tolerance performance map with business Pt-C catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiments present invention solely for the purpose of illustration, but not the scope being intended to limit the present invention in any manner.
Embodiment 1:
(1) 0.56g sodium sulfate, 2.5g tripolycyanamide, 7.2mL formaldehyde are dissolved in 40mL deionized water, regulate pH value of solution=6.0～9.0, with graphite flake be positive pole, stainless steel substrates for negative pole, apply 10V unidirectional current.Expansion is taken out dry after completing, then in tube furnace 650 DEG C of calcining 3h, obtain N doping expanded graphite；
(2) N doping expanded graphite step (1) prepared logical 10V unidirectional current electricity stripping in the 0.5M ammonium sulfate of pH=6.0～9.0, product sucking filtration, washing that electricity peels, dries, and obtains product.Identifying through XRD, by SEM, TEM technology, product is that electricity peels off nitrogen-doped graphene.
Embodiment 2:
(1) 2.84g sodium sulfate, 2.5g dicyandiamide, 3.6mL formaldehyde are dissolved in 40mL deionized water, regulate pH value of solution=6.0～9.0, with graphite flake be positive pole, stainless steel substrates for negative pole, apply 2V unidirectional current.Expansion is taken out dry after completing, then in tube furnace 750 DEG C of calcining 2h, obtain N doping expanded graphite；
(2) N doping expanded graphite step (1) prepared logical 10V unidirectional current electricity stripping in the 0.1M ammonium sulfate of pH=6.0～9.0, product sucking filtration, washing that electricity peels, dries, and obtains product.Identifying through XRD, by SEM, TEM technology, product is that electricity peels off nitrogen-doped graphene..
Embodiment 3:
(1) 5.6g sodium sulfate, 2.5g dicyandiamide, 25.2mL formaldehyde are dissolved in 40mL deionized water, regulate pH value of solution=6.0～9.0, with graphite flake be positive pole, stainless steel substrates for negative pole, apply 10V unidirectional current.Expansion is taken out dry after completing, then in tube furnace 550 DEG C of calcining 6h, obtain N doping expanded graphite；
(2) N doping expanded graphite step (1) prepared logical 15V unidirectional current electricity stripping in the 0.1M ammonium sulfate of pH=6.0～9.0, product sucking filtration, washing that electricity peels, dries, and obtains product.Identifying through XRD, by SEM, TEM technology, product is that electricity peels off nitrogen-doped graphene.
Embodiment 4:
(1) prepared electricity is peeled off nitrogen-doped graphene to grind, disperse in deionized water, be made into 1mg/mL solution, pipette the 7 uniform drop coatings of μ L in rotating disk electrode (r.d.e), make electricity and peel off nitrogen-doped graphene modified electrode；
(2) electricity of preparation being peeled off nitrogen-doped graphene glass carbon modified electrode in the saturated 0.1MKOH solution of oxygen, experimental technique is linear sweep voltammetry, rotating speed 1600rpm, and voltage range is-0.8～0.3V, and result is as shown in Figure 4.
Comparative example 1:
(1) business Pt-C catalyst is ground, disperse in deionized water, be made into 1mg/mL solution, pipette the 7 uniform drop coatings of μ L in rotating disk electrode (r.d.e), make business Pt-C catalyst electrode；
(2) being placed in by business Pt-C catalyst electrode in the 0.1MKOH solution that oxygen is saturated, experimental technique is linear sweep voltammetry, rotating speed 1600rpm, and voltage range is-0.8～0.3V, and experimental result is as shown in Figure 4.
Embodiment 5:
(1) electricity peels off nitrogen-doped graphene modified electrode preparation process with embodiment 4.
(2) electricity being peeled off nitrogen-doped graphene modified electrode and is placed in the 0.1MKOH solution that nitrogen is saturated, experimental technique is time current curve, and initial voltage is-0.25V, and experimental period is 8000s.Leading to oxygen when 1000s in solution, add 3.64mL methanol when 4500s in solution, result is as shown in Figure 5.
Comparative example 2:
(1) business Pt-C catalyst electrode preparation process is with comparative example 1.
(2) being placed in by business Pt-C catalyst electrode in the 0.1MKOH solution that nitrogen is saturated, experimental technique is time current curve, and initial voltage is-0.25V, and experimental period is 8000s.Leading to oxygen when 1000s in solution, add 3.64mL methanol when 4500s in solution, result is as shown in Figure 5.
Claims (7)
1. the preparation method that an electrochemical stripping prepares nitrogen-doped graphene, it is characterised in that step is as follows:
A, with graphite for positive pole, stainless steel substrates is negative pole, in electrolyte, nitrogenous precursor and formaldehyde mixed solution, electrochemical stripping under certain pH, dry；Then with argon shield, calcine under uniform temperature, obtain N doping expanded graphite；
B, the step a N doping expanded graphite prepared electricity in electrolyte solution is peeled off, sucking filtration, washing, dry, obtain electric stripping nitrogen-doped graphene.
2. the preparation method that a kind of electrochemical stripping described in claim 1 prepares nitrogen-doped graphene, it is characterised in that: in described step a, electrolyte is sodium sulfate or ammonium sulfate, and concentration is 0.1～1mol/L.
3. the preparation method that a kind of electrochemical stripping described in claim 1 prepares nitrogen-doped graphene, it is characterised in that: in described step a, nitrogenous precursor is cyanamide, cdicynanmide or tripolycyanamide, and is 1:2～1:7 with the mol ratio of formaldehyde.
4. the preparation method that a kind of electrochemical stripping described in claim 1 prepares nitrogen-doped graphene, it is characterised in that: in described step a, the pH of solution is 6.0～9.0.
5. the preparation method that a kind of electrochemical stripping described in claim 1 prepares nitrogen-doped graphene, it is characterised in that: the DC voltage applied in described step a is 2～10V；Calcining heat is 550～750 DEG C, and the time is 2～6h.
6. the preparation method that a kind of electrochemical stripping described in claim 1 prepares nitrogen-doped graphene, it is characterised in that: in described step b, electrolyte is ammonium sulfate or metabisulfite solution, and concentration is 0.5～1.5mol/L.
7. the preparation method that a kind of electrochemical stripping described in claim 1 prepares nitrogen-doped graphene, it is characterised in that: in described step b, electricity peels off the unidirectional current applied is 5～15V.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108037171A (en) * | 2017-12-26 | 2018-05-15 | 南京师范大学 | The preparation method and application of the nitrogen-doped graphene quantum dot of high dispersive in a kind of water phase |
| CN108117066A (en) * | 2017-12-19 | 2018-06-05 | 浙江工业大学 | A kind of nitrogen-doped graphene quantum dot electrochemical preparation method |
| CN108658064A (en) * | 2018-08-08 | 2018-10-16 | 广东电网有限责任公司 | A kind of nitrogen-doped graphene and preparation method thereof |
| CN108793141A (en) * | 2018-07-12 | 2018-11-13 | 西安交通大学 | A method of electrochemical cathode stripping prepares graphene in alkali metal organic solution |
| CN108840327A (en) * | 2018-07-30 | 2018-11-20 | 湖南理工学院 | A kind of electrochemical method preparing nitrogen-doped graphene material |
| CN109437185A (en) * | 2018-12-13 | 2019-03-08 | 华侨大学 | A kind of preparation method of the graphite containing nitrogen semi-conductor |
| CN109790640A (en) * | 2016-08-08 | 2019-05-21 | 得克萨斯州A&M大学系统 | The material and reactor and its manufacturing method of electrochemistry extension |
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| CN103611555A (en) * | 2013-11-20 | 2014-03-05 | 东华大学 | Nitrogen-doped graphene catalyst and preparation method and application thereof |
| CN104882637A (en) * | 2014-02-28 | 2015-09-02 | 苏州宝时得电动工具有限公司 | Electrolyte solutions and electrochemical energy storage device |
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| CN103611555A (en) * | 2013-11-20 | 2014-03-05 | 东华大学 | Nitrogen-doped graphene catalyst and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109790640A (en) * | 2016-08-08 | 2019-05-21 | 得克萨斯州A&M大学系统 | The material and reactor and its manufacturing method of electrochemistry extension |
| CN108117066A (en) * | 2017-12-19 | 2018-06-05 | 浙江工业大学 | A kind of nitrogen-doped graphene quantum dot electrochemical preparation method |
| CN108037171A (en) * | 2017-12-26 | 2018-05-15 | 南京师范大学 | The preparation method and application of the nitrogen-doped graphene quantum dot of high dispersive in a kind of water phase |
| CN108037171B (en) * | 2017-12-26 | 2020-02-14 | 南京师范大学 | Preparation method and application of nitrogen-doped graphene quantum dots with high dispersion in water phase |
| CN108793141A (en) * | 2018-07-12 | 2018-11-13 | 西安交通大学 | A method of electrochemical cathode stripping prepares graphene in alkali metal organic solution |
| CN108840327A (en) * | 2018-07-30 | 2018-11-20 | 湖南理工学院 | A kind of electrochemical method preparing nitrogen-doped graphene material |
| CN108658064A (en) * | 2018-08-08 | 2018-10-16 | 广东电网有限责任公司 | A kind of nitrogen-doped graphene and preparation method thereof |
| CN108658064B (en) * | 2018-08-08 | 2021-07-30 | 广东电网有限责任公司 | Nitrogen-doped graphene and preparation method thereof |
| CN109437185A (en) * | 2018-12-13 | 2019-03-08 | 华侨大学 | A kind of preparation method of the graphite containing nitrogen semi-conductor |
| CN109437185B (en) * | 2018-12-13 | 2022-03-04 | 华侨大学 | Preparation method of nitrogen-containing semiconductor graphite |
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Application publication date: 20160713 |