CN105417532A - One-step preparation method for high nitrogen doped graphene - Google Patents
One-step preparation method for high nitrogen doped graphene Download PDFInfo
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Abstract
The invention discloses a preparation method of high nitrogen doped graphene. The method comprises the following steps of: using a nitrogen source and a carbon source as raw materials, and carrying out effective mixing and drying to obtain a mixture; putting the mixture in an inert atmosphere, warming and heating the mixture to 300-600 DEG C, and carrying out heat preservation for a period of time; then continuously heating the mixture to 700-1200 DEG C, and carrying out heat preservation for a period of time to finally generate a black solid, namely the high nitrogen doped graphene. The preparation method disclosed by the invention is simple in process; the high-quality nitrogen doped graphene is obtained through a solid-phase reaction one-step method; and the nitrogen doped graphene is easy for industrial mass production. Moreover, the material has many nitrogen doped active sites, and has good electro-catalysis oxygen reduction activity as a non-noble metal catalyst.
Description
Technical field
The present invention relates to the single stage method preparation of high nitrogen doped Graphene.
Background technology
High nitrogen doped Graphene has excellent electricity, optics, calorifics and mechanical property, become the study hotspot of scientific domain gradually, have broad application prospects in the fields such as microelectronics, gas sensor, support of the catalyst, opto-electronic conversion and energy storage material of receiving.Such as nitrogen-atoms in Graphene lattice and edge adulterate, can form a large amount of hole after inert atmosphere calcining, its rich surface is containing pyridine type and pyrroles's type N doping atom.Show through theoretical analog calculation, this high nitrogen doped Graphene has extra storage lithium performance (Nat.Commun.2014,5,5261).Compared with simple Graphene, the non-precious metal catalyst that high nitrogen doped Graphene reduces as electrocatalytic oxidation, close to the effect (Chem.Rev.2015,115,4823) of business Pt/C catalyzer.
At present, high nitrogen doped Graphene realizes commercial applications and still needs satisfied 3 key conditions: low cost, high stability and scale volume production.At present, the synthetic method of common nitrogen-doped graphene is roughly utilize graphite linings to carry out physical or chemical treatment to obtain the laminate structure be separated, in building-up process, add the N doping that suitable nitrogenous source realizes Graphene simultaneously, specifically comprise graphite oxide chemical reduction method, chemical Vapor deposition process and solvent-thermal method etc., but mostly all there is complicated process of preparation, yield poorly and high in cost of production defect in these methods, be difficult to realize industrial production, and there is the lower problem of N doping amount.
Summary of the invention
Given this, the invention provides one and utilize common carbon source under the high temperature conditions, single stage method obtains the preparation method of high nitrogen doped Graphene, and described method is simply controlled, and has the potentiality of scale operation.
Enforcement of the present invention is realized by following technical scheme:
(1) nitrogenous source and carbon source are dissolved in deionized water; The above-mentioned aqueous solution obtains white solid after abundant combination drying.
Wherein, carbon source is at least one of fructose, glucose, maltose, sugarcane sugar and starch, and nitrogenous source is at least one of thiocarbamide, urea, cyanamide, Dyhard RU 100 and trimeric cyanamide;
The mass ratio of described nitrogenous source, carbon source and deionized water is 20 ~ 100:1:25 ~ 160;
(2) heat up described white solid calcining in an inert atmosphere, and calcining temperature is 300 ~ 600 DEG C, and is incubated 1 ~ 4 hour, and period nitrogenous source decomposition discharges ammonia and multiple nitrogen carbide gas, and forms g-C
3n
4;
Wherein said heat-up rate is 2 ~ 6 DEG C/min;
Described rare gas element preferred nitrogen or argon gas, gas flow rate is 20 ~ 90sccm;
(3) continue increasing calcining temperature to 700 ~ 1200 DEG C subsequently, and be incubated 2 ~ 6 hours, the g-C formed during temperature raises
3n
4as template, connect the intermediate carbon of aromatic ring structure at its surperficial key;
During described temperature, g-C
3n
4decompose, intermediate carbon at high temperature forms the Graphene of N doping;
Wherein said heat-up rate is 4 ~ 10 DEG C/min;
Described rare gas element preferred nitrogen or argon gas, gas flow rate is 20 ~ 90sccm;
(4) in content of the present invention, gained black product is high nitrogen doped Graphene, and wherein carbon/nitrogen Elements Atom ratio is 5 ~ 10.
Beneficial effect
(1) the method for the invention, by simple solid state reaction under high-temperature pressure, single stage method obtains high nitrogen doped Graphene, and preparation technology is simple, and the plant and instrument without the need to costliness just can be prepared in enormous quantities, is easy to industrialization and produces.
(2) the present invention is raw materials used is common nitrogenous source and carbon source, cheap and without the need to any special processing, effectively reduce production cost.
(3) by described method of the present invention, obtain high nitrogen doped Graphene, as non-precious metal catalyst, there is good oxygen reduction reaction performance.
Accompanying drawing explanation
Fig. 1 is in the embodiment of the present invention 1, the scanning electron microscope (SEM) photograph of high nitrogen doped Graphene;
Fig. 2 is in the embodiment of the present invention 1, the transmission electron microscope picture of high nitrogen doped Graphene;
Fig. 3 is in the embodiment of the present invention 1, the x-ray photoelectron power spectrum of high nitrogen doped Graphene;
Fig. 4 is in the embodiment of the present invention 1, the cyclic voltammogram of high nitrogen doped Graphene;
Fig. 5 is in the embodiment of the present invention 1, the oxygen reduction reaction performance map of high nitrogen doped Graphene.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.Specific examples described herein only for explaining the present invention, is not intended to limit the present invention.
Embodiment 1
(1) 6g urea and 0.3g sucrose are dissolved in the deionized water of 20mL, after stirring, obtain the aqueous solution, after above-mentioned solution drying, obtain white powder;
(2) described white powder is placed in tube furnace, in nitrogen atmosphere, is heated to 300 DEG C with the temperature rise rate of 4 DEG C/min, be incubated 1 hour, gas flow rate is 40sccm;
(3) continue increasing calcining temperature to 900 DEG C subsequently, heat-up rate is 8 DEG C/min and is incubated 2 hours, and nitrogen flow rate remains 40sccm;
(4), after calcining, black product is cooled to room temperature under nitrogen protection, obtains high nitrogen doped Graphene after grinding.Fig. 1 is the scanning electron microscope (SEM) photograph that the present embodiment prepares high nitrogen doped Graphene, can observe obviously curling laminate structure, and with a large amount of fold risen and fallen.Fig. 2 is the transmission electron microscope picture that the present embodiment prepares high nitrogen doped Graphene, can observe translucent fold thin film layer, illustrates that the Graphene number of plies obtained is less, does not occur obvious agglomeration, have high-ratio surface sum highly porous structure.Fig. 3 is the x-ray photoelectron power spectrum that the present embodiment prepares high nitrogen doped Graphene, explanation has nitrogen-doping, wherein nitrogen element is entrained in carbon atom with the form of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen, carbon/nitrogen Elements Atom ratio is 6.8, this doping can impel the generation in non-electrical neutral active site, is beneficial to the adsorption of oxygen;
(5) in order to verify high nitrogen doped Graphene in the above embodiment of the present invention further, being modified and being carried out cyclic voltammetric and oxygen reduction reaction active testing in electrode surface:
By high nitrogen doped for 4mg graphene dispersion in the ethanol and 5wt%nafion mixing solutions of 1ml (9:1, V/V), drip after ultrasonic disperse and be coated on glass-carbon electrode, dry as working electrode in air.
On electrochemical workstation, select Ag/AgCl (KCl, 3M) and Pt plate electrode respectively as reference electrode with to electrode.Cyclic voltammetric and rotating ring disk electrode (r.r.d.e) test is carried out in 0.1MKOH electrolyte solution.Logical 30 minutes nitrogen or oxygen before electrolyte solution test, cyclic voltammetry window is 0.2 to-0.8V, sweeps speed for 10mVs
-1.And in rotating ring disk electrode (r.r.d.e) test, test window is 0.2 to-0.8V, is with 10mVs at rotating speed under the condition of 400 to 1600rpm
-1test.
(6) Fig. 4 is the 0.1MKOH electrolyte solution cyclic voltammetry curve that nitrogen or oxygen are saturated, as we know from the figure, in the solution environmental that oxygen is saturated, there is obvious oxygen reduction peak at-0.20V place, then there is no reduction peak in the solution environmental that nitrogen is saturated, illustrate that in this embodiment, high nitrogen doped Graphene has significant catalytic activity.
(7) Fig. 5 is the rotating ring disk electrode (r.r.d.e) test under high nitrogen doped Graphene different rotating speeds, illustrates that current density increases along with the raising of rotating speed, accelerates the solution diffusion of electrode surface.Data by experiment, further demonstrate the electrochemical activity that this material is good, infer high-specific surface area, high pore texture and high nitrogen doped be the reason causing good oxygen reduction reaction activity.
Embodiment 2
(1) 6g Dyhard RU 100 and 0.3g fructose are dissolved in the deionized water of 20mL, after stirring, obtain the aqueous solution, after above-mentioned solution drying, obtain white powder;
(2) described white powder is placed in tube furnace, in nitrogen atmosphere, is heated to 300 DEG C with the temperature rise rate of 4 DEG C/min, be incubated 1 hour, gas flow rate is 40sccm;
(3) continue increasing calcining temperature to 900 DEG C subsequently, heat-up rate is 8 DEG C/min and is incubated 2 hours, and nitrogen flow rate remains 40sccm;
(4), after calcining, black product is cooled to room temperature under nitrogen protection, obtains high nitrogen doped Graphene after grinding.High nitrogen doped Graphene scanning electron microscope (SEM) photograph prepared by the present embodiment, can observe obviously curling laminate structure, and with a large amount of fold risen and fallen.High nitrogen doped Graphene transmission electron microscope picture prepared by the present embodiment, can observe translucent fold thin film layer, illustrates that the Graphene number of plies obtained is less, does not occur obvious agglomeration, have high-ratio surface sum highly porous structure.High nitrogen doped Graphene x-ray photoelectron power spectrum prepared by the present embodiment, explanation has nitrogen-doping, wherein nitrogen element is entrained in carbon atom with the form of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen, carbon/nitrogen Elements Atom ratio is 8.4, this doping can impel the generation in non-electrical neutral active site, is beneficial to the adsorption of oxygen;
(5) in order to verify high nitrogen doped Graphene in the above embodiment of the present invention further, being modified and being carried out cyclic voltammetric and oxygen reduction reaction active testing in electrode surface:
By high nitrogen doped for 4mg graphene dispersion in the ethanol and 5wt%nafion mixing solutions of 1ml (9:1, V/V), drip after ultrasonic disperse and be coated on glass-carbon electrode, dry as working electrode in air.
On electrochemical workstation, select Ag/AgCl (KCl, 3M) and Pt plate electrode respectively as reference electrode with to electrode.Cyclic voltammetric and rotating ring disk electrode (r.r.d.e) test is carried out in 0.1MKOH electrolyte solution.Logical 30 minutes nitrogen or oxygen before electrolyte solution test, cyclic voltammetry window is 0.2 to-0.8V, sweeps speed for 10mVs
-1.And in rotating ring disk electrode (r.r.d.e) test, test window is 0.2 to-0.8V, is with 10mVs at rotating speed under the condition of 400 to 1600rpm
-1test.
(6) nitrogen or the saturated 0.1MKOH electrolyte solution cyclic voltammetry curve of oxygen, as we know from the figure, in the solution environmental that oxygen is saturated, there is obvious oxygen reduction peak at-0.22V place, then there is no reduction peak in the solution environmental that nitrogen is saturated, illustrate that in this embodiment, high nitrogen doped Graphene has significant catalytic activity.
(7) the rotating ring disk electrode (r.r.d.e) test under high nitrogen doped Graphene different rotating speeds, illustrates that current density increases along with the raising of rotating speed, accelerates the solution diffusion of electrode surface.Data by experiment, further demonstrate the electrochemical activity that this material is good, infer high-specific surface area, high pore texture and high nitrogen doped be the reason causing good oxygen reduction reaction activity.
Embodiment 3
1) 6g Dyhard RU 100 and 0.3g fructose are dissolved in the deionized water of 20mL, after stirring, obtain the aqueous solution, after above-mentioned solution drying, obtain white powder;
(2) described white powder is placed in tube furnace, in nitrogen atmosphere, is heated to 300 DEG C with the temperature rise rate of 4 DEG C/min, be incubated 1 hour, gas flow rate is 40sccm;
(3) continue increasing calcining temperature to 1000 DEG C subsequently, heat-up rate is 8 DEG C/min and is incubated 2 hours, and nitrogen flow rate remains 40sccm;
(4), after calcining, black product is cooled to room temperature under nitrogen protection, obtains high nitrogen doped Graphene after grinding.High nitrogen doped Graphene scanning electron microscope (SEM) photograph prepared by the present embodiment, can observe obviously curling laminate structure, and with a large amount of fold risen and fallen.High nitrogen doped Graphene transmission electron microscope picture prepared by the present embodiment, can observe translucent fold thin film layer, illustrates that the Graphene number of plies obtained is less, does not occur obvious agglomeration, have high-ratio surface sum highly porous structure.High nitrogen doped Graphene x-ray photoelectron power spectrum prepared by the present embodiment, explanation has nitrogen-doping, wherein nitrogen element is entrained in carbon atom with the form of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen, carbon/nitrogen Elements Atom ratio is 9.1, this doping can impel the generation in non-electrical neutral active site, is beneficial to the adsorption of oxygen;
(5) in order to verify high nitrogen doped Graphene in the above embodiment of the present invention further, being modified and being carried out cyclic voltammetric and oxygen reduction reaction active testing in electrode surface:
By high nitrogen doped for 4mg graphene dispersion in the ethanol and 5wt%nafion mixing solutions of 1ml (9:1, V/V), drip after ultrasonic disperse and be coated on glass-carbon electrode, dry as working electrode in air.
On electrochemical workstation, select Ag/AgCl (KCl, 3M) and Pt plate electrode respectively as reference electrode with to electrode.Cyclic voltammetric and rotating ring disk electrode (r.r.d.e) test is carried out in 0.1MKOH electrolyte solution.Logical 30 minutes nitrogen or oxygen before electrolyte solution test, cyclic voltammetry window is 0.2 to-0.8V, sweeps speed for 10mVs
-1.And in rotating ring disk electrode (r.r.d.e) test, test window is 0.2 to-0.8V, is with 10mVs at rotating speed under the condition of 400 to 1600rpm
-1test.
(6) nitrogen or the saturated 0.1MKOH electrolyte solution cyclic voltammetry curve of oxygen, as we know from the figure, in the solution environmental that oxygen is saturated, there is obvious oxygen reduction peak at-0.25V place, then there is no reduction peak in the solution environmental that nitrogen is saturated, illustrate that in this embodiment, high nitrogen doped Graphene has significant catalytic activity.
(7) the rotating ring disk electrode (r.r.d.e) test under high nitrogen doped Graphene different rotating speeds, illustrates that current density increases along with the raising of rotating speed, accelerates the solution diffusion of electrode surface.Data by experiment, further demonstrate the electrochemical activity that this material is good, infer high-specific surface area, high pore texture and high nitrogen doped be the reason causing good oxygen reduction reaction activity.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (7)
1. a preparation method for high nitrogen doped Graphene, is characterized in that, comprises the steps:
(1) required nitrogenous source and carbon source are dissolved in deionized water;
(2) above-mentioned aqueous solution drying obtains the white solid of effectively mixing afterwards;
(3) above-mentioned white solid is warming up to 300 ~ 600 DEG C, and is incubated for some time, pass into protection of inert gas simultaneously;
(4) this mixture continues to be warming up to 700 ~ 1200 DEG C, and insulation for some time also passes into identical protection of inert gas; Black product after question response is cooled to room temperature, collects product and grinds, finally obtaining high nitrogen doped Graphene.
2. the preparation method of high nitrogen doped Graphene according to claim 1, it is characterized in that, the mass ratio of step (1) described nitrogenous source, carbon source and deionized water is 20 ~ 100:1:25 ~ 160.
3. the preparation method of high nitrogen doped Graphene according to claim 1, it is characterized in that, carbon source used is at least one of fructose, glucose, maltose, sugarcane sugar and starch, and nitrogenous source used is at least one of thiocarbamide, urea, cyanamide, Dyhard RU 100 and trimeric cyanamide.
4. the preparation method of high nitrogen doped Graphene according to claim 1, it is characterized in that, in step (3), described temperature rise rate is 2 ~ 6 DEG C/min, is incubated 1 ~ 4 hour.
5. the preparation method of high nitrogen doped Graphene according to claim 1, it is characterized in that, in step (4), described temperature rise rate is 4 ~ 10 DEG C/min, is incubated 2 ~ 6 hours.
6. the preparation method of high nitrogen doped Graphene according to right 4 and 5, it is characterized in that, the rare gas element passed into is nitrogen or argon gas, and gas flow is 20 ~ 90sccm.
7. the preparation method of high nitrogen doped Graphene according to right 1, it is characterized in that, in described high nitrogen doped Graphene, carbon/nitrogen Elements Atom ratio is 5 ~ 10.
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| CN115626638A (en) * | 2022-09-30 | 2023-01-20 | 苏州大学 | Nitrogen-doped graphene and preparation method and application thereof |
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