CN107857249B - Preparation method of nitrogen-doped annular hollow nano carbon material - Google Patents
Preparation method of nitrogen-doped annular hollow nano carbon material Download PDFInfo
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Abstract
The invention provides a preparation method of a nitrogen-doped annular hollow nano carbon material, belonging to the field of material science. The method firstly coats the nitrogenous polymer on a ring C3N4On a template, followed by high temperature calcination of it, the high temperature being such that C is formed3N4Decompose to produce largeNitrogen-containing gas can be used as a pore-forming agent and a nitrogen source, and the polymer is carbonized to obtain the nitrogen-doped annular hollow nano carbon material. The material has unique structure, high nitrogen content and wide application prospect in the aspects of super capacitors, lithium ion batteries, electrochemical catalysts and the like. The method has the characteristics of simple and convenient operation, easy industrial production and small environmental pollution, and is an important preparation method of the nitrogen-doped annular hollow nano carbon material.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a preparation method of a nitrogen-doped annular hollow nano carbon material.
Background
The carbon material has the characteristics of good thermal stability, high mechanical stability, developed pore structure, excellent conductivity, large specific surface area and the like, and shows great application potential in the fields of separation, adsorption, catalysis, gas storage, energy storage and conversion and the like2O3[Xianluo Hu,et al.Advanced Materials,2007,19(17):2324]And Au nanorings [ Yan Feng, et. NanoLetters,2004,4(7):1193]And TiO2Nanorings [ Sun Fengjiang, et al chemistry of materials,2006,18(16):3774]However, the synthesis process is complicated and the yield is extremely low. The hollow ring-shaped nano structure is between one-dimensional and two-dimensional materials and is unique in structure and innerThe outer surface can be simultaneously utilized, the specific surface area is large, and the material is expected to have excellent performance.
In addition, heteroatom doping is an important means for further improving the performance of carbon materials. Especially, nitrogen atoms can be doped into the carbon skeleton to regulate the physical and chemical properties of the carbon skeleton, so that the functions of the porous carbon material are enhanced, and even new functions are endowed to the carbon material. Research shows that after nitrogen atoms are introduced into the carbon skeleton, lone-pair electrons in the nitrogen atoms can be endowed with sp2The negative charge of delocalized pi system in the hybrid carbon skeleton enhances the conductivity of the carbon material [ Kurak K.A., et al. journal of Physical chemistry C,2009, (113): 6730%](ii) a The nitrogen atom doped with rich electrons can regulate and control the energy band structure of the carbon material, reduce the valence band of the carbon material, increase the electron density on the Fermi level of the carbon material and enhance the chemical stability thereof (Kim D.P., et al. chemistry Materials,1991, (3): 686)]. Typically, the carbon material is nitrogen doped by post-treating the carbon material or by direct pyrolysis of a nitrogen-containing precursor. However, the maximum value of the content of nitrogen introduced by a post-treatment nitrogen-doping method (such as ammonia high-temperature heat treatment) in the prior art is not more than 10 wt.%, and the formed nitrogen-containing functional groups are generally unstable and mainly distributed on the surface of the carbon material, and the surface functionalization cannot change most of the properties of the carbon skeleton. The template-assisted direct pyrolysis nitrogen-containing precursor method can be used for preparing the porous carbon material with uniform pore size and can realize bulk phase doping of high-content nitrogen elements. Common template agents comprise hard templates (such as micro/nano silicon spheres, mesoporous silicon, foamed nickel, magnesium oxide and the like) and soft templates (such as triblock copolymers), nitrogen-rich precursors adopted comprise various polymers such as polyacrylonitrile, polypyrrole, melamine and the like, but the removal steps of the templates are relatively complicated, and the used reagents are high in corrosivity (etching by strong acid or strong base), so that the environment is harmed if the reagents are prepared in batches.
Therefore, how to synthesize the annular hollow nano carbon material with a novel structure in a large scale by a simple and green method becomes a great challenge. The invention develops an environment-friendly and efficient preparation technology of the annular hollow nano carbon material with the self-sacrifice template and the in-situ doped nitrogen element, and can undoubtedly fill the blank of international and domestic research in the field of carbon materials.
Disclosure of Invention
The invention provides a preparation method of a nitrogen-doped annular hollow nano carbon material, which comprises the following steps of coating a nitrogen-containing polymer on an annular C3N4Followed by subjecting it to a high temperature calcination treatment at a high temperature to form C3N4Decomposing to generate a large amount of nitrogen-containing gas which can be used as a pore-forming agent and a nitrogen source, and simply and efficiently obtaining the nitrogen-doped annular hollow nano carbon material.
The technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped annular hollow nano carbon material comprises the following steps:
(1) cyclic g-C3N4Dispersing a template in a solvent, stirring and carrying out ultrasonic treatment to obtain a template solution;
(2) adding a nitrogen-containing polymer monomer into the template solution, and continuously stirring for polymerization and coating reaction to coat the nitrogen-containing polymer on the ring g-C3N4A surface;
the nitrogen-containing polymer monomer is dopamine, aniline or pyrrole;
the concentration of the nitrogen-containing polymer monomer is 0.5-8 mg/mL; nitrogen-containing polymer monomers with cyclic g-C3N4The mass ratio of the templates is 1: 1-1: 4;
when the nitrogen-containing polymer monomer is dopamine, no other reactant is added in the polymerization coating reaction process;
when the nitrogen-containing polymer monomer is aniline or pyrrole, a surfactant, an acid and an initiator are added while the aniline or the pyrrole is added; the concentration of the surfactant is not more than 4 mg/mL; the concentration of the acid is not more than 3 mg/mL; the concentration of the initiator is not more than 0.5 mg/mL;
the polymerization coating reaction temperature is 10-35 ℃, and the time is 2-96 h;
(3) centrifuging the solution after polymerization and coating reaction, washing with water and ethanol for several times, and drying to obtain polymer-coated cyclic g-C3N4；
(4) Polymer-coated cyclic g-C3N4Placing in a tubular furnace, calcining under the protection of inert gas, wherein the cyclic g-C is obtained in the calcining process3N4Decomposing, simultaneously carrying out pyrolysis polymerization on the polymer, calcining, and cooling to room temperature to obtain the nitrogen-doped annular hollow nano carbon material.
The cyclic g-C in the step (1)3N4The template is prepared by adopting a chemical vapor deposition method, and the specific method comprises the following steps: the method comprises the steps of carrying out deposition reaction by taking melamine as a raw material and nano silicon dioxide spheres as a template, etching the deposition product by hydrofluoric acid, centrifugally washing, and freeze-drying to obtain annular g-C3N4And (5) template.
The solvent in the step (1) is one or a mixture of water, ethanol, ether, acetonitrile, Tris buffer solution or phosphate buffer solution.
The cyclic g-C in the step (1)3N4The concentration of the template in the solvent is 1-8mg/mL, and the ultrasonic time is 10min-4 h.
And (3) in the step (2), the surfactant is one or a mixture of more than two of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and polyvinylpyrrolidone (PVP).
In the step (2), the acid is one or the mixture of more than two of hydrochloric acid, sulfuric acid, phytic acid and nitric acid.
In the step (2), the initiator is Na2S2O8、(NH4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、Ce(SO4)2、AlCl3、MnO2And BPO (benzoyl peroxide).
The drying temperature in the step (3) is 50-100 ℃, and the time is 12-36 h.
And (4) the inert gas in the step (4) is one or a mixture of more than two of nitrogen, argon and helium.
In the step (4), the calcining heating rate is 2-10 ℃/min, the temperature is 500-1000 ℃, and the time is 1-3 h.
The doped annular hollow nano carbon material has the characteristics of high nitrogen content, unique structure and the like, and has potential wide application prospects in the aspects of super capacitors, lithium ion batteries, electrochemical catalysts and the like.
The invention has the beneficial effects that:
1. the template is environment-friendly and pollution-free;
2. the template is removed while carbonization, and the process is simple;
3. the thickness of the prepared nitrogen-doped annular hollow nano carbon material can be controlled by the proportion of the template to the polymer monomer or the polymerization time;
4. a large amount of nitrogen-containing gas generated during template decomposition can be used as a pore-forming agent and a nitrogen source;
5. the nitrogen content of the prepared nitrogen-doped annular hollow nano carbon material is about 10 wt.% after element analysis.
Drawings
Fig. 1 is a flow chart of the preparation of nitrogen-doped annular hollow nanocarbon material.
FIG. 2 is a diagram of cyclic g-C prepared by the prior art3N4Scanning electron microscopy of the template.
FIG. 3 is a scanning electron microscope photograph of the poly-dopamine-derived nitrogen-doped cyclic hollow nanocarbon material (labeled PDA-N-CNRs-3) prepared in example 1.
FIG. 4 is a TEM photograph of the poly-dopamine-derived nitrogen-doped ring-shaped hollow nanocarbon material (labeled PDA-N-CNRs-3) prepared in example 1.
FIG. 5 is a TEM photograph of the poly-dopamine-derived nitrogen-doped ring-shaped hollow nanocarbon material (labeled PDA-N-CNRs-1) prepared in example 2.
FIG. 6 is a scanning electron micrograph of the polyaniline-derived nitrogen-doped ring-shaped hollow nanocarbon material (labeled PANI-N-CNRs-0.357) prepared in example 3.
FIG. 7 is a scanning electron micrograph of the polypyrrole-derived nitrogen-doped cyclic hollow nanocarbon material (labeled PPy-N-CNRs-0.338) prepared in example 4.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
The preparation process of the nitrogen-doped annular hollow nano carbon material is shown schematically, and the specific preparation process is as follows:
example 1:
100mg of cyclic g-C3N4Dispersing in 50mL Tris buffer (pH 8.5), and ultrasonic treating for 20 min to obtain cyclic g-C with concentration of 2mg/mL3N4And (4) suspending the solution. 300mg of dopamine was added to the above liquid. After stirring at room temperature for 12h, centrifugation was carried out and washing was carried out several times with water and ethanol, respectively. Drying at 60 ℃ for 36h, and coating the surface with poly-dopamine cyclic g-C3N4Placing the mixture in a corundum boat, heating the mixture to 800 ℃ at the heating rate of 5 ℃/min in an argon atmosphere in a tube furnace, and keeping the temperature for 1h to obtain the nitrogen-doped annular hollow nano carbon material (the product is marked as PDA-N-CNRs-3). FIG. 2 shows a ring g-C3N4The scanning electron microscope photo shows a ring-shaped structure and is uniform in size. Fig. 3 shows a scanning electron micrograph of the obtained nitrogen-doped annular hollow nanocarbon material under low magnification, which shows that the shape of the template is copied and the material is an annular structure with uniform dimension. It can be further seen from the high magnification scanning electron micrograph of the PDA-N-CNRs-3 sample shown in FIG. 4 that it is a hollow structure with a hollow inner ring diameter of about 80nm, an outer ring diameter of about 140nm, and a wall thickness of about 6.6 nm.
Example 2:
100mg of cyclic g-C3N4Dispersing in 50mL Tris buffer (pH 8.5), and subjecting to ultrasonic treatment for 10min to obtain cyclic g-C with concentration of 2mg/mL3N4And (4) suspending the solution. 100mg of dopamine was added to the above liquid. After stirring at room temperature for 12h, centrifugation was carried out and washing was carried out several times with water and ethanol, respectively. Drying at 80 ℃ for 24h, and coating the surface with poly-dopamine cyclic g-C3N4Placing the mixture in a corundum boat, heating the mixture to 800 ℃ at the heating rate of 10 ℃/min in a tube furnace in the nitrogen atmosphere, and keeping the temperature for 1h to obtain the nitrogen-doped annular hollow nano carbon material (the product is marked as PDA-N-CNRs-1). PDA-N-CNRs illustrated from FIG. 5The high magnification scanning electron micrograph of the sample-1 shows that the sample is a hollow structure, the diameter of a hollow inner ring is about 100nm, the diameter of an outer ring is about 140nm, and the wall thickness is about 3.7 nm.
Example 3:
100mg of cyclic g-C3N4And 5mg sodium dodecyl benzene sulfonate are added into 40mL water, stirred and ultrasonically treated for 4 hours to obtain the cyclic g-C with the concentration of 2.5mg/mL3N4And (4) suspending the solution. Thereafter, 35. mu.L of aniline, 0.25mL of phytic acid (25%), and 110mg of ammonium persulfate were added to the above liquid, respectively. After stirring at room temperature for 2h, centrifugation was carried out and washing was carried out several times with water and ethanol, respectively. Drying at 100 ℃ for 12h, and coating polyaniline-coated cyclic g-C3N4Placing the mixture in a corundum boat, heating the mixture to 600 ℃ at the heating rate of 5 ℃/min in an argon atmosphere in a tube furnace, and keeping the temperature for 2 hours to obtain the nitrogen-doped annular hollow nano carbon material (the product is marked as PANI-N-CNRs-0.357). FIG. 6 shows a scanning electron microscope image of a polyaniline-derived nitrogen-doped annular hollow nanocarbon material PANI-N-CNRs-0.357 sample, which shows that the shape of the template is copied and the annular hollow structure with uniform size is maintained.
Example 4:
100mg of cyclic g-C3N4And 5mg of sodium dodecyl benzene sulfonate are added into 40mL of water, stirred and ultrasonically treated for 2 hours to obtain cyclic g-C with the concentration of 2.5mg/mL3N4And (4) suspending the solution. Thereafter, 35. mu.L of pyrrole, 1mL of hydrochloric acid (0.1mol/L), and 110mg of ammonium persulfate were added to the above liquids, respectively. After stirring at room temperature for 2h, centrifugation was carried out and washing was carried out several times with water and ethanol, respectively. Drying at 100 ℃ for 12h, and coating the surface with polypyrrole-containing cyclic g-C3N4Placing the mixture in a corundum boat, heating to 900 ℃ at the heating rate of 2 ℃/min in a helium atmosphere in a tube furnace, and keeping the temperature for 1h to obtain the nitrogen-doped annular hollow nano carbon material (the product is marked as PPy-N-CNRs-0.338). FIG. 7 is a scanning electron micrograph of a polypyrrole-derived nitrogen-doped annular hollow nanocarbon material PPy-N-CNRs-0.338 sample, which shows that the morphology of the template is replicated and the annular hollow structure with uniform size is maintained.
Claims (9)
1. A preparation method of a nitrogen-doped annular hollow nano carbon material is characterized by comprising the following steps:
(1) cyclic g-C3N4Dispersing a template in a solvent, stirring and carrying out ultrasonic treatment to obtain a template solution;
said cyclic g-C3N4The concentration of the template in the solvent is 1-8mg/mL, and the ultrasonic time is 10min-4 h;
(2) adding a nitrogen-containing polymer monomer into the template solution, and continuously stirring for polymerization and coating reaction to coat the nitrogen-containing polymer on the ring g-C3N4A surface;
the nitrogen-containing polymer monomer is dopamine, aniline or pyrrole;
the concentration of the nitrogen-containing polymer monomer is 0.5-8 mg/mL; nitrogen-containing polymer monomers with cyclic g-C3N4The mass ratio of the templates is 1: 1-1: 4;
when the nitrogen-containing polymer monomer is dopamine, no other reactant is added in the polymerization coating reaction process;
when the nitrogen-containing polymer monomer is aniline or pyrrole, a surfactant, an acid and an initiator are added while the aniline or the pyrrole is added; the concentration of the surfactant is not more than 4 mg/mL; the concentration of the acid is not more than 3 mg/mL; the concentration of the initiator is not more than 0.5 mg/mL;
the polymerization coating reaction temperature is 10-35 ℃, and the time is 2-96 h;
(3) centrifuging the solution after polymerization and coating reaction, washing with water and ethanol for several times, and drying to obtain polymer-coated cyclic g-C3N4；
(4) Polymer-coated cyclic g-C3N4Placing in a tubular furnace, calcining under the protection of inert gas, wherein the cyclic g-C is obtained in the calcining process3N4Decomposing, simultaneously carrying out pyrolysis polymerization on the polymer, and cooling to room temperature after calcining to obtain the nitrogen-doped annular hollow nano carbon material;
the calcination temperature rise rate is 2-10 ℃/min, the temperature is 500-.
2. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 1, wherein in the step (1), the ring-shaped g-C is formed3N4The template is prepared by adopting a chemical vapor deposition method, and the specific method comprises the following steps: the method comprises the steps of carrying out deposition reaction by taking melamine as a raw material and nano silicon dioxide spheres as a template, etching the deposition product by hydrofluoric acid, centrifugally washing, and freeze-drying to obtain annular g-C3N4A template; in the step (1), the solvent is one or more of water, ethanol, ether, acetonitrile, Tris buffer solution or phosphate buffer solution.
3. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 1 or 2, wherein the surfactant in the step (2) is one or a mixture of more than two of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and polyvinylpyrrolidone; the acid is one or more of hydrochloric acid, sulfuric acid, phytic acid and nitric acid; the initiator is Na2S2O8、(NH4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、Ce(SO4)2、AlCl3、MnO2And benzoyl peroxide, or a mixture of two or more thereof.
4. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 1 or 2, wherein the drying temperature in the step (3) is 50-100 ℃ and the time is 12-36 h.
5. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 3, wherein the drying temperature in the step (3) is 50-100 ℃ and the drying time is 12-36 h.
6. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 1, 2 or 5, wherein the inert gas in the step (4) is one or a mixture of two or more of nitrogen, argon and helium.
7. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 3, wherein the inert gas in the step (4) is one or a mixture of two or more of nitrogen, argon and helium.
8. The method for preparing nitrogen-doped annular hollow nanocarbon material according to claim 4, wherein the inert gas in the step (4) is one or a mixture of two or more of nitrogen, argon and helium.
9. The nitrogen-doped annular hollow nanocarbon material obtained by the method for preparing the nitrogen-doped annular hollow nanocarbon material according to any one of claims 1 to 8 is applied to supercapacitors, lithium ion batteries and electrochemical catalysts.
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| CN108394888A (en) * | 2018-04-09 | 2018-08-14 | 安徽大学 | A kind of preparation method of N doping meso-porous hollow Nano carbon balls |
| CN108493461B (en) * | 2018-05-08 | 2021-01-19 | 大连理工大学 | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof |
| CN109136979A (en) * | 2018-08-08 | 2019-01-04 | 东华大学 | The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation |
| CN109126683B (en) * | 2018-09-11 | 2021-06-25 | 哈尔滨工程大学 | Modified C3N4Method for producing a material |
| CN109437156B (en) * | 2018-11-13 | 2022-01-14 | 上海师范大学 | Preparation method of nitrogen-doped carbon nanotube |
| CN111864193B (en) * | 2019-04-30 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Heteroatom modified hollow micro carbon sphere, preparation method thereof and application thereof in lithium-sulfur battery anode material |
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| CN112499615B (en) * | 2020-12-01 | 2022-04-12 | 大连理工大学 | Nano polymer ring, nano carbon ring and preparation method thereof |
| CN113668012B (en) * | 2021-08-12 | 2022-07-12 | 中国石油大学(北京) | Iron/ruthenium nitrogen-doped porous carbon electrocatalyst and preparation method and application thereof |
| CN113651313B (en) * | 2021-09-28 | 2023-06-06 | 绍兴道普新材料科技有限公司 | Hollow submicron nitrogen-doped carbon tube and preparation method thereof |
| CN116377473B (en) * | 2023-03-17 | 2023-11-07 | 大连理工大学 | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof |
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| CN104961121B (en) * | 2015-06-24 | 2017-05-10 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
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