CN107572509B - Nitrogen-doped hollow carbon/graphite nodule nano material and preparation method thereof - Google Patents
Nitrogen-doped hollow carbon/graphite nodule nano material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped hollow carbon/graphite nodule nano material and a preparation method thereof. The method comprises the steps of firstly using spherical cuprous oxide as a hard template agent, forming an organic/inorganic compound by using an organic carbon source and an organic nitrogen source through a hydrothermal reaction, then carrying out high-temperature roasting in an inert atmosphere to obtain a copper/nitrogen-containing carbon/graphite spherical nano composite material, and finally removing copper in the composite material to obtain the spherical nitrogen-doped hollow carbon/graphite nano material. The material has an internal hollow structure, the thickness of the spherical shell can be adjusted, and the nitrogen doping amount is higher. In addition, the preparation method adopted by the invention is simple and feasible, the used template can be recovered, the cost is low, the repeatability is good, and the large-scale production is easy.
Description
Technical Field
The invention relates to a nitrogen-doped hollow carbon/graphite nodule nano material and a preparation method thereof, belonging to the technical field of inorganic nano materials.
Background
The development and utilization of new energy is an important issue in the present human society. The storage and conversion of energy into new energy sources and the emergence and application of new energy sources provide a guarantee basis. Among a plurality of energy storage systems, the super capacitor has received great attention from people due to the advantages of long cycle life, environmental friendliness, safety, high specific energy density and the like. The electrode material is a key influence factor of the performance of the supercapacitor, so that the preparation and performance research of the electrode material with high specific capacitance are the key points of the research of the supercapacitor.
Carbon/graphite materials have been widely paid attention to by people due to their unique morphology and properties, and can be classified into carbon tubes, carbon microspheres, carbon fibers and the like according to the form of the carbon/graphite materials, wherein the carbon microspheres can be classified into solid carbon microspheres and hollow carbon microspheres according to the structure thereof. The hollow carbon microspheres have a large cavity structure, a large specific surface area and good chemical and thermal stability, so that the hollow carbon microspheres are widely applied to the fields of gas storage media, supercapacitors, fuel cells, catalysts and the like. The hollow porous carbon/graphite spheres are combined with the two structures, so that the hollow porous carbon/graphite spheres have more excellent performance and are more widely applied.
In recent years, with the increasingly intensive research on the preparation of hollow carbon microsphere materials and the functional modification thereof, doped carbon materials such as N, S and B play an important role in determining the material properties, because they can improve the properties of the materials such as surface polarity, conductivity, surface alkalinity and biocompatibility by changing the electron and crystal structures. For example, nitrogen doping in the carbon skeleton enhances conductivity, stability, catalytic activity, etc., such that nitrogen-doped carbon is on the catalyst support, CO2Has potential application prospect in the aspects of adsorption, super capacitor and the like.
Through research and development in these years, the preparation methods of hollow carbon microspheres are becoming mature, and can be classified into the following methods, namely, a template method (soft template and hard template), a Chemical Vapor Deposition (CVD) method and a hydrothermal method. The temperature for preparing the hollow carbon spheres by the chemical vapor deposition method is higher, and hollow fibers are easily formed in the product; the morphology controllability of the hollow carbon spheres prepared by the hydrothermal method is poor, the morphology controllability of the hollow carbon spheres prepared by the template method is good, and various structural parameters of the hollow carbon spheres can be controlled by changing the template and the carbon source method. At present, the soft template method usually adopts an organic surfactant as a template, and generates a hole or hollow structure through a self-assembly process between a precursor molecule and the surfactant. And removing the template agent after roasting, thereby obtaining the carbon spheres with hollow structures. The method has poor repeatability, and the synthesis of the hollow spheres is not easy to control. The hard template method is usually performed by using previously synthesized monodisperse spheres such as spherical SiO2Polymer latex Particles (PS), etc. as hard template agents. In the process of preparing the hollow carbon spheres, a layer of high molecular polymer is coated on the surface of the hard template agent, and then the organic polymer on the surface of the hard template agent is carbonized through high-temperature roasting, so that the composite spheres of the carbon-coated hard template agent are obtained. And removing the template agent such as silicon dioxide to obtain the hollow carbon spheres. The method has good repeatability, and hollow carbon spheres with different sizes can be obtained by controlling the size of the spheres serving as the hard template agent.
In conclusion, hollow spheres with good repeatability can be obtained by using the hard template agent, but the hollow graphite spheres cannot be obtained because the currently used hard template is mainly silicon dioxide or polymer spheres and the heating temperature is not more than 850 ℃ at most. Meanwhile, the hard template agent cannot be recycled and reused, which increases the cost of the template preparation method to a certain extent. In addition, many people only care about the formation of the hollow sphere and pay little attention to the thickness of the hollow spherical shell.
Disclosure of Invention
The invention aims to provide a hetero-element hollow carbon/graphite nodule nano material with adjustable spherical shell thickness and controllable nitrogen doping amount and a preparation method thereof. The size of the hollow sphere can be adjusted according to the size of the selected template.
In the invention, cuprous oxide is used as a hard template agent, the organic emulsion is coated on the surface of the cuprous oxide by combining with an organic nitrogen source and an organic carbon source, then the obtained product is roasted at high temperature in the atmosphere of inert gas through hydrothermal reaction, the precursor is carbonized/graphitized at high temperature in the heating process, the cuprous oxide is reduced into copper, the carbon/graphite is coated on the copper to form a carbon/graphite coating shape, and the hollow structure of the template agent is removed by an etching method, thus finally obtaining the nitrogen-doped hollow carbon/graphite sphere nano material. By changing the proportion of the organic carbon source, the nitrogen source and the like in the synthesis process, the hollow carbon/graphite nodules with different thicknesses can be obtained. In the preparation process, the hard template agent is etched and dissolved into copper chloride, and then can be used as a raw material for preparing the cuprous oxide micro-nano particles again, so that the cuprous oxide micro-nano particles can be continuously used as the hard template agent of the hollow carbon/graphite nodules, and the effect of recycling is achieved.
The technical scheme of the invention is specifically introduced as follows.
A preparation method of a nitrogen-doped hollow carbon/graphite nodule nano material comprises the following steps:
(1) in a solvent, cuprous oxide micro-nano particles are used as a hard template agent, an organic nitrogen source and an organic carbon source are stirred and react for 12-30 h at room temperature under the condition of adding an alkaline substance, then, the mixed solution is transferred to a hydrothermal kettle for hydrothermal treatment, the hydrothermal temperature is controlled to be 50-200 ℃, the reaction lasts for 2-12h, after natural cooling, the obtained reaction solution is subjected to suction filtration, washing and drying, and an organic/inorganic compound is obtained;
(2) roasting the organic/inorganic compound obtained in the step (1) in an inert atmosphere to obtain a copper/nitrogen-containing carbon/graphite spherical nano composite material;
(3) and (3) mixing the copper/nitrogen-containing carbon/graphite spherical nano composite material obtained in the step (2) with hydrochloric acid, stirring at room temperature, then dropwise adding a hydrogen peroxide solution, continuously stirring for reacting for 24-48 h, and carrying out suction filtration, washing and drying on the reaction solution to obtain the nitrogen-doped hollow carbon/graphite spherical rice material.
In the invention, in the step (1), stirring and reacting for 20-26 h; the hydrothermal temperature is 80-120 ℃, and the reaction time is 10-12 h.
In the invention, in the step (1), the alkaline substance is one or more of strong ammonia water, sodium hydroxide or potassium hydroxide; the organic nitrogen source is one or more of aniline, m-aminophenol or melamine; the organic carbon source is one of formaldehyde, acetaldehyde or furfural; the solvent is one or two of methanol, ethanol, ethylene glycol or deionized water.
In the invention, in the step (1), the mass ratio of the hard template agent, the alkaline substance, the organic nitrogen source, the organic carbon source and the solvent is 1 (0.01-1): (0.1-5): (0.1-5):(1-120).
In the invention, in the step (2), the roasting procedure is as follows: controlling the heating rate to be 1-5 ℃/min, firstly heating to 295-305 ℃, keeping the temperature for 50-70 min, then continuously heating to 600-1000 ℃, roasting for 6-20 h, and naturally cooling to obtain the copper/nitrogen-containing carbon/graphite spherical nano composite material. Preferably, when the roasting temperature is 600-850 ℃, preparing the copper/nitrogen-containing carbon spherical composite material; when the roasting temperature is higher than 850 ℃ and lower than or equal to 1000 ℃, the copper/graphite spherical nano composite material is prepared.
In the invention, in the step (3), the molar concentration of the hydrochloric acid is 1-6 mol/L, and the mass fraction of the hydrogen peroxide solution is 1-30%; the feeding ratio of the copper/nitrogen-containing carbon/graphite spherical nano composite, the hydrochloric acid and the hydrogen peroxide solution is 1g (10-100) ml (10-100).
In the invention, in the step (3), the stirring reaction is continued for 24-48 h.
The invention also provides a nitrogen-doped hollow carbon/graphite nodule nano material prepared by the preparation method, which is black powder, has the powder diameter of about 600nm, is hollow in the interior of a spherical structure, is uniform in size distribution and has high product purity.
Compared with the prior art, the invention has the beneficial effects that:
the nitrogen-doped hollow carbon/graphite nodule nano material prepared by the method has the advantages of simple equipment and process, low cost, shorter period, higher yield, continuous large-scale production and easy industrial implementation. And the prepared product has uniform and controllable structure, good crystallinity and good application prospect.
Drawings
Fig. 1 is a scanning electron micrograph of the nitrogen-doped hollow carbon sphere nanomaterial prepared in example 1.
Fig. 2 is a transmission electron micrograph of the nitrogen-doped hollow carbon sphere nanomaterial prepared in example 1.
Fig. 3 is an X-ray diffraction pattern of the nitrogen-doped hollow carbon sphere nanomaterial prepared in example 1.
Fig. 4 is a scanning electron micrograph of the nitrogen-doped hollow carbon sphere nanomaterial prepared in example 2.
Fig. 5 is a scanning electron micrograph of the nitrogen-doped hollow carbon sphere nanomaterial prepared in example 3.
Fig. 6 is a raman spectrum of the nitrogen-doped hollow graphite nodule nanomaterial prepared in example 4.
Detailed Description
The present invention will be further described with reference to the following detailed description, but the present invention is not limited to the following embodiments.
The methods described in the various examples of the present invention are conventional methods unless otherwise specified.
The starting materials used in the various examples of the present invention were all available from published commercial sources unless otherwise specified.
The amount of chemical used in the various embodiments of the present invention is determined in predetermined ranges, in grams, milliliters, etc. units of measure.
The information on the model and manufacturer of the instrument or equipment used in various embodiments of the invention is as follows:
air-blast drying oven, model DHG-9920A, manufacturer: Shanghai-Hengchang scientific instruments, Inc.;
vacuum drying oven, DZF-6030A, Shanghai-Heng scientific instruments Ltd;
tube furnace, model SL1700 ii, shanghai glie test instruments ltd;
x-ray diffractometer (XRD), X PERT PRO Dutch Pasnake corporation;
transmission Electron Microscope (TEM) JEM-2100 Japan Electron Co., Ltd;
scanning Electron Microscope (SEM), S-3400N Hitachi, Japan;
raman spectrometer, DXR-Raman, Thermo Fisher Scientific.
Example 1
A preparation method of a nitrogen-doped hollow carbon/graphite nodule nano material specifically comprises the following steps:
(1) 50ml of 0.4M/L copper chloride dihydrate solution was measured, and then 100ml of 1M/L sodium hydroxide solution was stirred at high speed at room temperature in the presence of a surfactant to prepare a mixed emulsion. And then adding 60ml of 0.5M/L glucose solution, continuing to stir for 10min, adding 15ml of 0.1M/L hydrazine hydrate solution as a reducing agent, continuing to stir for 1h to obtain brick red suspension, standing, filtering, washing and drying to obtain the spherical cuprous oxide with the particle size of about 600 nm.
(2) And (2) in a solvent, adopting cuprous oxide obtained in the step (1) as a hard template agent, an organic nitrogen source and an organic carbon source as precursors, stirring and reacting for 24 hours at room temperature in the presence of an alkaline substance, then transferring the solution into a container with a polytetrafluoroethylene lining, placing the container in a stainless steel reaction kettle, sealing, carrying out hydrothermal treatment, controlling the temperature to be 180 ℃, reacting for 12 hours, naturally cooling, carrying out suction filtration on the obtained reaction solution, cleaning, and carrying out vacuum drying on a filter cake at the temperature of below 60 ℃ to obtain the organic/inorganic compound.
(3) And (3) controlling the temperature rising speed of the organic/inorganic compound obtained in the step (2) to be 1 ℃/min under the atmosphere of nitrogen or argon, firstly raising the temperature to 300 ℃, keeping the temperature for 1h, then continuing raising the temperature to 850 ℃ and roasting for 6h, and enabling the temperature rising speed to be 2 ℃/min. And naturally cooling to room temperature to obtain the copper/nitrogen-containing carbon sphere nano composite material.
The alkaline substance is ammonia water with the mass fraction of 25%;
the organic nitrogen source is m-aminophenol;
the organic carbon source is formaldehyde;
the solvent is a mixed solution consisting of ethanol and deionized water according to a volume ratio of 5: 2;
the dosage of the template agent cuprous oxide, the alkaline substance, the organic nitrogen source, the organic carbon/graphite source and the solvent is calculated according to the mass ratio, namely the dosage of the cuprous oxide: basic substance, organic nitrogen source, organic carbon source: the solvent is as follows: 1:0.04: 0.5: the ratio of 0.7:100 was calculated
(4) Mixing the copper/nitrogen-containing carbon sphere nano composite material obtained in the step (3) with hydrochloric acid, stirring at room temperature, slowly dropwise adding a proper amount of hydrogen peroxide solution, continuously stirring for reacting for more than 24 hours, and performing suction filtration, washing and drying on the obtained reaction solution to obtain a nitrogen-doped hollow carbon sphere nano material;
the molar concentration of the hydrochloric acid is 6 mol/L;
the mass fraction of the hydrogen peroxide solution is 10 percent;
and (3) calculating the dosage of the copper/nitrogen-containing carbon sphere nano composite obtained in the step (3), hydrochloric acid and hydrogen peroxide solution according to the proportion of 1g to 50 ml.
Observing the obtained nitrogen-doped hollow carbon sphere nano material by using a scanning electron microscope, wherein as shown in figure 1, the obtained nitrogen-doped hollow carbon sphere nano material has the particle size of about 600nm, uniform size distribution, regular appearance and spherical shape;
and observing the obtained nitrogen-doped hollow carbon sphere nano material by adopting a transmission electron microscope. As shown in fig. 2, it can be seen that the sample has a relatively uniform and regular hollow spherical morphology, the surface of the carbon sphere is smooth and rough, and the average diameter is about 600 nm;
the nitrogen-doped hollow carbon sphere nanomaterial obtained as described above was characterized by an X-ray diffractometer, and the wide-angle XRD pattern of the obtained sample, as shown in fig. 3, showed two diffraction peaks at about 24 ° 71 and 44 ° 92, indicating (002) and (100) diffraction peaks of inorganic carbon/graphite, and further, no other peaks were observed in the XRD pattern, indicating that no impurities were present. (100) The peaks are relatively weak, indicating their imperfect character.
Example 2
The process for preparing the nitrogen-doped hollow graphite nodule nano material in the embodiment is the same as the process in the embodiment 1, except that the dosage ratio of the template agent cuprous oxide, the alkaline substance, the organic nitrogen source, the organic graphite source and the solvent in the step (2) in the embodiment 1 is changed into: namely cuprous oxide: basic substance, organic nitrogen source: organic graphite source: the solvent is as follows: 1:0.04: 0.7: 1.02:100, so that nitrogen-doped hollow carbon sphere nano materials with different thicknesses can be obtained. An SEM photograph of the nitrogen-doped hollow carbon sphere nanomaterial prepared by this example is shown in fig. 4.
Example 3
The process for preparing the nitrogen-doped hollow carbon/graphite nodule nano-material in this example is the same as that in example 1, except that the calcination temperature in step (3) in example 1 is changed from 850 ℃ to 750 ℃. Finally, the nitrogen-doped hollow carbon sphere nano material is prepared. An SEM photograph of the nitrogen-doped hollow carbon sphere nanomaterial prepared by this example is shown in fig. 5.
Example 4
The process for preparing the nitrogen-doped hollow carbon/graphite nodule nano-material in this example is the same as that in example 1, except that the calcination temperature in step (3) in example 1 is changed from 850 ℃ to 1000 ℃. Finally preparing the obtained nitrogen-doped hollow graphite sphere nano material. The raman spectrum of the nitrogen-doped hollow graphite nodule nanomaterial prepared in this example is shown in fig. 6, and it can be seen that the relative intensity belonging to defect peak D is lower than that of graphite peak G, and the relative intensity ID/IGApproximately equal to 0.81, which shows that the hollow graphite nodule nanometer material with high order can be obtained by the method.
In conclusion, the nitrogen-doped hollow carbon/graphite nodule nano material has a spherical shape, and the interior of the material is a hollow structure, so that the specific structure not only endows the hollow carbon/graphite nodule nano material with better chemical stability, acid and alkali resistance, biocompatibility and surface functionalized diverse selectivity, but also can modify carbon/graphite nodules, and therefore, the nitrogen-doped hollow carbon/graphite nodule nano material has potential application prospects in the aspects of biosensors, supercapacitors, fuel cells, catalysts and the like.
The foregoing is merely an example of the embodiments of the present invention, and it should be noted that, for a person skilled in the art, several modifications and variations can be made without departing from the principle of the present technology, and these modifications and variations should be considered as the protection scope of the present invention.
Claims (7)
1. A preparation method of a nitrogen-doped hollow carbon sphere nano material or a nitrogen-doped hollow graphite sphere nano material is characterized by comprising the following steps:
(1) in a solvent, cuprous oxide micro-nano particles are used as a hard template agent, an organic nitrogen source and an organic carbon source are stirred and react for 12-30 h at room temperature under the condition of adding an alkaline substance, then, the mixed solution is transferred to a hydrothermal kettle for hydrothermal treatment, the hydrothermal temperature is controlled to be 50-200 ℃, the reaction lasts for 2-12h, after natural cooling, the obtained reaction solution is subjected to suction filtration, washing and drying, and an organic/inorganic compound is obtained;
(2) roasting the organic/inorganic compound obtained in the step (1) in an inert atmosphere to obtain a copper/nitrogen-containing carbon sphere nano composite material or a copper/nitrogen-containing graphite sphere nano composite material;
(3) mixing the copper/nitrogen-containing carbon sphere nano composite material or the copper/nitrogen-containing graphite sphere nano composite material obtained in the step (2) with hydrochloric acid, stirring at room temperature, then dropwise adding a hydrogen peroxide solution, continuously stirring and reacting for 24-48 h, carrying out suction filtration, washing and drying on the reaction solution to obtain nitrogen-doped hollow carbon spheres or nitrogen-doped hollow graphite spheres;
wherein, when the roasting temperature is 600-850 ℃, the copper/nitrogen-containing carbon spherical composite material is prepared; when the roasting temperature is higher than 850 ℃ and lower than or equal to 1000 ℃, the copper/nitrogen-containing graphite spherical nano composite material is prepared.
2. The preparation method according to claim 1, wherein in the step (1), the reaction is carried out for 20-26 hours under stirring; the hydrothermal temperature is 80-120 ℃, and the reaction time is 10-12 h.
3. The preparation method according to claim 1, wherein in the step (1), the alkaline substance is one or more of concentrated ammonia water, sodium hydroxide or potassium hydroxide; the organic nitrogen source is one or more of aniline, m-aminophenol or melamine; the organic carbon source is one of formaldehyde, acetaldehyde or furfural; the solvent is one or two of methanol, ethanol, ethylene glycol or deionized water.
4. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the hard template agent, the basic substance, the organic nitrogen source, the organic carbon source and the solvent is 1 (0.01-1): (0.1-5): (0.1-5):(1-120).
5. The method according to claim 1, wherein in the step (2), the firing procedure is as follows: controlling the heating rate to be 1-5 ℃/min, firstly heating to 295-305 ℃, keeping the temperature for 50-70 min, then continuing heating to 600-1000 ℃, roasting for 6-20 h, and naturally cooling to obtain the copper/nitrogen-containing carbon sphere nano composite material or the copper/nitrogen-containing graphite sphere nano composite material.
6. The preparation method according to claim 1, wherein the roasting time is 6-10 hours.
7. The preparation method according to claim 1, wherein in the step (3), the molar concentration of the hydrochloric acid is 1-6 mol/L, and the mass fraction of the hydrogen peroxide solution is 1-30%; the feeding ratio of the copper/nitrogen-containing carbon sphere nano composite material or the copper/nitrogen-containing graphite sphere nano composite material to the hydrochloric acid and hydrogen peroxide solution is 1g (10-100) ml (10-100).
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| CN110028053A (en) * | 2019-05-16 | 2019-07-19 | 济宁医学院 | A kind of preparation method and applications of high nitrogen doped amount nano cages material |
| CN110713176B (en) * | 2019-11-27 | 2021-10-22 | 北京航空航天大学 | Preparation of three-dimensional grading porous carbon material and method for regulating and controlling pore diameter of three-dimensional grading porous carbon material |
| CN117568694A (en) * | 2023-11-16 | 2024-02-20 | 北京科技大学顺德创新学院 | Three-dimensional graphite sphere reinforced copper-based heat conduction composite material and preparation method thereof |
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