CN108017047B - Rambutan-like aza-hollow mesoporous carbon sphere nano material and preparation method thereof - Google Patents
Rambutan-like aza-hollow mesoporous carbon sphere nano material and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 229940011182 cobalt acetate Drugs 0.000 claims description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 38
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 229910017665 NH4HF2 Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
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- B01J35/33—
-
- B01J35/647—
Abstract
The invention belongs to the technical field of material synthesis, and particularly relates to a method for synthesizing a composite materialA rambutan-like aza mesoporous hollow carbon sphere nano material and a preparation method thereof, belonging to the technical field of electrocatalysis. The invention provides a method for preparing SiO with a spherical shape2As a hard template, metal acetate and melamine are added into methanol and mixed. High-temperature calcining, removing the template and washing. The rambutan-like aza hollow mesoporous carbon sphere material has the nano particles with the size of 360-450 nanometers, the diameter of the hollow cavity of 30-50 nanometers, the aperture of the mesoporous pore passage of 40-50 nanometers, the width of the carbon nano tube of 10-15 nanometers and the specific surface area of 350-400 m-2g‑1. The material is mainly applied to the electrocatalysis direction, such as oxygen reduction reaction, and provides a possibility for replacing noble metal platinum in the future.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a rambutan-like aza hollow mesoporous carbon sphere nano material and a preparation method thereof, belonging to the technical field of electrocatalysis.
Background
The contradiction between the energy shortage and the environmental pollution and the economic development is increasingly sharp, so that the contradiction becomes a bottleneck restricting the economic and social development of China. Therefore, the development of new energy storage materials and adsorption materials is receiving much attention from the nation and researchers. The hollow carbon nano material has a unique spatial structure, presents special optical, electrical and catalytic properties, particle transportation and other characteristics, and is widely applied to the aspects of super capacitors, water treatment, lithium ion batteries, photochemical batteries, catalysts and the like, wherein the mesoporous hollow carbon spheres are widely applied to various fields due to the large inner cavities and rich pore canals, and particularly can effectively adsorb pollutants in water or gas so as to achieve the purpose of purifying water or gas, so the mesoporous hollow carbon spheres have potential huge application prospects. This makes more and more new technologies used in the preparation of hollow carbon spheres, and greatly pushes the synthesis of hollow carbon sphere materials towards controllability. The low cost is developed. At present, the preparation methods of the hollow carbon spheres mainly comprise chemical vapor deposition, an impact compression method, a metal reduction method and a hydrothermal synthesis method. Supercritical method, template method, etc. The synthesis of the hollow carbon spheres by the template method is to take substances with easily synthesized and controlled shapes as a core template, deposit a carbon source on the template by a physical or chemical method to form a core-shell structure, and remove the template by calcination or solution soaking to obtain the hollow carbon spheres with controllable shape and size. Compared with other methods, the template method has a plurality of advantages, which are mainly shown in that: (1) the nuclear template is easy to synthesize and controllable in size; (2) the synthetic process is simple and is suitable for mass production; (3) the synthesized hollow carbon sphere has good structural controllability. The hollow carbon nano material is mainly divided into a tubular carbon nano material and a hollow carbon sphere.
In recent years, a plurality of non-noble metals are supported on hollow mesoporous carbon spheres as substrates to further improve the electrocatalytic performance of the hollow mesoporous carbon spheres, and for example, the non-noble metals such as cobalt, iron, nickel and oxides thereof are embedded into the surfaces of carbon materials. According to the literature report, the electrical conductivity of the carbon nano tube is better than that of the hollow carbon sphere, and if the surface of the hollow mesoporous carbon sphere is combined with the carbon nano tube, the electrical conductivity of the carbon sphere can be enhanced. Based on the design of a simple and easy strategy, the novel structure with the rambutan-like hollow mesoporous carbon spheres is prepared, and compared with a single hollow mesoporous carbon sphere, the structure has the advantage that the oxygen reduction performance is obviously improved.
Disclosure of Invention
The invention aims to provide a high-performance rambutan-like aza mesoporous hollow carbon sphere nano material which is low in cost, simple and convenient in method and stable in performance.
In order to realize the rambutan-like aza-mesoporous hollow carbon sphere nano material with a special structure, the invention adopts the technical scheme that: the invention provides a method for preparing SiO with a spherical shape2As a hard template, metal acetate and melamine are added into methanol and mixed. High-temperature calcining, removing the template and washing. The rambutan-like aza hollow mesoporous carbon sphere material has the nano particles with the size of 360-450 nanometers, the diameter of the hollow cavity of 30-50 nanometers, the aperture of the mesoporous pore passage of 40-50 nanometers, the width of the carbon nano tube of 10-15 nanometers and the specific surface area of 350-400 m-2g-1. The material is mainly applied to the electrocatalysis direction, such as oxygen reduction reaction, and provides a possibility for replacing noble metal platinum in the future.
The invention also provides a preparation method of the rambutan-like aza mesoporous hollow carbon sphere nano material, which comprises the following specific steps:
(1) solution a: mixing and stirring ethanol and tetraethyl orthosilicate to obtain a solution a.
b, solution: and mixing and stirring ethanol, water and ammonia water to obtain a solution b.
And (3) quickly pouring the solution a into the solution b, mixing and stirring, adding a mixed solution of resorcinol and formaldehyde for reacting for 24 hours, and transferring the mixture into a reaction kettle for reacting for 24 hours at 100 ℃. Cooled to room temperature and washed. Washing is carried out by ethanol and deionized water, and vacuum freeze drying is carried out to obtain the intermediate product, namely the phenolic resin-coated silicon dioxide spheres.
(2) And (2) dispersing the intermediate product obtained in the step (1) in methanol, adding melamine, stirring cobalt acetate, and performing ultrasonic dispersion.
The mass volume ratio of the intermediate product to the methanol to the melamine to the cobalt acetate is as follows: 0.2-1 g: 5ml-30 ml: 0.3-1.5 g: 0.05-0.5 g.
(3) And (3) stirring the mixed solution in the step (2) at room temperature until the methanol is evaporated to dryness.
(4) And (4) placing the solid powder evaporated to dryness in the step (3) in a forced air drying oven for further drying, and keeping the temperature at 70 ℃ for 2 hours.
(5) Grinding the dried solid in the step (4), placing the ground solid in a square boat, keeping the temperature at 600-900 ℃ for 2h in a nitrogen or argon atmosphere at the temperature rising rate of 5 ℃/min in a semi-closed state, and then using 4M NH4HF2Dissolving SiO2To obtain the rambutan-like aza hollow mesoporous carbon sphere material.
The invention has the beneficial effects that: the invention firstly mixes and stirs the silicon dioxide ball coated by the phenolic resin with the cobalt acetate and the melamine thereof to be dry, and uses 4M NH after calcining4HF2The silica template is removed. Preparing a hollow mesoporous carbon sphere with the surface capable of growing the CNT in situ, namely a rambutan-like structure. The method is favorable for avoiding the agglomeration of the carbon tubes, further improves the specific surface area of the hollow carbon spheres, is easier for mass transfer, and can be widely applied in the future.
Drawings
FIG. 1 is an SEM photograph of the rambutan-like aza hollow mesoporous carbon sphere material prepared by the invention.
FIG. 2 is a TEM photograph of the rambutan-like aza hollow mesoporous carbon sphere material prepared by the present invention.
FIG. 3 shows the electrocatalytic oxygen reduction performance of a non-noble metal and nitrogen co-doped rambutan-like hollow mesoporous carbon sphere catalyst.
Detailed Description
The invention is explained in further detail below with reference to the drawings.
Example (a): dispersing 1.0g of phenolic resin coated silicon dioxide spheres in 20ml of methanol solution, carrying out ultrasonic treatment for 30min, adding 0.3g of cobalt acetate and no melamine, stirring, carrying out ultrasonic dispersion for 30min, drying in an oven at 70 ℃, transferring and placing in a square boat, heating to 800 ℃ at a heating rate of 5 ℃/min under a semi-closed state, and keeping for 2h in a nitrogen or argon atmosphere. Cooled to room temperature and then treated with 4M NH4HF2Dissolving SiO2And after the reaction is finished, washing the obtained substance with ethanol and deionized water, and carrying out vacuum freeze drying to obtain the aza hollow mesoporous carbon spheres (N-HMCS). The structure does not introduce metal precursor, so that the structure of the carbon tube, namely the rambutan-like structure on the surface of the carbon ball, is not finally generated.
Example (b): dispersing 1.0g of phenolic resin coated silicon dioxide spheres in 20ml of methanol solution, performing ultrasonic treatment for 30min, adding 1.0g of melamine without adding cobalt acetate, stirring, performing ultrasonic dispersion for 30min, drying in an oven at 70 ℃, transferring and placing in a square boat, heating to 700, 800 and 900 ℃ respectively at a heating rate of 5 ℃/min in a semi-closed state, and keeping for 2h in a nitrogen or argon atmosphere. Cooled to room temperature and then dissolved SiO with 4M NH4HF22And after the reaction is finished, washing the obtained substance with ethanol and deionized water, and carrying out vacuum freeze drying to obtain the cobalt-doped hollow mesoporous carbon spheres (Co-HMCS). In the structure, because the precursor melamine of a carbon source and a nitrogen source is not introduced, a carbon tube, namely a rambutan-like structure on the surface of a carbon sphere is not finally generated.
Example (iii): dispersing 0.2g of phenolic resin coated silicon dioxide spheres in 5ml of methanol solution, carrying out ultrasonic treatment for 30min, adding 0.3g of cobalt acetate, adding 1g of melamine, stirring for 30min, drying at 70 ℃, transferring the mixture into a square boat, heating to 800 ℃ at a heating rate of 5 ℃/min in a semi-closed state, and keeping the mixture in a nitrogen or argon atmosphere for a period of timeIs 2 h. Cooled to room temperature and then treated with 4M NH4HF2Dissolving SiO2And after the reaction is finished, washing the obtained substance with ethanol and deionized water, and carrying out vacuum freeze drying to obtain the rambutan-like aza hollow mesoporous carbon spheres. The structure simultaneously introduces precursors of melamine and cobalt acetate of a carbon source and a nitrogen source as metal precursors, and finally generates a high-conductivity carbon tube, namely a hollow mesoporous carbon sphere with a rambutan-like structure.
FIG. 1 is an SEM photograph of the rambutan-like aza hollow mesoporous carbon sphere material prepared by the invention. Carbon tubes with high conductivity, diameter of 10-15nm and length of 50-100nm are uniformly distributed on the surface of the carbon sphere through in-situ growth. Also after treatment with ammonium bifluoride, some of the fugitive material or particles exposed on the carbon spheres were removed, resulting in pores of 20-30nm on the surface. The method can also solve the bottleneck that the carbon tubes are easy to agglomerate.
FIG. 2 is a TEM photograph of the rambutan-like aza hollow mesoporous carbon sphere material prepared by the present invention. It can be seen that the carbon tubes are grown epitaxially and vertically from the surface of the carbon spheres.
FIG. 3 shows the electrocatalytic oxygen reduction performance of a non-noble metal and nitrogen co-doped rambutan-like hollow mesoporous carbon sphere catalyst. In the figure, the effect of generating the aza-carbon spheres with the structure of rambutan-like can be seen to be optimal by using melamine as a carbon source and a nitrogen source through non-metal doping. The metal is introduced into a carbon sphere system, but under the condition of not adding melamine, a rambutan-like structure with a carbon tube cannot be generated, and the difference of the ORR performance of the electrocatalysts is larger compared with the rambutan-like structure.
Claims (7)
1. A rambutan-like aza hollow mesoporous carbon sphere nanomaterial is characterized in that the nanomaterial is a hollow mesoporous carbon sphere with CNT grown in situ on the surface of a rambutan-like structure, the size of the nanoparticle is 360-450 nm, the diameter of a hollow cavity is 30-50 nm, the aperture of a mesoporous pore channel is 40-50 nm, the width of a carbon nanotube is 10-15nm, and the length of the carbon nanotube is 50-100 nm; the specific surface area is 350-400m2g-1Can be applied to the field of electrocatalysis; the preparation method comprises the following steps: will be provided withDispersing silicon dioxide balls wrapped by phenolic resin in methanol, adding melamine, stirring cobalt acetate, and performing ultrasonic dispersion to obtain a mixed solution; stirring the mixed solution at room temperature until the solid powder after the methanol is evaporated to dryness is dried and ground, placing the powder in a square boat, heating the powder to 600-900 ℃ in a semi-closed state, keeping the temperature for 2 hours in a nitrogen or argon atmosphere, and then dissolving SiO2To obtain the rambutan-like aza hollow mesoporous carbon sphere material.
2. The preparation method of the rambutan-like aza-hollow mesoporous carbon sphere nanomaterial as claimed in claim 1, wherein the silica spheres wrapped by phenolic resin are dispersed in methanol, melamine is added, cobalt acetate is added, and stirring and ultrasonic dispersion are performed to obtain a mixed solution; stirring the mixed solution at room temperature until the solid powder after the methanol is evaporated to dryness is dried and ground, placing the powder in a square boat, heating the powder to 600-900 ℃ in a semi-closed state, keeping the temperature for 2 hours in a nitrogen or argon atmosphere, and then dissolving SiO2To obtain the rambutan-like aza hollow mesoporous carbon sphere material.
3. The preparation method of the rambutan-like aza-hollow mesoporous carbon sphere nanomaterial as claimed in claim 2, wherein the mass-to-volume ratio of the phenolic resin-coated silica spheres, methanol, melamine and cobalt acetate is as follows: 0.2-1 g: 5ml-30 ml: 0.3-1.5 g: 0.05-0.5 g.
4. The preparation method of the rambutan-like aza-hollow mesoporous carbon sphere nanomaterial as claimed in claim 2, wherein the drying is performed at a temperature of 70 ℃ for 2 h.
5. The method for preparing the rambutan-like aza-hollow mesoporous carbon sphere nanomaterial as claimed in claim 2, wherein the temperature rise rate is 5 ℃/min.
6. The method for preparing rambutan-like aza hollow mesoporous carbon sphere nano material of claim 2, which is characterized in thatCharacterized in that 4M NH is adopted4HF2Dissolving SiO2。
7. The preparation method of the rambutan-like aza-hollow mesoporous carbon sphere nanomaterial as claimed in claim 2, wherein the preparation method of the phenolic resin-coated silica spheres comprises the following steps: mixing and stirring ethanol and tetraethyl orthosilicate to obtain a solution a; mixing and stirring ethanol, water and ammonia water to obtain a solution b; and (3) quickly pouring the solution a into the solution b, mixing and stirring, adding a mixed solution of m-diphenol and formaldehyde for reaction for 24 hours, transferring the mixture into a reaction kettle for reaction for 24 hours at 100 ℃, cooling to room temperature, washing by using ethanol and deionized water, and carrying out vacuum freeze drying to obtain the intermediate product, namely the phenolic resin coated silica spheres.
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