CN110038614B - Cobalt nitride loaded nitrogen-doped carbon material and preparation method thereof - Google Patents
Cobalt nitride loaded nitrogen-doped carbon material and preparation method thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- -1 Cobalt nitride Chemical class 0.000 title claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 21
- 239000010941 cobalt Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 30
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 28
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 26
- 229960003638 dopamine Drugs 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002077 nanosphere Substances 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008247 solid mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000012265 solid product Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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Abstract
The invention provides a preparation method of a cobalt nitride loaded nitrogen-doped carbon material, belonging to the field of preparation of nano composite materials. The method comprises the steps of taking ZnO nanospheres as templates, coating dopamine outside the ZnO nanospheres to prepare a ZnO core-shell structure precursor, introducing cobalt into the ZnO core-shell structure in the form of cobalt nitrate, grinding the cobalt in the presence of melamine, and calcining the obtained solid product at high temperature to obtain Co4An N-loaded nitrogen-doped carbon material. The invention also provides Co prepared by the method4The N-loaded nitrogen-doped carbon material has excellent electrocatalytic performance and can be widely applied to aspects of oxygen reduction, oxygen precipitation and the like.
Description
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to a preparation method of a cobalt nitride loaded nitrogen-doped carbon material.
Background
The nitrogen-doped carbon material has the characteristics of large specific surface area, good conductivity, many active sites, simple and convenient preparation method and the like, and is considered to be an ideal catalyst carrier in the electrochemical field. On the other hand, the transition metal nitride is formed by doping nitrogen element in the transition metal, so that the transition metal nitride has electron donor characteristics, and the conductivity and the stability of the transition metal nitride are enhanced. The transition metal nitride and the nitrogen-doped carbon material are compounded to obtain the bifunctional catalyst with excellent performance, the dispersity of the transition metal nitride can be improved, the catalytic performance of the catalyst is effectively improved, and the method has important significance for realizing commercial application of energy conversion and storage.
At present, there are many methods for preparing transition metal and nitrogen co-doped carbon materials, such as Wei and the like firstly preparing phenolic resin-F127 single micelle, and then mixing the single micelle with sulfur, ferric acetate and the like to prepare sulfur-pretreated porous Fe/N/C material [ q.wei, g.zhang, x.yang, y.fu, g.yang, n.chen, w.chen, s.sun, j.mater.chem.a 2018,6, 4605-4610 ]; su et al used a solvent thermal carbonization method to prepare a Co/N-C composite material [ Y.Su, Y.Zhu, H.Jiang, J.Shen, X.Yang, W.Zou, J.Chen, C.Li, Nanoscale2014,6, 15080-plus 15089] by using cobalt acetate, dopamine hydrochloride and ammonia water as raw materials through one-step hydrothermal method. However, most methods are complicated in preparation process, expensive and not easy to obtain raw materials, and are difficult to obtain the composite material with controllable morphology and good dispersibility, which is not favorable for wide application of the prepared composite material.
Disclosure of Invention
The invention aims to solve the problems of uncontrollable appearance and poor dispersibility of the existing nitrogen-doped composite material, and provides a preparation method of a cobalt nitride-loaded nitrogen-doped carbon material.
The invention firstly provides a preparation method of a cobalt nitride loaded nitrogen-doped carbon material, which comprises the following steps:
step one, preparing a ZnO core-shell structure precursor
1) Dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, trihydroxymethyl aminomethane and ZnO nanospheres in water, and uniformly stirring to obtain a mixed solution;
2) dissolving dopamine in deionized water, then adding the dopamine into the mixed solution, and stirring for reaction to obtain a precursor with a ZnO core-shell structure;
step two, preparing Co4N-loaded nitrogen-doped carbon material
1) Weighing cobalt nitrate, adding the cobalt nitrate into a ZnO core-shell structure precursor aqueous solution, and slowly adding hydrazine hydrate into the solution to react to obtain a reaction solution;
2) centrifuging and washing the reaction solution to obtain a product, and then adding melamine into the product to fully grind to obtain a solid mixture;
3) putting the solid mixture into a quartz boat, heating to 800-1000 ℃ under the protection of nitrogen, and carrying out heat treatment for 1-3 h to obtain Co4An N-loaded nitrogen-doped carbon material.
Preferably, in the first step, the mass ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the tris (hydroxymethyl) aminomethane to the ZnO nanospheres to the dopamine is (0.05-0.20): (0.01-0.15): (0.08-0.12): (0.20-0.60).
Preferably, the stirring reaction in the step one 2) is performed at room temperature for 1 to 3 hours.
Preferably, the mass ratio of the cobalt nitrate to the ZnO core-shell structure precursor in the step two 1) is 1: 2-1: 10.
Preferably, the mass g of cobalt nitrate in the step two 1): the volume ml of hydrazine hydrate is (0.01-0.50): (2-10).
Preferably, the reaction temperature in the second step 1) is room temperature, and the reaction time is 20-60 minutes.
Preferably, the mass ratio of the cobalt nitrate to the melamine in the second step is (0.01-0.50): (0.01-0.50).
The invention also provides the cobalt nitride loaded nitrogen-doped carbon material prepared by the preparation method.
The invention has the advantages of
The invention provides a preparation method of a cobalt nitride loaded nitrogen-doped carbon material. Then cobalt is introduced into the ZnO core-shell structure in the form of cobalt nitrate, grinding is carried out in the presence of melamine, and the obtained solid product is calcined at high temperature to obtain Co4An N-loaded nitrogen-doped carbon material. By controlling the mass ratio of the ZnO nanospheres to the cobalt nitrate and the mass ratio of the cobalt nitrate-ZnO core-shell structure precursor to the melamine, the morphology of the obtained material can be adjusted, and Co with uniform morphology can be obtained4An N-loaded nitrogen-doped carbon material. The method has simple process and cheap and easily-obtained raw materials.
The invention provides Co prepared by the method4The N-loaded nitrogen-doped carbon material is a bifunctional catalyst formed by compounding a transition metal nitride and a nitrogen-doped carbon material, and has the advantages of uniform metal dispersion and large specific surface area, so that the material has excellent electro-catalytic performance, and can be widely applied to aspects of oxygen reduction, oxygen precipitation and the like.
Drawings
FIG. 1 shows Co prepared in example 1 of the present invention4Transmission Electron Microscopy (TEM) images of N-loaded nitrogen-doped carbon materials.
FIG. 2 shows the present inventionCo prepared in Bright example 14X-ray diffraction (XRD) pattern of N-supported nitrogen-doped carbon material.
FIG. 3 shows Co prepared in example 1 of the present invention4A linear scan of the N-supported nitrogen-doped carbon material and a commercial Pt/C catalyst for oxygen reduction under the same conditions.
Detailed Description
The invention firstly provides a preparation method of a cobalt nitride loaded nitrogen-doped carbon material, which comprises the following steps:
step one, preparing a ZnO core-shell structure precursor
1) Dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), Tris (hydroxymethyl) aminomethane (Tris) and ZnO nanospheres in water, and uniformly stirring to obtain a mixed solution;
2) dissolving dopamine in deionized water, then adding the dopamine into the mixed solution, stirring for reaction, and then centrifuging, washing and drying the reaction solution to obtain a precursor with a ZnO core-shell structure; the reaction temperature is preferably room temperature, and the reaction time is preferably 1-3 hours;
the mass ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to the trihydroxymethyl aminomethane to the ZnO nanospheres to the dopamine is preferably (0.05-0.20): (0.01-0.15): (0.08-0.12): (0.20-0.60).
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is commercially available, and the ZnO nanospheres are prepared by adopting the existing preparation method, and are specifically referred to in the documents (X.Song, L.Guo, X.Liao, J.Liu, J.Sun, X.Li, Small 2017,13, 1700238).
Step two, preparing Co4N-loaded nitrogen-doped carbon material
1) Weighing cobalt nitrate, adding the cobalt nitrate into a ZnO core-shell structure precursor aqueous solution, slowly adding hydrazine hydrate into the solution for reaction, wherein the reaction temperature is preferably room temperature, the reaction time is preferably 20-60 minutes, and a reaction solution is obtained after the reaction; the mass ratio of the cobalt nitrate to the ZnO core-shell structure precursor in the ZnO core-shell structure precursor aqueous solution is preferably 1: 2-1: 10; the mass g of the cobalt nitrate is as follows: the volume ml of hydrazine hydrate is preferably (0.01-0.50): (2-10);
2) centrifuging and washing the reaction solution to obtain a product, and then adding melamine into the product to fully grind to obtain a solid mixture; the mass ratio of the cobalt nitrate to the melamine is preferably (0.01-0.50): (0.01 to 0.50);
3) putting the solid mixture into a quartz boat, heating to 800-1000 ℃ under the protection of nitrogen, and carrying out heat treatment for 1-3 h to obtain Co4An N-loaded nitrogen-doped carbon material.
The invention also provides the cobalt nitride loaded nitrogen-doped carbon material prepared by the preparation method. The material of the invention is prepared by compounding transition metal nitride and nitrogen-doped carbon material, is a bifunctional catalyst, has uniform metal dispersion and larger specific surface area, and has excellent electrocatalytic performance.
The following examples illustrate Co of the present invention4The preparation of the N-loaded nitrogen-doped carbon material is described in further detail.
Example 1
Firstly, preparing ZnO precursor with core-shell structure
1) Dissolving 0.08g P123, 0.12g of Tris and 0.10g of ZnO nanospheres in water, stirring and uniformly mixing to obtain a mixed water solution;
2) dissolving 0.40g of dopamine in deionized water, adding the solution into the solution, and stirring and reacting for 1 hour at room temperature;
3) and centrifuging the solution after reaction, washing the solution for a plurality of times by using ethanol, and drying the solution in an oven to obtain the precursor with the ZnO core-shell structure.
II, preparing Co4N-loaded nitrogen-doped carbon material
1) Weighing 0.04g of cobalt nitrate, adding the cobalt nitrate into 10ml of aqueous solution in which 0.08g of ZnO core-shell structure precursor is dissolved, then slowly adding 5ml of hydrazine hydrate into the solution, and stirring and reacting for 60min at room temperature;
2) centrifuging the solution after reaction, and washing with ethanol for several times;
3) adding 0.50g of melamine into the obtained product, and fully grinding to obtain a solid mixture;
4) putting the solid mixture into a quartz boat, raising the temperature to 900 ℃ by a program under the protection of nitrogen, and carrying out heat treatment for 1h to obtain Co4An N-loaded nitrogen-doped carbon material.
FIG. 1 shows Co prepared in example 1 of the present invention4Transmission Electron Microscopy (TEM) image of N-loaded nitrogen-doped carbon material showing Co4The N is uniformly dispersed and has uniform size.
FIG. 2 shows Co prepared in example 1 of the present invention4X-ray diffraction (XRD) pattern of N-loaded nitrogen-doped carbon material indicating Co loading4N。
FIG. 3 shows Co prepared in example 1 of the present invention4A linear scan of the N-supported nitrogen-doped carbon material and a commercial Pt/C catalyst for oxygen reduction under the same conditions. The figure shows that the Co produced is compared to commercial Pt/C4The N-loaded nitrogen-doped carbon material has more excellent electro-catalytic oxygen reduction performance.
Example 2
Firstly, preparing ZnO precursor with core-shell structure
1) Dissolving 0.20g P123, 0.15g Tris and 0.08g ZnO nanosphere in water, stirring and uniformly mixing to obtain a mixed water solution;
2) dissolving 0.20g of dopamine in deionized water, adding the solution into the solution, and stirring and reacting for 3 hours at room temperature;
3) and centrifuging the solution after reaction, washing the solution for a plurality of times by using ethanol, and drying the solution in an oven to obtain the precursor with the ZnO core-shell structure.
II, preparing Co4N-loaded nitrogen-doped carbon material
1) Weighing 0.50g of cobalt nitrate, adding the cobalt nitrate into 10ml of aqueous solution in which 2.00g of ZnO core-shell structure precursor is dissolved, then slowly adding 2ml of hydrazine hydrate into the solution, and stirring and reacting for 40min at room temperature;
2) centrifuging the solution after reaction, and washing with ethanol for several times;
3) adding 0.30g of melamine into the obtained product, and fully grinding to obtain a solid mixture;
4) putting the solid mixture into a quartz boat, raising the temperature to 800 ℃ by a program under the protection of nitrogen, and carrying out heat treatment for 2h to obtain Co4An N-loaded nitrogen-doped carbon material.
Example 3
Firstly, preparing ZnO precursor with core-shell structure
1) Dissolving 0.05g P123, 0.01g Tris and 0.12g ZnO nanosphere in water, stirring and uniformly mixing to obtain a mixed water solution;
2) dissolving 0.60g of dopamine in deionized water, adding the solution into the solution, and stirring and reacting for 2 hours at room temperature;
3) and centrifuging the solution after reaction, washing the solution for a plurality of times by using ethanol, and drying the solution in an oven to obtain the precursor with the ZnO core-shell structure.
II, preparing Co4N-loaded nitrogen-doped carbon material
1) Weighing 0.01g of cobalt nitrate, adding the cobalt nitrate into 10ml of aqueous solution in which 0.1g of ZnO core-shell structure precursor is dissolved, then slowly adding 10ml of hydrazine hydrate into the solution, and stirring and reacting for 20min at room temperature;
2) centrifuging the solution after reaction, and washing with ethanol for several times;
3) adding 0.01g of melamine into the obtained product, and fully grinding to obtain a solid mixture;
4) putting the solid mixture into a quartz boat, raising the temperature to 1000 ℃ by a program under the protection of nitrogen, and carrying out heat treatment for 1h to obtain Co4An N-loaded nitrogen-doped carbon material.
Example 4
Firstly, preparing ZnO precursor with core-shell structure
1) Dissolving 0.12g P123, 0.05g Tris and 0.12g ZnO nanosphere in water, stirring and uniformly mixing to obtain a mixed water solution;
2) dissolving 0.50g of dopamine in deionized water, adding the solution into the solution, and stirring and reacting for 1.5 hours at room temperature;
3) and centrifuging the solution after reaction, washing the solution for a plurality of times by using ethanol, and drying the solution in an oven to obtain the precursor with the ZnO core-shell structure.
II, preparing Co4N-loaded nitrogenDoped carbon material
1) Weighing 0.35g of cobalt nitrate, adding the cobalt nitrate into 10ml of aqueous solution in which 0.9g of ZnO core-shell structure precursor is dissolved, then slowly adding 6ml of hydrazine hydrate into the solution, and stirring and reacting for 30min at room temperature;
2) centrifuging the solution after reaction, and washing with ethanol for several times;
3) adding 0.10g of melamine into the obtained product, and fully grinding to obtain a solid mixture;
4) putting the solid mixture into a quartz boat, raising the temperature to 800 ℃ by a program under the protection of nitrogen, and carrying out heat treatment for 3h to obtain Co4An N-loaded nitrogen-doped carbon material.
Claims (8)
1. A preparation method of a cobalt nitride loaded nitrogen-doped carbon material is characterized by comprising the following steps:
step one, preparing a ZnO core-shell structure precursor
1) Dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, trihydroxymethyl aminomethane and ZnO nanospheres in water, and uniformly stirring to obtain a mixed solution;
2) dissolving dopamine in deionized water, then adding the dopamine into the mixed solution, and stirring for reaction to obtain a precursor with a ZnO core-shell structure;
step two, preparing Co4N-loaded nitrogen-doped carbon material
1) Weighing cobalt nitrate, adding the cobalt nitrate into a ZnO core-shell structure precursor aqueous solution, and slowly adding hydrazine hydrate into the solution to react to obtain a reaction solution;
2) centrifuging and washing the reaction solution to obtain a product, and then adding melamine into the product to fully grind to obtain a solid mixture;
3) putting the solid mixture into a quartz boat, heating to 800-1000 ℃ under the protection of nitrogen, and carrying out heat treatment for 1-3 h to obtain Co4An N-loaded nitrogen-doped carbon material.
2. The method for preparing the cobalt nitride-loaded nitrogen-doped carbon material according to claim 1, wherein in the first step, the mass ratio of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, the tris (hydroxymethyl) aminomethane, the ZnO nanospheres and the dopamine is (0.05-0.20): (0.01-0.15): (0.08-0.12): (0.20-0.60).
3. The method as claimed in claim 1, wherein the stirring reaction temperature in the step one 2) is room temperature and the time is 1-3 hours.
4. The preparation method of the cobalt nitride-loaded nitrogen-doped carbon material according to claim 1, wherein the mass ratio of the cobalt nitrate to the ZnO core-shell structure precursor in the ZnO core-shell structure precursor aqueous solution in the step two 1) is 1:2 to 1: 10.
5. The method for preparing a cobalt nitride-supported nitrogen-doped carbon material according to claim 1, wherein the mass g of the cobalt nitrate in the second step 1) is as follows: the volume ml of hydrazine hydrate is (0.01-0.50): (2-10).
6. The method for preparing a cobalt nitride-supported nitrogen-doped carbon material as claimed in claim 1, wherein the reaction temperature in the second step 1) is room temperature, and the reaction time is 20-60 minutes.
7. The method for preparing the nitrogen-doped carbon material loaded with the cobalt nitride according to claim 1, wherein the mass ratio of the cobalt nitrate to the melamine in the second step is (0.01-0.50): (0.01-0.50).
8. A cobalt nitride-supported nitrogen-doped carbon material obtained by the production method according to any one of claims 1 to 7.
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| CN112831078B (en) * | 2021-02-08 | 2022-08-16 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
| CN112831855B (en) * | 2021-02-08 | 2022-05-31 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide functional fiber for X, gamma ray protection |
| CN114214634B (en) * | 2021-11-05 | 2023-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation, product and application of graphite plate loaded porous nano-sheet cobalt nitride-zinc oxide |
| CN114944495B (en) * | 2022-04-21 | 2023-09-26 | 同济大学 | Difunctional oxygen electrocatalyst with CoN/MnO double active sites and preparation and application thereof |
| CN114959783B (en) * | 2022-04-29 | 2023-10-27 | 青岛科技大学 | Co grown in situ in N-C framework 4 Preparation method of N quantum dot electrode material |
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| CN107899598A (en) * | 2017-10-26 | 2018-04-13 | 中国科学院长春应用化学研究所 | A kind of preparation method of cobalt, nitrogen co-doped nanometer particle carbon nanotube composite material |
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| CN101791566A (en) * | 2010-04-20 | 2010-08-04 | 青岛科技大学 | New method for nitrating ZnO based compound nano material |
| CN107899598A (en) * | 2017-10-26 | 2018-04-13 | 中国科学院长春应用化学研究所 | A kind of preparation method of cobalt, nitrogen co-doped nanometer particle carbon nanotube composite material |
| CN108295881A (en) * | 2018-01-29 | 2018-07-20 | 中南大学 | A kind of Co4The hollow nanocages composite material and preparation method of N/N doped carbons and application |
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