CN110038614A - A kind of nitrogen-doped carbon material and preparation method thereof of cobalt nitride load - Google Patents
A kind of nitrogen-doped carbon material and preparation method thereof of cobalt nitride load Download PDFInfo
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- CN110038614A CN110038614A CN201910417833.0A CN201910417833A CN110038614A CN 110038614 A CN110038614 A CN 110038614A CN 201910417833 A CN201910417833 A CN 201910417833A CN 110038614 A CN110038614 A CN 110038614A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- -1 cobalt nitride Chemical class 0.000 title claims abstract description 30
- 239000010941 cobalt Substances 0.000 title claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 24
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 19
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 19
- 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
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000008247 solid mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 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 9
- 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 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 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
- 238000010438 heat treatment Methods 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
- 238000003756 stirring Methods 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 239000011807 nanoball Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000012265 solid product Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940043379 ammonium hydroxide Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 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
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GUGLPELUECBSDK-UHFFFAOYSA-N phenol;urea Chemical compound NC(N)=O.OC1=CC=CC=C1 GUGLPELUECBSDK-UHFFFAOYSA-N 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
-
- B01J35/33—
-
- B01J35/393—
-
- B01J35/396—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
Abstract
The present invention provides a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load, belongs to nanocomposite preparation field.This method is using ZnO nano ball as template, dopamine is coated outside ZnO nano ball, prepare ZnO core-shell structure presoma, then cobalt is introduced into ZnO core-shell structure in the form of cobalt nitrate, it is ground under the conditions of existing for the melamine, Co can be obtained by high-temperature calcination in obtained solid product4The nitrogen-doped carbon material of N load.The present invention also provides the Co of above method preparation4The nitrogen-doped carbon material of N load, material of the invention have excellent electrocatalysis characteristic, can be widely applied to hydrogen reduction and oxygen precipitation etc..
Description
Technical field
The invention belongs to nanocomposite preparation fields, and in particular to a kind of nitrogen-doped carbon material of cobalt nitride load
Preparation method.
Background technique
The carbon material of N doping has the characteristics that large specific surface area, good conductivity, active site are mostly easy with preparation method,
It is considered as a kind of very ideal catalyst carrier in electrochemical field.On the other hand, transition metal nitride is in transition
Nitrogen doped in metal makes it have electron donor feature, enhances its electric conductivity and stability.By transitional metal nitride
The progress of the carbon material of object and N doping is compound, and the bifunctional catalyst that can be had excellent performance, transition metal can be improved in it
The dispersibility of nitride effectively improves the catalytic performance of catalyst, for realizing that the business application of energy conversion and storage has
Significance.
Currently, the preparation method about transition metal and nitrogen co-doped carbon material has very much, such as Wei first prepares phenol
Urea formaldehyde-F127 list micella, then itself and sulphur, ferric acetate etc. have been mixed with out the pretreated porous Fe of sulphur/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 etc. uses solvent heat carbonizatin method, prepares using cobalt acetate, Dopamine hydrochloride, ammonium hydroxide as one step hydro-thermal of raw material
Co/N-C composite material [Y.Su, Y.Zhu, H.Jiang, J.Shen, X.Yang, W.Zou, J.Chen, C.Li, Nanoscale
2014,6,15080-15089].But most methods preparation process is relatively complicated, using expensive raw material price and is not easy to obtain,
And it is more difficult to get morphology controllable, the preferable composite material of dispersibility, is unfavorable for the extensive use of prepared composite material.
Summary of the invention
The purpose of the present invention is to solve the composite material pattern of existing N doping is uncontrollable, bad dispersibility is asked
Topic, and a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load is provided.
Present invention firstly provides a kind of preparation methods of the nitrogen-doped carbon material of cobalt nitride load, specifically include following step
It is rapid:
Step 1: preparation ZnO core-shell structure presoma
1) by polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, trishydroxymethylaminomethane and
ZnO nano ball is soluble in water, stirs evenly, and obtains mixed liquor；
2) dopamine is dissolved in deionized water, is then added in above-mentioned mixed liquor, is stirred to react, obtain ZnO nucleocapsid
Structured forerunner；
Step 2: preparation Co4The nitrogen-doped carbon material of N load
1) it weighs cobalt nitrate to be added in ZnO core-shell structure precursor water solution, is then slowly added to water into the solution
Hydrazine reaction is closed, reaction solution is obtained；
2) by reaction solution after centrifuge washing, product is obtained, then melamine is added in above-mentioned product and is carried out
It is fully ground, obtains solid mixture；
3) above-mentioned solid mixture is put into quartz boat, is warming up to 800~1000 DEG C under nitrogen protection, heat treatment 1~
3h obtains Co4The nitrogen-doped carbon material of N load.
Preferably, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, three in the step 1
The mass ratio of hydroxymethyl aminomethane, ZnO nano ball and dopamine is (0.05~0.20): (0.01~0.15): (0.08~
0.12): (0.20~0.60).
Preferably, the step 1 2) in be stirred to react temperature be room temperature, the time be 1~3 hour.
Preferably, the step 2 1) in the mass ratio of cobalt nitrate and ZnO core-shell structure presoma be 1:2~1:10.
Preferably, the step 2 1) in cobalt nitrate quality g: hydrazine hydrate volume ml be (0.01~0.50): (2
~10).
Preferably, the step 2 1) reaction temperature be room temperature, the reaction time be 20~60 minutes.
Preferably, the mass ratio of cobalt nitrate and melamine is (0.01~0.50) in the step 2: (0.01~
0.50)。
The present invention also provides the nitrogen-doped carbon materials for the cobalt nitride load that above-mentioned preparation method obtains.
Beneficial effects of the present invention
The present invention provides a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load, and this method is with ZnO nano ball
For template, dopamine is coated outside ZnO nano ball, prepares ZnO core-shell structure presoma.Then by cobalt with the shape of cobalt nitrate
Formula is introduced into ZnO core-shell structure, is ground under the conditions of existing for the melamine, obtained solid product is forged by high temperature
Co can be obtained in burning4The nitrogen-doped carbon material of N load.Pass through control ZnO nano ball and cobalt nitrate and cobalt nitrate-ZnO nucleocapsid
The mass ratio of structured forerunner and melamine, the pattern of adjustable resulting materials can obtain the uniform Co of pattern4N load
Nitrogen-doped carbon material.The method process is simple, raw material is cheap and easy to get.
The Co provided by the invention prepared in aforementioned manners4The nitrogen-doped carbon material of N load, by transition metal nitride and
The carbon material progress of N doping is compound, is a kind of bifunctional catalyst, and metal dispersion is uniform, has biggish specific surface area, makes
Obtaining material has excellent electrocatalysis characteristic, can be widely applied to hydrogen reduction and oxygen precipitation etc..
Detailed description of the invention
Fig. 1 is Co prepared by the embodiment of the present invention 14Transmission electron microscope (TEM) figure of the nitrogen-doped carbon material of N load.
Fig. 2 is Co prepared by the embodiment of the present invention 14X-ray diffraction (XRD) figure of the nitrogen-doped carbon material of N load.
Fig. 3 is Co prepared by the embodiment of the present invention 14The nitrogen-doped carbon material and commercialized Pt/C catalyst of N load exist
To the linear scan figure of hydrogen reduction under the conditions of same.
Specific embodiment
Present invention firstly provides a kind of preparation methods of the nitrogen-doped carbon material of cobalt nitride load, specifically include following step
It is rapid:
Step 1: preparation ZnO core-shell structure presoma
1) by polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), trihydroxy methyl amino first
Alkane (Tris) and ZnO nano ball are soluble in water, stir evenly, obtain mixed liquor；
2) dopamine is dissolved in deionized water, is then added in above-mentioned mixed liquor, is stirred to react, then by reaction solution
It is centrifuged, washed and dried, obtain ZnO core-shell structure presoma；The reaction temperature is preferably room temperature, and the reaction time is excellent
It is selected as 1~3 hour；
Polyethylene oxide-polypropylene oxide-polyethylene oxide the triblock copolymer, trishydroxymethylaminomethane,
The mass ratio of ZnO nano ball and dopamine is preferably (0.05~0.20): (0.01~0.15): (0.08~0.12): (0.20~
0.60)。
Polyethylene oxide-the polypropylene oxide-polyethylene oxide triblock copolymer (P123) source be it is commercially available,
ZnO nano ball is prepared using existing preparation method, particular reference [X.Song, L.Guo, X.Liao, J.Liu,
J.Sun,X.Li,Small 2017,13,1700238]。
Step 2: preparation Co4The nitrogen-doped carbon material of N load
1) it weighs cobalt nitrate to be added in ZnO core-shell structure precursor water solution, is then slowly added to water into the solution
Hydrazine reaction is closed, the reaction temperature is preferably room temperature, and the reaction time is preferably 20~60 minutes, is reacted after reaction response
Liquid；The mass ratio of ZnO core-shell structure presoma in the cobalt nitrate and ZnO core-shell structure precursor water solution is preferably 1:
2~1:10；The volume ml of the quality g: hydrazine hydrate of the cobalt nitrate is preferably (0.01~0.50): (2~10)；
2) by reaction solution after centrifuge washing, product is obtained, then melamine is added in above-mentioned product and is carried out
It is fully ground, obtains solid mixture；The mass ratio of the cobalt nitrate and melamine is preferably (0.01~0.50):
(0.01~0.50)；
3) above-mentioned solid mixture is put into quartz boat, is warming up to 800~1000 DEG C under nitrogen protection, heat treatment 1~
3h obtains Co4The nitrogen-doped carbon material of N load.
The present invention also provides the nitrogen-doped carbon materials for the cobalt nitride load that above-mentioned preparation method obtains.Material of the invention is
The progress of the carbon material of transition metal nitride and N doping is compound, it is a kind of bifunctional catalyst, metal dispersion is uniform, has
Biggish specific surface area, so that material has excellent electrocatalysis characteristic.
Below by specific embodiment to Co of the present invention4The preparation of the nitrogen-doped carbon material of N load is done further detailed
Explanation.
Embodiment 1
One, ZnO core-shell structure presoma is prepared
1) 0.08g P123,0.12g Tris and 0.10g ZnO nano ball is soluble in water, it stirs, is uniformly mixed, obtains
Mixed aqueous solution；
2) 0.40g dopamine is dissolved in deionized water, is added in above-mentioned solution, is stirred to react 1h at room temperature；
3) solution after reaction is centrifuged, for several times with ethanol washing, is dried in an oven later, obtains ZnO nucleocapsid
Structured forerunner.
Two, Co is prepared4The nitrogen-doped carbon material of N load
1) weigh 0.04g cobalt nitrate and be added to 10ml dissolved in 0.08g ZnO core-shell structure precursor water solution, then to
It is slowly added to 5ml hydrazine hydrate in the solution, is stirred to react 60min at room temperature；
2) solution after reaction is centrifuged, for several times with ethanol washing；
3) 0.50g melamine is added in above-mentioned products therefrom and is fully ground, obtain solid mixture；
4) above-mentioned solid mixture is put into quartz boat, temperature programming is to 900 DEG C under nitrogen protection, and heat treatment 1h to obtain the final product
To Co4The nitrogen-doped carbon material of N load.
Fig. 1 is Co prepared by the embodiment of the present invention 14Transmission electron microscope (TEM) figure of the nitrogen-doped carbon material of N load, the figure
Show Co4N is uniformly dispersed, size uniformity.
Fig. 2 is Co prepared by the embodiment of the present invention 14X-ray diffraction (XRD) figure of the nitrogen-doped carbon material of N load, the figure
Show that load is Co4N。
Fig. 3 is Co prepared by the embodiment of the present invention 14The nitrogen-doped carbon material and commercialized Pt/C catalyst of N load exist
To the linear scan figure of hydrogen reduction under the conditions of same.The chart is bright compared with commercialized Pt/C, the Co of preparation4N load
Nitrogen-doped carbon material has superior electrocatalytic oxidation reducing property.
Embodiment 2
One, ZnO core-shell structure presoma is prepared
1) 0.20g P123,0.15g Tris and 0.08g ZnO nano ball is soluble in water, it stirs, is uniformly mixed, obtains
Mixed aqueous solution；
2) 0.20g dopamine is dissolved in deionized water, is added in above-mentioned solution, is stirred to react 3h at room temperature；
3) solution after reaction is centrifuged, for several times with ethanol washing, is dried in an oven later, obtains ZnO nucleocapsid
Structured forerunner.
Two, Co is prepared4The nitrogen-doped carbon material of N load
1) weigh 0.50g cobalt nitrate and be added to 10ml dissolved in 2.00g ZnO core-shell structure precursor water solution, then to
It is slowly added to 2ml hydrazine hydrate in the solution, is stirred to react 40min at room temperature；
2) solution after reaction is centrifuged, for several times with ethanol washing；
3) 0.30g melamine is added in above-mentioned products therefrom and is fully ground, obtain solid mixture；
4) above-mentioned solid mixture is put into quartz boat, temperature programming is to 800 DEG C under nitrogen protection, and heat treatment 2h to obtain the final product
To Co4The nitrogen-doped carbon material of N load.
Embodiment 3
One, ZnO core-shell structure presoma is prepared
1) 0.05g P123,0.01g Tris and 0.12g ZnO nano ball is soluble in water, it stirs, is uniformly mixed, obtains
Mixed aqueous solution；
2) 0.60g dopamine is dissolved in deionized water, is added in above-mentioned solution, is stirred to react 2h at room temperature；
3) solution after reaction is centrifuged, for several times with ethanol washing, is dried in an oven later, obtains ZnO nucleocapsid
Structured forerunner.
Two, Co is prepared4The nitrogen-doped carbon material of N load
1) weigh 0.01g cobalt nitrate and be added to 10ml dissolved in 0.1g ZnO core-shell structure precursor water solution, then to
It is slowly added to 10ml hydrazine hydrate in the solution, is stirred to react 20min at room temperature；
2) solution after reaction is centrifuged, for several times with ethanol washing；
3) 0.01g melamine is added in above-mentioned products therefrom and is fully ground, obtain solid mixture；
4) above-mentioned solid mixture is put into quartz boat, to 1000 DEG C, heat treatment 1h is for temperature programming under nitrogen protection
Obtain Co4The nitrogen-doped carbon material of N load.
Embodiment 4
One, ZnO core-shell structure presoma is prepared
1) 0.12g P123,0.05g Tris and 0.12g ZnO nano ball is soluble in water, it stirs, is uniformly mixed, obtains
Mixed aqueous solution；
2) 0.50g dopamine is dissolved in deionized water, is added in above-mentioned solution, is stirred to react 1.5h at room temperature；
3) solution after reaction is centrifuged, for several times with ethanol washing, is dried in an oven later, obtains ZnO nucleocapsid
Structured forerunner.
Two, Co is prepared4The nitrogen-doped carbon material of N load
1) weigh 0.35g cobalt nitrate and be added to 10ml dissolved in 0.9g ZnO core-shell structure precursor water solution, then to
It is slowly added to 6ml hydrazine hydrate in the solution, is stirred to react 30min at room temperature；
2) solution after reaction is centrifuged, for several times with ethanol washing；
3) 0.10g melamine is added in above-mentioned products therefrom and is fully ground, obtain solid mixture；
4) above-mentioned solid mixture is put into quartz boat, temperature programming is to 800 DEG C under nitrogen protection, and heat treatment 3h to obtain the final product
To Co4The nitrogen-doped carbon material of N load.
Claims (8)
1. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load, which is characterized in that specifically includes the following steps:
Step 1: preparation ZnO core-shell structure presoma
1) polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, trishydroxymethylaminomethane and ZnO is received
Rice ball is soluble in water, stirs evenly, obtains mixed liquor；
2) dopamine is dissolved in deionized water, is then added in above-mentioned mixed liquor, is stirred to react, obtain ZnO core-shell structure
Presoma；
Step 2: preparation Co4The nitrogen-doped carbon material of N load
1) it weighs cobalt nitrate to be added in ZnO core-shell structure precursor water solution, is then slowly added to hydrazine hydrate into the solution
Reaction, obtains reaction solution；
2) by reaction solution after centrifuge washing, product is obtained, then melamine is added in above-mentioned product and is carried out sufficiently
Grinding, obtains solid mixture；
3) above-mentioned solid mixture is put into quartz boat, 800~1000 DEG C is warming up under nitrogen protection, 1~3h of heat treatment is
Obtain Co4The nitrogen-doped carbon material of N load.
2. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load according to claim 1, which is characterized in that institute
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, trishydroxymethylaminomethane, ZnO in step 1 is stated to receive
The mass ratio of rice ball and dopamine is (0.05~0.20): (0.01~0.15): (0.08~0.12): (0.20~0.60).
3. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load according to claim 1, which is characterized in that institute
State step 1 2) in be stirred to react temperature be room temperature, the time be 1~3 hour.
4. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load according to claim 1, which is characterized in that institute
State step 2 1) in the mass ratio of cobalt nitrate and ZnO core-shell structure presoma be 1:2~1:10.
5. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load according to claim 1, which is characterized in that institute
State step 2 1) in cobalt nitrate quality g: hydrazine hydrate volume ml be (0.01~0.50): (2~10).
6. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load according to claim 1, which is characterized in that institute
State step 2 1) reaction temperature be room temperature, the reaction time be 20~60 minutes.
7. a kind of preparation method of the nitrogen-doped carbon material of cobalt nitride load according to claim 1, which is characterized in that institute
Stating the mass ratio of cobalt nitrate and melamine in step 2 is (0.01~0.50): (0.01~0.50).
8. the nitrogen-doped carbon material for the cobalt nitride load that preparation method described in claim 1-7 any one obtains.
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| CN112831078A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
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| CN114214634A (en) * | 2021-11-05 | 2022-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of graphite plate loaded porous nanosheet cobalt nitride-zinc oxide, product and application |
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| CN113713840A (en) * | 2020-05-25 | 2021-11-30 | 台州学院 | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof |
| CN113713840B (en) * | 2020-05-25 | 2023-07-25 | 台州学院 | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof |
| CN112831078A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
| WO2022166151A1 (en) * | 2021-02-08 | 2022-08-11 | 南通大学 | PREPARATION METHOD FOR TUNGSTEN/GADOLINIUM OXIDE FUNCTIONAL FIBER HAVING CORE-SHELL STRUCTURE FOR X AND γ RAY PROTECTION |
| CN112831855A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide functional fiber for X, gamma ray protection |
| CN114214634A (en) * | 2021-11-05 | 2022-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of graphite plate loaded porous nanosheet cobalt nitride-zinc oxide, product and application |
| 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 |
| CN114944495A (en) * | 2022-04-21 | 2022-08-26 | 同济大学 | Bifunctional oxygen electrocatalyst with CoN/MnO double-active sites and preparation and application thereof |
| CN114959783A (en) * | 2022-04-29 | 2022-08-30 | 青岛科技大学 | Co grown in situ in N-C framework 4 Preparation method of N quantum dot electrode material |
| 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 |
| CN116253636B (en) * | 2023-02-17 | 2023-09-19 | 中南大学 | Co (cobalt) 4 Application of N/CNE nano material |
| CN116253636A (en) * | 2023-02-17 | 2023-06-13 | 中南大学 | Co (cobalt) 4 Application of N/CNE nano material |
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