CN110265225B - Method for preparing nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material - Google Patents
Method for preparing nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 239000004005 microsphere Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 18
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 16
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 62
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 10
- 239000007921 spray Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005507 spraying Methods 0.000 claims abstract description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910015421 Mo2N Inorganic materials 0.000 claims description 15
- 229910003178 Mo2C Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 3
- 239000012298 atmosphere Substances 0.000 claims 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 4
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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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Abstract
The invention provides a method for preparing a nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material, which comprises the following steps of: 1) preparing a precursor: selecting ferric chloride, ammonium heptamolybdate, ammonium citrate and sodium chloride as raw materials, mixing and dissolving the raw materials in deionized water, and spraying the obtained uniform mixed solution into balls by using a spray dryer to prepare a precursor; 2) preparing a nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material: and (2) calcining the precursor prepared in the step (1) in a tubular furnace, cooling to room temperature to obtain a calcined product, and removing NaCl to obtain the nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material.
Description
Technical Field
The invention relates to a method for preparing nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticles by using an industrial production technology (spray drying method), and belongs to the technical field of nano material preparation.
Background
The nitrogen-doped three-dimensional porous carbon microsphere has excellent physicochemical properties such as: the porous carbon microsphere has the advantages of large specific surface area, high mechanical strength, excellent electrical conductivity, thermal conductivity and the like, so that the porous carbon microsphere can be applied to various fields, particularly the electrochemical field, the porous carbon microsphere can be used as a loading matrix to load various nano metal particles or metal-based nano materials due to rich pore structures and doped nitrogen atoms, and the prepared composite material can be applied to various fields as a high-performance electrode material, such as: positive and negative electrode materials of sodium ion batteries and lithium ion batteries, supercapacitors, lithium-sulfur batteries, lithium metal batteries and electrocatalytic hydrogen evolution and oxygen absorption.
Currently, hydrothermal and solvent thermal combination template technology is the mainstream method for preparing porous spherical carbon-supported metals and compounds thereof. However, the hydrothermal and solvent thermal combination template technology has the disadvantages of high production cost, complex process and low yield, and is not suitable for large-scale industrial production and preparation. Meanwhile, loading a plurality of metal-based materials on the nitrogen-doped porous carbon microspheres is difficult to realize. These severely limit their practical applications and performance improvements in the electrochemical field. Therefore, the mass and high-purity preparation of the nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticles is still a difficult problem.
Disclosure of Invention
The invention aims to provide a method for simply preparing nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticles; the method has the advantages of simple process and low cost, and the obtained nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material has uniform and consistent appearance and high yield, and is suitable for large-scale industrial production. The technical solution of the present invention for solving the above technical problems is,
a method for preparing a nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material comprises the following steps:
1) preparation of the precursor
Selecting ferric chloride (FeCl)3) Ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), ammonium citrate (C)6H5O7(NH4)3) And sodium chloride (NaCl) as raw materials, mixing and dissolving the raw materials in deionized water, and spraying the obtained uniform mixed solution into balls by using a spray dryer to prepare a precursor, which is marked as NaCl @ FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。
2) Preparation of nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material
Heating the precursor prepared in the step 1 to 780-790 ℃ at a speed of 8 ℃/min in a high-purity argon atmosphere in a tubular furnace, preserving heat for more than or equal to 2h, and cooling to room temperature to obtain a calcined product, which is recorded as Fe/Mo2C/Mo2N @ N-3DC @ NaCl, and then adding Fe/Mo2C/Mo2N @ N-3DC @ NaCl to remove NaCl and obtain Fe/Mo2C/Mo2N @ N-3DC to obtain the nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material.
In step 1), according to Fe3+:Mo:C:Na+The mass ratio of the raw materials is (0.2-0.5) to (2-3) to (25-35) to 100, and the raw materials are mixed and dissolved in deionized water.
Compared with the prior art, the method has the following advantages: (1) NaCl (recyclable) is used as a template, and cheap FeCl is used3、C6H5O7(NH4)3And (NH4)6Mo7O24·4H2O is used as a raw material, so that the cost is greatly saved; (2) the prepared nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material has high purity, high yield, good controllability, simple preparation process and equipment and easy large-scale industrial practical production and application in the future.
Drawings
FIG. 1 shows Fe/Mo after NaCl removal by water washing prepared by the present invention2C/Mo2XRD pattern of N @ N-3 DC;
FIG. 2 shows a precursor NaCl @ FeCl prepared by the present invention3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2SEM image of O;
FIG. 3 shows a calcined product Fe/Mo prepared by the present invention2C/Mo2N @ N-3DC @ NaCl;
FIG. 4 shows Fe/Mo after NaCl removal by water washing prepared by the present invention2C/Mo2SEM image of N @ N-3 DC;
FIG. 5 shows Fe/Mo after NaCl removal by water washing prepared by the present invention2C/Mo2N @ N-3DC (is Mo)2C) TEM image of (a).
FIG. 6 shows Fe/Mo after NaCl removal by water washing prepared by the present invention2C/Mo2N @ N-3DC (is Mo)2N) TEM images.
FIG. 7 shows Fe/Mo after NaCl removal by water washing prepared by the present invention2C/Mo2TEM image of N @ N-3DC (as Fe).
FIG. 8 shows Fe/Mo after NaCl removal by water washing prepared by the present invention2C/Mo2HRTEM image of N @ N-3DC (as Fe).
Nothing in this specification is said to apply to the prior art.
Specific examples of the production method of the present invention are given below. These examples are only intended to illustrate the preparation process of the present invention in detail and do not limit the scope of protection of the claims of the present application.
Example 1
According to Fe3+:Mo:C:Na+The mass ratio of (a) to (b) is 0.5:2:30:100, 0.19g of FeCl32.9g of C6H5O7(NH4)30.842g (NH4)6Mo7O24·4H2O and 15g NaCl in 115mL deionized water and stirred at room temperature for 8h to ensure C6H5O7(NH4)3Fully complexing with metal salt. Homogenizing the obtained mixtureThe solution was spray dried by a spray dryer. In this process, it is being involved (NH4)6Mo7O24.4H2O、C6H5O7(NH4)3And FeCl3The NaCl is self-assembled to form hollow spheres, and the sizes of the spheres are normally distributed. Because the water on the surface of the liquid drop is rapidly volatilized at high temperature, the water in the liquid drop carries NaCl to migrate to the surface, and the self-assembly of the liquid drop is caused to form a hollow spherical precursor NaCl @ FeCl in a very short time3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2And O. Placing the precursor in a tube furnace, introducing argon to remove air, heating to 790 ℃ at a speed of 8 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a calcined product Fe/Mo2C/Mo2N @ N-3DC @ NaCl. Washing the product with deionized water and absolute ethyl alcohol for three times, and drying to obtain a sample Fe/Mo2C/Mo2N@N-3DC。
Example 2
According to Fe3+:Mo:C:Na+The mass ratio of (a) to (b) is 0.25:2.5:30:100, 0.097g of FeCl32.9g of C6H5O7(NH4)31.053g (NH4)6Mo7O24·4H2O and 15g NaCl in 115mL deionized water and stirred at room temperature for 12h to ensure C6H5O7(NH4)3Fully complexing with metal salt. The resulting homogeneous solution was spray-dried by a spray dryer. In this process, it is being involved (NH4)6Mo7O24.4H2O、C6H5O7(NH4)3And FeCl3The NaCl is self-assembled to form hollow spheres, and the sizes of the spheres are normally distributed. Because the water on the surface of the liquid drop is rapidly volatilized at high temperature, the water in the liquid drop carries NaCl to migrate to the surface, and the self-assembly of the liquid drop is caused to form a hollow spherical precursor NaCl @ FeCl in a very short time3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2And O. Placing the precursor in a tube furnace, introducing argon to remove air, heating to 780 ℃ at the speed of 8 ℃/min, preserving heat for 3h, and cooling to room temperature to obtain a calcined product Fe/Mo2C/Mo2N @ N-3DC @ NaCl. Washing the product with deionized water and absolute ethyl alcohol for three times, and drying to obtain a sample Fe/Mo2C/Mo2N@N-3DC。
Example 3
According to Fe3+:Mo:C:Na+The ratio of the amounts of substances of (a) to (b) is 0.21:1.4:21:100, 0.116g of FeCl32.9g of C6H5O7(NH4)30.842g (NH4)6Mo7O24·4H2O and 20g NaCl in 115mL deionized water and stirred at room temperature for 6h to ensure C6H5O7(NH4)3Fully complexing with metal salt. The resulting homogeneous solution was spray-dried by a spray dryer. In this process, it is being involved (NH4)6Mo7O24.4H2O、C6H5O7(NH4)3And FeCl3The NaCl is self-assembled to form hollow spheres, and the sizes of the spheres are normally distributed. Because the water on the surface of the liquid drop is rapidly volatilized at high temperature, the water in the liquid drop carries NaCl to migrate to the surface, and the self-assembly of the liquid drop is caused to form a hollow spherical precursor NaCl @ FeCl in a very short time3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2And O. Placing the precursor in a tube furnace, introducing argon to remove air, heating to 785 ℃ at a speed of 8 ℃/min, preserving heat for 2.5h, and cooling to room temperature to obtain a calcined product Fe/Mo2C/Mo2N @ N-3DC @ NaCl. Washing the product with deionized water and absolute ethyl alcohol for three times, and drying to obtain a sample Fe/Mo2C/Mo2N@N-3DC。
Claims (3)
1. A method for preparing a nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material comprises the following steps:
1) preparation of the precursor
Selecting ferric chloride FeCl3Ammonium heptamolybdate (NH4)6Mo7O24·4H2O, ammonium citrate C6H5O7(NH4)3And sodium chloride (NaCl) as raw materials, mixing and dissolving the raw materials in deionized water, and spraying the obtained uniform mixed solution into balls by using a spray dryer to prepare a precursor, which is marked as NaCl @ FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O；
2) Preparation of nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material
Heating the precursor prepared in the step 1) to 780-790 ℃ in a tubular furnace in an inert atmosphere, preserving the heat for more than or equal to 2 hours, and cooling to room temperature to obtain a calcined product, namely Fe/Mo2C/Mo2N @ N-3DC @ NaCl, and then adding Fe/Mo2C/Mo2N @ N-3DC @ NaCl to remove NaCl and obtain Fe/Mo2C/Mo2N @ N-3DC to obtain the nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material.
2. The process according to claim 1, wherein in step 1), as Fe3+:Mo:C:Na+The mass ratio of the raw materials is (0.2-0.5) to (2-3) to (25-35) to 100, and the raw materials are mixed and dissolved in deionized water.
3. The method according to claim 1, wherein in the step 2), the temperature is raised to 780-790 ℃ at 8 ℃/min in a tube furnace under a high-purity argon atmosphere.
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| CN201910436829.9A CN110265225B (en) | 2019-05-23 | 2019-05-23 | Method for preparing nitrogen-doped three-dimensional porous carbon microsphere loaded molybdenum carbide/molybdenum nitride and iron nanoparticle composite material |
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| CN113292052A (en) * | 2021-04-29 | 2021-08-24 | 上海师范大学 | Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof |
| CN113707884A (en) * | 2021-06-23 | 2021-11-26 | 信阳师范学院 | 3D Mo2C-Mo3N2In-situ preparation method and application of/rGO heterostructure material |
| CN114105108B (en) * | 2021-11-23 | 2023-09-12 | 西南大学 | Method for preparing metal nanoparticle anchored molybdenum nitride with assistance of carbon quantum dots, product and application thereof |
| CN114790001B (en) * | 2022-05-06 | 2023-10-03 | 河南农业大学 | Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof |
| CN115108536B (en) * | 2022-07-05 | 2023-06-23 | 南昌航空大学 | Carbon-encapsulated molybdenum nitride surface-modified few-layer molybdenum selenide nanosheet sodium storage material, and forming method and application thereof |
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