CN110265225A - The method for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material - Google Patents
The method for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material Download PDFInfo
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- CN110265225A CN110265225A CN201910436829.9A CN201910436829A CN110265225A CN 110265225 A CN110265225 A CN 110265225A CN 201910436829 A CN201910436829 A CN 201910436829A CN 110265225 A CN110265225 A CN 110265225A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 16
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 15
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 15
- 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 61
- 239000011780 sodium chloride Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 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 claims abstract description 3
- 239000011259 mixed solution Substances 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 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000007921 spray Substances 0.000 abstract description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000243 solution Substances 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
- 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
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000003917 TEM image Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002086 nanomaterial 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
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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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
-
- B01J35/33—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of method for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material, the following steps are included: 1) prepare presoma: selecting iron chloride, ammonium heptamolybdate, ammonium citrate and sodium chloride is raw material, in deionized water by the above raw material mixed dissolution, resulting uniform mixed solution is sprayed balling-up using spray dryer, so that presoma be made；2) the three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride of N doping and iron nano-particle composite material are prepared: presoma made from step 1 is calcined in tube furnace, it is cooled to room temperature, calcined product is obtained, removal NaCl obtains the three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride of N doping and iron nano-particle composite material.
Description
Technical field
The three-dimensional porous carbosphere of N doping is prepared using Industrialized processing technique (spray drying process) the present invention relates to a kind of
The method for loading molybdenum carbide/molybdenum nitride and iron nano-particle, belongs to technical field of nanometer material preparation.
Background technique
The three-dimensional porous carbosphere of N doping has excellent physicochemical property, such as: big specific surface area, high machinery
Intensity, excellent electric conductivity and thermal conductivity etc., thus it can be applied in numerous areas, especially in electrochemical field, be enriched
Pore structure and doping nitrogen-atoms make the porous carbon microsphere can by as load matrix load a variety of nano-metal particles or
Metal-based nano material, this kind of composite material of preparation can be used as high performance electrode material and apply in multiple fields, for example: sodium from
Sub- battery and lithium ion battery plus-negative plate material, electrochemical capacitance, lithium-sulfur cell, lithium metal battery and electrocatalytic hydrogen evolution and oxygen uptake
Deng.
Currently, hydro-thermal, solvent heat combination mould plate technique are the mainstreams for preparing porous spherical carbonaceous carried metal and its compound
Method.But hydro-thermal and solvent heat combination mould plate technique production cost are higher, and process is complex, and yield is lower, are not suitable for big rule
The preparation of mould industrialized production.Meanwhile various metals sill mutual load being even more difficult on the porous carbon microsphere of N doping
It realizes.These all seriously limit it in the raising of the practical application and performance of electrochemical field.So high-volume and high-purity
Prepare N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle is equally still a problem.
Summary of the invention
The object of the present invention is to provide it is a kind of simply prepare the three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride of N doping and
The method of iron nano-particle；This method process is simple, low in cost, the three-dimensional porous carbosphere load carbonization of obtained N doping
Molybdenum/molybdenum nitride and iron nano-particle composite material pattern uniformity, yield are big, are suitble to large-scale industrial production.The present invention
Solve above-mentioned technical problem technical solution be,
A kind of side preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material
Method, comprising the following steps:
1) presoma is prepared
Select iron chloride (FeCl3), ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), ammonium citrate (C6H5O7(NH4)3) and chlorine
Changing sodium (NaCl) is raw material, in deionized water by the above raw material mixed dissolution, by resulting uniform mixed solution using by spraying
Drying machine is sprayed balling-up, so that presoma be made, is denoted as NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。
2) the three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride of N doping and iron nano-particle composite material are prepared
Presoma made from step 1 is warming up to 780~790 DEG C under high-purity argon gas atmosphere in tube furnace with 8 DEG C/min,
Heat preservation is more than or equal to 2h, is cooled to room temperature, obtains calcined product, is denoted as Fe/Mo2C/Mo2N@N-3DC@NaCl, then by Fe/
Mo2C/Mo2N@N-3DC@NaCl removal NaCl obtains Fe/Mo2C/Mo2N@N-3DC to get arrive the three-dimensional porous carbosphere of N doping
Load molybdenum carbide/molybdenum nitride and iron nano-particle composite material.
In step 1), according to Fe3+:Mo:C:Na+The ratio between amount of substance be (0.2-0.5): (2-3): (25-35): 100
Relationship, in deionized water by raw material mixed dissolution.
Compared with prior art, the method for the present invention has the advantage that (1) using NaCl (recyclable to recycle) as mould
Plate uses cheap FeCl3、C6H5O7(NH4)3(NH4)6Mo7O24·4H2Cost is greatly saved as raw material in O；(2) institute
The three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride of the N doping of preparation and iron nano-particle composite material purity is high, yield is big,
Controllability is good, and preparation process and equipment are simple, is easy to the following heavy industrialization production application.
Detailed description of the invention
Fig. 1 is the Fe/Mo prepared by the present invention after washing removes NaCl2C/Mo2The XRD spectrum of N@N-3DC；
Fig. 2 is presoma NaCl@FeCl prepared by the present invention3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2The SEM of O schemes
Picture；
Fig. 3 is calcined product Fe/Mo prepared by the present invention2C/Mo2The SEM image of N@N-3DC@NaCl；
Fig. 4 is Fe/Mo after being washed removal NaCl prepared by the present invention2C/Mo2The SEM image of N@N-3DC；
Fig. 5 is Fe/Mo after being washed removal NaCl prepared by the present invention2C/Mo2N@N-3DC is (for Mo2C TEM figure)
Picture.
Fig. 6 is Fe/Mo after being washed removal NaCl prepared by the present invention2C/Mo2N@N-3DC is (for Mo2N TEM figure)
Picture.
Fig. 7 is Fe/Mo after being washed removal NaCl prepared by the present invention2C/Mo2The TEM image of N@N-3DC (for Fe).
Fig. 8 is Fe/Mo after being washed removal NaCl prepared by the present invention2C/Mo2The HRTEM of N@N-3DC (for Fe) schemes
Picture.
The present invention does not address place and is suitable for the prior art.
The specific embodiment of preparation method of the present invention is given below.Preparation that these embodiments are only used for that the present invention will be described in detail
Method is not intended to limit the protection scope of the claim of this application.
Embodiment 1
According to Fe3+:Mo:C:Na+The ratio between amount of substance be 0.5:2:30:100 relationship, by the FeCl of 0.19g3, 2.9g
C6H5O7(NH4)3, (NH4) of 0.842g6Mo7O24·4H2The NaCl of O and 15g is dissolved in 115mL deionized water, stirs at room temperature
8h is mixed to guarantee C6H5O7(NH4)3It is sufficiently complexed with metal salt.Gained uniform solution is done by spraying by spray dryer
It is dry.In the process, by burden (NH4)6Mo7O24.4H2O、C6H5O7(NH4)3And FeCl3NaCl be self-assembly of open circles
Ball, the size of ball is at normal distribution.Since at high temperature, the water of droplet surface volatilizees rapidly, the water of drop internal is carry
NaCl is migrated to surface, it is caused to be self-assembly of georama presoma NaCl@FeCl in a very short period of time3-C6H5O7
(NH4)3-(NH4)6Mo7O24·4H2O.Presoma is placed in tube furnace, first leads to argon gas to exclude air, then with 8 DEG C/min
Be warming up to 790 DEG C, keep the temperature 2h, after be cooled to room temperature, obtain calcined product Fe/Mo2C/Mo2N@[email protected] is spent
Three times, drying obtains sample F e/Mo for ionized water and dehydrated alcohol washing2C/Mo2N@N-3DC。
Embodiment 2
According to Fe3+:Mo:C:Na+The ratio between amount of substance be 0.25:2.5:30:100 relationship, by the FeCl of 0.097g3,
The C of 2.9g6H5O7(NH4)3, (NH4) of 1.053g6Mo7O24·4H2The NaCl of O and 15g is dissolved in 115mL deionized water, in room temperature
Lower stirring 12h is to guarantee C6H5O7(NH4)3It is sufficiently complexed with metal salt.Gained uniform solution is sprayed by spray dryer
Mist is dry.In the process, by burden (NH4)6Mo7O24.4H2O、C6H5O7(NH4)3And FeCl3NaCl be self-assembly of sky
Heart ball, the size of ball is at normal distribution.Since at high temperature, the water of droplet surface volatilizees rapidly, the water of drop internal is taken
It migrates with NaCl to surface, it is caused to be self-assembly of georama presoma NaCl@FeCl in a very short period of time3-
C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O.Presoma is placed in tube furnace, first leads to argon gas to exclude air, then with 8
DEG C/min is warming up to 780 DEG C, keep the temperature 3h, after be cooled to room temperature, obtain calcined product Fe/Mo2C/Mo2N@[email protected] will produce
Object deionized water and dehydrated alcohol wash three times, and drying obtains sample F e/Mo2C/Mo2N@N-3DC。
Embodiment 3
According to Fe3+:Mo:C:Na+The ratio between amount of substance be 0.21:1.4:21:100 relationship, by the FeCl of 0.116g3,
The C of 2.9g6H5O7(NH4)3, (NH4) of 0.842g6Mo7O24·4H2The NaCl of O and 20g is dissolved in 115mL deionized water, in room temperature
Lower stirring 6h is to guarantee C6H5O7(NH4)3It is sufficiently complexed with metal salt.Gained uniform solution is sprayed by spray dryer
It is dry.In the process, by burden (NH4)6Mo7O24.4H2O、C6H5O7(NH4)3And FeCl3NaCl be self-assembly of it is hollow
Ball, the size of ball is at normal distribution.Since at high temperature, the water of droplet surface volatilizees rapidly, the water of drop internal is carried
NaCl migrate to surface, cause it to be self-assembly of georama presoma NaCl@FeCl in a very short period of time3-C6H5O7
(NH4)3-(NH4)6Mo7O24·4H2O.Presoma is placed in tube furnace, first leads to argon gas to exclude air, then with 8 DEG C/min
Be warming up to 785 DEG C, keep the temperature 2.5h, after be cooled to room temperature, obtain calcined product Fe/Mo2C/Mo2N@[email protected] is used
Three times, drying obtains sample F e/Mo for deionized water and dehydrated alcohol washing2C/Mo2N@N-3DC。
Claims (3)
1. a kind of side for preparing N doping three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride and iron nano-particle composite material
Method, comprising the following steps:
1) presoma is prepared
Select iron chloride (FeCl3), ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), ammonium citrate (C6H5O7(NH4)3) and sodium chloride
(NaCl) it is raw material, in deionized water by the above raw material mixed dissolution, resulting uniform mixed solution is utilized into spray drying
Machine is sprayed balling-up, so that presoma be made, is denoted as NaCl@FeCl3-C6H5O7(NH4)3-(NH4)6Mo7O24·4H2O。
2) the three-dimensional porous carbosphere load molybdenum carbide/molybdenum nitride of N doping and iron nano-particle composite material are prepared
Presoma made from step 1) is warming up to 780~790 DEG C under an inert atmosphere in tube furnace, heat preservation is more than or equal to
2h is cooled to room temperature, obtains calcined product, is denoted as Fe/Mo2C/Mo2N@N-3DC@NaCl, then by Fe/Mo2C/Mo2N@N-
3DC@NaCl removal NaCl obtains Fe/Mo2C/Mo2N@N-3DC loads molybdenum carbide/nitrogen to get to the three-dimensional porous carbosphere of N doping
Change molybdenum and iron nano-particle composite material.
2. the method according to claim 1, wherein in step 1), according to Fe3+:Mo:C:Na+Amount of substance it
Than for (0.2-0.5): (2-3): (25-35): 100 relationship, in deionized water by raw material mixed dissolution.
3. the method according to claim 1, wherein in step 1), with 8 under high-purity argon gas atmosphere in tube furnace
DEG C/min is warming up to 780~790 DEG C.
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