CN105621377B - The preparation method of nitrided iron based on metal-organic framework materials - Google Patents
The preparation method of nitrided iron based on metal-organic framework materials Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the nitrided iron based on metal-organic framework materials, it is characterised in that including step：Metal-organic framework materials are positioned in tubular heater, with 1 20 DEG C/min temperature programmings to 300 600 DEG C of nitriding temperature, and 10 24h is kept under this condition, iron nitride material is obtained by nitridation reaction；Room temperature is cooled to after nitridation reaction is complete, being passed through inert gas prevents nitrided iron from aoxidizing, and the nitrogen source gas are ammonia and/or nitrogen.In the inventive method the performance of iron nitride material can be preferably controlled by the use of metal organic framework material or its formed body as source of iron, its higher specific surface area, pore volume and tenor；Metal organic framework material or its formed body provide abundant pore canal system, and nitrogen source gas can be contacted sufficiently with metallic atom, be advantageous to the conversion of nano silicon nitride iron material, improve the yield and quality of nitrided iron.
Description
Technical field
The invention belongs to field of magnetic material preparation, in particular it relates to a kind of magnetic material preparation method containing iron.
Background technology
Metal nitride, with the property of three kinds of covalent compound, ionic crystals and metal materials, there is special thing
Physicochemical property, the especially metal nitride with high-specific surface area, it is anti-in multiple catalysis such as ammonia synthesis, hydrodesulfurization, denitrogenation
There is very strong precious metal catalyst attribute in answering and widely paid close attention to.Nitrided iron is a kind of good magnetic material, in magnetic
There is good application prospect in terms of fluid, while be also a kind of good catalysis material, in F- T synthesis and ammonia synthesis reaction
In there is good catalytic activity.
The method that prior art prepares nitrided iron is mostly using inorganic molysite or oxide as source of iron, passes through reduction nitridation
The methods of method, vapour deposition process, sol-gel process, high warm method, prepares nitrided iron, but the nitrided iron of above method synthesis
Grain specific surface area is smaller, limits it in catalysis and the application of field of magnetic material.
Patent CN103145106 provides a kind of preparation method of nitrided iron nano-powder, this method using iron hydroxide as
Source of iron, synthesis nitridation iron powder body is prepared under the conditions of ammonia atmosphere mesohigh, but this method operating pressure is higher, is unfavorable for filling
The safe operation put, the nitrided iron powder specific-surface area detection that in addition prepared by this method are relatively low.
Optimal performance of the different preparation methods depending on synthetic material, and source of iron in the synthesis of metal nitride
Select most important.The present invention provides source of iron using metal-organic framework materials as presoma first, using temperature programming nitrogen
Change method prepares the iron nitride material for having synthesized high-specific surface area.
The content of the invention
In order to overcome above-mentioned technical problem, it is an object of the present invention to provide a kind of based on metal-organic framework materials
The preparation method of nitrided iron.
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of preparation method of the nitrided iron based on metal-organic framework materials, including step：
Metal-organic framework materials are positioned in tubular heater, by nitrogen source gas with volume space velocity 4000-10000h-1
By reactor, with 1-20 DEG C/min temperature programmings to 300-600 DEG C of nitriding temperature, and 10-24h is kept under this condition, obtained
To iron nitride material；Room temperature is cooled to after nitridation reaction is complete, being passed through inert gas prevents nitrided iron from aoxidizing, wherein, the nitrogen
Source gas is ammonia and/or nitrogen.
Wherein, the metal-organic framework materials are that organic compound and metallic atom form porous crystalline by coordinate bond
Material, the organic compound are one kind in bidentate, three tooth dicarboxylic acids or polycarboxylic acid ligand compound and its derivative, preferably
From terephthalic acid (TPA), M-phthalic acid, trimesic acid, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, richness
One kind in horse acid, 2- hydroxyterephthalic acids.
Iron compound is the one or more of iron chloride, ferric nitrate, ferric sulfate, ferric acetate, ferric carbonate or its hydrate, excellent
Elect ferric nitrate, ferric sulfate, more preferably iron chloride as.
Wherein, the metal-organic framework materials are the metal-organic framework materials of iron content, and relative crystallinity is more than 50%,
Preferably greater than 80%；BET specific surface area is 1000-5000m2/ g, preferably 2000-3000m2/g。
Further, also doped with other metallic atoms, other described metallic atoms in the metal-organic framework materials
The atom of II-III main group and transition metal in the periodic table of elements, specially copper, zinc, aluminium, calcium, titanium, magnesium, nickel are former
One or more in son.
Wherein, in the methods of the invention in metal-organic framework materials also doped with other metallic atoms, other described gold
Category atom is copper, zinc, aluminium, calcium, titanium, magnesium, the Bromide of nickel, chlorate, sulfate, nitrate, acetate, carbonate, preferably
For copper chloride.
Preferably, the nitriding temperature refers to the decomposition temperature higher than metal-organic framework materials, specifically 350-500
DEG C, the inert gas is the one or more in helium, argon gas, Krypton.
The preparation method of the metal-organic framework materials can use techniques known in the art means, as the present invention
A preferable technical scheme, the preparation method of the metal-organic framework materials is by molysite, more bidentate organic compounds, N, N-
Dimethylformamide, according to mol ratio (0.5-2):(0.5-2):(200-350), it is put into the reactor for being lined with polytetrafluoroethylene (PTFE)
In, 10-30h is reacted at a temperature of 100-200 DEG C, obtains the metal-organic framework materials containing iron；The molysite be iron chloride,
Ferric nitrate, ferric sulfate, ferric acetate, the one or more of ferric carbonate or its hydrate.
Wherein, the raw material that prepared by the metal-organic framework materials also includes the soluble salt of other metallic atoms, it is described its
The soluble salt of his metallic atom and iron chloride mol ratio are 0.1-1：1.The soluble salt of other metallic atoms be copper, zinc, aluminium,
Calcium, titanium, magnesium, the Bromide of nickel, chlorate, sulfate, nitrate, acetate, preferably carbonate, copper chloride.
Compared with prior art, the inventive method has advantages below：
1. by the use of metal organic framework material or its formed body as source of iron in the inventive method, its higher specific surface area,
Pore volume and tenor can preferably control the performance of iron nitride material；
2. metal organic framework material or its formed body provide abundant pore canal system, nitrogen source gas can sufficiently with gold
Belong to atomic contacts, be advantageous to the conversion of nano silicon nitride iron material, improve the yield and quality of nitrided iron；
3. preparing in the MOF materials process containing iron and adding a certain amount of metal ion, the Heat-resistant stable of material is improved
Property, improve nitrided iron crystal structure.The inventive method is simple to operate, practical, has higher actual application value.
Brief description of the drawings
Fig. 1 is the XRD of the MOF materials of 1-4 of embodiment of the present invention synthesis.
Fig. 2 is the XRD of the iron nitride material of 5-7 of embodiment of the present invention synthesis.
Fig. 3 is the SEM figures for the MOF materials that the embodiment of the present invention 3 synthesizes.
Fig. 4 is the SEM figures for the iron nitride material that the embodiment of the present invention 6 synthesizes.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Unless stated otherwise, the technology used in the present invention means, it is this area conventional technology.
Embodiment 1
According to mol ratio it is 0.5 by iron chloride, terephthalic acid (TPA), N,N-dimethylformamide, copper chloride:0.5: 200:
0.05 is put into the stainless steel cauldron for being lined with polytetrafluoroethyllining lining, and reaction solution reacts 10h at a temperature of 100 DEG C, produces
To the MOF materials containing iron, relative crystallinity is that to test its specific surface area be 1045m to 87%, BET2/g。
Embodiment 2
According to mol ratio it is 2 by iron chloride, terephthalic acid (TPA), N,N-dimethylformamide, copper chloride:2: 350: 0.2
It is put into the stainless steel cauldron for being lined with polytetrafluoroethyllining lining, reaction solution reacts 30h at a temperature of 200 DEG C, that is, is contained
There are a MOF materials of iron, relative crystallinity is that to test its specific surface area be 1186m to 90%, BET2/g。
Embodiment 3
According to mol ratio it is 1 by iron chloride, terephthalic acid (TPA), N,N-dimethylformamide, copper chloride:0.8:280:
0.07 is put into the stainless steel cauldron for being lined with polytetrafluoroethyllining lining, and reaction solution reacts 24h at a temperature of 150 DEG C, produces
To the MOF materials containing iron, relative crystallinity is that to test its specific surface area be 1268m to 98%, BET2/ g, SEM photograph is as schemed
3。
Embodiment 4
According to mol ratio it is 1 by iron chloride, terephthalic acid (TPA), N,N-dimethylformamide:0.8:280 are put into and are lined with poly- four
In the stainless steel cauldron of PVF liner, reaction solution reacts 24h at a temperature of 150 DEG C, that is, obtains the MOF materials containing iron
Material, relative crystallinity is that 95%, BET is 1124m2/g。
Embodiment 5
3 made metal-organic framework materials of embodiment are positioned in tubular heater, by nitrogen source gas with volume space velocity
4000h-1By reactor, with 1 DEG C/min temperature programmings to 350 DEG C of nitriding temperature, and 10h is kept under this condition, obtain nitrogen
Change iron material；
Room temperature is cooled to after nitridation reaction is complete, being passed through argon gas prevents nitrided iron from aoxidizing.
It is 35 m that BET, which tests its specific surface area,2/g。
Embodiment 6
3 made metal-organic framework materials of embodiment are positioned in tubular heater, by nitrogen source gas with volume space velocity
6000h-1By reactor, with 10 DEG C/min temperature programmings to 420 DEG C of nitriding temperature, and 15h is kept under this condition, obtain nitrogen
Change iron material；
Room temperature is cooled to after nitridation reaction is complete, being passed through argon gas prevents nitrided iron from aoxidizing.
The SEM of obtained product such as Fig. 4, it is 41m that BET, which tests its specific surface area,2/g。
Embodiment 7
3 made metal-organic framework materials of embodiment are positioned in tubular heater, by nitrogen with volume space velocity 10000h-1
By reactor, with 20 DEG C/min temperature programmings to 500 DEG C of nitriding temperature, and 24h is kept under this condition, obtain nitrogenizing iron material
Material；
Room temperature is cooled to after nitridation reaction is complete, being passed through argon gas prevents nitrided iron from aoxidizing.
It is 32 m that BET, which tests its specific surface area,2/g。
Comparative example 1
After 1mol/L iron nitrate solutions and 2mol/L citric acid solutions uniformly mixing, 90 DEG C are heated to, after keeping 1h,
Product is calcined 2h in 120 DEG C of dry 12h, at 550 DEG C and obtains Fe2O3Powder.
By Fe2O3Powder is positioned in tubular heater, by nitrogen with volume space velocity 6000h-1By reactor, with 10
DEG C/min temperature programmings keep 15h under this condition to 420 DEG C of nitriding temperature, obtain iron nitride material；
Room temperature is cooled to after nitridation reaction is complete, being passed through argon gas prevents nitrided iron from aoxidizing.
It is 12 m that BET, which tests its specific surface area,2/g。
Comparative example 2
4 made metal-organic framework materials of embodiment are positioned in tubular heater, by nitrogen source gas with volume space velocity
6000h-1By reactor, with 10 DEG C/min temperature programmings to 420 DEG C of nitriding temperature, and 15h is kept under this condition, obtain nitrogen
Change iron material；
Room temperature is cooled to after nitridation reaction is complete, being passed through argon gas prevents nitrided iron from aoxidizing.
It is 23m that BET, which tests its specific surface area,2/g。
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (6)
1. a kind of preparation method of the nitrided iron based on metal-organic framework materials, it is characterised in that including step：
Metal-organic framework materials are positioned in tubular heater, by nitrogen source gas with volume space velocity 4000-10000h-1Pass through
Tubular heater, with 1-20 DEG C/min temperature programmings to 300-600 DEG C of nitriding temperature, and 10-24h is kept under this condition, lead to
Cross nitridation reaction and obtain iron nitride material；
Room temperature is cooled to after nitridation reaction is complete, being passed through inert gas prevents nitrided iron from aoxidizing, wherein, the nitrogen source gas are ammonia
Gas and/or nitrogen；
Wherein, the preparation method of the metal-organic framework materials is：The raw material of preparation include molysite, more bidentate organic compounds,
DMF, it is according to mol ratio (0.5-2):(0.5-2):(200-350), the raw material of preparation also include chlorination
Copper, copper chloride and iron chloride mol ratio are 0.1-1：1；
The raw material of preparation is put into the reactor for being lined with polytetrafluoroethylene (PTFE)；10-30h is reacted at a temperature of 100-200 DEG C, is obtained
Metal-organic framework materials containing iron；The molysite is iron chloride, ferric nitrate, ferric sulfate, ferric acetate, ferric carbonate or its hydration
The one or more of thing.
2. preparation method as claimed in claim 1, it is characterised in that the metal-organic framework materials be organic compound and
Metallic atom forms porous crystalline material by coordinate bond, and the organic compound is that bidentate, three tooth dicarboxylic acids or polycarboxylic acid are matched somebody with somebody
One kind in body compound and its derivative；Described metal-organic framework materials be iron content metal-organic framework materials, phase
50% is more than to crystallinity, BET specific surface area 1000-5000m2/g。
3. preparation method as claimed in claim 2, it is characterised in that the organic compound is selected from terephthalic acid (TPA), isophthalic
Dioctyl phthalate, trimesic acid, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, fumaric acid, 2- hydroxyls are to benzene two
One kind in formic acid.
4. preparation method as claimed in claim 2, it is characterised in that the relative crystallinity of described metal-organic framework materials
For 80-95%；BET specific surface area is 2000-3000m2/g。
5. preparation method as claimed in claim 1, it is characterised in that also doped with other in the metal-organic framework materials
Metallic atom, the atom of II-III main group and transition metal of other the described metallic atoms in the periodic table of elements, specifically
For the one or more in copper, zinc, aluminium, calcium, titanium, magnesium, nickle atom.
6. preparation method according to claim 1, it is characterised in that the nitriding temperature is 350-500 DEG C, the inertia
Gas is the one or more in helium, argon gas, Krypton.
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| CN108147959A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of functionalized modification ferrous metal organic framework materials and preparation method thereof |
| CN110589894A (en) * | 2019-09-17 | 2019-12-20 | 北京化工大学 | Preparation method of hollow metal oxide nano material |
| CN112038082A (en) * | 2020-08-28 | 2020-12-04 | 常州古金磁性材料科技有限公司 | Method for preparing iron-nitrogen magnetic material by using high-pressure nitriding method |
| CN112058299B (en) * | 2020-09-10 | 2021-11-16 | 中山大学 | Multi-shell nickel-based nitride nano composite material and preparation method and application thereof |
| CN114068964B (en) * | 2021-11-18 | 2022-11-15 | 天津大学 | ZIF-L derived monodisperse FeNx active site loaded hierarchical porous carbon and preparation method and application thereof |
| CN114554819B (en) * | 2022-02-25 | 2024-05-03 | 山东大学 | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof |
| CN116550356B (en) * | 2023-01-10 | 2024-01-23 | 安徽大学 | High-conversion-rate high-purity Fe2N catalyst and preparation method and application thereof |
| CN115991458B (en) * | 2023-02-27 | 2024-05-31 | 中国科学院生态环境研究中心 | Defect-rich spherical boron nitride assembled by nano-flakes as well as preparation method and application thereof |
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Effective date of registration: 20230822 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |