CN105621377A - Preparation method of iron nitride based on metal organic framework material - Google Patents
Preparation method of iron nitride based on metal organic framework material Download PDFInfo
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Abstract
The invention provides a preparation method of iron nitride based on a metal organic framework material, and is characterized in that the preparation method comprises the steps: placing a metal organic framework material in a tubular heating furnace, carrying out program heating at a speed of 1-20 DEG C/min to a nitridation temperature of 300-600 DEG C, keeping for 10-24 h under the condition, and thus obtaining an iron nitride material through a nitridation reaction; and after completion of the nitridation reaction, cooling to room temperature, and introducing inert gas to prevent oxidation of iron nitride, wherein the nitrogen-source gas is ammonia and/or nitrogen gas. According to the method, the metal organic framework material or a molding body thereof is used as an iron source, and higher specific surface area, pore volume and metal content of the metal organic framework material or the molding body thereof can well control performance of the iron nitride material; the metal organic framework material or the molding body thereof provides a rich pore system, and the nitrogen-source gas can fully make contact with metal atoms, so as to be conducive to transformation of the nano iron nitride material and improve the yield and quality of the iron nitride.
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 ferrum.
Background technology
Metal nitride, character with covalent compound, ionic crystals and three kinds of materials of metal, there are special physicochemical properties, especially there is the metal nitride of high-specific surface area, in multiple catalytic reaction such as ammonia synthesis, hydrodesulfurization, denitrogenation, there is very strong precious metal catalyst attribute and paid close attention to widely. Nitrided iron is a kind of good magnetic material, has good application prospect in magnetic fluid, is also a kind of good catalysis material simultaneously, has good catalysis activity in F-T synthesis and ammonia synthesis reaction.
Prior art is prepared the method for nitrided iron and is mostly using inorganic molysite or oxide as source of iron, nitrided iron is prepared by methods such as reduction nitridation method, vapour deposition process, sol-gel process, high temperature full-boiled process, but the nitrided iron specific grain surface of said method synthesis is long-pending less, limits its application in catalysis Yu field of magnetic material.
The preparation method that patent CN103145106 provides a kind of nitrided iron nano-powder, the method is with hydrated ferric oxide. for source of iron, prepare synthesis when ammonia atmosphere mesohigh and nitrogenize iron powder body, but the method operation pressure is higher, being unfavorable for the safe operation of device, the nitrided iron powder specific-surface area detection that additionally prepared by the method is relatively low.
Different preparation methoies depends on the best serviceability of synthetic material, and in the synthesis of metal nitride, the selection of source of iron is most important. The present invention adopts metal-organic framework materials to provide source of iron as presoma first, and the temperature programmed nitridation method preparation of employing has synthesized the iron nitride material of high-specific surface area.
Summary of the invention
In order to overcome above-mentioned technical problem, it is an object of the invention to, it is provided that the preparation method of a kind of nitrided iron based on metal-organic framework materials.
The technical scheme 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 is positioned in tubular heater, by nitrogen source gas with volume space velocity 4000-10000h-1By reactor, with 1-20 DEG C/min temperature programming to nitriding temperature 300-600 DEG C, and keep 10-24h under this condition, obtain iron nitride material; Being cooled to room temperature after nitridation reaction is complete, pass into noble gas and prevent nitrided iron from aoxidizing, wherein, described nitrogen source gas is ammonia and/or nitrogen.
Wherein, described metal-organic framework materials is organic compound and metallic atom forms porous crystalline material by coordinate bond, described organic compound is the one in bidentate, three tooth dicarboxylic acids or polycarboxylic acid ligand compound and derivant thereof, preferably be selected from p-phthalic acid, M-phthalic acid, trimesic acid, 1,4-naphthalene dicarboxylic acids, 1, one in 5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, fumaric acid, 2-hydroxyterephthalic acid.
Iron compound is one or more of iron chloride, ferric nitrate, iron sulfate, iron acetate, ferric carbonate or its hydrate, it is preferred to ferric nitrate, iron sulfate, more preferably iron chloride.
Wherein, described metal-organic framework materials is the metal-organic framework materials of iron content, and relative crystallinity is more than 50%, it is preferable that more than 80%; BET specific surface area is 1000-5000m2/ g, it is preferred to 2000-3000m2/g��
Further, also doped with other metallic atoms in described metal-organic framework materials, other metallic atoms described are selected from the atom of II-III main group in the periodic table of elements and transition metal, are specially one or more in copper, zinc, aluminum, calcium, titanium, magnesium, nickle atom.
Wherein, in the methods of the invention also doped with other metallic atoms in metal-organic framework materials, other metallic atoms described are copper, zinc, aluminum, calcium, titanium, magnesium, the Bromide of nickel, chlorate, sulfate, nitrate, acetate, carbonate, it is preferred to copper chloride.
Preferably, described nitriding temperature means above the decomposition temperature of metal-organic framework materials, specifically 350-500 DEG C, and described noble gas is one or more in helium, argon, Krypton.
The preparation method of described metal-organic framework materials can adopt technological means known in the art, as a currently preferred technical scheme, the preparation method of described metal-organic framework materials is by iron salt, many bidentate organic compounds, N, dinethylformamide, according to mol ratio (0.5-2): (0.5-2): (200-350), put in the reactor being lined with politef, at 100-200 DEG C of temperature, react 10-30h, obtain the metal-organic framework materials containing ferrum; Described iron salt is one or more of iron chloride, ferric nitrate, iron sulfate, iron acetate, ferric carbonate or its hydrate.
Wherein, raw material prepared by described metal-organic framework materials also includes the soluble salt of other metallic atoms, and the soluble salt of other metallic atoms described and iron chloride mol ratio are 0.1-1:1. The soluble salt of other metallic atoms described is copper, zinc, aluminum, calcium, titanium, magnesium, the Bromide of nickel, chlorate, sulfate, nitrate, acetate, carbonate, it is preferred to copper chloride.
Compared with prior art, the inventive method has the advantage that
1. utilizing metallic organic framework material or its molded body as source of iron in the inventive method, its higher specific surface area, pore volume and tenor can control the performance of iron nitride material preferably;
2. metallic organic framework material or its molded body provide abundant pore canal system, and nitrogen source gas can contact with metallic atom fully, is conducive to the conversion of nano silicon nitride iron material, improve productivity and the quality of nitrided iron;
3. preparation adds a certain amount of metal ion containing in the MOF materials process of ferrum, improves the heat-resistant stability of material, improves nitrided iron crystal structure. The inventive method is simple to operate, practical, has higher actual application value.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the MOF material of embodiment of the present invention 1-4 synthesis.
Fig. 2 is the XRD figure of the iron nitride material of embodiment of the present invention 5-7 synthesis.
Fig. 3 is the SEM figure of the MOF material of the embodiment of the present invention 3 synthesis.
Fig. 4 is the SEM figure of the iron nitride material of the embodiment of the present invention 6 synthesis.
Detailed description of the invention
Following example are used for illustrating 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, for the technological means that this area is conventional.
Embodiment 1
By iron chloride, p-phthalic acid, N, dinethylformamide, copper chloride are that 0.5:0.5:200:0.05 puts into and is lined with in teflon-lined stainless steel cauldron according to mol ratio, reaction solution reacts 10h at 100 DEG C of temperature, namely the MOF material containing ferrum is obtained, relative crystallinity is 87%, and it is 1045m that BET tests its specific surface area2/g��
Embodiment 2
By iron chloride, p-phthalic acid, N, dinethylformamide, copper chloride are that 2:2:350:0.2 puts into and is lined with in teflon-lined stainless steel cauldron according to mol ratio, reaction solution reacts 30h at 200 DEG C of temperature, namely the MOF material containing ferrum is obtained, relative crystallinity is 90%, and it is 1186m that BET tests its specific surface area2/g��
Embodiment 3
By iron chloride, p-phthalic acid, N, dinethylformamide, copper chloride are that 1:0.8:280:0.07 puts into and is lined with in teflon-lined stainless steel cauldron according to mol ratio, reaction solution reacts 24h at 150 DEG C of temperature, namely the MOF material containing ferrum is obtained, relative crystallinity is 98%, and it is 1268m that BET tests its specific surface area2/ g, SEM photograph is Fig. 3 such as.
Embodiment 4
By iron chloride, p-phthalic acid, N, dinethylformamide is that 1:0.8:280 puts into and is lined with in teflon-lined stainless steel cauldron according to mol ratio, and reaction solution reacts 24h at 150 DEG C of temperature, namely obtains the MOF material containing ferrum, relative crystallinity is 95%, and BET is 1124m2/g��
Embodiment 5
The made metal-organic framework materials of embodiment 3 is positioned in tubular heater, by nitrogen source gas with volume space velocity 4000h-1By reactor, with 1 DEG C/min temperature programming to nitriding temperature 350 DEG C, and keep 10h under this condition, obtain iron nitride material;
It is cooled to room temperature after nitridation reaction is complete, passes into argon and prevent nitrided iron from aoxidizing.
It is 35m that BET tests its specific surface area2/g��
Embodiment 6
The made metal-organic framework materials of embodiment 3 is positioned in tubular heater, by nitrogen source gas with volume space velocity 6000h-1By reactor, with 10 DEG C/min temperature programming to nitriding temperature 420 DEG C, and keep 15h under this condition, obtain iron nitride material;
It is cooled to room temperature after nitridation reaction is complete, passes into argon and prevent nitrided iron from aoxidizing.
It is 41m that the SEM of the product obtained such as Fig. 4, BET test its specific surface area2/g��
Embodiment 7
The made metal-organic framework materials of embodiment 3 is positioned in tubular heater, by nitrogen with volume space velocity 10000h-1By reactor, with 20 DEG C/min temperature programming to nitriding temperature 500 DEG C, and keep 24h under this condition, obtain iron nitride material;
It is cooled to room temperature after nitridation reaction is complete, passes into argon and prevent nitrided iron from aoxidizing.
It is 32m that BET tests its specific surface area2/g��
Comparative example 1
After 1mol/L iron nitrate solution and 2mol/L citric acid solution Homogeneous phase mixing, heating is to 90 DEG C, and after keeping 1h, product, at 120 DEG C of dry 12h, obtains Fe at 550 DEG C of roasting 2h2O3Powder.
By Fe2O3Powder is positioned in tubular heater, by nitrogen with volume space velocity 6000h-1By reactor, with 10 DEG C/min temperature programming to nitriding temperature 420 DEG C, and keep 15h under this condition, obtain iron nitride material;
It is cooled to room temperature after nitridation reaction is complete, passes into argon and prevent nitrided iron from aoxidizing.
It is 12m that BET tests its specific surface area2/g��
Comparative example 2
The made metal-organic framework materials of embodiment 4 is positioned in tubular heater, by nitrogen source gas with volume space velocity 6000h-1By reactor, with 10 DEG C/min temperature programming to nitriding temperature 420 DEG C, and keep 15h under this condition, obtain iron nitride material;
It is cooled to room temperature after nitridation reaction is complete, passes into argon and prevent nitrided iron from aoxidizing.
It is 23m that BET tests its specific surface area2/g��
Although, above the present invention is described in detail with a general description of the specific embodiments, but on basis of the present invention, it is possible to it is made some modifications or improvements, and this will be apparent to those skilled in the art. Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (7)
1. the preparation method based on the nitrided iron of metal-organic framework materials, it is characterised in that include step:
Metal-organic framework materials is positioned in tubular heater, by nitrogen source gas with volume space velocity 4000-10000h-1By tubular heater, with 1-20 DEG C/min temperature programming to nitriding temperature 300-600 DEG C, and keep 10-24h under this condition, obtain iron nitride material by nitridation reaction;
Being cooled to room temperature after nitridation reaction is complete, pass into noble gas and prevent nitrided iron from aoxidizing, wherein, described nitrogen source gas is ammonia and/or nitrogen.
2. preparation method as claimed in claim 1, it is characterized in that, described metal-organic framework materials is organic compound and metallic atom forms porous crystalline material by coordinate bond, described organic compound is the one in bidentate, three tooth dicarboxylic acids or polycarboxylic acid ligand compound and derivant thereof, preferably be selected from p-phthalic acid, M-phthalic acid, trimesic acid, 1, one in 4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, fumaric acid, 2-hydroxyterephthalic acid; Described metal-organic framework materials is the metal-organic framework materials of iron content, and relative crystallinity is more than 50%, and BET specific surface area is 1000-5000m2/g��
3. preparation method as claimed in claim 2, it is characterised in that the relative crystallinity of described metal-organic framework materials is 80-95%; BET specific surface area is 2000-3000m2/g��
4. preparation method as claimed in claim 1, it is characterized in that, also doped with other metallic atoms in described metal-organic framework materials, other metallic atoms described are selected from the atom of II-III main group in the periodic table of elements and transition metal, are specially one or more in copper, zinc, aluminum, calcium, titanium, magnesium, nickle atom.
5. preparation method according to claim 1, it is characterised in that described nitriding temperature is 350-500 DEG C, described noble gas is one or more in helium, argon, Krypton.
6. according to the arbitrary described preparation method of claim 1-5, it is characterized in that, the preparation method of described metal-organic framework materials is: by iron salt, many bidentate organic compounds, N, dinethylformamide, according to mol ratio (0.5-2): (0.5-2): (200-350), put in the reactor being lined with politef, at 100-200 DEG C of temperature, react 10-30h, obtain the metal-organic framework materials containing ferrum; Described iron salt is one or more of iron chloride, ferric nitrate, iron sulfate, iron acetate, ferric carbonate or its hydrate.
7. preparation method according to claim 6, it is characterised in that raw material prepared by described metal-organic framework materials also includes the soluble salt of other metallic atoms, and the soluble salt of other metallic atoms described and iron chloride mol ratio are 0.1-1:1; The soluble salt of other metallic atoms described is copper, zinc, aluminum, calcium, titanium, magnesium, the Bromide of nickel, chlorate, sulfate, nitrate, acetate, carbonate, it is preferred to copper chloride.
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Cited By (8)
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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 |
| CN112058299A (en) * | 2020-09-10 | 2020-12-11 | 中山大学 | Multi-shell nickel-based nitride nano composite material and preparation method and application thereof |
| CN114068964A (en) * | 2021-11-18 | 2022-02-18 | 天津大学 | ZIF-L derived monodisperse FeNx active site loaded hierarchical porous carbon and preparation method and application thereof |
| CN114554819A (en) * | 2022-02-25 | 2022-05-27 | 山东大学 | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof |
| CN115991458A (en) * | 2023-02-27 | 2023-04-21 | 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 |
| CN116550356A (en) * | 2023-01-10 | 2023-08-08 | 安徽大学 | High-conversion-rate high-purity Fe2N catalyst and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN112058299A (en) * | 2020-09-10 | 2020-12-11 | 中山大学 | Multi-shell nickel-based nitride nano composite material and preparation method and application thereof |
| CN114068964A (en) * | 2021-11-18 | 2022-02-18 | 天津大学 | ZIF-L derived monodisperse FeNx active site loaded hierarchical porous carbon and preparation method and application thereof |
| CN114554819A (en) * | 2022-02-25 | 2022-05-27 | 山东大学 | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof |
| CN116550356A (en) * | 2023-01-10 | 2023-08-08 | 安徽大学 | High-conversion-rate high-purity Fe2N catalyst and preparation method and application 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 |
| CN115991458A (en) * | 2023-02-27 | 2023-04-21 | 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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