CN112893858B - Preparation method of nickel-carbon-based material - Google Patents

Preparation method of nickel-carbon-based material Download PDF

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CN112893858B
CN112893858B CN201911134141.1A CN201911134141A CN112893858B CN 112893858 B CN112893858 B CN 112893858B CN 201911134141 A CN201911134141 A CN 201911134141A CN 112893858 B CN112893858 B CN 112893858B
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nickel
acid
carbon
mother liquor
based material
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CN112893858A (en
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王峰
张健
王业红
张志鑫
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30

Abstract

The invention relates to a preparation method of a nickel-carbon-based material. The preparation method of the nickel-carbon-based material comprises the following steps: respectively dispersing soluble nickel salt and binary organic acid in an amide organic solvent to prepare mother liquor with a certain concentration. Under the condition of stirring, adding Ni2+(iii) 20:1 to 1:10 of organic acid radical, and mixing the mother liquor. Stirring for 0.5-10 h, transferring to a pressure container, and standing for 12-72 h at 200-300 ℃. Separating the precipitate, washing with alcohol, and vacuum drying to obtain the nickel-carbon-based material. The material has high thermal stability and a specific surface area as high as 234m2The catalyst is expected to be applied to the fields of electrodes, magnetism, catalysis and other materials.

Description

Preparation method of nickel-carbon-based material
Technical Field
The invention belongs to the technical field of preparation of carbon-based materials, and particularly relates to preparation of a nickel-carbon-based material.
Background
Nickel is a transition metal element with a large content in the earth crust and is a commonly used catalytic and magnetic material. Since the catalytic hydrogenation of nickel-based catalysts was achieved by Normann in 1902, the research of nickel-based materials has attracted the attention of researchers. Particularly, in recent years, research on nickel-based materials, including preparation methods and application fields thereof, has been remarkably developed, and novel nickel-based materials have been developed and widely used for hydrogenation of carbonyl compounds, magnetic materials, and the like.
Patent CN105289614A discloses the preparation of a nickel-carbon catalyst for hydrogen production, which is prepared by preparing Ni-MOF material, and then obtaining nickel-carbon material through pyrolysis and carbonization. Patent CN105436498A discloses a preparation method of nickel-carbon nano composite microspheres, which comprises preparing nickel hydroxide, dehydroxylating, mixing with pyrrole, pyridine or acrylonitrile, and synthesizing nickel-carbon nano composite microspheres under high temperature and sealing conditions. Patent CN104492442A discloses a nickel oxide carbon nanotube catalyst, which is obtained by coprecipitation of carbon nanotubes treated with poly (diallyldimethylammonium chloride) and nickel chloride. Patent CN108314007A discloses a carbon nanotube material filled with elemental nickel. Patent CN102303126A discloses a flower-like nickel-carbon nanotube composite material. Although the synthesis of the nickel-carbon-based material has made a certain progress, the synthesis process needs a plurality of steps, and the material structure is difficult to control. Therefore, it is necessary to develop a method for preparing a nickel-carbon material with simple operation and easily controlled structure.
Disclosure of Invention
The invention has the significance of developing a synthesis method of the nickel-carbon-based material, having simple preparation process, large specific surface area and high stability of the material, and being hopeful to be applied to the fields of materials such as electrodes, magnetism, catalysis and the like.
The nickel-carbon material is prepared by the following scheme: respectively dispersing soluble nickel salt and binary organic acid in an amide organic solvent to prepare mother liquor with a certain concentration; wherein the Ni ion concentration is: ni2+: 0.01-2.5 mol/L, wherein the concentration of organic acid radical ions in the binary organic acid mother liquor is as follows: -COOH is 0.01-2.5 mol/L; under the condition of stirring, adding Ni2+The mol ratio of the/COOH is 20: 1-1: 10, the mother liquor is mixed, stirred for 0.5-10 h, transferred to a synthesis kettle, and kept stand for 12-72 h at the temperature of 200-300 ℃; separating the precipitate, washing with alcohol, and vacuum drying to obtain the nickel-carbon-based material. The nickel-based compound is one or more of nickel nitrate, nickel chloride and nickel acetate; the binary organic acid is: one or more of oxalic acid, malonic acid, succinic acid, suberic acid, 2, 5-furandicarboxylic acid, 2, 5-pyridinedicarboxylic acid, terephthalic acid and isophthalic acid. The amide organic solvent is: one or more of formamide, N-methylformamide, N-ethylformamide, N-dimethylformamide and N, N-diethylformamide. The preferred temperatures in the synthesis kettle are: the temperature is 250-300 ℃, and the standing time is as follows: 12h to 24 h. The alcohol used for alcohol washing may be one or both of methanol and ethanol; the temperature of vacuum drying is 80-100 ℃, and the drying time is 12-24 h.
The preparation method of the nickel-carbon material related by the invention takes the synthesis of nickel nitrate hydrate and 2, 5-furandicarboxylic acid in N, N-dimethylformamide as an example, and the principle is as follows: (1) generating a coordination polymer by the coordination of nickel and 2, 5-furandicarboxylic acid; (2) through high-temperature long-time crystallization treatment, the 2, 5-furandicarboxylic acid is gradually deoxidized and carbonized to form a loose structure.
Description of the drawings:
fig. 1 is a scanning electron microscope image of the nickel-carbon material in example 1, which is a porous loose structure.
The specific implementation mode is as follows:
in order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1
14.5g of hydrated nickel nitrate and 18g of terephthalic acid are respectively added into an organic solvent of 400mL of N, N-diethylformamide and 1L N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed and stirred for 8.5h to obtain a mother liquor. Placing the mother liquor into a reaction bottle, sealing, reacting at 240 deg.C for 48 hr, centrifuging, washing with ethanol for three times, and vacuum drying at 100 deg.C to obtain nickel-carbon material with reduced nickel and particle diameter of about 10nm, wherein the nickel-carbon material is porous material with specific surface area of 234m2/g。
Example 2
28.6g of nickel chloride hexahydrate and 9.96g of isophthalic acid are respectively added into an organic solvent of 240mL of N-ethylformamide and 60mL of N-ethylformamide for dissolution; after dissolving, mixing the two solutions, and stirring for 8h to obtain mother liquor. Placing the mother liquor into a reaction bottle, sealing, reacting at 250 deg.C for 60 hr, centrifuging, washing with methanol for three times, vacuum drying at 80 deg.C to obtain nickel-carbon material with reduced nickel and particle size of about 20nm, wherein the nickel-carbon material is porous material with specific surface area of 188m2/g。
Example 3
6.26g of hydrated nickel nitrate and 45g of 2, 5-furandicarboxylic acid are respectively added into an organic solvent of 1L N, N-diethylformamide and 400mL of N, N-diethylformamide for dissolution; after dissolving, mixing the two solutions, and stirring for 3h to obtain mother liquor. Placing the mother liquor into a reaction bottle, sealing, reacting at 300 deg.C for 72 hr, centrifuging, washing with ethanol for three times, and vacuum drying at 100 deg.C to obtain nickel-carbon material with reduced nickelThe particle size is about 15nm, the nickel-carbon material is a porous material, and the specific surface area of the nickel-carbon material is 211m2/g。
Example 4
96g of nickel acetate tetrahydrate and 23.9g of 2, 5-furandicarboxylic acid were dispersed in 2.5L of 2L N, N-dimethylformamide, respectively, to prepare a mother liquor. Mixing the above mother solutions, reacting for 2.5h, transferring to a pressure vessel, and standing at 240 deg.C for 72 h. Separating the precipitate, washing with ethanol for three times, vacuum drying at 80 deg.C to obtain the nickel-carbon catalyst, wherein the nickel is reduced, particle size is about 23nm, the nickel-carbon material is porous material, and specific surface area is 178m2/g。
Example 5
14.5g of nickel acetate tetrahydrate and 18g of terephthalic acid are respectively added into an organic solvent of 400mL of N, N-diethylformamide and 5L N, N-diethylformamide for dissolution; after dissolution, the two solutions were mixed and stirred for 8.5h to obtain a mother liquor. Putting the mother liquor into a reaction bottle, sealing, reacting at 300 deg.C for 72h, taking out, centrifuging, washing with methanol for three times, vacuum drying at 100 deg.C to obtain nickel-based material with reduced nickel and particle size of 28nm, wherein the nickel-carbon material is porous material with specific surface area of 178m2/g。
Example 6
28.6g of nickel chloride hexahydrate and 9.96g of isophthalic acid are respectively added into an organic solvent of 240mL of N-ethylformamide and 60mL of N-ethylformamide for dissolution; after dissolving, mixing the two solutions, and stirring for 8h to obtain mother liquor. Putting the mother liquor into a reaction bottle, sealing, reacting at 250 deg.C for 48h, centrifuging, washing with methanol for three times, vacuum drying at 90 deg.C to obtain nickel-carbon-based material with reduced nickel and particle size of about 30nm, wherein the nickel-carbon-based material is porous material with specific surface of 153m2/g。
Example 7
Adding 62.6g of nickel chloride hexahydrate and 4.5g of 2, 5-furandicarboxylic acid into an organic solvent of 10L N, N-diethylformamide and 400mL of N, N-diethylformamide respectively for dissolving; after dissolution, the two solutions are mixed,stirring for 3h to obtain mother liquor. Putting the mother liquor into a reaction bottle, sealing, reacting at 300 deg.C for 60h, taking out, centrifuging, washing with methanol for three times, vacuum drying at 85 deg.C to obtain nickel-carbon-based material with reduced nickel and particle size of 15nm, wherein the nickel-carbon-based material is porous material with specific surface area of 198m2/g。
Example 8
96g of nickel acetate tetrahydrate and 23.9g of adipic acid were dispersed in 2.5L of 2L N, N-dimethylformamide to prepare a mother liquor. Mixing the above mother solutions, reacting for 2.5 hr, transferring to pressure vessel, and standing at 280 deg.C for 48 hr. Separating the precipitate, washing with ethanol for three times, and vacuum drying at 100 deg.C to obtain the nickel-carbon material, wherein the nickel is reduced and has particle diameter of about 25nm, and the nickel-carbon material is porous material with specific surface of 154m2/g。

Claims (6)

1. A preparation method of a nickel-carbon-based material is characterized by comprising the following steps: respectively dispersing soluble nickel salt and binary organic acid in an amide organic solvent to prepare a mother solution;
the Ni ion concentration in the soluble nickel salt mother liquor is as follows: ni2+：0.01 ~ 2.5 mol/L；
The concentration of organic acid radical ions in the binary organic acid mother liquor is as follows: -COOH is 0.01-2.5 mol/L;
under the condition of stirring, adding Ni2+The mol ratio of the/COOH is 20: 1-1: 10, the mother liquor is mixed, stirred for 0.5-10 h, transferred to a synthesis kettle, and the mixture is subjected to reaction at 210 DEG oC ~ 300 oStanding for 12-72 h at the temperature of C; separating the precipitate, washing with alcohol, and vacuum drying to obtain the nickel-carbon-based material.
2. The method of claim 1, wherein:
the nickel-based compound is one or more of nickel nitrate, nickel chloride and nickel acetate;
the binary organic acid is: one or more of oxalic acid, malonic acid, succinic acid, suberic acid, 2, 5-furandicarboxylic acid, 2, 5-pyridinedicarboxylic acid, terephthalic acid and isophthalic acid.
3. The method of claim 1, wherein:
the amide organic solvent is: one or more of formamide, N-methylformamide, N-ethylformamide, N-dimethylformamide and N, N-diethylformamide.
4. The method of claim 1, wherein:
the preferred temperatures in the synthesis kettle are: 250oC ~ 300 oC, standing for: 12-24 h.
5. The method of claim 1, wherein:
the alcohol used for alcohol washing is one or two of methanol and ethanol;
the temperature of vacuum drying is 80 deg.CoC ~ 100 oAnd C, drying for 12-24 hours.
6. The method of claim 1, wherein:
the Ni ion concentration is: 0.1-1.0 mol/L;
the concentration of the organic acid radical ions is as follows: 0.1-1.0 mol/L;
under the condition of stirring, adding Ni2+And (4) mixing the mother liquor with the molar ratio of 4: 1-1: 4, stirring for 1-4 h, and transferring to a synthesis kettle.
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