CN113649045A - Modified titanium nitride nanotube with Ni-MOF as precursor and preparation method and application thereof - Google Patents

Modified titanium nitride nanotube with Ni-MOF as precursor and preparation method and application thereof Download PDF

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CN113649045A
CN113649045A CN202110946588.XA CN202110946588A CN113649045A CN 113649045 A CN113649045 A CN 113649045A CN 202110946588 A CN202110946588 A CN 202110946588A CN 113649045 A CN113649045 A CN 113649045A
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titanium nitride
precursor
mof
nitride nanotube
modified titanium
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CN113649045B (en
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谭杰
周秋曼
廖美妃
王鑫江
潘湛昌
胡光辉
魏志钢
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Guangdong University of Technology
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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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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
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    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
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Abstract

The invention belongs to the field of nano material preparation, and discloses a modified titanium nitride nanotube taking Ni-MOF as a precursor, and a preparation method and application thereof. Dissolving a nickel source and an organic ligand in an organic solvent, filtering, drying, mixing the precursor of the obtained Ni-MOF with a titanium source dissolved in the solvent, reacting at 100-200 ℃, cooling, filtering, washing and drying after the reaction is finished, mixing the obtained intermediate product and a carbon source to obtain a precursor after the reaction is subjected to air firing at 250-550 ℃, and nitriding the precursor at 600-900 ℃ to obtain the nickel-doped titanium nitride nanotube, namely the modified titanium nitride nanotube. The nickel-doped titanium nitride nanotube has a coral-like tubular structure and a large specific surface area; good conductivity, stability and the like; the method is easy and safe to operate, low in cost, capable of realizing large-scale production and widely applied to the field of catalytic carriers.

Description

Modified titanium nitride nanotube with Ni-MOF as precursor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a modified titanium nitride nanotube taking Ni-MOF as a precursor, and a preparation method and application thereof.
Background
In recent years, transition metal nitrides (VN, RuN, BN, TiN and CrN) represent a class of multifunctional materials with excellent thermochemical and electrochemical properties. Among transition metal nitrides, titanium nitride (TiN) is a material having a high melting point, high hardness, high temperature chemical stability, and excellent thermal and electrical conductivity, and belongs to a face-centered cubic structure. TiN materials are widely applied to metal ceramics, catalyst carriers, energy-saving coatings, semiconductor materials, electrode materials and the like. The TiN with the nanotube structure has larger specific surface area and specific pore volume, so that a complex and rapid charge transfer network can be constructed, the electron transfer capability is further improved, and the application value of the TiN in the electrochemical field is favorably realized.
Metal Organic Frameworks (MOFs), also known as porous coordination polymers, are a class of crystalline porous materials composed of organic ligands and metal ions/clusters. MOFs have found widespread use in many fields due to their unique characteristics, including structural diversity, customizability, high surface area, etc. Patent CN 106770544a describes a synthesis method of Ni-MOF ultrathin nanobelts, which have fast electrochemical response and excellent electrochemical stability and can be used for electrochemical sensing. The Ni-MOF nanobelt has a large specific surface area, is particularly sensitive to surface adsorption, and can be applied to the fields of sensors and the like because electrons of the Ni-MOF nanobelt are rapidly transferred and the resistance of the Ni-MOF nanobelt is changed due to the change of external environments (such as temperature, humidity, concentration and other factors). Patent CN 109174188B introduces a preparation method of a heteroatom-doped Ni-MOF composite electrocatalyst, and the heteroatom is used for regulating and controlling the charge density of adjacent carbon atoms to form rich active sites on the surface of the prepared composite electrocatalyst, thereby improving the electrocatalytic activity of the material. CN 103464784B discloses a preparation method of carbon-supported nano nickel. Dissolving nickel salt in an organic solvent, adding an organic ligand to obtain a mixed solution, and transferring the mixed solution into a high-pressure reaction kettle to perform high-temperature reaction; filtering and drying to obtain the nickel-containing organic framework compound. And finally, placing the nickel-containing organic framework compound in a tubular furnace, and calcining the nickel-containing organic framework compound at a high temperature by using inert gas to obtain the carbon-supported nano nickel. The process has the advantages of low cost, simple preparation process, easy control of reaction, regular appearance of the obtained product and the like. CN110504110A discloses a method for preparing Ni-MOF by using a polypyridyl metal organic framework. Mixing nickel-based metal and two organic ligands, adding the mixture into an aqueous solution, uniformly mixing, and then transferring the solution into a reaction kettle for high-temperature reaction to prepare the Ni-MOF. The Ni-MOF has the advantages of high specific capacitance, good cycling stability, long service life, high reaction response speed and the like, and can be used as a material for preparing a super capacitor. The prior art mainly has the following problems: (1) the preparation process needs a hard template or a surfactant, so that the problems of difficult separation, low purity, uneven dispersion and the like of the nano material are easily caused; (2) the prepared nano material mainly takes carbon as a framework, partial depression is easily formed in the preparation process, the chemical property of the nano material is not stable enough, the corrosion resistance is poor, and the nano material is easy to corrode under an acidic condition; (3) the prepared nano material has no regular morphology and the controllability of the particle size is not high.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention provides a preparation method of a modified titanium nitride nanotube taking Ni-MOF as a precursor. The method adopts a nickel metal organic framework and a titanium nitride composite material as a carrier to prepare the titanium nitride nanotube with a special coral-like tubular shape, and the titanium nitride nanotube has a large specific surface area, high conductivity and good electrochemical stability.
The invention also aims to provide the modified titanium nitride nanotube prepared by the method.
Still another object of the present invention is to provide the use of the above-mentioned modified titanium nitride nanotubes.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a modified titanium nitride nanotube taking Ni-MOF as a precursor comprises the following specific steps:
s1, dissolving a nickel source and an organic ligand in an organic solvent, filtering and drying to obtain a precursor of Ni-MOF;
s2, mixing a precursor of the Ni-MOF with a titanium source dissolved in a solvent, reacting at 100-200 ℃, cooling, filtering, washing, drying after the reaction is finished, and performing air-firing at 250-550 ℃ to obtain an intermediate product;
and S3, mixing the intermediate product and a carbon source to obtain a precursor, and performing nitridation treatment on the precursor at the temperature of 600-900 ℃ to obtain the nickel-doped titanium nitride nanotube, namely the modified titanium nitride nanotube.
Preferably, the nickel source in step S1 is one or more of nickel sulfate, nickel acetate, nickel nitrate or nickel chloride; the organic ligand is more than one of naphthalene tetracarboxylic anhydride, 2, 5-dihydroxy terephthalic acid, trimesic acid or terephthalic acid; the organic solvent is more than one of methanol, ethanol, formaldehyde, acetaldehyde, DMF or water; the mass ratio of the nickel source to the organic ligand is (1-10) to 1; the volume ratio of the total mass of the nickel source and the organic ligand to the organic solvent is (0.01-0.1) g:1 mL.
Preferably, the dosage ratio of the precursor of the Ni-MOF, the titanium source and the solvent in the step S2 is (0.1-1) g, (1-4) g, (50-100) mL.
Preferably, in step S2, the titanium source is one or more of titanyl sulfate, tetraethyl titanate, tetrabutyl titanate, and tetrapentyl titanate; the solvent is any two or more of methanol, ethanol, isopropanol, propylene glycol, glycerol or diethyl ether.
Preferably, the hydrothermal reaction time in the step S2 is 5-20 h; the drying temperature is 60-80 ℃, and the drying time is 4-12 h; the empty burning time is 3-10 h.
Preferably, the carbon source in step S3 is one or more of melamine, dicyandiamide, and dopamine hydrochloride; the mass ratio of the intermediate product to the carbon source is 1 (5-15).
Preferably, the calcination time in step S3 is 4-8 h.
A modified titanium nitride nanotube is prepared by the method.
Preferably, the modified titanium nitride nanotube has a coral-like tubular structure, and the average diameter of the modified titanium nitride nanotube is 50-200 nm.
The modified titanium nitride nanotube is applied to the field of catalytic carriers.
Compared with the prior art, the invention has the following beneficial effects:
1. the modified titanium nitride nanotube taking Ni-MOF as the precursor has a coral-like tubular shape and a large specific surface area (300-550 m)2/g), good conductivity and good electrochemical stability.
2. The method of the invention has the advantages of simple equipment requirement, simple and convenient operation, safety, low cost and contribution to large-scale production. Is expected to be widely applied in the field of catalytic carriers.
Drawings
FIG. 1 shows the results of electrochemical testing of Ni/TiN NTs prepared in example 3.
FIG. 2 is an XRD spectrum of Ni/TiN NTs prepared in example 3.
FIG. 3 is an SEM photograph of the Ni/TiN NTs prepared in example 3.
FIG. 4 is an SEM photograph of the Ni/TiN NTs prepared in example 5.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Weighing 2.0g of nickel chloride and 0.5g of naphthalene tetracarboxylic anhydride, dissolving in 60mL of ethanol, uniformly mixing, transferring to 100mL of polytetrafluoroethylene lining, ultrasonically stirring, putting into an oven, preserving heat at 180 ℃ for 20h, centrifuging, washing, putting a sample in the oven, and drying at 60 ℃ for 6h to obtain a precursor of Ni-MOF, which is abbreviated as Ni-MOF-1.
Example 2
Weighing 1.2g of nickel acetate and 0.5g of terephthalic acid, dissolving in 100mL of DMF, uniformly mixing, transferring to a 150mL flask, ultrasonically stirring, putting into an oil bath, keeping the temperature at 140 ℃ for 24h, centrifuging, washing, and drying the sample in a drying oven at 60 ℃ for 16h to obtain a precursor of Ni-MOF, which is abbreviated as Ni-MOF-2.
Example 3
1. Weighing 0.5g of Ni-MOF-1 prepared in example 1 and 1.5g of titanyl sulfate, sequentially adding the Ni-MOF-1 and the titanyl sulfate into a 100mL polytetrafluoroethylene lining, adding 25mL of isopropanol and 25mL of diethyl ether into the lining, carrying out ultrasonic treatment for 10min to uniformly mix reactants, and reacting for 12h at 150 ℃; and filtering and washing the reaction kettle when the reaction kettle is naturally cooled to room temperature, and drying the reaction kettle in an oven at the temperature of 60 ℃ for 8 hours. Then, carrying out air-firing for 3h at 500 ℃ to obtain an intermediate product;
2. and (3) mixing the intermediate product with melamine according to the mass ratio of 1: (5-15) fully mixing to obtain a precursor; nitriding the precursor for 5 hours at high temperature in a tube furnace at 700 ℃ to obtain the nickel-doped titanium nitride nanotube (Ni/TiN NTs), namely the modified titanium nitride nanotube which has a coral-like tubular structure and a large specific surface area (300-550 m)2/g)。
FIG. 1 shows the results of electrochemical testing of Ni/TiN NTs prepared in example 3. As can be seen from FIG. 1, after 50 scans, no specific redox peak exists, which indicates that the Ni/TiN NTs have good electrochemical stability. FIG. 2 is an XRD spectrum of Ni/TiN NTs prepared in example 3. As can be seen from FIG. 2, the peak positions of Ni/TiN NTs correspond to TiN standard card PDF #38-1420, and no nickel diffraction peak is observed, because the nickel is added in a small amount. FIG. 3 is an SEM photograph of the Ni/TiN NTs prepared in example 3. As can be seen from FIG. 3, the average diameter of Ni/TiN NTs is 50 to 200 nm.
Example 4
1. 0.8g of Ni-MOF-1 prepared in example 1 and 3.0g of tetrapentyl titanate were weighed and added to a 100mL polytetrafluoroethylene inner liner in this order, and then 25mL of propylene glycol and 25mL of methanol were added to the inner liner, and the reaction mixture was mixed by sonication for 10 min. Reacting for 12 hours at 180 ℃; filtering and washing the reaction kettle when the reaction kettle is naturally cooled to room temperature, and then drying the reaction kettle in a 70 ℃ drying oven for 13 hours; then, carrying out air-firing at 550 ℃ for 2h to obtain an intermediate product;
2. and (3) mixing the intermediate product with dicyandiamide according to the mass ratio of 1: (5-15) fully mixing to obtain a precursor. Nitriding the precursor for 5 hours at high temperature in a tube furnace at 800 ℃ to obtain the Ni-MOF modified titanium nitride nanotube which has a coral-like tubular structure and a large specific surface area (300-550 m)2/g)。
Example 5
1. 0.5g of Ni-MOF-2 prepared in example 2 and 0.5g of tetraethyl titanate were weighed and added to a 100mL polytetrafluoroethylene liner in sequence, and then 25mL of propanol and 25mL of diethyl ether were added to the liner and the mixture was mixed by sonication for 10 min. Reacting for 12 hours at 150 ℃; and filtering and washing the reaction kettle when the reaction kettle is naturally cooled to room temperature, and drying the reaction kettle in an oven at the temperature of 60 ℃ for 15 hours. Then, carrying out air-firing at 500 ℃ for 5 hours to obtain an intermediate product;
2. and (3) mixing the intermediate product with melamine according to the mass ratio of 1: (5-15) fully mixing to obtain a precursor; nitriding the precursor for 5 hours at high temperature in a tube furnace at 700 ℃ to obtain the Ni-MOF modified titanium nitride nanotube which has a coral-like tubular structure and a large specific surface area (300-550 m)2In terms of/g). FIG. 4 is an SEM photograph of the Ni/TiN NTs prepared in example 5. As can be seen from FIG. 4, the average diameter of Ni/TiN NTs is 50 to 200 nm.
Example 6
1. 0.2g of Ni-MOF-2 prepared in example 2 and 3.1g of tetrabutyl titanate are weighed and sequentially added into a 100mL polytetrafluoroethylene lining, 26mL of glycerol and 26mL of methanol are added into the lining, and ultrasonic treatment is carried out for 10min to uniformly mix reactants. Reacting at 130 ℃ for 16h, filtering and washing when the reaction kettle is naturally cooled to room temperature, and drying in an oven at 70 ℃ for 13 h. Then, carrying out air-firing at 550 ℃ for 2h to obtain an intermediate product;
2. mixing the intermediate product with dopamine hydrochlorideThe quantity ratio is 1: (5-15) fully mixing to obtain a precursor; nitriding the precursor for 5 hours at high temperature in a tube furnace at 800 ℃ to obtain the Ni-MOF modified titanium nitride nanotube which has a coral-like tubular structure and a large specific surface area (300-550 m)2/g)。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a modified titanium nitride nanotube taking Ni-MOF as a precursor is characterized by comprising the following specific steps:
s1, dissolving a nickel source and an organic ligand in an organic solvent, filtering and drying to obtain a precursor of Ni-MOF;
s2, mixing a precursor of the Ni-MOF with a titanium source dissolved in a solvent, reacting at 100-200 ℃, cooling, filtering, washing, drying after the reaction is finished, and performing air-firing at 250-550 ℃ to obtain an intermediate product;
and S3, mixing the intermediate product and a carbon source to obtain a precursor, and performing nitridation treatment on the precursor at the temperature of 600-900 ℃ to obtain the nickel-doped titanium nitride nanotube, namely the modified titanium nitride nanotube.
2. The method for preparing the modified titanium nitride nanotube with Ni-MOF as the precursor of claim 1, wherein the nickel source in step S1 is one or more of nickel sulfate, nickel acetate, nickel nitrate or nickel chloride; the organic ligand is more than one of naphthalene tetracarboxylic anhydride, 2, 5-dihydroxy terephthalic acid, trimesic acid or terephthalic acid; the organic solvent is more than one of methanol, ethanol, formaldehyde, acetaldehyde, DMF or water; the mass ratio of the nickel source to the organic ligand is (1-10) to 1; the volume ratio of the total mass of the nickel source and the organic ligand to the organic solvent is (0.01-0.1) g:1 mL.
3. The method for preparing the modified titanium nitride nanotube taking Ni-MOF as the precursor in claim 1, wherein the dosage ratio of the precursor of Ni-MOF, the titanium source and the solvent in step S2 is (0.1-1) g, (1-4) g, (50-100) mL.
4. The method for preparing the modified titanium nitride nanotube taking Ni-MOF as the precursor according to claim 1, wherein the titanium source in step S2 is one or more of titanyl sulfate, tetraethyl titanate, tetrabutyl titanate and tetrapentyl titanate; the solvent is any two or more of methanol, ethanol, isopropanol, propylene glycol, glycerol or diethyl ether.
5. The method for preparing the modified titanium nitride nanotube taking Ni-MOF as the precursor according to claim 1, wherein the hydrothermal reaction time in the step S2 is 5-20 h; the drying temperature is 60-80 ℃, and the drying time is 4-12 h; the empty burning time is 3-10 h.
6. The method for preparing the modified titanium nitride nanotube with Ni-MOF as the precursor of claim 1, wherein the carbon source in step S3 is more than one of melamine, dicyandiamide and dopamine hydrochloride; the mass ratio of the intermediate product to the carbon source is 1 (5-15).
7. The method for preparing the modified titanium nitride nanotube with Ni-MOF as the precursor of claim 1, wherein the calcining time in the step S3 is 4-8 h.
8. A modified titanium nitride nanotube, wherein the modified titanium nitride nanotube is prepared by the method of any one of claims 1 to 7.
9. The modified titanium nitride nanotube of claim 8, wherein the modified titanium nitride nanotube has a coral-like tubular structure and an average diameter of 50 to 200 nm.
10. Use of the modified titanium nitride nanotubes of claim 8 or 9 in the field of catalytic supports.
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CN117225452B (en) * 2023-11-16 2024-02-02 常熟理工学院 TiN-Ni photo-thermal catalyst with hollow structure, and preparation method and application thereof

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