CN108298510A - A kind of two dimension transition metal nitride and preparation method thereof - Google Patents
A kind of two dimension transition metal nitride and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B21/0615—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 transition metals other than titanium, zirconium or hafnium
- C01B21/0622—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 transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B21/0615—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 transition metals other than titanium, zirconium or hafnium
- C01B21/0625—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 transition metals other than titanium, zirconium or hafnium with copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The present invention relates to a kind of two-dimentional transition metal nitrides and preparation method thereof.Its technical solution is：By the identical a piece of aluminium foil of size and a piece of metal target foil or by the identical a piece of aluminium foil of size and two kinds of metal target foils it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic, dry, alignment is stacked, and obtains stacking neat metal foil；Adjustment duo mill roll gap is 0.1mm, is rolled after stacking neat metal foil doubling, and doubling and rolling 15 ~ 50 times repeatedly, impregnates 12 ~ 48h, filtering is ultrasonically treated in ethanol solution, takes suspension, centrifuges, and filters in aggressive agent altogether；Redisperse centrifuges, filtering, dry to get target two dimension transition metal foil；Finally by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, 300 ~ 800 DEG C are warming up to the rate of 2 ~ 5 DEG C/min, 3 ~ 12h is to get two-dimentional transition metal nitride for heat preservation.The present invention has the characteristics that production efficiency is high, simple for process and product thickness is controllable.
Description
Technical field
The invention belongs to transition metal nitride technical fields.More particularly to a kind of two-dimentional transition metal nitride and its system
Preparation Method.
Background technology
Transition metal nitride, which has been reported to have, to be widely applied, and carbon material is compared, and transition metal nitride has more
Big specific capacitance, compares transition metal oxide electrode material, and transition metal nitride shows more excellent high rate performance
And fast charging and discharging performance, such as BxN (B=Ti, V, Mo, Nb, W) is a kind of excellent electrochemical energy storage with potentiality to be exploited
Material.Additionally due to transition metal nitride has excellent hydrogen absorption, activation and transfer ability, in hydrogen-involved reaction as added hydrogen de-
Sulphur (HDS), hydrodenitrogeneration (HDN), electrolysis water hydrogen reduction reaction (HER) in all have good catalytic performance, therefore transition is golden
Belong to nitride to be with a wide range of applications in catalytic field.
" a kind of preparation method of two-dimensional metallic compound-material "（CN106672921A）Patented technology, the technology is by target
Metal front liquid is coated on salt, cleaned, filter and be dried to obtain after nitride is obtained by the reaction under specific temperature and atmosphere
Two-dimensional metallic nitride.Although this method safety and environmental protection, complex process, production efficiency is not high and product thickness is difficult to control.
Liu et al.（Liu H,Tang H, Fang M, et al. 2D Metals by Repeated Size
Reduction.[J]. Advanced Materials, 2016, 28(37):8170-8176.）Calendering repeatedly is disclosed to prepare
The method of two-dimensional metallic piece, but pure two-dimensional metallic foil is only stopped at, there is no make extending to this method preparing two dimension in turn
Metal nitride.
Invention content
The present invention is directed to overcome prior art defect, and it is an object of the present invention to provide a kind of production efficiency is high, simple for process, product is thick
The preparation method of the controllable two-dimentional transition metal nitride of degree.
To achieve the above object, the step of the technical solution adopted in the present invention is：
Step 1: first a piece of aluminium foil and a piece of metal target foil are dipped in absolute ethyl alcohol, or first by a piece of aluminium foil and two kinds of mesh
Mark metal foil it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic 10 ~ 30min, the length of the aluminium foil and the metal target foil
× width × thickness is equal, and thickness is 0.1mm；Again by the aluminium foil after cleaning and the metal target foil after cleaning in nitrogen atmosphere
With 40 ~ 60 DEG C under the conditions of dry 20 ~ 40min, then by after drying aluminium foil and it is dry after four sides of metal target foil be aligned
It stacks, obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 15 ~ 50 natural number.
Step 4: the primary product is placed in aggressive agent, 12 ~ 48h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 300 ~ 800 DEG C, and 3 ~ 12h is to get two-dimentional transition metal nitride for heat preservation.
Aluminium foil purity >=99.99%.
The metal target foil is one kind in Cu, Fe, Co, Ni foil, purity >=99.99% of the metal target foil.
The body of roll that the width of the aluminium foil and the metal target foil is less than or equal to duo mill is long.
The nitrogen gas purity ＞ 99%.
The aggressive agent is sodium hydroxide solution or is potassium hydroxide solution, a concentration of 2 ~ 6mol/L of the aggressive agent.
The ethanol solution is the mixture of distilled water and absolute ethyl alcohol, wherein：Distilled water: absolute ethyl alcohol volume ratio is 1:
（0.5~1.5）.
The purity of the ammonia is more than 99%.
Due to the adoption of the above technical scheme, the present invention has the positive effect that compared with prior art：
1, the present invention use calendering-erosion sacrificial layer-nitridation synthetic method, it is previously prepared go out two-dimensional metallic foil, two-dimensional structure
It can accelerate the process of nitridation reaction, at relatively low temperature, be not necessarily to template or surfactant, you can in a short time
Ultra-thin two-dimentional transition metal nitride is made, production efficiency is high, is suitable for industrialization large-scale production.
2, aluminium foil and the doubling of metal target foil and rolling are total to doubling repeatedly and rolled 15 ~ 50 times, reselection by the present invention
Aluminium layer is corroded, obtains target two-dimensional metallic foil through ultrasound, centrifugation, then the heat under the conditions of ammonia or nitrogen atmosphere, 300 ~ 800 DEG C
3 ~ 12h is to get two-dimentional transition metal nitride for processing, simple for process.
3, the present invention can be by adjusting the thickness of rolling number control targe two-dimensional metallic foil, and then controls two-dimentional transition gold
Belong to the thickness of nitride.
Therefore, the present invention has the characteristics that production efficiency is high, simple for process and product thickness is controllable.
Specific implementation mode
In present embodiment：
Aluminium foil purity >=99.99%.
Purity >=99.99% of the metal target foil.
The body of roll that the width of the aluminium foil and the metal target foil is less than or equal to duo mill is long.
The nitrogen gas purity ＞ 99%.
A concentration of 2 ~ 6mol/L of the aggressive agent.
The ethanol solution is the mixture of distilled water and absolute ethyl alcohol, wherein：Distilled water: absolute ethyl alcohol volume ratio is 1:
（0.5~1.5）.
The purity of the ammonia is more than 99%.
It is repeated no more in embodiment.
Embodiment 1
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first a piece of aluminium foil and a piece of metal target foil are dipped in absolute ethyl alcohol, it is cleaned by ultrasonic 10 ~ 30min, the aluminium
The length x width x thickness of foil and the metal target foil is equal, and thickness is 0.1mm；Again by after cleaning aluminium foil and cleaning
Dry 20 ~ the 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C of metal target foil afterwards, then by after drying aluminium foil and drying
The four sides alignment of metal target foil afterwards is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 15 ~ 30 natural number.
Step 4: the primary product is placed in aggressive agent, impregnate 12 at ambient temperature ~ for 24 hours, filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 300 ~ 500 DEG C, and 9 ~ 12h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional cobalt nitride.
The metal target foil is cobalt foil.
The aggressive agent is sodium hydroxide solution.
Embodiment 2
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first a piece of aluminium foil and a piece of metal target foil are dipped in absolute ethyl alcohol, it is cleaned by ultrasonic 10 ~ 30min, the aluminium
The length x width x thickness of foil and the metal target foil is equal, and thickness is 0.1mm；Again by after cleaning aluminium foil and cleaning
Dry 20 ~ the 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C of metal target foil afterwards, then by after drying aluminium foil and drying
The four sides alignment of metal target foil afterwards is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 20 ~ 35 natural number.
Step 4: the primary product is placed in aggressive agent, 18 ~ 30h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 400 ~ 600 DEG C, and 7 ~ 10h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional nickel oxide.
The metal target foil is nickel foil.
The aggressive agent is sodium hydroxide solution.
Embodiment 3
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first a piece of aluminium foil and a piece of metal target foil are dipped in absolute ethyl alcohol, it is cleaned by ultrasonic 10 ~ 30min, the aluminium
The length x width x thickness of foil and the metal target foil is equal, and thickness is 0.1mm；Again by after cleaning aluminium foil and cleaning
Dry 20 ~ the 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C of metal target foil afterwards, then by after drying aluminium foil and drying
The four sides alignment of metal target foil afterwards is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 30 ~ 45 natural number.
Step 4: the primary product is placed in aggressive agent, 24 ~ 36h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 500 ~ 700 DEG C, and 5 ~ 8h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional nitrided iron.
The metal target foil is iron foil.
The aggressive agent is potassium hydroxide solution.
Embodiment 4
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first a piece of aluminium foil and a piece of metal target foil are dipped in absolute ethyl alcohol, it is cleaned by ultrasonic 10 ~ 30min, the aluminium
The length x width x thickness of foil and the metal target foil is equal, and thickness is 0.1mm；Again by after cleaning aluminium foil and cleaning
Dry 20 ~ the 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C of metal target foil afterwards, then by after drying aluminium foil and drying
The four sides alignment of metal target foil afterwards is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 35 ~ 50 natural number.
Step 4: the primary product is placed in aggressive agent, 30 ~ 48h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 600 ~ 800 DEG C, and 3 ~ 6h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional copper nitride.
The metal target foil is copper foil.
The aggressive agent is potassium hydroxide solution.
Embodiment 5
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first by a piece of aluminium foil and two kinds of metal target foils it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic 10 ~ 30min,
The length x width x thickness of the aluminium foil and described two metal target foils is equal, and thickness is 0.1mm；It again will be after cleaning
Aluminium foil and the metal target foil after cleaning dry 20 ~ 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C, then will be after drying
The four sides alignment of metal target foil after aluminium foil and drying is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 15 ~ 30 natural number.
Step 4: the primary product is placed in aggressive agent, impregnate 12 at ambient temperature ~ for 24 hours, filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 300 ~ 500 DEG C, and 9 ~ 12h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional cobalt nitride/nickel oxide.
Described two metal target foils are cobalt foil and nickel foil.
The aggressive agent is sodium hydroxide solution.
Embodiment 6
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first by a piece of aluminium foil and two kinds of metal target foils it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic 10 ~ 30min,
The length x width x thickness of the aluminium foil and described two metal target foils is equal, and thickness is 0.1mm；It again will be after cleaning
Aluminium foil and the metal target foil after cleaning dry 20 ~ 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C, then will be after drying
The four sides alignment of metal target foil after aluminium foil and drying is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 20 ~ 35 natural number.
Step 4: the primary product is placed in aggressive agent, 18 ~ 30h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 400 ~ 600 DEG C, and 7 ~ 10h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional cobalt nitride/nitrided iron.
Described two metal target foils are cobalt foil and iron foil.
The aggressive agent is sodium hydroxide solution.
Embodiment 7
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first by a piece of aluminium foil and two kinds of metal target foils it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic 10 ~ 30min,
The length x width x thickness of the aluminium foil and described two metal target foils is equal, and thickness is 0.1mm；It again will be after cleaning
Aluminium foil and the metal target foil after cleaning dry 20 ~ 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C, then will be after drying
The four sides alignment of metal target foil after aluminium foil and drying is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 30 ~ 45 natural number.
Step 4: the primary product is placed in aggressive agent, 24 ~ 36h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 500 ~ 700 DEG C, and 5 ~ 8h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional nickel oxide/nitrided iron.
Described two metal target foils are nickel foil and iron foil.
The aggressive agent is potassium hydroxide solution.
Embodiment 8
A kind of two dimension transition metal nitride and preparation method thereof.The step of preparation method is：
Step 1: first by a piece of aluminium foil and two kinds of metal target foils it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic 10 ~ 30min,
The length x width x thickness of the aluminium foil and described two metal target foils is equal, and thickness is 0.1mm；It again will be after cleaning
Aluminium foil and the metal target foil after cleaning dry 20 ~ 40min under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C, then will be after drying
The four sides alignment of metal target foil after aluminium foil and drying is stacked, and obtains stacking neat metal foil.
Step 2: adjustment duo mill roll gap is 0.1mm, neat metal foil is stacked through the duo mill one by described
Secondary rolling, the metal foil after once being rolled.
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary
Metal foil after rolling；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnIt is secondary
Metal foil after rolling is to get primary product；nFor 35 ~ 50 natural number.
Step 4: the primary product is placed in aggressive agent, 30 ~ 48h is impregnated at ambient temperature, and filtering obtains two
Grade product.
Step 5: the secondary products are dipped in ethanol solution, 3 ~ 6h is ultrasonically treated under the conditions of 360 ~ 400W, then
The suspension for taking 3/4 centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product.
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C.
Step 7: by the target two dimension transition metal foil under ammonia or nitrogen atmosphere, with the rate liter of 2 ~ 5 DEG C/min
Temperature is to 600 ~ 800 DEG C, and 3 ~ 6h is to get two-dimentional transition metal nitride for heat preservation.
The two dimension transition metal nitride is two-dimentional cobalt nitride/copper nitride.
Described two metal target foils are cobalt foil and copper foil.
The aggressive agent is potassium hydroxide solution.
Present embodiment has the positive effect that compared with prior art：
1, present embodiment use calendering-erosion sacrificial layer-nitridation synthetic method, it is previously prepared go out two-dimensional metallic foil,
Two-dimensional structure can accelerate the process of nitridation reaction, at relatively low temperature, be not necessarily to template or surfactant, you can
Ultra-thin two-dimentional transition metal nitride is made in short time, production efficiency is high, is suitable for industrialization large-scale production.
2, present embodiment is by aluminium foil and the doubling of metal target foil and rolling, doubling and rolling 15 ~ 50 times repeatedly altogether,
Reselection corrodes aluminium layer, and target two-dimensional metallic foil is obtained through ultrasound, centrifugation, then in ammonia or nitrogen atmosphere, 300 ~ 800 DEG C
Under the conditions of heat treatment 3 ~ 12h to get two-dimentional transition metal nitride, it is simple for process.
3, present embodiment can be by adjusting the thickness of rolling number control targe two-dimensional metallic foil, and then controls two
Tie up the thickness of transition metal nitride.
Therefore, present embodiment has the characteristics that production efficiency is high, simple for process and product thickness is controllable.
Claims (9)
1. a kind of preparation method of two dimension transition metal nitride, it is characterised in that the step of preparation method is：
Step 1: first a piece of aluminium foil and a piece of metal target foil are dipped in absolute ethyl alcohol, or first by a piece of aluminium foil and two kinds of mesh
Mark metal foil it is each it is a piece of be dipped in absolute ethyl alcohol, be cleaned by ultrasonic 10 ~ 30min, the length of the aluminium foil and the metal target foil
× width × thickness is equal, and thickness is 0.1mm；Again by the aluminium foil after cleaning and the metal target foil after cleaning in nitrogen atmosphere
With 40 ~ 60 DEG C under the conditions of dry 20 ~ 40min, then by after drying aluminium foil and it is dry after four sides of metal target foil be aligned
It stacks, obtains stacking neat metal foil；
Step 2: adjustment duo mill roll gap is 0.1mm, the neat metal foil of the stacking is once rolled through the duo mill
System, the metal foil after once being rolled；
Step 3: by the metal foil doubling after the primary rolling, then through the secondary rolling of the duo mill, obtain secondary rolling
Metal foil afterwards；..., it willnMetal foil doubling after -1 rolling, then through the duo millnSecondary rolling, obtainsnSecondary rolling
Metal foil afterwards is to get primary product；nFor 15 ~ 50 natural number；
Step 4: the primary product is placed in aggressive agent, 12 ~ 48h is impregnated at ambient temperature, and filtering obtains two level production
Object；
Step 5: the secondary products are dipped in ethanol solution, it is ultrasonically treated 3 ~ 6h under the conditions of 360 ~ 400W, then takes 3/
4 suspension centrifuges 10min with the rate of 10000rpm, and filtering obtains three-level product；
Step 6: the three-level product is scattered in ethanol solution, 10min, filtering are centrifuged with the rate of 10000rpm；Then at
Dry 20 ~ 40min is to get target two dimension transition metal foil under the conditions of nitrogen atmosphere and 40 ~ 60 DEG C；
Step 7: the target two dimension transition metal foil is warming up under ammonia or nitrogen atmosphere with the rate of 2 ~ 5 DEG C/min
300 ~ 800 DEG C, 3 ~ 12h is to get two-dimentional transition metal nitride for heat preservation.
2. the preparation method of two dimension transition metal nitride according to claim 1, it is characterised in that the aluminium foil purity
≥99.99%。
3. the preparation method of two dimension transition metal nitride according to claim 1, it is characterised in that the metal target
Foil is one kind in Cu, Fe, Co, Ni foil, purity >=99.99% of the metal target foil.
4. the preparation method of two dimension transition metal nitride according to claim 1, it is characterised in that the aluminium foil and institute
The width for stating metal target foil is long less than or equal to the body of roll of duo mill.
5. the preparation method of two dimension transition metal nitride according to claim 1, it is characterised in that the nitrogen gas purity
＞ 99%.
6. the preparation method of two dimension transition metal nitride according to claim 1, it is characterised in that the aggressive agent is
Sodium hydroxide solution is potassium hydroxide solution, a concentration of 2 ~ 6mol/L of the aggressive agent.
7. the preparation method of two dimension transition metal nitride according to claim 1, it is characterised in that the ethanol solution
For the mixture of distilled water and absolute ethyl alcohol, wherein：Distilled water: absolute ethyl alcohol volume ratio is 1:（0.5~1.5）.
8. it is according to claim 1 two dimension transition metal nitride preparation method, it is characterised in that the ammonia it is pure
Degree is more than 99%.
9. it is a kind of two dimension transition metal nitride, it is characterised in that it is described two dimension transition metal nitride be according to claim 1 ~
Two-dimentional transition metal nitride prepared by the preparation method of any one of the 8 two-dimentional transition metal nitrides.
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| CN109081318A (en) * | 2018-09-06 | 2018-12-25 | 西北工业大学 | A kind of three-dimensional ordered mesoporous cobalt nitride and its preparation method and application |
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| CN101533720A (en) * | 2009-04-10 | 2009-09-16 | 南开大学 | Metal nitride electrode material for dye-sensitized solar cell |
| CN104008888A (en) * | 2014-06-13 | 2014-08-27 | 上海利物盛企业集团有限公司 | Preparation method of composite material and electrode slice for super capacitor |
| CN105774120A (en) * | 2016-03-31 | 2016-07-20 | 清华大学 | Metal nanosheet and manufacture method thereof |
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| CN101533720A (en) * | 2009-04-10 | 2009-09-16 | 南开大学 | Metal nitride electrode material for dye-sensitized solar cell |
| CN104008888A (en) * | 2014-06-13 | 2014-08-27 | 上海利物盛企业集团有限公司 | Preparation method of composite material and electrode slice for super capacitor |
| CN105774120A (en) * | 2016-03-31 | 2016-07-20 | 清华大学 | Metal nanosheet and manufacture method thereof |
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| LIU,HW等: "2D Metals by Repeated Size Reduction", 《ADVANCED MATERIALS》 * |
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| CN109081318A (en) * | 2018-09-06 | 2018-12-25 | 西北工业大学 | A kind of three-dimensional ordered mesoporous cobalt nitride and its preparation method and application |
| CN109081318B (en) * | 2018-09-06 | 2021-08-24 | 西北工业大学 | Three-dimensional ordered mesoporous cobalt nitride and preparation method and application thereof |
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