CN108311166B - Two-dimensional transition metal phosphide and preparation method thereof - Google Patents
Two-dimensional transition metal phosphide and preparation method thereof Download PDFInfo
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- CN108311166B CN108311166B CN201810110112.0A CN201810110112A CN108311166B CN 108311166 B CN108311166 B CN 108311166B CN 201810110112 A CN201810110112 A CN 201810110112A CN 108311166 B CN108311166 B CN 108311166B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
Abstract
The invention relates to a two-dimensional transition metal phosphide and a preparation method thereof. The technical scheme is as follows: immersing aluminum foils and target metal foils with the same size or immersing the aluminum foils and the two target metal foils with the same size in absolute ethyl alcohol, ultrasonically cleaning, drying, aligning and stacking to obtain uniformly stacked metal foils; adjusting the roll gap of a two-roll mill to be 0.1mm, repeatedly folding and rolling the well-stacked metal foil for 15-50 times, soaking in an etchant for 12-48 hours, filtering, carrying out ultrasonic treatment in an ethanol solution, taking a suspension, centrifuging and filtering twice, and drying to obtain the target two-dimensional transition metal foil; finally, placing the porcelain boat with the target two-dimensional transition metal foil paved at the bottom in the downwind direction of the constant temperature area of the vacuum tube furnace, and placing the porcelain boat with the solid phosphorus source paved at the bottom in the upwind direction of the constant temperature area of the vacuum tube furnace; and (4) flowing argon and preserving the heat for 3-12 hours at the temperature of 300-800 ℃ to obtain the two-dimensional transition metal phosphide. The invention has high production efficiency, simple process and controllable product thickness.
Description
Technical Field
The invention belongs to the technical field of transition metal phosphide. In particular to a two-dimensional transition metal phosphide and a preparation method thereof.
Background
Transition metal phosphide has been reported to have wide application, such as phosphide of Ti, Ta, Mo, W can be used as high-temperature oxidation resistant coating material, Mo3P、LaRu2P2GaP and InP are superconductive and can be used in the electrical field. Transition metal phosphide nano materials such as iron phosphide, cobalt phosphide and nickel phosphide nano materials have large specific surface area, good conductivity and can stably exist in strong acid and strong alkali solutions, so that the transition metal phosphide nano materials are widely concerned in the field of catalysis, and particularly show excellent catalytic performance in hydrogen production by catalytic electrolysis of water. In recent years, researches on catalysts with two-dimensional structures find that the two-dimensional materials have extremely large specific surface area, so that the proportion of active atoms in the total number of atoms is greatly increased, the effective utilization rate of the materials can be improved, the catalytic performance can be improved, and the two-dimensional transition metal phosphide materials have a wide application prospect in the field of catalysis.
The patent technology of 'a preparation method of a two-dimensional metal compound material' (CN 106672921A) is characterized in that a target metal precursor solution is coated on salt, and after a phosphide is obtained through reaction at a specific temperature and in an atmosphere, the two-dimensional metal phosphide is obtained through cleaning, suction filtration and drying. Although the method is safe and environment-friendly, the process is complex, the production efficiency is not high, and the thickness of the product is difficult to control.
Liu et al (Liu H, Tang H, Fang M, et al, 2D Metals by Repeated irradiated reduction. [ J ]. Advanced Materials, 2016, 28(37): 8170-.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a two-dimensional transition metal phosphide with high production efficiency, simple process and controllable product thickness.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
firstly, soaking an aluminum foil and a target metal foil in absolute ethyl alcohol, or soaking an aluminum foil and two target metal foils in absolute ethyl alcohol respectively, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths, the thicknesses and the thicknesses of the aluminum foil and the target metal foils are equal, and the thicknesses are both 0.1 mm; drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and at 40-60 ℃, and then stacking the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the metal foil which is stacked uniformly;
adjusting the roll gap of a two-roll mill to be 0.1mm, and carrying out primary rolling on the neatly stacked metal foil through the two-roll mill to obtain a primary rolled metal foil;
step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 15 to 50;
step four, placing the primary product into an etchant, soaking for 12-48 hours at room temperature, and filtering to obtain a secondary product;
step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product;
dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil;
step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 300-800 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 3-12 h to obtain the two-dimensional transition metal phosphide.
The purity of the aluminum foil is more than or equal to 99.99 percent.
The target metal foil is one of Cu, Fe, Co and Ni foil, and the purity of the target metal foil is more than or equal to 99.99%.
The widths of the aluminum foil and the target metal foil are less than or equal to the length of the roll body of the two-roll mill.
The nitrogen purity is > 99%.
The aggressive agent is a sodium hydroxide solution or a potassium hydroxide solution, and the concentration of the aggressive agent is 2-6 mol/L.
The ethanol solution is a mixture of distilled water and absolute ethanol, wherein: the volume ratio of the distilled water to the absolute ethyl alcohol is 1: 0.5-1.5.
The solid phosphorus source is red phosphorus or sodium hypophosphite monohydrate, the mole number of the solid phosphorus source is equal to that of the target two-dimensional transition metal foil, and the purity of the solid phosphorus source is more than 99%.
The purity of the argon is more than 99%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the invention adopts a synthesis method of calendering-eroding sacrificial layer-phosphorization to prepare the two-dimensional metal foil in advance, the two-dimensional structure can accelerate the process of phosphorization reaction, and the ultrathin two-dimensional transition metal phosphide can be prepared in a short time at a relatively low temperature without a template agent or a surfactant, so that the production efficiency is high, and the method is suitable for industrial large-scale production.
2. The method comprises the steps of folding and rolling an aluminum foil and a target metal foil for 15-50 times, selectively eroding an aluminum layer, carrying out ultrasonic treatment and centrifugation to obtain a target two-dimensional metal foil, and carrying out heat treatment on the target two-dimensional metal foil and a solid phosphorus source in a vacuum tube furnace at 300-800 ℃ for 3-12 hours in an argon flowing atmosphere to obtain the two-dimensional transition metal phosphide, wherein the process is simple.
3. The invention can control the thickness of the target two-dimensional metal foil by adjusting the rolling times, thereby controlling the thickness of the two-dimensional transition metal phosphide.
Therefore, the invention has the characteristics of high production efficiency, simple process and controllable product thickness.
Detailed Description
In this embodiment:
the purity of the aluminum foil is more than or equal to 99.99 percent.
The purity of the target metal foil is more than or equal to 99.99%.
The widths of the aluminum foil and the target metal foil are less than or equal to the length of the roll body of the two-roll mill.
The nitrogen purity is > 99%.
The concentration of the aggressive agent is 2-6 mol/L.
The ethanol solution is a mixture of distilled water and absolute ethanol, wherein: the volume ratio of the distilled water to the absolute ethyl alcohol is 1: 0.5-1.5.
The mole number of the solid phosphorus source is equal to that of the target two-dimensional transition metal foil, and the purity of the solid phosphorus source is more than 99%.
The purity of the argon gas is more than 99 percent.
The detailed description is omitted in the embodiments.
Example 1
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and a target metal foil in absolute ethyl alcohol, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foil are equal, and the thicknesses of the aluminum foil and the target metal foil are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 15 to 30.
And step four, placing the primary product into an etchant, soaking for 12-24 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 300-500 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 9-12 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional cobalt phosphide.
The target metal foil is a cobalt foil.
The erosion agent is sodium hydroxide solution.
The solid phosphorus source is sodium hypophosphite monohydrate.
Example 2
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and a target metal foil in absolute ethyl alcohol, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foil are equal, and the thicknesses of the aluminum foil and the target metal foil are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 20 to 35.
And step four, placing the primary product into an etchant, soaking for 18-30 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 400-600 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 7-10 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional nickel phosphide.
The target metal foil is a nickel foil.
The erosion agent is sodium hydroxide solution.
The solid phosphorus source is sodium hypophosphite monohydrate.
Example 3
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and a target metal foil in absolute ethyl alcohol, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foil are equal, and the thicknesses of the aluminum foil and the target metal foil are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 30 to 45.
And step four, placing the primary product into an etchant, soaking for 24-36 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 500-700 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 5-8 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional iron phosphide.
The target metal foil is an iron foil.
The erosion agent is potassium hydroxide solution.
The solid phosphorus source is red phosphorus.
Example 4
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and a target metal foil in absolute ethyl alcohol, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foil are equal, and the thicknesses of the aluminum foil and the target metal foil are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 35 to 50.
And step four, placing the primary product into an etchant, soaking for 30-48 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 600-800 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 3-6 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional copper phosphide.
The target metal foil is a copper foil.
The erosion agent is potassium hydroxide solution.
The solid phosphorus source is red phosphorus.
Example 5
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and two target metal foils in absolute ethyl alcohol respectively, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foils are equal, and the thicknesses of the aluminum foil and the target metal foils are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 15 to 30.
And step four, placing the primary product into an etchant, soaking for 12-24 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 300-500 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 9-12 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional cobalt phosphide/nickel phosphide.
The two target metal foils are cobalt foil and nickel foil.
The erosion agent is sodium hydroxide solution.
The solid phosphorus source is sodium hypophosphite monohydrate.
Example 6
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and two target metal foils in absolute ethyl alcohol respectively, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foils are equal, and the thicknesses of the aluminum foil and the target metal foils are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 20 to 35.
And step four, placing the primary product into an etchant, soaking for 18-30 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 400-600 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 7-10 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional cobalt phosphide/iron phosphide.
The two target metal foils are cobalt foil and iron foil.
The erosion agent is sodium hydroxide solution.
The solid phosphorus source is sodium hypophosphite monohydrate.
Example 7
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and two target metal foils in absolute ethyl alcohol respectively, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foils are equal, and the thicknesses of the aluminum foil and the target metal foils are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil after the primary rolling, and performing secondary rolling by the two-roller rolling mill to obtain gold after the secondary rollingA metal foil; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 30 to 45.
And step four, placing the primary product into an etchant, soaking for 24-36 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 500-700 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 5-8 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional nickel phosphide/iron phosphide.
The two target metal foils are nickel foil and iron foil.
The erosion agent is potassium hydroxide solution.
The solid phosphorus source is red phosphorus.
Example 8
A two-dimensional transition metal phosphide and a preparation method thereof. The preparation method comprises the following steps:
firstly, soaking an aluminum foil and two target metal foils in absolute ethyl alcohol respectively, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths and the thicknesses of the aluminum foil and the target metal foils are equal, and the thicknesses of the aluminum foil and the target metal foils are 0.1 mm; and drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and 40-60 ℃, and then stacking the four edges of the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the stacked metal foil.
And step two, adjusting the roll gap of the two-roll mill to be 0.1mm, and rolling the uniformly stacked metal foil through the two-roll mill for one time to obtain the metal foil after one-time rolling.
Step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 35 to 50.
And step four, placing the primary product into an etchant, soaking for 30-48 hours at room temperature, and filtering to obtain a secondary product.
And step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product.
Dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; and drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil.
Step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 600-800 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 3-6 h to obtain the two-dimensional transition metal phosphide.
The two-dimensional transition metal phosphide is two-dimensional cobalt phosphide/copper phosphide.
The two target metal foils are cobalt foil and copper foil.
The erosion agent is potassium hydroxide solution.
The solid phosphorus source is red phosphorus.
Compared with the prior art, the specific implementation mode has the following positive effects:
1. the invention adopts a synthesis method of calendering-eroding sacrificial layer-phosphorization to prepare the two-dimensional metal foil in advance, the two-dimensional structure can accelerate the process of phosphorization reaction, and the ultrathin two-dimensional transition metal phosphide can be prepared in a short time at a relatively low temperature without a template agent or a surfactant, so that the production efficiency is high, and the method is suitable for industrial large-scale production.
2. The method comprises the steps of folding and rolling an aluminum foil and a target metal foil for 15-50 times, selectively eroding an aluminum layer, carrying out ultrasonic treatment and centrifugation to obtain a target two-dimensional metal foil, and carrying out heat treatment on the target two-dimensional metal foil and a solid phosphorus source in a vacuum tube furnace at 300-800 ℃ in an argon atmosphere for 3-12 hours to obtain the two-dimensional transition metal phosphide, wherein the process is simple.
3. The invention can control the thickness of the target two-dimensional metal foil by adjusting the rolling times, thereby controlling the thickness of the two-dimensional transition metal phosphide.
Therefore, the specific implementation mode has the characteristics of high production efficiency, simple process and controllable product thickness.
Claims (10)
1. A preparation method of two-dimensional transition metal phosphide is characterized by comprising the following steps:
firstly, soaking an aluminum foil and a target metal foil in absolute ethyl alcohol, or soaking an aluminum foil and two target metal foils in absolute ethyl alcohol respectively, and ultrasonically cleaning for 10-30 min, wherein the lengths, the widths, the thicknesses and the thicknesses of the aluminum foil and the target metal foils are equal, and the thicknesses are both 0.1 mm; drying the cleaned aluminum foil and the cleaned target metal foil for 20-40 min under the condition of nitrogen atmosphere and at 40-60 ℃, and then stacking the dried aluminum foil and the dried target metal foil in an aligned manner to obtain the metal foil which is stacked uniformly;
adjusting the roll gap of a two-roll mill to be 0.1mm, and carrying out primary rolling on the neatly stacked metal foil through the two-roll mill to obtain a primary rolled metal foil;
step three, folding the metal foil subjected to primary rolling in half, and performing secondary rolling by the two-roller rolling mill to obtain a metal foil subjected to secondary rolling; … …, willnFolding the metal foil after 1 time of rolling and then passing through the two-roller millnSecondary rolling to obtainnObtaining a first-grade product after secondary rolling of the metal foil;nis a natural number of 15 to 50;
step four, placing the primary product into an etchant, soaking for 12-48 hours at room temperature, and filtering to obtain a secondary product;
step five, soaking the secondary product in an ethanol solution, carrying out ultrasonic treatment for 3-6 h under the condition of 360-400W, then taking 3/4 suspension, centrifuging for 10min at the speed of 10000rpm, and filtering to obtain a tertiary product;
dispersing the third-stage product in an ethanol solution, centrifuging at the speed of 10000rpm for 10min, and filtering; drying for 20-40 min under the conditions of nitrogen atmosphere and 40-60 ℃ to obtain the target two-dimensional transition metal foil;
step seven, uniformly paving the target two-dimensional transition metal foil at the bottom of a square porcelain boat, and uniformly paving the solid phosphorus source at the bottom of another same porcelain boat; placing the ceramic boat containing the target two-dimensional transition metal foil in the downwind direction of a constant-temperature area of a vacuum tube furnace, and placing the ceramic boat containing the solid phosphorus source in the upwind direction of the constant-temperature area of the vacuum tube furnace; and in the flowing argon atmosphere, heating to 300-800 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 3-12 h to obtain the two-dimensional transition metal phosphide.
2. The method according to claim 1, wherein the purity of the aluminum foil is not less than 99.99%.
3. The method of claim 1, wherein the target metal foil is one of Cu, Fe, Co and Ni foil, and the purity of the target metal foil is greater than or equal to 99.99%.
4. The method according to claim 1, wherein the aluminum foil and the target metal foil have a width less than or equal to a length of a roll body of a two-roll mill.
5. The method according to claim 1, wherein the nitrogen purity is > 99%.
6. The method according to claim 1, wherein the aggressive agent is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the aggressive agent is 2-6 mol/L.
7. The method according to claim 1, wherein the ethanol solution is a mixture of distilled water and absolute ethanol, wherein: the volume ratio of the distilled water to the absolute ethyl alcohol is 1: 0.5-1.5.
8. The method according to claim 1, wherein the solid phosphorus source is red phosphorus or sodium hypophosphite monohydrate, the number of moles of the solid phosphorus source is equal to the number of moles of the target two-dimensional transition metal foil, and the purity of the solid phosphorus source is greater than 99%.
9. The method according to claim 1, wherein the argon gas has a purity of > 99%.
10. A two-dimensional transition metal phosphide, characterized in that the two-dimensional transition metal phosphide is a two-dimensional transition metal phosphide prepared by the method for preparing a two-dimensional transition metal phosphide according to any one of claims 1 to 9.
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