CN108706641B - Preparation method of ultrathin sulfide nanosheet - Google Patents
Preparation method of ultrathin sulfide nanosheet Download PDFInfo
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- CN108706641B CN108706641B CN201810809623.1A CN201810809623A CN108706641B CN 108706641 B CN108706641 B CN 108706641B CN 201810809623 A CN201810809623 A CN 201810809623A CN 108706641 B CN108706641 B CN 108706641B
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- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
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- 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
Abstract
The invention relates to a preparation method of a two-dimensional material, in particular to a preparation method of an ultrathin sulfide nanosheet. The invention utilizes a liquid nitrogen auxiliary stripping method to simply and effectively prepare a large number of high-quality single-layer or few-layer two-dimensional platinum sulfide nano sheets and reduce the cost of noble metal catalysis.
Description
Technical Field
The invention relates to a preparation method of an atomic-level two-dimensional platinum sulfide sheet, belonging to the technical field of energy and material science.
Background
In recent years, two-dimensional materials have received wide attention from researchers. By reducing the thickness of the bulk material to the atomic thickness, local atomic arrangements such as coordination number, bond length, bond angle, and atomic disorder will be subject to variation. The thin thickness of the atoms will result in more exposed internal atoms and should easily induce the formation of various defects, which undoubtedly have a significant effect on their physicochemical properties. Due to the ultra-high specific surface area, ultra-thin thickness and strong quantum confinement of two-dimensional electrons, these atomically thin 2D materials can not only exhibit the intrinsic properties of bulk materials, but also produce new properties not possessed by corresponding bulk materials.
Two-dimensional materials are widely classified into the following groups. The simplest structures and graphene and hexagonal boron nitride, Transition Metal Disulfides (TMDs) with a sandwich structure formed by a single layer of metal atoms and two layers of chalcogen or halogen (such as PtS)2，PtSe2，MoS2And WS2) And metal halides (PbI)2And MgBr 2); layered metal oxides (e.g. MnO) embodying structural diversity of the layered structure2And MnO3) All the compounds with plane structures and anisotropic bonding can be peeled into nanosheets in a bottom-up manner. Because the single-layer two-dimensional material obtained after stripping has a plurality of special properties, the stripping and application of the two-dimensional material become an effective way for developing new materials and applications.
An atomically thin 2D material can provide more surface active sites. With the progress of research, many researchers found that the radial dimension of a two-dimensional material has a significant influence on the electrical, optical and thermal properties of the material. When the radial dimensions of two-dimensional materials are reduced to 20nm and below, which are classified as quantum dots, catalytic reactions generally tend to occur on atoms of low coordination number, such as edge, corner or step atoms, which are generally considered as surface active sites. At present, the research of two-dimensional quantum dots belongs to the early stage, and a plurality of potential properties are needed to be further researched and developed. Therefore, the development of a universal, high-yield and green two-dimensional quantum dot preparation method is still urgently needed.
Disclosure of Invention
The invention relates to a preparation method of atomic-level two-dimensional sulfide nanosheets, which is characterized in that the existing preparation method is improved, a large number of high-quality single-layer or few-layer two-dimensional platinum sulfide nanosheets are simply and effectively prepared by a liquid nitrogen-assisted stripping method, and the cost of noble metal catalysis is reduced.
The preparation method of the ultrathin two-dimensional sulfide provided by the invention comprises the following steps of:
(1) respectively weighing platinum powder and sulfur powder according to the Pt/S atomic ratio of 1:2, uniformly mixing the platinum powder and the sulfur powder, transferring the mixture into a quartz test tube, and sealing the quartz test tube.
(2) Placing the sealed quartz tube in the step (1) into a tube furnace, heating at a set temperature of 600-900 ℃, and reacting by using a chemical vapor deposition method to obtain gray black PtS2And (3) solid powder.
(3) Opening the quartz tube in the step (2) and taking out the gray black PtS2And (3) a solid.
(4) Weighing the gray black PtS in the step (3)2Adding the solid into a mixed solvent to obtain a mixed solution; the mixed solvent consists of water and a solvent; the solvent is one of acetone, isopropanol, tetrahydrofuran, methanol, chloroform, n-butanol, hexane, xylene and acetonitrile.
The gray black PtS2The mass volume ratio of the solid powder to the mixed solvent is 0.02-0.5 g: 10-200mL, wherein the volume ratio of the solvent to the water in the mixed solvent is 1: 1-3: 1; preferably 2: 1.
(5) Performing liquid nitrogen freezing treatment on the mixed solution obtained in the step (4) for the first time, performing ultrasonic stripping treatment on the mixed solution, finally centrifuging, and taking supernatant to move into a clean test tube; and then freezing by using liquid nitrogen for the second time, and obtaining the dried solid ultrathin sulfide nanosheet by using a freeze drying instrument.
The first liquid nitrogen freezing time is 1-4h, preferably 2 h.
The second liquid nitrogen freezing time is 10min, and the treatment is only to freeze the block, so as to conveniently obtain a fluffy and dry sample.
The ultrasonic stripping treatment time is 2-12h, preferably 4h, and the power is 100-200W.
The centrifugal speed is 500-16500rpm, preferably 2000 rpm.
(6) Ultrasonically mixing the ultrathin sulfide nanosheets and the load material in the step (5) in an ethanol solution, wherein the mass ratio of the ultrathin sulfide nanosheets to the load material is 0.0001-0.05:1, filtering the mixed solution, and washing the filtrate with water until the residual solvent is removed; and drying the filtered substance in a forced air drying oven to obtain the single-layer or few-layer two-dimensional platinum sulfide nanosheet compound.
The ultrasonic time is 1-4 h; the drying temperature is 60 ℃.
The PtS2The mass ratio to the supporting material is preferably 0.005: 1.
The load material is any one of mesoporous carbon nitride, graphene, a carbon tube, carbon spheres, zinc oxide, silicon oxide, aluminum oxide, iron oxide, manganese oxide or a molecular sieve.
The invention obtains high-quality single-layer or few-layer PtS by selecting the volume ratio of solvent to water, the liquid nitrogen freezing time, the ultrasonic stripping treatment time and the centrifugal rotating speed2A two-dimensional nanoplatelet material.
The invention provides a single-layer or few-layer PtS2The preparation method has the advantages that: the method can obtain high-quality single-layer or few-layer PtS with high efficiency and wide application range2The two-dimensional quantum dot material has simple preparation process and easy operation, and the process does not introduce a solvent which is difficult to treat. The invention not only can prepare single-layer or few-layer PtS2In addition, the single-layer or few-layer PtS prepared by the invention2Has excellent performance, such as single-layer or few-layer PtS supported on mesoporous carbon nitride prepared by the invention2Not only remarkably reduceThe cost of noble metal catalysis, and certain photocatalytic hydrogen production performance.
Drawings
FIG. 1 shows a single or few layers of PtS prepared by the method of the invention2The transmission electron microscope of (2) demonstrates the synthesis of the nanosheets.
FIG. 2 shows a single or few layers of PtS prepared by the method of the invention2An atomic force microscope image of (a); characterization by atomic force microscopy of PtS indicating a monolayer or few layers2The layer thickness of (a) was 0.781nm, in concert with the transmission diagram, demonstrating successful synthesis of nanoplatelets.
FIG. 3 shows a single-layer or a few-layer PtS prepared by the method of example 4 of the present invention2The loaded mesoporous carbon nitride is used for testing the photocatalytic hydrogen production performance under the condition of not adding platinum.
Detailed Description
The following describes embodiments of the method of the invention:
example 1:
firstly, according to the Pt/S atomic ratio of 1:2, evenly mixing platinum powder and sulfur powder, transferring the mixture into a quartz test tube, and sealing the quartz test tube. Placing the sealed quartz tube in a tube furnace, heating at 600 deg.C, and reacting to obtain pure gray black PtS2And (3) solid powder. 0.005g of PtS is taken in the form of gray black2Adding 60mL of mixed solution (volume ratio: 2:1) of isopropanol and water into the solid, freezing the mixed solution for 2h by using liquid nitrogen, further carrying out ultrasonic stripping treatment for 4h, finally centrifuging at 500rpm, and taking the supernatant and transferring the supernatant into a clean test tube for later use. Freezing with liquid nitrogen for 10min to obtain dried solid. The mass ratio of the ultrathin sulfide nanosheets to the mesoporous carbon nitride is 0.005:1, ultrasonic mixing is carried out in an ethanol solution, the mixed solution is filtered, and filtered substances are washed by water until residual solvent is removed; and drying the filtered substance in a forced air drying oven to obtain the single-layer or few-layer two-dimensional platinum sulfide nanosheet compound.
Example 2: (We have changed the stripping solvent compared with example 1)
First, the Pt/S atomic ratio is 1:2The platinum powder and the sulfur powder are evenly mixed and then transferred into a quartz test tube for sealing treatment. Placing the sealed quartz tube in a tube furnace, heating at 600 deg.C, and reacting to obtain pure gray black PtS2And (3) solid powder. 0.005g of PtS is taken in the form of gray black2Adding 60mL of mixed solution (volume ratio: 2:1) of acetone and water into the solid, freezing the mixed solution for 2h by using liquid nitrogen, further carrying out ultrasonic stripping treatment for 4h, finally centrifuging at 500rpm, and taking the supernatant and transferring the supernatant into a clean test tube for later use. Freezing with liquid nitrogen for 10min to obtain dried solid. The mass ratio of the ultrathin sulfide nanosheets to the mesoporous carbon nitride is 0.005:1, ultrasonic mixing is carried out in an ethanol solution, the mixed solution is filtered, and filtered substances are washed by water until residual solvent is removed; and drying the filtered substance in a forced air drying oven to obtain the single-layer or few-layer two-dimensional platinum sulfide nanosheet compound.
The effect of example 2 is superior to that of example 1, and mainly shows that the peeling effect is more sufficient, and thinner and more ultrathin platinum sulfide nanosheets can be peeled.
Example 3: (compared with example 2, we have changed the volume ratio of solvent to water)
Firstly, according to the Pt/S atomic ratio of 1:2, evenly mixing platinum powder and sulfur powder, transferring the mixture into a quartz test tube, and sealing the quartz test tube. Placing the sealed quartz tube in a tube furnace, heating at 600 deg.C, and reacting to obtain pure gray black PtS2And (3) solid powder. 0.005g of PtS is taken in the form of gray black2Adding 60mL of mixed solution of acetone and water (volume ratio: 1:1) into the solid, freezing the mixed solution by liquid nitrogen for 2h, further carrying out ultrasonic stripping for 4h, finally centrifuging at 500rpm, and taking the supernatant and transferring the supernatant into a clean test tube for later use. Freezing with liquid nitrogen for 10min to obtain dried solid. The mass ratio of the ultrathin sulfide nanosheets to the mesoporous carbon nitride is 0.005:1, ultrasonic mixing is carried out in an ethanol solution, the mixed solution is filtered, and filtered substances are washed by water until residual solvent is removed; drying the filtrate in a forced air drying oven to obtain a monolayer orA two-dimensional platinum sulfide nanosheet composite having a reduced number of layers.
Example 3 is superior to example 1 but inferior to example 2 in effect, and is more sufficient than example 1 but inferior to example 2 in peeling effect.
Example 4: (compared with example 2, we have changed the centrifugation speed)
Firstly, according to the Pt/S atomic ratio of 1:2, evenly mixing platinum powder and sulfur powder, transferring the mixture into a quartz test tube, and sealing the quartz test tube. Placing the sealed quartz tube in a tube furnace, heating at 600 deg.C, and reacting to obtain pure gray black PtS2And (3) solid powder. 0.005g of PtS is taken in the form of gray black2Adding 60mL of mixed solution (volume ratio: 2:1) of acetone and water into the solid, freezing the mixed solution for 2h by using liquid nitrogen, further carrying out ultrasonic stripping treatment for 4h, finally centrifuging at 2000rpm, and taking the supernatant and transferring the supernatant into a clean test tube for later use. Freezing with liquid nitrogen for 10min to obtain dried solid. The mass ratio of the ultrathin sulfide nanosheets to the mesoporous carbon nitride is 0.005:1, ultrasonic mixing is carried out in an ethanol solution, the mixed solution is filtered, and filtered substances are washed by water until residual solvent is removed; and drying the filtered substance in a forced air drying oven to obtain the single-layer or few-layer two-dimensional platinum sulfide nanosheet compound.
The effect of example 4 is better than that of example 2, and the mass ratio of the compound obtained in example 4 is lower than that of example 2, but after the layer thickness of the obtained catalyst is centrifuged at an optimized centrifugation speed, thinner vulcanized platinum nanosheets can be obtained, and the utilization efficiency of the catalyst is improved.
Examples 5 to 11
The rest is the same as the example 4, but the stripping solvent is respectively changed into tetrahydrofuran, methanol, trichloromethane, n-butanol, hexane, xylene and acetonitrile by acetone, and the effect is poorer than that of the example 4; but is superior to isopropanol.
Claims (8)
1. A preparation method of ultrathin sulfide nanosheets is characterized by comprising the following specific steps:
(1) respectively weighing platinum powder and sulfur powder according to the Pt/S atomic ratio of 1:2, uniformly mixing the platinum powder and the sulfur powder, transferring the mixture into a quartz test tube, and sealing the quartz test tube;
(2) placing the sealed quartz tube in the step (1) into a tube furnace, heating at a set temperature of 600-900 ℃, and reacting by using a chemical vapor deposition method to obtain gray black PtS2A solid powder;
(3) opening the quartz tube in the step (2) and taking out the gray black PtS2A solid;
(4) weighing the gray black PtS in the step (3)2Adding the solid into a mixed solvent to obtain a mixed solution; the mixed solvent consists of water and a solvent; the solvent is one of acetone, isopropanol, tetrahydrofuran, methanol, chloroform, n-butanol, hexane, xylene and acetonitrile;
(5) performing liquid nitrogen freezing treatment on the mixed solution obtained in the step (4) for the first time, performing ultrasonic stripping treatment on the mixed solution, finally centrifuging, and taking supernatant to move into a clean test tube; after the second liquid nitrogen freezing treatment, a freeze drying instrument is used for obtaining a dried solid ultrathin sulfide nanosheet;
in step (4), the gray-black PtS2The mass volume ratio of the solid powder to the mixed solvent is 0.02-0.5 g: 10-200mL, wherein the volume ratio of the solvent to the water in the mixed solvent is 1: 1-3: 1; the solvent is acetone. .
2. The method for preparing ultrathin sulfide nanosheets of claim 1, wherein in step (4), the volume ratio of the solvent to the water is 2: 1.
3. a process for the preparation of ultra-thin sulfide nanoplates as in claim 1, wherein in step (5); the first liquid nitrogen freezing time is 1-4 h; the second liquid nitrogen freezing time is 10 min; the ultrasonic stripping treatment time is 2-12h, and the power is 100-200W; the centrifugal speed is 500-16500 rpm.
4. A process for the preparation of ultra-thin sulfide nanoplates as in claim 3, wherein in step (5); the first time of liquid nitrogen freezing is 2 hours; the ultrasonic stripping treatment time is 4 hours; the centrifugal speed was 2000 rpm.
5. A method of preparing a nanoplate composite using ultrathin sulfide nanoplates prepared by the method of claim 1, comprising the steps of: ultrasonically mixing the ultrathin sulfide nanosheet and the load material in an ethanol solution, wherein the mass ratio of the ultrathin sulfide nanosheet to the load material is 0.0001-0.05:1, filtering the mixed solution, and washing the filtrate with water until the residual solvent is removed; and drying the filtered substance in a forced air drying oven to obtain the single-layer or few-layer two-dimensional platinum sulfide nanosheet compound.
6. The method of claim 5, wherein the sonication time is 1-4 hours; the drying temperature is 60 ℃.
7. The method of claim 5, wherein PtS2The mass ratio to the supporting material was 0.005: 1.
8. The method of claim 5, wherein the supporting material is any one of mesoporous carbon nitride, graphene, carbon tubes, carbon spheres, zinc oxide, silicon oxide, aluminum oxide, iron oxide, manganese oxide, or molecular sieves.
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