CN116495789B - Preparation method and application of ultrathin rhenium sulfide nanosheets - Google Patents
Preparation method and application of ultrathin rhenium sulfide nanosheets Download PDFInfo
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- CN116495789B CN116495789B CN202310447371.3A CN202310447371A CN116495789B CN 116495789 B CN116495789 B CN 116495789B CN 202310447371 A CN202310447371 A CN 202310447371A CN 116495789 B CN116495789 B CN 116495789B
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- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002135 nanosheet Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- -1 transition metal sulfide Chemical class 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 10
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 9
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 9
- 229920002530 polyetherether ketone Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 238000002309 gasification Methods 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 7
- 239000002064 nanoplatelet Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a preparation method of an ultrathin rhenium sulfide nanosheet and application of the ultrathin rhenium sulfide nanosheet serving as an electrocatalyst in hydrogen production by water electrolysis, and belongs to the field of preparation of transition metal electrocatalysts. The invention prepares the ultrathin rhenium sulfide nanosheets with controllable thickness through a rapid gasification reaction by utilizing a microwave-assisted hydrothermal method, has simple preparation process and high efficiency, provides a brand new thought for ultrathin preparation of sulfide nanosheets, and also provides a brand new effective simple way for preparing ultrathin transition metal sulfide nanosheets.
Description
Technical Field
The invention belongs to the field of preparation of transition metal electrocatalysts, and particularly relates to a preparation method of an ultrathin rhenium sulfide nanosheet and application of the ultrathin rhenium sulfide nanosheet in hydrogen production by water electrolysis.
Background
With the continuous progress of human society, the increasing demand for energy has brought about increasingly serious environmental problems and energy crisis, and therefore, a need has arisen to seek a clean and renewable high-efficiency energy source. Electrocatalytic decomposition of water is a safe, sustainable and environmentally friendly hydrogen production strategy. At present, commercial platinum (Pt) based catalysts are proved to be the most effective electrocatalysts for promoting Hydrogen Evolution Reaction (HER), but the global reserves of platinum metal are very low and expensive, and the disadvantages of low catalytic activity, poor stability and the like under alkaline conditions exist, so that the development of the hydrogen production technology by an electrolytic water method is severely restricted. Therefore, there is an urgent need to develop a low-cost, high-activity, high-stability material to solve this problem.
The two-dimensional layered transition metal sulfide has the advantages of low cost, simple preparation, excellent electrical, optical, mechanical, electrochemical and catalytic properties, and great application potential in the fields of microelectronics, sensors, electrochemical energy storage and energy catalysis. The thickness of the transition metal sulfide nano-sheet is still difficult to accurately regulate and control, and a single-layer or few-layer rhenium sulfide nano-sheet can be prepared by the current CVD method, but the cost is high, a complex transfer process is required, and large-scale preparation is difficult; although the solution method can be simply prepared, the thickness of the nano-sheet is often difficult to regulate. Therefore, development of a method for preparing ultrathin nanosheets by low-cost solution method is needed.
Disclosure of Invention
Based on the prior art, the technical problem to be solved by the invention is to provide a preparation method of an ultrathin rhenium sulfide nanosheet, and to effectively realize high-efficiency electrocatalytic HER performance by using the ultrathin rhenium sulfide nanosheet.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The preparation method of the ultrathin rhenium sulfide nanosheets comprises the following steps:
1) Dispersing ammonium perrhenate, thiourea and hydroxylamine hydrochloride in water, stirring to obtain a homogeneous clear solution (ammonium perrhenate is dissolved in hot water and may be heated appropriately if room temperature is low to obtain a clear solution);
2) Transferring the solution obtained in the step 1) into a PEEK high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, putting a piece of foam nickel into the PEEK high-temperature high-pressure reaction kettle to be completely immersed in the solution, carrying out microwave-assisted hydrothermal reaction, naturally cooling to room temperature, washing the reacted foam nickel with deionized water and ethanol respectively, and drying to prepare the ultrathin rhenium sulfide nano-sheet on the foam nickel in situ.
Further, the molar ratio of ammonium perrhenate, thiourea and hydroxylamine hydrochloride used in step 1) is 1 (1-5): 1-5.
Further, the microwave power of the microwave-assisted hydrothermal reaction in the step 2) is 400-1000W, the reaction temperature is 100-250 ℃, and the reaction time is 1-5 h.
Further, the temperature of the drying in the step 2) is 60 ℃ and the time is 30min.
The prepared ultrathin rhenium sulfide nanosheets can be used as electrocatalysts for decomposing water to prepare hydrogen.
The invention has the remarkable advantages that:
The invention provides a method for directly preparing ultrathin rhenium sulfide nano-sheets by a microwave-assisted hydrothermal method, which uses microwave hydrothermal rapid gasification to prepare ultrathin nano-sheets, has simple preparation process and high efficiency, and provides a brand new thought for ultrathin preparation of sulfide nano-sheets.
Drawings
Fig. 1 is an SEM image of the hot rhenium sulfide prepared without microwave assistance of the comparative example.
Fig. 2 is an SEM image of the ultrathin rhenium sulfide nanosheets prepared in example 1.
Fig. 3 is an SEM image of the ultrathin rhenium sulfide nanosheets prepared in example 2.
Fig. 4 is a TEM image of ultrathin rhenium sulfide nanoplatelets prepared in example 3.
Fig. 5 is an SEM image of the ultrathin rhenium sulfide nanosheets prepared in example 3.
Fig. 6 is an XRD spectrum of the ultra-thin rhenium sulfide nanoplatelets prepared in example 3.
Fig. 7 is an LSV curve of the ultrathin rhenium sulfide nanoplatelets obtained in example 2 and example 3.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Comparative example
(1) Taking 1mmol of ammonium perrhenate, 1mmol of thiourea and 2mmol of hydroxylamine hydrochloride, dissolving the ammonium perrhenate, the thiourea and the hydroxylamine hydrochloride in 30 mL water together, and obtaining a clear and uniform precursor solution by means of ultrasonic or magnetic stirring and the like;
(2) Transferring the precursor solution obtained in the step (1) into a PEEK high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining of 100 ml, putting a piece of foamed nickel with the size of 1 multiplied by 2 square centimeters into the precursor solution, completely immersing the foamed nickel into the precursor solution, carrying out hydrothermal reaction at 160 ℃ for 3h, and naturally cooling to room temperature;
(3) And (3) washing the foam nickel reacted in the step (2) with deionized water and ethanol for a plurality of times, and then vacuum drying at 60 ℃ for 1 h to obtain the ultrathin rhenium sulfide nanosheets.
Example 1
(1) Taking 1mmol of ammonium perrhenate, 1mmol of thiourea and 2mmol of hydroxylamine hydrochloride, dissolving the ammonium perrhenate, the thiourea and the hydroxylamine hydrochloride in 30 mL water together, and obtaining a clear and uniform precursor solution by means of ultrasonic or magnetic stirring and the like;
(2) Transferring the precursor solution obtained in the step (1) into a PEEK high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining of 100 ml, putting a piece of foamed nickel with the size of 1 multiplied by 2 square centimeters into the precursor solution, completely immersing the foamed nickel into the precursor solution, performing hydrothermal reaction at the temperature of 160 ℃ with the assistance of 500W microwaves for 3h, and naturally cooling to room temperature;
(3) And (3) washing the foam nickel reacted in the step (2) with deionized water and ethanol for a plurality of times, and then vacuum drying at 60 ℃ for 1 h to obtain the ultrathin rhenium sulfide nanosheets.
Example 2
(1) Taking 1mmol of ammonium perrhenate, 1mmol of thiourea and 2mmol of hydroxylamine hydrochloride, dissolving the ammonium perrhenate, the thiourea and the hydroxylamine hydrochloride in 30 mL water together, and obtaining a clear and uniform precursor solution by means of ultrasonic or magnetic stirring and the like;
(2) Transferring the precursor solution obtained in the step (1) into a PEEK high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining of 100ml, putting a piece of foamed nickel with the size of 1 multiplied by 2 square centimeters into the precursor solution, completely immersing the foamed nickel into the precursor solution, performing hydrothermal reaction at the temperature of 160 ℃ with the assistance of 1000W microwaves for 3h, and naturally cooling to room temperature;
(3) And (3) washing the foam nickel reacted in the step (2) with deionized water and ethanol for a plurality of times, and then vacuum drying at 60 ℃ for 1 h to obtain the ultrathin rhenium sulfide nanosheets.
FIGS. 1 to 3 are SEM images of ultrathin rhenium sulfide nanoplatelets obtained in examples 1 and 2, respectively, of rhenium sulfide prepared by single pure water thermal process of comparative example 1. As can be seen from the comparison of fig. 1-3, the rhenium sulfide prepared by the hydrothermal reaction has no obvious flaky morphology, the obtained rhenium sulfide can form the flaky morphology by the microwave-assisted treatment, and the microwave power can play an obvious role in regulating and controlling the thickness of the obtained rhenium sulfide nano-sheet. From this, it was demonstrated that ultra-thin nanoplatelets can be obtained by simple microwave-assisted treatment
Example 3
(1) Taking 1mmol of ammonium perrhenate, 1mmol of thiourea and 2mmol of hydroxylamine hydrochloride, dissolving the ammonium perrhenate, the thiourea and the hydroxylamine hydrochloride in 30 mL water together, and obtaining a clear and uniform precursor solution by means of ultrasonic or magnetic stirring and the like;
(2) Transferring the precursor solution obtained in the step (1) into a PEEK high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining of 100 ml, putting a piece of foamed nickel with the size of 1 multiplied by 2 square centimeters into the PEEK high-temperature high-pressure reaction kettle, completely immersing the foamed nickel into the precursor solution, carrying out hydrothermal reaction at the temperature of 200 ℃ under the assistance of 600W microwaves for 1h, and naturally cooling to the room temperature;
(3) And (3) washing the foam nickel reacted in the step (2) with deionized water and ethanol for several times respectively, and then vacuum drying at 60 ℃ for 1h to obtain the ultrathin rhenium sulfide nanosheets.
Fig. 4 to 6 are TEM images, SEM images and XRD patterns of the ultrathin rhenium sulfide nanosheets obtained in example 3, respectively. As can be seen from the figure, the obtained material belongs to rhenium disulfide, and has uniform size and ultrathin sheet layers.
Fig. 7 is an LSV curve of the ultrathin rhenium sulfide nanoplatelets obtained in examples 2 and 3 in 1.0M KOH electrolyte. As demonstrated by the figure, the thinner rhenium sulfide nanoplatelets of example 3 have more excellent HER performance.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (2)
1. The application of the ultrathin rhenium sulfide nano-sheet in the electrocatalytic decomposition of water to prepare hydrogen is characterized in that the preparation of the ultrathin rhenium sulfide nano-sheet comprises the following steps:
1) Dispersing ammonium perrhenate, thiourea and hydroxylamine hydrochloride into water, and stirring to obtain a uniform clear solution;
2) Transferring the solution obtained in the step 1) into a PEEK high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, putting a piece of foam nickel into the PEEK high-temperature high-pressure reaction kettle to be completely immersed in the solution, carrying out microwave-assisted hydrothermal reaction, naturally cooling to room temperature, washing the reacted foam nickel with deionized water and ethanol respectively, and drying to prepare ultrathin rhenium sulfide nano-sheets on the foam nickel in situ;
the molar ratio of ammonium perrhenate, thiourea and hydroxylamine hydrochloride used in the step 1) is 1 (1-5): 1-5;
the microwave power of the microwave-assisted hydrothermal reaction in the step 2) is 600W, the reaction temperature is 200 ℃, and the reaction time is 1 h.
2. The use according to claim 1, wherein the drying in step 2) is carried out at a temperature of 60 ℃ for a period of 30min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277064A (en) * | 2016-07-22 | 2017-01-04 | 电子科技大学 | A kind of method preparing rhenium disulfide nanometer sheet |
| CN110143616A (en) * | 2019-04-30 | 2019-08-20 | 陕西科技大学 | A kind of preparation method of the rhenium disulfide nanometer sheet of vertical-growth |
| CN113976104A (en) * | 2021-11-10 | 2022-01-28 | 江苏纳欧新材料有限公司 | Preparation method and application of rare earth vanadate two-dimensional nanosheet photocatalytic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277064A (en) * | 2016-07-22 | 2017-01-04 | 电子科技大学 | A kind of method preparing rhenium disulfide nanometer sheet |
| CN110143616A (en) * | 2019-04-30 | 2019-08-20 | 陕西科技大学 | A kind of preparation method of the rhenium disulfide nanometer sheet of vertical-growth |
| CN113976104A (en) * | 2021-11-10 | 2022-01-28 | 江苏纳欧新材料有限公司 | Preparation method and application of rare earth vanadate two-dimensional nanosheet photocatalytic material |
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