CN112047313A - Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet - Google Patents
Preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheet Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002135 nanosheet Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003708 ampul Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000010453 quartz Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 238000004806 packaging method and process Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 239000010410 layer Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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- 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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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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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
- Y02E60/32—Hydrogen storage
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Abstract
The invention provides a preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheets, which comprises the following steps: packaging blocky Black Phosphorus (BP) and simple substance calcium in a quartz ampoule tube, heating to 700-750 ℃, preserving heat for 50-70 min, cooling to 480-520 ℃, preserving heat for 2-3 h, then slowly cooling to 140-160 ℃, and finally cooling to room temperature to obtain Ca-doped black phosphorus crystals (Ca-BP crystals); and (3) preparing the prepared calcium-doped black phosphorus crystal into a calcium-doped black phosphorus crystal dispersion liquid with the concentration of 0.6-1 g/L by using N-methylpyrrolidone (NMP) as a dispersing agent, and centrifuging the calcium-doped black phosphorus crystal dispersion liquid after ultrasonic dispersion to obtain the calcium-doped modified two-dimensional black phosphorus nanosheet. The invention can simultaneously passivate and stabilize the two-dimensional black phosphorus nanosheets and improve the hydrogen storage performance thereof, can effectively improve the chemical stability of the two-dimensional black phosphorus nanosheets, and realizes mild and efficient hydrogen storage.
Description
Technical Field
The invention relates to the technical field of application of environmental nano materials in green energy, in particular to a preparation and hydrogen storage method of calcium-doped modified two-dimensional black phosphorus nanosheets.
Background
The two-dimensional black phosphorus has an excellent lamellar structure and a nano effect, and is considered to be a graphene nano material with the greatest application prospect. The two-dimensional black phosphorus nanosheet is controllable in layer dimension, multiple in interlayer adsorption vacancy and strong in mild combination and hydrogen release capacity, so that the two-dimensional black phosphorus nanosheet can be used as a potential functional material for storing green energy hydrogen. However, the two-dimensional black phosphorus has poor environmental stability, and is easily reacted with oxygen and water at normal temperature and pressure to generate phosphate, so that the phosphate is degraded, and the application of the two-dimensional black phosphorus in the field of hydrogen storage is limited.
The key problem to be solved primarily is black phosphorus passivation-stabilization when the two-dimensional black phosphorus nanosheet is used for hydrogen storage. The conventional two-dimensional black phosphorus passivation-stabilization method mainly comprises three methods: the method comprises the following steps of surface physical coating including an electronic packaging method and a covering and wrapping method, surface functionalization and element doping. Although the two-dimensional black phosphorus can achieve the stabilization effect through coating passivation, the requirement of hydrogen storage cannot be achieved, and the main reason is that hydrogen molecules cannot be in contact and combined with the black phosphorus layer due to the fact that hydrogen cannot be completely contacted with the black phosphorus in the implementation process of the surface physical coating method. The main principle of the black phosphorus surface functionalization method is that hydrophobic functional groups which are contacted with black phosphorus and can effectively limit water are grafted between two-dimensional black phosphorus layers or surfaces, so that the purpose of isolating the black phosphorus from water exposure is achieved, the method can also achieve the purpose of stabilizing the black phosphorus, but hydrogen molecules are easily combined with foreign body functional groups on the black phosphorus surface in the hydrogen storage process, so that the hydrogen molecules are difficult to analyze and store and release. The black phosphorus element doping method is to introduce other elements into a Black Phosphorus (BP) nanosheet structure by means of covalent bonding and the like, so that the reaction bond energy is improved, and the chemical reaction activity of black phosphorus is reduced.
Therefore, the invention aims to provide a new method which can passivate and stabilize the two-dimensional black phosphorus and can improve the hydrogen storage performance of the two-dimensional black phosphorus, thereby simultaneously solving the problems of the stability of the two-dimensional black phosphorus and the hydrogen storage function.
Disclosure of Invention
The invention aims to provide a preparation and hydrogen storage method of a calcium-doped two-dimensional black phosphorus crystal nanosheet, aiming at the problems of poor stability and low hydrogen storage efficiency of the two-dimensional black phosphorus nanosheet.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of calcium-doped modified two-dimensional black phosphorus nanosheets comprises the following steps:
step 1, preparing a calcium element doped black phosphorus crystal (Ca-BP crystal): packaging blocky Black Phosphorus (BP) and simple substance calcium in a quartz ampoule tube according to the mass ratio of 10-50: 1, then placing the quartz ampoule tube in a heating furnace, heating to 700-750 ℃, preserving heat for 50-70 min, cooling to 480-520 ℃, preserving heat for 2-3 h, cooling to 140-160 ℃, and then naturally cooling to room temperature to obtain a calcium-doped black phosphorus crystal;
step 2, preparing a calcium element doped modified two-dimensional black phosphorus nanosheet (Ca-2D-BP): and (2) taking the calcium-doped black phosphorus crystal prepared in the step (1), preparing a calcium-doped black phosphorus crystal dispersion liquid with the concentration of 0.6-1 g/L by taking N-methylpyrrolidone (NMP) as a dispersing agent, and performing ultrasonic dispersion to obtain the calcium-doped modified two-dimensional black phosphorus nanosheet.
Further, the heating rate and the cooling rate in the step 1 are both 3-5 ℃/min.
Further, in the step 1, the purity of the black phosphorus is more than 99.998%, and the purity of the calcium is 99.9%.
Further, the ultrasonic dispersion conditions of step 2 are that the frequency: 40-45 kHz, power: 100%, the ultrasonic time is: 6-7 h.
Further, the ultrasonic dispersion of step 2 adopts a water bath mode, and the temperature of the water bath is ensured to be less than 30 ℃ in the process.
Further, before the calcium element doped black phosphorus crystal dispersion liquid is prepared in the step 2, wet grinding is carried out on the calcium element doped black phosphorus crystal for 25-35 min, and N-methyl pyrrolidone is used as a dispersing agent in the wet grinding.
And further, centrifuging the calcium-doped modified two-dimensional black phosphorus nanosheet dispersion obtained after ultrasonic dispersion in the step 2, wherein the rotating speed in the centrifuging process is 3000-5000 rpm, the centrifuging time is 8-12 min, and obtaining a supernatant, wherein the calcium-doped modified two-dimensional black phosphorus nanosheet (Ca-2D-BP) is 5-7 atomic layers thick and the size is 3.8-4 nm.
The invention also provides a calcium-doped modified two-dimensional black phosphorus nanosheet, which is prepared based on the method.
The invention also provides a hydrogen storage method of the calcium-doped modified two-dimensional black phosphorus nanosheet, which comprises the steps of placing the calcium-doped modified two-dimensional black phosphorus nanosheet on a silicon wafer, drying the silicon wafer for 1-2 hours at the temperature of 400-450 ℃, and then cooling the silicon wafer to room temperature; and transferring the mixture to an anhydrous and oxygen-free environment, introducing hydrogen, controlling the reaction temperature to be 200-250 ℃ and the reaction time to be 0.5-1.5 h, and combining the hydrogen and the calcium-doped modified two-dimensional black phosphorus nanosheet to realize hydrogen storage.
Furthermore, calcium doped modified two-dimensional black phosphorus nanosheets with the thickness of 5-7 atomic layers and the size of 3.8-4 nm have the hydrogen storage rate of 1.5-3.0 wt%.
Compared with the prior art, the invention has the advantages that:
1. the calcium-doped modified two-dimensional black phosphorus nanosheet (Ca-2D-BP) prepared by the invention enables the two-dimensional black phosphorus to be incompletely exposed in the environment in an element-doped manner, so that the good stability of the two-dimensional black phosphorus is ensured;
2. the calcium-doped modified two-dimensional black phosphorus nanosheet (Ca-2D-BP) prepared by the method disclosed by the invention has the advantages that the thickness of 5-7 atomic layers is 3.8-4 nm, the specific surface area of the calcium-doped modified two-dimensional black phosphorus nanosheet is increased, the adsorption capacity is improved, and meanwhile, calcium can be combined with hydrogen under a mild condition to form a chemical bond, so that the hydrogen storage effect is achieved.
Drawings
Fig. 1 is a morphology chart of Ca-doped modified two-dimensional black phosphorus nanosheets prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a preparation and hydrogen storage method of a calcium-doped modified two-dimensional black phosphorus nanosheet, which comprises the following steps:
(1) preparation of Ca-doped BP crystals
The block BP and the simple substance calcium are packaged together in a quartz ampoule tube with the length of 20 cm, the inner diameter of 0.8 cm and the wall thickness of 0.1 cm according to the mass ratio of 10: 1. Firstly, horizontally placing a quartz ampoule tube in a heating furnace, heating to 700 ℃ at the speed of 3 ℃/min, keeping the temperature for 50min, then cooling to 480 ℃, keeping the temperature for 2h, then slowly cooling to 140 ℃ at the speed of 3 ℃/min, and finally naturally cooling to room temperature to obtain the Ca-BP crystal.
(2) Preparation of Ca-doped modified two-dimensional BP crystal nanosheet (Ca-2D-BP)
Weighing 30mg of Ca-BP crystal prepared in the step 1 by using an electronic balance, transferring the Ca-BP crystal into a mortar, adding a small amount of N-methylpyrrolidone (NMP) into the mortar, repeatedly grinding for 25min, transferring the ground Ca-BP dispersion liquid into a 50mL centrifuge tube, adding NMP to a constant volume of 30mL, soaking the centrifuge tube in water, treating for 6h under the ultrasonic condition of 40kHz and 100%, and cooling by using ice blocks in the water bath ultrasonic process to ensure that the temperature is lower than 30 ℃. Centrifuging the Ca-BP after ultrasonic treatment for 8min at 3000rpm, and then sucking the supernatant by a pipette gun to obtain the final product Ca-2D-BP (the appearance is shown in figure 1).
(3) Hydrogen storage method
And (3) placing the supernatant Ca-2D-BP prepared in the step (2) on a silicon chip, drying for 1h at 400 ℃, taking out and cooling to room temperature, then transferring the supernatant to a glass tube, introducing hydrogen in an anhydrous and oxygen-free environment, and heating for 0.5h at 200 ℃ to combine the hydrogen with the Ca-2D-BP to realize hydrogen storage, wherein the hydrogen storage rate reaches 2.2 wt%.
Example 2
The embodiment provides a preparation and hydrogen storage method of a calcium-doped modified two-dimensional black phosphorus nanosheet, which comprises the following steps:
(1) preparation of Ca-doped BP crystals
The block BP and the simple substance calcium are packaged together in a quartz ampoule tube with the length of 20 cm, the inner diameter of 0.8 cm and the wall thickness of 0.1 cm according to the mass ratio of 30: 1. Firstly, horizontally placing a quartz ampoule tube in a heating furnace, heating to 750 ℃ at the speed of 4 ℃/min, keeping the temperature for 60min, then cooling to 500 ℃ and keeping the temperature for 2.5h, then slowly cooling to 150 ℃ at the speed of 4 ℃/min, and finally naturally cooling to room temperature to obtain the Ca-BP crystal.
(2) Preparation of Ca-doped modified two-dimensional BP crystal nanosheet (Ca-2D-BP)
35mg of the Ca-BP crystal prepared in 1 was weighed by an electronic balance, transferred to a mortar, a small amount of N-methylpyrrolidone (NMP) was added to the mortar, and repeatedly ground for 30min, and then the ground Ca-BP dispersion was transferred to a 50mL centrifuge tube, and NMP was added to a constant volume of 40 mL. The centrifuge tube was immersed in water and treated under ultrasonic conditions of 45kHz and 100% for 6.5 h. In the process of water bath ultrasound, ice blocks are used for cooling treatment, and the temperature is ensured to be less than 30 ℃. Centrifuging the Ca-BP after ultrasonic treatment for 10min at 4000rpm, and then sucking the supernatant by a pipette gun to obtain the final product Ca-2D-BP.
(3) Hydrogen storage method
And (3) placing the supernatant Ca-2D-BP prepared in the step (2) on a silicon chip, drying for 2h at 450 ℃, taking out and cooling to room temperature, then transferring the supernatant to a glass tube, introducing hydrogen in an anhydrous and oxygen-free environment, and heating for 1h at 250 ℃, so that the hydrogen and the Ca-2D-BP can be combined to realize hydrogen storage, and the hydrogen storage rate reaches 2.85 wt%.
Example 3
The embodiment provides a preparation and hydrogen storage method of a calcium-doped modified two-dimensional black phosphorus nanosheet, which comprises the following steps:
(1) preparation of Ca-doped BP crystals
The block BP and the simple substance calcium are packaged together in a quartz ampoule tube with the length of 20 cm, the inner diameter of 0.8 cm and the wall thickness of 0.1 cm according to the mass ratio of 50: 1. Firstly, horizontally placing a quartz ampoule tube in a heating furnace, heating to 725 ℃ at the speed of 5 ℃/min, keeping the temperature for 70min, then cooling to 520 ℃ and keeping for 3h, then slowly cooling to 160 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the Ca-BP crystal.
(2) Preparation of Ca-doped modified two-dimensional BP crystal nanosheet (Ca-2D-BP)
40mg of Ca-BP crystal prepared in 1 was weighed by an electronic balance, transferred to a mortar, a small amount of N-methylpyrrolidone (NMP) was added to the mortar, and then repeatedly ground for 35min, and then the ground Ca-BP dispersion was transferred to a 50mL centrifuge tube, and NMP was added to a constant volume of 50 mL. Soaking the centrifuge tube in water, treating for 7h under the conditions of 42.5kHz and 100% of ultrasonic wave, and cooling with ice blocks in the process of water bath ultrasonic wave to ensure that the temperature is less than 30 ℃. Centrifuging the Ca-BP after ultrasonic treatment for 12min at 5000rpm, and then sucking the supernatant by a pipette gun to obtain the final product Ca-2D-BP.
(3) Hydrogen storage method
And (3) placing the supernatant Ca-2D-BP prepared in the step (2) on a silicon chip, drying for 1.5h at 425 ℃, taking out and cooling to room temperature, then transferring the supernatant Ca-2D-BP into a glass tube, introducing hydrogen in an anhydrous and oxygen-free environment, and heating for 1.5h at 225 ℃ to combine the hydrogen with the Ca-2D-BP to realize hydrogen storage, wherein the hydrogen storage rate reaches 1.97 wt%.
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (8)
1. A preparation method of calcium-doped modified two-dimensional black phosphorus nanosheets is characterized by comprising the following steps:
step 1, preparing a calcium element doped black phosphorus crystal: packaging the massive black phosphorus and simple substance calcium in a quartz ampoule tube according to the mass ratio of 10-50: 1, then placing the quartz ampoule tube in a heating furnace, heating to 700-750 ℃, preserving heat for 50-70 min, cooling to 480-520 ℃, preserving heat for 2-3 h, cooling to 140-160 ℃, and then naturally cooling to room temperature to obtain calcium-doped black phosphorus crystals;
step 2, preparing calcium-doped modified two-dimensional black phosphorus nanosheets: and (2) taking the calcium-doped black phosphorus crystal prepared in the step (1), preparing a calcium-doped black phosphorus crystal dispersion liquid with the concentration of 0.6-1 g/L by taking N-methylpyrrolidone as a dispersing agent, and performing ultrasonic dispersion to obtain the calcium-doped modified two-dimensional black phosphorus nanosheet.
2. The preparation method of the calcium-doped modified two-dimensional black phosphorus nanosheet according to claim 1, wherein the heating and cooling rates in step 1 are both 3-5 ℃/min.
3. The preparation method of the calcium-doped modified two-dimensional black phosphorus nanosheet according to claim 1, wherein the ultrasonic dispersion conditions of the step 2 are that the frequency: 40-45 kHz, power: 100%, the ultrasonic time is: 6-7 h.
4. The preparation method of the calcium-doped modified two-dimensional black phosphorus nanosheet according to claim 1, wherein the calcium-doped modified two-dimensional black phosphorus nanosheet dispersion obtained after ultrasonic dispersion in step 2 is centrifuged, the rotation speed in the centrifugation process is 3000-5000 rpm, the centrifugation time is 8-12 min, and a supernatant is obtained, wherein the calcium-doped modified two-dimensional black phosphorus nanosheet is about 5-7 atomic layers thick and has a size of 3.8-4 nm.
5. The preparation method of the calcium-doped modified two-dimensional black phosphorus nanosheet as claimed in claim 1, wherein the ultrasonic dispersion in step 2 is performed in a water bath manner, wherein the temperature of the water bath is ensured to be less than 30 ℃.
6. The preparation method of the calcium-doped modified two-dimensional black phosphorus nanosheet according to claim 1, wherein the calcium-doped black phosphorus crystal is wet-ground for 25-35 min before the calcium-doped black phosphorus crystal dispersion liquid is prepared in step 2, and the wet-grinding uses N-methylpyrrolidone as a dispersing agent.
7. A calcium-doped modified two-dimensional black phosphorus nanosheet, which is prepared based on the method of any one of claims 1 to 6.
8. A hydrogen storage method based on the calcium-doped modified two-dimensional black phosphorus nanosheet of claim 7, wherein the calcium-doped modified two-dimensional black phosphorus nanosheet is placed on a silicon wafer, dried at 400-450 ℃ for 1-2 h, and then cooled to room temperature; and transferring the mixture to an anhydrous and oxygen-free environment, introducing hydrogen, controlling the reaction temperature to be 200-250 ℃ and the reaction time to be 0.5-1.5 h, and combining the hydrogen and the calcium-doped modified two-dimensional black phosphorus nanosheet to realize hydrogen storage.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113562691A (en) * | 2021-08-27 | 2021-10-29 | 昆明理工大学 | New application of nano black phosphorus in hydrogen storage field |
| CN114988378A (en) * | 2021-03-02 | 2022-09-02 | 中国科学院理化技术研究所 | N-doped black phosphorus alkene photocatalyst and preparation method and application thereof |
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| CN114988378A (en) * | 2021-03-02 | 2022-09-02 | 中国科学院理化技术研究所 | N-doped black phosphorus alkene photocatalyst and preparation method and application thereof |
| CN114988378B (en) * | 2021-03-02 | 2023-07-28 | 中国科学院理化技术研究所 | N-doped black phosphazene photocatalyst, and preparation method and application thereof |
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