CN110911469A - Controllable preparation MoS2-Cu2WS4Microwave water-phase synthesis method of two-dimensional heterojunction material - Google Patents
Controllable preparation MoS2-Cu2WS4Microwave water-phase synthesis method of two-dimensional heterojunction material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract 6
- 239000000243 solution Substances 0.000 claims description 53
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 20
- 239000012498 ultrapure water Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 17
- 239000002356 single layer Substances 0.000 claims description 15
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- SCBKKGZZWVHHOC-UHFFFAOYSA-N 2,2-bis(sulfanyl)propanoic acid Chemical compound CC(S)(S)C(O)=O SCBKKGZZWVHHOC-UHFFFAOYSA-N 0.000 claims description 2
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- HCTNQQPHPIGLQV-UHFFFAOYSA-N azanium;3-sulfanylpropanoate Chemical compound [NH4+].[O-]C(=O)CCS HCTNQQPHPIGLQV-UHFFFAOYSA-N 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 229960001913 mecysteine Drugs 0.000 claims description 2
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 4
- IDIDJDIHTAOVLG-VKHMYHEASA-N S-methylcysteine Chemical compound CSC[C@H](N)C(O)=O IDIDJDIHTAOVLG-VKHMYHEASA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- -1 mercapto compound Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
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- 238000005119 centrifugation Methods 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 150000003573 thiols Chemical class 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 1
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- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 239000008236 heating water Substances 0.000 description 1
- MCYHPZGUONZRGO-VKHMYHEASA-N methyl L-cysteinate Chemical compound COC(=O)[C@@H](N)CS MCYHPZGUONZRGO-VKHMYHEASA-N 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/22—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds
- H01L29/2203—Cd X compounds being one element of the 6th group of the Periodic System
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02557—Sulfides
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/22—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds
- H01L29/221—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds including two or more compounds, e.g. alloys
- H01L29/225—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds including two or more compounds, e.g. alloys in different semiconductor regions, e.g. heterojunctions
Abstract
The invention discloses a controllable preparation method of MoS2‑Cu2WS4A microwave aqueous phase synthesis method of a two-dimensional heterojunction material is characterized in that a cuprous compound and a thiotungstic acid compound are used as reaction precursors, ammonia water and a mercapto compound are used as ligands, and a microwave aqueous phase method is adopted to synthesize MoS2Cu grown on surface of nanosheet2WS4Nanosheets, producing MoS of different sizes2‑Cu2WS4A two-dimensional heterojunction material. The method has the advantages of simple reaction conditions, rapid batch synthesis, strong controllability and the like. MoS prepared by the invention2‑Cu2WS4The two-dimensional heterojunction material has unique photoelectric property, excellent photo-thermal property and higher specific surface area, and has potential application value in the fields of biomedicine, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of nano materials, and particularly relates to controllable preparation of MoS2-Cu2WS4A microwave water phase synthesis method of a two-dimensional heterojunction material.
Background
Since the discovery of graphene in 2004, research on two-dimensional nanomaterials in the fields of condensed-state physics, material science, chemistry, nanotechnology, and the like has been exponentially increased. Due to many excellent properties of two-dimensional materials, the search for two-dimensional nanomaterials like graphene is also under development. For example, non-graphene two-dimensional materials represented by Transition Metal Dichalcogenides (TMDs) have wide application potential in the fields of optoelectronics, catalysis, energy, biosensing, antibiosis, bioimaging, tumor treatment and the like (Chem Rev, 2017, 117, 6225).
Due to the close relationship between the properties of the two-dimensional TMDs nanosheets and the sizes, the appearances and the phase states of the two-dimensional TMDs nanosheets, heterojunction materials formed by stacking different two-dimensional materials in a selected sequence on the basis of a single-component two-dimensional layered material become an emerging research hotspot in recent years. The properties of the two-dimensional heterojunction material can be artificially regulated and controlled by stacking and combining the two-dimensional nanosheets with different properties (electricity, optics and the like). Because only weak van der waals acting force exists between the two-dimensional heterojunction material layers, and covalent bonds or ionic bonds are not formed, adjacent layers are not limited by lattice matching in the material preparation process. Meanwhile, the two-dimensional heterojunction has no component transition, so that a carrier (potential field) gradient with a steep atomic level can be formed, and the two-dimensional heterojunction built on the two-dimensional heterojunction has very strong carrier separation capacity. Currently, researchers in various countries around the world put a lot of effort to prepare novel nanomaterials based on two-dimensional TMDs heterojunction, and show great development potential in the aspects of energy storage, photoelectrochemistry, electronic devices, biomedical applications, and the like (Adv Mater, 2014, 26, 1886).
Cu2WS4(CWS) is a typical two-dimensional transition metal chalcogenide having a layered structure. The metal atoms in the monolayer CWS are covalently bonded to the chalcogen nonmetal atoms, and the layers are connected by weak van der Waals force, so that the sheet-like nanomaterial is easily formed. With a conventional binary metal chalcogenide (MoS) having a hexagonal structure2、WS2Etc.), the CWS has a tetragonal crystal structure, has an energy band gap of 1.74 eV, is a semiconductor material which can be excited by visible light, and has wide application prospects in the fields of energy storage, photoelectrochemistry, electronic devices, biomedicine and the like (ACS Nano, 2016,10, 4587; Nano Letters, 2016, 16, 2393). The synthesis of CWS has received much attention from scientists due to its excellent physicochemical and photoelectric properties.
Due to MoS2And CWS are typical two-dimensional layered materials, and MoS is constructed2-Cu2WS4The two-dimensional heterojunction is expected to develop a new material with new photoelectric properties through structure and performance regulation. In this patent, we use microwave heating water phase synthesis method to form MoS in single layer by selecting suitable reaction precursor and microwave synthesis conditions, such as changing reaction temperature and reaction time2CWS nanosheet with controllable growth on nanosheet surface and effective MoS control2-Cu2WS4(MS-CWS) two-dimensional heterojunction material morphology and size change. The MS-CWS two-dimensional heterojunction material prepared by the method has high quality and adjustable size, and meanwhile, the method has the advantages of simple process, easily controlled process and the like.
Disclosure of Invention
The invention provides a controllable preparation method of MoS2-Cu2WS4A microwave water phase synthesis method of a two-dimensional heterojunction material aims to solve the problems in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
controllable preparation MoS2-Cu2WS4The microwave water phase synthesis method of the two-dimensional heterojunction material comprises the following steps:
step 1: single layer MoS formulation2A nanosheet aqueous solution, the solution being light brown in color;
step 2: preparing a thiotungstate aqueous solution, wherein the color of the solution is yellow;
and step 3: preparing a cuprous ion complex aqueous solution to obtain a colorless transparent solution;
and 4, step 4: MoS2-Cu2WS4Preparation of precursor solution: transferring the mixed solution obtained in the step 3 into the solution obtained in the step 1 to obtain a light brown transparent solution, performing water bath ultrasonic treatment at room temperature for 1-20 min, and adding the solution obtained in the step 2 to obtain MoS2-Cu2WS4A precursor solution;
and 5: MoS2-Cu2WS4Microwave-assisted growth of two-dimensional heterojunction material: weighing 3 mL of MoS obtained in step 42-Cu2WS4Placing the precursor solution in a microwave reaction tube, placing the microwave reaction tube on a microwave reactor, setting the heating temperature to be 60-180 ℃, the heating time to be 1-60 min, selecting the power to be 50-150W, and the pressure to be 10-200 PSI;
step 6: MoS2-Cu2WS4And (3) purifying and storing the two-dimensional heterojunction material: the product of step 5 was centrifugally purified using ultra pure water washing to obtain a precipitate, and the final product was dispersed in ultra pure water and stored in a refrigerator at 4 ℃.
Further, in the step 2, the thiotungstate is ammonium thiotungstate.
Further, in the step 3, the cuprous ion complex aqueous solution comprises ammonia water, organic thiol and cuprous compound.
Further, in the step 3, the organic thiol is one or a mixture of several of thioglycolic acid, cysteine, mercaptoethanol, mercaptopropionic acid, 3-mercapto-2-butanol, dimercaptopropionic acid, dithiocarboxylic acid, ammonium mercaptopropionate and cysteine methyl ester;
further, in the step 3, the cuprous compound is any one of cuprous iodide, cuprous bromide, cuprous oxide, cuprous chloride, cuprous acetate, cuprous hydroxide and cuprous sulfate.
Further, in the step 3, the preparation method of the cuprous ion complex aqueous solution comprises the following steps: weighing a cuprous compound in a centrifuge tube, adding ultrapure water, performing ultrasonic dispersion, adding an organic mercaptan aqueous solution, performing ultrasonic treatment, and adding ammonia water to obtain a colorless transparent solution;
further, in the step 6, the rotation speed of centrifugal purification is 3000-15000 rpm, and the centrifugal time is 3-60 min.
Further, added MoS2The molar weight of the thiotungstate, the inorganic cuprous compound, the organic mercaptan and the ammonia water meets MoS2: WS4 2-: Cu+: SH : NH3The molar ratio is (1-10): 1-100): 1-500.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a microwave-assisted synthesis method to realize the controllable preparation of the MS-CWS two-dimensional heterojunction material. The morphology and the size of the CWS nanosheet in the prepared MS-CWS two-dimensional heterojunction material are uniform and controllable, the CWS nanosheet can be stably stored for a long time, and the method is suitable for the fields of catalysis, photoelectricity and biomedicine. The method has the advantages of simple preparation, high reaction speed and strong controllability.
Drawings
FIG. 1 is a transmission electron micrograph of a MS-CWS two-dimensional heterojunction material with different magnifications prepared in example 1 of the invention, wherein n isMPA: nCWS precursorIs 200: 1.
FIG. 2 is a transmission electron micrograph of the MS-CWS two-dimensional heterojunction material with different magnifications prepared in example 2 of the invention, wherein n isMPA: nNH3·H2OIs 1: 4.
Fig. 3 is a high-power transmission electron microscope photograph, a dark field electron microscope photograph and an element spectrogram photograph of the MS-CWS two-dimensional heterojunction material prepared in embodiment 2 of the present invention, wherein: (a) high power transmission electron microscope photograph; (b) dark field electron microscope photographs; (c) and (d), (e) and (f) are photographs of elemental spectra of Mo, S, W, Cu, and the like, respectively.
FIG. 4 is an atomic force microscope photograph of the MS-CWS two-dimensional heterojunction material prepared in example 2 of the present invention.
FIG. 5 is an X-ray diffraction pattern of the MS-CWS two-dimensional heterojunction material prepared in example 2 of the invention.
Fig. 6 shows an ultraviolet absorption visible spectrum of the MS-CWS two-dimensional heterojunction material and the single-layer molybdenum disulfide nanosheet prepared in embodiment 2 of the present invention.
FIG. 7 shows that the MS-CWS two-dimensional heterojunction material, the single-layer molybdenum disulfide nanosheet and pure water prepared in embodiment 2 of the invention are irradiated by a 808 nm laser (0.6W/cm)2) Photothermal temperature rise curve at 5 min.
Detailed Description
The present invention will be further described with reference to the following examples.
Controllable preparation MoS2-Cu2WS4The microwave water phase synthesis method of the two-dimensional heterojunction material comprises the following steps: single layer MoS2Preparing a nanosheet aqueous solution; preparing a thiotungstate aqueous solution; preparing a cuprous ion complex aqueous solution; MoS2-Cu2WS4Preparing a precursor solution; MoS2-Cu2WS4Microwave-assisted growth of a two-dimensional heterojunction material; MoS2-Cu2WS4And purifying and storing the two-dimensional heterojunction material.
Example 1
1. Preparation of aqueous solution of monolayer molybdenum disulfide nanosheet
Using a pipette to transfer 0.43 mL of monolayer molybdenum disulfide solution (375 mu mol/mL) into a 50 mL centrifuge tube, and adding 9.57 mL of ultrapure water to prepare the monolayer molybdenum disulfide solution (0.10 mu mol/mL), wherein the color of the solution is light brown;
2. preparation of ammonium thiotungstate solution
Weighing 0.01 mmol of ammonium thiotungstate (3.75 mg) into a 50 mL centrifuge tube, adding 10 mL of ultrapure water, and stirring for dissolving, wherein the color of the solution is yellow;
3. preparation of cuprous ion complex solution
Weighing 0.01 mmol of cuprous oxide (1.44 mg) into a centrifuge tube with the volume of 50 mL, adding 8.61 mL of ultrapure water, performing ultrasonic treatment for 2 min to disperse the cuprous oxide, adding 0.39 mL of mercaptopropionic acid aqueous solution (0.1M; pH of 3-3), performing ultrasonic treatment for 1min, and adding 3 mL of ammonia water (5M) to obtain a colorless transparent solution;
4. preparation of MS-CWS precursor
Using a pipette, 1 mL of the ammonium thiotungstate solution prepared in step 2 was transferred to a 10 mL centrifuge tube, and 1.5 mL of ultrapure water was added to dilute the solution to 1/4 of the original concentration.
Using a pipette, 1 mL of the cuprous ion complex solution prepared in step 3 was transferred to a 10 mL centrifuge tube, and 1.5 mL of ultrapure water was added to dilute the cuprous ion complex solution to 1/4 of the original concentration.
And transferring the diluted cuprous ion complex solution into a single-layer molybdenum disulfide solution by using a liquid transfer device, performing ultrasonic treatment for 1min, and adding the ammonium thiotungstate solution diluted in the same proportion to obtain a yellow transparent precursor solution.
5. Microwave-assisted growth of MS-CWS two-dimensional heterojunction material
Measuring MS-CWS precursor solution with volume of 3 mL, placing in a 10 mL special microwave tube, placing on a microwave reactor, selecting power of 150W and pressure of 150 PSI, setting heating time of 5 min, and microwave heating temperature of 120 ℃ respectively.
6. Purification and preservation of MS-CWS two-dimensional heterojunction material
And transferring the prepared MS-CWS two-dimensional heterojunction material into a centrifugal tube for centrifugal separation. The selected centrifugation speed is 8,000 rpm, and the centrifugation time is 5 min. The final product was dispersed in ultrapure water and stored in a refrigerator at 4 ℃ under the same centrifugation conditions, using ultrapure water for 3 purifications.
Example 2
1. Preparation of aqueous solution of monolayer molybdenum disulfide nanosheet
Using a pipette to transfer 0.43 mL of monolayer molybdenum disulfide solution (375 mu mol/mL) into a 50 mL centrifuge tube, and adding 9.57 mL of ultrapure water to prepare the monolayer molybdenum disulfide solution (0.1 mu mol/mL), wherein the color of the solution is light brown;
2. preparation of ammonium thiotungstate solution
Weighing 0.01 mmol of ammonium thiotungstate (3.75 mg) into a 50 mL centrifuge tube, adding 10 mL of ultrapure water, and stirring for dissolving, wherein the color of the solution is yellow;
3. preparation of cuprous ion complex solution
Respectively weighing 0.01 mmol of cuprous oxide (1.44 mg) in a centrifuge tube with a volume of 50 mL, adding 8.61 mL of ultrapure water, performing ultrasonic treatment for 2 min to disperse the cuprous oxide, adding 0.39 mL of mercaptopropionic acid aqueous solution (0.1M; pH of 3), performing ultrasonic treatment for 1min, and adding 4.2 mL of ammonia water (5M) to obtain colorless transparent solution;
4. preparation of MS-CWS precursor
Using a pipette, 1 mL of the ammonium thiotungstate solution prepared in step 2 was transferred to a 10 mL centrifuge tube, and 1.5 mL of ultrapure water was added to dilute the solution to 1/4 of the original concentration.
Using a pipette, 1 mL of the cuprous ion complex solution prepared in step 3 was transferred to a 10 mL centrifuge tube, and 1.5 mL of ultrapure water was added to dilute the cuprous ion complex solution to 1/4 of the original concentration.
And transferring the diluted cuprous ion complex solution into a single-layer molybdenum disulfide solution by using a liquid transfer device, performing ultrasonic treatment for 1min, and adding the ammonium thiotungstate solution diluted in the same proportion to obtain a yellow transparent precursor solution.
5. Microwave-assisted growth of MS-CWS two-dimensional heterojunction material
Measuring MS-CWS precursor solution with volume of 3 mL, placing in a 10 mL special microwave tube, placing on a microwave reactor, selecting power of 150W and pressure of 150 PSI, setting heating time of 5 min, and microwave heating temperature of 120 ℃ respectively.
6. Purification and preservation of MS-CWS two-dimensional heterojunction material
And transferring the prepared MS-CWS two-dimensional heterojunction material into a centrifugal tube for centrifugal separation. The selected centrifugation speed is 8,000 rpm, and the centrifugation time is 5 min. The final product was dispersed in ultrapure water and stored in a refrigerator at 4 ℃ under the same centrifugation conditions, using ultrapure water for 3 purifications.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (8)
1. Controllable preparation MoS2-Cu2WS4The microwave aqueous phase synthesis method of the two-dimensional heterojunction material is characterized by comprising the following steps of:
step 1: single layer MoS formulation2A nanosheet aqueous solution, the solution being light brown in color;
step 2: preparing a thiotungstate aqueous solution, wherein the color of the solution is yellow;
and step 3: preparing a cuprous ion complex aqueous solution to obtain a colorless transparent solution;
and 4, step 4: MoS2-Cu2WS4Preparation of precursor solution: transferring the mixed solution obtained in the step 3 into the solution obtained in the step 1 to obtain a light brown transparent solution, performing water bath ultrasound for 1-20 min, and adding the solution obtained in the step 2 to obtain MoS2-Cu2WS4A precursor solution;
and 5: MoS2-Cu2WS4Microwave-assisted growth of two-dimensional heterojunction material: weighing 3 mL of MoS obtained in step 42-Cu2WS4Placing the precursor solution in a microwave reaction tube, placing the microwave reaction tube on a microwave reactor, setting the heating temperature to be 60-180 ℃, the heating time to be 1-60 min, selecting the power to be 50-150W, and the pressure to be 10-200 PSI;
step 6: MoS2-Cu2WS4And (3) purifying and storing the two-dimensional heterojunction material: the product of step 5 was centrifugally purified using ultra pure water washing to obtain a precipitate, and the final product was dispersed in ultra pure water and stored in a refrigerator at 4 ℃.
2. Controllably preparable MoS according to claim 12-Cu2WS4The microwave water phase synthesis method of the two-dimensional heterojunction material is characterized in that in the step 2, the thiotungstate is ammonium thiotungstate.
3. Controllably preparable MoS according to claim 12-Cu2WS4The microwave water phase synthesis method of the two-dimensional heterojunction material is characterized in that in the step 3, the cuprous ion complex aqueous solution comprises ammonia water, organic mercaptan and cuprous compounds.
4. Controllably preparable MoS according to claim 12-Cu2WS4The microwave water phase synthesis method of the two-dimensional heterojunction material is characterized in that in the step 3, the organic mercaptan is one or a mixture of more of thioglycolic acid, cysteine, mercaptoethanol, mercaptopropionic acid, 3-mercapto-2-butanol, dimercaptopropionic acid, dithiocarboxylic acid, ammonium mercaptopropionate and methyl cysteine.
5. Controllably preparable MoS according to claim 12-Cu2WS4The microwave aqueous phase synthesis method of the two-dimensional heterojunction material is characterized in that in the step 3, the cuprous compound is any one of cuprous iodide, cuprous bromide, cuprous oxide, cuprous chloride, cuprous acetate, cuprous hydroxide and cuprous sulfate.
6. Controllably preparable MoS according to claim 12-Cu2WS4The microwave aqueous phase synthesis method of the two-dimensional heterojunction material is characterized in that in the step 3, the preparation method of the cuprous ion complex aqueous solution comprises the following steps: weighing a cuprous compound in a centrifuge tube, adding ultrapure water, carrying out ultrasonic dispersion, adding an organic mercaptan aqueous solution, carrying out ultrasonic treatment, and adding ammonia water to obtain a colorless transparent solution.
7. Controllably preparable MoS according to claim 12-Cu2WS4Microwave aqueous phase of two-dimensional heterojunction materialThe synthesis method is characterized in that in the step 6, the rotation speed of centrifugal purification is 3000-15000 rpm, and the centrifugal time is 3-60 min.
8. Controllably preparable MoS according to claim 12-Cu2WS4The microwave water phase synthesis method of the two-dimensional heterojunction material is characterized in that the added MoS2The molar weight of the thiotungstate, the inorganic cuprous compound, the organic mercaptan and the ammonia water meets MoS2: WS4 2-: Cu+: SH : NH3The molar ratio is (1-10): 1-100): 1-500.
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