CN106277064B - A kind of method for preparing rhenium disulfide nanometer sheet - Google Patents
A kind of method for preparing rhenium disulfide nanometer sheet Download PDFInfo
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- CN106277064B CN106277064B CN201610580163.0A CN201610580163A CN106277064B CN 106277064 B CN106277064 B CN 106277064B CN 201610580163 A CN201610580163 A CN 201610580163A CN 106277064 B CN106277064 B CN 106277064B
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- nanometer sheet
- rhenium disulfide
- rhenium
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- C01G47/00—Compounds of rhenium
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
Abstract
The invention discloses a kind of method for preparing rhenium disulfide nanometer sheet, belong to New Two Dimensional field of nano material preparation.The present invention using ammonium perrhenate as rhenium source, thiocarbamide as sulphur source, above-mentioned three kinds of reactants are dissolved in aqueous solvent by hydroxylamine hydrochloride as reducing agent, chemically reacted by adjusting reaction temperature and reaction time, then by product cleaning, after drying process, final synthesis rhenium disulfide nanometer sheet.Operating process of the present invention is simple, and efficiency high, reproducible, cost are low, can be prepared on a large scale out high-quality rhenium disulfide nanometer sheet, meanwhile, the present invention provides reliable sample preparation methods for rhenium disulfide nanometer sheet in the application of electrical and optical aspect.
Description
Technical field
The invention belongs to New Two Dimensional field of nano material preparation, particularly a kind of side for preparing rhenium disulfide nanometer sheet
Method.
Background technology
Two-dimensional semiconductor is a kind of emerging electronic material with graphene similar structures, possesses excellent electricity, light
The performances such as, magnetics, mechanics, can be applied to different technical fields, thus the focus as current material science research field
One of.Among numerous two-dimensional semiconductor materials, the sulfide ReS of rhenium (Re)2Be just be found recently have faint interlayer
Coupling and the two-dimensional semiconductor material of unique distortion 1T structures.The symmetry of lattice structure is the key factor for determining material character
One of.Most of studied two-dimensional materials all have high lattice symmetry, so as to show isotropism.Reduce transition metal
Lattice symmetry can induce some in sulfide (TMDs) material has the anisotropy of importance on Science and Technology
Property.And rhenium disulfide (ReS2) inherently low-symmetry lattice material, therefore its electrical properties and optical property are with each
Anisotropy.Due to rhenium disulfide (ReS2) have faint layer coupling the characteristics of so that individual layer and the rhenium disulfide (ReS of multilayer2)
All it is direct band gap, the change of the number of plies is to rhenium disulfide (ReS2) band structure it is almost too not big change, simply direct band gap
Size occurs in that faint change.These unique properties allow rhenium disulfide (ReS2) scene effect transistor and photo-detector side
Face has huge application value.
In the past few decades, because nano material possesses excellent physical and chemical performance and its in following photoelectron
Potential application in device, researcher just concentrates on main attention in the preparation method research of nano material.
At present, the synthetic method of rhenium disulfide nanometer sheet has following report：T.Fujita etc. is entitled in document
《Chemically exfoliated ReS2nanosheets》(《ReS prepared by chemical stripping method2Nanometer sheet》) middle using chemistry
Lift-off technology has prepared rhenium disulfide nanometer sheet, and this method needs to carry out under inert gas shielding environment, and use
Lithium compound is inflammable in atmosphere, is made troubles to operation and dangerous.N.Al-Dulaimi etc. is entitled in document
《Sequential bottom-up and top-down processing for the synthesis of transition
metal dichalcogenide nanosheets:the case of rhenium disulfide(ReS2)》(《Order is certainly
Descend and go up and handle to synthesize transition metal dichalcogenide nanometer sheet from top to bottom：Rhenium disulfide (ReS2) situation》) in use
Spraying assistant chemical vapor deposition and liquid phase peel off two kinds of technologies, have prepared rhenium disulfide nanometer layer, and this method needs two steps
Operation, spraying assistant chemical vapor deposition needs high temperature, and technique is cumbersome.J.Gao etc. is entitled in document《Vertically
Oriented Arrays of ReS2Nanosheets for Electrochemical Energy Storage and
Electrocatalysis》(《The ReS arranged for electrochemical energy storage and the vertical orientation of electro-catalysis2Nanometer sheet》) middle useization
Learn gas phase deposition technology and prepared vertical orientated rhenium disulfide nanometer sheet, the process needs complicated control condition and high
Reaction temperature.Therefore, at present low cost, rhenium disulfide nanometer sheet can be prepared on a large scale still have huge challenge.
Hydro-thermal method has been widely used for the preparation of nano material, and the principle of hydro-thermal method is to reaction using air dry oven
System heating, pressurization, create high temperature, the environment of high pressure, so that the preparation of material is carried out, compared with other preparation methods,
Hydro-thermal method has following advantage：Yield is high, can carry out large-scale production；Reaction condition is gentle, it is not necessary to very high temperature；Atmosphere can
Control, it is not necessary to inert atmosphere；Technique is simple, and cost is low, it is not necessary to complicated instrument；Reactor is closed, pollutes small.
The content of the invention
In order to solve the above problems, the invention provides the side that a kind of utilization hydro-thermal reaction prepares rhenium disulfide nanometer sheet
Method, the present invention is using ammonium perrhenate, hydroxylamine hydrochloride, thiocarbamide as raw material, and water is solvent, during by adjusting reaction temperature, hydro-thermal reaction
Between, so as to prepare rhenium disulfide nanometer sheet.The present invention is simple to operate, it is not necessary to complicated reaction controlling condition, reaction temperature
It is low, it is easy to which that large-scale production goes out high-quality rhenium disulfide nanometer sheet；In addition, invention has the advantages of high efficiency, reproducible, cost is low
It is honest and clean, provide reliable sample preparation methods in the application of electrical and optical aspect for rhenium disulfide nanometer sheet.
The present invention is achieved through the following technical solutions：
A kind of method for preparing rhenium disulfide nanometer sheet, specifically includes following steps：
Ammonium perrhenate, hydroxylamine hydrochloride, thiocarbamide is soluble in water for 1: 1~5: 2~6 according to the amount ratio of material, and preparation is obtained
Ammonium perrhenate, hydroxylamine hydrochloride, thiocarbamide total soluble matters substance withdrawl syndrome are 0.1~0.4mol/L mixed solution；By the mixing
Solution is shifted in hydrothermal reaction kettle, and heating hydrothermal reaction kettle is up to reaction temperature and is incubated to maintain chemical reaction to carry out, preferably
Ground, reaction temperature is 160~260 DEG C, and the reaction time is 6~48 hours；After reaction terminates, hydrothermal reaction kettle temperature is cooled to
Room temperature, it is with water and alcohol that product cleaning in hydrothermal reaction kettle is clean, rhenium disulfide nanometer sheet is finally made after drying process.
Wherein, heating hydrothermal reaction kettle is generally put into baking oven heating using by hydrothermal reaction kettle, by adjusting oven temperature
To regulate and control reaction temperature, by stopping baking oven heating hydrothermal reaction kettle and hydrothermal reaction kettle being cooled into room temperature come terminating reaction,
So as to control the reaction time.
The present invention using ammonium perrhenate as rhenium source, thiocarbamide as sulphur source, hydroxylamine hydrochloride as reducing agent, hydroxylamine hydrochloride and
Ammonium perrhenate reacts to form ReO42-, thiocarbamide, which is hydrolyzed, generates product and ReO42-Reaction forms rhenium disulfide nano particle, in this hair
Rhenium disulfide nano particle assembles to form rhenium disulfide nanometer sheet under bright hydrothermal condition.The invention has the advantages that：Behaviour
Make process simple, it is efficiency high, reproducible, with low cost, high-quality rhenium disulfide nanometer sheet can be prepared on a large scale out；This hair
It is bright to provide reliable sample preparation methods in the application of electrical and optical aspect for rhenium disulfide nanometer sheet.
Brief description of the drawings
The X-ray diffractogram for the rhenium disulfide nanometer sheet that Fig. 1 is prepared for the present invention；
The Raman spectrogram for the rhenium disulfide nanometer sheet that Fig. 2 is prepared for the present invention；
The x-ray photoelectron energy spectrum diagram for the rhenium disulfide nanometer sheet that Fig. 3 is prepared for the present invention；
The transmission electron microscope figure for the rhenium disulfide nanometer sheet that Fig. 4 is prepared for the present invention.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, with reference to embodiments with Figure of description pair
The present invention is further elaborated：
Embodiment 1：
Weigh 0.5360 gram of ammonium perrhenate, 0.4170 gram of hydroxylamine hydrochloride and 0.6850 gram of thiocarbamide and be dissolved in 60 milliliters of water and stir
Mix 30 minutes, the mixed solution that ammonium perrhenate, hydroxylamine hydrochloride, the amount concentration of thiocarbamide total material are 0.28mol/L is made；Will be described
Mixed solution is shifted in 100 milliliters of hydrothermal reaction kettle inner bag, and hydrothermal reaction kettle then is put into the baking oven that temperature is 240 DEG C
In, insulation is carried out for 24 hours with maintaining to chemically react；After reaction terminates, stop baking oven heating, hydrothermal reaction kettle is taken out and cooled down
It is then with water and alcohol that product cleaning in hydrothermal reaction kettle is clean to room temperature, dried under the conditions of 60 DEG C, finally obtained two sulphur
Change rhenium nanometer sheet.
Fig. 1 is the X-ray diffractogram of rhenium disulfide nanometer sheet manufactured in the present embodiment, as can be seen from Figure 1 the present embodiment
The product finally synthesized is consistent with the standard PDF cards of rhenium disulfide, belongs to anorthic system, therefore prepared by the embodiment of the present invention
Rhenium disulfide nanometer sheet is gone out.
Embodiment 2：
Weigh 0.5360 gram of ammonium perrhenate, 0.1040 gram of hydroxylamine hydrochloride and 0.3045 gram of thiocarbamide and be dissolved in 60 milliliters of water and stir
Mix 30 minutes, the mixed solution that ammonium perrhenate, hydroxylamine hydrochloride, the amount concentration of thiocarbamide total material are 0.13mol/L is made；Will be described
Mixed solution is shifted in 100 milliliters of hydrothermal reaction kettle inner bag, and hydrothermal reaction kettle then is put into the baking oven that temperature is 240 DEG C
In, insulation is carried out for 6 hours with maintaining to chemically react；After reaction terminates, stop baking oven heating, hydrothermal reaction kettle is taken out and is cooled to
Room temperature, it is then with water and alcohol that product cleaning in hydrothermal reaction kettle is clean, dried under the conditions of 60 DEG C, curing is finally made
Rhenium nanometer sheet.
Fig. 2 is the Raman spectrogram of rhenium disulfide nanometer sheet manufactured in the present embodiment, is as can be seen from Figure 2 existed
161.7cm-1And 211.4cm-1There are two Characteristic Raman peaks of rhenium disulfide.
Embodiment 3：
Weigh 0.5360 gram of ammonium perrhenate, 0.6950 gram of hydroxylamine hydrochloride and 0.7612 gram of thiocarbamide and be dissolved in 60 milliliters of water and stir
Mix 30 minutes, the mixed solution that ammonium perrhenate, hydroxylamine hydrochloride, the amount concentration of thiocarbamide total material are 0.37mol/L is made；Will be described
Mixed solution is shifted in 100 milliliters of hydrothermal reaction kettle inner bag, and hydrothermal reaction kettle then is put into the baking oven that temperature is 160 DEG C
In, insulation is carried out for 24 hours with maintaining to chemically react；After reaction terminates, stop baking oven heating, hydrothermal reaction kettle is taken out and cooled down
It is then with water and alcohol that product cleaning in hydrothermal reaction kettle is clean to room temperature, dried under the conditions of 60 DEG C, finally obtained two sulphur
Change rhenium nanometer sheet.
Fig. 3 is the x-ray photoelectron energy spectrum diagram of rhenium disulfide prepared by the embodiment of the present invention, be can be seen that from figure (a)：Re
The 4f valence states of atom correspond respectively to the 4f of Re atoms at 42.2eV and 44.6eV7/2The 4f of track and Re atoms5/2Track,
It can be seen that from figure (b)：The 2p of S atom3/2The 2p of track and S atom1/2Track is at 162.5eV and 163.7eV, therefore
It is consistent with rhenium disulfide crystal corresponding parametric values.
Embodiment 4：
Weigh 0.5360 gram of ammonium perrhenate, 0.4170 gram of hydroxylamine hydrochloride and 0.6850 gram of thiocarbamide and be dissolved in 60 milliliters of water and stir
Mix 30 minutes, the mixed solution that ammonium perrhenate, hydroxylamine hydrochloride, the amount concentration of thiocarbamide total material are 0.28mol/L is made；Will be described
Mixed solution is shifted in 100 milliliters of hydrothermal reaction kettle inner bag, and hydrothermal reaction kettle then is put into the baking oven that temperature is 260 DEG C
In, insulation is carried out for 48 hours with maintaining to chemically react；After reaction terminates, stop baking oven heating, hydrothermal reaction kettle is taken out and cooled down
It is then with water and alcohol that product cleaning in hydrothermal reaction kettle is clean to room temperature, dried under the conditions of 60 DEG C, finally obtained two sulphur
Change rhenium nanometer sheet.
Fig. 4 is the transmission electron microscope photo of rhenium disulfide manufactured in the present embodiment, and two are can be clearly seen that from Fig. 4
Lattice fringe spacing in sulfuration rhenium nanometer sheet, figure is 0.61nm, corresponding to (100) crystal face of rhenium disulfide.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (2)
1. a kind of method for preparing rhenium disulfide nanometer sheet, it is characterised in that comprise the following steps：By ammonium perrhenate, hydrochloric acid hydroxyl
Amine, thiocarbamide are soluble in water for 1: 1~5: 2~6 according to the amount ratio of material, and preparation obtains the total thing of ammonium perrhenate, hydroxylamine hydrochloride, thiocarbamide
The amount concentration of matter is 0.1~0.4mol/L mixed solution, and the mixed solution is shifted in hydrothermal reaction kettle, heats hydro-thermal
Reactor is to 160~260 DEG C and is incubated the progress to maintain chemical reaction in 6~48 hours, after reaction terminates, by hydrothermal reaction kettle
Temperature is cooled to room temperature, with water and alcohol by product cleaning in hydrothermal reaction kettle, and rhenium disulfide is finally made after drying process
Nanometer sheet.
2. a kind of method for preparing rhenium disulfide nanometer sheet according to claim 1, it is characterised in that hydrothermal reaction kettle leads to
Cross baking oven heating.
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| CN110838586B (en) * | 2018-08-15 | 2023-02-10 | 深圳国家能源新材料技术研发中心有限公司 | Rhenium sulfide nano tube and preparation method and application thereof |
| CN110838572B (en) * | 2018-08-15 | 2022-08-19 | 深圳国家能源新材料技术研发中心有限公司 | Nano composite material and preparation method and application thereof |
| CN109546098A (en) * | 2018-10-11 | 2019-03-29 | 天津大学 | The preparation method of redox graphene load ReS2 for lithium sulfur battery anode material |
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| CN110002504B (en) * | 2019-04-30 | 2021-04-27 | 陕西科技大学 | Preparation method of rhenium disulfide nanosheet |
| CN110538662A (en) * | 2019-07-01 | 2019-12-06 | 天津大学 | Preparation method of cobalt-doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution |
| CN110508292A (en) * | 2019-07-15 | 2019-11-29 | 天津大学 | The preparation method of metal-doped rhenium disulfide nano-chip arrays for electro-catalysis complete solution water |
| CN111072069B (en) * | 2019-09-25 | 2021-06-29 | 江南大学 | Method for preparing visible light response 2D rhenium disulfide and application |
| CN111170370A (en) * | 2020-01-19 | 2020-05-19 | 华南师范大学 | Manufacturing method of rhenium disulfide supercapacitor based on biological template growth |
| CN111354935A (en) * | 2020-03-24 | 2020-06-30 | 东华大学 | Defect-rich rhenium sulfide/nitrogen-doped biomass-based carbon fiber composite material and preparation method thereof |
| CN112018351A (en) * | 2020-08-13 | 2020-12-01 | 五邑大学 | Nano ReS2Mxene composite material and preparation method thereof |
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