CN107601443A - A kind of preparation method of ultra-thin tungsten selenide nanometer sheet - Google Patents
A kind of preparation method of ultra-thin tungsten selenide nanometer sheet Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of ultra-thin tungsten selenide nanometer sheet, and in particular to using oil phase method preparation tungsten selenide, the material has the property of catalysis benzylamine coupling generation imines, and the invention belongs to material preparation and applied technical field.Using Schlenk line routes, using oleyl amine, oleic acid, octadecylene, n- dodecyl mereaptan as solvent, using the selenium source of certain ratio and tungsten source as reactant, under certain reaction temperature, thickness is prepared less than 2 nanometers, featheriness ultrathin nanometer piece, the nanometer sheet has the function that the coupling of efficient catalytic benzylamine into N benzylidenei benzylamines, in hexamethylene and acetonitrile solvent, the yield that benzylamine is coupled to obtain N benzylidenei benzylamines respectively reaches 95%, 96%.The specific surface area of catalyst is big, high catalytic efficiency, low without using noble metal, cost.Preparation process of the present invention is simple, operation is easy, without using organic masterplate and surfactant, is adapted to industrialized production；Obtained tungsten selenide thing is mutually pure, and specific surface area is big, and reusing is high.
Description
Technical field
The invention belongs to material preparation and applied technical field, and in particular to prepare a kind of ultra-thin tungsten selenide using oil phase method
Nanometer sheet, the material have the property of catalysis benzylamine coupling generation imines.
Background technology
Recent selenide semiconductor nano material due to a variety of physicochemical properties, including thermoelectric property, dielectric property and
Its potential application and as current research focus.This material has a relatively low band gap mostly, and high absorption coefficient is good
Good light resistance, hypotoxicity, high photoelectric transformation efficiency.One of compound important as selenides family, tungsten selenide material
It is made up of two-dimentional Se-W-Se layer structure, wherein W atomic planes are in two hexagon Se atomic planes
Between.Combined in selenizing tungsten layer by strong covalent bond, and interlayer is combined by Van der Waals force.Because Coating combination is very weak,
So it is easy to prepare individual layer tungsten selenide by micromechanics stripping means.Although micromechanics stripping method can effectively prepare high-quality
The individual layer tungsten selenide nano material of amount and high-flatness, but extensive and controllable preparation can not be realized, hence it is imperative that visiting
Rope goes out a kind of new preparation method.James, et al.（J. Am. Chem. Soc. 2013, 135, 223）Pass through chemistry
Vapor Transport has synthesized p-type tungsten selenide crystal；Zou, et al.（J. Mater. Chem. A 2015 , 3, 18090−
18097）Pass through chemical vapour deposition technique（CVD）Generation is in the dispersed tungsten selenide nano flake in electro spinning nano fiber surface；
And 3D dendroid tungsten selenides are grown on conductive carbon nanotube fiber mat with CVD（J. Mater. Chem. A 2015, 3,
12149−12153）.Patents have：（1）Application number CN201010572042.4, title：A kind of two tungsten selenide nano-clathrates
Preparation method, a kind of two tungsten selenide nano-clathrates with core shell structure are obtained by synthesis in solid state, this application is in
The term of validity；（2）Application number CN201210374547.9, title：A kind of preparation method of the selenizing tungsten nanowires of high orientation two, is adopted
WO is prepared with hydrothermal method2Nano wire, then the high-purity selenium selenizing that this nano wire purity is more than 99.9% is obtained again
Two selenizing tungsten nanowires of high orientation were obtained, this application is in the term of validity.
As can be seen that the preparation method of tungsten selenide nanometer sheet is many from above-mentioned narration and citing, but mostly react bar
Part requires higher, technical difficulty is larger, seldom has been reported that synthesis of the tungsten selenide nanometer sheet in solution.The application with it is above-mentioned
Document report is different, and inventor uses oil phase method, using selenium powder, tungsten hexachloride as raw material, with oleyl amine, oleic acid, octadecylene, positive 12
Mercaptan is solvent, prepares ultra-thin tungsten selenide nanometer sheet；The material is coupled generation imines to benzylamine and shows higher catalysis
Performance.
The content of the invention
It is an object of the invention to provide a kind of preparation method with catalytic property material and its for being catalyzed benzylamine generation
Imines.The preparation process of this method is simple, reproducible, and can largely synthesize, suitable for industrialized production.It is obtained super
Thin nanometer sheet has higher catalytic performance, is catalyzed benzylamine high conversion rate up to 96%.
The preparation method step of the ultrathin nanometer piece of the present invention is as follows：
A. by 2.2 mMs of selenium powders（0.174 g）Add in 2.4 milliliters of oleyl amines and 2.4 milliliters of n- dodecyl mereaptan mixed solutions,
Magnetic agitation to selenium powder is completely dissolved at room temperature.
B. by 1 mM of tungsten chloride（0.397 g）10 milliliters of oleyl amines, 10 milliliters of oleic acid and 10 milliliters of octadecylenes are added to mix
Close in solution, magnetic agitation, vacuum nitrogen circulates three times, removes air and vapor in reaction system.Reaction solution is heated
To 140 DEG C, vacuumize 30 minutes, remove low-boiling-point substance；It is warming up to 300 DEG C.
C. selenium source predecessor A is expelled in B, after temperature recovery to reaction 60 minutes is continued after 300 DEG C, reaction terminates
After place reaction liquid into 10 milliliters of centrifuge tubes, add 3 milliliters of chloroforms to disperse reaction solution, add the washing of 3 milliliters of ethanol, with 6000
Rpm rotating speed, centrifuge 5 minutes, after staying sediment to wash 3 times repeatedly, product is dried in 60 DEG C of vacuum drying chambers.
Described reactant selenium source is selenium powder；
Described reactant tungsten source is tungsten hexachloride；
The reaction vessel is 100 milliliters of three-neck flasks；
The reaction scheme is Schlenk line routes.
The tungsten selenide nanometer sheet prepared with the present invention is catalyzed benzylamine coupling method：Measure 55 microlitres（0.1 mM）Benzyl
Amine is dissolved in 500 microlitres of different solvents, test reaction conversion ratio after a period of time.
Five kinds of n-hexane, hexamethylene, N-N dimethylformamides, absolute ethyl alcohol, acetonitrile solvents are chosen, for catalytic performance
Test.
Concrete operations are as follows：
Magneton is put into glass tube, adds 30 milligrams of tungsten selenide products to take 55 microlitres with liquid-transfering gun as catalyst（0.1 mmoles
You）Benzylamine is added in glass tube, then adds 500 microlitres of solvents, is reacted 30 hours in 60 DEG C of magnetic agitations under closed environment
Afterwards, catalyst is centrifuged, quantitative analysis is carried out to product with gas-chromatography, obtains conversion ratio.
Described solvent is all chromatographically pure rank；
Described reactant benzylamine consumption is 0.1 mM, concentration is 2 ' 10-4 M；
Described catalyst tungsten selenide dosage is 30 milligrams；
Described gas-chromatography is Japanese Shimadzu GC-2010 plus.
Tungsten selenide nanometer sheet prepared by the present invention has good catalytic performance to benzylamine coupling reaction, and the preparation of material and
Detection method is simple, can largely synthesize, and dosage is few, reusable.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of the tungsten selenide nanometer sheet prepared in embodiment 1（SEM）；
Fig. 2 is the transmission electron microscope picture of the tungsten selenide nanometer sheet prepared in embodiment 1（TEM）；
Fig. 3 is the SEAD figure of the tungsten selenide nanometer sheet prepared in embodiment 1（SAED）And high resolution TEM
Figure（HRTEM）；
Fig. 4 is the X-ray powder diffraction figure of the tungsten selenide nanometer sheet prepared in embodiment 1（XRD）；
Fig. 5 is the Raman figure of the tungsten selenide nanometer sheet prepared in embodiment 1（Raman）；
Fig. 6 is the conversion ratio block diagram for being catalyzed benzylamine coupling in embodiment 2 under different solvents；
Embodiment：
Specific description is done to the present invention with reference to embodiments：
Embodiment 1：The preparation of tungsten selenide nanometer sheet：
By 2.2 mMs of selenium powders（0.174 g）Add in 2.4 milliliters of oleyl amines and 2.4 milliliters of n- dodecyl mereaptan mixed solutions, room temperature
Lower magnetic agitation is completely dissolved to obtain selenium source predecessor to selenium powder.By 1 mM of tungsten chloride（0.397 g）Add 10 milliliters of oil
In amine, 10 milliliters of oleic acid and 10 milliliters of octadecylene mixed solutions, magnetic agitation, vacuum nitrogen circulates three times, removes reaction system
In air and vapor.Reaction solution is heated to 140 DEG C, vacuumized 30 minutes, removes low-boiling-point substance；Be tod when being warming up to 300 DEG C
Selenium source predecessor is injected, and is reacted 60 minutes after temperature recovery, and reaction is placed reaction liquid into 10 milliliters of centrifuge tubes after terminating, and is added
3 milliliters or so chloroforms disperse reaction solution, then add 3 milliliters of ethanol washing reaction liquids, with 6000 rpms of rotating speeds, centrifugation 5
Minute, after staying sediment to wash 3 times repeatedly, final product is dried to obtain in 60 DEG C of vacuum drying chambers.
Transmitted using JEOL JEM-2100（TEM）, selected diffraction（SAED）, high resolution transmission electron microscopy
（HRTEM）Morphology characterization is carried out to obtained sample, using the KW X-ray diffractometers of SmartLab 9（XRD）、inVia-
Reflex laser Raman spectrometers（Raman）Sample thing is mutually characterized.
The transmission electron microscope picture of scanning electron microscope (SEM) photograph and Fig. 2 samples from Fig. 1 samples can be seen that sample as the ultra-thin nanometer of featheriness
The anthogram of piece composition, thickness are less than 2 nm；By standard card JCPDS No：Knowable to 38-1388, the choosing of Fig. 3 tungsten selenide nanometer sheets
Area's electron diffraction diagram（SAED）Tungsten selenide is corresponded to respectively（100）、（103）、（006）、（105）、（110）、（008）、（002）It is brilliant
Face, high resolution TEM figure（HRTEM）In the nm of spacing of lattice 0.625,0.287 nm, correspond to tungsten selenide respectively
（002）、（100）Crystal face.The X-ray powder diffraction figure of Fig. 4 products（XRD）, with PDF card JCPDS No：38-1388 is consistent；From
250 cm of Fig. 5 Raman spectrograms-1At left and right it is evident that tungsten selenide characteristic peak,
Embodiment 2：Catalytic coupling of the tungsten selenide nanometer sheet to benzylamine：
The tungsten selenide nanometer sheet prepared with the present invention is catalyzed benzylamine coupling method：Measure 55 microlitres of benzylamines and be dissolved in 500 microlitres not
With in solvent, test reaction conversion ratio after a period of time.
Five kinds of n-hexane, hexamethylene, N-N dimethylformamides, absolute ethyl alcohol, acetonitrile solvents are chosen, for catalytic performance
Test.
Concrete operations are as follows：
Magneton is put into glass tube, adds 30 milligrams of tungsten selenide products to take 55 microlitres with liquid-transfering gun as catalyst（0.1 mmoles
You）Benzylamine is added in glass tube, then adds 500 microlitres of solvents, is reacted 30 hours in 60 DEG C of magnetic agitations under closed environment
Afterwards, add homogeneous solvent to centrifuge catalyst after diluting, quantitative analysis is carried out to product with gas-chromatography, obtains conversion ratio.
From Fig. 6 block diagram as can be seen that when solvent is hexamethylene and acetonitrile, benzylamine is coupled to obtain N- benzylideneis
The yield of benzylamine is up to 95%, 96% respectively.
Claims (2)
1. a kind of preparation method of ultra-thin tungsten selenide nanometer sheet, specific step is by 2.2 mMs of selenium powders（0.174 g）Add
In 2.4 milliliters of oleyl amines and 2.4 milliliters of n- dodecyl mereaptan mixed solutions, magnetic agitation is completely dissolved to obtain selenium source to selenium powder at room temperature
Predecessor；By 1 mM of tungsten chloride（0.397 g）It is molten to add 10 milliliters of oleyl amines, 10 milliliters of oleic acid and 10 milliliters of octadecylene mixing
In liquid, magnetic agitation, vacuum nitrogen circulates three times, removes air and vapor in reaction system；Reaction solution is heated to 140
DEG C, vacuumize 30 minutes, remove low-boiling-point substance；Selenium source predecessor is injected when being warming up to 300 DEG C, after temperature recovery to after 300 DEG C,
Continue reaction 60 minutes, reaction is placed reaction liquid into 10 milliliters of centrifuge tubes after terminating, and adds 3 milliliters or so chloroforms scattered anti-
Liquid is answered, then adds 3 milliliters of ethanol washing reaction liquids, with 6000 rpms of rotating speeds, centrifuges 5 minutes, stays sediment to wash repeatedly 3 times
Afterwards, it is dried to obtain final product in 60 DEG C of vacuum drying chambers.
2. the tungsten selenide nanometer sheet that preparation method as claimed in claim 1 obtains produces the catalytic of imine reaction for benzylamine
Can, the specific experiment step that it is detected is as follows：In glass tube plus 30 milligrams of tungsten selenide products are as catalyst, taken with liquid-transfering gun
55 microlitres（0.1 mM）Benzylamine is added in glass tube, 500 microlitres of solvents is then added, in 60 DEG C of magnetic force under closed environment
After stirring reaction 30 hours, catalyst is centrifuged, quantitative analysis is carried out to product with gas-chromatography, analysis is found when solvent is
When hexamethylene, acetonitrile, the yield that benzylamine is coupled to obtain N- benzylidenei benzylamines is up to 95%, 96% respectively, so as to for benzyl
The catalysis of amine.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108766864A (en) * | 2018-03-28 | 2018-11-06 | 广东工业大学 | A method of preparing two-dimentional tungsten selenide rule laminar sheet in quartz plate substrate |
| CN111392698A (en) * | 2020-04-14 | 2020-07-10 | 西北大学 | Nickel ditelluride micron ball and preparation method and application thereof |
| CN111470539A (en) * | 2019-10-20 | 2020-07-31 | 安徽大学 | Preparation method of high-efficiency catalytic benzylamine oxidative coupling catalyst |
| CN111807333A (en) * | 2020-07-28 | 2020-10-23 | 安徽大学 | Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice |
| CN112142110A (en) * | 2019-06-28 | 2020-12-29 | 安徽大学 | Preparation method of tungsten sulfide nanosheet with catalytic performance |
| CN112520709A (en) * | 2020-11-24 | 2021-03-19 | 北京科技大学 | Preparation and application method of ultrathin tungsten diselenide nanoflower |
| CN112897476A (en) * | 2021-01-15 | 2021-06-04 | 南京工业大学 | Gas sensor material bismuth selenide/bismuth oxychloride compound and preparation method and application thereof |
| CN113683062A (en) * | 2021-08-24 | 2021-11-23 | 安徽大学 | Graphite composite SnSe2Method for preparing thermoelectric material |
| CN114988373A (en) * | 2022-06-28 | 2022-09-02 | 安徽大学 | Quasi-two-dimensional selenium nanosheet and preparation method thereof |
| CN115739129A (en) * | 2022-12-01 | 2023-03-07 | 武汉大学 | Nano layered hexagonal phase noble metal selenide and preparation method and application thereof |
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| CN112142110B (en) * | 2019-06-28 | 2023-04-07 | 安徽大学 | Preparation method of tungsten sulfide nanosheet with catalytic performance |
| CN112142110A (en) * | 2019-06-28 | 2020-12-29 | 安徽大学 | Preparation method of tungsten sulfide nanosheet with catalytic performance |
| CN111470539A (en) * | 2019-10-20 | 2020-07-31 | 安徽大学 | Preparation method of high-efficiency catalytic benzylamine oxidative coupling catalyst |
| CN111392698A (en) * | 2020-04-14 | 2020-07-10 | 西北大学 | Nickel ditelluride micron ball and preparation method and application thereof |
| CN111807333A (en) * | 2020-07-28 | 2020-10-23 | 安徽大学 | Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice |
| CN112520709A (en) * | 2020-11-24 | 2021-03-19 | 北京科技大学 | Preparation and application method of ultrathin tungsten diselenide nanoflower |
| CN112897476A (en) * | 2021-01-15 | 2021-06-04 | 南京工业大学 | Gas sensor material bismuth selenide/bismuth oxychloride compound and preparation method and application thereof |
| CN113683062A (en) * | 2021-08-24 | 2021-11-23 | 安徽大学 | Graphite composite SnSe2Method for preparing thermoelectric material |
| CN114988373A (en) * | 2022-06-28 | 2022-09-02 | 安徽大学 | Quasi-two-dimensional selenium nanosheet and preparation method thereof |
| CN114988373B (en) * | 2022-06-28 | 2024-03-01 | 安徽大学 | Quasi two-dimensional selenium nano-sheet and preparation method thereof |
| CN115739129A (en) * | 2022-12-01 | 2023-03-07 | 武汉大学 | Nano layered hexagonal phase noble metal selenide and preparation method and application thereof |
| CN115739129B (en) * | 2022-12-01 | 2024-02-20 | 武汉大学 | Nanometer layered hexagonal phase noble metal selenide and preparation method and application thereof |
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