CN106698518B - The method that hydro-thermal method prepares the lamella molybdenum disulfide of mercaptan modification - Google Patents
The method that hydro-thermal method prepares the lamella molybdenum disulfide of mercaptan modification Download PDFInfo
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- CN106698518B CN106698518B CN201710035410.3A CN201710035410A CN106698518B CN 106698518 B CN106698518 B CN 106698518B CN 201710035410 A CN201710035410 A CN 201710035410A CN 106698518 B CN106698518 B CN 106698518B
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The present invention provides a kind of MoS of mercaptan modification2The preparation method of nanoscale twins material, specific embodiment are as follows：（1）The preparation of water-soluble molybdenum source presoma.By a certain amount of MoO2(ACAC)2It is dissolved in SHCH2It in COOH aqueous solutions, and is heated to 100 DEG C of constant temperature 1 hour, NaOH solution is added dropwise and adjusts pH to 11.0；（2）The preparation of surface modification lamella molybdenum disulfide material.By a certain amount of Na2S is mixed with above-mentioned solution, is transferred in pyroreaction kettle and is reacted；（3）Purifying.After solution obtained by the reaction dialysis a period of time, the molybdenum disulfide lamella nanoscale twins material of mercaptan modification is obtained.The present invention is lamella MoS2The surface modification of material provides a kind of simple and feasible, simple operation method.
Description
Technical field
The present invention relates to the hydro-thermal method technologies of preparing of the lamella molybdenum disulfide of mercaptan modification, belong to nano science field.
Background technology
Transient metal sulfide lamella two-dimensional material is a type graphene matrix layer two-dimensional material, and two-dimentional molybdenum disulfide is received
Rice lamella is widely used in catalysis, the energy, photoelectricity are set because it is with good electron mobility and larger specific surface area
It is standby to wait in fields.In addition, transient metal sulfide sheet layer material is also a kind of important sensing material, wherein molybdenum disulfide is made
For one kind in two-dimensional nano sheet layer material, the chemical constitution with " sandwich " formula, layer is interior to link two S by a Mo atom
Atom, and be made of between layers Van der Waals key.Its band gap is gradually increased with the reduction of lamellar spacing by 1.2eV
To 1.8eV, reliable theoretical construct support is provided in the application of optoelectronic device and spectrum sensing for it.
Class sheet layer material provides effective surface-active site to reach good sensing effect to surface modification thus.Cause
This, there is the preparation method for grasping the molybdenum disulfide sheet layer material of surface modification important theory directive significance and practical application to anticipate
Justice.Currently, lamella molybdenum disulfide material preparation in terms of be broadly divided into " from top to down " and " to it is lower and on " two methods.
" from top to down " method includes electrochemical stripping method and insertion-stripping method etc., " to it is lower and on " method include hydro-thermal method and
Vapour deposition process etc..Although having the preparation method of the various two-dimensional slice molybdenum disulfide materials of document report, in monolayer
The document that surface modification is done in two-dimensional material rarely has, and is unfavorable for extensive realization and the selective application of sensing.Therefore, we are still
So need to explore a kind of simple preparation method of the lamella molybdenum disulfide material with surface modification functional group.
Invention content
The present invention efficiently uses water-soluble improvement result of the protective agent to presoma molybdenum source, provides a kind of simple, efficient
MoS2The preparation method of nanoscale twins material.The method includes the steps of：
（1）The preparation of water-soluble precursor：A certain amount of molybdenum source is dissolved in water-soluble thiocarboxylic acid solution, and is heated
To 100 DEG C of constant temperature 1 hour, NaOH solution is added dropwise and adjusts pH to 11.0；
（2）The preparation of surface modification lamella molybdenum disulfide material：A certain amount of sulphur source is mixed with above-mentioned solution, is transferred to
It is reacted 20 ~ 40 hours at 220 DEG C in pyroreaction kettle；
（3）Purifying：Solution obtained by the reaction is dialysed in bag filter after a period of time, obtains the curing of mercaptan modification
Molybdenum nanoscale twins material；
The synthetic method of the present invention is characterized in：Reaction raw materials of the present invention it is cheap, ready availability.Solvent is pure water.
The present invention is successfully realized preparation and the performance modification of lamella molybdenum disulfide material, and easy to operate, safety is cheap.
The present invention is successfully realized modification of the thiol molecule on molybdenum disulfide sheet layer material, and the material after modification is made to have
There are good water-soluble, stability and fluorescent characteristic.
Description of the drawings
Fig. 1 are TGA-MoS prepared by the present invention2The TEM of nanoscale twins schemes；
Fig. 2 are TGA-MoS prepared by the present invention2The XRD diagram of nanoscale twins；
Fig. 3 are TGA-MoS prepared by the present invention2The FT-IR of nanoscale twins schemes；
Fig. 4-6. is TGA-MoS prepared by the present invention2The XPS of nanoscale twins schemes.
Specific embodiment
The MoS of TGA modifications of the present invention is illustrated below by example2The preparation method of nanoscale twins material.This example
Implemented under the premise of being scheme with the present invention, detailed specific operating process is described further.
Embodiment 1
1）By 5 mL, 0.01M thioglycolic acids（SHCH2COOH）It is dissolved in 95 mL pure water, then in magnetic agitation
Under the conditions of（Rotating speed：500 r∙min-1）0.081 g MoO are added2(ACAC)2（Molybdenum source is 1 with protective agent molar ratio:2）, and add
Heat to 100 °C keep 1 hour；
2）Above-mentioned solution ph is adjusted to 11.0 with 0.1 M NaOH solutions, adds 0.5 g Na2S solution ultrasounds
It 10 minutes, is subsequently transferred to react 20 hours for 220 °C in pyroreaction kettle；
3）The product bag filter that will be obtained（Mw: 500）Dialysis, to remove impurity；
4）The faint yellow clear of product has good water-soluble dispersion performance, is irradiated under 365 nm ultraviolet lamps, can
Observe that blue-fluorescence, material thickness are distributed as 0.67 ~ 1.03 nm（Monolayer）.
1 collection of products of example is used for TEM, XRD, FT-IR, the analysis of the material characterizations such as XPS.
Embodiment 2
1）By 5 mL, 0.01M thioglycolic acids（SHCH2COOH）It is dissolved in 90 mL pure water, then in magnetic agitation
Under the conditions of（Rotating speed：500 r∙min-1）0.041 g MoO are added2(ACAC)2（Molybdenum source is 1 with protective agent molar ratio:4）, and add
Heat to 100 °C keep 1 hour；
2）Above-mentioned solution ph is adjusted to 11.0 with 0.1 M NaOH solutions, adds 0.5 g Na2S solution ultrasounds
It 10 minutes, is subsequently transferred to react 20 hours for 220 °C in pyroreaction kettle；
3）The light yellow suspension bag filter that will be obtained（Mw: 500）Dialysis, it is miscellaneous to remove organic molecule and metal
Matter；
4）Product clear has good water-soluble, dispersibility, glimmering in blue under 365 nm ultra violet lamps
Light.
Embodiment 3
1）By 15 mL, 0.01M thioglycolic acids（SHCH2COOH）It is dissolved in 90 mL pure water, then in magnetic agitation
Under the conditions of（Rotating speed：500 r∙min-1）0.081 g MoO are added2(ACAC)2（Molybdenum source is 1 with protective agent molar ratio:6）, and add
Heat to 100 °C keep 1 hour；
2）Above-mentioned solution ph is adjusted to 11.0 with 0.1 M NaOH solutions, adds 0.5 g Na2S solution ultrasounds
It 10 minutes, is subsequently transferred to react 20 hours for 220 °C in pyroreaction kettle；
3）The light yellow suspension bag filter that will be obtained（Mw: 500）Dialysis, it is miscellaneous to remove organic molecule and metal
Matter；
4）Product clear has good water-soluble, dispersibility, glimmering in blue under 365 nm ultra violet lamps
Light.
Embodiment 4
1）By 5 mL, 0.01M thiomalic acids（HOOCCH(SH)CH2COOH）It is dissolved in 90 mL pure water, then in magnetic
Under conditions of power stirring（Rotating speed：500 r∙min-1）0.081 g MoO are added2(ACAC)2（Molybdenum source is 1 with protective agent molar ratio:
2）, and be heated to 100 °C and kept for 1 hour；
2）Above-mentioned solution ph is adjusted to 11.0 with 0.1 M NaOH solutions, adds 0.5 g Na2S solution ultrasounds
It 10 minutes, is subsequently transferred to react 20 hours for 220 °C in pyroreaction kettle；
3）The light yellow suspension bag filter that will be obtained（Mw: 500）Dialysis, it is miscellaneous to remove organic molecule and metal
Matter；
4）Product clear has good water-soluble, dispersibility, glimmering in blue under 365 nm ultra violet lamps
Light.
Embodiment 5
1）By 5 mL, 0.01M thioglycolic acids（SHCH2COOH）It is dissolved in 95 mL pure water, then in magnetic agitation
Under the conditions of（Rotating speed：500 r∙min-1）0.081 g MoO are added2(ACAC)2（Molybdenum source is 1 with protective agent molar ratio:2）, and add
Heat to 100 °C keep 1 hour；
2）Above-mentioned solution ph is adjusted to 11.0 with 0.1 M NaOH solutions, adds 0.5 g Na2S solution ultrasounds
It 10 minutes, is subsequently transferred to react 30 hours for 220 °C in pyroreaction kettle；
3）The product bag filter that will be obtained（Mw: 500）Dialysis, to remove impurity；
4）Product clear has good water-soluble dispersion performance, has good water-soluble dispersion performance, 365
It is irradiated under nm ultraviolet lamps, faint blue-fluorescence can be observed, material thickness is distributed as 2 ~ 3 nm（2 ~ 3 molecular layers）.
Embodiment 6
1）By 5 mL, 0.01M thioglycolic acids（SHCH2COOH）It is dissolved in 95 mL pure water, then in magnetic agitation
Under the conditions of（Rotating speed：500 r∙min-1）0.081 g MoO are added2(ACAC)2（Molybdenum source is 1 with protective agent molar ratio:2）, and add
Heat to 100 °C keep 1 hour；
2）Above-mentioned solution ph is adjusted to 11.0 with 0.1 M NaOH solutions, adds 0.5 g Na2S solution ultrasounds
It 10 minutes, is subsequently transferred to react 40 hours for 220 °C in pyroreaction kettle；
3）The product bag filter that will be obtained（Mw: 500）Dialysis, to remove impurity；
4）Product clear has good water-soluble dispersion performance, has good water-soluble dispersion performance, 365
It is irradiated under nm ultraviolet lamps, unstressed configuration, material thickness is distributed as>10 nm.
Claims (4)
1. a kind of hydro-thermal method prepares the MoS of mercaptan modification2The method of nanoscale twins material, this method mainly include the following steps that：
（1）The preparation of water-soluble precursor：A certain amount of molybdenum source is dissolved in water-soluble thiocarboxylic acid solution, and is heated to 100 DEG C
Constant temperature 1 hour adjusts pH to 11.0；（2）The preparation of surface modification lamella molybdenum disulfide material：By a certain amount of sulphur source with it is above-mentioned
Solution mixes, and is transferred in pyroreaction kettle and is reacted 20 ~ 40 hours at 220 DEG C；（3）Purifying：Solution obtained by the reaction is existed
It dialyses in bag filter after a period of time, obtains the molybdenum disulfide nano sheet layer material of mercaptan modification；The molybdenum source is acetylacetone,2,4-pentanedione
Molybdenum, the sulphur source are vulcanized sodium, and the thiocarboxylic acid is thioglycolic acid or thiomalic acid, is filled in forerunner's production procedure
Work as protective agent；The molybdenum disulfide nano sheet layer material for the mercaptan modification being prepared has good water-soluble dispersion performance, in purple
Under outer light irradiation, blue-fluorescence can be observed.
2. the method as described in claim 1, which is characterized in that acetyl acetone and protective agent molar ratio range are 1：2~1：6.
3. the method as described in claim 1, which is characterized in that thiocarboxylic acid can not only be used for protective agent and stabilizer, and can solve
Certainly the problem of reaction raw materials molybdenum source low aqueous solubility.
4. the method as described in claim 1, which is characterized in that the molybdenum disulfide nano sheet layer material of prepared mercaptan modification
Thickness distribution from monolayer to several molecular layers etc..
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| CN110078124A (en) * | 2019-04-18 | 2019-08-02 | 哈尔滨理工大学 | A kind of mercaptan modification molybdenum disulfide composite material and preparation method |
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