CN108394935B - A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet - Google Patents
A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet Download PDFInfo
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Abstract
The present invention provides a kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, comprising steps of MoS4 2‑The preparation of intercalation LDHs compound；The MoS that will be obtained4 2‑Intercalation LDHs compound is calcined under inert gas protection, obtains MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound；Through removing mixed-metal oxides, MoS is obtained2Individual layer nanometer sheet.Method of the invention is simple, at low cost, it is easy to accomplish, high yield, MoS2Individual layer nanometer sheet ratio is high, and is easy to industrial applications.
Description
Technical field
The present invention relates to a kind of methods of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, belong to two-dimension nano materials
Preparation field.
Background technique
Transition metal dichalcogenide has huge application potential in fields such as light, elctro-catalyst and energy storage materials.
MoS2Individual layer nanometer sheet is because having direct band gap structure (~1.9eV), high current switching ratio and superior field-effect electron transfer
The properties such as rate and be concerned.MoS2The performance of individual layer nanometer sheet is substantially better than its multi-layer nano piece, but its extensive, high yield
Preparation still has challenge.Typical preparation MoS2The method of individual layer nanometer sheet can be attributed to four classes: mechanical stripping method, liquid phase ultrasound
Stripping method, chemical vapour deposition technique and lithium intercalation up-stripping method.Mechanical stripping method and liquid phase ultrasound stripping method low yield are changed
It learns that vapour deposition process is at high cost, complex process, is difficult to realize heavy industrialization application.Electrochemistry assists the stripping of lithium ion intercalation
It is high from method yield, but the environmentally sensitive property of stripping process is high, and experiment condition is harsh, and easily makes MoS2The semiconductor property of material meets with
The individual layer nanometer sheet of semiconductor phase is unable to get to destruction.
Such as, Chinese patent literature CN106563130A discloses a kind of strip preparation method of molybdenum disulfide nano sheet, packet
It includes following steps: albumin and molybdenum disulfide powder is added to the water；By gained mixed dispersion liquid through Ultrasonic Cell Disruptor ultrasound
6-10 hours, then gradient centrifugation 10-20 minutes, it is molten that the solution after centrifugation is divided into upper layer, middle layer, lower layer according to a certain volume
Liquid can accordingly obtain the molybdenum disulfide nano sheet solution of single layer, few layer and multilayer.The inventive method simple process, is prepared into
The molybdenum disulfide nano sheet arrived has good sensitivity in terms of photoacoustic imaging radiography.But above method yield is lower, energy consumption
Greatly, there is also the possibility for smashing molybdenum disulfide nano sheet ultrasound for ultrasound removing, it is difficult to realize heavy industrialization application.
For another example, Chinese patent literature CN104418387A discloses a kind of molybdenum disulfide nano thin slice and preparation method thereof.
In an inert atmosphere, sulphur source is contacted to molybdenum source steam and is carried out chemical vapor deposition, two sulphur of setting are formed on the substrate
Change molybdenum nano flake；The reaction condition of the chemical vapor deposition are as follows: reaction temperature be 690~750 DEG C, the reaction time be 5~
60min.The molybdenum disulfide nano thin slice overwhelming majority is single layer.But the invention use chemical vapour deposition technique, higher cost,
Technique is relative complex, the high requirements on the equipment, it is difficult to realize heavy industrialization application.
Therefore, one kind is found to be simple to operate and friendly to environment, is at low cost, being easily achieved, yield height, being easy to industrialized
MoS2Individual layer nanometer sheet synthetic method, to MoS2The industrial applications of two-dimension nano materials are of great significance.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet
Method.Method of the invention is simple, at low cost, it is easy to accomplish, high yield, and it is easy to industrial applications.
Term explanation:
LDHs: layered double hydroxide (Layered Double Hydroxide, LDH) is hydrotalcite
The general designation of (Hydrotalcite, HT) and houghite compound (Hydrotalcite-Like Compounds, HTLCs), by
A series of supramolecular materials of these compound intercalations assembling are known as hydrotalcite intercalation material (LDHs).
Mixed-metal oxides: the entitled MixedMetal Oxides of English is abbreviated as MMO.
A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, comprising steps of
(1)MoS4 2-The preparation of intercalation LDHs compound；
(2) MoS for obtaining step (1)4 2-Intercalation LDHs compound is calcined under inert gas protection, obtains MoS2Single layer
Nanometer sheet/mixed-metal oxides (MMO) compound；Through removing mixed-metal oxides, MoS is obtained2Individual layer nanometer sheet.
Preferred according to the present invention, LDHs described in step (1) has hydrotalcite crystal structure；Chemical formula is [M2+ 1-xM3+ x
(OH)2]x+[An- x/n]x-·mH2O, wherein M2+For bivalent metal ion, M3+For trivalent metal ion, An-For n valence anion, x
For M in every mole of LDHs3+Molar fraction；N=1~2, x=0.15~0.35, m=0.5~6.
Preferably, the M2+For Mg2+、Ca2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+One of；The M3+For
Al3+、Cr3+、Mn3+、Fe3+、Co3+Or Ni3+One of；The An-For OH-、Cl-、CO3 2-Or NO3 -One of；It is further excellent
Choosing, the M2+For Mg2+、Ca2+Or Zn2+One of, M3+For Al3+, An-For Cl-、NO3 -Or CO3 2-One of.
It is preferred according to the present invention, in step (1), with (NH4)2MoS4、Na2MoS4Or K2MoS4For MoS4 2-Source, using from
Sub- exchange process, structural remodeling method or coprecipitation prepare MoS4 2-Intercalation LDHs compound.
Preferably, the MoS4 2-Source is (NH4)2MoS4。
Preferably, the ion-exchange prepares MoS4 2-Intercalation LDHs compound, comprising steps of
Divalent metal nitrate and trivalent metal nitrate is soluble in water, obtain solution A；By NaOH, KOH or mass concentration
It is soluble in water for the ammonium hydroxide of 20-30%, obtain solution B；Under inert gas shielding, stirring condition, simultaneously by solution A and solution B
It is added dropwise in de aerated water C, and controlling final pH is 9.5~10.0, and 20-40min is stirred at room temperature；Then under inert gas shielding,
70-90 DEG C of curing 10-15h, is filtered, washed, dries to obtain NO3 -The LDHs of intercalation；By NO3 -The LDHs and MoS of intercalation4 2-Source adds
Enter in de aerated water, obtain suspension D, under inert gas shielding, 20-60 DEG C of stirring 12-36h is filtered, washed, dries to obtain MoS4 2-
Intercalation LDHs compound.
It is further preferred that the divalent metal nitrate is Mg (NO3)2、Ca(NO3)2Or Zn (NO3)2One of, three
Valence metal nitrate is Al (NO3)3。
It is further preferred that the molar ratio of the divalent metal nitrate and trivalent metal nitrate is (0.65-0.85):
(0.15-0.35), the molar concentration of total metal nitrate is 0.1-1mol/L in the solution A.
It is further preferred that the molar concentration of NaOH, ammonia or KOH are 0.1-1moL/L in the solution B.
It is further preferred that the molar ratio of NaOH, ammonia or KOH are 1:(2- in total metal nitrate and solution B in solution A
3)。
It is further preferred that the volume ratio of the de aerated water C and solution A is (0.1-2): 1.
It is further preferred that the NO3 -The LDHs and MoS of intercalation4 2-The mass ratio in source is 1:(0.5-3).
It is further preferred that in the suspension D, NO3 -The mass concentration of the LDHs of intercalation is 5-20%.
Preferably, the structural remodeling method prepares MoS4 2-Intercalation LDHs compound, comprising steps of
Divalent metal salt, trivalent metal salt, urea is soluble in water, solution E is obtained, 20-30h is stirred at 80-100 DEG C, is passed through
It is filtered, washed, dries to obtain CO3 2-The LDHs of intercalation；400-550 DEG C of calcining 1-3h obtains MMO；By MMO and MoS4 2-Source is added de-
In air water, suspension F is obtained, under inert gas shielding, 20-60 DEG C of stirring 12-36h；It is filtered, washed, dries to obtain MoS4 2-Intercalation
LDHs compound.
It is further preferred that the divalent metal salt is Mg (NO3)2, trivalent metal salt is Al (NO3)3。
It is further preferred that the molar ratio of the divalent metal salt and trivalent metal salt is (0.65-0.85): (0.15-
0.35), urea and total metal salt molar ratio are 3.3-10:1.
It is further preferred that the molar concentration of total metal salt is 0.1-0.5mol/L in the solution E.
It is further preferred that the MMO and MoS4 2-The mass ratio in source is 1:(0.5-5).
It is further preferred that the mass concentration of MMO is 5-20% in the suspension F.
Preferably, the coprecipitation prepares MoS4 2-Intercalation LDHs compound, comprising steps of
Divalent metal nitrate, trivalent metal nitrate is soluble in water, obtain solution G；By NaOH, KOH or mass concentration
For the ammonium hydroxide and MoS of 20-30%4 2-Source is soluble in water, obtains Solution H；Under inert gas shielding, stirring condition, by solution G and
Solution H is added dropwise in de aerated water I simultaneously, and control final pH is 9.5~10.0, and 20-40min is stirred at room temperature；Then inert gas
Under protection, 70-90 DEG C of curing 10-15h；It is filtered, washed, dries to obtain MoS4 2-Intercalation LDHs compound.
It is further preferred that the divalent metal nitrate is Mg (NO3)2、Zn(NO3)2Or Ca (NO3)2, trivalent metal nitre
Hydrochlorate is Al (NO3)3。
It is further preferred that the molar ratio of the divalent metal nitrate and trivalent metal nitrate is (0.65-0.85):
(0.15-0.35)。
It is further preferred that the molar concentration of total metal nitrate is 0.1-1mol/L in the solution G.
It is further preferred that the KOH, mass concentration are the ammonium hydroxide or NaOH of 20-30% and rubbing for total metal nitrate
You are than being 2-3:1.
It is further preferred that MoS in the Solution H4 2-Source and trivalent metal nitrate molar ratio are (0.5-2): 1.
It is further preferred that MoS in the Solution H4 2-The mass concentration in source is 2-4%.
It is further preferred that the volume ratio of the de aerated water I and solution G is (0.1-2): 1.
According to the present invention preferably, it is calcined described in the step of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet (2)
Temperature is 400-550 DEG C, and calcination time is 1-4 hours, and heating rate is 1-10 DEG C/min.
According to the present invention preferably, in the step of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet (2), the removal
The method of mixed-metal oxides are as follows: use molar concentration for the aqueous solution soaking MoS of the acid of 0.3-5mol/L2Single layer nanometer
Piece/mixed-metal oxides (MMO) compound 10-16h, is filtered, washed to obtain MoS2Individual layer nanometer sheet；The aqueous solution of the acid
For one of hydrochloric acid, sulfuric acid or phosphate aqueous solution, preferably aqueous hydrochloric acid solution；The MoS2Individual layer nanometer sheet/mixed metal
The volume ratio of the aqueous solution of the quality and acid of oxide (MMO) compound is 0.01-0.03g/mL.
It is preferred according to the present invention, the MoS that step (2) is obtained2Individual layer nanometer sheet ultrasonic disperse in a solvent, obtains MoS2
Individual layer nanometer sheet dispersion.
Preferably, the solvent is one of water, organic solvent or aqueous surfactant solution；The organic solvent is
One of methyl pyrrolidone, isopropanol or ethyl alcohol；The aqueous surfactant solution is ten that mass concentration is 0.1-1%
Six alkyl trimethyl ammonium bromide aqueous solutions；It is described ultrasound be probe sonication, ultrasonic time 10-60min: the MoS2Single layer is received
MoS in rice piece pure water dispersion2The mass concentration of individual layer nanometer sheet is 0.01-0.5mg/L.
According to the present invention, MoS4 2-Ion calcining and decomposing is converted into MoS2Actual yield close to 100% (a small amount of MoS4 2-From
Son is oxidized in calcination process, and mass fraction is less than 2%).The MoS that the method for the present invention is prepared2In individual layer nanometer sheet,
MoS2Individual layer nanometer sheet accounting rate is 95-98%.
It technical characterstic of the invention and has the beneficial effect that:
1, the LDHs of the method for the present invention preparation has layered crystal structure, laminate band structure positive charge, and interlayer presence can hand over
The anion changed.Since its special anion intercalated and commutative properties makes it in adsorbent, drug conveying and micro-nano reaction
The fields such as device are widely applied.The present invention synthesizes MoS using LDHs interlayer as microreactor, using its " confinement effect "2It is single
Layer nanometer sheet；First by MoS4 2-It is inserted into LDHs interlayer, obtains MoS4 2-Intercalation LDHs compound, then calcines, makes MoS4 2-In layer
Between be decomposed to form MoS in the confined space2Individual layer nanometer sheet obtains MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO's) answers
Object is closed, MMO acid is dissolved and is removed, MoS is finally obtained2Individual layer nanometer sheet；Synthesis process of the present invention is simple, and mild condition is required to set
Standby simple, energy consumption is small, at low cost, is easy to industrialization production.
2, the present invention prepares MoS as template using LDHs2Individual layer nanometer sheet, on the one hand, since the confinement of its laminate is imitated
It answers, the MoS made2It is present in MMO with monolithic form, mixing for multi-layer nano piece is overcome from principle, to obtains
The MoS of high concentration, high accounting rate2Individual layer nanometer sheet；On the other hand, preparing different size LDHs nanometer sheets can realize to MoS2It is single
The controlledly synthesis of layer nanometer sheet lateral dimension.
3, " from bottom to top " of the invention directly obtains MoS in LDHs interlayer2The strategy of individual layer nanometer sheet is shelled compared to machinery
From, solve mechanical stripping effect it is poor, strongly by solvent, removing is time-consuming, after removing monolithic accounting rate low (10% or less) and
The shortcomings that low yield；And complicated intercalation process and harsh environment condition are needed compared to Li intercalation stripping, the present invention can obtain
Obtain the pure semiconductor phase MoS of free from admixture ion doping2Individual layer nanometer sheet has broader application range.In addition the present invention obtains
The MoS obtained2Individual layer nanometer sheet/mixed-metal oxides (MMO) can be used as solid material and save molybdenum disulfide individual layer nanometer sheet, resistance
The aggregation of molybdenum disulfide individual layer nanometer sheet is stopped.
4, MoS prepared by the present invention2Single layer MoS in nanometer sheet2Nanometer sheet accounting rate is high (95-98%), MoS4 2-Ion is forged
Burning decomposition and inversion is MoS2Actual yield close to 100%, and nanometer sheet lateral dimension is uniform, MoS2The thickness of individual layer nanometer sheet
For 0.8-1.1nm, lateral dimension is 80-120nm (preparation of calcining reconstruction method)；MoS prepared by the present invention2Individual layer nanometer sheet can divide
It dissipates in different dispersions, extends its application range, wherein in pure water dispersion, MoS2Mass-volume concentration is reachable
0.41mg/mL。
5, molybdenum disulfide individual layer nanometer sheet prepared by the present invention is applied to electrocatalytic hydrogen evolution, due to its single-layer sheet accounting rate
Height, size is smaller, can expose more edge active sites.The few layer of nanometer sheet compared to direct ultrasound removing is shown more
Superior catalytic performance.
Detailed description of the invention
Fig. 1 is MoS in embodiment 14 2-Intercalation LDHs compound, MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO)
Compound and MoS2The XRD diagram of individual layer nanometer sheet.
Fig. 2 is MoS in embodiment 12The TEM of individual layer nanometer sheet schemes.
Fig. 3 is MoS in embodiment 12Atomic force microscope (AFM) figure of individual layer nanometer sheet；The figure in the upper left corner Fig. 3 is
The MoS of 0.2g/L, 0.04g/L2The photo of individual layer nanometer sheet pure water dispersion liquid.
Fig. 4 is MoS in embodiment 12Luminescence generated by light (PL) figure of individual layer nanometer sheet.
Fig. 5 is MoS in embodiment 12Individual layer nanometer sheet percentage statistical chart.
Fig. 6 is MoS in application examples 12Individual layer nanometer sheet electrocatalytic hydrogen evolution polarization curve.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
Embodiment 1
A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, comprising steps of
(1) MoS is prepared using structural remodeling method4 2-Intercalation LDHs compound.Take 1000ml deionized water, 34g
(0.1326mol)Mg(NO3)2·6H2O、25g(0.0666mol)Al(NO3)3·9H2Three mouthfuls of burnings are added in O and (1mol) 60g urea
In bottle, stirring at normal temperature 0.5h dissolves solid, and flows back for 24 hours in 90 DEG C of oil baths.It is filtered, washed, 60 DEG C of dry 12h are obtained
CO3 -The LDHs of intercalation, then by CO3 -The LDHs of intercalation 400 DEG C of calcining 2h in Muffle furnace obtain metal oxide MMO.It weighs
2.0g MMO and 4.0g (NH4)2MoS4It is put into 10ml deionised degassed water, and for 24 hours in stirred under nitrogen atmosphere.Then will divide
Dispersion liquid is filtered, washed, 60 DEG C of dry 12h, obtains MoS4 2-Intercalation LDHs compound.
(2) by 2gMoS4 2-Intercalation LDHs composite powder is placed in tube furnace, N2450 DEG C of calcining 2h are warming up under protection,
Heating rate is 5 DEG C/min.Naturally after being cooled to room temperature, MoS is obtained2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound.
Take 1gMoS2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound is added in 100ml 0.5mol/L hydrochloric acid, is stirred at room temperature
12h, then through filtering, wash, MoS be obtained by filtration2Individual layer nanometer sheet filter cake.Take 0.2g filter cake (moisture content 61wt%) direct
It is distributed in 200mL deionized water, using probe sonication, ultrasonic disperse 30min, 2000rpm centrifugation 10min takes supernatant liquor,
Up to MoS2The deionized water dispersion liquid of individual layer nanometer sheet.
The MoS that the present embodiment obtains2In nanometer sheet, the accounting rate of individual layer nanometer sheet is 95.1%.
MoS manufactured in the present embodiment2In nanometer sheet dispersion liquid, the mass content of individual layer nanometer sheet is about 0.36mg/mL.
Fig. 1 is MoS in the present embodiment4 2-Intercalation LDHs compound, MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO)
Compound and MoS2The XRD diagram of individual layer nanometer sheet；As shown in Figure 1, MoS4 2-The interlamellar spacing of intercalation LDHs compound is 1.05nm,
Prove MoS4 2-Anion is successfully plugged into the interlayer of LDHs；MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound
(002) diffraction maximum disappear, it was demonstrated that MoS2Exist in the composite with form of single sheet；MoS2002 diffraction maximum of individual layer nanometer sheet is micro-
It is weak, it was demonstrated that the MoS obtained after dissolution MMO2Ordered stacks do not occur for individual layer nanometer sheet, still exist with form of single sheet.
Fig. 2 is MoS in the present embodiment2The TEM of individual layer nanometer sheet schemes；MoS as shown in Figure 22Single-layer sheet contrast is lower, laterally
Having a size of about 100nm, prove to be successfully prepared molybdenum disulfide single-layer sheet.
Fig. 3 is MoS in the present embodiment2Atomic force microscope (AFM) figure of individual layer nanometer sheet；The MoS obtained as shown in Figure 32
Individual layer nanometer sheet thickness is about 1nm, and lateral dimension about 100nm is consistent with TEM result.
Fig. 4 is MoS in the present embodiment2Luminescence generated by light (PL) figure of individual layer nanometer sheet；High yield is successfully obtained as shown in Figure 4
High-quality semiconductor phase MoS2Individual layer nanometer sheet
Fig. 5 is MoS in the present embodiment2Individual layer nanometer sheet percentage statistical chart；As shown in Figure 5, MoS manufactured in the present embodiment2
In nanometer sheet, the accounting rate of individual layer nanometer sheet is 95.1%, and the thickness of individual layer nanometer sheet is concentrated mainly between 0.8-1.1nm.
Embodiment 2
A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, comprising steps of
(1) MoS is prepared using ion-exchange4 2-Intercalation LDHs compound.Take 5.1g (0.0198mol) Mg (NO3)2·
6H2O and 3.8g (0.01mol) Al (NO3)3·9H2O, which is dissolved in 100ml deionized water, obtains solution A.3.2g NaOH is taken to be dissolved in
Solution B is obtained in 100ml deionized water.Under nitrogen protection, solution A and solution B are added drop-wise to 50ml simultaneously under agitation
In deionised degassed water, and controlling final pH is 10.0, and 30min is stirred at room temperature；Then it is placed in 80 DEG C of baking ovens under nitrogen protection
Middle curing 12h.It is filtered, washed, 60 DEG C of vacuum drying 12h, obtains NO3 -The LDHs of intercalation.Weigh LDHs prepared by 1.0g with
1.0g(NH4)2MoS4It is added in 10ml deionised degassed water, N2Under protection, 40 DEG C of stirrings are for 24 hours.It is filtered, washed, is dried in vacuo
Obtain MoS4 2-Intercalation LDHs compound.
(2) by 5gMoS4 2-Intercalation LDHs composite powder is placed in tube furnace, N2450 DEG C of calcining 2h are warming up under protection,
Heating rate is 5 DEG C/min.Naturally after being cooled to room temperature, MoS is obtained2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound.
Take 2gMoS2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound is added in 100ml 0.5mol/L hydrochloric acid, is stirred at room temperature
Then 12h is filtered, is washed, obtains MoS2Individual layer nanometer sheet filter cake.Take 0.2g MoS2(moisture content is individual layer nanometer sheet filter cake
65%) it is added in 200mL isopropanol, using probe sonication, ultrasonic disperse 30min, 2000rpm centrifugation 10min takes upper layer clear
Liquid is to get MoS2The isopropanol dispersion liquid of individual layer nanometer sheet.
The present embodiment MoS2Nanometer sheet actual yield is close to 100%, the MoS of acquisition2In nanometer sheet, individual layer nanometer sheet is accounted for
Ratio is 96%.
MoS manufactured in the present embodiment2In nanometer sheet dispersion liquid, the mass content of individual layer nanometer sheet is 0.33mg/ml.
Embodiment 3
A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, comprising steps of
(1) MoS is prepared using coprecipitation4 2-Intercalation LDHs compound.Take 5.1g (0.0198mol) Mg (NO3)2·6H2O
With 3.8g (0.01mol) Al (NO3)3·9H2O, which is dissolved in 100ml deionized water, obtains solution G.Take 3.2g (0.08mol) hydroxide
Sodium and 2.6g (0.01mol) (NH4)2MoS4It is dissolved in 100ml deionized water and obtains Solution H.Under nitrogen protection, by solution G and molten
Liquid H is added drop-wise in 50ml deionised degassed water simultaneously under agitation, and 30min is stirred at room temperature, and controlling final pH is 10.0.
Then it is placed under inert gas shielding in 80 DEG C of baking ovens and cures 12h, be filtered, washed, 60 DEG C of vacuum drying 12h, obtain MoS4 2-It inserts
Layer LDHs compound
(2) by 5gMoS4 2-Intercalation LDHs composite powder is placed in tube furnace, N2550 DEG C of calcining 1h are warming up under protection,
Heating rate is 5 DEG C/min.Naturally after being cooled to room temperature, MoS is obtained2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound.
Take 2g MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound is added in 100ml 0.5mol/L hydrochloric acid, and room temperature is stirred
12h is mixed, then filtered, washed, obtain MoS2Individual layer nanometer sheet filter cake.Take 0.2gMoS2(moisture content is individual layer nanometer sheet filter cake
51%) it is added in 200ml deionized water, using probe sonication, ultrasonic disperse 30min, 2000rpm centrifugation 10min takes upper layer clear
Liquid is to get MoS2Individual layer nanometer sheet aqueous dispersions.
MoS in the present embodiment4 2-Ion calcining and decomposing is converted into MoS2Individual layer nanometer sheet actual yield is obtained close to 100%
MoS2In nanometer sheet, the accounting rate of individual layer nanometer sheet is 98%.
MoS manufactured in the present embodiment2In nanometer sheet dispersion liquid, the mass content of individual layer nanometer sheet is 0.41mg/L.
Embodiment 4
A kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, as described in Example 1, not with embodiment 1
With:
Step (2) are as follows: by 5gMoS4 2-Intercalation LDHs composite powder is placed in tube furnace, N2450 DEG C are warming up under protection
1h is calcined, heating rate is 5 DEG C/min.Naturally after being cooled to room temperature, MoS is obtained2Individual layer nanometer sheet/mixed-metal oxides (MMO)
It is compound.Take 2gMoS2In the compound addition 100ml 0.5mol/L sulfuric acid of individual layer nanometer sheet/mixed-metal oxides (MMO), room temperature
12h is stirred, then filtered, washed, obtain MoS2Individual layer nanometer sheet filter cake.Take 0.2g MoS2Individual layer nanometer sheet filter cake (moisture content
53%) it is added in 200mL deionized water, using probe sonication, ultrasonic disperse 30min, 2000rpm centrifugation 10min takes upper layer clear
Liquid is to get MoS2Individual layer nanometer sheet aqueous dispersions.
MoS in the present embodiment4 2-It is decomposed into MoS2Actual yield is close to 100%, the MoS of acquisition2In nanometer sheet, single layer nanometer
The accounting rate of piece is 97%.
MoS manufactured in the present embodiment2In nanometer sheet dispersion liquid, the mass content of individual layer nanometer sheet is 0.41mg/mL.
Comparative example 1
Prepared by the method for Chinese patent literature CN106495221A embodiment 1 single layer molybdenum disulfide nano sheet ethyl alcohol,
Deionized water, methyl pyrrolidone, isopropanol dispersion liquid.
Only find that (monolithic accounts for there are a small amount of single-layer sheet in methyl pyrrolidone, ethyl alcohol and isopropanol dispersion liquid by characterizing
Ratio is lower than 10%), and most nanometer sheets are few layer structure (less than 10 layers), and remove time-consuming, and peeling effect is worse in pure water, nothing
Method obtains the MoS of high concentration, high yield, high single layer accounting rate2Individual layer nanometer sheet dispersion liquid.
Application examples 1
The MoS that the present invention is obtained2The MoS that individual layer nanometer sheet and comparative example 1 obtain2Nanometer sheet carries out electrocatalytic hydrogen evolution
It can evaluation.Electro-chemical test is in 0.5mol/LH2SO4It carries out in solution, is tested using three-electrode system.
Test result is as shown in Fig. 6 polarization curve, the resulting MoS of the present invention2Individual layer nanometer sheet (MoS2Single-layer sheet), it rises
Beginning current potential is -0.083V, in 10mA/cm2Current density when, overpotential be -0.251V, hence it is evident that obtained better than comparative example 1
Molybdenum disulfide nano sheet (MoS2Few synusia) Hydrogen Evolution Performance.
Claims (5)
1. a kind of method of space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet, comprising steps of
(1)MoS4 2-The preparation of intercalation LDHs compound；
(2) MoS for obtaining step (1)4 2-Intercalation LDHs compound is calcined under inert gas protection, obtains MoS2Single layer nanometer
Piece/mixed-metal oxides (MMO) compound；Through removing mixed-metal oxides, MoS is obtained2Individual layer nanometer sheet；The calcining
Temperature is 400-550 DEG C, and calcination time is 1-4 hours, and heating rate is 1-10 DEG C/min；
In step (1), with (NH4)2MoS4、Na2MoS4Or K2MoS4For MoS4 2-Source, using ion-exchange or structural remodeling legal system
Standby MoS4 2-Intercalation LDHs compound；
The ion-exchange prepares MoS4 2-Intercalation LDHs compound, comprising steps of by divalent metal nitrate and trivalent metal
Nitrate is soluble in water, obtains solution A；The ammonium hydroxide for being 20-30% by NaOH, KOH or mass concentration is soluble in water, obtains solution B；?
Under inert gas shielding, stirring condition, solution A and solution B are added dropwise in de aerated water C simultaneously, and control final pH be 9.5~
10.0,20-40min is stirred at room temperature；Then under inert gas shielding, 70-90 DEG C of curing 10-15h is filtered, washed, is dried
NO3 -The LDHs of intercalation；By NO3 -The LDHs and MoS of intercalation4 2-Source is added in de aerated water, obtains suspension D, under inert gas shielding,
20-60 DEG C of stirring 12-36h, is filtered, washed, dries to obtain MoS4 2-Intercalation LDHs compound；
The structural remodeling method prepares MoS4 2-Intercalation LDHs compound, comprising steps of by divalent metal salt, trivalent metal salt, urine
Element is soluble in water, obtains solution E, stirs 20-30h at 80-100 DEG C, is filtered, washed, dries to obtain CO3 2-The LDHs of intercalation；400-
550 DEG C of calcining 1-3h obtain MMO；By MMO and MoS4 2-Source is added in de aerated water, obtains suspension F, under inert gas shielding, 20-
60 DEG C of stirring 12-36h；It is filtered, washed, dries to obtain MoS4 2-Intercalation LDHs compound.
2. the method for space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet according to claim 1, which is characterized in that institute
State MoS4 2-Source is (NH4)2MoS4。
3. the method for space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet according to claim 1, which is characterized in that from
Sub- exchange process prepares MoS4 2-In intercalation LDHs compound, including one or more in the following conditions:
A, the divalent metal nitrate is Mg (NO3)2、Ca(NO3)2Or Zn (NO3)2One of, trivalent metal nitrate is
Al(NO3)3；
B, the molar ratio of the divalent metal nitrate and trivalent metal nitrate is (0.65-0.85): (0.15-0.35), institute
The molar concentration for stating total metal nitrate in solution A is 0.1-1mol/L；
C, the molar concentration of NaOH, ammonia or KOH are 0.1-1moL/L in the solution B；
D, the molar ratio of NaOH, ammonia or KOH are 1:2-3 in total metal nitrate and solution B in solution A；
E, the volume ratio of the de aerated water C and solution A is (0.1-2): 1；
F, the NO3 -The LDHs and MoS of intercalation4 2-The mass ratio in source is 1:(0.5-3)；
G, in the suspension D, NO3 -The mass concentration of the LDHs of intercalation is 5-20%.
4. the method for space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet according to claim 1, which is characterized in that knot
Structure reconstruction method prepares MoS4 2-In intercalation LDHs compound, including one or more in the following conditions:
A, the divalent metal salt is Mg (NO3)2, trivalent metal salt is Al (NO3)3；
B, the divalent metal salt and trivalent metal salt molar ratio are (0.65-0.85): (0.15-0.35), urea and total metal
Salt molar ratio is 3.3-10:1；
C, the molar concentration of total metal salt is 0.1-0.5mol/L in the solution E；
D, the MMO and MoS4 2-The mass ratio in source is 1:(0.5-5)；
E, in the suspension F, the mass concentration of MMO is 5-20%.
5. the method for space confinement method synthesis of carbon/molybdenum disulfide individual layer nanometer sheet according to claim 1, which is characterized in that step
Suddenly in (2), including one or more in the following conditions:
A, the method for the removal mixed-metal oxides are as follows: use molar concentration for the aqueous solution soaking of the acid of 0.3-5mol/L
MoS2Individual layer nanometer sheet/mixed-metal oxides (MMO) compound 10-16h, is filtered, washed to obtain MoS2Individual layer nanometer sheet；Institute
The aqueous solution for stating acid is one of hydrochloric acid, sulfuric acid or phosphate aqueous solution；The MoS2Individual layer nanometer sheet/mixed-metal oxides
(MMO) volume ratio of the aqueous solution of the quality of compound and acid is 0.01-0.03g/mL；
B, the MoS that will be obtained2Individual layer nanometer sheet ultrasonic disperse in a solvent, obtains MoS2Individual layer nanometer sheet dispersion；
The solvent is one of water, organic solvent or aqueous surfactant solution；The organic solvent is crassitude
One of ketone, isopropanol or ethyl alcohol；The aqueous surfactant solution is the cetyl front three that mass concentration is 0.1-1%
Bromide aqueous ammonium；It is described ultrasound be probe sonication, ultrasonic time 10-60min: the MoS2Individual layer nanometer sheet dispersion
MoS in system2The mass concentration of individual layer nanometer sheet is 0.01-0.5mg/L.
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| CN102583347A (en) * | 2012-02-17 | 2012-07-18 | 北京化工大学 | Method for preparing graphene by using interlaminar two-dimensional confinement space of inorganic laminar material |
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| CN102583347A (en) * | 2012-02-17 | 2012-07-18 | 北京化工大学 | Method for preparing graphene by using interlaminar two-dimensional confinement space of inorganic laminar material |
| CN102910622A (en) * | 2012-10-25 | 2013-02-06 | 常州大学 | Preparation method of two-dimensional nano-graphene |
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