CN105016315A - Preparation method of graphene oxide composite material - Google Patents
Preparation method of graphene oxide composite material Download PDFInfo
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- CN105016315A CN105016315A CN201510385492.5A CN201510385492A CN105016315A CN 105016315 A CN105016315 A CN 105016315A CN 201510385492 A CN201510385492 A CN 201510385492A CN 105016315 A CN105016315 A CN 105016315A
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Abstract
The invention relates to a preparation method of a graphene oxide composite material, and relates to composite materials. According to the invention, MA powder is added into a GO water solution; the mixed solution is subjected to an ultrasonic treatment, such that a dispersed solution containing MA/GO is obtained, wherein M is transition metal or bismuth, A is a chalcogen, MA is a sulfide or selenide of M, GO is graphene oxide, and MA/GO is a composite material of MA and GO; the upper-layer liquid of the obtained dispersed solution is subjected to low-speed centrifugation, supernatant is subjected to high-speed centrifugation, a precipitate is cleaned and dispersed in water, such that a MA/GO water solution is obtained; or the upper-layer liquid of the dispersed solution is subjected to stepped centrifugation with a speed of 2000-13000rpm, such that MA/GO with different sizes can be obtained. The structure of the obtained graphene oxide composite material is adjustable. The dispersed solution has good stability in water solution, and can be applied in a solution system. With the method, composite materials with different sizes, thicknesses and structures can be prepared, and the composite materials have good dispersity at pH 3-9.
Description
Technical field
The present invention relates to matrix material, be specifically related to a kind of preparation method of graphene oxide composite material.
Background technology
Because graphene oxide composite material has excellent physico-chemical property, therefore show the performance more excellent than independent two-dimensional material in fields such as biosensor, photo-thermal therapy, catalyzer, Photoelectric Detection, lithium ion batteries.
[1-5]at present, the preparation method of graphene oxide composite material mainly chemical Vapor deposition process (being called for short CVD).
[6-8]although the composite property prepared by CVD method is very superior, preparation process is very complicated, and cost is higher, and productivity ratio is lower.Meanwhile, the matrix material of preparation is solid phase, can not be water-soluble, is not suitable for applying in solution system.Therefore, find a kind of simple method efficiently and be full of challenge for the water miscible graphene oxide composite material of extensive preparation in the aqueous solution.
Summary of the invention
The object of the invention is to the above-mentioned shortcoming existed to overcome prior art, not only structure is adjustable to provide obtained graphene oxide composite material, and in aqueous there is good stability, can be used for the preparation method of a kind of graphene oxide composite material of solution system.
The present invention includes following steps:
1) joined in the GO aqueous solution by MA powder, obtain mixed solution, after mixed solution is ultrasonic, obtain the dispersion liquid containing MA/GO, wherein, M represents transition metal or bismuth, and A represents oxygen family element, and MA represents the sulfide of M or the selenide of M; GO represents graphene oxide; MA/GO represents the matrix material of MA and GO;
2) by step 1) the upper liquid low-speed centrifugal of gained dispersion liquid, then by the supernatant liquor high speed centrifugation after low-speed centrifugal, be dispersed in water after the sediment undergoes washing of gained, obtain the MA/GO aqueous solution; Or
By step 1) to carry out substep with 2000 ~ 13000rpm centrifugal for the upper liquid of gained dispersion liquid, obtains the MA/GO of different size.
In step 1) in, described transition metal can be selected from tungsten or molybdenum etc., and described oxygen family element can be selected from selenium or sulphur etc., and described MA can be selected from WS
2, Bi
2se
3, MoSe
2deng in one; The mass ratio of described MA and GO can be 1: (0.1 ~ 2), and preferably 1: (0.5 ~ 1.7), is preferably 1: 0.25; The pH of described mixed solution can be 3 ~ 9, and preferably 6 ~ 8; The described ultrasonic time can be 2 ~ 60h;
In step 1) in, the preparation method of the described GO aqueous solution can be: be raw material with natural graphite powder, add SODIUMNITRATE, the vitriol oil obtains mixed solution, potassium permanganate is added in mixed solution, then react at 30 ~ 40 DEG C, water is added again in reaction mixture, and reaction is continued at 90 ~ 100 DEG C, finally add water termination reaction again, add the superoxol that massfraction is 30% again, obtain oxidation graphite solid through washing, centrifugal, drying, oxidation graphite solid obtains the finely dispersed GO aqueous solution through ultrasonic in water;
The described vitriol oil refers to that (concentration refers to H to concentration
2sO
4the aqueous solution in H
2sO
4mass percent) be more than or equal to 70% H
2sO
4the aqueous solution;
The mass ratio of described natural graphite powder, SODIUMNITRATE and potassium permanganate can be 2: 1: 6, and the mass volume ratio of described natural graphite powder and the vitriol oil can be 1g: 23mL.
In step 2) in, the speed of described low-speed centrifugal can be 400 ~ 3000rpm, and ultracentrifugal speed can be 5000 ~ 20000rpm; Described substep is centrifugal to be comprised: with 2000rpm low-speed centrifugal collecting precipitation 1 and supernatant 1 respectively, supernatant 1 is centrifugal with 6000rpm again, collecting precipitation 2 and supernatant 2 respectively, supernatant 2 is again with 10000rpm centrifugal collecting precipitation 3 and supernatant 3 respectively, supernatant 3 is again with 13000rpm centrifugal collecting precipitation 4 and supernatant 4 respectively, and wherein said precipitation 1, precipitation 2, precipitation 3 and precipitation 4 are the MA/GO of different size.
Adopt the graphene oxide composite material structure of gained of the present invention adjustable, and gained graphene oxide composite material dispersion liquid have good stability in aqueous, can apply in solution system.By analytical procedures such as ultraviolet, Raman, atomic force microscope (AFM), transmission electron microscope (TEM), XRD, dynamic light scattering (DLS), Zeta potentials, carry out sign to the structure of matrix material and dispersing property to prove, the matrix material of different size, thickness and structure can be prepared by the present invention, and this matrix material is have good dispersiveness in 3 ~ 9 scopes at pH, preparation process environmental protection simultaneously, simple to operate, cost is lower, and the industrialization being conducive to graphene oxide composite material is produced.
Accompanying drawing explanation
Fig. 1 is the atomic force microscope figure of the GO precipitation that the embodiment of the present invention 1 adopts 2000rpm centrifugal.
Fig. 2 is the graphic representation that height that Fig. 1 is corresponding is adjusted the distance.
Fig. 3 be 6000rpm prepared by the embodiment of the present invention 1 centrifugal after GO precipitation atomic force microscope figure.
Fig. 4 is the graphic representation that height that Fig. 3 is corresponding is adjusted the distance.
Fig. 5 be 10000rpm prepared by the embodiment of the present invention 1 centrifugal after GO precipitation atomic force microscope figure.
Fig. 6 is the graphic representation that height that Fig. 5 is corresponding is adjusted the distance.
Fig. 7 be 13000rpm prepared by the embodiment of the present invention 1 centrifugal after GO precipitation atomic force microscope figure.
Fig. 8 is the graphic representation that height that Fig. 7 is corresponding is adjusted the distance.
Fig. 9 be 13000rpm prepared by the embodiment of the present invention 1 centrifugal after the atomic force microscope figure of GO supernatant.
Figure 10 is the graphic representation that height that Fig. 9 is corresponding is adjusted the distance.
Figure 11 is the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and independent GO and MoS
2uV-vis spectrogram.
Figure 12 is the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and independent GO and MoS
2the XRD figure of body material.
Figure 13 is the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and MoS
2the Raman spectrogram of body material.
Figure 14 is the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and independent GO and MoS
2zeta current potential under condition of different pH.
Figure 15 be the graphene oxide lamella prepared by the embodiment of the present invention 2 larger time MoS
2the TEM (a) of/GO and high resolution radio mirror (HRTEM, b) figure.
Figure 16 be the graphene oxide lamella prepared by the embodiment of the present invention 2 more moderate time form size suitable MoS
2the TEM (a) of/GO and HRTEM (b) figure.
Figure 17 be the graphene oxide lamella prepared by the embodiment of the present invention 2 more moderate time form size suitable GO/MoS
2the TEM (a) of/GO sandwich structure and HRTEM (b) figure.
Figure 18 be the graphene oxide lamella prepared by the embodiment of the present invention 2 smaller time MoS
2the TEM (a) of/GO and HRTEM (b) figure.
Figure 19 is the MoS of the different size prepared by the embodiment of the present invention 2
2/ GO and independent GO and MoS
2the UV-vis spectrogram of body material.
Figure 20 is the MoS of the different size prepared by the embodiment of the present invention 2
2the DLS figure of/GO.
Figure 21 be the 2000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.
Figure 22 be the 2000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation.
Figure 23 is the graphic representation that height that Figure 22 is corresponding is adjusted the distance.
Figure 24 be the 6000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.
Figure 25 be the 6000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation.
Figure 26 is the graphic representation that height that Figure 25 is corresponding is adjusted the distance.
Figure 27 be the 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.
Figure 28 be the 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation.
Figure 29 is the graphic representation that height that Figure 28 is corresponding is adjusted the distance.
Figure 30 be the 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.
Figure 31 be the 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation, confirms further at the MoS successfully preparing 100 ~ 200nm
2/ GO.
Figure 32 is the graphic representation that height that Figure 31 is corresponding is adjusted the distance.
Figure 33 is the Bi prepared by the embodiment of the present invention 3
2se
3the TEM (a) of/GO and HRTEM (b) figure.
Figure 34 is the Bi prepared by the embodiment of the present invention 3
2se
3the AFM figure of/GO.
Figure 35 is the graphic representation that height that Figure 34 is corresponding is adjusted the distance.
Figure 36 is the MoSe prepared by the embodiment of the present invention 3
2the TEM (a) of/GO and HRTEM (b) figure.
Figure 37 is the MoSe prepared by the embodiment of the present invention 3
2the AFM figure of/GO.
Figure 38 is the graphic representation that height that Figure 37 is corresponding is adjusted the distance.
Figure 39 is the WS prepared by the embodiment of the present invention 3
2the TEM (a) of/GO and HRTEM (b) figure.
Figure 40 is the WS prepared by the embodiment of the present invention 3
2the AFM figure of/GO.
Figure 41 is the graphic representation that height that Figure 40 is corresponding is adjusted the distance.
Embodiment
Below by embodiment, the invention will be further described by reference to the accompanying drawings.
The preparation of embodiment 1 graphene oxide (GO)
Accurately take 2g natural graphite powder and 1g SODIUMNITRATE adds round-bottomed flask, mix with the 46mL vitriol oil under the condition of ice bath; Again 6g potassium permanganate is successively joined above-mentioned mixed solution lentamente, keep mixeding liquid temperature lower than 20 DEG C of stirring reaction 2h, be then transferred to by mixed solution in the oil bath of 35 DEG C and continue reaction 30min, now reaction system is brown viscous liquid; Then in mixed solution, successively add 92mL deionized water lentamente, and temperature is risen to 95 DEG C of continuation reaction 3h, mixed solution becomes glassy yellow by brown, finally adds 400mL pure water termination reaction, adds the H that 6mL massfraction is 30% simultaneously
2o
2with unreacted potassium permanganate in solution.Be cooled to after room temperature until above-mentioned solution and carry out suction filtration, use 100mL aqueous hydrochloric acid (1: 10) and a large amount of pure water repetitive scrubbing filter cake successively, the metal ion that removing is residual and hydrochloric acid.Again filter cake is dispersed in pure water again, ultrasonic 5h makes it disperse, then with 2000rpm low-speed centrifugal 20min respectively collecting precipitation and supernatant, 2000rpm is centrifugal obtain be precipitated as large-sized GO, supernatant, again with the centrifugal 20min of 6000rpm, distinguishes collecting precipitation and supernatant; Centrifugal at 10000rpm and 13000rpm respectively again according to this method, collecting precipitation and supernatant respectively.
The atomic force microscope figure of the GO precipitation that the embodiment of the present invention 1 adopts 2000rpm centrifugal is see Fig. 1.Atomic force microscope figure illustrates the GO nanometer sheet successfully having prepared size 1 ~ 2 μm.Fig. 2 provides the graphic representation that height corresponding to Fig. 1 is adjusted the distance.Illustrate that the GO nanometer sheet thickness of preparation is at about 1nm.Fig. 3 provide 6000rpm prepared by the embodiment of the present invention 1 centrifugal after GO precipitation atomic force microscope figure.Atomic force microscope figure illustrates the GO nanometer sheet successfully having prepared size 700 ~ 900nm.Fig. 4 provides the graphic representation that height corresponding to Fig. 3 is adjusted the distance.Illustrate that the GO nanometer sheet thickness of preparation is at about 1nm.Fig. 5 provide 10000rpm prepared by the embodiment of the present invention 1 centrifugal after GO precipitation atomic force microscope figure.Atomic force microscope figure illustrates the GO nanometer sheet successfully having prepared size 300 ~ 600nm.Fig. 6 provides the graphic representation that height corresponding to Fig. 5 is adjusted the distance.Illustrate that the GO nanometer sheet thickness of preparation is at about 1nm.Fig. 7 provide 13000rpm prepared by the embodiment of the present invention 1 centrifugal after GO precipitation atomic force microscope figure.Atomic force microscope figure illustrates the GO nanometer sheet successfully having prepared size 200 ~ 300nm.Fig. 8 provides the graphic representation that height corresponding to Fig. 7 is adjusted the distance.Illustrate that the GO nanometer sheet thickness of preparation is at about 1nm.Fig. 9 provide 13000rpm prepared by the embodiment of the present invention 1 centrifugal after the atomic force microscope figure of GO supernatant.Atomic force microscope figure illustrates the GO nanometer sheet successfully having prepared size 100 ~ 200nm.Figure 10 provides the graphic representation that height corresponding to Fig. 9 is adjusted the distance.Illustrate that the GO nanometer sheet thickness of preparation is at about 1nm.
Embodiment 2 MoS
2the preparation of/GO matrix material
Accurately take the MoS of 500mg and 325 order fineness
2it is in the GO solution of 0.25mg/mL that body material powder joins 500mL concentration, and regulating the pH to 7 of mixing solutions, is then ultrasonic 40h in the ultrasonic apparatus of 250W in electric power by this mixed system.Gained dispersion liquid is left standstill 48h, obtains upper strata dispersion liquid 2/3rds part.A part is put into 2000rpm low-speed centrifugal 20min in whizzer, collects the supernatant fraction of centrifugal gained.The upper liquid of gained is put into 12000rpm high speed centrifugation 20min in whizzer again, removes supernatant fraction.By lower floor's material deionized water of gained in supercentrifuge 12000rpm repeatedly centrifugal 20min cleaning several times, the material finally collected is dispersed in pure water and obtains MoS
2/ GO.Another part in order to prepare the matrix material of different size, with 2000rpm low-speed centrifugal 20min respectively collecting precipitation and supernatant, 2000rpm is centrifugal obtain be precipitated as large-sized GO, supernatant again with the centrifugal 20min of 6000rpm, collecting precipitation and supernatant respectively; Centrifugal at 10000rpm and 13000rpm respectively again according to this method, collecting precipitation and supernatant respectively.
Figure 11 provides the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and independent GO and MoS
2uV-vis spectrogram, as can be seen from the figure, with independent MoS
2and GO, MoS
2there is both characteristic peak in/GO, GO characteristic peak is at 224nm, MoS simultaneously
2characteristic peak appear at and 612nm and 672nm, preliminary proof has successfully prepared MoS
2/ GO.Figure 12 provides the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and independent GO and MoS
2the XRD figure of body material.XRD figure display and MoS
2body material is compared, MoS
2the a lot of peak of XRD of/GO all disappears, but strengthens at the peak of (002) crystal face, shows MoS
2body material is successfully peeled off.Figure 13 provides the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and MoS
2the Raman spectrogram of body material.XRD figure display and MoS
2body material is compared, MoS
2the E of/GO matrix material
1 2gthere is blue shift, show prepared MoS
2few layer MoS in/GO matrix material
2the number of plies be 1-3 layer.Figure 14 provides the MoS prepared by the embodiment of the present invention 2
2/ GO matrix material and independent GO and MoS
2zeta current potential under condition of different pH.As seen from the figure, prepared MoS
2/ GO solution is 3 to 9 compare independent GO and MoS at pH
2there is excellent stability.Figure 15 provide graphene oxide lamella prepared by the embodiment of the present invention 2 larger time MoS
2the TEM (a) of/GO and high resolution radio mirror (HRTEM, b) figure.As seen from the figure, the sheet of fold be GO, GO larger time, mainly form the structure that less curing molybdenum sheet is adsorbed on GO surface.The spacing that b schemes 0.27nm ascribes MoS to
2(100) crystal face, the lamella confirming the graphenic surface being adsorbed on fold is further MoS
2.Figure 16 provide graphene oxide lamella prepared by the embodiment of the present invention 2 more moderate time form the suitable MoS of size
2the TEM (a) of/GO and HRTEM (b) figure.As seen from the figure, when GO is more moderate, form the MoS that size is suitable
2sheet is adsorbed on the structure on GO surface.The spacing that b schemes 0.62nm ascribes MoS to
2(002) crystal face, the lamella confirming the graphenic surface being adsorbed on fold is further MoS
2.Figure 17 provide graphene oxide lamella prepared by the embodiment of the present invention 2 more moderate time form the suitable GO/MoS of size
2the TEM (a) of/GO sandwich structure and HRTEM (b) figure.As seen from the figure, when GO is more moderate, the GO/MoS that also can be formed
2/ GO sandwich structure.The spacing that b schemes 0.62nm and 0.27nm ascribes MoS to respectively
2(002) and (100) crystal face, GO does not have obvious spacing, and that confirm further to be formed is GO/MoS
2/ GO sandwich structure.Figure 18 provide graphene oxide lamella prepared by the embodiment of the present invention 2 smaller time MoS
2the TEM (a) of/GO and HRTEM (b) figure.As seen from the figure, when GO is smaller, the less GO of main formation is adsorbed on MoS
2the structure on surface.MoS has been covered because little GO is excessive
2, so can't see MoS
2lattice fringe.Figure 19 provides the MoS of the different size prepared by the embodiment of the present invention 2
2/ GO and independent GO and MoS
2the UV-vis spectrogram of body material, as can be seen from the figure along with centrifugal speed is increased to 13000rpm from 2000rpm, MoS
2/ GO goes out few layer MoS at 672nm
2characteristic peak generation blue shift, show successfully to have prepared the MoS of different size and thickness
2/ GO.Figure 20 provides the MoS of the different size prepared by the embodiment of the present invention 2
2the DLS figure of/GO.DLS confirms successfully to have prepared the MoS of different size in the solution further
2/ GO.Figure 21 provide 2000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.SEM and TEM figure confirms successfully to have prepared the MoS of 700nm ~ 1 μm
2/ GO.Figure 22 provide 2000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation, confirms further successfully preparing the MoS of 700nm ~ 1 μm
2/ GO.Figure 23 provides the graphic representation that height corresponding to Figure 22 is adjusted the distance.The MoS of the centrifugal rear preparation of 2000rpm is described
2/ GO thickness is at 30 ~ 50nm.Figure 24 provide 6000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.SEM and TEM figure confirms successfully to have prepared the MoS of 300 ~ 600nm
2/ GO.Figure 25 provide 6000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation, confirms further at the MoS successfully preparing 400 ~ 600nm
2/ GO.Figure 26 provides the graphic representation that height corresponding to Figure 25 is adjusted the distance.The MoS of the centrifugal rear preparation of 6000rpm is described
2/ GO thickness is at 10 ~ 20nm.Figure 27 provide 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.SEM and TEM figure confirms successfully to have prepared the MoS of 200 ~ 400nm
2/ GO.Figure 28 provide 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation, confirms further at the MoS successfully preparing 200 ~ 400nm
2/ GO.Figure 29 provides the graphic representation that height corresponding to Figure 28 is adjusted the distance.The MoS of the centrifugal rear preparation of 10000rpm is described
2/ GO thickness is at 4 ~ 8nm.Figure 30 provide 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the SEM of/GO precipitation, TEM schemes.SEM and TEM figure confirms successfully to have prepared the MoS of 100 ~ 200nm
2/ GO.Figure 31 provide 10000rpm prepared by the embodiment of the present invention 2 centrifugal after MoS
2the AFM figure of/GO precipitation, confirms further at the MoS successfully preparing 100 ~ 200nm
2/ GO.Figure 32 provides the graphic representation that height corresponding to Figure 31 is adjusted the distance.The MoS of the centrifugal rear preparation of 10000rpm is described
2/ GO thickness is at 1 ~ 4nm.
Embodiment 3 WS
2/ GO, Bi
2se
3/ GO, MoSe
2the preparation of/GO matrix material
Accurately take the tungsten disulfide (WS of 500mg and 325 order fineness respectively
2), bismuth selenide (Bi
2se
3), selenizing molybdenum (MoSe
2) to join 500mL concentration be respectively in the GO solution of 0.25mg/mL to body material powder, regulating the pH to 7 of mixing solutions, is then ultrasonic 40h in the ultrasonic apparatus of 250W in electric power by this mixed system.Gained dispersion liquid is left standstill 48h, obtains upper strata dispersion liquid.Be put into 2000rpm low-speed centrifugal 20min in whizzer, collect the supernatant fraction of centrifugal gained.The upper liquid of gained is put into 12000rpm high speed centrifugation 20min in whizzer again, removes supernatant fraction.By lower floor's material deionized water of gained in supercentrifuge 12000rpm repeatedly centrifugal 20min cleaning several times, the material finally collected is dispersed in pure water and obtains based on the few layer tungsten disulfide (WS of GO
2/ GO), bismuth selenide (Bi
2se
3/ GO), selenizing molybdenum (MoSe
2/ GO) etc. Two-dimensional Composites.
Figure 33 provides the Bi prepared by the embodiment of the present invention 3
2se
3the TEM (a) of/GO and HRTEM (b) figure.Schemed from a, the Bi of preparation
2se
3/ GO lamella size is at 200 ~ 600nm.Schemed from b, the spacing of 0.21nm ascribes Bi to
2se
3(110) crystal face.Figure 34 provides the Bi prepared by the embodiment of the present invention 3
2se
3the AFM figure of/GO.Obviously can see the few layer of Bi being adsorbed on the low GO surface of contrast
2se
3, size is about 200 ~ 600nm.Figure 35 provides the graphic representation that height corresponding to Figure 34 is adjusted the distance.Bi prepared by explanation
2se
3bi in/GO
2se
3be about 2 ~ 4 layers.Figure 36 provides the MoSe prepared by the embodiment of the present invention 3
2the TEM (a) of/GO and HRTEM (b) figure.Schemed from a, the MoSe of preparation
2/ GO lamella size is at 200 ~ 400nm.Schemed from b, the spacing of 0.28nm ascribes Bi to
2se
3(10-10) crystal face.Figure 37 provides the MoSe prepared by the embodiment of the present invention 3
2the AFM figure of/GO.Obviously can see the few layer of Bi being adsorbed on the low GO surface of contrast
2se
3, size is about 200 ~ 400nm.Figure 38 provides the graphic representation that height corresponding to Figure 37 is adjusted the distance.MoSe prepared by explanation
2moSe in/GO
2it is 1 ~ 2 layer.Figure 39 provides the WS prepared by the embodiment of the present invention 3
2the TEM (a) of/GO and HRTEM (b) figure.Schemed from a, the WS of preparation
2/ GO lamella size is at 100 ~ 300nm.Schemed from b, the spacing of 0.27nm ascribes WS to
2(100) crystal face.Figure 40 provides the WS prepared by the embodiment of the present invention 3
2the AFM figure of/GO.Obviously can see the few layer of WS being adsorbed on the low GO surface of contrast
2, size is about 100 ~ 300nm.Figure 41 provides the graphic representation that height corresponding to Figure 40 is adjusted the distance.WS prepared by explanation
2wS in/GO
2it is 1 ~ 2 layer.
The detection of embodiment 4, different size GO and Two-dimensional Composites thereof
The GO of the different size in embodiment 1 is carried out to the detection of atomic force microscope (AFM).To the MoS in embodiment 2 and 3
2/ GO matrix material carries out UV, visible light (UV-vis) spectrum, scanning electron microscope (SEM), transmission electron microscope (TEM), AFM, X-ray diffraction (XRD), Raman (Raman) spectrum, dynamic light scattering (DLS), Zeta potential is measured.For WS
2/ GO, Bi
2se
3/ GO and MoSe
2the signs such as the Two-dimensional Composites such as/GO carry out TEM, AFM.
Claims (10)
1. a preparation method for graphene oxide composite material, is characterized in that comprising the following steps:
1) MA powder is joined in the GO aqueous solution, obtains mixed solution, after mixed solution is ultrasonic, obtain the dispersion liquid containing MA/GO,
Wherein, M represents transition metal or bismuth, and A represents oxygen family element, and MA represents the sulfide of M or the selenide of M; GO represents graphene oxide; MA/GO represents the matrix material of MA and GO;
2) by step 1) the upper liquid low-speed centrifugal of gained dispersion liquid, then by the supernatant liquor high speed centrifugation after low-speed centrifugal, be dispersed in water after the sediment undergoes washing of gained, obtain the MA/GO aqueous solution; Or
By step 1) to carry out substep with 2000 ~ 13000rpm centrifugal for the upper liquid of gained dispersion liquid, obtains the MA/GO of different size.
2. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, is characterized in that in step 1) in, described transition metal is selected from tungsten or molybdenum, and described oxygen family element are selected from selenium or sulphur.
3. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, is characterized in that in step 1) in, described MA is selected from WS
2, Bi
2se
3, MoSe
2in one.
4. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, is characterized in that in step 1) in, the mass ratio of described MA and GO is 1: (0.1 ~ 2), preferably 1: (0.5 ~ 1.7), is preferably 1: 0.25.
5. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, is characterized in that in step 1) in, the pH of described mixed solution is 3 ~ 9, preferably 6 ~ 8; The described ultrasonic time can be 2 ~ 60h.
6. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, it is characterized in that in step 1) in, the preparation method of the described GO aqueous solution is: be raw material with natural graphite powder, add SODIUMNITRATE, the vitriol oil obtains mixed solution, potassium permanganate is added in mixed solution, then react at 30 ~ 40 DEG C, water is added again in reaction mixture, and reaction is continued at 90 ~ 100 DEG C, finally add water termination reaction again, add the superoxol that massfraction is 30% again, through washing, centrifugal, drying obtains oxidation graphite solid, oxidation graphite solid obtains the finely dispersed GO aqueous solution through ultrasonic in water.
7. the preparation method of a kind of graphene oxide composite material as claimed in claim 6, is characterized in that the described vitriol oil is the H that mass percentage concentration is more than or equal to 70%
2sO
4the aqueous solution.
8. the preparation method of a kind of graphene oxide composite material as claimed in claim 6, it is characterized in that the mass ratio of described natural graphite powder, SODIUMNITRATE and potassium permanganate is 2: 1: 6, the mass volume ratio of described natural graphite powder and the vitriol oil is 1g: 23mL.
9. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, is characterized in that in step 2) in, the speed of described low-speed centrifugal is 400 ~ 3000rpm, and ultracentrifugal speed is 5000 ~ 20000rpm.
10. the preparation method of a kind of graphene oxide composite material as claimed in claim 1, it is characterized in that in step 2) in, described substep is centrifugal to be comprised: with 2000rpm low-speed centrifugal collecting precipitation 1 and supernatant 1 respectively, supernatant 1 is centrifugal with 6000rpm again, collecting precipitation 2 and supernatant 2 respectively, supernatant 2 is again with 10000rpm centrifugal collecting precipitation 3 and supernatant 3 respectively, supernatant 3 is again with 13000rpm centrifugal collecting precipitation 4 and supernatant 4 respectively, and wherein said precipitation 1, precipitation 2, precipitation 3 and precipitation 4 are the MA/GO of different size.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109486264A (en) * | 2018-11-29 | 2019-03-19 | 安徽牡东通讯光缆有限公司 | A kind of corrosion-resistant optical cable epoxide resin coating material |
| CN111902361A (en) * | 2018-01-17 | 2020-11-06 | 汉阳大学校产学协力团 | Selenium-containing composite material, method for producing same, lithium ion and lithium selenium secondary battery comprising same, and lithium ion capacitor |
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| CN103692763A (en) * | 2013-12-06 | 2014-04-02 | 深圳先进技术研究院 | Peeling method of two-dimensional layered nano material |
| CN104143630A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Application of graphene-nanometer metal oxide composite material in lithium sulfur battery |
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| CN104143630A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Application of graphene-nanometer metal oxide composite material in lithium sulfur battery |
| CN103692763A (en) * | 2013-12-06 | 2014-04-02 | 深圳先进技术研究院 | Peeling method of two-dimensional layered nano material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111902361A (en) * | 2018-01-17 | 2020-11-06 | 汉阳大学校产学协力团 | Selenium-containing composite material, method for producing same, lithium ion and lithium selenium secondary battery comprising same, and lithium ion capacitor |
| CN111902361B (en) * | 2018-01-17 | 2023-08-04 | 汉阳大学校产学协力团 | Composite material containing selenium, preparation method thereof, lithium ion and lithium selenium secondary battery containing composite material and lithium ion capacitor |
| CN109486264A (en) * | 2018-11-29 | 2019-03-19 | 安徽牡东通讯光缆有限公司 | A kind of corrosion-resistant optical cable epoxide resin coating material |
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