CN103432992A - Method for preparing graphene coated nanometer material composite - Google Patents
Method for preparing graphene coated nanometer material composite Download PDFInfo
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- CN103432992A CN103432992A CN2013103702410A CN201310370241A CN103432992A CN 103432992 A CN103432992 A CN 103432992A CN 2013103702410 A CN2013103702410 A CN 2013103702410A CN 201310370241 A CN201310370241 A CN 201310370241A CN 103432992 A CN103432992 A CN 103432992A
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Abstract
The invention relates to a method for preparing a graphene coated nanometer material composite, relating to the method for preparing a graphene composite. According to the method, the problems that the original surface properties of the nanometer material are damaged by extra functionalized molecules on the surface of the graphene coated nanometer material composite prepared by the existing method and the cost is high are solved. The method comprises the following steps of firstly, dissolving the nanometer material into deionized water, secondly, dissolving the oxidized graphene into the deionized water, thirdly, freeze drying the mixed solution, and fourthly, putting a sample into a muffle furnace, calcining in an inert gas, and obtaining the graphene coated nanometer material composite. According to the graphane coating technology, the surface characteristic of the nanometer material is not damaged, the step in the traditional method that the surface of the nanometer material needs positive charge finishing is omitted, and the cost is lowered. The method is applied in the field of photocatalysis.
Description
Technical field
The present invention relates to the preparation method of graphene complex.
Background technology
21 century, environment and energy problem are the ultimate challenges of facing mankind.Photocatalitic Technique of Semiconductor is effectively curbed environmental pollution and efficiently utilizes the effective way of solar energy for we provide a kind of.Yet, often there will be the compound phenomenon of photo-generated carrier fast in photochemical catalyst, thereby cause lower photocatalysis efficiency.In order to overcome this shortcoming, the researcher utilizes and builds the catalytic property that composite is optimized homogenous material, improves catalytic activity.Graphene (GE) is a two-dimentional sp
2the carbon structure of hydridization is a zero gap semiconductor.It has some unique character, as the electron mobility (200000cm of superelevation
2v
-1s
-1), large specific area (2630m
2/ g) and high light transmittance (99.7%).Due to these unique character, Graphene is considered to for modifying and cut the excellent material of photochemical catalyst.For this reason, researcher has built a large amount of nano composite materials based on Graphene, improves the photocatalysis performance of homogenous material.The main form of composite is that different metal or semiconductor material growing are on the Graphene surface.The cooperative effect of nano material and Graphene can effectively suppress the compound of photo-generated carrier, and the absorption region of expansion material to light increases the avtive spot of material surface and can improve the chemical stability of catalyst.Although it is above that the composite based on Graphene has advantages of, still there are in actual applications some problems.Due to nanometer particle load, on the surface of Graphene, cause both contacts area less and may in photocatalytic process, cause surperficial inactivation, these all will reduce the catalytic effect of composite.It is exactly the surface in nano material graphene coated that the most promising mode goes to address the above problem.On the one hand: increase the contact area of bi-material, on the other hand: Graphene, as protective layer, reduces the poisoning probability of nano-material surface.
Current researcher utilizes the electrostatic attraction effect of Graphene and nano material to be coated.Feng et al. seminar has prepared the Co of graphene coated
3o
4composite.They utilize aminopropyl trimethoxysilane (APS) to Co
3o
4surface is modified, and makes it with positive charge.The Graphene surface is with negative electrical charge, and the principle that they utilize the two positive and negative charge to attract, make graphene coated at Co
3o
4surface, prepare GE@Co
3o
4composite construction.The people such as Shao et al utilize same principle to prepare ZnO NPs-GO compound.This seminar utilizes polycyclic aromatic hydrocarbon to carry out the positive charge modification to the surface of ZnO.Although said method has been realized the coating of Graphene at nano-material surface, the functionalization molecule that material surface is extra, for example APS, can destroy the surface nature that nano material has originally, and cost is also higher.For this reason, the nano material compound that the universal method of developing non-functionalization removes to build graphene coated is very important.
Summary of the invention
The objective of the invention is can destroy in order to solve the extra functionalization molecule of graphene coated nano material composite surface that existing method prepares surface nature and the higher problem of cost that nano material has originally, a kind of preparation method of graphene coated nano material compound is provided.
The preparation method of graphene coated nano material compound of the present invention, realize by following steps:
One, nano material 0.05～0.1g is dissolved in 100～150mL deionized water, ultrasonic 20～40min, obtain solution A;
Two, graphene oxide 0.005～0.01g is dissolved in 50～60mL deionized water, ultrasonic dispersion 5～10min, obtain solution B;
Three, the solution B obtained in step 2 is joined in the solution A that step 1 obtains, ultrasonic 1～2h, obtain mixed solution, after then mixed solution being placed in to the freezing 30～90s of liquid nitrogen, then being placed in freeze drier and carrying out freeze drying;
Four, the dried sample of step 3 is placed in to Muffle furnace, under 500～600 ℃, inert gas conditions, calcines 2～3h, obtain graphene coated nano material compound.
Invention mechanism
The invention provides the nano material compound that a kind of non-functionalization, environmental friendliness and pervasive preparation method construct graphene coated.
Preparation method of the present invention utilizes cryodesiccated method to realize the surface of graphene coated in nano material, and the synthesis mechanism schematic diagram as shown in Figure 5.
At first mixing nano material and graphene oxide are ultrasonic, then drop into and carry out freezingly in liquid nitrogen, finally carry out freeze drying, is mainly to utilize draught head to realize the surface of graphene coated at semi-conducting material.In cryodesiccated process, the ice face with above the air place have an interface (called after solid-air interface), owing to constantly vacuumizing, the rarefaction of air of ice face top, air pressure is lower, however ice flash freezing in liquid nitrogen, have a large amount of air, air pressure is higher.So just produced a draught head at the solid-air interface place, along with the continuous evaporation of hydrone, Graphene and nano material are come this interface, because Graphene has the characteristic of easy deformation, under the effect of pressure differential, graphene coated is on the surface of nano particle.
The present invention also provides the preparation method of graphene coated nano material compound, by following steps, realizes:
One, nano material 0.05～0.1g is dissolved in 100～150mL deionized water, ultrasonic 20～40min, obtain solution A;
Two, Graphene 0.005～0.01g is dissolved in 50～60mL deionized water, ultrasonic dispersion 5～10min, obtain solution B;
Three, the solution B obtained in step 2 is joined in the solution A that step 1 obtains, ultrasonic 1～2h, obtain mixed solution, after then mixed solution being placed in to the freezing 30～90s of liquid nitrogen, be placed in again freeze drier and carry out freeze drying, obtain graphene coated nano material compound.
Beneficial effect of the present invention:
1, the method for the method and other traditional electrostatic attraction is very different, the method is without nano-material surface being carried out to the modification of positive charge, traditional electrostatic attraction method modification is not only loaded down with trivial details, not easy to operate, and the modification of a large amount of amination molecules also can exert an influence to the surface of nano material, the restriction practical application, in addition, the use of a large amount of amination molecules, can improve cost prepared by composite greatly, and be difficult for being prepared on a large scale.
The graphene coated technology that the inventive method provides is without the surface characteristic of destroying nano material, removed the step that nano material in the conventional method needs the finishing positive charge, reduced cost;
2, this preparation method utilizes External Force Acting, realize the coating of Graphene to nano material, do not rely on kind, size and the pattern of nano material fully, tightly rely on a simple physical principle to realize the coating of Graphene at material surface, simple, the easy row of the method, can synthesize on a large scale this type of composite, these advantages are to utilize electrostatic attraction structure composite institute inaccessiable;
3, the ZnO/GE compound of embodiment mono-preparation is applied in the research of photocatalytic degradation methylene blue dye, the ZnO/GE composite to the curve of methylene blue dye adsorption capacity as shown in Figure 3, the curve of ZnO/GE compound and ZnO photocatalytic degradation ability as shown in Figure 4, ZnO/GE composite prepared by the method is compared with ZnO, adsorption capacity to methylene blue dye has improved 20 times, and photo-catalysis capability has improved 4 times.
The accompanying drawing explanation
The transmission electron microscope picture that the ultrasonic dispersion of ZnO/GE compound that Fig. 1 is preparation in embodiment mono-is latter 15000 times;
The transmission electron microscope picture that the ultrasonic dispersion of ZnO/GE compound that Fig. 2 is preparation in embodiment mono-is latter 30000 times, wherein A is ZnO, B is Graphene;
The curve of the ZnO/GE composite that Fig. 3 is preparation in embodiment mono-to the methylene blue dye adsorption capacity;
The ZnO/GE composite that Fig. 4 is preparation in embodiment mono-and the curve of ZnO photocatalytic degradation ability, wherein
the curve that means blank group photocatalytic degradation ability,
the curve that means ZnO photocatalytic degradation ability,
the curve that means the ZnO/GE composite photocatalytic degradation ability of preparation in embodiment mono-;
The synthesis mechanism schematic diagram that Fig. 5 is graphene coated nano material compound of the present invention.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method of present embodiment graphene coated nano material compound, carry out according to the following steps:
One, nano material 0.05～0.1g is dissolved in 100～150mL deionized water, ultrasonic 20～40min, obtain solution A;
Two, graphene oxide 0.005～0.01g is dissolved in 50～60mL deionized water, ultrasonic dispersion 5～10min, obtain solution B;
Three, the solution B obtained in step 2 is joined in the solution A that step 1 obtains, ultrasonic 1～2h, obtain mixed solution, after then mixed solution being placed in to the freezing 30～90s of liquid nitrogen, then being placed in freeze drier and carrying out freeze drying;
Four, the dried sample of step 3 is placed in to Muffle furnace, under 500～600 ℃, inert gas conditions, calcines 2～3h, obtain graphene coated nano material compound.
The beneficial effect of present embodiment:
1, the method for the method and other traditional electrostatic attraction is very different, the method is without nano-material surface being carried out to the modification of positive charge, traditional electrostatic attraction method modification is not only loaded down with trivial details, not easy to operate, and the modification of a large amount of amination molecules also can exert an influence to the surface of nano material, the restriction practical application, in addition, the use of a large amount of amination molecules, can improve cost prepared by composite greatly, and be difficult for being prepared on a large scale.
The graphene coated technology that the inventive method provides is without the surface characteristic of destroying nano material, removed the step that nano material in the conventional method needs the finishing positive charge, reduced cost;
2, this preparation method utilizes External Force Acting, realize the coating of Graphene to nano material, do not rely on kind, size and the pattern of nano material fully, tightly rely on a simple physical principle to realize the coating of Graphene at material surface, simple, the easy row of the method, can synthesize on a large scale this type of composite, these advantages are to utilize electrostatic attraction structure composite institute inaccessiable;
3, the ZnO/GE compound of embodiment mono-preparation is applied in the research of photocatalytic degradation methylene blue dye, the ZnO/GE composite to the curve of methylene blue dye adsorption capacity as shown in Figure 3, the curve of ZnO/GE compound and ZnO photocatalytic degradation ability as shown in Figure 4, ZnO/GE composite prepared by the method is compared with ZnO, adsorption capacity to methylene blue dye has improved 20 times, and photo-catalysis capability has improved 4 times.
The specific embodiment two: present embodiment is different from the specific embodiment one: the nano material described in step 1 is ZnO microballoon, CdS microballoon or TiO
2nanometer sheet.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two: prepared by following steps by described ZnO microballoon:
One, the zinc acetate of 0.25～0.3g is dissolved in the deionized water of 3～6mL, ultrasonic 5～10min, stir 5～10min, obtains zinc acetate solution;
Two, the CTAB of 0.3～0.6g is dissolved in 50～70mL ethylene glycol, ultrasonic 5～10min, stir 5～10min;
Three, the solution again step 2 obtained joins in the zinc acetate solution that step 1 obtains, and stirs 25～40min, obtains mixed liquor;
Four, mixed liquor step 3 obtained is placed in the reactor of 100mL, then be placed in baking oven, after 135～160 ℃ of reaction 4～8h, treat that product is cooled to room temperature, replace centrifuge washing 4～5 times with deionized water and absolute ethyl alcohol, obtain the ZnO microballoon after oven dry.
Other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: prepared by following steps by described CdS microballoon:
One, 1.4～2.0mmol cadmium acetate and 35～50mmol thiocarbamide are dissolved in 30～50mL deionized water, stir 25～50min, obtain mixed liquor;
Two, mixed liquor step 1 obtained is placed in the 50mL reactor, then is placed in baking oven, after 135～160 ℃ of reaction 4～8h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4～5 times, obtains the CdS microballoon after oven dry.
Other is identical with one of specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: described TiO
2by following steps, prepared by nanometer sheet:
One, 1～3mL butyl titanate is dissolved in 25～40mL isopropyl alcohol, ultrasonic dispersion 5～10min, form solution;
Two, add 0.2～0.4mL hydrofluoric acid in the solution obtained to step 1, mix, obtain mixed liquor;
Three, the mixed liquor again step 2 obtained is placed in the 50mL reactor, then is placed in baking oven, after 180～200 ℃ of reaction 20～25h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4～5 times, obtains TiO after oven dry
2nanometer sheet.
Other is identical with one of specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five: described in step 4, under 500 ℃, inert gas conditions, calcine 2h.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to six: described inert gas is argon gas or nitrogen.Other is identical with one of specific embodiment one to six.
The specific embodiment eight: the preparation method of present embodiment graphene coated nano material compound, carry out according to the following steps:
One, nano material 0.05～0.1g is dissolved in 100～150mL deionized water, ultrasonic 20～40min, obtain solution A;
Two, Graphene 0.005～0.01g is dissolved in 50～60mL deionized water, ultrasonic dispersion 5～10min, obtain solution B;
Three, the solution B obtained in step 2 is joined in the solution A that step 1 obtains, ultrasonic 1～2h, obtain mixed solution, after then mixed solution being placed in to the freezing 30～90s of liquid nitrogen, be placed in again freeze drier and carry out freeze drying, obtain graphene coated nano material compound.
The specific embodiment nine: present embodiment is different from the specific embodiment eight: the ultrasonic time described in step 2 is 10min.Other is identical with the specific embodiment eight.
The specific embodiment ten: present embodiment is different from the specific embodiment eight or nine: the ultrasonic time described in step 3 is 1h, and being placed in the liquid nitrogen cooling time is 60s.Other is identical with the specific embodiment eight or nine.
Verify beneficial effect of the present invention by following examples:
Embodiment mono-:
The preparation method of present embodiment graphene coated nano material compound, realize by following steps:
1, ZnO microballoon preparation:
One, the zinc acetate of 0.27g is dissolved in the deionized water of 4mL, ultrasonic 5min, stir 5min, obtains zinc acetate solution;
Two, the CTAB of 0.5g is dissolved in 60mL ethylene glycol, ultrasonic 5min, stir 5min;
Three, the solution again step 2 obtained joins in the zinc acetate solution that step 1 obtains, and stirs 30min, obtains mixed liquor;
Four, mixed liquor step 3 obtained is placed in the reactor of 100mL, then is placed in baking oven, after 150 ℃ of reaction 5h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4 times, obtains the ZnO microballoon after oven dry.
2, ZnO microballoon/GE compound preparation:
One, ZnO microballoon 0.1g is dissolved in the 100mL deionized water, ultrasonic 30min, obtain ZnO solution;
Two, graphene oxide 0.01g is dissolved in the 50mL deionized water, ultrasonic dispersion 10min is brown color to solution, obtains graphene oxide solution;
Three, the graphene oxide solution obtained in step 2 is joined in the ZnO solution that step 1 obtains, ultrasonic 1h, obtain mixed solution, after then mixed solution being placed in to the freezing 60s of liquid nitrogen, then being placed in freeze drier and carrying out freeze drying;
Four, the dried sample of step 3 is placed in to Muffle furnace, under 500 ℃, argon gas condition, calcines 2h, obtain ZnO microballoon/GE compound.
In order to exist firmly active force in the composite that proves structure between Graphene and nano particle, ZnO/GE compound prepared by the present embodiment carries out ultrasonic dispersion, the transmission electron microscope picture that ultrasonic dispersion is latter 15000 times as shown in Figure 1, the transmission electron microscope picture that ultrasonic dispersion is latter 30000 times as shown in Figure 2, wherein in Fig. 2, A is ZnO, B is Graphene, and result shows that Graphene still firmly is coated on the surface of nano material, the phenomenon come off do not occur.Due to Graphene, in the coating process, the interface of the two is airfree existence, thus sample under air conditions, will by atmospheric pressure around, so large pressure will make Graphene tightly be coated on nano-material surface.
ZnO/GE compound prepared by the present embodiment is applied in the research of photocatalytic degradation methylene blue dye, the ZnO/GE composite to the curve of methylene blue dye adsorption capacity as shown in Figure 3, the curve of ZnO/GE compound and ZnO photocatalytic degradation ability as shown in Figure 4, wherein
the curve that means blank group photocatalytic degradation ability,
the curve that means ZnO photocatalytic degradation ability,
mean the curve of ZnO/GE composite photocatalytic degradation ability prepared by the present embodiment, result shows to compare with ZnO, and the sample after the coated graphite alkene of ZnO surface has improved 20 times to the adsorption capacity of dyestuff, and photo-catalysis capability has improved 4 times.
Embodiment bis-:
The preparation method of present embodiment graphene coated nano material compound, realize by following steps:
1, CdS microballoon preparation:
One, 1.6mmol cadmium acetate and 40mmol thiocarbamide are dissolved in the 40mL deionized water, stir 30min, obtain mixed liquor;
Two, mixed liquor step 1 obtained is placed in the 50mL reactor, then is placed in baking oven, after 140 ℃ of reaction 5h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4 times, obtains the CdS microballoon after oven dry.
2, CdS microballoon/GE compound preparation:
One, CdS microballoon 0.1g is dissolved in the 100mL deionized water, ultrasonic 30min, obtain CdS solution;
Two, Graphene 0.01g is dissolved in the 50mL deionized water, ultrasonic dispersion 10min is brown color to solution, obtains graphene solution;
Three, the graphene solution obtained in step 2 is joined in the CdS solution that step 1 obtains, ultrasonic 1h, obtain mixed solution, after then mixed solution being placed in to the freezing 60s of liquid nitrogen, be placed in again freeze drier and carry out freeze drying, obtain CdS microballoon/GE compound.
The graphene coated technology that the present embodiment provides is without the surface characteristic of destroying nano material, removed the step that nano material in the conventional method needs the finishing positive charge, reduced cost.
The preparation method of the present embodiment utilizes External Force Acting, realize the coating of Graphene to nano material, do not rely on kind, size and the pattern of nano material fully, tightly rely on a simple physical principle to realize the coating of Graphene at material surface, simple, the easy row of the method, can synthesize this type of composite on a large scale.
Embodiment tri-:
The preparation method of present embodiment graphene coated nano material compound, realize by following steps:
1, TiO
2nanometer sheet:
One, the 2mL butyl titanate is dissolved in the 30mL isopropyl alcohol, ultrasonic dispersion 10min, form solution;
Two, add 0.35mL hydrofluoric acid in the solution obtained to step 1, mix, obtain mixed liquor;
Three, the mixed liquor again step 2 obtained is placed in the 50mL reactor, then is placed in baking oven, after 200 ℃ of reaction 24h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4 times, obtains TiO after oven dry
2nanometer sheet.
2, TiO
2nanometer sheet/GE compound:
One, by TiO
2nanometer sheet 0.05g is dissolved in the 100mL deionized water, and ultrasonic 30min, obtain TiO
2solution;
Two, graphene oxide 0.007g is dissolved in the 50mL deionized water, ultrasonic dispersion 10min is brown color to solution, obtains graphene oxide solution;
Three, the graphene oxide solution obtained in step 2 is joined to the TiO that step 1 obtains
2in solution, ultrasonic 1h, obtain mixed solution, after then mixed solution being placed in to the freezing 60s of liquid nitrogen, then being placed in freeze drier and carrying out freeze drying;
Four, the dried sample of step 3 is placed in to Muffle furnace, under 500 ℃, argon gas condition, calcines 2h, obtain TiO
2nanometer sheet/GE compound.
The graphene coated technology that the present embodiment provides is without the surface characteristic of destroying nano material, removed the step that nano material in the conventional method needs the finishing positive charge, reduced cost.
The preparation method of the present embodiment utilizes External Force Acting, realize the coating of Graphene to nano material, do not rely on kind, size and the pattern of nano material fully, tightly rely on a simple physical principle to realize the coating of Graphene at material surface, simple, the easy row of the method, can synthesize this type of composite on a large scale.
Claims (10)
1. the preparation method of a graphene coated nano material compound is characterized in that it comprises the following steps:
One, nano material 0.05～0.1g is dissolved in 100～150mL deionized water, ultrasonic 20～40min, obtain solution A;
Two, graphene oxide 0.005～0.01g is dissolved in 50～60mL deionized water, ultrasonic dispersion 5～10min, obtain solution B;
Three, the solution B obtained in step 2 is joined in the solution A that step 1 obtains, ultrasonic 1～2h, obtain mixed solution, after then mixed solution being placed in to the freezing 30～90s of liquid nitrogen, then being placed in freeze drier and carrying out freeze drying;
Four, the dried sample of step 3 is placed in to Muffle furnace, under 500～600 ℃, inert gas conditions, calcines 2～3h, obtain graphene coated nano material compound.
2. the preparation method of a kind of graphene coated nano material compound according to claim 1, is characterized in that the nano material described in step 1 is ZnO microballoon, CdS microballoon or TiO
2nanometer sheet.
3. the preparation method of a kind of graphene coated nano material compound according to claim 2 is characterized in that prepared by following steps by described ZnO microballoon:
One, the zinc acetate of 0.25～0.3g is dissolved in the deionized water of 3～6mL, ultrasonic 5～10min, stir 5～10min, obtains zinc acetate solution;
Two, the CTAB of 0.3～0.6g is dissolved in 50～70mL ethylene glycol, ultrasonic 5～10min, stir 5～10min;
Three, the solution again step 2 obtained joins in the zinc acetate solution that step 1 obtains, and stirs 25～40min, obtains mixed liquor;
Four, mixed liquor step 3 obtained is placed in the reactor of 100mL, then be placed in baking oven, after 135～160 ℃ of reaction 4～8h, treat that product is cooled to room temperature, replace centrifuge washing 4～5 times with deionized water and absolute ethyl alcohol, obtain the ZnO microballoon after oven dry.
4. the preparation method of a kind of graphene coated nano material compound according to claim 2 is characterized in that prepared by following steps by described CdS microballoon:
One, 1.4～2.0mmol cadmium acetate and 35～50mmol thiocarbamide are dissolved in 30～50mL deionized water, stir 25～50min, obtain mixed liquor;
Two, mixed liquor step 1 obtained is placed in the 50mL reactor, then is placed in baking oven, after 135～160 ℃ of reaction 4～8h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4～5 times, obtains the CdS microballoon after oven dry.
5. the preparation method of a kind of graphene coated nano material compound according to claim 2, is characterized in that described TiO
2by following steps, prepared by nanometer sheet:
One, 1～3mL butyl titanate is dissolved in 25～40mL isopropyl alcohol, ultrasonic dispersion 5～10min, form solution;
Two, add 0.2～0.4mL hydrofluoric acid in the solution obtained to step 1, mix, obtain mixed liquor;
Three, the mixed liquor again step 2 obtained is placed in the 50mL reactor, then is placed in baking oven, after 180～200 ℃ of reaction 20～25h, treats that product is cooled to room temperature, with deionized water and absolute ethyl alcohol, replaces centrifuge washing 4～5 times, obtains TiO after oven dry
2nanometer sheet.
6. the preparation method of a kind of graphene coated nano material compound according to claim 1, is characterized in that calcining 2h described in step 4 under 500 ℃, inert gas conditions.
7. according to the preparation method of the described a kind of graphene coated nano material compound of claim 1 or 6, it is characterized in that described inert gas is argon gas or nitrogen.
8. the preparation method of a graphene coated nano material compound is characterized in that it comprises the following steps:
One, nano material 0.05～0.1g is dissolved in 100～150mL deionized water, ultrasonic 20～40min, obtain solution A;
Two, Graphene 0.005～0.01g is dissolved in 50～60mL deionized water, ultrasonic dispersion 5～10min, obtain solution B;
Three, the solution B obtained in step 2 is joined in the solution A that step 1 obtains, ultrasonic 1～2h, obtain mixed solution, after then mixed solution being placed in to the freezing 30～90s of liquid nitrogen, be placed in again freeze drier and carry out freeze drying, obtain graphene coated nano material compound.
9. the preparation method of a kind of graphene coated nano material compound according to claim 8, is characterized in that the ultrasonic time described in step 2 is 10min.
10. the preparation method of a kind of graphene coated nano material compound according to claim 8, is characterized in that the ultrasonic time described in step 3 is 1h, and being placed in the liquid nitrogen cooling time is 60s.
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| CN103721724B (en) * | 2013-12-23 | 2016-01-06 | 聊城大学 | A kind of preparation method of cadmium sulfide/graphene composite material |
| CN103769167A (en) * | 2014-01-28 | 2014-05-07 | 陕西科技大学 | Method for preparing photocatalytic material with graphene-covered cadmium sulfide nuclear shell structure |
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| CN103877971A (en) * | 2014-03-07 | 2014-06-25 | 中国科学院东北地理与农业生态研究所 | Efficient visible-light-induced photocatalyst and preparation method thereof |
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| CN109529883A (en) * | 2018-11-13 | 2019-03-29 | 北京工业大学 | A method of Cd/S core-shell nanostructure is prepared using pulse laser liquid phase ablation |
| CN112480717A (en) * | 2019-09-11 | 2021-03-12 | 哈尔滨工业大学 | Method for preparing core-shell structure nano composite particles by aerogel method |
| CN112480717B (en) * | 2019-09-11 | 2022-05-03 | 哈尔滨工业大学 | Method for preparing core-shell structure nano composite particles by aerogel method |
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| CN112642426A (en) * | 2020-12-23 | 2021-04-13 | 上海聚治新材料科技有限公司 | Preparation method of noble metal/graphene-supported manganese-zinc-based weak photocatalyst |
| CN112642426B (en) * | 2020-12-23 | 2023-09-12 | 上海聚治新材料科技有限公司 | Preparation method of noble metal/graphene supported manganese-zinc-based weak photocatalyst |
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