CN104492409A - Preparation method for TiO2 crystal/graphene nanocomposite - Google Patents
Preparation method for TiO2 crystal/graphene nanocomposite Download PDFInfo
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- CN104492409A CN104492409A CN201410665391.9A CN201410665391A CN104492409A CN 104492409 A CN104492409 A CN 104492409A CN 201410665391 A CN201410665391 A CN 201410665391A CN 104492409 A CN104492409 A CN 104492409A
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- graphene
- graphene oxide
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Abstract
The invention discloses a preparation method for a TiO2 crystal/graphene nanocomposite. The preparation method comprises the following steps: preparing graphene oxide by using a Hermer method; mixing the prepared graphene oxide with ethanol so as to form a graphene oxide ethanol solution; adding organic titanate into the graphene oxide ethanol solution via vigorous stirring so as to form a mixed solution; adding the mixed solution into a hydrothermal reaction kettle; heating the hydrothermal reaction kettle; after natural cooling of the hydrothermal reaction kettle, centrifugally filtering suspension in the hydrothermal reaction kettle so as to obtain a black solid material; washing the black solid material until filter liquor is colorless; putting the washed black material into an oven and carrying out drying so as to obtain black powder; and calcining the black powder in inert gas so as to form the TiO2 crystal/graphene nanocomposite. The preparation method for the TiO2 crystal/graphene nanocomposite provided by the invention can overcome the technical problem that the morphology of the TiO2 crystal/graphene nanocomposite is difficult to control in the prior art.
Description
Technical field
The invention belongs to chemical industry and environmental area, more specifically, relate to a kind of TiO
2the preparation method of crystal/graphene nanometer composite.
Background technology
A large amount of greenhouse gases are as CO
2, CH
4deng the greenhouse effects that cause of discharge become global concern focus.In recent years, CO in the air caused due to human production activity
2the increase of concentration has accelerated the impact of greenhouse effects on global climate.How effectively control CO
2discharge has become the task of top priority of various countries.Utilize photo catalytic reduction technology by CO
2be converted into methane, carbon monoxide, the organic matters such as methyl alcohol reduce CO
2discharge is a kind of effective way.It is at reduction CO
2cO is also achieved while discharge
2recycling.Photo catalytic reduction technology utilizes semi-conducting material to promote the carrying out of reaction as photochemical catalyst, when energy is mapped to catalyst surface higher than the illumination of semiconductor energy gap, conduction band will be transitted to from valence band by moral electronics in vitalizing semiconductor, be formed and there is very strong active electron hole pair, make CO
2reduction reaction carried out.TiO
2strong owing to having photochemical catalytic oxidation ability, resistance to photoetch, with low cost, the advantage such as nontoxic, by the most widely used photochemical catalyst.But because Photon-Electron electrons hole is at TiO
2surface is compound easily, and its larger energy gap, TiO
2only can show lower photocatalytic activity under ultraviolet light, at visible ray catalytically inactive.Therefore, current facing challenges is the compound how effectively stoping electron-hole pair, and its photoresponse scope is expanded to visible ray.
Graphene has carbon atom sp
2individual layer two graphite-structures that hydridization is formed.Graphene has large specific area, can significantly improve the adsorption capacity to reactant.Graphene also has unique electronic property, as high electron mobility, by itself and TiO
2the separation that compound can effectively suppress photo-generate electron-hole right, improves light-catalyzed reaction efficiency.In addition, TiO
2with Graphene compound after visible ray also shown absorb more by force, greatly can improve its catalytic activity under visible light.Therefore, design and prepare new and effective TiO
2/ graphene composite catalyst is TiO
2the study hotspot of photocatalysis field and emphasis.
TiO
2tiO in/graphene complex
2crystal morphology has considerable influence to its catalytic activity.Recently, many researchers utilize various method, as hydro-thermal method, and the TiO of synthesis different-shape such as chemical reduction method (spheric granules, nanometer rods, nanometer sheet etc.)
2/ graphene complex.But the synthetic method of report can only for the TiO of the single specific morphology of synthesis at present
2/ graphene complex, several cannot have the TiO of different-shape by control synthesis condition Fast back-projection algorithm
2crystal/graphene complex.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of TiO
2the preparation method of crystal/graphene nanometer composite, its object is to, and solves the TiO existed in existing method
2the unmanageable technical problem of/graphene complex pattern.
For achieving the above object, according to one aspect of the present invention, provide a kind of TiO
2the preparation method of crystal/graphene nanometer composite, comprises the following steps:
(1) use He Mo legal system for graphene oxide, and the graphene oxide of preparation is mixed with ethanol, to form graphene oxide ethanolic solution;
(2) with vigorous stirring, organic titanate is added in the graphene oxide ethanolic solution that step (1) formed, to form mixed solution;
(3) add in hydrothermal reaction kettle by the mixed solution formed in step (2), heat this hydrothermal reaction kettle, wherein the heat time is 12-24 hour, and heating-up temperature is 100-180 DEG C;
(4) after hydrothermal reaction kettle cools naturally, by suspension centrifugal filtration wherein, to obtain black solid material;
(5) black solid material that step (4) obtains is washed, until filtrate be colourless after, this atrament is put into baking oven and dries, to obtain black powder;
(6) black powder that step (5) obtains is calcined in inert gas, thus form TiO
2crystal/graphene nanometer composite.
Preferably, the volume ratio of organic titanate and graphene oxide ethanolic solution is 1:150-170.
Preferably, this method is included in after step (2) and before step (3) further, in the mixed solution of formation according to organic titanate between the volume ratio of 1:1.15-1.35 add hydrofluoric acid and the step stirred.
Preferably, organic titanate is butyl titanate or isopropyl titanate.
Preferably, the calcination time in step (6) is 2-3 hour, and calcining heat is 450-550 DEG C, and heating rate is 5-10 DEG C/min.
In general, the above technical scheme conceived by the present invention compared with prior art, can obtain following beneficial effect:
(1) TiO existed in existing method can be solved
2/ graphene complex pattern is difficult to control problem: owing to adopting HF as stabilizing agent, and by adjusting solvent thermal response time and temperature, can to TiO
2crystal face, the shape and particle diameter etc. of crystal regulate and control, therefore can good control TiO
2/ graphene complex pattern.
(2) TiO for preparing of the present invention
2tiO in/graphene complex
2crystal good dispersion: owing to graphene oxide well being mixed with organic titanate in ethanolic solution, after solvent thermal reaction, TiO
2graphenic surface can be dispersed in very uniformly, thus there is good dispersiveness.
Accompanying drawing explanation
Fig. 1 is the TiO adopting method provided by the invention to prepare
2the transmission electron microscope picture of nano cubic/graphene nanometer composite.
Fig. 2 is the TiO adopting method provided by the invention to prepare
2the transmission electron microscope picture of nanosphere/graphene nanometer composite.
Fig. 3 is the TiO adopting method provided by the invention to prepare
2the transmission electron microscope picture of nanometer rods/graphene nanometer composite.
Fig. 4 is the TiO adopting method provided by the invention to prepare
2the transmission electron microscope picture of nanometer sheet/graphene nanometer composite.
Fig. 5 is the TiO adopting method provided by the invention to prepare
2the transmission electron microscope picture of nanometer sheet/graphene nanometer composite.
Fig. 6 is the TiO adopting method provided by the invention to prepare
2the transmission electron microscope picture of nanosphere condensate/graphene nanometer composite.
Fig. 7 adopts method provided by the invention to prepare TiO
2nanometer rods condensate/graphene nanometer composite.
Fig. 8 is TiO of the present invention
2the flow chart of the preparation method of crystal/graphene nanometer composite.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
As shown in Figure 8, TiO of the present invention
2the preparation method of crystal/graphene nanometer composite comprises the following steps:
(1) use He Mo (Hummer) legal system for graphene oxide, and the graphene oxide of preparation is mixed with ethanol, to form graphene oxide ethanolic solution;
(2) with vigorous stirring, organic titanate added in the graphene oxide ethanolic solution that step (1) formed, to form mixed solution according to the volume ratio of 1:150-170;
Preferably, also in the mixed solution formed, hydrofluoric acid can be added according to the volume ratio of 1:1.15-1.35 between organic titanate and stirs, to regulate and control to wish the TiO obtained further
2the pattern of/graphene complex; In the present embodiment, organic titanate is butyl titanate or isopropyl titanate;
(3) add in hydrothermal reaction kettle by the mixed solution formed in step (2), heat this hydrothermal reaction kettle, wherein the heat time is 12-24 hour, and heating-up temperature is 100-180 DEG C;
(4) after hydrothermal reaction kettle cools naturally, by suspension centrifugal filtration wherein, to obtain black solid material;
(5) black solid material that step (4) obtains is washed, until filtrate be colourless after, this atrament is put into baking oven and dries, to obtain black powder;
(6) black powder that step (5) obtains is calcined 2-3 hour in inert gas, calcining heat is 450-550 DEG C, and heating rate is 5-10 DEG C/min, thus forms TiO
2crystal/graphene nanometer composite.
Embodiment 1 TiO
2the synthesis of nano cubic/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, then add 0.8ml hydrofluoric acid, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 12h at 180 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 1, gained TiO
2tiO in nano cubic/graphene nanometer composite
2even particle distribution, for cube shaped, crystal grain is about 50nm.
Embodiment 2 TiO
2the synthesis of nanosphere/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 12h at 100 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h in nitrogen atmosphere at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 2, gained TiO
2tiO in nanosphere/graphene nanometer composite
2particle arrangement is comparatively fine and close, and for spherical, crystal grain is about 20nm.
Embodiment 3 TiO
2the synthesis of nanometer rods/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, then add 0.8ml hydrofluoric acid, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 18h at 100 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h in nitrogen atmosphere at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 3, gained TiO
2tiO in nanosphere/graphene nanometer composite
2particle is corynebacterium, is evenly distributed, and size is about 20 × 60nm.
Embodiment 4 TiO
2the synthesis of nanometer sheet/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, then add 0.8ml hydrofluoric acid, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 18h at 180 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h in nitrogen atmosphere at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 4, gained TiO
2tiO in nanometer sheet/graphene nanometer composite
2particle is sheet, and size is about 10 × 40 × 50nm, TiO
2nanometer sheet regular shape, complete, crystallinity is good.
Embodiment 5 TiO
2the synthesis of nanometer sheet/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, then add 0.8ml hydrofluoric acid, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 12h at 150 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h in nitrogen atmosphere at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 4, gained TiO
2tiO in nanometer sheet/graphene nanometer composite
2particle is sheet, and size is about 10 × 50 × 60nm, TiO
2nanometer sheet shape is not exclusively regular, and crystallization degree is general, and surface exists unformed shape.
The synthesis of embodiment 6 nanosphere condensate/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 15h at 100 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h in nitrogen atmosphere at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 6, gained TiO
2tiO in nanosphere condensate/graphene nanometer composite
2particle is spherical, and crystal grain is about 10nm, and obvious agglomeration has appearred in particle, and each aggregate is made up of 10 ~ 20 nanospheres, and aggregate diameter is about 60nm.
Embodiment 7 TiO
2the synthesis of nanometer rods condensate/graphene nanometer composite
He Mofa is adopted to synthesize graphene oxide.Get 160mg graphene oxide, be dispersed in 160ml absolute ethyl alcohol, ultrasonic 2h, is dispersed in absolute ethyl alcohol to graphene oxide.With vigorous stirring 1ml butyl titanate is dropwise joined in dissolving, then add 0.8ml hydrofluoric acid, after stirring 30min, obtain homogeneous solution.Finally mixed solution is moved in teflon-lined water heating kettle, solvent heat 18h at 150 DEG C.After reaction terminates, question response still naturally cools to room temperature, product is taken out, with absolute ethyl alcohol and deionized water centrifuge washing filter cake multipass after centrifugal filtration, until centrifugal go out supernatant be colourless.Then the solid sample obtained is put into vacuum drying chamber to dry.Finally the sample of drying is calcined 2h in nitrogen atmosphere at 450 DEG C, heating rate is 10 DEG C/min.
As shown in Figure 7, gained TiO
2tiO in nanometer rods condensate/graphene nanometer composite
2exist with nanometer rods aggregate form, distribution is comparatively even, and aggregate diameter is about 250nm, for some nanometer rods are polymerized,
The equipment that the method needs is simple, and required precursor species kind is few, synthesizes convenient, fast, relative inexpensiveness, is conducive to industrialization promotion.In addition, the TiO synthesized with prior art
2crystal/graphene nanometer composite is compared, the TiO of this method synthesis
2tiO in crystal/Graphene
2crystal has fabulous dispersiveness and good crystallinity, and this is extremely meaningful for its photocatalytic activity of raising.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a TiO
2the preparation method of crystal/graphene nanometer composite, is characterized in that, comprises the following steps:
(1) use He Mo legal system for graphene oxide, and the graphene oxide of preparation is mixed with ethanol, to form graphene oxide ethanolic solution;
(2) with vigorous stirring, organic titanate is added in the graphene oxide ethanolic solution that step (1) formed, to form mixed solution;
(3) add in hydrothermal reaction kettle by the mixed solution formed in step (2), heat this hydrothermal reaction kettle, wherein the heat time is 12-24 hour, and heating-up temperature is 100-180 DEG C;
(4) after hydrothermal reaction kettle cools naturally, by suspension centrifugal filtration wherein, to obtain black solid material;
(5) black solid material that step (4) obtains is washed, until filtrate be colourless after, this atrament is put into baking oven and dries, to obtain black powder;
(6) black powder that step (5) obtains is calcined in inert gas, thus form TiO
2crystal/graphene nanometer composite.
2. preparation method according to claim 1, is characterized in that, the volume ratio of organic titanate and graphene oxide ethanolic solution is 1:150-170.
3. preparation method according to claim 1, it is characterized in that, be included in after step (2) further and before step (3), in the mixed solution of formation according to organic titanate between the volume ratio of 1:1.15-1.35 add hydrofluoric acid and the step stirred.
4. preparation method according to claim 1, is characterized in that, organic titanate is butyl titanate or isopropyl titanate.
5. preparation method according to claim 1, is characterized in that, the calcination time in step (6) is 2-3 hour, and calcining heat is 450-550 DEG C, and heating rate is 5-10 DEG C/min.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868112A (en) * | 2015-05-12 | 2015-08-26 | 吉林大学 | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof |
| CN105336940A (en) * | 2015-10-20 | 2016-02-17 | 深圳先进技术研究院 | Sodium titanate nanowire/graphene composite negative electrode material, and preparation method thereof |
| CN105576212A (en) * | 2016-02-19 | 2016-05-11 | 东莞市迈科科技有限公司 | Method for preparing titanium dioxide nanosheet coated graphene anode material of lithium ion battery |
| CN105772038A (en) * | 2016-01-08 | 2016-07-20 | 浙江大学 | Application of material for removing bromate in water through ultraviolet photocatalysis in removal of bromate in water |
| CN105772037A (en) * | 2016-01-08 | 2016-07-20 | 浙江大学 | Material for removing bromate in water through ultraviolet photocatalysis and preparation method thereof |
| CN106311206A (en) * | 2016-09-09 | 2017-01-11 | 北京优碳环能科技有限公司 | Titanium dioxide/graphene composite nanometer photocatalyst, method for preparing same and application of titanium dioxide/graphene composite nanometer photocatalyst |
| CN106395800A (en) * | 2016-08-26 | 2017-02-15 | 南通大学 | Preparation method of TiO2 intercalated graphene oxide |
| CN108745336A (en) * | 2018-05-08 | 2018-11-06 | 福建工程学院 | Titanium dioxide nanoplate/reduced graphene composite photo-catalyst and preparation method thereof |
| CN109718752A (en) * | 2019-01-27 | 2019-05-07 | 安徽大学 | A kind of graphene/TiO2Nanocomposite and preparation method thereof |
| CN110433834A (en) * | 2019-08-30 | 2019-11-12 | 福建工程学院 | A kind of MXene/TiO of two-dimensional slice material modification2The preparation and application of composite material |
| CN111743192A (en) * | 2020-07-10 | 2020-10-09 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
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| CN104868112B (en) * | 2015-05-12 | 2017-06-20 | 吉林大学 | Carbon coating titanium dioxide nanoplate array and graphene combination electrode material and preparation method thereof |
| CN104868112A (en) * | 2015-05-12 | 2015-08-26 | 吉林大学 | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof |
| CN105336940A (en) * | 2015-10-20 | 2016-02-17 | 深圳先进技术研究院 | Sodium titanate nanowire/graphene composite negative electrode material, and preparation method thereof |
| CN105336940B (en) * | 2015-10-20 | 2018-06-05 | 深圳先进技术研究院 | A kind of sodium titanate nano wire/graphene composite negative pole material and preparation method thereof |
| CN105772038B (en) * | 2016-01-08 | 2018-03-06 | 浙江大学 | A kind of ultraviolet catalytic goes application of the material of bromate in water removal in bromate in going water removal |
| CN105772037A (en) * | 2016-01-08 | 2016-07-20 | 浙江大学 | Material for removing bromate in water through ultraviolet photocatalysis and preparation method thereof |
| CN105772038A (en) * | 2016-01-08 | 2016-07-20 | 浙江大学 | Application of material for removing bromate in water through ultraviolet photocatalysis in removal of bromate in water |
| CN105772037B (en) * | 2016-01-08 | 2018-03-06 | 浙江大学 | A kind of ultraviolet catalytic removes material of bromate and preparation method thereof in water removal |
| CN105576212A (en) * | 2016-02-19 | 2016-05-11 | 东莞市迈科科技有限公司 | Method for preparing titanium dioxide nanosheet coated graphene anode material of lithium ion battery |
| CN106395800B (en) * | 2016-08-26 | 2019-04-19 | 南通大学 | A kind of preparation method of TiO2 intercalation graphene oxide |
| CN106395800A (en) * | 2016-08-26 | 2017-02-15 | 南通大学 | Preparation method of TiO2 intercalated graphene oxide |
| CN106311206A (en) * | 2016-09-09 | 2017-01-11 | 北京优碳环能科技有限公司 | Titanium dioxide/graphene composite nanometer photocatalyst, method for preparing same and application of titanium dioxide/graphene composite nanometer photocatalyst |
| CN108745336A (en) * | 2018-05-08 | 2018-11-06 | 福建工程学院 | Titanium dioxide nanoplate/reduced graphene composite photo-catalyst and preparation method thereof |
| CN109718752A (en) * | 2019-01-27 | 2019-05-07 | 安徽大学 | A kind of graphene/TiO2Nanocomposite and preparation method thereof |
| CN109718752B (en) * | 2019-01-27 | 2021-11-12 | 安徽大学 | graphene/TiO2Nanocomposite and method for preparing same |
| CN110433834A (en) * | 2019-08-30 | 2019-11-12 | 福建工程学院 | A kind of MXene/TiO of two-dimensional slice material modification2The preparation and application of composite material |
| CN111743192A (en) * | 2020-07-10 | 2020-10-09 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
| CN111743192B (en) * | 2020-07-10 | 2022-05-17 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
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