CN108862266B - Preparation method of graphene oxide nano material - Google Patents

Preparation method of graphene oxide nano material Download PDF

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CN108862266B
CN108862266B CN201810858330.2A CN201810858330A CN108862266B CN 108862266 B CN108862266 B CN 108862266B CN 201810858330 A CN201810858330 A CN 201810858330A CN 108862266 B CN108862266 B CN 108862266B
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CN108862266A (en
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李鹏飞
陈洪月
吕进国
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Liaoning Technical University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite

Abstract

The invention discloses a preparation method of a graphene oxide nano material, which comprises the following steps: s1, carrying out ultrasonic treatment on GO powder in deionized water for a first preset time to obtain a GO aqueous solution; s2, putting the GO aqueous solution with the first preset volume into a round-bottom flask, slowly adding butanol with the second preset volume into the round-bottom flask, and standing for 10 minutes; s3, slowly introducing nitrogen or carbon dioxide from the bottom of the round-bottom flask through a quartz tube, simultaneously carrying out constant-temperature water bath for a second preset time, and standing for 2 hours; s4, sucking a lower layer liquid with a third preset volume from the bottom of the round-bottom flask through a glass suction pipe; s5, continuously shaking the round-bottom flask for 5 minutes, and transferring the liquid in the round-bottom flask into a beaker. The preparation method provided by the invention can realize surface modification of the titanium dioxide material on the GO two-dimensional nano material. GO is not easy to generate coagulation phenomenon in the process of the modification technology, multilayer GO cannot be formed, and the generation of a large amount of titanium dioxide monomer particles is inhibited.

Description

Preparation method of graphene oxide nano material
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a graphene oxide nano material.
Background
The excellent mechanical property is the basis and precondition for the development of engineering application of the material. The brittleness problem of ceramic materials severely restricts the application: because the ceramic material has the polycrystalline structure characteristic of ionic bond or covalent bond, a slippage system capable of promoting the material to deform is lacked, so that the ceramic material is easy to generate cracks after being loaded, and the service life and the stability of the material are reduced.
The graphene oxide-Graphene Oxide (GO) serving as a two-dimensional carbon nano material has high specific surface area and excellent mechanical and tribological properties, is one of materials with very high strength and toughness, and has large contact area with a ceramic matrix due to the two-dimensional shape characteristics, so that stress is transferred favorably, the fracture toughness of the ceramic is improved, and the improvement on the fracture toughness of the ceramicIts brittle nature. Therefore, GO is an ideal toughening phase for toughening ceramic composites. With Al2O3For example, the ceramic may be GO powder and Al2O3Ball milling and blending the powder, heating and pressurizing for sintering to prepare GO-toughened Al2O3A ceramic material.
In Al2O3Although the GO toughening material added into the ceramic material plays a certain toughening role, compared with the high toughness of GO, the toughening effect of simply adding GO into the ceramic powder is not ideal. At present GO toughens Al2O3Under the present circumstances of ceramics, further research and development are required to develop the toughness of graphene-based materials.
When the ceramic is sintered, the solid powder is heated and pressed, and the powder material deforms and flows to form a ceramic block. However, GO and Al2O3The interface of the ceramic matrix is made of different materials, and the wettability of the two materials is poor. The fluidity of the materials between the ceramic powder and the ceramic powder is poor, gas is easy to remain, and a plurality of pores are formed inside the sintered ceramic powder; and, when stressed, stress from Al2O3When the ceramic matrix phase is transferred to the GO phase, the bonding force between the two phases is very weak, so that stress is not easy to transfer, the strong toughness of the GO cannot be effectively exerted, and cracks are easy to grow between the two phase interfaces.
Little titanium dioxide material on the surface of GO is used as a transition layer, so that on one hand, the GO has better fitting property and interface bonding strength; on the other hand, titanium dioxide material and Al2O3The ceramic material has good wettability (therefore, titanium dioxide is often used for Al2O3Additive for ceramics), Al at sintering2O3The molecular mobility between the ceramic and the titanium dioxide material is large, which is beneficial to exhaust and forms a better interface layer. Therefore, the GO surface is modified with titanium dioxide to enhance the GO material and Al2O3Wettability between ceramic matrix phases, and toughening Al for preparing GO with better toughening effect2O3Ceramic materials provide a solid foundation. The existing method for adsorbing the titanium dioxide material on the surface of GO is mainly used in the fields of optics, catalysis and the like. Different from the above application fieldsFor GO toughening of Al2O3Ceramic, there are special requirements: in order to uniformly disperse GO in a ceramic matrix, the agglomeration phenomenon of GO nano materials cannot occur during the surface modification of GO. The prior art method has the following disadvantages:
(1) GO is prone to coagulation during the surface modification process. Coagulation is a chemical phenomenon that when an electrolyte solution is added to a colloid, the added cations (or anions) neutralize the charges carried by the colloid particles, so that the colloid particles aggregate into larger particles, thereby forming precipitates to be separated out from the dispersant. The best dispersing solvent of GO is water, titanium ions are adsorbed on the surface of GO after titanium salt is added into the water, and the GO surface modified titanium dioxide material is obtained through oxidation treatment after drying. However, the above method introduces Ti, which is a high-valent cation4+GO absorbs OH-in water and is negatively charged, Ti4+So that GO is rapidly aggregated in water to form macroscopic flocculent aggregation, an ideal nanoscale flaky GO material cannot be obtained, and the GO is not easily used for toughening Al2O3A ceramic.
(2) GO does not disperse well in other solvents. In order to avoid the problem of GO coagulation, some researches adopt an organic solvent to disperse GO and then introduce organic salt of titanium, most commonly TBT-tetrabutyl titanate. Hydrolysis of TBT occurs to produce titanium ions or titanium hydroxide (Ti (OH)4) Dried together with GO, heated and oxidized to form a mixture of GO and titanium dioxide. However, GO has poor dispersibility in organic solvents, and generally exists in the form of multiple layers (more than 10 layers) of GO or even graphite oxide. The multilayer GO modified by titanium dioxide is formed, and the multilayer GO is attracted only by Van der Waals force. The material is used as a toughening phase in ceramics, and when the materials are stressed, multiple layers of GO are easy to separate and move to generate cracks, so that the fracture toughness of the ceramics is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a graphene oxide nano material, which can realize the surface modification of a GO two-dimensional nano material on a titanium dioxide material. GO is not easy to generate coagulation phenomenon in the process of the modification process, multilayer GO (more than 10 layers or even graphite oxide) can not be formed, and the generation of a large amount of titanium dioxide monomer particles is inhibited.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a graphene oxide nano material comprises the following steps:
s1, carrying out ultrasonic treatment on GO powder in deionized water for a first preset time to obtain a GO aqueous solution;
s2, putting the GO aqueous solution with a first preset volume into a round-bottom flask, slowly adding butanol with a second preset volume into the round-bottom flask, and standing for 10 minutes;
s3, slowly introducing nitrogen or carbon dioxide from the bottom of the round-bottom flask through a quartz tube, simultaneously carrying out constant-temperature water bath for a second preset time, and standing for 2 hours;
s4, sucking a third preset volume of lower-layer liquid from the bottom of the round-bottom flask through a glass suction pipe;
s5, continuously shaking the round-bottom flask for 5 minutes, transferring the liquid in the round-bottom flask into a beaker, and standing for 5 minutes;
s6, preparing a mixed solution of tetrabutyl titanate and absolute ethyl alcohol;
s7, slowly dripping the mixed solution into the beaker through a glass dropper, and continuously stirring in the beaker through a glass rod;
s8, centrifugally washing the substances in the beaker, and drying the precipitate left after centrifugal washing at a first preset temperature for a third preset time;
and S9, heating the powder obtained after drying treatment for a fourth preset time in an air environment to obtain the GO nano material with the surface modified with titanium dioxide.
Further, in the preparation method of the graphene oxide nanomaterial, in step S1, the first preset time is 30 minutes, and the content of GO in the GO aqueous solution is 0.5-2 mg/mL.
Further, in the preparation method of the graphene oxide nanomaterial, in step S2, the first preset volume is 300 mL, the second preset volume is 200mL, and the capacity of the round-bottom flask is 1000 mL.
Further, in the preparation method of the graphene oxide nanomaterial, in step S3, the second preset time is 2 hours, and the temperature of the thermostatic water bath is 50-80 ℃.
Further, in the above preparation method of a graphene oxide nanomaterial, in step S4, the third predetermined volume is the first predetermined volume-V, and V is 15 to 45 mL.
Further, in the preparation method of the graphene oxide nanomaterial, in step S6, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the mixed solution is 1:4-1:20, and the content of tetrabutyl titanate in the mixed solution is 0.2-1.2 mg/mL.
Further, in the preparation method of the graphene oxide nanomaterial, in step S8, the first preset temperature is 80 ℃, the third preset time is 24-48 hours, and the rotational speed of the centrifugal washing is 3000-6000 r/min.
Further, in the preparation method of the graphene oxide nanomaterial, in step S9, the fourth preset time is 30-45 minutes, and the heating temperature is 120-300 ℃.
The invention has the beneficial effects that: the preparation method provided by the invention can realize surface modification of the titanium dioxide material on the GO two-dimensional nano material. GO is not easy to generate coagulation phenomenon in the process of the modification process, multilayer GO (more than 10 layers or even graphite oxide) can not be formed, and the generation of a large amount of titanium dioxide monomer particles is inhibited.
1. Immiscible butanol and water are mixed to form a large number of "water + GO" droplets in the butanol. Because butanol is slightly soluble in water, water is adsorbed on the surface of GO molecules and is partially soluble in butanol solution due to the amphiphilicity of GO. Generally GO is not easily dispersed in alcohol solution, and exists in the alcohol solution in the form of multi-layer GO or graphite oxide, and the single-layer or few-layer GO is dispersed in butanol through steps S1-S5.
2. And the TBT is slowly hydrolyzed on the surface of the GO molecule. Hydrolysis of TBT to produce titania (typically Ti (OH) in solution)4) For the most extensive applicationsThe method for preparing the nano titanium dioxide is adopted, but TBT can be rapidly hydrolyzed when meeting water, and cannot be easily adhered to the surface of GO in a water system solution. After the treatment (step (1-4)) of the technical scheme, a large number of micro-droplets of 'water + GO' are formed in butanol. Because butanol is slightly soluble in water, water is adsorbed on the surface of GO molecules and is partially soluble in butanol solution due to the amphiphilicity of GO. In the butanol solution, only the vicinity of the GO molecules can provide water molecules required by TBT hydrolysis reaction, TBT hydrolysis occurs in the vicinity of the GO molecules, and titanium dioxide precursors are adhered to the surfaces of the GO molecules.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a graphene oxide nanomaterial provided in an embodiment of the present invention.
Fig. 2 is a scanning electron microscope image of the graphene oxide material with a small amount of titanium dioxide surface-modified, prepared in the embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Technical scheme one of the prior art
Molecular assembling method, chemical reaction in water solution, adding Ti salt or Al salt to GO water solution to generate Ti4+Ions or Al3+Ions, making GO surface adsorb Ti4+Ions or Al3+Ion, heating and drying to make Ti on GO surface4+Ions or Al3+The ions contact oxygen in the air to produce titanium dioxide.
The first technical scheme has the following defects:
addition of titanium or aluminium salts to aqueous GO solutions will produce Ti in water4+Ions or Al3+Ions. Addition of high valence (greater than one valence) metal ions to the GO aqueous solution can cause coagulation of GO molecules. The principle is as follows: the GO molecules are negatively charged in water, metal ions are positively charged, and the metal ions can be adsorbed on the surfaces of the GO molecules; one high valence metal ion adsorbs several GO molecules simultaneously, so that almost all GO molecules are polymerized by the metal ion. Therefore, the first technical scheme easily causes the GO nano-materials to form agglomeration, cannot be well dispersed, and further cannot be aggregated with the ceramicsThe particles are uniformly mixed into powder to be sintered. The ceramic material sintered by the powder has uneven distribution of microcosmic components, GO is gathered, cracks are easy to generate, and the fracture toughness of the ceramic is reduced.
Technical scheme two of the prior art
Tetrabutyl titanate (TBT) is added into an organic solvent, the organic solvent is mixed with GO, water is slowly added, and titanium is adsorbed on the surface of GO molecules after TBT is hydrolyzed.
The second technical scheme has the following defects:
GO does not readily disperse in organic solvents, typically yielding multi-layered GO (more than 10 layers), even approaching the thickness of graphite oxide. The multilayer GO modified by titanium dioxide is formed, and the multilayer GO is attracted only by Van der Waals force. The material is used as a toughening phase in ceramics, and when the materials are stressed, multiple layers of GO are easy to separate and move to generate cracks, so that the fracture toughness of the ceramics is reduced.
Aiming at the defects in the prior art, the embodiment of the invention provides a preparation method of a graphene oxide nano material, which can realize the surface modification of a GO two-dimensional nano material on a titanium dioxide material. GO is not easy to generate coagulation phenomenon in the process of the modification process, multilayer GO (more than 10 layers or even graphite oxide) can not be formed, and the generation of a large amount of titanium dioxide monomer particles is inhibited. The specific technical scheme is as follows:
as shown in fig. 1, a method for preparing a graphene oxide nanomaterial includes:
s1, carrying out ultrasonic treatment on GO powder in deionized water for a first preset time to obtain a GO aqueous solution;
s2, putting the GO aqueous solution with the first preset volume into a round-bottom flask, slowly adding butanol with the second preset volume into the round-bottom flask, and standing for 10 minutes;
s3, slowly introducing nitrogen or carbon dioxide from the bottom of the round-bottom flask through a quartz tube, simultaneously carrying out constant-temperature water bath for a second preset time, and standing for 2 hours;
s4, sucking a lower layer liquid with a third preset volume from the bottom of the round-bottom flask through a glass suction pipe;
s5, continuously shaking the round-bottom flask for 5 minutes, transferring the liquid in the round-bottom flask into a beaker, and standing for 5 minutes;
s6, preparing a mixed solution of tetrabutyl titanate and absolute ethyl alcohol;
s7, slowly dripping the mixed solution into a beaker through a glass dropper, and continuously stirring in the beaker through a glass rod;
s8, centrifugally washing the substances in the beaker, and drying the precipitate left after centrifugal washing at a first preset temperature for a third preset time;
and S9, heating the powder obtained after drying treatment for a fourth preset time in an air environment to obtain the GO nano material with the surface modified with titanium dioxide.
In step S1, the first preset time is 30 minutes, and the content of GO in the GO water solution is 0.5-2 mg/mL.
In step S2, the first predetermined volume is 300-500mL, the second predetermined volume is 200mL, and the capacity of the round-bottom flask is 1000 mL.
In step S3, the second preset time is 2 hours, and the temperature of the thermostatic water bath is 50-80 ℃.
In step S4, the third predetermined volume is equal to the first predetermined volume — V, and V is 15 to 45 mL.
In step S6, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the mixed solution is 1:4-1:20, and the content of tetrabutyl titanate in the mixed solution is 0.2-1.2 mg/mL.
In step S8, the first preset temperature is 80 ℃, the third preset time is 24-48 hours, and the rotation speed of the centrifugal washing is 3000-6000 r/min.
In step S9, the fourth predetermined time is 30-45 minutes, and the heating temperature is 120-300 ℃.
Example one
(1) And (3) carrying out ultrasonic treatment on GO powder in deionized water for 30 minutes (ultrasonic power is 180W) to prepare a GO aqueous solution, wherein the GO content is 0.5-2mg/mL (within the content range, GO can be fully dispersed in water, and multilayer GO or graphite oxide does not exist).
(2) And taking the GO aqueous solution, storing the GO aqueous solution into a round bottom flask with the volume of 500mL (300-. In this flask, butanol is insoluble in water and will be in the upper layer of the solution; the GO aqueous solution is positioned at the lower layer, the volume of the GO aqueous solution is about half of the volume of the flask, and the area of a layering interface of the GO solution and butanol is larger.
(3) Nitrogen or carbon dioxide was slowly introduced from the bottom of the flask through a quartz tube while a constant temperature water bath of 50 to 80 ℃ was carried out for 2 hours. Thereafter, the mixture was allowed to stand for 2 hours. The purpose is to precipitate GO molecules in the GO aqueous solution to the vicinity of the layered interface of butanol and water.
(4) The lower layer of liquid is sucked out from the bottom of the round bottom beaker by a glass suction pipe, and the volume V of the sucked liquid is as follows: v ═ V (V1-15mL) - (V1-45 mL).
(5) The round bottom flask was shaken repeatedly for 5 minutes. Thereafter, the liquid was transferred to a beaker and allowed to stand for 5 minutes.
(6) Preparing a mixed solution of TBT and absolute ethyl alcohol, wherein the volume ratio of the TBT to the absolute ethyl alcohol is 1:4-1:20, the TBT content in the solution is 0.2-1.2 mL, about 0.2-1.2mg, and the TBT content is similar to the GO in quality.
(7) And (4) slowly dripping the solution in the step (6) into the beaker in the step (5) by using a glass dropper, and continuously stirring in the beaker by using a glass rod.
(8) The material in the beaker is centrifugally washed at 3000-.
(9) The resulting powder was heated to 120 ℃ for 30-45 minutes in an air environment at 300 ℃. A GO material with a small amount of titanium dioxide surface modified was obtained, and its microscopic scanning electron micrograph is shown in fig. 2.
And (3) carrying out chromatography on GO molecules in the GO aqueous solution on the aqueous solution, and discharging water at the lower layer through the step (4) to leave only 30mL of water, wherein the GO molecules are positioned near the layering surface of the aqueous solution and butanol. Although butanol is difficult to dissolve in water, part of GO can be mixed into butanol solution to form suspension by repeatedly shaking droplets which are wrapped by water according to the amphipathy of GO molecules. At this time, the state of the GO material is still single-layered or few-layered, so the GO in the produced titanium dioxide modified GO material is also single-layered or few-layered. TBT can be dissolved in butanol, then TBT is dropped into butanol suspension liquid through the step (6), TBT generates hydrolysis reaction when meeting water drops wrapped by GO in butanol, and dioxide is generated on the surface of GO moleculesPrecursor of titanium Ti (OH)xBecause the butanol contains very little water and only water molecules around the GO molecules, TBT hydrolysis only occurs around the GO molecules and adheres to the GO molecules, water molecules are few and have the inhibitory effect of ethanol and butanol, and Ti (OH) is generatedxVery slowly, large titanium dioxide particles monomer or Ti (OH) are not easily generated4Monomers, i.e. realizing the vast majority of Ti (OH)xAttaching onto GO molecule surface, drying to remove water, butanol and ethanol impurities, heating at high temperature to obtain Ti (OH)xWill be converted into titanium dioxide (TiO)2)。
Water molecules exist in butanol in a state of a large number of microdroplets, the total content is low, the stability of the water microdroplets in the butanol is kept by the amphipathy of GO molecules, the connection among the microdroplets is isolated by the large number of butanol molecules, and after TBT hydrolysis, the surface of the GO molecules has high-valence titanium Ti4+Ions, but the GO molecules cannot contact each other due to the isolation of butanol; also, as more TBT hydrolyzes on the GO surface, the GO surface adsorbs more Ti (OH)xPreventing contact between GO molecules. Therefore, GO is not easy to generate coagulation phenomenon.
The definition of key terms used herein is as follows:
toughening-increasing the fracture toughness of the ceramic matrix.
Ball milling is a common process for mixing powder particles.
Fracture toughness, a property that measures the ability of a brittle material to resist fracture, the greater the fracture toughness, the less brittle the material will fail.
Modification, namely modifying the surface of GO by modifying titanium dioxide on the surface of GO so as to improve the surface characteristic of GO and increase the wettability of GO with an Al2O3 ceramic matrix.
Improve the wettability-when the ceramic is sintered, the solid powder is heated and pressed, and the powder material is deformed and flows to form a ceramic block. However, GO and Al2O3The interface of ceramic matrix contact is anisotropic material, and the mobility of material between them is poor, leaves gas easily, makes the inside form many blowholes after the pottery sinters — namely: the two materials have poor wettability. GO surface modificationAfter titanium dioxide, with Al2O3The wettability is greatly improved.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.

Claims (1)

1. A preparation method of a graphene oxide nano material is characterized by comprising the following steps:
s1, carrying out ultrasonic treatment on GO powder in deionized water for a first preset time to obtain a GO aqueous solution; the first preset time is 30 minutes, and the content of GO in the GO aqueous solution is 0.5-2 mg/mL;
s2, putting the GO aqueous solution with a first preset volume into a round-bottom flask, slowly adding butanol with a second preset volume into the round-bottom flask, and standing for 10 minutes; the first preset volume is 300-500mL, the second preset volume is 200mL, and the capacity of the round-bottom flask is 1000 mL;
s3, slowly introducing nitrogen or carbon dioxide from the bottom of the round-bottom flask through a quartz tube, simultaneously carrying out constant-temperature water bath for a second preset time, and standing for 2 hours; the second preset time is 2 hours, and the temperature of the constant-temperature water bath is 50-80 ℃;
s4, sucking a lower-layer liquid with a third preset volume from the bottom of the round-bottom flask through a glass suction pipe, wherein the third preset volume is the first preset volume-V, and V is 15-45 mL;
s5, continuously shaking the round-bottom flask for 5 minutes, transferring the liquid in the round-bottom flask into a beaker, and standing for 5 minutes;
s6, preparing a mixed solution of tetrabutyl titanate and absolute ethyl alcohol, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the mixed solution is 1:4-1:20, and the content of tetrabutyl titanate in the mixed solution is 0.2-1.2 mg/mL;
s7, slowly dripping the mixed solution into the beaker through a glass dropper, and continuously stirring in the beaker through a glass rod;
s8, centrifugally washing the substances in the beaker, and drying the precipitate left after centrifugal washing at a first preset temperature for a third preset time; the first preset temperature is 80 ℃, the third preset time is 24-48 hours, and the rotational speed of centrifugal washing is 3000-;
s9, heating the powder obtained after drying treatment for a fourth preset time in an air environment to obtain the GO nano material with the surface modified with titanium dioxide; the fourth preset time is 30-45 minutes, and the heating temperature is 120-300 ℃.
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CN103337611A (en) * 2013-07-10 2013-10-02 厦门大学 Preparation method of graphene-titanium dioxide composite material
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CN103337611A (en) * 2013-07-10 2013-10-02 厦门大学 Preparation method of graphene-titanium dioxide composite material
CN105688809A (en) * 2016-01-26 2016-06-22 西南科技大学 Preparing method for graphene oxide/titanium dioxide nanometer tube composite material
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