CN104815637A - Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material - Google Patents

Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material Download PDF

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CN104815637A
CN104815637A CN201510153765.3A CN201510153765A CN104815637A CN 104815637 A CN104815637 A CN 104815637A CN 201510153765 A CN201510153765 A CN 201510153765A CN 104815637 A CN104815637 A CN 104815637A
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graphene
flower
graphite oxide
shaped composite
hydro
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CN104815637B (en
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莫尊理
王雅雯
郭瑞斌
缑浩
张平
胡惹惹
魏晓娇
陈芳
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Northwest Normal University
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Abstract

The invention discloses a method for hydrothermal method preparation of a graphene-loaded flower-type titanium dioxide composite material and belongs to the technical field of composite materials. The method utilizes graphite oxide and a titanium salt as precursors, a low carbon alcohol-water mixed solvent as a medium and a surfactant as a soft template and comprises carrying out functionalization modification on the graphite oxide, adding an acid solution of the titanium salt into the modified graphite oxide, carrying out stirring so that the titanium ions are combined to the functionalized graphite oxide, adding the functionalized graphite oxide into a reactor, and carrying out a hydro-thermal reaction process so that the graphene-loaded flower-type titanium dioxide composite material is prepared by one step. The graphene-loaded flower-type titanium dioxide composite material comprises a rutile phase titanium dioxide nanometer rod-assembled flower-type structure with nanometer rod diameters of 15-35nm on the graphene surface, and through graphene connection, the structure has high specific surface area and can promote electron transmission on the material. Therefore, the graphene-loaded flower-type titanium dioxide composite material has good application prospects in the fields of photocatalysis, solar cells and gas-sensitive sensors.

Description

Hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material
Technical field
The invention belongs to technical field of composite materials, relate to the preparation method of Graphene/flower-shaped composite titania material, particularly relate to a kind of with graphite oxide and titanium salt for presoma, prepared the method for graphene-supported flower-shaped composite titania material by hydro-thermal method.
Background technology
As everyone knows, the performance of material and some geometrical factors such as pattern, size, crystal structure etc. have relation closely.Therefore, control to synthesize the study hotspot that the inorganic material with clear and definite pattern just becomes current technical field of material chemistry.Wherein, the micrometer structure be made up of nano structured unit, as multi-stage nano/micrometer structure that nanometer rods, nanometer sheet or nano wire assemble, because it also avoid the shortcomings such as nano material is easily reunited, stability is bad while the advantage-skin effect possessing nano material and quantum size effect, thus the preparation of this kind of material and performance development are received much concern at Material Field.
Titanium dioxide because stable chemical nature, resistance to acids and bases are good, nontoxic, abundance and low cost and other advantages, be considered to research one of metal oxide semiconductor material the most widely at present.Based on its functional character, the performance development of titanium dioxide has related to the numerous areas such as photocatalysis, solar cell, gas sensor, ultracapacitor.How to allow titanium dioxide show high-performance in actual applications, researchers have also been made large quantifier elimination.Wherein, synthesis has the nano/micron structure titanium dioxide of the many avtive spots of high-ratio surface sum is one of method of head it off.As the people such as Zhu [ACS Appl.Mater.Interfaces 2011,3,3448-3453] have synthesized the flower-like structure be made up of titanium dioxide nanoplate by one step hydro thermal method, find the P25 that the photocatalysis performance of this material will be sold far above business.The people such as Sun [J.Am.Chem.Soc.2011,133,19314-19317] the dendritic rutile titanium dioxide of three-dimensional tree that is made up of nanometer rods by water heat transfer for template with surfactant softex kw study its chemical property and find, this titanium dioxide has higher charge/discharge capacitance and good cyclical stability compared to anatase titanium dioxide particle.In addition, researchers find that in titanium dioxide, introduce other constituent unit formation composite also can improve performance, broaden application field.
Graphene is a kind of bi-dimensional cellular shape lattice structure by the tightly packed one-tenth of monolayer carbon atom.The structure of this uniqueness makes Graphene show the performance of many excellences.If Graphene theoretical specific surface area is up to 2630m 2/ g, has good thermal conductivity and electron mobility at a high speed.The composite that Graphene and titanium dioxide are formed, the electronic conduction ability of Graphene excellence is not only utilized to accelerate being separated of titanium dioxide photoinduced electron and hole, its large specific area also can be utilized simultaneously to add the absorption property of material, thus improve photocatalysis performance and the electricity conversion of material.
At present, Graphene and the research of other three-dimensional metal oxide as composites such as nickel oxide, manganese dioxide, zinc oxide have been reported, and all shown excellent performance, but often with Graphene and slaine for precursor power, cost is high, and is difficult to make good compound between flower-like structure and Graphene.Research prepared by Graphene/three-dimensional composite titania material is also relatively less.As the people such as Liu [J. Mater. Chem. A, 2013,1,12255-12262] obtain Graphene/flower-shaped composite titania material with flower-shaped titanium dioxide and graphite oxide for precursor power, find that its photocatalysis efficiency is 3.4 times of P25.But its preparation process also wants more than two steps, complex process.Therefore, find that a kind of technique is simple, the high and low cost of morphology controllable degree and the preparation method of environmental protection just seems particularly important.
Summary of the invention
The object of the invention is for problems of the prior art, provide a kind of with graphite oxide and titanium salt for presoma, prepared the method for graphene-supported flower-shaped composite titania material by hydro-thermal method one step.
One, the preparation of composite
The present invention prepares the method for graphene-supported flower-shaped composite titania material, for medium with the mixed solvent of low-carbon (LC) alcohol and water, take surfactant as dressing agent, first graphite oxide is carried out functional modification, add the acid solution of titanium salt subsequently, stirring makes titanium ion complexing on the graphene oxide of functionalization, finally adds in reactor and carries out hydro-thermal reaction, obtain graphene-supported flower-shaped composite titania material.
Its concrete preparation technology is: by graphite oxide ultrasonic disperse in the mixed solvent of low-carbon (LC) alcohol and water, then adds surfactant stirring 1 ~ 2h; Then the acid solution adding titanium salt continues stirring 2 ~ 3h, is finally placed in reactor, and in 120 ~ 180 DEG C of reaction 12 ~ 24h, filter, washing, 50 DEG C of vacuum drying, obtain graphene-supported flower-shaped composite titania material.
Described titanium salt is isopropyl titanate or butyl titanate, and the acid solution of titanium salt is concentrated hydrochloric acid solution.
The mass ratio of graphite oxide and titanium salt is 10:1 ~ 20:1.
Surfactant is polyvinylpyrrolidone or softex kw; The mass ratio of graphite oxide and surfactant is 1:3 ~ 1:10.
In the mixed solvent of low-carbon alcohols (methyl alcohol, ethanol, propyl alcohol, ethylene glycol etc.) and water, the volume ratio of low-carbon alcohols and water is 1:1 ~ 5:1, preferred 1:1.
Two, the structure of composite and pattern
Below by X-ray diffraction analysis, scanning electron microscope analysis, thermogravimetric analysis, BET analysis, analytic explanation is carried out to the structure of graphene-supported flower-shaped composite titania material prepared by the present invention and pattern.
1, X-ray diffraction analysis
Fig. 1 is the X-ray diffractogram that the present invention prepares Graphene/flower-shaped composite titania material.The characteristic diffraction peak presented as can be seen from figure, prepared composite has complete crystalline state.Wherein 2 θ angles are that 27.3 °, 36.1 °, 39.2 °, 41.0 °, 43.9 °, 54.2 °, 56.4 °, 62.9 °, 69.0 ° and the 69.8 ° diffraction maximums locating to occur are consistent with the standard card JCPDS:21-1276 of red schorl phase titanium dioxide, show that the crystalline phase of titanium dioxide in composite is rutile.In 2 θ=24.5, ° place's diffraction maximum is 002 crystal face characteristic diffraction peak of Graphene, shows that graphite oxide has been reduced in order to Graphene.In summary it can be seen that prepared material is composited by red schorl phase titanium dioxide and Graphene.
2, scanning electron microscope analysis
Fig. 2 be 150 DEG C, pvp concentration is 8mg/ml, the reaction time is ESEM (SEM) figure under the different amplification of the product that 24h obtains.Fig. 2 (a) is the SEM figure of amplification 20000 times, Fig. 2 (b) is the SEM figure that composite amplifies 50000 times.As can be seen from Fig. 2 (a) and 2 (b), by being about 300 ~ 400 nm, the flower-like structure uniform load of the titanium dioxide nano-rod composition of diameter about 15 ~ 35nm is on the graphenic surface that the number of plies is less, and diameter be about 1 ~ 1.5um flower-like structure between be interconnected by Graphene, there is not stacking agglomeration.
3, thermogravimetric analysis
Fig. 3 is the thermal multigraph of Graphene/flower-shaped composite titania material.The mass loss occurred between 30 ~ 200 DEG C in figure is caused by the evaporation of residual moisture in composite and organic solvent.200 ~ 500 DEG C to be that organo-functional group residual on surface organic matter and Graphene decomposes weightless.500 DEG C of weightlessness being the decomposition of carbon skeleton later and causing.
4, BET analyzes
Flower-shaped titanium dioxide (the TiO prepared when not adding graphite oxide is respectively in Fig. 4 2) and Graphene/flower-shaped composite titania material (G/TiO 2) nitrogen adsorption desorption isotherm figure (BET).Bi-material all presents IV type thermoisopleth, presents H3 type hysteresis loop when being partial to high relative pressure, shows to have the space being greater than 50nm to exist.The BET specific surface area of the flower-shaped titanium dioxide that the same terms obtains is 124.4m 2/ g, and the BET specific surface area of Graphene/flower-shaped composite titania material reduces by comparison to some extent, is 93.5m 2/ g, this is mainly because the coating function of Graphene causes, but also more than in document the Graphene reported and flower-shaped titanium dioxide, flower shape zinc oxide, flower-shaped manganese oxide specific area much bigger.This feature makes this material all show huge application prospect at catalyst carrier, field of Environment Protection.
The present invention has the following advantages relative to prior art:
1, the present invention with graphite oxide and titanium salt for raw material, the composite of two-dimensional graphene/three-dimensional flower-shaped titanium dioxide has been obtained by one step hydro thermal method, prepare the method for Graphene and three-dimensional structure metal oxide composite compared to other, cost is lower, technique is more simple, reaction condition is gentle, pollution-free, be easy to large-scale production;
2, the present invention adds surfactant as soft template in preparation process, and titanium dioxide flower-like structure can be guided to grow in the both sides of Graphene, and, regular flower-like structure stable to acquisition plays an important role.In addition, the overall appearance of material can also be controlled by the mass ratio adjusting graphite oxide and titanium salt;
3, the reduction of the present invention's graphene oxide in water-heat process and the growth of titanium dioxide flower-like structure are carried out simultaneously, and the growth of flower-like structure between graphene layer can suppress the π-π of its interlayer to adsorb, and ensures the quality that Graphene has had; And Graphene can connect titanium dioxide flower-like structure, make between material component, to form the entirety be interconnected, the transmission of electronics on material can be promoted.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of Graphene/flower-shaped composite titania material prepared by the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of Graphene/flower-shaped composite titania material prepared by the present invention.
Fig. 3 is the thermal multigraph of Graphene/flower-shaped composite titania material prepared by the present invention.
Fig. 4 is the nitrogen adsorption desorption isotherm figure of Graphene/flower-shaped composite titania material prepared by the present invention.
Detailed description of the invention
Be described further below by the preparation, structure, pattern etc. of instantiation to Graphene of the present invention/flower-shaped composite titania material.
Embodiment 1
(1) preparation of graphite oxide: take and to add after 1.5g crystalline flake graphite mixes with 4.5g potassium permanganate in 180mL to the mixed acid solution of sulfuric acid and phosphoric acid (volume ratio 9:1), at 30 ~ 40 DEG C after stirring reaction 1h, be warming up to 50 DEG C and continue reaction 12h.Be cooled to room temperature after reaction terminates, product slowly poured in the frozen water containing 10mL hydrogen peroxide, leave standstill, after removing supernatant, suction filtration, the hydrochloric acid with 5% carrys out abundant washing leaching cake, until without SO in filtrate 4 2-, subsequently by deionized water and ethanol alternately washing extremely neutrality, namely obtain required graphite oxide in 50 DEG C of vacuum drying 12 ~ 24h.
(2) preparation of Graphene/flower-shaped composite titania material: take 8mg graphite oxide and join in the mixed solution of 20ml ethylene glycol and 20ml water, ultrasonic 10 ~ 24h; Graphite to be oxidized ultrasonic evenly after, adding 5ml concentration is wherein stir 1h in the aqueous povidone solution of 8mg/ml; Measuring 0.5ml isopropyl titanate is added drop-wise in 10ml concentrated hydrochloric acid, dropwise joins in the solution of above-mentioned graphite oxide after being uniformly mixed, and continues to stir 2h; Then join in 100ml polytetrafluoroethylene (PTFE) reactor, 150 DEG C of reaction 24h, after being cooled to room temperature, filter, wash, are drying to obtain graphene-supported flower-shaped composite titania material.In product, better, Size Distribution is narrower, and the flower-like structure being about 1 ~ 1.5um is positioned between graphene layer, and define 3-D solid structure, abloom rate is up to 99% for Graphene and titanium dioxide composite effect.
Embodiment 2
(1) preparation of graphite oxide is with example 1.
(2) preparation of Graphene/flower-shaped composite titania material: take 12mg graphite oxide and join in the mixed solution of 30ml propyl alcohol and 10ml water, ultrasonic 10 ~ 24h.Graphite to be oxidized ultrasonic evenly after, adding 5ml concentration is wherein in the aqueous povidone solution of 8mg/ml, stirs 1h.Measuring 0.5ml isopropyl titanate is added drop-wise in 5ml concentrated hydrochloric acid, dropwise joins in the solution of above-mentioned graphite oxide after being uniformly mixed, and continues to stir 2h.Then liquid joins in 100ml polytetrafluoroethylene (PTFE) reactor, and 150 DEG C of reaction 24h, after being cooled to room temperature, filter, wash, are drying to obtain graphene-supported flower-shaped composite titania material.In product, Graphene is in tiling shape, and the titanium dioxide Size Distribution of flower-like structure increases slightly, and the flower-like structure that diameter is about 1 ~ 2um grows uniformly on the surface of Graphene, and the diameter forming the nanometer rods of flower-like structure is about 16nm.
Embodiment 3
(1) preparation of graphite oxide is with example 1.
(2) preparation of Graphene/flower-shaped composite titania material: take 8mg graphite oxide and join in the mixed solution of 20ml ethylene glycol and 20ml water, ultrasonic 10 ~ 24h; Graphite to be oxidized ultrasonic evenly after, adding 5ml concentration is wherein in the softex kw aqueous solution of 8mg/ml, stirs 1h; Measuring 0.5ml isopropyl titanate is added drop-wise in 5ml concentrated hydrochloric acid, dropwise join in the alcohol solution of graphite oxide after being uniformly mixed, continue to stir 2h, then join in 100ml polytetrafluoroethylene (PTFE) reactor, 180 DEG C of reaction 20h, after being cooled to room temperature, filter, wash, be drying to obtain graphene-supported flower-shaped composite titania material.Characterize and find, in this composite, diameter is about the flower-shaped titanium dioxide of 3 ~ 4um is be 35nm by diameter, and the nanometer rods being about 680nm is formed, and is dispersed in uniformly between graphene layer.
Embodiment 4
(1) preparation of graphite oxide is with example 1.
(2) preparation of Graphene/flower-shaped composite titania material: take 8mg graphite oxide and join in the mixed solution of 20ml ethylene glycol and 20ml water, ultrasonic 10 ~ 24h; Graphite to be oxidized ultrasonic evenly after, adding 5ml concentration is wherein in the aqueous povidone solution of 8mg/ml, stirs 1h.Measuring 0.5ml isopropyl titanate is added drop-wise in 10ml concentrated hydrochloric acid, dropwise joins in the solution of above-mentioned graphite oxide after being uniformly mixed, and continues to stir 2h; Then join in 100ml polytetrafluoroethylene (PTFE) reactor, 150 DEG C of reaction 12h, after being cooled to room temperature, filter, wash, are drying to obtain graphene-supported flower-shaped composite titania material.Be about 25nm by diameter in product, the flower-like structure intercalation being about the 800nm ~ 1.2um of the nanometer rods composition of the aplysia punctata of 300nm is distributed between graphene layer.
Embodiment 5
(1) preparation of graphite oxide is with example 1.
(2) preparation of Graphene/flower-shaped composite titania material: take 8mg graphite oxide and join in the mixed solution of 20ml methyl alcohol and 20ml water, ultrasonic 10 ~ 24h; Graphite to be oxidized ultrasonic evenly after, adding 5ml concentration is wherein in the aqueous povidone solution of 8mg/ml, stirs 1h.Measuring 0.5ml butyl titanate is added drop-wise in 10ml concentrated hydrochloric acid, dropwise joins in the solution of above-mentioned graphite oxide after being uniformly mixed, and continues to stir 2h; Then join in 100ml polytetrafluoroethylene (PTFE) reactor, 150 DEG C of reaction 24h, after being cooled to room temperature, filter, wash, are drying to obtain graphene-supported flower-shaped composite titania material.In product, the flower-like structure of diameter about 3 ~ 4um is evenly distributed between graphene layer.

Claims (8)

1. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material, for medium with the mixed solvent of low-carbon (LC) alcohol and water, take surfactant as dressing agent, first graphite oxide is carried out functional modification, add the acid solution of titanium salt subsequently, stirring makes titanium ion complexing on the graphene oxide of functionalization, finally adds in reactor and carries out hydro-thermal reaction, obtain graphene-supported flower-shaped composite titania material.
2. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 1, it is characterized in that: by graphite oxide ultrasonic disperse in the mixed solvent of low-carbon (LC) alcohol and water, then adds surfactant stirring 1 ~ 2h; Then the acid solution adding titanium salt continues stirring 2 ~ 3h, is finally placed in reactor, and in 120 ~ 180 DEG C of reaction 12 ~ 24h, filter, washing, in 50 DEG C of vacuum drying, obtains graphene-supported flower-shaped composite titania material.
3. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 1 or 2, it is characterized in that: described titanium salt is isopropyl titanate or butyl titanate, and the acid solution of titanium salt is concentrated hydrochloric acid solution.
4. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 1 or 2, it is characterized in that: described surfactant is polyvinylpyrrolidone or softex kw.
5. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 4, it is characterized in that: the mass ratio of graphite oxide and surfactant is 1:3 ~ 1:10.
6. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 1 or 2, it is characterized in that: the mass ratio of graphite oxide and titanium salt is 10:1 ~ 20:1.
7. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 1 or 2, it is characterized in that: described low-carbon alcohols is methyl alcohol, ethanol, propyl alcohol, ethylene glycol.
8. hydro-thermal method prepares the method for graphene-supported flower-shaped composite titania material as claimed in claim 1 or 2, it is characterized in that: in the mixed solvent of described low-carbon (LC) alcohol and water, and the volume ratio of low-carbon alcohols and water is 1:1 ~ 5:1.
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CN112599366A (en) * 2020-11-24 2021-04-02 张茜茜 TiO22Nano flower loaded nitrogen-doped graphene supercapacitor material and preparation method thereof
CN112993278A (en) * 2021-02-05 2021-06-18 青岛科技大学 Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof
CN113178569A (en) * 2021-03-22 2021-07-27 黑龙江工业学院 Preparation method of pillared layer carrier semiconductor type natural graphite composite lithium battery negative electrode material
CN113948691A (en) * 2021-10-15 2022-01-18 佛山科学技术学院 Titanium dioxide composite material and application thereof as energy storage material
CN113948691B (en) * 2021-10-15 2023-03-10 佛山科学技术学院 Titanium dioxide composite material and application thereof as energy storage material
CN116386928A (en) * 2023-06-02 2023-07-04 山东科技大学 Sodium alginate/titanium dioxide composite porous electrode material and preparation method thereof
CN116386928B (en) * 2023-06-02 2023-08-04 山东科技大学 Sodium alginate/titanium dioxide composite porous electrode material and preparation method thereof

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