CN104815637B - 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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CN104815637B
CN104815637B CN201510153765.3A CN201510153765A CN104815637B CN 104815637 B CN104815637 B CN 104815637B CN 201510153765 A CN201510153765 A CN 201510153765A CN 104815637 B CN104815637 B CN 104815637B
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graphene
flower
titanium dioxide
graphite oxide
hydro
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CN104815637A (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

The method that hydro-thermal method prepares graphene-supported flower-shaped composite titania material
Technical field
The invention belongs to technical field of composite materials, is related to the preparation method of Graphene/flower-shaped composite titania material, More particularly to one kind is with graphite oxide and titanium salt as presoma, graphene-supported flower-shaped titanium dioxide is prepared by hydro-thermal method and is combined The method of material.
Background technology
It is well known that the performance of material has closely pass with some geometrical factors such as pattern, size, crystal structure etc. System.Therefore, inorganic material of the control synthesis with clear and definite pattern just becomes a study hotspot of current technical field of material chemistry. Wherein, the multi-stage nano that the micrometer structure being made up of nano structured unit, such as nanometer rods, nanometer sheet or nano wire assemble/ Micrometer structure, because it also avoid nanometer while the advantage-skin effect and quantum size effect for possessing nano material The shortcomings of material is easily reunited, stability is bad, so that the preparation of this kind of material and performance development enjoy pass in Material Field Note.
Titanium dioxide is considered as because of stable chemical nature, good, nontoxic resistance to acids and bases, abundance and low cost and other advantages It is to study one of widest metal oxide semiconductor material at present.Based on its functional character, the performance development of titanium dioxide Have been directed to the numerous areas such as photocatalysis, solaode, gas sensor, ultracapacitor.How titanium dioxide is allowed in reality High-performance is shown in the application of border, researchers have also been made substantial amounts of research.Wherein, synthesis has high-specific surface area and many The nano/micron structure titanium dioxide of avtive spot is one of the method for solving this problem.Such as Zhu et al. [ACS Appl.Mater.Interfaces 2011,3,3448-3453] synthesized by titanium dioxide nanoplate by one step hydro thermal method The flower-like structure of composition, finding the photocatalysis performance of the material will be far above the P25 that business is sold.Sun et al. [J.Am.Chem.Soc.2011,133,19314-19317] is logical by template of surfactant cetyl trimethylammonium bromide Cross hydro-thermal method and synthesized the three-dimensional dendroid rutile titanium dioxide that is made up of nanometer rods and studied its chemical property and find, should Titanium dioxide has higher charge/discharge capacitance and preferable cyclical stability compared to anatase titanium dioxide granule.This Outward, researchers have found that other components unit formation composite is introduced in titanium dioxide can also be improved performance, widen application Field.
Graphene be it is a kind of by monolayer carbon atom it is tightly packed into bi-dimensional cellular shape lattice structure.This unique structure Graphene is set to show many excellent performances.As Graphene theoretical specific surface area is up to 2630m2/ g, leads with good The electron mobility of hot and high speed.The composite that Graphene is formed with titanium dioxide, not merely with the electricity that Graphene is excellent Sub- conducting power accelerates the separation in titanium dioxide photoinduced electron and hole, while can also be increased using its big specific surface area The absorption property of material, so as to improve the photocatalysis performance and electricity conversion of material.
At present, Graphene and other three-dimensional metal oxides such as composite such as nickel oxide, manganese dioxide, Zinc Oxide grind Study carefully it has been reported that and shown excellent performance, but often prepared as presoma with Graphene and slaine, cost Height, and be difficult to make preferably to be combined between flower-like structure and Graphene.Prepared by Graphene/three-dimensional composite titania material grinds Study carefully also relatively fewer.If Liu et al. [J. Mater. Chem. A, 2013,1,12255-12262] is with flower-shaped titanium dioxide Graphene/flower-shaped composite titania material is prepared for presoma with graphite oxide, it is found that its photocatalysis efficiency is P25 3.4 times.But its preparation process is also wanted more than two steps, complex process.Therefore, find a kind of process is simple, morphology controllable degree it is high, The preparation method of inexpensive and environmental protection is just particularly important.
The content of the invention
The purpose of the present invention is for problems of the prior art, there is provided one kind is with graphite oxide and titanium salt as front Drive body, the method that graphene-supported flower-shaped composite titania material is prepared by the step of hydro-thermal method one.
First, the preparation of composite
The method that the present invention prepares graphene-supported flower-shaped composite titania material, is molten with the mixing of low-carbon (LC) alcohol and water Agent is medium, with surfactant as dressing agent, first graphite oxide is carried out into functional modification, is subsequently added the sour molten of titanium salt Liquid, stirring makes titanium ion complexation on the graphene oxide of functionalization, and being eventually adding in reactor carries out hydro-thermal reaction, obtains stone Black alkene load flower composite titania material.
Its concrete preparation technology is:By graphite oxide ultrasonic disperse in the mixed solvent of low-carbon (LC) alcohol and water, table is added Face activating agent stirs 1 ~ 2h;The acid solution for being subsequently adding titanium salt continues to stir 2 ~ 3h, is finally placed in reactor, in 120 ~ 180 DEG C reaction 12 ~ 24h, filter, washing, 50 DEG C vacuum drying, obtain graphene-supported flower-shaped composite titania material.
The titanium salt is isopropyl titanate or butyl titanate, and the acid solution of titanium salt is concentrated hydrochloric acid solution.
Graphite oxide is 10 with the mass ratio of titanium salt:1~20:1.
Surfactant is polyvinylpyrrolidone or cetyl trimethylammonium bromide;Graphite oxide and surfactant Mass ratio be 1:3~1:10.
Low-carbon alcohols(Methanol, ethanol, propanol, ethylene glycol etc.)In the mixed solvent of water, low-carbon alcohols are with the volume ratio of water 1:1~5:1, preferably 1:1.
2nd, the structure and pattern of composite
The graphite prepared to the present invention is analyzed below by X-ray diffraction analysis, scanning electron microscope analysis, thermogravimetric analysiss, BET The structure and pattern of alkene load flower composite titania material is analyzed explanation.
1st, X-ray diffraction analysis
Fig. 1 is the X-ray diffractogram that the present invention prepares Graphene/flower-shaped composite titania material.Present from figure Characteristic diffraction peak can be seen that prepared composite complete crystalline state.Wherein 2 θ angles be 27.3 °, 36.1 °, The diffraction maximum occurred at 39.2 °, 41.0 °, 43.9 °, 54.2 °, 56.4 °, 62.9 °, 69.0 ° and 69.8 ° and Rutile Type dioxy Change the standard card JCPDS of titanium:21-1276 is consistent, and the crystalline phase for showing titanium dioxide in composite is rutile.2 θ= Diffraction maximum is 002 crystal face characteristic diffraction peak of Graphene at 24.5 °, shows that graphite oxide has been reduced for Graphene.To sum up It can be seen that prepared material is composited by red schorl phase titanium dioxide and Graphene.
2nd, scanning electron microscope analysis
Fig. 2 be 150 DEG C, pvp concentration be 8mg/ml, the response time be the different amplification of product obtained in 24h under Scanning electron microscope(SEM)Figure.Fig. 2 (a) is the SEM figures of 20000 times of amplification, and Fig. 2 (b) is the SEM that composite amplifies 50000 times Figure.From Fig. 2 (a) and 2 (b) as can be seen that by 300 ~ 400 nm are about, the titanium dioxide nano-rod of diameter about 15 ~ 35nm is constituted Flower-like structure uniform load on the less graphenic surface of the number of plies, and diameter is about between the flower-like structure of 1 ~ 1.5um and passes through Graphene is connected with each other, and stacking agglomeration does not occur.
3rd, thermogravimetric analysiss
Fig. 3 is the thermal multigraph of Graphene/flower-shaped composite titania material.The mass loss occurred between 30 ~ 200 DEG C in figure Caused by the evaporation of residual moisture in composite and organic solvent.200 ~ 500 DEG C is on surface organic matter and Graphene The organo-functional group of residual decomposes weightless.500 DEG C be later carbon skeleton the weightlessness that causes of decomposition.
4th, BET analyses
Flower-shaped titanium dioxide (the TiO for being not added with being prepared during graphite oxide is respectively in Fig. 42) and Graphene/flower-shaped two Titanium oxide composite material (G/TiO2 ) nitrogen adsorption desorption isotherm figure (BET).Bi-material all presents IV type isothermal Line, when high relative pressure is partial to H3 type hysteresis loops are presented, and are shown with the presence of the space more than 50nm.The same terms system The BET specific surface area of the flower-shaped titanium dioxide for obtaining is 124.4m2/ g, and the BET ratios of Graphene/flower-shaped composite titania material Surface area has but reduced by comparison, is 93.5m2/ g, caused by this coating function mainly due to Graphene, but It is big with the specific surface area of flower-shaped titanium dioxide, flower shape zinc oxide, flower-shaped manganese oxide more than the Graphene reported in document Much.This feature causes the material all to show huge application prospect in catalyst carrier, field of environment protection.
The present invention has advantages below relative to prior art:
1st, the present invention has been obtained two-dimensional graphene/three-dimensional flower with graphite oxide and titanium salt as raw material by one step hydro thermal method The composite of shape titanium dioxide, compared to the method that other prepare Graphene and three dimensional structure metal oxide composite, Cost is relatively low, technique is simpler, reaction condition is gentle, it is pollution-free, be easy to large-scale production;
2nd, the present invention adds surfactant as soft template in preparation process, and titanium dioxide can be guided flower-shaped Structure growth plays an important role in the both sides of Graphene, the flower-like structure to being stablized, regular.Further, it is also possible to pass through to adjust The mass ratio of whole graphite oxide and titanium salt controls the overall appearance of material;
3rd, the present invention reduction of graphene oxide and growth of titanium dioxide flower-like structure in water-heat process is carried out simultaneously, Growth of the flower-like structure between graphene layer can suppress the π-π of its interlayer to adsorb, it is ensured that the quality that Graphene has had;And Graphene Titanium dioxide flower-like structure can be connected again, make to be formed between material component the entirety being interconnected, electronics can be promoted on material Transmission.
Description of the drawings
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.
Specific embodiment
Below by instantiation to preparation, structure, pattern of Graphene of the present invention/flower-shaped composite titania material etc. It is described further.
Embodiment 1
(1)The preparation of graphite oxide:Weigh and add after 1.5g crystalline flake graphites mix with 4.5g potassium permanganate 180mL to sulphuric acid In the mixed acid solution of phosphoric acid(Volume ratio 9:1), after stirring reaction 1h at 30 ~ 40 DEG C, it is warming up to 50 DEG C and continues to react 12h. Reaction is cooled to room temperature after terminating, and product is poured slowly in the frozen water containing 10mL hydrogen peroxide, stands, and removes supernatant Afterwards, sucking filtration, fully washs filter cake, until without SO in filtrate with 5% hydrochloric acid4 2-, subsequent deionized water and ethanol are alternately washed Wash to neutrality, be vacuum dried 12 ~ 24h in 50 DEG C and obtain final product required graphite oxide.
(2)The preparation of Graphene/flower-shaped composite titania material:Weigh 8mg graphite oxides and be added to 20ml ethylene glycol In the mixed solution of 20ml water, 10 ~ 24h of ultrasound;After graphite ultrasound to be oxidized is uniform, 5ml concentration is added thereto to for 8mg/ 1h is stirred in the aqueous povidone solution of ml;Measure 0.5ml isopropyl titanates to be added drop-wise in 10ml concentrated hydrochloric acid, stirring mixing It is added dropwise in the solution of above-mentioned graphite oxide after uniform, continues to stir 2h;It is then added to 100ml polytetrafluoroethyl-ne alkene reactions In kettle, 150 DEG C of reaction 24h, after being cooled to room temperature, filtration, washing, the graphene-supported flower-shaped titanium dioxide of drying to obtain are combined Material.Preferably, distribution of sizes is narrower, the flower-like structure position of about 1 ~ 1.5um for Graphene and titanium dioxide composite effect in product In between graphene layer, 3-D solid structure is defined, abloom rate is up to 99%.
Embodiment 2
(1)The preparation of graphite oxide is with example 1.
(2)The preparation of Graphene/flower-shaped composite titania material:Weigh 12mg graphite oxides be added to 30ml propanol and In the mixed solution of 10ml water, 10 ~ 24h of ultrasound.After graphite ultrasound to be oxidized is uniform, 5ml concentration is added thereto to for 8mg/ml Aqueous povidone solution in, stir 1h.Measure 0.5ml isopropyl titanates to be added drop-wise in 5ml concentrated hydrochloric acid, stirring mixing is equal During the solution of above-mentioned graphite oxide is added dropwise to after even, continue to stir 2h.Then liquid is added to 100ml polytetrafluoroethyl-ne alkene reactions In kettle, 150 DEG C of reaction 24h, after being cooled to room temperature, filtration, washing, the graphene-supported flower-shaped titanium dioxide of drying to obtain are combined Material.Graphene is in tiling shape in product, and the titanium dioxide distribution of sizes of flower-like structure slightly increases, and diameter is about 1 ~ 2um Flower-like structure be uniformly grown on the surface of Graphene, and the diameter of nanometer rods for constituting flower-like structure is about 16nm.
Embodiment 3
(1)The preparation of graphite oxide is with example 1.
(2)The preparation of Graphene/flower-shaped composite titania material:Weigh 8mg graphite oxides and be added to 20ml ethylene glycol In the mixed solution of 20ml water, 10 ~ 24h of ultrasound;After graphite ultrasound to be oxidized is uniform, 5ml concentration is added thereto to for 8mg/ In the cetyl trimethylammonium bromide aqueous solution of ml, 1h is stirred;Measure 0.5ml isopropyl titanates to be added drop-wise in 5ml concentrated hydrochloric acid, stir Mix and be added dropwise to after mix homogeneously in the alcohol-water solution of graphite oxide, continue to stir 2h, be then added to 100ml polytetrafluoroethyl-nes In alkene reaction kettle, 180 DEG C of reaction 20h, after being cooled to room temperature, filtration, washing, the graphene-supported flower-shaped titanium dioxide of drying to obtain Titanium composite material.Characterize and find, the flower-shaped titanium dioxide that diameter is about 3 ~ 4um in the composite is by a diameter of 35nm, length The nanometer bar construction of about 680nm, is uniformly dispersed between graphene layer.
Embodiment 4
(1)The preparation of graphite oxide is with example 1.
(2)The preparation of Graphene/flower-shaped composite titania material:Weigh 8mg graphite oxides and be added to 20ml ethylene glycol In the mixed solution of 20ml water, 10 ~ 24h of ultrasound;After graphite ultrasound to be oxidized is uniform, 5ml concentration is added thereto to for 8mg/ In the aqueous povidone solution of ml, 1h is stirred.Measure 0.5ml isopropyl titanates to be added drop-wise in 10ml concentrated hydrochloric acid, stirring is mixed It is added dropwise in the solution of above-mentioned graphite oxide after closing uniformly, continues to stir 2h;It is then added to 100ml politef anti- In answering kettle, 150 DEG C of reaction 12h, after being cooled to room temperature, filtration, washing, the graphene-supported flower-shaped titanium dioxide of drying to obtain are answered Condensation material.By diameter about 25nm in product, the flower-shaped knot of the 800nm ~ 1.2um of the nanometer rods composition of the aplysia punctata of 300nm is about Structure intercalation is distributed between graphene layer.
Embodiment 5
(1)The preparation of graphite oxide is with example 1.
(2)The preparation of Graphene/flower-shaped composite titania material:Weigh 8mg graphite oxides be added to 20ml methanol and In the mixed solution of 20ml water, 10 ~ 24h of ultrasound;After graphite ultrasound to be oxidized is uniform, 5ml concentration is added thereto to for 8mg/ml Aqueous povidone solution in, stir 1h.Measure 0.5ml butyl titanates to be added drop-wise in 10ml concentrated hydrochloric acid, stirring is mixed It is added dropwise in the solution of above-mentioned graphite oxide after closing uniformly, continues to stir 2h;It is then added to 100ml politef anti- In answering kettle, 150 DEG C of reaction 24h, after being cooled to room temperature, filtration, washing, the graphene-supported flower-shaped titanium dioxide of drying to obtain are answered Condensation material.The flower-like structure of diameter about 3 ~ 4um is evenly distributed between graphene layer in product.

Claims (5)

1. the method that hydro-thermal method prepares graphene-supported flower-shaped composite titania material, is with the mixed solvent of low-carbon (LC) alcohol and water For medium, with surfactant as dressing agent, first graphite oxide is carried out into functional modification, is subsequently added the acid solution of titanium salt, Stirring makes titanium ion complexation on the graphene oxide of functionalization, and being eventually adding in reactor carries out hydro-thermal reaction, obtains graphite Alkene load flower composite titania material;Concrete technology is:Graphite oxide ultrasonic disperse is molten in the mixing of low-carbon (LC) alcohol and water In agent, add surfactant and stir 1 ~ 2h;The acid solution for being subsequently adding titanium salt continues to stir 2 ~ 3h, is finally placed in reactor In, 12 ~ 24h is reacted in 120 ~ 180 DEG C, filter, washing, in 50 DEG C of vacuum drying, obtain graphene-supported flower-shaped titanium dioxide Composite;Graphite oxide is 1 with the mass ratio of surfactant:3~1:10;Graphite oxide is 10 with the mass ratio of titanium salt:1~ 20:1。
2. the method that hydro-thermal method as claimed in claim 1 prepares graphene-supported flower-shaped composite titania material, its feature exists In:The titanium salt is isopropyl titanate or butyl titanate, and the acid solution of titanium salt is concentrated hydrochloric acid solution.
3. the method that hydro-thermal method as claimed in claim 1 prepares graphene-supported flower-shaped composite titania material, its feature exists In:The surfactant is polyvinylpyrrolidone or cetyl trimethylammonium bromide.
4. the method that hydro-thermal method as claimed in claim 1 prepares graphene-supported flower-shaped composite titania material, its feature exists In:The low-carbon alcohols are methanol, ethanol, propanol, ethylene glycol.
5. the method that hydro-thermal method as claimed in claim 1 prepares graphene-supported flower-shaped composite titania material, its feature exists In:In the mixed solvent of the low-carbon (LC) alcohol and water, low-carbon alcohols are 1 with the volume ratio of water:1~5:1.
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