CN104332321A - Rutile type TiO2 nanorod oxidized grapheme composite material and preparation method thereof - Google Patents

Rutile type TiO2 nanorod oxidized grapheme composite material and preparation method thereof Download PDF

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CN104332321A
CN104332321A CN201410572363.2A CN201410572363A CN104332321A CN 104332321 A CN104332321 A CN 104332321A CN 201410572363 A CN201410572363 A CN 201410572363A CN 104332321 A CN104332321 A CN 104332321A
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CN104332321B (en
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周国伟
刘蕊蕊
孙彬
李世超
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Shandong Jiqing Technology Service Co ltd
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Qilu University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a Rutile type TiO2 nanorod oxidized graphene composite material and a preparation method thereof. The preparation method comprises the steps of: firstly, compounding rod-like TiO2 by regarding TBT as a titanium source and CTAB as a structure-directing agent by utilizing a hydrothermal method; then compounding GO by using a modified Hummers method; finally, self-assembling raw materials, namely, TiO2 nanorod and GO in water and methylbenzene at a room temperature to prepare the GO/TiO2 nanorod composite material. The preparation method disclosed by the invention is relatively simple; the used raw materials are low in cost, easy to obtain, safe and suitable for industrial production. The prepared GO/TiO2 nanorod composite material has such a shape that Rutile TiO2 nanorods are loaded on a GO nanometer chip. The preparation method is easy to control a weight ratio of TiO2 rods and GO in the composite; in addition, the initial appearances of the TiO2 and GO are not changed in the prepared GO/TiO2 nanorod composite material. A new idea for preparation of TiO2 in other appearances loaded on the GO chip is provided.

Description

Rutile TiO 2nanometer rods graphene oxide composite material and preparation method thereof
Technical field
The invention belongs to field of composite material preparation, be specifically related to a kind of rutile TiO 2nanometer rods graphene oxide composite material and preparation method thereof.
Background technology
Graphene is a kind of two-dimension single layer carbon atom in honeycomb lattice structure, has caused huge concern in experiment and pure science field.And graphene oxide (GO) is as a derivative of Graphene, it not only has unique electricity, heat, mechanical performance, there is the advantages such as abundant oxygen-containing functional group, hydrophily and controlled Electronic Performance simultaneously, caused in the preparation of advanced material and studied interest widely.
The appearance of energy crisis in recent years, exploring novel energy material is problem demanding prompt solution.Material with carbon element is due to good conductivity, chemical stability that surface area is large, high, and carbon network can provide the advantage such as path effectively to electro transfer, is a kind of excellent electrochemical material.But graphite electrode has its shortcoming part: circuit is easy to disconnect, structure is yielding and initial capacity has loss etc.In order to avoid these shortcomings, may be one settling mode effectively by inorganic nano-particle and GO compound.NiO/GO compound has been synthesized by electrophoretic deposition and heat treatment process as the people such as Wu report on Journal of materials chemistry 22 (2012) 2442 – 2448, be applied to the research of ultracapacitor, its specific capacity reaches 569F g -1.The people such as Chen report in water and Isopropanol Solvent on ACS Nano 4 (2010) 2822 – 2830, have prepared GO-MnO by solution processing methods simply 2nano-complex, and the research being applied to ultracapacitor, its specific capacity reaches 197.2F g -1.But TiO 2so far seldom report with the compound of GO, be particularly applied in electrochemical field, therefore compound both research has opened up their new application.
At present, the preparation method of titanium dioxide/GO composite material mainly contains the methods such as self assembly, ultrasonic and in-situ deposition.Such as, Chen etc. utilize self-assembly method with TiCl 3with GO as reactant, successfully prepare the GO/TiO with heterostructure 2nano-complex (ACS Nano 2010,46425 – 6432).Gao etc. mix GO and TiO under ultrasound condition 2microballoon, has prepared the GO/TiO of different quality ratio 2complex microsphere (GO and TiO 2mass ratio is respectively 1:100,3:100,7:100,11:100) (Chemistry-an asian journal 2013,8,2779 – 2786).
Self-assembly method has that temperature is low, simple to operate, pattern is easy to the advantages such as control, and by people's extensive use.Current self-assembling method prepares TiO 2there is following problem in/GO compound: TiO 2be easy to assemble, and dispersed bad; In recombination process, GO sheet is easy to broken.
Publication No. is that the Chinese patent literature of CN 102423702A (application number 201110456027.8) discloses a kind of graphene oxide/titanic oxide composite photochemical catalyst material and preparation method thereof, polyethylene glycol, glacial acetic acid and butyl titanate are joined in absolute ethyl alcohol be made into mixed liquor, then the water slurry of GO is added in mixed liquor, at the uniform velocity stir under room temperature, after dry, calcining obtains GO/ titanium dioxide composite photocatalyst.There is following feature in this patent: adopts one-step synthesis, namely at TiO 2while the synthesis of/GO compound, along with TiO 2the generation of pattern, there is TiO in the compound of one-step synthesis method 2wayward with the ratio of GO, and the TiO of load on GO sheet 2pattern is not easy to the shortcoming controlling or change; The mechanism of the method synthesis is upper and lower surface and the fringe region that titanium dioxide is distributed in graphene oxide composite material; The crystal formation of synthesis is Detitanium-ore-type; Reaction time is 1-5 days, and the time is longer; This preparation method needs to calcine 0.5 ~ 3 hour in 400 DEG C ~ 450 DEG C under inert gas shielding, consumes energy high; Material prepared by the method only can be used for photocatalysis.
The Chinese patent literature of application publication number CN 102492313B (application number 201110371024.4) discloses a kind of titanium dioxide and graphene oxide composite nano-grade sheet material and preparation method thereof, and the structure sheaf of titanium dioxide and graphene oxide composite nano-grade sheet comprises graphene oxide layer and is positioned at the titanium dioxide layer of these upper and lower both sides of graphene oxide layer.There is following feature in this patent: adopts one-step synthesis; Obtained material is sandwich structure; The crystal formation of synthesis is Detitanium-ore-type; Reaction needed completes under 20-60 DEG C of condition; This preparation method needs to calcine 0.5 ~ 3 hour in 400 DEG C ~ 450 DEG C under inert gas shielding, consumes energy high; Material prepared by the method only can be used for photocatalysis.
Summary of the invention
Object of the present invention is exactly to provide a kind of rutile TiO 2nanometer rods graphene oxide composite material and preparation method thereof.
To achieve these goals, the present invention adopts following technical scheme:
A kind of rutile TiO 2the preparation method of nanometer rods graphene oxide composite material, comprises the following steps:
(1) prepare titaniferous solution: under room temperature, join in concentrated hydrochloric acid and distilled water by butyl titanate (TBT), stir 20-40min, wherein the mass ratio of TBT, concentrated hydrochloric acid, distilled water is 0.01-0.8:8-12:15-30;
(2) under the condition constantly stirred, softex kw (CTAB) aqueous solution is dropwise joined by the titaniferous solution of step (1) gained, continue to stir 1.5-2.5h (preferred 2h) and form mixed solution, after the mixed solution obtained is incubated 12h-24h in 120 DEG C-180 DEG C, naturally cool to room temperature and obtain sediment, wherein in the CTAB aqueous solution, the mass ratio of CTAB and water is the mass ratio of 0.01-0.5:40-60, TBT and CTAB is 0.01-0.8:0.01-0.5;
(3) sediment step (2) obtained, after distilled water cleaning, is dried and is obtained product TiO under 75 DEG C-85 DEG C (preferably 80 DEG C) conditions 2, TiO is made in grinding 2powder;
(4) by TiO that step (3) obtains 2powder dispersion, in toluene, obtains the TiO that concentration is 0.01-0.05g/5-10mL 2dispersion liquid;
(5) by TiO that step (4) obtains 2dispersion liquid is poured in GO dispersion liquid, stirred at ambient temperature 12h-24h, then through suction filtration, washing, dry, obtain rutile TiO 2nanometer rods GO composite material, in described GO dispersion liquid, GO/ water is 0.001-0.005g/10-20mL.
The preparation method of GO is as follows: 1. by 2-3g graphite powder, the 20-50ml concentrated sulfuric acid, 2-3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into oil bath pan, be heated to 80 DEG C and stir 4-6h; 2. by step product 1. 400-500ml distilled water diluting, then suction filtration, forms filter cake, natural drying of spending the night; 3. filter cake spoon step 2. obtained is scraped in small beaker, adds the 100ml concentrated sulfuric acid, stirs, ultrasonic 1h; 4. in the solution after ultrasonic, slowly add 10-12g potassium permanganate, control temperature is less than 20 DEG C, stirs 4-6h, is then slowly warming up to 35-50 DEG C, stirs insulation 8h-15h; 5. then in solution, 120ml deionized water (slowly adding) is added, stirring at normal temperature reaction 2h; 6. 16-20ml hydrogen peroxide is finally added, (solution becomes glassy yellow from grey) obtains jonquilleous acidic oxidation graphene aqueous solution, centrifugal through washing repeatedly, ultrasonic 0.5-1h, obtain close to neutral graphene oxide solution, obtain the GO of sheet through freeze drying, powder is made in grinding.
The preparation method of the CTAB aqueous solution in described step (2): joined by CTAB in distilled water, constantly stirs until form clear solution at 30 DEG C-40 DEG C;
The composite material prepared by said method, this composite material pattern is rutile TiO 2(JCPDS card number21 – 1276) nanometer rods load in GO nanometer sheet, wherein TiO 2the diameter of nanometer rods is 50-150nm, and rod is long is 200-400nm.
The beneficial effect that the present invention produces:
1. adopt the TiO that method of the present invention is obtained 2nanometer rods GO composite material pattern is TiO 2nanometer rods load on stannic oxide/graphene nano sheet, wherein TiO 2nanometer rods is rutile-type, and diameter is 50-150nm, and rod is long is 200-400nm;
2. the TiO for preparing of the present invention 2in nanometer rods GO composite material, GO and TiO 2ratio controlled, chemical property is adjustable;
3. the TiO for preparing of the present invention 2in nanometer rods GO composite material, TiO 2nanometer rods good dispersion, does not significantly assemble, solves self-assembly method and prepare TiO 2gO composite material is easy to the problem of reuniting, and reduces the interfacial resistance in charge transfer process, gets ready for studying chemical property further;
4. the TiO for preparing of the present invention 2nanometer rods GO composite material, does not need heating, obtains under room temperature, and the environmental protection that saves time;
5. the present invention is the TiO of other patterns of load on GO sheet 2provide a kind of synthesis thinking newly.
The present invention utilizes self-assembly method with GO and TiO 2nanometer rods is reactant, and both, in toluene self assembly alternate with water two, successfully prepare rutile TiO 2nanometer rods GO compound.TiO 2nanometer rods load on GO sheet, and is not significantly assembled.Importantly GO and TiO in compound 2ratio be controlled, and along with the increase of GO ratio, chemical property presents certain regularity.Synthesis condition does not need heating, simple, environmental protection in addition, all has great importance in theoretical research and practical application.
Accompanying drawing explanation
Fig. 1 is GO and different GO and TiO 2tiO prepared by weight ratio 2high-resolution-ration transmission electric-lens (HRTEM) figure of nanometer rods/GO composite material, wherein, Fig. 1 a is the HRTEM of GO prepared by embodiment 1; Fig. 1 b is TiO prepared by embodiment 1 2the HRTEM of nanometer rods GO composite material, GO and TiO 2mass ratio be 24:5; Fig. 1 c is TiO prepared by embodiment 2 2the HRTEM of nanometer rods GO composite material, GO and TiO 2mass ratio be 12:5; Fig. 1 d is TiO prepared by embodiment 3 2the HRTEM of nanometer rods GO composite material, GO and TiO 2mass ratio be 6:5;
Fig. 2 is TiO prepared by embodiment 1 2nanometer rods and TiO 2field emission scanning electron microscope (FESEM) figure of nanometer rods/GO composite material, wherein, Fig. 2 a is TiO 2the FESEM of rod; Fig. 2 b is TiO prepared by embodiment 1 2the FESEM of nanometer rods GO composite material;
Fig. 3 is GO, TiO prepared by the embodiment of the present invention 3 2nanometer rods and TiO 2the XRD figure of nanometer rods GO composite material, wherein, Fig. 3 a is the XRD figure of GO prepared by embodiment 3; Fig. 3 b is TiO prepared by embodiment 3 2xRD figure; Fig. 3 c is TiO prepared by embodiment 3 2the XRD figure of nanometer rods GO composite material;
Fig. 4 is GO, TiO prepared by the embodiment of the present invention 3 2nanometer rods and TiO 2the Raman spectrogram of nanometer rods/GO composite material;
Fig. 5 is GO, TiO prepared by the embodiment of the present invention 1 2nanometer rods and TiO 2the cyclic voltammetry curve figure of nanometer rods GO composite material, cyclic voltammetry curve is 50mV s in sweep speed -1, 1mol L -1na 2sO 4electrolyte in measure.
Embodiment
Below by way of specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) with 3g graphite powder for raw material, (concrete steps of the Hummers method of modification are as follows: 1. by 3g graphite powder, the 20ml concentrated sulfuric acid, 2g K to adopt the Hummers method of modification 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into oil bath pan, be heated to 80 DEG C and stir 5h; 2. get 450ml distilled water diluting, then suction filtration, form filter cake, natural drying of spending the night; 3. filter cake spoon is scraped in small beaker, add the 100ml concentrated sulfuric acid, stir, ultrasonic 1h; 4. in the solution after ultrasonic, slowly add 11g potassium permanganate, control temperature is less than 20 DEG C, stirs 6h, is then slowly warming up to 50 DEG C, stirs insulation more than 8h; 5. then in solution, 120ml deionized water (slowly adding) is added, stirring at normal temperature reaction 2h; 6. finally add 17ml hydrogen peroxide, solution becomes glassy yellow from grey.) obtain jonquilleous acidic oxidation graphene aqueous solution, centrifugal through washing repeatedly, ultrasonic 1h, obtain, close to neutral graphene oxide solution, obtaining the GO of sheet through freeze drying, powder is made in grinding;
(2) 0.4374g CTAB is joined in 54.6g distilled water, constantly stir until form clear solution at 35 DEG C;
(3) under room temperature, 0.4084g TBT is joined in 10.21g concentrated hydrochloric acid and 17.40g distilled water, stir 20min;
(4) under the condition constantly stirred, the clear solution that step (2) obtains dropwise is joined by the solution of step (3) gained, continue to stir 2h and form mixed solution;
(5) mixed solution that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, at 150 DEG C of insulation 20h; After hydrothermal treatment consists, autoclave is naturally cooled to room temperature;
(7) by the sediment centrifugation that step (6) obtains, distilled water washs 3 times, and in air dry oven, dry 24h for 80 DEG C, grinding obtains TiO 2powder;
(8) by 0.024g TiO that step (7) obtains 2powder ultrasonic is dispersed in 10mL toluene, obtains TiO 2dispersion liquid;
(9) 0.005g GO ultrasonic disperse step (1) obtained, in the distilled water of 5mL, obtains the dispersion liquid of GO;
(10) by TiO that step (8) obtains 2dispersion liquid is poured in the GO dispersion liquid that step (9) obtains, stirred at ambient temperature 24h, then through suction filtration, washing, drying, obtains TiO 2nanometer rods GO composite material.
Embodiment 2
(1) with 3g graphite powder for raw material, the Hummers method (with embodiment 1) of modification is adopted to obtain jonquilleous acidic oxidation graphene aqueous solution, centrifugal through washing repeatedly, ultrasonic 1h, obtain close to neutral graphene oxide solution, obtain the GO of sheet through freeze drying, powder is made in grinding;
(2) 0.4374g CTAB is joined in 54.6g distilled water, constantly stir until form clear solution at 35 DEG C;
(3) under room temperature, 0.4084g TBT is joined in 10.21g concentrated hydrochloric acid and 17.40g distilled water, stir 20min;
(4) under the condition constantly stirred, the clear solution that step (2) obtains dropwise is joined by the solution of step (3) gained, continue to stir 2h and form mixed solution;
(5) mixed solution that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, protect steady 20h at 150 DEG C; After hydrothermal treatment consists, autoclave is naturally cooled to room temperature;
(7) by the sediment centrifugation that step (6) obtains, distilled water washs 3 times, and in air dry oven, dry 24h for 80 DEG C, grinding obtains TiO 2powder;
(8) by 0.012g TiO that step (7) obtains 2powder ultrasonic is dispersed in 10mL toluene, obtains TiO 2dispersion liquid;
(9) 0.005g GO ultrasonic disperse step (1) obtained, in the distilled water of 5mL, obtains the dispersion liquid of GO;
(10) by TiO that step (8) obtains 2dispersion liquid is poured in the GO dispersion liquid that step (9) obtains, stirred at ambient temperature 24h, then through suction filtration, washing, drying, obtains TiO 2nanometer rods GO composite material.
Embodiment 3
(1) with 3g graphite powder for raw material, the Hummers method (with embodiment 1) of modification is adopted to obtain jonquilleous acidic oxidation graphene aqueous solution, centrifugal through washing repeatedly, ultrasonic 1h, obtain close to neutral graphene oxide solution, obtain the GO of sheet through freeze drying, powder is made in grinding;
(2) 0.4374g CTAB is joined in 54.6g distilled water, constantly stir until form clear solution at 35 DEG C;
(3) under room temperature, 0.4084g TBT is joined in 10.21g concentrated hydrochloric acid and 17.40g distilled water, stir 20min;
(4) under the condition constantly stirred, the clear solution that step (2) obtains dropwise is joined by the solution of step (3) gained, continue to stir 2h and form mixed solution;
(5) mixed solution that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, protect steady 20h at 150 DEG C; After hydrothermal treatment consists, autoclave is naturally cooled to room temperature;
(7) by the sediment centrifugation that step (6) obtains, distilled water washs 3 times, and in air dry oven, dry 24h for 80 DEG C, grinding obtains TiO 2powder;
(8) by 0.006g TiO that step (7) obtains 2powder ultrasonic is dispersed in 10mL toluene, obtains TiO 2dispersion liquid;
(9) 0.005g GO ultrasonic disperse step (1) obtained, in the distilled water of 5mL, obtains the dispersion liquid of GO;
(10) by TiO that step (8) obtains 2dispersion liquid is poured in the GO dispersion liquid that step (9) obtains, stirred at ambient temperature 24h, then through suction filtration, washing, drying, obtains TiO 2nanometer rods GO composite material.
Embodiment 4
(1) with 3g graphite powder for raw material, the Hummers method (with embodiment 1) of modification is adopted to obtain jonquilleous acidic oxidation graphene aqueous solution, centrifugal through washing repeatedly, ultrasonic 1h, obtain close to neutral graphene oxide solution, obtain the GO of sheet through freeze drying, powder is made in grinding;
(2) 0.4374g CTAB is joined in 54.6g distilled water, constantly stir until form clear solution at 35 DEG C;
(3) under room temperature, 0.4084g TBT is joined in 10.21g concentrated hydrochloric acid and 17.40g distilled water, then add the urea of 1g, stir 20min;
(4) under the condition constantly stirred, the clear solution that step (2) obtains dropwise is joined by the solution of step (3) gained, continue to stir 2h and form mixed solution;
(5) mixed solution that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, protect steady 20h at 150 DEG C; After hydrothermal treatment consists, autoclave is naturally cooled to room temperature;
(7) by the sediment centrifugation that step (6) obtains, distilled water washs 3 times, and in air dry oven, dry 24h for 80 DEG C, grinding obtains TiO 2powder;
(8) by 0.012g TiO that step (7) obtains 2powder ultrasonic is dispersed in 10mL toluene, obtains TiO 2dispersion liquid;
(9) 0.005g GO ultrasonic disperse step (1) obtained, in the distilled water of 5mL, obtains the dispersion liquid of GO;
(10) by TiO that step (8) obtains 2dispersion liquid is poured in the GO dispersion liquid that step (9) obtains, stirred at ambient temperature 24h, then through suction filtration, washing, drying, obtains the TiO of N doping 2nanometer rods GO composite material.
In order to inquire into the TiO of preparation 2in nanometer rods GO composite material, GO and TiO 2ratio controlled, performance is controlled.Choose the composite material of embodiment 1, embodiment 2, embodiment 3 preparation, GO and TiO in composite material 2mass ratio be respectively 24:5,12:5 and 6:5.As can be seen from Figure 1 TiO 2nanometer rods in GO nanometer sheet, be it can also be seen that GO and TiO by successful load simultaneously 2the composite material of different quality ratio, TiO 2the dispersiveness of nanometer rods and the change of formability in regularity, along with TiO 2the increase of quality, TiO 2the dispersiveness of nanometer rods and formability first improve and are deteriorated, and therefore we find GO and TiO in regulation and control composite material 2mass ratio, pattern is had a certain impact, GO and TiO 2mass ratio be optimum when being 12:5.In addition, Fig. 1 a is the HRTEM figure of GO, and contrast with Fig. 1 b, 1c, 1d, before compound, GO nanometer sheet surface is smooth, obviously can find out TiO after compound 2nanometer rods in GO nanometer sheet, is further demonstrated TiO by successful load 2nanometer rods GO composite material is successfully prepared.
Research TiO 2tiO in nanometer rods/GO composite material 2the dispersiveness of nanometer rods has certain practical significance.Because TiO 2the dispersiveness of nanometer rods is relevant with specific area, and the difference of specific area directly affects its chemical property.As can be seen from Figure 1, GO and TiO 2mass ratio when 12:5, TiO 2the dispersiveness of nanometer rods is preferably.Determine the electrochemistry of the composite material of different proportion and contrast, it is shown in the results are shown in Table 1.Table 1 is the TiO of the embodiment of the present invention 1, embodiment 2 and embodiment 3 preparation 2the architectural feature of nanometer rods/GO composite material and chemical property have done a contrast, and the results are shown in Table 1.
Table 1
GO and TiO 2mass ratio when being 12:5, the composite material of preparation has less charge transfer resistance; Larger specific capacity; Good cyclical stability.The TiO wherein prepared in embodiment 2nanometer rods GO composite material, at sweep speed 5mV s -1under, its specific capacity reaches 100F/g, and specific capacity can calculate from accompanying drawing 5, and accompanying drawing 5 is TiO of preparation 2the cyclic voltammetry curve figure of nanometer rods GO composite material.Done charge-discharge performance test to it in addition, after scanning times is 3000 circles, capability retention still reaches more than 80%, shows excellent cyclical stability.
XRD can illustrate TiO 2the crystal formation of nanometer rods/GO composite material, from Fig. 3, we can find out TiO 2nanometer rods GO composite material is pure rutile type.Can prove equally in Raman spectrum, in figure 4.Also TiO is further demonstrated in addition 2nanometer rods GO composite material is successfully prepared, and does not change TiO after compound 2crystal formation.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.

Claims (9)

1. a rutile TiO 2the preparation method of nanometer rods graphene oxide composite material, is characterized in that, comprises the following steps:
(1) prepare titaniferous solution: under room temperature, joined by TBT in concentrated hydrochloric acid and distilled water, stir, wherein the mass ratio of TBT, concentrated hydrochloric acid, water is 0.01-0.8:8-12:15-30;
(2) under the condition constantly stirred, the CTAB aqueous solution is dropwise joined by the titaniferous solution of step (1) gained, continue to stir and form mixed solution, after the mixed solution obtained is incubated 12h-24h under 120 DEG C of-180 DEG C of conditions, cool to room temperature obtains sediment, by the sediment that obtains after distilled water cleaning, dry and obtain product TiO 2, TiO is made in grinding 2powder; Wherein in the CTAB aqueous solution, the mass ratio of CTAB and water is 0.01-0.5:40-60; The mass ratio of TBT and CTAB is 0.01-0.8:0.01-0.5;
(3) by TiO that step (2) obtains 2powder dispersion, in toluene, obtains the TiO that concentration is 0.01-0.05/5-10g/mL 2dispersion liquid;
(4) by TiO that step (3) obtains 2dispersion liquid is poured in GO dispersion liquid, stirred at ambient temperature 12h-24h, then through suction filtration, washing, dry, obtain rutile TiO 2nanometer rods graphene oxide composite material, in described GO dispersion liquid, the ratio of GO and water is 0.001-0.005/10-20g/mL, TiO 2be 0.01-0.05/0.001-0.005 with the mass ratio of GO.
2. preparation method as claimed in claim 1, is characterized in that, stirs 20-40min in described step (1).
3. preparation method as claimed in claim 1, is characterized in that, described step (2) continues to stir 1.5h-2.5h and forms mixed solution.
4. preparation method as claimed in claim 1, it is characterized in that, described step is dried in (2) under 75 DEG C of-85 DEG C of conditions.
5. preparation method as claimed in claim 4, is characterized in that, dry under 80 DEG C of conditions.
6. preparation method as claimed in claim 1, it is characterized in that, the preparation method of described GO is as follows:
1. by 2-3g graphite powder, the 20-50ml concentrated sulfuric acid, 2-3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into oil bath pan, be heated to 80 DEG C and stir 4-6h;
2. by step product 1. 400-500ml distilled water diluting, then suction filtration, forms filter cake, natural drying of spending the night;
3. the filter cake that 2. step obtains is scraped in beaker, add the 100ml concentrated sulfuric acid, stir, ultrasonic 1h;
4. slowly add 10-12g potassium permanganate, control temperature 10-20 DEG C in the solution 3. obtained to step, stir 4-6h, be then warming up to 35-50 DEG C, stir insulation 8-15h;
5. then in the solution of step 4. gained, 120ml deionized water is added, stirring at normal temperature reaction 2h;
6. finally add 16-20ml hydrogen peroxide, obtain jonquilleous acidic oxidation graphene aqueous solution, centrifugal through washing repeatedly, ultrasonic 0.5-1h, obtains neutral graphene oxide solution, obtains the GO of sheet through freeze drying, and powder is made in grinding.
7. preparation method as claimed in claim 1, is characterized in that, the preparation method of the CTAB aqueous solution in described step (2): joined by CTAB in distilled water, constantly stirs until form clear solution at 30 DEG C-40 DEG C.
8. the composite material prepared by the arbitrary described method of claim 1-7, this composite material pattern is rutile TiO 2nanometer rods load is in GO nanometer sheet.
9. composite material as claimed in claim 8, is characterized in that, described TiO 2the diameter of nanometer rods is 50-150nm, and rod is long is 200-400nm.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI554470B (en) * 2015-04-24 2016-10-21 Preparation of composite materials for supercapacitors
CN111792669A (en) * 2020-06-02 2020-10-20 杭州电子科技大学 TiO 22Nano-rod/multilayer graphene composite material and preparation method thereof
CN114349044A (en) * 2021-12-30 2022-04-15 杭州电子科技大学 Crystalline form and morphology control method of titanium dioxide on surface of multilayer graphene
CN115304098A (en) * 2022-09-20 2022-11-08 山东国瓷功能材料股份有限公司 Nano titanium dioxide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539108A (en) * 2013-10-22 2014-01-29 泰山医学院 Method for preparing graphene oxide
CN103771509A (en) * 2014-01-23 2014-05-07 齐鲁工业大学 Method for preparing uniform spherical mesoporous titanium dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539108A (en) * 2013-10-22 2014-01-29 泰山医学院 Method for preparing graphene oxide
CN103771509A (en) * 2014-01-23 2014-05-07 齐鲁工业大学 Method for preparing uniform spherical mesoporous titanium dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZIQI SUN等: ""Rational Design of 3D Dendritic TiO2 Nanostructures with Favorable Architectures"", 《J. AM. CHEM. SOC.》 *
刘蕊蕊等: ""金红石型TiO2氧化石墨烯复合材料的制备及其电化学性能"", 《中国化学会第29届学术年会摘要集—第33分会：纳米材料合成与组装》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI554470B (en) * 2015-04-24 2016-10-21 Preparation of composite materials for supercapacitors
CN111792669A (en) * 2020-06-02 2020-10-20 杭州电子科技大学 TiO 22Nano-rod/multilayer graphene composite material and preparation method thereof
CN111792669B (en) * 2020-06-02 2022-07-12 杭州电子科技大学 TiO 22Nano-rod/multilayer graphene composite material and preparation method thereof
CN114349044A (en) * 2021-12-30 2022-04-15 杭州电子科技大学 Crystalline form and morphology control method of titanium dioxide on surface of multilayer graphene
CN114349044B (en) * 2021-12-30 2024-01-30 杭州电子科技大学 Multilayer graphene surface titanium dioxide crystal form and morphology control method
CN115304098A (en) * 2022-09-20 2022-11-08 山东国瓷功能材料股份有限公司 Nano titanium dioxide

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