CN104891567A - Preparing method of tubular TiO2/reduced graphene oxide composite - Google Patents

Preparing method of tubular TiO2/reduced graphene oxide composite Download PDF

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CN104891567A
CN104891567A CN201510354419.1A CN201510354419A CN104891567A CN 104891567 A CN104891567 A CN 104891567A CN 201510354419 A CN201510354419 A CN 201510354419A CN 104891567 A CN104891567 A CN 104891567A
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graphene oxide
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CN104891567B (en
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周国伟
肖虹
刘蕊蕊
高婷婷
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Shandong Jiqing Technology Service Co ltd
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Qilu University of Technology
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Abstract

The invention discloses a preparing method of tubular TiO2/reduced graphene oxide composite. The preparing method includes: with TiOSO4 as a titanium source and Pluronic block copolymer (P123) as a soft template, synthesizing tubular TiO2 in mixed solution of ethyl alcohol, ethylene glycol and diethyl ether; synthesizing graphene oxide by means of the modified Hummers method; at high temperature, from the tubular TiO2 AND THE graphene oxide, assembling and preparing the tubular TiO2/reduced graphene oxide composite by a hydrothermal method. During the preparation of the tubular TiO2/reduced graphene oxide composite, no reducing agent is added; the graphene oxide is subjected to high-temperature hydrothermal reduction, which is green; the addition of the graphene oxide has no evident effect on the TiO2 shape; the TiO2 helps effectively maintain the tubular shape; the tubular TiO2/reduced graphene oxide composites different in proportion can be made by adjusting the ratio of the TiO2 to the graphene oxide.

Description

Tubulose TiO 2the preparation method of/redox graphene matrix material
Technical field
The present invention relates to tubulose TiO 2the preparation method of/redox graphene matrix material, belongs to inorganic semiconductor material preparation field.
Background technology
TiO 2because the chemical physical property that it is nontoxic, chemical stability is good and excellent is applied to multiple fields, as: photochemical catalysis, sensing, ultracapacitor and solar cell etc.Graphene be by carbon atom tightly packed formed there is hexagonal structure unit two-dimension plane structure, have that specific surface area is large, electronic mobility is high and the advantage such as good conductivity.But TiO 2electroconductibility poor, Graphene and TiO 2recombination energy increases its electroconductibility, specific surface area and electrical capacity, promotes the separation of its electron-hole pair.Existing TiO 2the preparation method of/graphene composite material, the matrix material obtained mostly is graphene-supported TiO 2particle, and TiO 2pattern uncontrollable, easily reunite; And need to add the reductive agents such as hydrazine hydrate in the process of graphene oxide reduction, this kind of reductive agent is not only poisonous but also large to environmental hazard.
Such as, yang etc. utilize sol-gel method and hydrothermal method to prepare TiO 2/ graphene composite material, wherein TiO 2nanoparticle agglomerates is serious, bad dispersibility (Min-Quan Yang, Nan Zhang, and Yi-Jun Xu.ACS Appl.Mater.Interfaces, 2013,5,1156-1164).The Chinese patent literature of application publication number CN 103936065 A (application number 201410119700.2) discloses a kind of TiO 2preparation method with graphene composite nano material, is reduced to Graphene by TERTIARY BUTYL AMINE by graphene oxide, adds titanium source and obtains TiO 2with graphene composite nano material, wherein TiO 2pattern be nano particle.And it is larger to environmental hazard to add TERTIARY BUTYL AMINE in preparation process.The Chinese patent literature of application publication number CN 102527366 A (application number 201210008265.7) discloses a kind of titanium dioxide nanotube graphene mixed light catalyzer and preparation method, with TiO 2for titanium source, adopt hydrothermal method to prepare matrix material, its preparation process needs repetitive scrubbing, and step is more.The pattern of matrix material is that Graphene covers TiO 2nanotube.The Chinese patent literature of Authorization Notice No. CN 102496700 B (application number 201110429717.4) discloses a kind of graphene-titanium dioxide nanotube composite material and preparation method, with P25 or anatase octahedrite TiO 2for titanium source, adopt hydrothermal method to prepare matrix material, its preparation process needs repetitive scrubbing, comparatively loaded down with trivial details.The pattern of matrix material is graphene-supported TiO 2nanotube.
Summary of the invention
The object of this invention is to provide a kind of tubulose TiO 2the preparation method of/redox graphene matrix material, the pattern of the matrix material that the method is prepared is the coated tubulose TiO of redox graphene 2, TiO 2pattern can effectively control, and adopt in preparation process high-temperature water thermal reduction replace reductive agent, environmental protection.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of tubulose TiO 2the preparation method of/redox graphene matrix material, first with TiOSO 4be soft template as titanium source, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123), synthesized in ethanol-glycol-ether mixing solutions long for 4-12 μm, wall thickness be 100-300nm and caliber is 0.5-1.5 μm of tubulose TiO 2; At 110-150 DEG C, with tubulose TiO 2be raw material with graphene oxide, adopt hydrothermal method self-assembly to prepare tubulose TiO 2/ redox graphene matrix material.
In the method, the TiO that the first step obtains 2pattern is tubulose, and in the recombination process of second step, TiO 2pattern can not change because of the compound with redox graphene, thus can effectively control TiO in matrix material 2pattern.Prepare in the process of matrix material at second step, adopt the method for high-temperature water thermal reduction to obtain redox graphene, do not need to add reductive agent, environmental protection.The tubulose TiO that the method obtains 2the pattern of/redox graphene matrix material is the coated tubulose TiO of redox graphene 2.
Specifically comprise the following steps:
(1) solvent-thermal method prepares tubulose TiO 2
1. be dissolved in by P123 in ethanol-glycol-ether mixing solutions, stirred at ambient temperature is to clear solution;
2. by TiOSO 4join in the clear solution of step 1. gained, stir 2-48h and obtain suspension liquid;
3. the suspension liquid that 2. step is prepared is transferred in autoclave, under 110-150 DEG C of condition, be incubated 12-48h, by autoclave cool to room temperature after hydrothermal treatment consists, be precipitated thing;
4. after the throw out centrifugation 3. step obtained, washing, centrifugal, dry, calcine 3-6h at 450-500 DEG C after grinding and obtain tubulose TiO 2, tubulose TiO 2long is 4-12 μm, and wall thickness is 100-300nm, and caliber is 0.5-1.5 μm;
(2) tubulose TiO is prepared 2/ redox graphene matrix material
1. by tubulose TiO 2be dispersed in water, ultrasonic, obtain tubulose TiO 2dispersion liquid; Wherein, described tubulose TiO 2with the adding proportion of distilled water be: (0.0500-0.2000) g:20mL
2. by graphene oxide powder dispersion in water, ultrasonic, obtain the dispersion liquid of graphene oxide; Wherein, the adding proportion of described graphene oxide and water is: (0.0025-0.0400) g:10mL;
3. step dispersion liquid 2. is under agitation added in step dispersion liquid 1., ultrasonic agitation 2-6h;
4. mixed dispersion liquid is transferred in autoclave, under 110-150 DEG C of condition, is incubated 12-48h, by autoclave cool to room temperature after hydrothermal treatment consists, be precipitated thing;
5. by after the throw out centrifugation that obtains, washing, centrifugal, dry, obtain tubulose TiO after grinding 2(redox graphene is coated on tubulose TiO to/redox graphene matrix material 2surface).
In step (1), raw materials used TiOSO 4, P123, ethanol, ether and ethylene glycol mol ratio be 1:0.00552-0.02758:54.622-109.243:15.340-36.680:28.659-57 .319, preferred proportion is 1:0.00552:71.008:19.942:37.257.
In step (1), the molecular weight of described P123 is 4000 ~ 7000g/moL, is preferably 5800g/moL.
Step (1) 2. in, optimum reacting time is 12h.
Step (1) 3. in, hydrothermal condition be preferably 110 DEG C insulation 24h.
Step (1) 4. in, calcination condition calcines 4h at being preferably 500 DEG C.
Step (2) 2. in, the preparation method of graphene oxide powder is as follows:
By Graphite Powder 99, the vitriol oil and K 2s 2o 8mixing, stirring, ultrasonic, 80 DEG C are stirred 6-8h; The product obtained is carried out drying, after drying, adds the vitriol oil and phosphoric acid, stir, ultrasonic; Solution after ultrasonic is cooled, then adds potassium permanganate, continue to stir 4-6h, be then warming up to 35 DEG C, stir insulation 8-12h; Then water is added, stirring at room temperature reaction 2-3h; Finally add hydrogen peroxide, through washing, be separated, ultrasonic and drying obtains graphene oxide.
Concrete preparation process is as follows:
1. by 2-5g Graphite Powder 99, the 30-80ml vitriol oil, 2-5g K 2s 2o 8join successively in beaker, stir, ultrasonic 5-30 minute, puts into water-bath, is heated to 80 DEG C and stirs 6-8h;
2. by step product distilled water diluting 1. to 1000ml, then suction filtration, drying at room temperature 8-12h;
3. the filter cake that 2. step obtains is added in beaker, add the 120-200ml vitriol oil, 20-50ml phosphoric acid, stir, ultrasonic 1-2h;
4. the solution after ultrasonic is placed in ice bath, cooling 0.5-1h, under agitation slowly add 12-30g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4-6h, is then warming up to 35 DEG C, stirs insulation 8-12h; 5. then in solution, 150-300ml distilled water is slowly added, stirring at room temperature reaction 2-3h;
6. finally add 16-40ml hydrogen peroxide, stir 0.5-2h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of PH ≈ 7, obtain graphene oxide through super-dry.
Step (2) 3. in, the described mixing ultrasonic agitation time is 2h.
Step (2) 4. in, hydrothermal condition be preferably 110 DEG C insulation 24h.
The present invention is with TiOSO 4for titanium source, tensio-active agent P123 is soft template, utilizes the solvent-thermal method of mixed solvent to prepare tubulose TiO 2, prepare graphene oxide with the Hummers method improved, then adopt hydrothermal method to obtain tubulose TiO 2/ redox graphene matrix material.
The present invention has following beneficial effect:
1, the tubulose TiO that obtains of the present invention 2/ redox graphene matrix material, tubulose TiO 2be about as 4-12 μm, wall thickness is about 100-300nm, and caliber is about 0.5-1.5 μm, and redox graphene is coated on tubulose TiO 2surface.
2, the present invention adopts two-step approach to prepare tubulose TiO 2/ redox graphene matrix material, graphene oxide and TiO 2ratio controlled; And TiO 2pattern can not change because of adding of redox graphene, be the TiO of other patterns 2/ redox graphene matrix material provides reference.
3, the present invention prepares tubulose TiO 2during/redox graphene matrix material, graphene oxide reduces under high-temperature water heat condition, does not need to add reductive agent, environmental protection.
Accompanying drawing explanation
Fig. 1 is the tubulose TiO of preparation 2and tubulose TiO 2the transmission electron microscope picture (TEM) of/redox graphene matrix material, wherein a is tubulose TiO 2tEM, b be embodiment 1 prepare tubulose TiO 2the TEM of/redox graphene matrix material;
Fig. 2 is the tubulose TiO of preparation 2and tubulose TiO 2the field emission scanning electron microscope figure (FESEM) of/redox graphene matrix material, wherein a is tubulose TiO 2fESEM, b be embodiment 1 prepare tubulose TiO 2the FESEM of/redox graphene matrix material;
Fig. 3 is the tubulose TiO of preparation 2, graphene oxide and tubulose TiO 2the x-ray diffraction pattern (XRD) of/redox graphene matrix material, wherein a is the XRD of graphene oxide; B is tubulose TiO 2xRD; C is tubulose TiO prepared by embodiment 1 2the XRD of/redox graphene matrix material.
Embodiment
Further illustrate below in conjunction with specific embodiment.
Embodiment 1
(1) tubulose TiO is prepared 2get 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml ether, stirred at ambient temperature 1h; Add 0.5000g TiOSO 4, stir 12h and obtain suspension liquid; Suspension liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, calcine 4h at grinding latter 500 DEG C and obtain tubulose TiO 2.
(2) graphene oxide is prepared by 3g Graphite Powder 99, the 30ml vitriol oil, 3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C and stir 6h; Slowly add distilled water diluting to 1000ml, then suction filtration, ambient temperature overnight is dry; The filter cake obtained is added in beaker, adds the 150ml vitriol oil, 20ml phosphoric acid, stir, ultrasonic 1h; Solution after ultrasonic is placed in ice bath, cooling 0.5h, under agitation slowly add 18g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4h, is then warming up to 35 DEG C, stirs insulation 8h; Then in solution, 250ml distilled water is slowly added, stirring at room temperature reaction 2h; Finally add 24ml hydrogen peroxide, stir 0.5h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of pH ≈ 7, obtain graphene oxide through super-dry.
(3) tubulose TiO is prepared 2the tubulose TiO that 0.0500g prepares by/redox graphene matrix material 2add in 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO 2dispersion liquid; The graphene oxide powder prepared by 0.0025g adds in 10ml distilled water, ultrasonic, stirs 1h, obtains the dispersion liquid of graphene oxide; Graphene oxide dispersion is under agitation added tubulose TiO 2in dispersion liquid, ultrasonic agitation 2h; Mixed dispersion liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, after grinding, obtain tubulose TiO 2/ redox graphene matrix material.
As shown in Figure 1,2 and 3, the tubulose TiO that the present embodiment 1 is obtained 2/ redox graphene matrix material, tubulose TiO 2be about as 4-12 μm, wall thickness is about 100-300nm, and caliber is about 0.5-1.5 μm, and redox graphene is coated on tubulose TiO 2surface.Fig. 1 a, 2a are TiO 2tubulose, Fig. 1 b, 2b are tubulose TiO 2/ redox graphene matrix material, as can be seen from the figure, after composite reduction graphene oxide, TiO 2still keep tubulose, do not change.Therefore, TiO can't be changed adding of redox graphene 2pattern.
Embodiment 2
(1) tubulose TiO is prepared 2get 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml ether, stirred at ambient temperature 1h; Add 0.5000g TiOSO 4, stir 12h and obtain suspension liquid; Suspension liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, calcine 4h at grinding latter 500 DEG C and obtain tubulose TiO 2.
(2) graphene oxide is prepared by 3g Graphite Powder 99, the 30ml vitriol oil, 3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C and stir 6h; Slowly add distilled water diluting to 1000ml, then suction filtration, ambient temperature overnight is dry; The filter cake obtained is added in beaker, adds the 150ml vitriol oil, 20ml phosphoric acid, stir, ultrasonic 1h; Solution after ultrasonic is placed in ice bath, cooling 0.5h, under agitation slowly add 18g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4h, is then warming up to 35 DEG C, stirs insulation 8h; Then in solution, 250ml distilled water is slowly added, stirring at room temperature reaction 2h; Finally add 24ml hydrogen peroxide, stir 0.5h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of pH ≈ 7, obtain graphene oxide through super-dry.
(3) tubulose TiO is prepared 2the tubulose TiO that 0.0500g prepares by/redox graphene matrix material 2add in 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO 2dispersion liquid; The graphene oxide powder prepared by 0.0050g adds in 10ml distilled water, ultrasonic, stirs 1h, obtains the dispersion liquid of graphene oxide; Graphene oxide dispersion is under agitation added tubulose TiO 2in dispersion liquid, ultrasonic agitation 2h; Mixed dispersion liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, after grinding, obtain tubulose TiO 2/ redox graphene matrix material.
Embodiment 3
(1) tubulose TiO is prepared 2get 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml ether, stirred at ambient temperature 1h; Add 0.5000g TiOSO 4, stir 12h and obtain suspension liquid; Suspension liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, calcine 4h at grinding latter 500 DEG C and obtain tubulose TiO 2.
(2) graphene oxide is prepared by 3g Graphite Powder 99, the 30ml vitriol oil, 3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C and stir 6h; Slowly add distilled water diluting to 1000ml, then suction filtration, ambient temperature overnight is dry; The filter cake obtained is added in beaker, adds the 150ml vitriol oil, 20ml phosphoric acid, stir, ultrasonic 1h; Solution after ultrasonic is placed in ice bath, cooling 0.5h, under agitation slowly add 18g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4h, is then warming up to 35 DEG C, stirs insulation 8h; Then in solution, 250ml distilled water is slowly added, stirring at room temperature reaction 2h; Finally add 24ml hydrogen peroxide, stir 0.5h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of pH ≈ 7, obtain graphene oxide through super-dry.
(3) tubulose TiO is prepared 2the tubulose TiO that 0.0500g prepares by/redox graphene matrix material 2add in 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO 2dispersion liquid; The graphene oxide powder prepared by 0.0075g adds in 10ml distilled water, ultrasonic, stirs 1h, obtains the dispersion liquid of graphene oxide; Graphene oxide dispersion is under agitation added tubulose TiO 2in dispersion liquid, ultrasonic agitation 2h; Mixed dispersion liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, after grinding, obtain tubulose TiO 2/ redox graphene matrix material.
Embodiment 4
(1) tubulose TiO is prepared 2get 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml ether, stirred at ambient temperature 1h; Add 0.5000g TiOSO 4, stir 12h and obtain suspension liquid; Suspension liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, calcine 4h at grinding latter 500 DEG C and obtain tubulose TiO 2.
(2) graphene oxide is prepared by 3g Graphite Powder 99, the 30ml vitriol oil, 3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C and stir 6h; Slowly add distilled water diluting to 1000ml, then suction filtration, ambient temperature overnight is dry; The filter cake obtained is added in beaker, adds the 150ml vitriol oil, 20ml phosphoric acid, stir, ultrasonic 1h; Solution after ultrasonic is placed in ice bath, cooling 0.5h, under agitation slowly add 18g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4h, is then warming up to 35 DEG C, stirs insulation 8h; Then in solution, 250ml distilled water is slowly added, stirring at room temperature reaction 2h; Finally add 24ml hydrogen peroxide, stir 0.5h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of pH ≈ 7, obtain graphene oxide through super-dry.
(3) tubulose TiO is prepared 2the tubulose TiO that 0.0500g prepares by/redox graphene matrix material 2add in 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO 2dispersion liquid; The graphene oxide powder prepared by 0.0100g adds in 10ml distilled water, ultrasonic, stirs 1h, obtains the dispersion liquid of graphene oxide; Graphene oxide dispersion is under agitation added tubulose TiO 2in dispersion liquid, ultrasonic agitation 2h; Mixed dispersion liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 24h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, after grinding, obtain tubulose TiO 2/ redox graphene matrix material.
Embodiment 5
(1) tubulose TiO is prepared 2get 0.2000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml ether, stirred at ambient temperature 1h; Add 0.5000g TiOSO 4, stir 2h and obtain suspension liquid; Suspension liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 12h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, calcine 6h at grinding latter 450 DEG C and obtain tubulose TiO 2.
(2) graphene oxide is prepared by 3g Graphite Powder 99, the 30ml vitriol oil, 3g K 2s 2o 8join successively in beaker, stir, ultrasonic 5 minutes, put into water-bath, be heated to 80 DEG C and stir 6h; Slowly add distilled water diluting to 1000ml, then suction filtration, ambient temperature overnight is dry; The filter cake obtained is added in beaker, adds the 150ml vitriol oil, 20ml phosphoric acid, stir, ultrasonic 1h; Solution after ultrasonic is placed in ice bath, cooling 0.5h, under agitation slowly add 18g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4h, is then warming up to 35 DEG C, stirs insulation 8h; Then in solution, 250ml distilled water is slowly added, stirring at room temperature reaction 2h; Finally add 24ml hydrogen peroxide, stir 0.5h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of pH ≈ 7, obtain graphene oxide through super-dry.
(3) tubulose TiO is prepared 2the tubulose TiO that 0.0500g prepares by/redox graphene matrix material 2add in 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO 2dispersion liquid; The graphene oxide powder prepared by 0.0025g adds in 10ml distilled water, ultrasonic, stirs 1h, obtains the dispersion liquid of graphene oxide; Graphene oxide dispersion is under agitation added tubulose TiO 2in dispersion liquid, ultrasonic agitation 2h; Mixed dispersion liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 110 DEG C of conditions, be incubated 12h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, after grinding, obtain tubulose TiO 2/ redox graphene matrix material.
Embodiment 6
(1) tubulose TiO is prepared 2get 0.1000g P123 in beaker, add 13ml ethanol, 6.5ml ethylene glycol, 6.5ml ether, stirred at ambient temperature 1h; Add 0.5000g TiOSO 4, stir 48h and obtain suspension liquid; Suspension liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 150 DEG C of conditions, be incubated 48h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, calcine 3h at grinding latter 500 DEG C and obtain tubulose TiO 2.
(2) graphene oxide is prepared by 3g Graphite Powder 99, the 30ml vitriol oil, 3g K 2s 2o 8join successively in beaker, stir, ultrasonic 30 minutes, put into water-bath, be heated to 80 DEG C and stir 8h; Slowly add distilled water diluting to 1000ml, then suction filtration, ambient temperature overnight is dry; The filter cake obtained is added in beaker, adds the 150ml vitriol oil, 20ml phosphoric acid, stir, ultrasonic 2h; Solution after ultrasonic is placed in ice bath, cooling 1h, under agitation slowly add 18g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 6h, is then warming up to 35 DEG C, stirs insulation 12h; Then in solution, 250ml distilled water is slowly added, stirring at room temperature reaction 3h; Finally add 24ml hydrogen peroxide, stir 2h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of pH ≈ 7, obtain graphene oxide through super-dry.
(3) tubulose TiO is prepared 2the tubulose TiO that 0.0500g prepares by/redox graphene matrix material 2add in 20ml distilled water, ultrasonic, stir 1h, obtain tubulose TiO 2dispersion liquid; The graphene oxide powder prepared by 0.0050g adds in 10ml distilled water, ultrasonic, stirs 6h, obtains the dispersion liquid of graphene oxide; Graphene oxide dispersion is under agitation added tubulose TiO 2in dispersion liquid, ultrasonic agitation 2h; Mixed dispersion liquid is transferred in teflon-lined autoclave, autoclave is tightened and puts into baking oven, under 150 DEG C of conditions, be incubated 48h, after hydrothermal treatment consists, autoclave naturally cooled to room temperature, be precipitated thing; By after the throw out centrifugation that obtains, use washing with alcohol, centrifugal, dry, after grinding, obtain tubulose TiO 2/ redox graphene matrix material.
The molecular weight of the P123 that embodiment 1 ~ 6 uses is 5800g/moL.
The tubulose TiO that embodiment 2 ~ 6 is obtained 2/ redox graphene matrix material, the result of its pattern and embodiment 1, there is no significant difference.Wherein, tubulose TiO 2be about as 4-12 μm, wall thickness is about 100-300nm, and caliber is about 0.5-1.5 μm, and redox graphene is coated on tubulose TiO 2surface forms matrix material.
Two-step approach is adopted to prepare tubulose TiO 2/ redox graphene matrix material, graphene oxide and TiO 2ratio controlled; And TiO 2pattern can not change because of adding of redox graphene, be the TiO of other patterns 2/ redox graphene matrix material provides reference.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; 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 (10)

1. a tubulose TiO 2the preparation method of/redox graphene matrix material, is characterized in that: first with TiOSO 4be soft template as titanium source, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123), synthesized in ethanol-glycol-ether mixing solutions long for 4-12 μm, wall thickness be 100-300nm and caliber is 0.5-1.5 μm of tubulose TiO 2; At 110-150 DEG C, with tubulose TiO 2be raw material with graphene oxide, adopt hydrothermal method self-assembly to prepare tubulose TiO 2/ redox graphene matrix material.
2. preparation method as claimed in claim 1, is characterized in that: specifically comprise the following steps:
(1) solvent-thermal method prepares tubulose TiO 2
1. be dissolved in by P123 in ethanol-glycol-ether mixing solutions, stirred at ambient temperature is to clear solution;
2. by TiOSO 4join in the clear solution of step (1) gained, stir 2-48h and obtain suspension liquid;
3. the suspension liquid that 2. step is prepared is transferred in autoclave, under 110-150 DEG C of condition, be incubated 12-48h, by autoclave cool to room temperature after hydrothermal treatment consists, be precipitated thing;
Wherein, raw materials used TiOSO 4, P123, ethanol, ether and ethylene glycol mol ratio be 1:0.00552-0.02758:54.622-109.243:15.340-36.680:28.659-57 .319;
4. after the throw out centrifugation 3. step obtained, washing, centrifugal, dry, calcine 3-6h at 450-500 DEG C after grinding and obtain tubulose TiO 2;
(2) tubulose TiO is prepared 2/ redox graphene matrix material
1. by tubulose TiO 2be dispersed in water, ultrasonic, obtain tubulose TiO 2dispersion liquid; Wherein, described tubulose TiO 2with the adding proportion of distilled water be: (0.0500-0.2000) g:20mL
2. by graphene oxide powder dispersion in water, ultrasonic, obtain the dispersion liquid of graphene oxide; Wherein, the adding proportion of described graphene oxide and water is: (0.0025-0.0400) g:10mL;
3. step dispersion liquid 2. is under agitation added in step dispersion liquid 1., ultrasonic agitation 2-6h;
4. mixed dispersion liquid is transferred in autoclave, under 110-150 DEG C of condition, is incubated 12-48h, by autoclave cool to room temperature after hydrothermal treatment consists, be precipitated thing;
5. by after the throw out centrifugation that obtains, washing, centrifugal, dry, obtain tubulose TiO after grinding 2/ redox graphene matrix material.
3. preparation method as claimed in claim 2, is characterized in that: raw materials used TiOSO 4, P123, ethanol, ether and ethylene glycol mol ratio be 1:0.00552:71.008:19.942:37.257.
4. preparation method as claimed in claim 2, is characterized in that: step (1) 2. in, optimum reacting time is 12h.
5. preparation method as claimed in claim 2, is characterized in that: step (1) 3. in, hydrothermal condition is preferably 110 DEG C of insulation 24h.
6. preparation method as claimed in claim 2, is characterized in that: step (1) 4. in, calcination condition calcines 4h at being preferably 500 DEG C.
7. preparation method as claimed in claim 2, is characterized in that: step (2) 2. in, the preparation method of graphene oxide powder is as follows:
By Graphite Powder 99, the vitriol oil and K 2s 2o 8mixing, stirring, ultrasonic, 80 DEG C are stirred 6-8h; The product obtained is carried out drying, after drying, adds the vitriol oil and phosphoric acid, stir, ultrasonic; Solution after ultrasonic is cooled, then adds potassium permanganate, continue to stir 4-6h, be then warming up to 35 DEG C, stir insulation 8-12h; Then water is added, stirring at room temperature reaction 2-3h; Finally add hydrogen peroxide, through washing, be separated, ultrasonic and drying obtains graphene oxide.
8. preparation method as claimed in claim 7, is characterized in that: specifically comprise the following steps:
1. by 2-5g Graphite Powder 99, the 30-80ml vitriol oil, 2-5g K 2s 2o 8join successively in beaker, stir, ultrasonic 5-30 minute, puts into water-bath, is heated to 80 DEG C and stirs 6-8h;
2. by step product distilled water diluting 1. to 1000ml, then suction filtration, drying at room temperature 8-12h;
3. the filter cake that 2. step obtains is added in beaker, add the 120-200ml vitriol oil, 20-50ml phosphoric acid, stir, ultrasonic 1-2h;
4. the solution after ultrasonic is placed in ice bath, cooling 0.5-1h, under agitation slowly add 12-30g potassium permanganate, control temperature is less than 5 DEG C, continues to stir 4-6h, is then warming up to 35 DEG C, stirs insulation 8-12h;
5. then in solution, 150-300ml distilled water is slowly added, stirring at room temperature reaction 2-3h;
6. finally add 16-40ml hydrogen peroxide, stir 0.5-2h, through washing repeatedly, centrifugal, ultrasonic, obtain the graphene oxide solution of PH ≈ 7, obtain graphene oxide through super-dry.
9. preparation method as claimed in claim 2, is characterized in that: step (2) 3. in, the described mixing ultrasonic agitation time is 2h.
10. preparation method as claimed in claim 2, is characterized in that: step (2) 4. in, hydrothermal condition is 110 DEG C of insulation 24h.
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