CN105536848A - Graphene composite and preparation method thereof - Google Patents
Graphene composite and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 126
- 239000004408 titanium dioxide Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002070 nanowire Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001133 acceleration Effects 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- -1 Graphene compound Chemical class 0.000 description 2
- 229910011208 Ti—N Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a graphene composite comprising nitrogen-doped reduced graphene oxide and nitrogen-doped titanium dioxide nanowires, wherein the length-diameter ratio of the titanium dioxide nanowires is larger than 10. The one-dimensional titanium dioxide nanowires are selected as an active component, have better electronic transmission channels and are beneficial to acceleration of electronic transmission and increase of the reaction rate. Meanwhile, the one-dimensional titanium dioxide nanowires can better prevent stacking of graphene sheets, more effectively use the characteristic of large specific surface of graphene, enlarge the reaction contact area and increase the catalytic reaction rate. A preparation method of the graphene composite adopts a simple process, raw materials are easy to store, the reaction is mild, energy consumption is lower, and the method is suitable for industrial application. Meanwhile, the titanium dioxide nanowires with controllable morphology are prepared firstly, then the graphene composite is prepared, the product cost is reduced effectively, and product quality controllability can be realized.
Description
Technical field
The present invention relates to field of graphene, be specifically related to graphene composite material that a kind of technique is simple, energy consumption is low and preparation method thereof.
Background technology
Graphene be a kind of by carbon atom by sp
2carbon lattice close-packed arrays forms the stratified material being similar to alveolate texture, there is good heat-conductive characteristic, mechanical performance, chemical stability, large specific area, this makes it have huge application prospect at many sciemtifec and technical spheres such as nanoelectronics, sensor, nano composite material, battery, ultracapacitor and hydrogen storages.
In addition, the electronic movement velocity of Graphene reaches 1/300 of the light velocity, has far exceeded the movement velocity of electronics in general conductor, much research all expect by with Graphene compound to reach the object improving material electrical property.
Chinese patent literature CN104415772A discloses the preparation method of a kind of N doping redox graphene/nitrogen-doped titanium dioxide composite, comprise and graphene oxide dispersion is mixed with TiO 2 particles, then gained mixture is carried out annealing in process in containing the atmosphere of ammonia, the concentration of ammonia is 10 ~ 15% (volumn concentrations), and annealing temperature is 500 ~ 800 DEG C.Because redox graphene has good electric conductivity and very high specific area, when after itself and titanium dioxide compound, namely the available light induced electron by titanium dioxide granule surface is led away in time, effectively prevents light induced electron and hole-recombination, thus improves the photocatalysis efficiency of composite.
But said method reaction temperature is tall and big 500 ~ 800 DEG C, and energy consumption is large; Meanwhile, ammonia level is higher, and in high temperature nitrating process, not only ammonia concentration is wayward, and easily occurs other security incidents such as leakage, and security control cost is high.
Summary of the invention
For this reason, to be solved by this invention is the problem that preparation method's technology difficulty is large, energy consumption is high of existing N doping redox graphene/nitrogen-doped titanium dioxide composite, thus provides graphene composite material that a kind of technique is simple, energy consumption is low and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of graphene composite material of the present invention, comprises N doping redox graphene and nitrogen-doped titanium dioxide nano line; The draw ratio of described titanium dioxide nano thread is greater than 10.
The mass ratio that described N doping redox graphene accounts for described nitrogen-doped titanium dioxide nano line is 1wt% ~ 10wt%.
The preparation method of a kind of graphene composite material of the present invention, comprises the steps:
S1, prepare titanium dioxide nano thread;
S2, described titanium dioxide nano thread, urea, graphene oxide are disperseed to be placed in hydrothermal reaction kettle by the mass ratio of 1 ~ 10:200 ~ 300:1 ~ 10 in water, 180 ~ 220 DEG C of reactions 5 ~ 20 hours.
Preferably, in described step S1, described titanium dioxide nano thread is anatase titanium dioxide nano wire.
Preferably, in described step S1, the draw ratio of described titanium dioxide nano thread is greater than 10.
Preferably, described step S1 comprises further:
S11, added by titanium dioxide P25 in the aqueous solution of NaOH of 10mol/L ~ 20mol/L, configuration concentration is the mixed liquor A of 0.1M ~ 1M;
S12, described mixed liquor A is placed in hydrothermal reaction kettle, 150 DEG C ~ 220 DEG C reactions 12 ~ 72 hours, obtain mixed liquid B;
S13, described mixed liquid B carried out to centrifuge washing to eluate for neutral, be precipitated A;
S14, hydrogen ion exchange is carried out to described precipitate A, and centrifuge washing to eluate is neutral, is precipitated B after oven dry;
S15, described precipitate B to be calcined 4 hours under 600 DEG C of conditions, obtain described titanium dioxide nano thread.
Preferably, in described step S14, the exchange reagent of described hydrogen ion exchange step is: concentration is the aqueous solution of nitric acid of 0.1mol/L ~ 0.5mol/L.
Preferably, in described step S2, the mass ratio of described titanium dioxide nano thread, described urea, described graphene oxide is 10:500:1.
Preferably, in described step S2, the condition of described hydro-thermal reaction is 200 DEG C of reactions 10 hours.
Preferably, at least one in centrifugation step, washing step, drying steps is also comprised after described step S2.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, a kind of graphene composite material of the present invention, comprises N doping redox graphene and nitrogen-doped titanium dioxide nano line; The draw ratio of described titanium dioxide nano thread is greater than 10.Reduced the energy gap of titanium dioxide by N doping, simultaneously composite nitrogen doped graphene makes described graphene composite material photocatalytically, can effective degradation of organic substances molecule, has significant visible light catalysis activity.
And the present invention chooses one-dimensional titanium dioxide nano wire as active component, and titanium dioxide nano thread not only has better electron propagation ducts, be conducive to accelerating electric transmission, improve reaction rate.Meanwhile, one-dimensional titanium dioxide nano wire also can better prevent the stacking of graphene sheet layer, more effectively utilizes the characteristic of Graphene Large ratio surface, increases reaction contact area, improves rate of catalysis reaction.
2, the preparation method of a kind of graphene composite material of the present invention, comprises the steps: S1, prepares titanium dioxide nano thread; S2, described titanium dioxide nano thread, urea, graphene oxide are disperseed to be placed in hydrothermal reaction kettle by the mass ratio of 1 ~ 10:200 ~ 300:1 ~ 10 in water, 180 ~ 220 DEG C of reactions 12 hours.Not only technique is simple, raw material is easily preserved for the preparation method of graphene composite material of the present invention, reaction temperature and, and energy consumption is lower, is applicable to commercial Application.Meanwhile, first prepare the titanium dioxide nano thread of morphology controllable, then prepare described graphene composite material, not only effectively reduce production cost, and it is controlled to realize product quality.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 be in embodiment 1, comparative example 1-3 obtain the XRD collection of illustrative plates of product;
Fig. 2 a be in embodiment 1 obtain the total spectrogram of XPS of product;
Fig. 2 b be in embodiment 1 obtain C1s swarming in the XPS spectrum figure of product;
Fig. 2 c be in embodiment 1 obtain O1s swarming in the XPS spectrum figure of product;
Fig. 2 d be in embodiment 1 obtain N1s swarming in the XPS spectrum figure of product;
Fig. 3 is the absorption spectrum of the product obtained in embodiment 1, comparative example 1-3;
Fig. 4 be in embodiment 1, comparative example 1-3 obtain the catalytic activity comparison diagram of product.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiments of the present invention are described in further detail.
The present invention can implement in many different forms, and should not be understood to be limited to embodiment set forth herein.On the contrary, provide these embodiments, make the disclosure to be thorough and complete, and design of the present invention fully will be conveyed to those skilled in the art, the present invention will only be limited by claim.
In following embodiment, NaOH, nitric acid, urea, graphene oxide, teflon-lined hydrothermal reaction kettle are commercially available; Titanium dioxide P25 is purchased from win wound Degussa (EVONIK-DEGUSSA).
Embodiment 1
The present embodiment provides a kind of preparation method of graphene composite material, comprises the steps:
S1, prepare titanium dioxide nano thread;
Be specially:
The aqueous solution 45ml of the NaOH of S11, configuration 15mol/L, adds 480mg titanium dioxide P25, mixes, obtained mixed liquor A;
S12, described mixed liquor A is placed in volume be 100ml there is teflon-lined hydrothermal reaction kettle, 180 DEG C of reactions 48 hours, obtain mixed liquid B;
S13, described mixed liquid B carried out to centrifuge washing to eluate for neutral, be precipitated A;
S14, hydrogen ion exchange is carried out to described precipitate A, then centrifuge washing to eluate is neutral, is precipitated B after oven dry; Described hydrogen ion exchange step is: described precipitate A is placed in the aqueous solution of nitric acid that concentration is 0.2mol/L, slowly stirs 12 hours, repeats 1-3 time.
S15, described precipitate B to be calcined 4 hours under 600 DEG C of conditions, obtain described titanium dioxide nano thread; Described titanium dioxide nano thread is anatase titanium dioxide nano wire; And the draw ratio of described titanium dioxide nano thread is greater than 10.
S2, the graphene oxide taking 30mg are dissolved in 30ml deionized water, ultrasonic disperse; Take the described titanium dioxide nano thread that step S1 described in 0.3g is obtained, low power ultrasound is scattered in described graphene oxide water solution;
Add 15g urea again, after being separated into homogeneous mixed liquor, stirring at room temperature 30min moves to be had in teflon-lined hydrothermal reaction kettle, and 200 DEG C are reacted 10 hours.After reaction terminates, obtain described graphene composite material through centrifugation step, washing step, drying steps.
As convertible embodiment of the present invention, only can also comprise at least one in centrifugation step, washing step, drying steps after described step S2, all can realize object of the present invention, belong to protection scope of the present invention.
Embodiment 2
The present embodiment provides a kind of preparation method of graphene composite material, comprises the steps:
S1, prepare titanium dioxide nano thread;
Be specially:
The aqueous solution 45ml of the NaOH of S11, configuration 10mol/L, adds 360mg titanium dioxide P25, mixes, obtained mixed liquor A;
S12, described mixed liquor A has been placed in teflon-lined hydrothermal reaction kettle, 150 DEG C of reactions 72 hours, obtain mixed liquid B;
S13, described mixed liquid B carried out to centrifuge washing to eluate for neutral, be precipitated A;
S14, hydrogen ion exchange is carried out to described precipitate A, then centrifuge washing to eluate is neutral, is precipitated B after oven dry; Described hydrogen ion exchange step is: described precipitate A is placed in the aqueous solution of nitric acid that concentration is 0.5mol/L, slowly stirs 12 hours, repeats 2 times.
S15, described precipitate B to be calcined 4 hours under 600 DEG C of conditions, obtain described titanium dioxide nano thread; Described titanium dioxide nano thread is anatase titanium dioxide nano wire; And the draw ratio of described titanium dioxide nano thread is greater than 10.
S2, the graphene oxide taking 75mg are dissolved in 30ml deionized water, ultrasonic disperse; Take the described titanium dioxide nano thread that step S1 described in 75mg is obtained, low power ultrasound is scattered in described graphene oxide water solution;
Add 15g urea again, after being separated into homogeneous mixed liquor, stirring at room temperature 30min moves to be had in teflon-lined hydrothermal reaction kettle, and 220 DEG C are reacted 5 hours.After reaction terminates, obtain described graphene composite material through centrifugation step, washing step, drying steps.
Embodiment 3
The present embodiment provides a kind of preparation method of graphene composite material, comprises the steps:
S1, prepare titanium dioxide nano thread;
Be specially:
The aqueous solution 45ml of the NaOH of S11, configuration 10mol/L, adds 3.6g titanium dioxide P25, mixes, obtained mixed liquor A;
S12, described mixed liquor A has been placed in teflon-lined hydrothermal reaction kettle, 220 DEG C of reactions 12 hours, obtain mixed liquid B;
S13, described mixed liquid B carried out to centrifuge washing to eluate for neutral, be precipitated A;
S14, hydrogen ion exchange is carried out to described precipitate A, then centrifuge washing to eluate is neutral, is precipitated B after oven dry; Described hydrogen ion exchange step is: described precipitate A is placed in the aqueous solution of nitric acid that concentration is 0.1mol/L, slowly stirs 12 hours, repeats 3 times.
S15, described precipitate B to be calcined 4 hours under 600 DEG C of conditions, obtain described titanium dioxide nano thread; Described titanium dioxide nano thread is anatase titanium dioxide nano wire; And the draw ratio of described titanium dioxide nano thread is greater than 10.
S2, the graphene oxide taking 30mg are dissolved in 30ml deionized water, ultrasonic disperse; Take the described titanium dioxide nano thread that step S1 described in 30mg is obtained, low power ultrasound is scattered in described graphene oxide water solution;
Add 3.6g urea again, after being separated into homogeneous mixed liquor, stirring at room temperature 30min moves to be had in teflon-lined hydrothermal reaction kettle, and 180 DEG C are reacted 20 hours.After reaction terminates, obtain described graphene composite material through centrifugation step, washing step, drying steps.
Embodiment 4
The present embodiment provides a kind of preparation method of graphene composite material, comprises the steps:
S1, prepare titanium dioxide nano thread;
Be specially:
The aqueous solution 45ml of the NaOH of S11, configuration 15mol/L, adds 1.8g titanium dioxide P25, mixes, obtained mixed liquor A;
S12, described mixed liquor A has been placed in teflon-lined hydrothermal reaction kettle, 200 DEG C of reactions 36 hours, obtain mixed liquid B;
S13, described mixed liquid B carried out to centrifuge washing to eluate for neutral, be precipitated A;
S14, hydrogen ion exchange is carried out to described precipitate A, then centrifuge washing to eluate is neutral, is precipitated B after oven dry; Described hydrogen ion exchange step is: described precipitate A is placed in the aqueous solution of nitric acid that concentration is 0.2mol/L, slowly stirs 12 hours, repeats 2 times.
S15, described precipitate B to be calcined 4 hours under 600 DEG C of conditions, obtain described titanium dioxide nano thread; Described titanium dioxide nano thread is anatase titanium dioxide nano wire; And the draw ratio of described titanium dioxide nano thread is greater than 10.
S2, the graphene oxide taking 300mg are dissolved in 30ml deionized water, ultrasonic disperse; Take the described titanium dioxide nano thread that step S1 described in 30mg is obtained, low power ultrasound is scattered in described graphene oxide water solution;
Add 15g urea again, after being separated into homogeneous mixed liquor, stirring at room temperature 30min moves to be had in teflon-lined hydrothermal reaction kettle, and 200 DEG C are reacted 10 hours.After reaction terminates, obtain described graphene composite material through centrifugation step, washing step, drying steps.
Comparative example 1
This comparative example provides a kind of anatase titanium dioxide nano wire, and its preparation method is with step S1 described in embodiment 1.
Comparative example 2
This comparative example provides a kind of nitrogen-doped titanium dioxide, and its preparation method, with embodiment 1, does not add graphene oxide unlike in described step S2.
Comparative example 3
This comparative example provides a kind of titanium dioxide and graphene composite catalyst, and its preparation method, with embodiment 1, does not add urea unlike in described step S2.
Test case 1
Carry out X-ray diffraction (X-raydiffraction, XRD) test to the product obtained in embodiment 1, comparative example 1-3, test collection of illustrative plates as shown in Figure 1.
Test case 2
Carry out X-ray photoelectron spectroscopic analysis (XPS) test to the graphene composite material described in embodiment 1, test collection of illustrative plates respectively as shown in Figure 2 a-2d.As can be seen from the total spectrogram of the XPS of Fig. 2 a: in embodiment 1 obtain product and contain this several element of C, N, O, Ti.The C1s swarming figure of Fig. 2 b can be divided into C=C, C=N, C-O, C-N, C=O, N-C=O, can find out that graphene oxide is by hydrothermal reduction, and N element is adulterated to Graphene simultaneously.Fig. 2 c is O1s swarming figure, can be divided into Ti-O, O-Ti-N, C-OH, can find out that N element is adulterated to titanium dioxide.Fig. 2 d is N1s swarming figure, can be divided into O-Ti-N, N-O, pyridine nitrogen, pyrroles's nitrogen and quaternary nitrogen, and explanation nitrogen element directly perceived has not only been doped in redox graphene, and also doping enters in titanium dioxide.
Test case 3
Carry out absorption spectrum test to the product obtained in embodiment 1, comparative example 1-3, test collection of illustrative plates as shown in Figure 3.
Test case 4
Catalytic activity test is carried out to the product obtained in embodiment 1, comparative example 1-3, test condition: under radiation of visible light, the degradation rate of methylene blue in 180min.The degradation rate test result of methylene blue as shown in Figure 4.It is to be appreciated that the blank group in Fig. 4 represents: do not add any catalyst or material in methylene blue.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among protection scope of the present invention.
Claims (10)
1. a graphene composite material, is characterized in that, comprises N doping redox graphene and nitrogen-doped titanium dioxide nano line; The draw ratio of described titanium dioxide nano thread is greater than 10.
2. graphene composite material according to claim 1, is characterized in that, the mass ratio that described N doping redox graphene accounts for described nitrogen-doped titanium dioxide nano line is 1wt% ~ 15wt%.
3. a preparation method for graphene composite material, is characterized in that, comprises the steps:
S1, prepare titanium dioxide nano thread;
S2, described titanium dioxide nano thread, urea, graphene oxide are disperseed to be placed in hydrothermal reaction kettle by the mass ratio of 1 ~ 10:200 ~ 600:1 ~ 10 in water, 180 ~ 220 DEG C of reactions 5 ~ 20 hours.
4. the preparation method of graphene composite material according to claim 3, is characterized in that, in described step S1, described titanium dioxide nano thread is anatase titanium dioxide nano wire.
5. the preparation method of the graphene composite material according to claim 3 or 4, is characterized in that, in described step S1, the draw ratio of described titanium dioxide nano thread is greater than 10.
6. the preparation method of the graphene composite material according to any one of claim 3-5, is characterized in that, described step S1 comprises further:
S11, added by titanium dioxide P25 in the aqueous solution of NaOH of 10mol/L ~ 20mol/L, configuration concentration is the mixed liquor A of 0.1M ~ 1M;
S12, described mixed liquor A is placed in hydrothermal reaction kettle, 150 DEG C ~ 220 DEG C reactions 12 ~ 72 hours, obtain mixed liquid B;
S13, described mixed liquid B carried out to centrifuge washing to eluate for neutral, be precipitated A;
S14, hydrogen ion exchange is carried out to described precipitate A, and centrifuge washing to eluate is neutral, is precipitated B after oven dry;
S15, described precipitate B to be calcined 4 hours under 600 DEG C of conditions, obtain described titanium dioxide nano thread.
7. the preparation method of graphene composite material according to claim 6, is characterized in that, in described step S14, the exchange reagent of described hydrogen ion exchange step is: concentration is the aqueous solution of nitric acid of 0.1mol/L ~ 0.5mol/L.
8. the preparation method of the graphene composite material according to any one of claim 3-7, is characterized in that, in described step S2, the mass ratio of described titanium dioxide nano thread, described urea, described graphene oxide is 10:500:1.
9. the preparation method of the graphene composite material according to any one of claim 3-8, is characterized in that, in described step S2, the condition of described hydro-thermal reaction is 200 DEG C of reactions 10 hours.
10. the preparation method of the graphene composite material according to any one of claim 3-9, is characterized in that, also comprises at least one in centrifugation step, washing step, drying steps after described step S2.
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