CN109529901A - A kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material - Google Patents
A kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 95
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 46
- 239000010936 titanium Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 60
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000010355 oscillation Effects 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002071 nanotube Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 10
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- B01J35/61—
Abstract
The present invention provides a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, carbon nano-tube material is pre-processed first, then it is reacted with ammonia water by carbon nanotube and nitrogen-doped carbon nanometer pipe material is prepared, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material is directly prepared finally by titanium dioxide is added；The nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material that the present invention is prepared can effectively reduce the problem of carbon nanotube is easily reunited, moreover, by the way that titanium dioxide is compound with nitrogen-doped carbon nanometer pipe, it can overcome the problems, such as titanium dioxide more difficult separation and recycling in use, simultaneously under the conditions of UV Light, there is more obvious catalytic degradation effect.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of nitrogen-doped carbon nanometer pipe composite titanium dioxide is compound
The preparation method of material.
Background technique
The research of carbon nanotube be it is extremely noticeable in current nano materials research field, it has a series of excellent
Point: have many advantages, such as that high mechanical strength, large specific surface area, conductivity are high, interfacial effect is strong, still, between carbon nanotube itself
There is very strong intermolecular force, and easily reunite, this has seriously affected its uniformly dividing in material and other solvents
The ability of dissipating, moreover, carbon nanotube possesses chemical inertness, and then it is caused to be restricted significantly using upper.
Nano titanium dioxide photocatalyst possesses more unique physics and chemical property, such as small-size effect, surface
Effect, quantum size effect, macro quanta tunnel effect etc., have always been considered as be it is a kind of close to ideal catalysis material it
One, but it there is also apparent disadvantages: band gap is big, only wavelength less than 400nm ultraviolet light and black light just may be used
To excite Ti0g to generate photo-generated carrier, it is allowed to show photocatalytic activity, how improves photocatalytic activity as far as possible, and
Its photoresponse is extended to visible-range, is always the important research content of field of titanium dioxide photocatalysis.
Summary of the invention
It is an object of the invention to: a kind of preparation side of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material is provided
Method can effectively reduce the problem of carbon nanotube is easily reunited, while enhance photocatalytic activity, moreover, by by two
Titanium oxide is compound with nitrogen-doped carbon nanometer pipe, can overcome titanium dioxide in use it is more difficult separation and recycling ask
Topic, while under the conditions of UV Light, there is apparent catalytic degradation effect.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, includes the following steps:
The pretreatment of S1, carbon nano-tube material: carbon nanotube is added in strong acid mixed solution, then under water bath condition,
Return stirring reaction, is added hydrogen peroxide and deionized water, and centrifuge separation after being washed with acetone soln, is dried the pre- place of acquisition
Carbon nano-tube material after reason；
The preparation of S2, nitrogen-doped carbon nanometer pipe material: the obtained carbon nanotube of step S1 and ammonium hydroxide are put into reactor,
Uniform stirring after the completion of stirring, dries simultaneously calcination processing, after the completion of calcining, it is cooled to 35 with the rate of temperature fall of 3 DEG C/min
DEG C, obtain nitrogen-doped carbon nanometer pipe material；
The preparation of S3, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material: the step S2 nitrogen-doped carbon being prepared is received
Nanotube material is add to deionized water, and supersonic oscillations 2h disperses nitrogen-doped carbon nanometer pipe, during supersonic oscillations,
After titanium dioxide and the oscillation of continual ultrasonic wave is added, it is stirred, after the completion of stirring, places it in vacuum oven,
Drying and processing, drying time 4-5h, drying temperature are 80-100 DEG C, and it is compound to obtain nitrogen-doped carbon nanometer pipe composite titanium dioxide
Material.
Preferably, strong acid mixed solution described in step S1 is sulfuric acid and nitric acid, and volume ratio 1:4 is mixed by strong acid
Close solution, can on carbon nano-tube material carboxyl grafting and hydroxyl, so as to improve bond strength between material interface and interface
Effect；
Preferably, water bath condition described in step S1, temperature is 90-100 DEG C, under water bath condition, makes carbon nanotube and strong
Sour mixed solution is heated evenly, and avoids the generation of bumping phenomenon；
Preferably, in return stirring reaction process described in step S1, mixing time 3-5h, mixing speed 500-700r/
Min, carbon nanotube can effectively be cut off by reacting cooperation mixed acid processing by return stirring, to reduce carbon nanotube major diameter
Than reducing carbon nanotube and mutually winding probability, increase its dispersion performance；
Preferably, ammonium hydroxide described in step S2 and its mass ratio of pretreated carbon nanotube are 5-10:1, are provided by ammonium hydroxide
The cloud density near nitrogen-atoms can be changed, so that it is fabulous to possess it in nitrogen source, the method for generating nitrogen-doped carbon nanometer pipe
Electronic effect and extremely superior photocatalysis performance；
Preferably, in calcination process described in step S2, it is first warming up to 450-500 DEG C, pre-burning 2-4h under nitrogen protection,
It is warming up to 700-750 DEG C again, calcines 3-6h, calcination process uses segmented mode, eliminates material by the process of pre-burning
Internal stress keeps material more stable, high-temperature calcination after low temperature presintering, the time required to reducing；
Preferably, its partial size of titanium dioxide described in step S3 makes two since it possesses biggish specific surface area for 19-23nm
Titanium oxide possesses higher photocatalysis performance, compound with nitrogen-doped carbon nanometer pipe by titanium dioxide, can significantly increase dioxy
Change the catalytic performance of titanium；
Preferably, ultrasound after titanium dioxide is added in stir process after addition titanium dioxide elder generation supersonic oscillations described in step S3
Wave vibrates 2h, during stir process, mixing speed 500-700r/min, mixing time 2-4h, at first supersonic oscillations
Reason, makes titanium dioxide be uniformly dispersed rapidly, after supersonic oscillations, stir process makes relatively large particle be uniformly dispersed.
Beneficial effect
1, the carbon nano-tube material pretreated without step S1, since it possesses relatively large draw ratio and relatively
Big outer surface is active, and easily mutually winding, to form reunion, seriously affects its dispersion performance and composite material between carbon pipe
Effect, pre-processed, carbon nanotube can be cut off by step S1, to reduce the draw ratio of carbon nanotube, reduced carbon and receive
The probability that mitron is mutually wound moreover can be on carbon nano-tube material after being pre-processed by S1, carboxyl grafting and hydroxyl
Base, so as to improve the effect of bond strength between material interface and interface.
2, by way of nitrogen-doped carbon nanometer pipe, the original chemical inertness of carbon nanotube is broken through, and utilize carbon nanometer
Biggish specific surface area of pipe itself, and then come into full contact with and carry out light-catalyzed reaction.
3, nitrogen-doped carbon nanometer pipe composite titanium dioxide is by titanium dioxide and biggish specific surface area nitrogen-doped carbon nanometer pipe
It is compound, photocatalytic activity and light-catalyzed reaction can be enhanced, to make it possess more superior photocatalysis performance, not only such as
This, by the way that titanium dioxide is compound with nitrogen-doped carbon nanometer pipe, can overcome titanium dioxide in use more difficult separation with
And the problem of recycling.
Detailed description of the invention
Fig. 1 be step S1 pretreatment front and back carbon nanotube SEM figure a, b be respectively carbon nanotube 100nm before pre-processing,
400nmSEM figure, c are carbon nanotube 400nmSEM figure after pretreatment；
Fig. 2 is the nitrogen-doped carbon nanometer pipe XPS spectrum figure that step S2 is prepared；
Fig. 3 is the nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material SEM figure that step S3 is prepared；
Fig. 4 be embodiment 1, embodiment 2, embodiment 3 prepare nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material carry out
Photocatalysis performance test curve figure；
Fig. 5 is that nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material prepared by comparative example 1 carries out photocatalysis performance test song
Line chart.
Specific embodiment
To facilitate the understanding of the present invention, below will be to invention is more fully described, still, the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein；On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
The present invention will be further described With reference to embodiment.
Embodiment 1
A kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, includes the following steps:
The pretreatment of S1, carbon nano-tube material: carbon nanotube is added in sulfuric acid and nitric acid mixed solution, sulphur in mixed solution
Acid, nitric acid volume ratio are 1:4, and then under water bath condition, bath temperature is 90 DEG C, return stirring reaction, return stirring reaction
In the process, mixing time 3h, mixing speed 500r/min, are added hydrogen peroxide and deionized water, and centrifuge separation is molten with acetone
After liquid washing, it is dried and obtains pretreated carbon nano-tube material；
The carbon nanotube SEM figure of above-mentioned steps S1 pretreatment front and back is as shown in Figure 1, a, b are respectively carbon nanometer before pre-processing in figure
Pipe 100nm, 400nmSEM scheme, and c is pretreated carbon nanotube 400nmSEM figure in figure, are schemed by a it is found that without pretreatment
The mutual wrapping phenomena of carbon nanotube it is more serious, by b figure it can be seen that carbon nanotube wrapping phenomena become apparent, by figure c can
Know, by pretreated carbon nanotube, has been grafted carboxyl and hydroxyl on the carbon nanotubes, and carbon nanotube is by pretreatment
After be cut off, so that carbon nanotube be avoided mutually to wind；
The preparation of S2, nitrogen-doped carbon nanometer pipe material: the obtained carbon nanotube of step S1 and ammonium hydroxide are added in reactor,
Ammonium hydroxide and its mass ratio of pretreated carbon nanotube are 5:1, and uniform stirring after the completion of stirring, dries simultaneously calcination processing, calcining
In treatment process, it is first warming up to 450 DEG C, pre-burning 2h under nitrogen protection, then be warming up to 700 DEG C, calcines 3h, calcining
After the completion, it is cooled to 35 DEG C with the rate of temperature fall of 3 DEG C/min, obtains nitrogen-doped carbon nanometer pipe material；
Nitrogen-doped carbon nanometer pipe XPS spectrum figure that above-mentioned steps S2 is prepared as shown in Fig. 2, nitrogen, oxygen, carbon content can be with
It is determined by XPS spectrum figure, XPS spectrum figure has shown that the content of nitrogen, oxygen, carbon in obtained nitrogen-doped carbon nanometer pipe is respectively
1.95%, 2.09%, 95.96%, and then prove in N doping to carbon nano-tube material；
The preparation of S3, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material: the step S2 nitrogen-doped carbon being prepared is received
Nanotube material is add to deionized water, and supersonic oscillations 2h disperses nitrogen-doped carbon nanometer pipe, during supersonic oscillations,
Titanium dioxide is added, titanium dioxide partial size is that 19nm is stirred, stir process process after continual ultrasonic wave vibrates 2h
In, mixing speed 500r/min, mixing time 2h after the completion of stirring, are placed it in vacuum oven, drying and processing,
Drying time is 4h, and drying temperature is 80 DEG C, obtains nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material；
Nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material SEM that above-mentioned steps S3 is prepared figure as shown in figure 3, by
SEM schemes it is found that by step S3, and titanium dioxide is successfully combined to nitrogen-doped carbon nanometer pipe material surface, and nitrogen-doped carbon nanometer
The initial characteristics when shape feature of pipe composite titanium dioxide material still keeps S2 that nitrogen-doped carbon nanometer pipe material is prepared.
Embodiment 2
A kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, includes the following steps:
The pretreatment of S1, carbon nano-tube material: carbon nanotube is added in sulfuric acid and nitric acid mixed solution, sulphur in mixed solution
Acid, nitric acid volume ratio are 1:4, and then under water bath condition, bath temperature is 95 DEG C, return stirring reaction, return stirring reaction
In the process, mixing time 4h, mixing speed 600r/min, are added hydrogen peroxide and deionized water, and centrifuge separation is molten with acetone
After liquid washing, it is dried and obtains pretreated carbon nano-tube material；
The preparation of S2, nitrogen-doped carbon nanometer pipe material: the obtained carbon nanotube of step S1 and ammonium hydroxide are added in reactor,
Ammonium hydroxide and its mass ratio of pretreated carbon nanotube are 8:1, and uniform stirring after the completion of stirring, dries simultaneously calcination processing, calcining
In treatment process, it is first warming up to 475 DEG C, pre-burning 3h under nitrogen protection, then be warming up to 725 DEG C, calcines 4.5h, forge
After the completion of burning, it is cooled to 35 DEG C with the rate of temperature fall of 3 DEG C/min, obtains nitrogen-doped carbon nanometer pipe material；
The preparation of S3, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material: the step S2 nitrogen-doped carbon being prepared is received
Nanotube material is add to deionized water, and supersonic oscillations 2h disperses nitrogen-doped carbon nanometer pipe, during supersonic oscillations,
Titanium dioxide is added, titanium dioxide partial size is that 19nm is stirred, stir process process after continual ultrasonic wave vibrates 2h
In, mixing speed 600r/min, mixing time 3h after the completion of stirring, are placed it in vacuum oven, drying and processing,
Drying time is 4.5h, and drying temperature is 90 DEG C, obtains nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material.
Embodiment 3
A kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, includes the following steps:
The pretreatment of S1, carbon nano-tube material: carbon nanotube is added in sulfuric acid and nitric acid mixed solution, sulphur in mixed solution
Acid, nitric acid volume ratio are 1:4, and then under water bath condition, bath temperature is 100 DEG C, return stirring reaction, return stirring reaction
In the process, mixing time 5h, mixing speed 700r/min, are added hydrogen peroxide and deionized water, and centrifuge separation is molten with acetone
After liquid washing, it is dried and obtains pretreated carbon nano-tube material；
The preparation of S2, nitrogen-doped carbon nanometer pipe material: the obtained carbon nanotube of step S1 and ammonium hydroxide are added in reactor,
Ammonium hydroxide and its mass ratio of pretreated carbon nanotube are 10:1, and uniform stirring after the completion of stirring, is dried simultaneously calcination processing, forged
It burns in treatment process, is first warming up to 500 DEG C, pre-burning 4h under nitrogen protection, then be warming up to 750 DEG C, calcine 6h, forge
After the completion of burning, it is cooled to 35 DEG C with the rate of temperature fall of 3 DEG C/min, obtains nitrogen-doped carbon nanometer pipe material；
The preparation of S3, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material: the step S2 nitrogen-doped carbon being prepared is received
Nanotube material is add to deionized water, and supersonic oscillations 2h disperses nitrogen-doped carbon nanometer pipe, during supersonic oscillations,
Titanium dioxide is added, titanium dioxide partial size is that 23nm is stirred, stir process process after continual ultrasonic wave vibrates 2h
In, mixing speed 700r/min, mixing time 4h after the completion of stirring, are placed it in vacuum oven, drying and processing,
Drying time is 5h, and drying temperature is 100 DEG C, obtains nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material.
Embodiment 4
The nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material that embodiment 1, embodiment 2, embodiment 3 are prepared carries out
Catalytic performance test, with ultraviolet light be unique light source, by degrade methyl blue test and assess to its performance, respectively by embodiment 1,
The nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material 20mg that embodiment 2, embodiment 3 are prepared is added to mass concentration
To place it under dark condition in the methyl blue solution of 40mg/L, magnetic agitation 60min, to make nitrogen-doped carbon nanometer
Pipe dioxide composite titanium composite material and methyl blue adsorption desorption balance, and it is anti-to place it in progress illumination under the ultraviolet light of 500W
It answers, in reaction process, maintains it under stirring condition, every 10min, take out 4ml liquid, be placed on UV, visible light spectrophotometric
Meter measures its absorbance, obtains the concentration of methyl blue at this time by the absorbance of maximum absorption wavelength；
Fig. 4 is that ordinate is the concentration and initial concentration ratio that the every 10min of methyl blue solution is measured, and abscissa is the curve of time
Figure, its catalysis of the nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material that embodiment 1, embodiment 2, embodiment 3 are prepared
Performance test curve respectively corresponds curve a in figure, curve c, curve b, as shown in Figure 4, under preceding 60min dark condition, curve
A, curve b, curve c are relatively gentle, illustrate that methyl blue concentration remains unchanged substantially under dark condition, the ultraviolet light light after 60min
According under the conditions of, curve a, curve b, curve c are substantially reduced, and show nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material
Under the conditions of UV Light, start catalytic degradation methyl blue, curve a, curve b, the curve c longitudinal axis be reduced to zero consumed by the time
Respectively 110min, 130min, 140min, curve c compared to curve a, curve b under the conditions of UV Light, downward trend
Obviously, and the curve longitudinal axis is reduced to 0 at first, the embodiment 1 corresponding compared to curve a of embodiment 2 corresponding to illustrative graph c and
The nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material photocatalytic degradation effect that the corresponding embodiment 3 of curve b is prepared
Obviously, from the foregoing, it will be observed that embodiment 1, embodiment 2, nitrogen-doped carbon nanometer pipe composite titanium dioxide composite wood prepared by embodiment 3
Expect photocatalytic degradation capability most preferably embodiment 2.
Comparative example 1
The present embodiment provides a kind of preparation methods of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, successively include following
Step:
The pretreatment of S1, carbon nano-tube material: carbon nanotube is added in sulfuric acid and nitric acid mixed solution, sulphur in mixed solution
Acid, nitric acid volume ratio are 1:10, and then under water bath condition, bath temperature is 70 DEG C, return stirring reaction, return stirring reaction
In the process, mixing time 2h, mixing speed 900r/min, are added hydrogen peroxide and deionized water, and centrifuge separation is molten with acetone
After liquid washing, it is dried and obtains pretreated carbon nano-tube material；
The preparation of S2, nitrogen-doped carbon nanometer pipe material: the obtained carbon nanotube of step S1 and ammonium hydroxide are added in reactor,
Ammonium hydroxide and its mass ratio of pretreated carbon nanotube are 14:1, and uniform stirring after the completion of stirring, is dried simultaneously calcination processing, forged
It burns in treatment process, under nitrogen protection, is warming up to 750 DEG C, 7h is calcined, after the completion of calcining, by it with 10 DEG C/min's
Rate of temperature fall cools to 40 DEG C, obtains nitrogen-doped carbon nanometer pipe material；
The preparation of S3, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material: the step S2 nitrogen-doped carbon being prepared is received
Nanotube material is add to deionized water, and supersonic oscillations 2h disperses nitrogen-doped carbon nanometer pipe, during supersonic oscillations,
Titanium dioxide is added, titanium dioxide partial size is 35nm, and after the oscillation of continual ultrasonic wave, is stirred, mixing speed is
400r/min, mixing time 5h after the completion of stirring, are placed it in vacuum oven, drying and processing, drying time 3h,
Drying temperature is 120 DEG C, obtains nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material.
The present embodiment is prepared nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material and carries out according to 4 method of embodiment
Methyl blueness test, the difference is that, the nitrogen-doped carbon that embodiment 1, embodiment 2, embodiment 3 are prepared
Nanotube dioxide composite titanium composite material 20mg is substituted for the nitrogen-doped carbon nanometer pipe dioxide composite that comparative example 1 is prepared
Titanium composite material 20mg, other Methyl blueness test process are same as Example 4.
Fig. 5 is that ordinate is the concentration and initial concentration ratio that the every 10min of methyl blue solution is measured, and abscissa is the time
Nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material its catalytic performance test curve graph that comparative example 1 is prepared, by Fig. 5
It is found that the photocatalytic degradation time for the nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material that comparative example 1 is prepared is
160min, it is compound compared to the nitrogen-doped carbon nanometer pipe composite titanium dioxide that embodiment 1, embodiment 2, embodiment 3 are prepared
The photocatalytic degradation efficiency of material is substantially reduced, so that the photocatalytic degradation time be caused to increase.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes
It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and
In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is
Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment
Change, modification and differentiation, still fall within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material, which is characterized in that including walking as follows
It is rapid:
The pretreatment of S1, carbon nano-tube material: carbon nanotube is added in strong acid mixed solution, then under water bath condition,
Return stirring reaction, is added hydrogen peroxide and deionized water, and centrifuge separation after being washed with acetone soln, is dried the pre- place of acquisition
Carbon nano-tube material after reason；
The preparation of S2, nitrogen-doped carbon nanometer pipe material: the obtained carbon nanotube of step S1 and ammonium hydroxide are put into reactor,
Even stirring after the completion of stirring, dries simultaneously calcination processing, after the completion of calcining, it is cooled to 35 with the rate of temperature fall of 3 DEG C/min
DEG C, obtain nitrogen-doped carbon nanometer pipe material；
The preparation of S3, nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material: the step S2 nitrogen-doped carbon being prepared is received
Nanotube material is add to deionized water, and supersonic oscillations 2h disperses nitrogen-doped carbon nanometer pipe, during supersonic oscillations,
After titanium dioxide and the oscillation of continual ultrasonic wave is added, it is stirred, after the completion of stirring, places it in vacuum oven,
Drying and processing, drying time 4-5h, drying temperature are 80-100 DEG C, and it is compound to obtain nitrogen-doped carbon nanometer pipe composite titanium dioxide
Material.
2. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, strong acid mixed solution described in step S1 is sulfuric acid and nitric acid, volume ratio 1:4.
3. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, water bath condition described in step S1, temperature is 90-100 DEG C.
4. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, in return stirring reaction process described in step S1, mixing time 3-5h, mixing speed 500-700r/
min。
5. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, ammonium hydroxide described in step S2 and its mass ratio of pretreated carbon nanotube are 5-10:1.
6. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, ammonium hydroxide described in step S2 and its mass ratio of pretreated carbon nanotube are 8:1.
7. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, in calcination process described in step S2, is warming up to 450-500 DEG C, pre-burning 2-4h under nitrogen protection, then will heat up
To 700-750 DEG C, 3-6h is calcined.
8. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, its partial size of titanium dioxide described in step S3 is 19-23nm.
9. a kind of preparation method of nitrogen-doped carbon nanometer pipe dioxide composite titanium composite material according to claim 1,
It is characterized in that, stir process after addition titanium dioxide elder generation supersonic oscillations described in step S3, ultrasonic wave after titanium dioxide is added
Vibrate 2h, during stir process, mixing speed 500-700r/min, mixing time 2-4h.
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