CN102718491A - Nanotube / powder blending phase metal oxide - Google Patents
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- CN102718491A CN102718491A CN2012100524775A CN201210052477A CN102718491A CN 102718491 A CN102718491 A CN 102718491A CN 2012100524775 A CN2012100524775 A CN 2012100524775A CN 201210052477 A CN201210052477 A CN 201210052477A CN 102718491 A CN102718491 A CN 102718491A
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Abstract
The invention discloses a nanotube / powder blending phase metal oxide, and belongs to the field of nanometer material science. Ti, Zn, Al, Zr, Ni, Co or alloy sheet thereof treated with surface polishing and cleaning are first anodized in an electrolyte to obtain a regular nanotube array film; the film is peeled, washed, dried and treated with mechanical milling to obtain a nanotube / powder blending phase; the material is treated with high temperature annealing before or after ball mill, or directly treated with high energy ball milling to obtain an optimum crystal type suitable for practical application. The nanometer material has advantages of large specific surface area, high surface activity, comprehensive multiple forms, simple preparation process, controllable component ratio, and convenience for doping, load and sensitized modification; besides, the material can be directly applied in dispersion usage or attached to different substrates for usage, is flexible and convenient, and has outstanding performance and application advantages in the fields of photocatalysis, solar cell, semiconductor device, sensor material, battery material and coating and polymer additive, etc.
Description
Technical field
The present invention relates to a kind of nanotube/powder blend attitude MOX, belong to the nanometer material science field.
Background technology
The development of Materials science is the force at the core that promotes social progress, and the lifting in each stage all is accompanied by the appearance of more advanced material and popularizes in history.Nanometer material science though developing history is of short duration, does not create the revolutionary achievement that is enough to change the world as a kind of emerge science technology, and it is shown up prominently in every field already.On some conventional arts, promote efficient on the one hand significantly; On the other hand, develop many new technologies by it and embody more and more significant values just gradually.Nanometer material science importance is unquestionable, and it will lead the development in science and technology of future direction.
Metal, as a kind of traditional material of making countless contributions for the mankind, we are incomparably familiar already.And in phase of history once, MOX is detested by we are human, because they always appear with full of stains or spots rusty stain, the metallic corrosion problem is all brought heavy losses to society every year.People are also always trying every means more simply from its oxide compound---obtain metal simple-substance the mineral.And nowadays, the development let us of nanometer material science recognizes that MOX not only is not good for nothing, and fully develops talents at present.Nano-metal-oxide will play a significant role in field of novel such as catalytic material, energy and material, intelligent materials.To be expected to solve at present some key issues such as resource, the energy, pollution if realize these nanotechnology practical applications, and can really bring the mankind into efficient, intelligent, a green beautiful world.
1972, Japanese scholar Fujishima A and Honda K found to utilize TiO first
2The monocrystalline electrode can be realized this phenomenon of photocatalysis Decomposition water generates hydrogen, thereby has disclosed the possibility of utilizing the direct hydrogen production by water decomposition of sun power.But its low efficient has fundamentally negated the actual application value of this invention.Along with the development of nanotechnology, scholars dare to attempting, and prepare the type material of various different nanostructures, start various nano modification methods, now till, the scientist of the U.S. prepares the TiO of gained
2Nano-tube array can have been brought up to phototranstormation efficiency more than 12%, is expected to realize the practical application of photolysis water hydrogen, has opened up the new road of green energy resource development and use.
Nanometer, symbol nm is a unit of length, 1nm=10
-9M.Nano material is meant the material that in three-dimensional space, has at least one dimension to be in nanoscale scope (1-100nm) or to be made up of as elementary cell them.Though notion is simple, regrettably, we still have too many unknown the beautiful hereto nanometer world.Thus, particularly necessary to some basic research works of nano material after yearning for the bright prospect of nanometer era, comprise that the preparation of nano material is synthetic, functionalization, modification to be raising the efficiency, and use-pattern even new Application Areas.As how simple preparation technology and method of modifying obtains efficiently, low cost, the nano material being convenient to utilize become problem origin.
Existing big quantity research proof TiO
2, ZnO or NiCo
2O
4Etc. many MOXs or compound is the semiconductor material of excellent property, in semiconducter device, photocatalyst applications, bright prospects is arranged, and its structure nanoization is the feasible solution that scholars generally acknowledge to raise the efficiency; Also have the nanomorphic of these materials of research to be used for battery material, sensitive material such as gas sensor, humidity sensor, wait the performance boost of each advanced field or traditional field such as coating, macromolecular material additive, effect is obvious.Yet these achievement major parts also can only be embodied in the middle of the breadboard research, and practical application still has long term distance in the productive life.Subject matter concentrate on material preparation process complicacy, Properties Control be stranded can, cost is high; Material property is single, and efficient also has much room for improvement; And environment for use is harsh, is of limited application.
Like TiO
2, the about 3.2eV of its anatase octahedrite phase energy gap, stable performance, safety non-toxic have wide application prospects in numerous areas such as photochemical catalysis, solar cell, semiconducter device.But conventional block materials or common nano-powder material photoelectric transformation efficiency are not high, and performance is low; And because energy gap is bigger, can only absorb the higher UV-light of energy, and in the earth surface sunlight this part account for 5% less than.Therefore, seek rational material structure obtaining high transformation efficiency, simple preparation method, and all are keys of material practical application to effective method of modifying of material visible-lightization etc.
To these problems, the present invention combines with new technology from comparatively sophisticated traditional technology, seeks material prepn and method of modifying; From the relation of material structure and performance, performance material compound state advantage improves material property; In conjunction with practical application, start out the nanotube/powder blend metal oxide materials that can be used for a plurality of fields such as photochemical catalysis, solar cell, semiconducter device, battery material, sensor material, coating and additive with the preparation of methods such as conventional anodization, ball milling, annealing.
Summary of the invention
The object of the present invention is to provide that a kind of preparation technology is simple, to be easy to modification, performance and application advantage outstanding, be suitable for nanotube/powder blend attitude MOX and preparation technology's and methods for using them thereof in photocatalytic applications, photolysis water hydrogen, solar cell, sensor material, battery material and fields such as coating, additive.
The technical scheme that the present invention is taked for its technical problem of solution is:
1, a kind of nanotube/powder blend attitude MOX is characterized in that, structure is nanotube, nano powder blend state.
2, aforesaid a kind of nanotube/powder blend attitude MOX is characterized in that its preparation method may further comprise the steps:
The sheet metal of step 1, sample pre-treatments: 0.02mm～2mm thickness is cut into 0.5cm
2～100cm
2Size also flattens; Preparation contains HF, HNO
3, H
2The polishing fluid of O, chemical rightenning 0.5min～3min; After the water flushing, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning successively; Cold wind dries up or dries subsequent use naturally;
Step 4, realization material crystal conversion: get the preceding nano-tube array rete of ball milling; Or gained nanotube behind the ball milling/powder blend attitude MOX is warming up to 200 ℃～800 ℃, the product of naturally cooling acquisition specific crystal formation or different crystal forms blend attitude behind insulation 0.5h～10h.
3, aforesaid a kind of nanotube/powder blend attitude MOX is characterized in that, directly dispersed uses, or attached to using on flat substrate, rough base or the flexible substrates.
4, aforesaid a kind of nanotube/powder blend attitude MOX is characterized in that, described sheet metal is Ti, Zn, Al, Zr, Ni, Co or its alloy.
5, aforesaid a kind of nanotube/powder blend attitude MOX is characterized in that described inert material is Pt, Au, Ag, Cu, stainless steel substrates or graphite.
6, aforesaid a kind of nanotube/powder blend attitude MOX is characterized in that, described anodic oxidation electrolyte, solute are that massfraction is 0.1%～5% NH
-4F, solvent are terepthaloyl moietie and H
2The O mass ratio is the mixed solution of 79:1～29:1.
Compared with prior art, the invention has the beneficial effects as follows: this kind nanotube/powder blend MOX has that specific surface area is big, surfactivity is high, and comprehensive polymorphic advantage improves series of advantages such as performance; And preparation technology is simple, selects different voltages, temperature, time in the anodic oxidation, or different electrolytes composition or proportioning, the pipe range of may command nanotube, caliber, thickness of pipe and pipe formation attitude, the convenient film of Nano tube array that obtains the desired structure parameter; Select different material, ball and solvent in the ball milling, and different ratios, with different ball milling speed and ball milling time control nanotube/nano powder ratio, thereby obtain different performance; Be easy to doping, load, sensitization modification etc. through anodic oxidation, ball milling, each step of annealing in the preparation process; Dusty material uses flexibly, can disperse to use, and also can be carried on flat substrate, rough base or the flexible substrates and use.This nano material all has outstanding performance and application advantage at aspects such as photocatalytic applications, solar cell, sensor material, battery material, coating, additives.
Description of drawings
Fig. 1 is a material prepn schema of the present invention.
Fig. 2 is an anodic oxidation device synoptic diagram of the present invention.
Fig. 3 comes off and exsiccant TiO through ultrasonic among the present invention
2Film of Nano tube array.
Fig. 4 be among the present invention behind the 5h ball milling nanotube/powder blend TiO
2Sem photograph.
Fig. 5 is nanotube among the present invention/powder blend TiO
2Disperse to be applied to photocatalytic degradation tropeolin-D and P25 type TiO
2Contrast.
Fig. 6 is nanotube among the present invention/powder blend TiO
2Be attached to slide glass photocatalytic degradation tropeolin-D and P25 type TiO
2Contrast.
Fig. 7 is that nanotube among the present invention/powder blend MOX is attached to and is applied to the gas sensor synoptic diagram on the grid electrode.
Fig. 8 is nanotube of the present invention/powder blend TiO
2Preparation efficient gas transmitter responds 50ppm formaldehyde.
Embodiment
The present invention is a kind of nanotube/powder blend MOX; Obtain blend attitude metal oxide nano-material through anodic oxidation, ball milling, high temperature annealing; Increase substantially material property, in fields such as photochemical catalysis, battery material, sensor material, additive, have outstanding performance and application advantage.
Below in conjunction with accompanying drawing and specific embodiment the present invention is explained further details.
Embodiment one:
Nanotube/powder blend TiO
2Preparation, preparation flow is shown in accompanying drawing 1:
1, pre-treatment: the metal Ti thin slice of certain thick 0.02mm, be cut into the 2cm*3cm size, flatten and be placed on volume ratio HF:HNO
3: H
2In the polishing fluid of O=1:4:5, chemical rightenning 1min; After the big water gaging flushing, use acetone, absolute ethyl alcohol, each ultrasonic cleaning 10min of deionized water successively; Cold wind dries up subsequent use.
2, anodic oxidation prepares TiO
2Film of Nano tube array: in the electrolytic solution, be anode through the Ti of pre-treatment sheet, stainless steel substrates or Pt sheet are counter electrode, add to obtain regular film of Nano tube array behind the 60V voltage anodic oxidation 24h.The electrolytic solution solute is 0.3%wtNH
4F, solvent are that quality is than terepthaloyl moietie: H
2The O=49:1 mixed solution.Shown in anodic oxidation device such as the accompanying drawing 2.The sample anodes oxidation finishes that the back is ultrasonic to come off until rete, and dry for standby after washing 2 to 3 times with the absolute ethyl alcohol bubble.Obtain product shown in accompanying drawing 3.
3, ball milling obtains nanotube/powder blend attitude: quality is than absolute ethyl alcohol, TiO
2, agate ball=1:2:20 places polytetrafluoroethyltank tank to carry out mechanical ball milling; Behind the ball milling 5h, oven dry separates the ball material, obtains nanotube/powder blend attitude TiO
2Material.
Gained anatase-phase nano pipe/powder blend attitude TiO
2The visual inspection powder shaped that is white in color, its microstructure is nanotube and nano powder blend state shown in sample scanning electron microscope diagram sheet in the accompanying drawing 4.
Show gained nanotube/powder blend TiO through X-ray diffraction analysis
2Change Detitanium-ore-type into by amorphous state, the effect of high-energy ball milling has realized the transformation of material crystal formation.
Embodiment two:
Annealing realizes crystal conversion:
In the present embodiment, obtain TiO by embodiment 1 same condition
2Behind the film, same ball milling condition ball milling 0.5h has obtained nanotube/powder blend TiO equally
2X-ray diffraction analysis shows that it is the anatase octahedrite phase that the part material transition is arranged.
Utilize retort furnace with gained nanotube/powder blend attitude TiO
2Be warming up to 600 ℃ under the air atmosphere, naturally cooling behind the insulation annealing 2h.Show through X-ray diffraction analysis, obtained anatase octahedrite mutually with the rutile nanotube of blend crystal formation/powder blend attitude TiO mutually
2
Embodiment three:
Ball milling obtains the nanotube/powder blend TiO of different components ratio
2:
In the present embodiment, obtain TiO by embodiment 1 same condition
2Behind the film, 450 ℃ of annealing 2h change the anatase octahedrite phase into; Quality is than absolute ethyl alcohol, TiO
2, agate ball=1:2:20 places polytetrafluoroethyltank tank, carries out mechanical ball milling 0.5h, 5h, 10h respectively.
Through scanning electron microscope analysis, all obtained nanotube/powder blend TiO through the ball milling of different time
2And along with the ball milling asynchronism(-nization), nanotube, two kinds of component structures of nano powder and content change, and the ball milling time is long more, and the residue pipe is short more, and content is few more; The specific area measuring also specific surface area of surface product also changes thereupon, shown in following table, increases with the ball milling time, and the product specific surface area constantly increases and is tending towards a saturation value.Explanation can be controlled each parameter easily, thereby reach the adjusting material property in preparation thus, improves the purpose of application efficiency according to reality.
Table different time milled sample specific surface area relatively
| Time/h | Specific surface area/m 2G -1 |
| 0 | 27.87 |
| 0.5 | 32.47 |
| 5 | 42.14 |
| 10 | 42.70 |
The nanotube that the present invention relates to/powder blend attitude TiO
2Surfactivity is high, gives full play to each effect of nano material and blend attitude advantage, and the effect of each several part performance synthesis can effectively improve photoelectric transformation efficiency, and photocatalytic activity is high; And in the preparation process of material, make things convenient for modification, improve whole efficiency; Owing to have the effect of higher surfactivity and mixed state comprehensive action, application has than conventional block materials or the common higher efficient of nano-powder material too at aspects such as gas sensor, battery materials.In the practical application, the powdered material can disperse to use, and also can adopt the mode of filming to load on the various complex surfaces and use, even can use the flexible substrates load, widens use range greatly.Can be used for fields such as photochemical catalysis, solar cell, semiconducter device, gas sensor, battery material, additive, outstanding performance and application advantage are all arranged.
Following embodiment will further specify the use of material.
Embodiment four:
The anatase-phase nano pipe that the present invention relates to/powder blend attitude TiO
2Directly disperse to be applied to photocatalytic degradation tropeolin-D:
Adopt the nanotube/powder blend attitude TiO of preparation gained in the embodiment of the invention one
2Degraded tropeolin-D, the detailed process of photochemical catalysis experiment is: take by weighing 0.1g nanotube/powder blend TiO
2Material, putting into 20mL concentration is methyl orange solution and the stirring and evenly mixing of 10mg/L; Soaking 30min makes material and tropeolin-D reach adsorption equilibrium; Adopt the 300W high voltage mercury lamp radiation, reaction set time section utilizes ultraviolet-visible pectrophotometer to measure the solution absorbance variation.
Prepare the tropeolin-D standardized solution of a series of concentration, measure it in the absorbancy that maximum absorption wavelength (510nm) is located with ultraviolet-visible pectrophotometer, match can be confirmed the linear relationship between absorbancy and the concentration.The residual concentration of tropeolin-D can be calculated by this linear equation in the solution after the material light catalysis degraded.The residual concentration of each time period and starting point concentration comparison can obtain corresponding degradation rate.
Accompanying drawing 6 is for adopting nanotube of the present invention/powder blend TiO
2Photocatalytic degradation tropeolin-D and P25 contrast.A is P25 type TiO
2, German Degussa company produces; B is the nanotube/powder blend TiO that the present invention relates to
2By figure, the same terms adopts nanotube of the present invention/powder blend TiO down
2Photocatalytic degradation methyl orange solution, effect are apparently higher than P25, and the short period of time degradation rate just can reach 65%, prove absolutely nanotube/powder blend TiO
2Photocatalysis performance is good.
Embodiment five:
The anatase-phase nano pipe that the present invention relates to/powder blend attitude TiO
2Be attached to and be applied to photocatalytic degradation tropeolin-D on the sheet glass:
Material load preparation: the nanotube/powder blend attitude TiO that takes by weighing preparation gained in the embodiment of the invention one
20.1g adding the mass ratio for preparing in advance is the solution 2mL of Macrogol 2000 0: water=1:1, dropper is added dropwise to 2 glycerine, uses agate to grind the crucible grinding and evenly processes slurry; Use glass stick in skim on the blade coating equably on the simple glass slide glass of 25mm*75mm, place 200 ℃ of sintering 2h behind 100 ℃ the loft drier oven dry 12h.
Photochemical catalysis experiment: identical with embodiment two; The sample for preparing is put into the methyl orange solution that 20mL concentration is 10mg/L; After immersion 30min makes material and tropeolin-D reach adsorption equilibrium; Adopt the 300W high voltage mercury lamp radiation, reaction set time section utilizes ultraviolet-visible pectrophotometer to measure the solution absorbance variation, and calculates degradation rate.
Use under the P25 similarity condition to experimentize, compare with it, the result is shown in accompanying drawing 7, and C is P25, and D is the nanotube/powder blend TiO that the present invention relates to
2It is thus clear that the same terms adopts the nanotube/powder blend TiO that the present invention relates to down
2Be attached to photocatalytic degradation methyl orange solution on the sheet glass, effect is apparently higher than P25, and illumination 5h degradation rate just can reach 67%, proves absolutely nanotube/powder blend TiO
2Be attached to and be applied to photochemical catalysis in the substrate, effect is obvious, excellent property.
Embodiment six:
The anatase-phase nano pipe that the present invention relates to/powder blend attitude TiO
2Be applied to gas sensor:
Use the nanotube/powder blend attitude TiO of preparation gained in the embodiment of the invention one
2The preparation gas sensor, substruction is shown in accompanying drawing 8.The preparation process: (1) plates two interlaced but discontiguous grid electrodes on the dielectric base of certain intensity, and connects lead, makes substrate; (2) adopt the nanotube/powder blend attitude TiO that the present invention relates to
2, add an amount of Terpineol 350 and mix and process slurry; (3) slurry applies on substrate and forms certain thickness rete, and sintering just can be made and becomes simple gas sensor under optimal temperature.Measure change in electric between two electrodes, can reflect the variation of gas concentration in the peripheral atmosphere.
Use nanotube/powder blend attitude TiO among the present invention
2Made gas sensor under ultraviolet lighting, the signal response of PARA FORMALDEHYDE PRILLS(91,95).The gas-sensitive property of the direct corresponding gas sensor of electrical signal changes, and gas sensor is connected in the testing cassete, and under formaldehydeless starting condition, signal shows as a stationary value; When the change atmosphere was 50ppm formaldehyde, signal changed the back rapidly and keeps stable; Purge testing cassete, along with atmosphere is recovered, signal also recovers at short notice gradually.
Thus it is clear that, adopt nanotube/powder blend attitude TiO among the present invention
2The gas sensor response of preparation gained is sensitive rapidly, the gas of lower concentration is changed also can reflect, and responding range is wide.Nanotube among the present invention/powder blend attitude TiO
2It is nano-TiO
2A kind of new form, the nano-TiO common of existing with it
2Powdered material is compared, and its structure is special, has bigger specific surface area and stronger adsorptive power, is suitable for multiple condition, thereby has more using value.And under UV-irradiation, adsorb nanotube/powder blend attitude TiO in the present invention
2Pollution substance on the gas sensor just can be removed efficiently.In actual the use, this transmitter can keep stable performance because of automatic cleaning action, thereby keeps original detectivity.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every technical spirit adopts the technical scheme that is equal to replacement or equivalent transformation formation to above embodiment according to the present invention, all still belongs in the protection domain of technical scheme of the present invention.
Claims (6)
1. nanotube/powder blend attitude MOX is characterized in that, structure is nanotube, nano powder blend state.
2. a kind of nanotube according to claim 1/powder blend attitude MOX is characterized in that its preparation method may further comprise the steps:
The sheet metal of step 1, sample pre-treatments: 0.02mm～2mm thickness is cut into 0.5cm
2～100cm
2Size also flattens; Preparation contains HF, HNO
3, H
2The polishing fluid of O, chemical rightenning 0.5min～3min; After the water flushing, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning successively; Cold wind dries up or dries subsequent use naturally;
Step 2, anonizing prepare film of Nano tube array: the sheet metal through pre-treatment in the electrolytic solution is an anode, is counter electrode with the noble electrode, adds 10V～120V voltage and carries out the regular film of Nano tube array that anodic oxidation 1h～120h obtains adequate thickness; The electrolytic solution solute is NH
-4F, solvent are terepthaloyl moietie and H
2The mixed solution of O; The ultrasonic shake of rete is fallen or peels off, wash 2 to 3 times with the absolute ethyl alcohol bubble after oven dry;
Step 3, acquisition nanotube/powder blend attitude: metal oxide nanotubes array film, agate ball place ball grinder with mass ratio 50:1～1:20, add solvent mechanical ball milling 10min～48h; The ball material is separated in loft drier oven dry back, obtains nanotube/powder blend attitude metal oxide materials;
Step 4, realization material crystal conversion: get the preceding nano-tube array rete of ball milling; Or gained nanotube behind the ball milling/powder blend attitude MOX is warming up to 200 ℃～800 ℃, the product of naturally cooling acquisition specific crystal formation or different crystal forms blend attitude behind insulation 0.5h～10h.
3. a kind of nanotube according to claim 1/powder blend attitude MOX is characterized in that, directly dispersed uses, or attached to using on flat substrate, rough base or the flexible substrates.
4. a kind of nanotube according to claim 2/powder blend attitude MOX is characterized in that described sheet metal is Ti, Zn, Al, Zr, Ni, Co or its alloy.
5. a kind of nanotube according to claim 2/powder blend attitude MOX is characterized in that described inert material is Pt, Au, Ag, Cu, stainless steel substrates or graphite.
6. a kind of nanotube according to claim 2/powder blend attitude MOX is characterized in that, described anodic oxidation electrolyte, solute are that massfraction is 0.1%～5% NH
-4F, solvent are terepthaloyl moietie and H
2The O mass ratio is the mixed solution of 79:1～29:1.
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| CN106140126A (en) * | 2015-05-15 | 2016-11-23 | 蓝石科技(开曼)有限公司 | A kind of powder composite photocatalyst material and preparation method thereof |
| CN106521604A (en) * | 2016-10-17 | 2017-03-22 | 北京科技大学 | Method for preparing nano-porous structure on surfaces of stainless steel and cobalt alloy |
| US10661265B2 (en) * | 2013-05-24 | 2020-05-26 | Council Of Scientific & Industrial Research | Semiconductor-oxides nanotubes-based composite particles useful for dye-removal and process thereof |
| US10882754B2 (en) * | 2016-11-22 | 2021-01-05 | South China University Of Technology | Method for preparing transparent free-standing titanium dioxide nanotube array film |
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| US10882754B2 (en) * | 2016-11-22 | 2021-01-05 | South China University Of Technology | Method for preparing transparent free-standing titanium dioxide nanotube array film |
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| CN102718491B (en) | 2013-09-18 |
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