CN102718491B - Nanotube / powder blending phase metal oxide - Google Patents
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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, andconvenience 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 metal oxide, 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 although 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 already in every field.One side is significant raising efficiency on some conventional arts; On the other hand, develop many new technologies by it and embody just gradually more and more important value.Nanometer material science importance is unquestionable, and it will the Fashion of Future development in science and technology 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, metal oxide was by we mankind detested, because they always present 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, metal oxide not only is not good for nothing, and fully develops talents.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 the mankind be brought into efficient, intelligent, a green beautiful world.
1972, Japanese scholars Fujishima A and Honda K found to utilize TiO first
2Single Crystalline Electrodes 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 refers to the material that has at least one dimension to be in nanoscale scope (1-100nm) or to be made of as elementary cell them in three-dimensional space.Although concept is simple, regrettably, we still have too many unknown for this beautiful Nanometer World.Thus, particularly necessary to some basic research works of nano material after yearning for the bright outlook of nanometer era, comprise that preparations of nanomaterials is synthetic, functionalization, modification to be raising the efficiency, and use-pattern even new Application Areas.Such as simple preparation technology how with the starting point that method of modifying obtains efficiently, low cost, the nano material being convenient to utilize become problem.
The existing TiO that studies have shown that in a large number
2, ZnO or NiCo
2O
4Be the semiconductor material of excellent property etc. all poly-metal deoxides or compound, in semiconducter device, photocatalyst applications, bright prospects arranged, and its structure nano is the feasible solutions that scholars generally acknowledge to raise the efficiency; Also there is the nanomorphic of these materials of research to be used for battery material, sensitive material such as gas sensor, humidity sensor, waits the performance boost of each advanced field or the traditional field such as coating, macromolecular material additive, successful.Yet these achievement major parts also can only be embodied in the middle of the research in laboratory, and practical application still has long term distance in the productive life.Subject matter concentrate on material preparation process complexity, 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.
Such as TiO
2, its Anatase energy gap is 3.2eV approximately, and stable performance, safety non-toxic have wide application prospects in the 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 larger, 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 for effective method of modifying of material visible-light etc.
For these problems, the present invention is combined with new technology from comparatively ripe traditional technology, seeks material preparation and method of modifying; From the relation of material structure and performance, performance Material cladding attitude advantage improves material property; In conjunction with practical application, start out with the methods such as conventional anodization, ball milling, annealing preparations and can be used for the nanotube in a plurality of fields such as photochemical catalysis, solar cell, semiconducter device, battery material, sensor material, coating and additive/powder blend metal oxide materials.
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 the nanotube in photocatalytic applications, photolysis water hydrogen, solar cell, sensor material, battery material and the fields such as coating, additive/powder blend attitude metal oxide and preparation technology's and methods for using them thereof.
The present invention is that the technical scheme that its technical problem of solution is taked is:
1, a kind of nanotube/powder blend attitude metal oxide is characterized in that, structure is nanotube, nano powder blend state.
2, aforesaid a kind of nanotube/powder blend attitude metal oxide 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 successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning; Cold wind dries up or naturally dries for subsequent use;
Step 4, realization material crystal conversion: get the front nano-tube array rete of ball milling, or gained nanotube behind the ball milling/powder blend attitude metal oxide 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 metal oxide is characterized in that, directly dispersed uses, or is attached on flat substrate, rough base or the flexible substrates and uses.
4, aforesaid a kind of nanotube/powder blend attitude metal oxide 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 metal oxide 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 metal oxide is characterized in that, described anodic oxidation electrolyte, solute are that massfraction is 0.1%～5% NH
-4F, solvent are ethylene glycol 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 metal oxide has that specific surface area is large, surfactivity is high, and comprehensive polymorphic advantage improves the 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, can control pipe range, caliber, thickness of pipe and the pipe formation attitude of nanotube, 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. by preparation process Anodic Oxidation, ball milling, each step of annealing; 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 material preparation flow figure of the present invention.
Fig. 2 is anodic oxidation device schematic diagram of the present invention.
Fig. 3 comes off and dry 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
2Scanning electron microscope (SEM) photograph.
Fig. 5 is nanotube among the present invention/powder blend TiO
2Disperse to be applied to photo-catalytic degradation of methyl-orange and P25 type TiO
2Contrast.
Fig. 6 is nanotube among the present invention/powder blend TiO
2Be attached to slide glass photo-catalytic degradation of methyl-orange and P25 type TiO
2Contrast.
Fig. 7 is that nanotube among the present invention/powder blend metal oxide is attached to and is applied to the gas sensor schematic diagram on the grid electrode.
Fig. 8 is nanotube of the present invention/powder blend TiO
2Preparation efficient gas sensor responds 50ppm formaldehyde.
Embodiment
The present invention is a kind of nanotube/powder blend metal oxide, obtain blend attitude metal oxide nano-material by anodic oxidation, ball milling, high temperature annealing, increase substantially material property, in the fields such as photochemical catalysis, battery material, sensor material, additive, have outstanding performance and application advantage.
Below in conjunction with the drawings and specific embodiments the present invention is described in further details.
Embodiment one:
Nanotube/powder blend TiO
2The preparation, preparation flow as shown in Figure 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 large water gaging flushing, use successively acetone, dehydrated alcohol, each ultrasonic cleaning 10min of deionized water; Cold wind dries up for 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 to 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 ethylene glycol: H
2The O=49:1 mixed solution.Anodic oxidation device as shown in Figure 2.Ultrasonic until rete came off after the sample anodes oxidation finished, and it is for subsequent use to wash 2 to 3 times post-dryings with the dehydrated alcohol bubble.Obtain product as shown in Figure 3.
3, ball milling obtains nanotube/powder blend attitude: quality is than dehydrated 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 Scan electron microscope picture 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 Anatase 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 the nanotube of Anatase and Rutile Type blend crystal formation/powder blend attitude TiO
2
Embodiment three:
The nanotube of ball milling acquisition different components ratio/powder blend TiO
2:
In the present embodiment, obtain TiO by embodiment 1 same condition
2Behind the film, 450 ℃ of annealing 2h change Anatase into; Quality is than dehydrated alcohol, TiO
2, agate ball=1:2:20 places polytetrafluoroethyltank tank, carries out respectively mechanical ball milling 0.5h, 5h, 10h.
Through scanning electron microscope analysis, all obtained nanotube/powder blend TiO through the ball milling of different time
2And along with Ball-milling Time is different, nanotube, two kinds of component structures of nano powder and content change, and Ball-milling Time is longer, and the residue pipe is shorter, and content is fewer; The specific area measuring also specific surface area of surface product also changes thereupon, as shown in following table, increases with Ball-milling Time, and the product specific surface area constantly increases and is tending towards a saturation value.Explanation can be controlled easily each parameter, 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
2· |
| 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, the effect of each several part performance synthesis, and energy Effective Raise photoelectric transformation efficiency, photocatalytic activity is high; And in the material preparation process, make things convenient for modification, improve whole efficiency; Owing to having the effect of higher surfactivity and mixed state comprehensive action, application has too than conventional block materials or the common higher efficient of nano-powder material at aspects such as gas sensor, battery materials.In the practical application, the material of powdery 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, greatly widens use range.Can be used for the 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 photo-catalytic degradation of methyl-orange:
The nanotube of preparation gained/powder blend attitude TiO in the employing 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 determined 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 can obtain corresponding degradation rate with the starting point concentration comparison.
Accompanying drawing 6 is for adopting nanotube of the present invention/powder blend TiO
2Photo-catalytic degradation of methyl-orange and P25 contrast.A is P25 type TiO
2, German Degussa company produces; B is the nanotube that the present invention relates to/powder blend TiO
2By figure, adopt nanotube of the present invention/powder blend TiO under the same terms
2Photocatalytic Degradation On Methyl Orange Solution, successful is higher than P25, and the short period of time degradation rate just can reach 65%, proves 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 photo-catalytic degradation of methyl-orange on the sheet glass:
Material load preparation: take by weighing the nanotube of preparation gained in the embodiment of the invention one/powder blend attitude TiO
20.1g adding the mass ratio for preparing in advance is the solution 2mL of PEG 20000: water=1:1, dropper is added dropwise to 2 glycerine, uses agate to grind the crucible grinding and evenly makes 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 and test, compare with it, the result as shown in Figure 7, C is P25, D is the nanotube that the present invention relates to/powder blend TiO
2As seen, the nanotube that employing the present invention relates under the same terms/powder blend TiO
2Be attached to Photocatalytic Degradation On Methyl Orange Solution on the sheet glass, successful is 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, successful, excellent property in the substrate.
Embodiment six:
The anatase-phase nano pipe that the present invention relates to/powder blend attitude TiO
2Be applied to gas sensor:
The nanotube of preparation gained/powder blend attitude TiO in the use embodiment of the invention one
2The preparation gas sensor, basic structure as shown in Figure 8.Preparation process: (1) plates two interlaced but discontiguous grid electrodes in the dielectric base of some strength, and connects wire, makes substrate; (2) adopt the nanotube that the present invention relates to/powder blend attitude TiO
2, add an amount of Terpineol 350 and mix and make slurry; (3) slurry apply to form certain thickness rete at substrate, 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 is 50ppm formaldehyde, after changing rapidly, signal keeps stablizing; Purge testing cassete, along with atmosphere is recovered, signal also recovers at short notice gradually.
As seen, 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 with it of existing
2Powdered material is compared, and its structure is special, has larger specific surface area and stronger adsorptive power, applicable multiple condition, thereby have more using value.And under UV-irradiation, adsorb in the present invention nanotube/powder blend attitude TiO
2Pollution substance on the gas sensor just can be removed efficiently.In actual the use, this sensor can retention be stable 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 imposed any restrictions, every technical scheme that above embodiment employing is equal to replacement or equivalent transformation formation according to the technology of the present invention essence all still belongs in the protection domain of technical solution of the present invention.
Claims (4)
1. nanotube/powder blend attitude metal oxide 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 successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning; Cold wind dries up or naturally dries for subsequent use;
Step 2, anonizing prepare film of Nano tube array: the sheet metal through pre-treatment in the electrolytic solution is anode, take noble electrode as to 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 ethylene glycol and H
2The mixed solution of O; The ultrasonic shake of rete is fallen or peel off, wash post-drying 2 to 3 times with the dehydrated alcohol bubble;
Step 3, acquisition nanotube/powder blend attitude: metal oxide nanotubes array films, agate ball place ball grinder with mass ratio 50:1～1:20, add solvent mechanical ball milling 10min～48h; Separate the ball material after the loft drier oven dry, obtain nanotube/powder blend attitude metal oxide materials;
Step 4, realization material crystal conversion: get the front nano-tube array rete of ball milling, or gained nanotube behind the ball milling/powder blend attitude metal oxide 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.
2. a kind of nanotube according to claim 1/powder blend attitude metal oxide is characterized in that, described sheet metal is Ti, Zn, Al, Zr, Ni, Co or its alloy.
3. a kind of nanotube according to claim 1/powder blend attitude metal oxide is characterized in that, described noble electrode is Pt, Au, Ag, Cu, stainless steel substrates or graphite.
4. a kind of nanotube according to claim 1/powder blend attitude metal oxide is characterized in that, described electrolytic solution, solute are that massfraction is 0.1%～5% NH
-4F, solvent are ethylene glycol and H
2The O mass ratio is the mixed solution of 79:1～29:1.
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| CN103628111B (en) * | 2013-11-12 | 2016-10-12 | 海南大学 | Large area Ti prepares TiO on the net2the method of nano-tube array |
| 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 |
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