CN104030361B - Method for preparing metal tungstate nanomaterial by use of micro-arc oxidation process and use of nanomaterial - Google Patents
Method for preparing metal tungstate nanomaterial by use of micro-arc oxidation process and use of nanomaterial Download PDFInfo
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Abstract
The invention relates to the field of micro-arc oxidation, industrial catalysis, photocatalysis, nanomaterials and nanotechnology, and in particular relates to a method for preparing a metal tungstate nanomaterial by use of a micro-arc oxidation process and a use of the nanomaterial. The preparation method of the metal tungstate nanomaterial comprises the following steps: by taking a valve metal or an alloy thereof as a substrate, putting the substrate in an electrolyte containing wolframate radicals, generating a rough and porous oxide film on the surface of the substrate by use of the micro-arc oxidation process, next, dipping in a metal salt solution and then carrying out annealing treatment, thereby obtaining the metal tungstate nanomaterial. The preparation method is simple in process and free from atmosphere protection; the adopted raw materials is low in production cost, pollution-free and environmentally friendly; meanwhile, as the metal oxide film is generated in situ on the surface of the substrate, the film is excellent in bonding force with the substrate. The prepared metal tungstate nanomaterial is quite uniform in dimension and even in growth and distribution. The prepared metal tungstate nanomaterial can be used as a photocatalytic material, an electroluminescent material, a hydrodesulfurization catalyst and the like.
Description
Technical field
The present invention relates to differential arc oxidation, Industrial Catalysis, photochemical catalysis, nano material and field of nanometer technology, be specifically related to the methods and applications that a kind of micro-arc oxidation prepares metal tungstates nano material.
Background technology
Nano material, because its median size is little, surface atom is many, specific surface area is huge, surface energy high, has the special performance that conventional material does not have.Therefore, nano material has very important application prospect in fields such as magnetics, electricity, optics, calorifics and life sciences, caused the close attention of countries in the world research institution and scientific research personnel, nanotechnology will become the dominant technology of 21 century even to have scholar to predict.Wherein, monodimension nanometer material, owing to having unique structure and topographical property and unique physicochemical property, has huge application prospect constructing in electronics, optics and environmental catalysis purification.
Metal tungstates nano material, owing to having very unique photoelectric characteristic, has extraordinary application prospect in fields such as oil hydrogenating desulfurization, ultracapacitor, scintillator, optical fiber, electroluminescent lamps, thus becomes the study hotspot of people.Numerous research shows, nano material faced blocks material has very superior performance, the metal tungstates of nano-scale has very large specific surface area, high light capture ability, photoelectric conversion ability and high catalytic performance, and the metal tungstates therefore how preparing nano-scale is a focus and the difficult point of needs research at present and solution.
At present, the report of the preparation method of metal tungstate mainly contains hydrothermal method, microwave method, mechanosynthesis, electrochemical synthesis, sputtering method etc., but aforesaid method in various degree to there is cost high, produce toxic gas, product morphology is difficult to the problems such as control, and due to preparation metal tungstates fewer, can only make a search use, the demand of application can not be met, there is not yet the report preparing metal tungstates nano material with micro-arc oxidation.
Summary of the invention
The object of the present invention is to provide a kind of micro-arc oxidation to prepare the methods and applications of metal tungstates nano material, the metal tungstates nano material specific surface area prepared by the method is large, easy control of structure, and process is convenient, is convenient to produce.
For achieving the above object, technical solution of the present invention is as follows:
A kind of micro-arc oxidation prepares the method for metal tungstates nano material, the method utilizes micro-arc oxidation at valve metal or its alloy surface in-situ preparation layer of metal sull, then pickling process is utilized to introduce active ingredient at film surface, by sample anneal 10 ~ 300min at 450 DEG C ~ 1200 DEG C after end to be impregnated.
Described micro-arc oxidation prepares the method for metal tungstates nano material, and metal is selected from Ni, Fe, Mn, Co, Zn or Cu.
Described micro-arc oxidation prepares the method for metal tungstates nano material, and the concrete steps of preparation metal tungstates nano material are as follows:
(1) prepare the electrolytic solution of differential arc oxidation, under magnetic stirring, in the container filling deionized water, add (0.02 ~ 1.2) mol/L Na
3pO
412H
2o, (0.02 ~ 1.2) mol/L Na
2b
4o
710H
2o, (0.002 ~ 0.1) mol/L Na
2wO
42H
2o, (0.01 ~ 0.8) mol/L M (CH
3cOO)
2, magnetic agitation is even, and wherein M is any one in Ni, Cu, Co, Mn, Fe, Zn;
(2) industrially pure titanium is placed in the made electrolytic solution of step 1 and carries out differential arc oxidation, the time of differential arc oxidation is 5 ~ 90min, and current density is 1 ~ 100A/dm
2;
(3) sample prepared by step 2 is put into the M (NO of 0.01 ~ 10mol/L
3)
2flood 10 ~ 300min in solution, wherein M is any one in Ni, Cu, Co, Mn, Fe, Zn;
(4) sample prepared by step 3 is placed in tube furnace air and carries out anneal, annealing temperature is 450 ~ 1200 DEG C, and soaking time is 10 ~ 500min, then cools to room temperature with the furnace and can obtain tungstate nano material.
Described micro-arc oxidation prepares the method for metal tungstates nano material, and the pattern of metal tungstates nano material is nano wire, nano particle, nanometer sheet or nanotube.
Described micro-arc oxidation prepares the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is nanometer wire, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, wherein said nanowire diameter is 20 ~ 500nm, length is 2 ~ 3 μm, the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is very homogeneous.
Described micro-arc oxidation prepares the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is Nanoparticulate, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, and wherein said grain diameter is 100 ~ 1000nm.
Described micro-arc oxidation prepares the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is nano-sheet, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, wherein said nanometer sheet thickness is 50 ~ 500nm, long edge lengths is 3 ~ 4 μm, and width edge length is 2 ~ 3 μm, and long side direction is along the growth of [100] direction, broadside is along the growth of [010] direction, and nanometer sheet smooth surface is even.
Described micro-arc oxidation prepares the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is nanotube-shaped, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, wherein said nanotube external diameter is 500 ~ 2000nm, diameter of bore is 500 ~ 1000nm, and nanotube wall thickness is 100 ~ 500nm.
Described micro-arc oxidation prepares metal tungstates applications to nanostructures, and prepared tungstate nano material is as photocatalyst material, electroluminescent material or Hydrobon catalyst.
Design philosophy of the present invention is:
Find through research, micro-arc oxidation is as a kind of method preparing transition metal tungstate nano material newly, compared with the methods such as hydrothermal method, microwave method, mechanosynthesis, electrochemical synthesis, sputtering method, it is simple that it has technique, reproducible, prepare material to be easy to control, the advantage such as environmentally friendly, has been widely applied to material preparation and modification field.
The present invention utilizes micro-arc oxidation, using industrially pure titanium as substrate, in the electrolytic solution containing metal ion and wolframate radical, carry out differential arc oxidation, generate oxide film that is coarse, porous at matrix surface, then adopt dipping-heat treatment technics to prepare metal tungstates nano material.Wherein, the micro-arc oxidation films of rough porous, not only as the body material preparing tungstate, also for dip treating provides larger specific surface area, is conducive to steeping fluid and is adsorbed onto on film.Dip treating is in order to adsorbing metal ions in zone of oxidation, regulates and controls the size of tungstate material, pattern and crystal structure degree finally by thermal treatment process.
The present invention has following advantage and technique effect:
1, the present invention utilizes the method for differential arc oxidation to prepare metal tungstates nano material, can grow on the matrix of arbitrary shape, and operation of equipment is simple, can carry out scale operation, can control the growth of nano material, and film-substrate cohesion is good.The present invention can obtain metal tungstates nano material, size uniform, and specific surface area is large.
2, the metal tungstates appearance of nano material that prepared by the present invention has wire, particulate state, sheet and tubulose, wherein: one is nano wire, nanowire diameter is 20 ~ 500nm, and length is 2 ~ 3 μm, the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is very homogeneous; One is nano particle, and the particle diameter of nano particle is 100 ~ 1000nm; One is nanometer sheet, and nanometer sheet is rectangular-shaped, and thickness is 50 ~ 500nm, long edge lengths is 3 ~ 4 μm, and width edge length is 2 ~ 3 μm, and long side direction is along the growth of [100] direction, broadside is along the growth of [010] direction, and nanometer sheet smooth surface is even; One is nanotube, and nanotube is cuboidal columnar, and the external diameter of nanotube is 500 ~ 2000 μm, and internal diameter is 500 ~ 1000nm, and wall thickness is 100 ~ 500nm.
3, the low in raw material price that the present invention is used, electrolytic solution can recycled for multiple times, and cost is lower, simple to operate, is easy to control.
4, be at metallic surface in-situ preparation as the oxide film of substrate in the present invention, film-substrate cohesion is very superior.
5, the oxide film that the differential arc oxidation in the present invention obtains is porous, can provide larger specific surface area for tungstate nano Material growth.
In a word, novelty of the present invention is mainly embodied in the preparation that this for traditional differential arc oxidation method is incorporated into tungstate nano material by us, and can control pattern and the kind of material.Simpler compared with other prepares tungstate nano MATERIALS METHODS (as: Hydrothermal Synthesis, collosol and gel etc.), material parameter controls easier, and material crystalline is better.
Accompanying drawing explanation
Fig. 1 is NiWO prepared by embodiments of the invention 1
4x-ray powder diffraction (XRD) structure iron of nano wire.
Fig. 2 is NiWO prepared by embodiments of the invention 1
4scanning electron microscope (SEM) photo of nano wire.
Fig. 3 is NiWO prepared by embodiments of the invention 2
4scanning electron microscope (SEM) photo of nano particle.
Fig. 4 is ZnWO prepared by embodiments of the invention 3
4scanning electron microscope (SEM) photo of nanometer sheet.
Fig. 5 is ZnWO prepared by embodiments of the invention 4
4scanning electron microscope (SEM) photo of nanotube.
Embodiment
In the specific embodiment of the present invention, micro-arc oxidation prepares the method for metal tungstates nano material, utilize micro-arc oxidation, using industrially pure titanium (GR1) as substrate, differential arc oxidation is carried out in the electrolytic solution containing metal ion and wolframate radical, oxide film that is coarse, porous is generated at matrix surface, then dipping-heat treatment technics is adopted, for some time is flooded in certain density metal-salt, then in tube type resistance furnace, carry out anneal namely prepare metal tungstates nano material, specifically comprise the steps:
(1) prepare the electrolytic solution of differential arc oxidation, under magnetic stirring, in the container filling deionized water, add the Na of (0.02 ~ 1.2) mol/L
3pO
412H
2the Na of O, (0.02 ~ 1.2) mol/L
2b
4o
710H
2the Na of O, (0.002 ~ 0.1) mol/L
2wO
42H
2m (the CH of O, (0.01 ~ 0.8) mol/L
3cOO)
2, magnetic agitation is even; Wherein, M in described in Ni, Cu, Co, Mn, Fe, Zn any one.
Preferably, Na
3pO
412H
2o:0.04 ~ 0.09mol/L, Na
2b
4o
710H
2o:0.03 ~ 0.06mol/L, Na
2wO
42H
2o:0.002 ~ 0.006mol/L, M (CH
3cOO)
2: 0.02 ~ 0.08mol/L.
(2) using industrially pure titanium as substrate, then carry out pre-treatment to it, ultrasonic time 15min is to remove the greasy dirt on surface first in acetone, then inserts acidic solution H under room temperature
2o:HNO
3: treatment time 60s in HF=5:4:1 (volume ratio), its objective is the oxide film removing substrate surface.
(3) industrially pure titanium after step 2 being processed is placed in the made electrolytic solution of step 1 and carries out differential arc oxidation, and the time of differential arc oxidation is 5 ~ 90min, and current density is 1 ~ 100A/dm
2.
Preferably, the time of differential arc oxidation: 10 ~ 45min, current density: 1 ~ 50A/dm
2.
(4) sample prepared by step 3 is put into the M (NO of 0.01 ~ 10mol/L
3)
210 ~ 300min is flooded in solution; Wherein, M in described in Ni, Cu, Co, Mn, Fe, Zn any one.
Preferably, M (NO
3)
2strength of solution: 0.05 ~ 1mol/L, dipping time 30 ~ 120min.
(5) sample prepared by step 4 is placed in silica tube, anneal is carried out in heating in atmosphere, and the temperature rise rate of silica tube is that 5 ~ 30 DEG C/min is heated to 450 ~ 1200 DEG C, insulation 10 ~ 500min.
Preferably, temperature rise rate: 5 ~ 15 DEG C/min, Heating temperature: 650 ~ 850 DEG C, soaking time 10 ~ 240min.
Then cool to room temperature with the furnace, can obtain tungstate nano material, the pattern of metal tungstates is as follows:
(1) nanometer wire, can obtain NiWO in the following way
4nano wire: Ti substrate is at 0.04 ~ 0.09mol/L Na
3pO
412H
2o, 0.03 ~ 0.06mol/L Na
2b
4o
710H
2o, 0.002 ~ 0.006mol/LNa
2wO
42H
2o, 0.02 ~ 0.08mol/L Ni (CH
3cOO)
2electrolytic solution in differential arc oxidation 5 ~ 10min, current density is 1 ~ 10A/dm
2, prepare differential arc oxidation sample.Then at the Ni (NO of 0.1 ~ 1mol/L
3)
2after flooding 30 ~ 120min in solution, anneal 30 ~ 60min in tube furnace, annealing temperature is 650 ~ 850 DEG C, can obtain NiWO
4nano wire.Wherein, nanowire diameter is 20 ~ 500nm, and length is 2 ~ 3 μm, and the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is very homogeneous;
(2) Nanoparticulate, can obtain NiWO in the following way
4nano particle: Ti substrate is at 0.04 ~ 0.09mol/L Na
3pO
412H
2o, 0.03 ~ 0.06mol/L Na
2b
4o
710H
2o, 0.002 ~ 0.006mol/LNa
2wO
42H
2o, 0.02 ~ 0.08mol/L Ni (CH
3cOO)
2electrolytic solution in differential arc oxidation 10 ~ 30min, current density is 10 ~ 50A/dm
2, prepare differential arc oxidation sample.Then at the Ni (NO of 0.1 ~ 1mol/L
3)
2after flooding 30 ~ 120min in solution, anneal 30 ~ 60min in tube furnace, annealing temperature is 650 ~ 850 DEG C, can obtain NiWO
4nano particle.Wherein, the particle diameter of nano particle is 100 ~ 1000nm;
(3) nano-sheet, can obtain ZnWO in the following way
4nanometer sheet: Ti substrate is at 0.04 ~ 0.09mol/L Na
3pO
412H
2o, 0.03 ~ 0.06mol/L Na
2b
4o
710H
2o, 0.002 ~ 0.006mol/LNa
2wO
42H
2o, 0.02 ~ 0.08mol/L Zn (CH
3cOO)
2electrolytic solution in differential arc oxidation 10 ~ 45min, current density is 1 ~ 50A/dm
2, prepare differential arc oxidation sample.Then at the Zn (NO of 0.1 ~ 1mol/L
3)
2after flooding 30 ~ 120min in solution, anneal 120 ~ 240min in tube furnace, annealing temperature is 700 ~ 800 DEG C, can obtain ZnWO
4nanometer sheet.Wherein, nanometer sheet is rectangular-shaped, and thickness is 50 ~ 500nm, and long edge lengths is 3 ~ 4 μm, and width edge length is 2 ~ 3 μm, and long side direction is along the growth of [100] direction, and broadside is along the growth of [010] direction, and nanometer sheet smooth surface is even;
(4) nanotube-shaped, can ZnWO be obtained in the following way
4nanotube: Ti substrate is at 0.04 ~ 0.09mol/L Na
3pO
412H
2o, 0.03 ~ 0.06mol/L Na
2b
4o
710H
2o, 0.002 ~ 0.006mol/LNa
2wO
42H
2o, 0.02 ~ 0.08mol/L Zn (CH
3cOO)
2electrolytic solution in differential arc oxidation 10 ~ 45min, current density is 1 ~ 50A/dm
2, prepare differential arc oxidation sample.Then at the Zn (NO of 0.1 ~ 1mol/L
3)
2after flooding 30 ~ 120min in solution, anneal 30 ~ 120min in tube furnace, annealing temperature is 800 ~ 900 DEG C, can obtain ZnWO
4nanotube.Wherein, nanotube is cuboidal columnar, and the external diameter of nanotube is 500 ~ 2000 μm, and internal diameter is 500 ~ 1000nm, and wall thickness is 100 ~ 500nm.
Below in conjunction with drawings and Examples in detail the present invention is described in detail.For the detailed description of these embodiments, be construed as those skilled in the art to be put into practice by the present invention, and by using other embodiment, when not departing from spirit and the scope of appended claims, shown example can be changed and/or change.In addition, although disclose special characteristic of the present invention in an embodiment, this special characteristic can suitably be changed, and realizes function of the present invention.
Embodiment 1
The present embodiment be on Ti sheet after differential arc oxidation, dipping and sintering, grow NiWO
4nano wire, specific as follows:
1, in beaker, add 1L deionized water, under magnetic agitation condition, add 25.08gNa
3pO
412H
2o, 12.97g Na
2b
4o
710H
2o and 1.98g Na
2wO
42H
2o, adds 19.91g Ni (CH after mixing
3cOO)
2, continue to stir 5h, namely obtain the electrolytic solution of differential arc oxidation.
2, using industrially pure titanium (Gr1) as substrate, first titanium sheet is cut into suitable size, then pre-treatment is carried out to it.Ti sheet is put into the ultrasonic 15min of acetone, the greasy dirt on surface is removed, then with the acetone that deionized water rinsing is residual, then Ti sheet is at room temperature put into H
2o:HNO
3: HF=5:4:1 (volume ratio) process 60s remove surface zone of oxidation, finally use deionized water and absolute ethanol washing clean.
3, step 1 gained electrolytic solution is put into stainless steel electrolytic groove, then using the anode electrode of pretreated Ti sheet as differential arc oxidation, stainless steel electrolytic groove, as cathode electrode, carries out differential arc oxidation.Its current density is 1A/dm
2, the time of differential arc oxidation is 10min.
4, the sample of step 3 gained is put into the Ni (NO of 0.1mol/L
3)
21h is flooded in solution, then dry at 100 DEG C in loft drier.
5, the sample of step 4 gained is placed in tube furnace, rises to 850 DEG C with the temperature rise rate of 10 DEG C/min, and be incubated 30min, then cool to room temperature with the furnace, can NiWO be obtained
4nano wire.
Utilize the NiWO that aforesaid method grows
4the XRD method that utilizes nano wire detects its phase composition.As shown in Figure 1, from NiWO
4the XRD figure spectrum of nano wire in 20 ~ 80 degree of range of diffraction can be determined, products therefrom is two-phase, Rutile Type TiO
2and NiWO
4phase, wherein Rutile Type TiO
2for NiWO
4the substrate of nanoparticle growth, through differential arc oxidation gained.
Utilize the NiWO that aforesaid method grows
4nano wire utilizes scanning electron microscope method to detect its pattern and distribution of sizes.As shown in Figure 2, from NiWO
4the stereoscan photograph of nano wire can be found out, the NiWO grown under the present embodiment condition
4nanowire diameter is about 100nm, and length is 2 ~ 3 μm, and the diameter of single nano-wire is very homogeneous, and nanowire surface does not have adhered particles, does not also observe metal catalyst at nanowire growth end.
The NiWO of aforesaid method growth
4the crystal mass of nano wire utilizes high-resolution-ration transmission electric-lens and electron diffraction technique phenetic analysis.Viewed high-resolution-ration transmission electric-lens atomic response display NiWO
4nano wire is monocrystalline, and crystals degree of crystallinity is very complete, does not have the crystal structure defects such as twin and dislocation.The direction of growth of nano wire is along the growth of [100] direction.
Embodiment 2
Difference from Example 1 is, the present embodiment, by controlling current density and the differential arc oxidation time of differential arc oxidation, can obtain the NiWO that pattern is different
4pattern, specific as follows:
1, in beaker, add 1L deionized water, under magnetic agitation condition, add 25.08gNa
3pO
412H
2o, 12.97g Na
2b
4o
710H
2o and 2.64g Na
2wO
42H
2o, adds 24.88g Ni (CH after mixing
3cOO)
2, continue to stir 5h.
2, using industrially pure titanium as substrate, pre-treatment is carried out to it.By substrate at H
2o:HNO
3: HF=5:4:1 (volume ratio) processes 60s, then uses deionized water wash 4 times, absolute ethanol washing 2 times.
3, step 1 gained electrolytic solution is put into electrolyzer, pretreated industrially pure titanium, as the anode electrode of differential arc oxidation, carries out differential arc oxidation.Its current density is 10A/dm
2, the time of differential arc oxidation is 15min.
4, the sample of step 3 gained is put into the Ni (NO of 0.5mol/L
3)
21h is flooded in solution, then dry at 100 DEG C in loft drier.
5, be placed in tube furnace by the sample of step 4 gained, anneal at 850 DEG C, annealing time is 30min, can obtain NiWO
4nano particle,
Utilize the NiWO that aforesaid method grows
4the XRD method that utilizes nano particle detects its phase composition, from NiWO
4can determine in the XRD figure spectrum of nano particle in 20 ~ 80 degree of range of diffraction, products therefrom is two-phase, and wherein one is Rutile Type TiO mutually
2, it is the principal phase obtained after Ti sheet differential arc oxidation, as growth NiWO
4nano particle substrate, another is NiWO mutually
4nano particle.
Utilize the NiWO that aforesaid method grows
4nano particle utilizes scanning electron microscope method detector pattern and distribution of sizes.As shown in Figure 3, from NiWO
4the stereoscan photograph of nano particle can be found out, the NiWO grown under the present embodiment condition
4nano particle, particle diameter be 100 ~ 1000nm, nano particle has certain corner angle, and surface does not have adhered particles.
The NiWO of aforesaid method growth
4the crystal mass of nano particle utilizes high-resolution-ration transmission electric-lens and electron diffraction technique phenetic analysis.Viewed high-resolution-ration transmission electric-lens atomic response display NiWO
4nano particle is monocrystalline, and crystals degree of crystallinity is very complete, does not have the crystal structure defects such as twin and dislocation.
Embodiment 3
Difference from Example 1 is, the present embodiment becomes to assign to obtain different metal tungstates materials by changing electrolytic solution and steeping fluid, specific as follows:
1, in beaker, add 1L deionized water, under magnetic agitation condition, add 38.14gNa
3pO
412H
2o, 12.97g Na
2b
4o
710H
2o and 1.98g Na
2wO
42H
2o, adds 21.95g Zn (CH after mixing
3cOO)
2, continue to stir 5h.
2, using industrially pure titanium as substrate, pre-treatment is carried out to it.By substrate at H
2o:HNO
3: HF=5:4:1 (volume ratio) processes 60s, then uses deionized water wash 4 times, absolute ethanol washing 2 times.
3, step 1 gained electrolytic solution is put into electrolyzer, pretreated industrially pure titanium, as the anode electrode of differential arc oxidation, carries out differential arc oxidation.Its current density is 10A/dm
2, the time of differential arc oxidation is 10min.
4, the sample of step 3 gained is put into the Zn (NO of 0.5mol/L
3)
21h is flooded in solution, then dry at 100 DEG C in loft drier.
5, be placed in tube furnace by the sample of step 4 gained, anneal at 750 DEG C, annealing time is 4h, can obtain ZnWO
4nanometer sheet.
Utilize the ZnWO that aforesaid method grows
4nanometer sheet utilizes XRD method to detect.From ZnWO
4can determine in the XRD figure spectrum of nanometer sheet in 20 ~ 80 degree of range of diffraction, products therefrom is two-phase, and wherein one is Rutile Type TiO mutually
2, it is the principal phase obtained after Ti sheet differential arc oxidation, as growth ZnWO
4nanometer sheet substrate, another is ZnWO mutually
4nanometer sheet, wherein Rutile Type TiO
2for ZnWO
4the substrate of nanoparticle growth, through differential arc oxidation gained.
Utilize the ZnWO that aforesaid method grows
4nanometer sheet utilizes surface sweeping electron microscopy to detect its pattern and distribution of sizes.As shown in Figure 4, from ZnWO
4the stereoscan photograph of nanometer sheet can be found out, the ZnWO grown under the present embodiment condition
4in rectangular-shaped, nanometer sheet thickness dimensions is about 250nm, and length is 3 ~ 4 μm, and width is about 2 μm, and nanometer sheet smooth surface is even, does not have adhered particles.
The ZnWO of aforesaid method growth
4the crystal mass of nanometer sheet utilizes high-resolution-ration transmission electric-lens and electron diffraction technique phenetic analysis.Viewed high-resolution-ration transmission electric-lens atomic response display ZnWO
4nanometer sheet is monocrystalline, and crystals degree of crystallinity is very complete, does not have the crystal structure defects such as twin and dislocation; The nanometer sheet length direction of growth is [100], and width growth direction is [010].
Embodiment 4
Difference from Example 3 is, the present embodiment can change ZnWO by changing annealing temperature
4pattern, specific as follows:
1, in beaker, add 1L deionized water, under magnetic agitation condition, add 38.14gNa
3pO
412H
2o, 12.97g Na
2b
4o
710H
2o and 1.98g Na
2wO
42H
2o, adds 21.95g Zn (CH after mixing
3cOO)
2, continue to stir 1h.
2, using industrially pure titanium as substrate, pre-treatment is carried out to it.By substrate at H
2o:HNO
3: HF=5:4:1 (volume ratio) processes 60s, then uses deionized water wash 4 times, absolute ethanol washing 2 times.
3, step 1 gained electrolytic solution is put into electrolyzer, pretreated industrially pure titanium, as the anode electrode of differential arc oxidation, carries out differential arc oxidation.Its current density is 10A/dm
2, the time of differential arc oxidation is 10min.
4, the sample of step 3 gained is put into the Zn (NO of 0.1mol/L
3)
21h is flooded in solution, then dry at 100 DEG C in loft drier.
5, be placed in tube furnace by the sample of step 4 gained, anneal at 850 DEG C, annealing time is 60min, can obtain ZnWO
4nanotube.
Utilize the ZnWO that aforesaid method grows
4the XRD method that utilizes nanotube detects its phase composition, from ZnWO
4can determine in the XRD figure spectrum of nanotube in 20 ~ 80 degree of range of diffraction, products therefrom is two-phase, and wherein one is Rutile Type TiO mutually
2, it is the principal phase obtained after Ti sheet differential arc oxidation, as growth ZnWO
4the nano tube based end, another is ZnWO mutually
4nanotube, wherein Rutile Type TiO
2for ZnWO
4the substrate of nanoparticle growth, through differential arc oxidation gained.
Utilize the ZnWO that aforesaid method grows
4nanotube utilizes scanning electron microscope method to detect its pattern and distribution of sizes.As shown in Figure 5, from ZnWO
4the stereoscan photograph of nanotube can be found out, the ZnWO grown under the present embodiment condition
4nanotube is cubic column, and external diameter is 800 ~ 2000nm, and internal diameter is 500 ~ 1000nm, and wall thickness is 200 ~ 400nm.
The ZnWO of aforesaid method growth
4the crystal mass of nanotube utilizes high-resolution-ration transmission electric-lens and electron diffraction technique phenetic analysis.Viewed high-resolution-ration transmission electric-lens atomic response display ZnWO
4nanotube is monocrystalline, and crystals degree of crystallinity is very complete, does not have the crystal structure defects such as twin and dislocation.
Embodiment result shows, the metal tungstates nano material size prepared by the present invention is comparatively homogeneous, and growth distribution is even.This preparation method's technical process is simple, and do not need atmosphere protection, raw materials production cost is low, pollution-free, environmentally friendly, simultaneously owing to being at matrix surface in-situ preparation metal oxide film, so the bonding force of rete and matrix is very good.Prepared tungstate nano material can do photocatalyst material, electroluminescent material or Hydrobon catalyst etc.
Above-described is only optimum embodiment cited by the present invention.It may be noted that; for all technician of the art; under the obvious respects of the spirit and illustrated principle that do not depart from appended claims, can also change shown example and/or change, these changes also should be considered the scope of the present invention.
Claims (7)
1. a micro-arc oxidation prepares the method for metal tungstates nano material, it is characterized in that, the method utilizes micro-arc oxidation at valve metal or its alloy surface in-situ preparation layer of metal sull, then pickling process is utilized to introduce active ingredient at film surface, by sample anneal 10 ~ 300min at 450 DEG C ~ 1200 DEG C after end to be impregnated;
Metal is selected from Ni, Fe, Mn, Co, Zn or Cu.
2. micro-arc oxidation according to claim 1 prepares the method for metal tungstates nano material, it is characterized in that, the concrete steps of preparation metal tungstates nano material are as follows:
(1) prepare the electrolytic solution of differential arc oxidation, under magnetic stirring, in the container filling deionized water, add (0.02 ~ 1.2) mol/L Na
3pO
412H
2o, (0.02 ~ 1.2) mol/L Na
2b
4o
710H
2o, (0.002 ~ 0.1) mol/L Na
2wO
42H
2o, (0.01 ~ 0.8) mol/L M (CH
3cOO)
2, magnetic agitation is even, and wherein M is any one in Ni, Cu, Co, Mn, Fe, Zn;
(2) industrially pure titanium is placed in the made electrolytic solution of step 1 and carries out differential arc oxidation, the time of differential arc oxidation is 5 ~ 90min, and current density is 1 ~ 100A/dm
2;
(3) sample prepared by step 2 is put into the M (NO of 0.01 ~ 10mol/L
3)
2flood 10 ~ 300min in solution, wherein M is any one in Ni, Cu, Co, Mn, Fe, Zn;
(4) sample prepared by step 3 is placed in tube furnace air and carries out anneal, annealing temperature is 450 ~ 1200 DEG C, and soaking time is 10 ~ 500min, then cools to room temperature with the furnace and can obtain tungstate nano material.
3. micro-arc oxidation according to claim 1 and 2 prepares the method for metal tungstates nano material, it is characterized in that, the pattern of metal tungstates nano material is nano wire, nano particle, nanometer sheet or nanotube.
4. micro-arc oxidation according to claim 3 prepares the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is nanometer wire, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, wherein said nanowire diameter is 20 ~ 500nm, length is 2 ~ 3 μm, and the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is very homogeneous.
5. micro-arc oxidation according to claim 3 prepares the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is Nanoparticulate, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, and wherein said grain diameter is 100 ~ 1000nm.
6. micro-arc oxidation according to claim 3 prepares the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is nano-sheet, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, wherein said nanometer sheet thickness is 50 ~ 500 nm, long edge lengths is 3 ~ 4 μm, width edge length is 2 ~ 3 μm, long side direction is along the growth of [100] direction, broadside is along the growth of [010] direction, and nanometer sheet smooth surface is even.
7. micro-arc oxidation according to claim 3 prepares the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is nanotube-shaped, it comprises a kind of metal tungstates being selected from Ni, Cu, Co, Mn, Fe or Zn, wherein said nanotube external diameter is 500 ~ 2000 nm, diameter of bore is 500 ~ 1000nm, and nanotube wall thickness is 100 ~ 500nm.
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