CN104030361A - 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 PDF

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CN104030361A
CN104030361A CN201410242788.7A CN201410242788A CN104030361A CN 104030361 A CN104030361 A CN 104030361A CN 201410242788 A CN201410242788 A CN 201410242788A CN 104030361 A CN104030361 A CN 104030361A
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arc oxidation
nano material
metal
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metal tungstates
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CN104030361B (en
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姜辛
姜亚南
翟朝峰
刘宝丹
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Institute of Metal Research of CAS
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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

A kind of micro-arc oxidation is prepared the methods and applications of metal tungstates nano material
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 is prepared 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, cause countries in the world research institution and scientific research personnel's close attention, even had scholar to predict that nanotechnology will become the dominant technology of 21 century.Wherein, monodimension nanometer material is owing to having unique structure and pattern characteristic and unique physicochemical property, has huge application prospect constructing aspect 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, thereby becomes people's study hotspot.Numerous research shows, the relative block materials of nano 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 metal tungstates therefore how to prepare nano-scale is focus and the difficult point of needs research at present and solution.
At present, the preparation method's of metal tungstate report mainly contains hydrothermal method, microwave method, mechanical synthesis method, electrochemical synthesis, sputtering method etc., but aforesaid method in various degree exist cost high, produce toxic gas, product pattern is difficult to the problems such as control, and because the metal tungstates of preparation is fewer, use can only make a search, can not meet the demand of application, there is not yet the report of 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 of preparing by the method is large, easy control of structure, and it is convenient to process, and is convenient to produce.
For achieving the above object, technical solution of the present invention is as follows:
A kind of micro-arc oxidation is prepared the method for metal tungstates nano material, the method utilizes micro-arc oxidation to generate layer of metal sull at valve metal or its alloy surface original position, then utilize pickling process to introduce active ingredient at film surface, after end to be impregnated by sample anneal 10~300min at 450 ℃~1200 ℃.
Described micro-arc oxidation is prepared the method for metal tungstates nano material, and metal is selected from Ni, Fe, Mn, Co, Zn or Cu.
Described micro-arc oxidation is prepared the method for metal tungstates nano material, and the concrete steps of preparation metal tungstates nano material are as follows:
(1) electrolytic solution of preparation differential arc oxidation, under magnetic agitation, adds (0.02~1.2) mol/L Na to filling in the container of deionized water 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 in Ni, Cu, Co, Mn, Fe, Zn;
(2) industrially pure titanium is placed in to 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) the prepared sample of step 2 is put into the M (NO of 0.01~10mol/L 3) 2in solution, flood 10~300min, wherein M is any in Ni, Cu, Co, Mn, Fe, Zn;
(4) the prepared sample of step 3 is placed in to tube furnace air and carries out anneal, annealing temperature is 450~1200 ℃, and soaking time is 10~500min, then cools to room temperature with the furnace and can obtain tungstate nano material.
Described micro-arc oxidation is prepared 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 is prepared the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is nanometer wire, the metal tungstates that it comprises a kind of Ni of being selected from, Cu, Co, Mn, Fe or Zn, wherein said nanowire diameter is 20~500nm, length is 2~3 μ m, the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is homogeneous very.
Described micro-arc oxidation is prepared the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is Nanoparticulate, the metal tungstates that it comprises a kind of Ni of being selected from, Cu, Co, Mn, Fe or Zn, wherein said grain diameter is 100~1000nm.
Described micro-arc oxidation is prepared the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is nano-sheet, the metal tungstates that it comprises a kind of Ni of being selected from, Cu, Co, Mn, Fe or Zn, wherein said nanometer sheet thickness is 50~500nm, long edge lengths is 3~4 μ m, and width edge length is 2~3 μ m, 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 is prepared the method for metal tungstates nano material, a kind of pattern of metal tungstates nano material is nanotube-shaped, the metal tungstates that it comprises a kind of Ni of being selected from, 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 is prepared the application of metal tungstates nano material, and prepared tungstate nano material is as photocatalyst material, electroluminescent material or Hydrobon catalyst.
Design philosophy of the present invention is:
Through research, find, micro-arc oxidation is as a kind of new method of preparing transition metal tungstate nano material, compare with methods such as hydrothermal method, microwave method, mechanical synthesis method, electrochemical synthesis, sputtering methods, it is simple that it has technique, reproducible, prepare material and 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 that contains metal ion and wolframate radical, carry out differential arc oxidation, at matrix surface, generate oxide film coarse, porous, 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 of 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 for adsorbing metal ions in zone of oxidation, finally by thermal treatment process, regulates and controls size, pattern and the crystal structure degree of tungstate material.
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 on the matrix of arbitrary shape, grow, 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: a kind of is nano wire, nanowire diameter is 20~500nm, and length is 2~3 μ m, the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is homogeneous very; Be a nano particle, the particle diameter of nano particle is 100~1000nm; Be a nanometer sheet, it is rectangular-shaped that nanometer sheet is, and thickness is 50~500nm, and long edge lengths is 3~4 μ m, and width edge length is 2~3 μ m, 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; Be a nanotube, nanotube is a cube column, and the external diameter of nanotube is 500~2000 μ m, and internal diameter is 500~1000nm, and wall thickness is 100~500nm.
3, the present invention's cost of material used is cheap, and electrolytic solution can recycled for multiple times, and cost is lower, simple to operate, is easy to control.
4, in the present invention, the oxide film as substrate is to generate in metallic surface original position, and 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 to be mainly embodied in us this method of traditional differential arc oxidation to be incorporated into the preparation of tungstate nano material, and can control pattern and the kind of material.Prepare tungstate nano material method (as: Hydrothermal Synthesis, collosol and gel etc.) with other and compare simplyr, it is easier that material parameter is controlled, and material crystallinity is better.
Accompanying drawing explanation
Fig. 1 is the NiWO of embodiments of the invention 1 preparation 4the X-ray powder diffraction of nano wire (XRD) structure iron.
Fig. 2 is the NiWO of embodiments of the invention 1 preparation 4the scanning electron microscope of nano wire (SEM) photo.
Fig. 3 is the NiWO of embodiments of the invention 2 preparations 4the scanning electron microscope of nano particle (SEM) photo.
Fig. 4 is the ZnWO of embodiments of the invention 3 preparations 4the scanning electron microscope of nanometer sheet (SEM) photo.
Fig. 5 is the ZnWO of embodiments of the invention 4 preparations 4the scanning electron microscope of nanotube (SEM) photo.
Embodiment
In the specific embodiment of the present invention, micro-arc oxidation is prepared the method for metal tungstates nano material, utilize micro-arc oxidation, using industrially pure titanium (GR1) as substrate, in the electrolytic solution that contains metal ion and wolframate radical, carry out differential arc oxidation, at matrix surface, generate oxide film coarse, porous, then adopt dipping-heat treatment technics, in certain density metal-salt, flood for some time, then in tube type resistance furnace, carry out anneal and prepare metal tungstates nano material, specifically comprise the steps:
(1) electrolytic solution of preparation differential arc oxidation, under magnetic agitation, to filling the Na that adds (0.02~1.2) mol/L in the container of deionized water 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 be described in Ni, Cu, Co, Mn, Fe, Zn in any.
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 it is carried out to pre-treatment, first in acetone, ultrasonic time 15min, to remove surperficial greasy dirt, 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 of removing substrate surface.
(3) industrially pure titanium after step 2 processing is placed in to 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.
Preferably, the time of differential arc oxidation: 10~45min, current density: 1~50A/dm 2.
(4) the prepared sample of step 3 is put into the M (NO of 0.01~10mol/L 3) 2in solution, flood 10~300min; Wherein, M be described in Ni, Cu, Co, Mn, Fe, Zn in any.
Preferably, M (NO 3) 2strength of solution: 0.05~1mol/L, dipping time 30~120min.
(5) the prepared sample of step 4 is placed in to silica tube, in air, anneal is carried out in heating, and the temperature rise rate of silica tube is that 5~30 ℃/min is heated to 450~1200 ℃, insulation 10~500min.
Preferably, temperature rise rate: 5~15 ℃/min, Heating temperature: 650~850 ℃, 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 of 0.1~1mol/L (NO 3) 2in solution, flood after 30~120min, anneal 30~60min in tube furnace, annealing temperature is 650~850 ℃, can obtain NiWO 4nano wire.Wherein, nanowire diameter is 20~500nm, and length is 2~3 μ m, and the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is homogeneous very;
(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 of 0.1~1mol/L (NO 3) 2in solution, flood after 30~120min, anneal 30~60min in tube furnace, annealing temperature is 650~850 ℃, 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 of 0.1~1mol/L (NO 3) 2in solution, flood after 30~120min, anneal 120~240min in tube furnace, annealing temperature is 700~800 ℃, can obtain ZnWO 4nanometer sheet.Wherein, it is rectangular-shaped that nanometer sheet is, and thickness is 50~500nm, and long edge lengths is 3~4 μ m, and width edge length is 2~3 μ m, 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 obtain ZnWO 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 of 0.1~1mol/L (NO 3) 2in solution, flood after 30~120min, anneal 30~120min in tube furnace, annealing temperature is 800~900 ℃, can obtain ZnWO 4nanotube.Wherein, nanotube is a cube column, and the external diameter of nanotube is 500~2000 μ m, 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.Detailed description for these embodiment, being construed as those skilled in the art can put into practice by the present invention, and can, by using other embodiment, in the situation that do not depart from spirit and the category of the present invention of appended claims, example illustrated be changed and/or be changed.In addition, although announced in an embodiment special characteristic of the present invention, 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, obtain the electrolytic solution that differential arc oxidation is used.
2, using industrially pure titanium (Gr1) as substrate, first titanium sheet is cut into suitable size, then it is carried out to pre-treatment.Ti sheet is put into the ultrasonic 15min of acetone, surperficial greasy dirt is removed, then use the residual acetone of deionized water rinsing, then Ti sheet is at room temperature put into H 2o:HNO 3: HF=5:4:1 (volume ratio) processes 60s and removes surperficial zone of oxidation, finally uses deionized water and absolute ethanol washing clean.
3, step 1 gained electrolytic solution is put into stainless steel electrolytic groove, the anode electrode using pretreated Ti sheet as differential arc oxidation then, 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) 2in solution, flood 1h, then dry at 100 ℃ in loft drier.
5, the sample of step 4 gained is placed in tube furnace, with the temperature rise rate of 10 ℃/min, rises to 850 ℃, and be incubated 30min, then cool to room temperature with the furnace, can obtain NiWO 4nano wire.
Utilize the NiWO of aforesaid method growth 4the XRD method of utilizing nano wire detects its phase composition.As shown in Figure 1, from NiWO 4the XRD figure of nano wire in 20~80 degree range of diffraction composed and 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 of aforesaid method growth 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 growing under the present embodiment condition 4nanowire diameter is about 100nm, and length is 2~3 μ m, and the diameter of single nano-wire is homogeneous very, and nanowire surface does not have adhered particles, at nanowire growth end, does not also observe metal catalyst.
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 atom picture shows NiWO 4nano wire is monocrystalline, and crystals degree of crystallinity is very complete, there is no 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 different NiWO of pattern 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, usining industrially pure titanium carries out pre-treatment as substrate 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) 2in solution, flood 1h, then dry at 100 ℃ in loft drier.
5, the sample of step 4 gained is placed in tube furnace, anneal at 850 ℃, annealing time is 30min, can obtain NiWO 4nano particle,
Utilize the NiWO of aforesaid method growth 4the XRD method of utilizing nano particle detects its phase composition, from NiWO 4in the XRD figure spectrum of nano particle in 20~80 degree range of diffraction, can determine, products therefrom is two-phase, and wherein one is Rutile Type TiO mutually 2, it is resulting principal phase after Ti sheet differential arc oxidation, as growth NiWO 4nano particle substrate, another is NiWO mutually 4nano particle.
Utilize the NiWO of aforesaid method growth 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 growing 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 atom picture shows NiWO 4nano particle is monocrystalline, and crystals degree of crystallinity is very complete, there is no 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 with steeping fluid by changing electrolytic solution, 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, usining industrially pure titanium carries out pre-treatment as substrate 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) 2in solution, flood 1h, then dry at 100 ℃ in loft drier.
5, the sample of step 4 gained is placed in tube furnace, anneal at 750 ℃, annealing time is 4h, can obtain ZnWO 4nanometer sheet.
Utilize the ZnWO of aforesaid method growth 4nanometer sheet utilizes XRD method to detect.From ZnWO 4in the XRD figure spectrum of nanometer sheet in 20~80 degree range of diffraction, can determine, products therefrom is two-phase, and wherein one is Rutile Type TiO mutually 2, it is resulting principal phase 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 of aforesaid method growth 4nanometer sheet utilizes surface sweeping Electronic Speculum method 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 growing under the present embodiment condition 4be rectangular-shaped, nanometer sheet thickness diameter is about 250nm, and length is 3~4 μ m, and width is about 2 μ m, and nanometer sheet smooth surface is even, there is no 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 atom picture shows ZnWO 4nanometer sheet is monocrystalline, and crystals degree of crystallinity is very complete, there is no the crystal structure defects such as twin and dislocation; The nanometer sheet length direction of growth is [100], and the width direction of growth 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, usining industrially pure titanium carries out pre-treatment as substrate 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) 2in solution, flood 1h, then dry at 100 ℃ in loft drier.
5, the sample of step 4 gained is placed in tube furnace, anneal at 850 ℃, annealing time is 60min, can obtain ZnWO 4nanotube.
Utilize the ZnWO of aforesaid method growth 4the XRD method of utilizing nanotube detects its phase composition, from ZnWO 4in the XRD figure spectrum of nanotube in 20~80 degree range of diffraction, can determine, products therefrom is two-phase, and wherein one is Rutile Type TiO mutually 2, it is resulting principal phase 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 of aforesaid method growth 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 growing 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 atom picture shows ZnWO 4nanotube is monocrystalline, and crystals degree of crystallinity is very complete, there is no the crystal structure defects such as twin and dislocation.
Embodiment result shows, the prepared metal tungstates nano material size of the present invention is homogeneous comparatively, and growth distribution is even.This preparation method's technical process is simple, does not need atmosphere protection, and raw materials production cost is low, pollution-free, environmentally friendly, simultaneously owing to being to generate metal oxide film in matrix surface original position, so the bonding force of rete and matrix is very good.Prepared tungstate nano material can be done photocatalyst material, electroluminescent material or Hydrobon catalyst etc.
Above-described is only the cited optimum embodiment of the present invention.It may be noted that; all technician for the art; not departing from the spirit of appended claims and the category situation of principle shown in the present, can also example illustrated be changed and/or be changed, these changes also should be considered the scope of the present invention.

Claims (9)

1. a micro-arc oxidation is prepared the method for metal tungstates nano material, it is characterized in that, the method utilizes micro-arc oxidation to generate layer of metal sull at valve metal or its alloy surface original position, then utilize pickling process to introduce active ingredient at film surface, after end to be impregnated by sample anneal 10~300min at 450 ℃~1200 ℃.
2. micro-arc oxidation according to claim 1 is prepared the method for metal tungstates nano material, it is characterized in that, metal is selected from Ni, Fe, Mn, Co, Zn or Cu.
3. micro-arc oxidation according to claim 1 is prepared 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) electrolytic solution of preparation differential arc oxidation, under magnetic agitation, adds (0.02~1.2) mol/L Na to filling in the container of deionized water 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 in Ni, Cu, Co, Mn, Fe, Zn;
(2) industrially pure titanium is placed in to 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) the prepared sample of step 2 is put into the M (NO of 0.01~10mol/L 3) 2in solution, flood 10~300min, wherein M is any in Ni, Cu, Co, Mn, Fe, Zn;
(4) the prepared sample of step 3 is placed in to tube furnace air and carries out anneal, annealing temperature is 450~1200 ℃, and soaking time is 10~500min, then cools to room temperature with the furnace and can obtain tungstate nano material.
4. according to the micro-arc oxidation described in claim 1 or 3, prepare 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.
5. micro-arc oxidation according to claim 4 is prepared the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is nanometer wire, the metal tungstates that it comprises a kind of Ni of being selected from, Cu, Co, Mn, Fe or Zn, wherein said nanowire diameter is 20~500nm, length is 2~3 μ m, and the direction of growth is along preferred orientation [100] growth, and the diameter of single nano-wire is homogeneous very.
6. micro-arc oxidation according to claim 4 is prepared the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is Nanoparticulate, the metal tungstates that it comprises a kind of Ni of being selected from, Cu, Co, Mn, Fe or Zn, wherein said grain diameter is 100~1000nm.
7. micro-arc oxidation according to claim 4 is prepared the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is nano-sheet, the metal tungstates that it comprises a kind of Ni of being selected from, Cu, Co, Mn, Fe or Zn, wherein said nanometer sheet thickness is 50~500nm, long edge lengths is 3~4 μ m, width edge length is 2~3 μ m, 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.
8. micro-arc oxidation according to claim 4 is prepared the method for metal tungstates nano material, it is characterized in that, a kind of pattern of metal tungstates nano material is nanotube-shaped, the metal tungstates that it comprises a kind of Ni of being selected from, 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.
9. micro-arc oxidation is prepared an application for metal tungstates nano material, it is characterized in that, prepared tungstate nano material is as photocatalyst material, electroluminescent material or Hydrobon catalyst.
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CN108251849A (en) * 2018-01-15 2018-07-06 中国科学院海洋研究所 A kind of photoelectric material and its restorative procedure for being used to improve stainless steel corrosion resistance
CN111926364A (en) * 2020-08-11 2020-11-13 苏州村野智能科技有限公司 Preparation method of self-lubricating composite ceramic layer on surface of aluminum alloy
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