CN109225201A - A kind of preparation method and application of micro-nano tungsten oxide - Google Patents
A kind of preparation method and application of micro-nano tungsten oxide Download PDFInfo
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- CN109225201A CN109225201A CN201810954025.3A CN201810954025A CN109225201A CN 109225201 A CN109225201 A CN 109225201A CN 201810954025 A CN201810954025 A CN 201810954025A CN 109225201 A CN109225201 A CN 109225201A
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- 239000004065 semiconductor Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 37
- 230000008569 process Effects 0.000 abstract description 13
- 239000007791 liquid phase Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000006193 liquid solution Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of preparation method of micro-nano tungsten oxide, by dispersing filter paper into sodium tungstate solution, makes that the gel presoma formed after pH is adjusted to be sufficiently adhering on filter paper, later by filtering and roasting, obtains tungsten oxide product.The present invention also proposes the product and its application that the preparation method obtains.Preparation method provided by the present invention has merged the advantages of liquid phase method raw material is uniformly mixed with solid phase method simple process, its core is using a kind of substance being easily removed as carrier, it can be directly transferred to progress calcination process in Muffle furnace after its load tungsten presoma and obtain oxidation tungsten product, without being further processed；And method therefor high-efficient simple, environmentally protective, process is short, product is controllable；Raw materials required for the reaction is all the raw material being conveniently easy to get in the market；Preparing resulting tungsten oxide has the characteristics that better crystallinity degree, of uniform size, soilless sticking, photocatalysis performance are good, can be widely applied to dyestuff degradation and other field of semiconductor photocatalyst.
Description
Technical field
The invention belongs to micro-nano material fields, and in particular to a kind of preparation of micro/nano level tungsten oxide material and its answer
With.
Background technique
Tungsten oxide is a kind of widely used n-type semiconductor metal oxide, as a kind of cheap and stable transition gold
Belong to oxide, tungsten oxide has photocatalysis, gas because the height of its structure is adjustable and unique physical and chemical performance is concerned
The excellent performances such as quick, photochromic, electrochromism, be widely used in photocatalytic degradation, gas sensor, Flied emission equipment,
In the equipment such as electrochromic device.Relative to same type of material TiO2, ZnO, NiO etc., tungsten oxide has narrower forbidden bandwidth, because
This absorbable light using visible light wave range in sunlight, and it is not only limited to ultraviolet light.
Preparation method has significant impact to the physicochemical properties of material, because it directly affects synthesized material
Crystal structure, particle size, service performance and practical application etc..There are many methods for preparing tungsten oxide at present, according to raw material
Property and reaction process difference can be broadly divided into: vapor phase method, liquid phase method and solid phase method.Vapor- phase synthesis be it is a kind of using heating, etc.
The various energy such as ionic drive or light radiation make the chemical substance of gaseous state or steam-like in gas phase or gas-solid interface in reactor
On through chemically reacting form the technology of solid deposited object, physical vapour deposition (PVD) (PVD) and chemical gas-phase method (CVD) are more commonly used
Vapor- phase synthesis technology.But vapor phase method general device higher cost, people usually consider to use liquid phase method at this time, compared to gas phase side
Method, liquid phase synthesizing method (LPS) can preferably control the pattern of material, and can realize that liquid phase is closed at quite low temperatures
At therefore, requirement of this method to energy and equipment is lower, greatly reduces cost.Liquid phase method mainly includes sol-gel
Method, hydro-thermal method, template and electrochemical process etc., but there is also some problems, as sol-gel transition is more difficult, after template
Phase treatment process is relatively complicated, hydro-thermal method needs further calcination processing, synthesis cycle longer etc..Solid phase method is by solid phase
Variation generallys use to manufacture powder and wolframic acid or ammonium tungstate etc. are directly heated decomposition containing tungsten oxide prepares tungstic acid,
It is characterized in that without phase transformation as the adjoint gas phase-solid phase of vapor phase method and liquid phase method, liquid-solid.For gas phase or liquid phase,
Molecule is very sensitive to the reaction of external condition, and for solid phase, the diffusion of molecule (atom) is very slow, Set Status be it is various,
The resulting solid phase powder of solid phase method and initial Solid raw materials can be same substance, may not be same substance.
Above-mentioned a variety of preparation methods still have some shortcomings.The available particle size of vapor phase method is small, with high purity
Tungsten oxide material, but this method is higher to equipment and technical requirements, and synthesis is difficult, at high cost, product controllability is poor, at present
Only rest on the laboratory research stage；Liquid phase method has the advantages that cost is relatively low, stable reaction, product are controllable, but its subsequent place
Reason process is cumbersome, synthesis cycle is longer；Although solid phase method simple process, obtained product is easy to reunite, needs separating twice, and
Quality is lower.
Summary of the invention
For short slab present in existing technology of preparing and deficiency, the primary purpose of the present invention is that providing a kind of micro-nano
The novel processing step of tungsten oxide；This method has merged the advantages of liquid phase method raw material is uniformly mixed with solid phase method simple process, tool
Have the advantages that process is short, simple and feasible, environmentally protective, product is controllable.
Another object of the present invention is to provide the micro-nanos with different-shape structure that a kind of above method is prepared
Rice tungsten oxide product.
A further object of the present invention is to provide the applications of the micro-nano tungsten oxide.
Realize above-mentioned purpose technical solution of the present invention are as follows:
A kind of preparation method of micro-nano tungsten oxide makes to adjust and is formed after pH by dispersing filter paper into sodium tungstate solution
Gel presoma is sufficiently adhering on filter paper, later by filtering and roasting, obtains tungsten oxide product.
Technical solution of the present invention is proposed in further detail below.
The preparation method of the micro-nano tungsten oxide, comprising steps of
(1) filter paper fragment is distributed in the water containing sodium tungstate, obtains dispersion；
(2) by dispersion obtained in step (1) when being stirred continuously with inorganic acid for adjusting pH, before obtaining glue
Drive liquid solution；
(3) it after the precursor solution for obtaining step (2) is stood, is rinsed and filters, obtain being attached on filter paper
Gluey tungsten presoma；
(4) filter paper that gluey tungsten presoma is attached in step (3) is subjected to high-temperature roasting processing, it is air-cooled after roasting
To room temperature, obtained product is tungsten oxide.
Wherein, concentration of sodium tungstate is 10-80g/L in dispersion described in step (1).
Wherein, inorganic acid described in step (2) is hydrochloric acid, sulfuric acid or nitric acid, and concentration 1-8mol/L adjusts dispersion
PH value is to pH=0.5-3.
Wherein, the time of standing described in step (3) is 0.5-12 hours.
Wherein, maturing temperature is 400-800 DEG C, calcining time 3-12 hours in step (4).Roasting crucible used can be with
For corundum crucible, high-temperature roasting carries out in Muffle furnace.
The further preferred technical solution of the present invention is, by be not added or be added in the sodium tungstate solution adjusting control agent come
Regulate and control product morphology, with the micro/nano level granular product or micron order hollow sphere product dispersed or one-dimensional product.It is one-dimensional
Product is usually nano wire, nanometer rods, the one-dimensional structure such as nanobelt.
A preferred technical solution of the invention is also to contain adjusting control agent, the adjusting control agent in the sodium tungstate solution
Mass ratio for one of zinc chloride, zinc sulfate, potassium sulfate, potassium chloride or a variety of, adjusting control agent and sodium tungstate is 0.5~1:
1。
The micro-nano tungsten oxide that the preparation method obtains.
Application of the micro-nano tungsten oxide in dyestuff degradation or semiconductor light electrotransformation.
The beneficial effects of the present invention are:
Preparation method provided by the present invention has merged the advantages of liquid phase method raw material is uniformly mixed with solid phase method simple process,
Its core is can be directly transferred to be roasted in Muffle furnace after loading tungsten presoma using a kind of substance being easily removed as carrier
Burning handles to obtain oxidation tungsten product, without being further processed；And method therefor high-efficient simple, environmentally protective, process is short, product can
Control；Raw materials required for the reaction is all the raw material being conveniently easy to get in the market；It is equal with better crystallinity degree, size to prepare resulting tungsten oxide
The features such as even, soilless sticking, photocatalysis performance are good can be widely applied to dyestuff degradation and other field of semiconductor photocatalyst.
Detailed description of the invention
Fig. 1 is the XRD diagram piece of 1 products therefrom of embodiment.
Fig. 2 is the SEM picture of 1 products therefrom of embodiment.
Fig. 3 is the SEM picture of 2 products therefrom of embodiment.
Fig. 4 is the XRD diagram piece of 2 products therefrom of embodiment.
Specific embodiment
Illustrate the present invention below by most preferred embodiment.Those skilled in the art institute it should be understood that, embodiment is only used to
It illustrates rather than for limiting the scope of the invention.
In embodiment, unless otherwise instructed, means used are the means of this field routine.
Embodiment 1:
It is distributed to after commercial filter paper is shredded in the 50ml pure water of the sodium tungstate containing 1g, after being sufficiently mixed uniformly, is placed in magnetic force
On blender, when being stirred continuously with 4mol/L hydrochloric acid conditioning solution pH value to pH=1, faint yellow gluey forerunner is obtained
Liquid solution；After the presoma is stood 3 hours, several times with pure water and ethyl alcohol repeated flushing, and it is obtained by filtration and is attached on filter paper
Gluey tungsten presoma, transfer them in corundum crucible later, in Muffle furnace in 600 DEG C high-temperature roasting 6 hours, Zhi Houkong
It is cooled to room temperature to get final tungsten oxide product is arrived.
The above-mentioned tungsten oxide product of 0.01g is weighed, is dissolved in the methylene blue solution that 100ml concentration is 10mg/L, is protected from light
Under the conditions of after uniform stirring 10min reaches adsorption equilibrium, above-mentioned mixed solution is placed in the xenon lamp equipped with filter plate (λ > 420nm)
Under light source, the process of tungsten oxide photocatalytic degradation methylene blue under light can be guaranteed that continuous magnetic force stirs in reaction process by simulation
It mixes and light source irradiates, and take supernatant to be detected in certain time.Prepared product has preferable photocatalytic degradation effect,
In 180min, degradation efficiency is up to 94%.
Fig. 1 is the XRD diagram for the tungsten oxide product that embodiment 1 obtains, peak value and monoclinic phase WO3It is corresponding, as seen from the figure
Prepared product crystallinity is good, and crystal phase is single, and no other impurities generate.Fig. 2 is the tungsten oxide product that embodiment 1 obtains
SEM picture can clearly be seen that prepared Product size distribution is relatively uniform in figure, be micro/nano level nutty structure,
Do not reunite.
Embodiment 2:
It is distributed to after commercial filter paper is shredded in the 50ml pure water of the sodium tungstate containing 1g, then to weigh 0.68g (5mM) zinc chloride molten
It after wherein, being sufficiently mixed uniformly, is placed on magnetic stirring apparatus, when being stirred continuously with 4mol/L hydrochloric acid conditioning solution acid
Basicity obtains faint yellow gluey precursor solution to pH=1；After the presoma is stood 3 hours, rushed repeatedly with pure water and ethyl alcohol
It washes several times, and the gluey tungsten presoma being attached on filter paper is obtained by filtration, transfer them in corundum crucible later, in Muffle furnace
It is interior in 600 DEG C high-temperature roasting 6 hours, be air-cooled to room temperature later to get to final tungsten oxide product.
Fig. 3 is the SEM picture for the tungsten oxide product that embodiment 2 obtains, and can clearly be seen that prepared product is in figure
The micrometre hollow sphere structure that nano particle assembles, size are more uniform.Fig. 4 is the XRD for the tungsten oxide product that embodiment 2 obtains
Figure, peak value correspond to monoclinic phase WO3(main) and hexagonal phase WO3, prepared product crystallinity is good as seen from the figure, removes main product
Beyond the region of objective existence is generated without other impurities.
The visible light photocatalytic degradation process under xenon lamp simulation is carried out later, and method and step is the same as embodiment 1.Products therefrom also has
There is preferable photocatalytic degradation effect, degradation efficiency is up to 99% in 180min.
Embodiment 3:
It is distributed to after commercial filter paper is shredded in the 50ml pure water of the sodium tungstate containing 1g, then to weigh 0.87g (5mM) potassium sulfate molten
It after wherein, being sufficiently mixed uniformly, is placed on magnetic stirring apparatus, when being stirred continuously with 4mol/L hydrochloric acid conditioning solution acid
Basicity obtains faint yellow gluey precursor solution to pH=1；After the presoma is stood 3 hours, rushed repeatedly with pure water and ethyl alcohol
It washes several times, and the gluey tungsten presoma being attached on filter paper is obtained by filtration, transfer them in corundum crucible later, in Muffle furnace
It is interior in 600 DEG C high-temperature roasting 6 hours, be air-cooled to room temperature later to get to final tungsten oxide product.
It is observed by SEM, it is seen that obtained tungsten oxide particles are one-dimensional rod-like pattern.XRD spectrum shows the peak value of product
With WO3Corresponding, no other impurities generate.
Embodiment 4:
It is distributed to after commercial filter paper is shredded in the 50ml pure water of the sodium tungstate containing 1g, after being sufficiently mixed uniformly, is placed in magnetic force
On blender, when being stirred continuously with 4mol/L hydrochloric acid conditioning solution pH value to pH=3, faint yellow gluey forerunner is obtained
Liquid solution；After the presoma is stood 3 hours, several times with pure water and ethyl alcohol repeated flushing, and it is obtained by filtration and is attached on filter paper
Gluey tungsten presoma, transfer them in corundum crucible later, in Muffle furnace in 600 DEG C high-temperature roasting 6 hours, Zhi Houkong
It is cooled to room temperature to get final tungsten oxide product is arrived.
The pH value of the present embodiment dispersion is slightly higher, and the product that scanning electron microscopic observation obtains slightly is reunited.Therefore preferably compared with
The dispersion of low ph value；But inorganic acid dosage has greater environmental impacts too much, therefore preferably in the pH value item of pH >=1
Part.
Embodiment 5:
It is distributed to after commercial filter paper is shredded in the 50ml pure water of the sodium tungstate containing 3g, after being sufficiently mixed uniformly, is placed in magnetic force
On blender, when being stirred continuously with 4mol/L hydrochloric acid conditioning solution pH value to pH=1, faint yellow gluey forerunner is obtained
Liquid solution；After the presoma is stood 3 hours, several times with pure water and ethyl alcohol repeated flushing, and it is obtained by filtration and is attached on filter paper
Gluey tungsten presoma, transfer them in corundum crucible later, in Muffle furnace in 600 DEG C high-temperature roasting 6 hours, Zhi Houkong
It is cooled to room temperature to get final tungsten oxide product is arrived.
Wolframic acid sodium content is higher in the present embodiment dispersion, and gained final product pattern is more irregular, is unfavorable for subsequent
Using, therefore preferably in the concentration conditions of 15-25g/L.
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of preparation method of micro-nano tungsten oxide, which is characterized in that by dispersing filter paper into sodium tungstate solution, make to adjust pH
The gel presoma formed afterwards is sufficiently adhering on filter paper, later by filtering and roasting, obtains tungsten oxide product.
2. the preparation method of micro-nano tungsten oxide according to claim 1, which is characterized in that comprising steps of
(1) filter paper fragment is distributed in the water containing sodium tungstate, obtains dispersion；
(2) by dispersion obtained in step (1) when being stirred continuously with inorganic acid for adjusting pH, obtain gluey presoma
Solution；
(3) it after the precursor solution for obtaining step (2) is stood, is rinsed and filters, obtain being attached to the glue on filter paper
Tungsten presoma；
(4) filter paper for being attached with gluey tungsten presoma in step (3) is subjected to high-temperature roasting processing, is air-cooled to room after roasting
Temperature, obtained product are tungsten oxide.
3. the preparation method of micro-nano tungsten oxide according to claim 2, which is characterized in that divide described in step (1)
Concentration of sodium tungstate is 10-80g/L in granular media system.
4. the preparation method of micro-nano tungsten oxide according to claim 2, which is characterized in that inorganic described in step (2)
Acid is hydrochloric acid, sulfuric acid or nitric acid, and concentration 1-8mol/L adjusts dispersion pH value to pH=0.5-3.
5. the preparation method of micro-nano tungsten oxide according to claim 2, which is characterized in that stood described in step (3)
Time be 0.5-12 hours.
6. the preparation method of micro-nano tungsten oxide according to claim 2, which is characterized in that the roasting temperature in step (4)
Degree is 400-800 DEG C, calcining time 3-12 hours.
7. the preparation method of micro-nano tungsten oxide according to claim 1-6, which is characterized in that by described
Adjusting control agent is not added or is added in sodium tungstate solution to regulate and control product morphology, with the micro/nano level granular product dispersed or micro-
Meter level hollow sphere product or one-dimensional product.
8. the preparation method of micro-nano tungsten oxide according to claim 7, which is characterized in that in the sodium tungstate solution also
Containing adjusting control agent, the adjusting control agent is one of zinc chloride, zinc sulfate, potassium sulfate, potassium chloride or a variety of, adjusting control agent and wolframic acid
The mass ratio of sodium is 0.5-1:1.
9. the micro-nano tungsten oxide that the described in any item preparation methods of claim 1-8 obtain.
10. application of the micro-nano tungsten oxide as claimed in claim 9 in dyestuff degradation or semiconductor light electrotransformation.
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