CN106995218A - A kind of brick-shaped monoclinic phase WO3Preparation method - Google Patents
A kind of brick-shaped monoclinic phase WO3Preparation method Download PDFInfo
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- CN106995218A CN106995218A CN201710171799.4A CN201710171799A CN106995218A CN 106995218 A CN106995218 A CN 106995218A CN 201710171799 A CN201710171799 A CN 201710171799A CN 106995218 A CN106995218 A CN 106995218A
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- 238000000034 method Methods 0.000 title description 13
- 239000000843 powder Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 12
- 239000010935 stainless steel Substances 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 69
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 69
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 68
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004973 liquid crystal related substance Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 31
- 230000001699 photocatalysis Effects 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of brick-shaped monoclinic phase WO3Preparation method：First, by a certain amount of surfactant, it is placed in tetrafluoroethene liner, uses a certain amount of deionized water dissolving, after strong acid treatment, ageing a period of time；Then a certain amount of tungstates is weighed, is dissolved in a certain amount of deionized water, clear solution is formed；Clear solution is added dropwise to dropwise again in the surfactant solution after acidifying, it is stirring while adding, form yellow suspension；Finally polytetrafluoroethyllining lining is placed in stainless steel cauldron, the hydro-thermal reaction certain time in the baking oven of certain temperature, through filtering, washing, alcohol wash, dry, calcine after obtain target WO3Powder.
Description
Technical field
The invention belongs to solid oxide material preparing technical field, more particularly to a kind of brick-shaped monoclinic phase WO3System
Preparation Method.
Background technology
Tungstic acid (WO3) it is a kind of typical n-type semiconductor, with excellent photocatalysis, gas sensing property, photochromic,
The performances such as opto-electronic conversion.Compared with other semiconductor light-catalysts, WO3Energy gap it is relatively low (2.7eV), thus in equal bar
TiO is better than to visible absorption performance under part2(energy gap is about 3.2eV), so having potential application in terms of photocatalysis
Prospect.Research has shown that tungstic acid crystal formation is more：Such as monocline, it is three oblique, orthogonal, cubic, cube (Zheng H, Ou J Z,
Straino M S,et al.Nanostructured tungsten oxide-properties,synthesis,and
applications,Adv.Funct.Mater.,2011,21:2175-2196), however, only monoclinic phase WO3Structure is relatively
Stably, thus in photocatalysis larger effect can be played.
With development of modern industry, organic dyestuff usage amount is increasing, causes Heavy environmental pollution, because they have
It is carcinogenic, mutagenesis, the negative effect such as teratogenesis；In addition, the feature such as refractory organicses and color depth of organic dyestuff, can block sunlight
Passed through in water, so as to reduce ornamental hydrophyte.Therefore, the sewage containing organic dyestuff must be handled before discharging,
Reach corresponding discharge standard.Photocatalytically degradating organic dye is that current development is very fast, is also the more field of research, actually should
It can play a significant role, because photocatalysis can not only make organic Colors decorporate, and can thoroughly have been decomposed by light degradation in
Machine macromolecular is nontoxic, harmless small molecule：Such as CO2, H2O.Due to WO3Energy gap is relatively low, can be to the visible ray in sunshine
Part carries out larger absorption, thus with potential using value in terms of photocatalytic degradation of dye sewage.At present, in related side
More work (Shen Z, Zhao Z, Qian J, et al.Synthesis of WO are carried out in face3-x nanomaterials
with controlled morphology and composition for highly efficient
photocatalysis,J.Mater.Res.,2016,31:1065-1076；Zhang J,Nosaka Y,Generation of
OH radicals and oxidation mechanism in photocatalysis of WO3and BiVO4powders,
J.Photochem.Photobiol.,A,2015,303:53-58；Wei W,Shaw S,Lee K,et al.Rapid anodic
formation of high aspect ratio WO3layers with self-ordered nanochannel
geometry and use in photocatalysis,Chem.Eur.J.,2012,18:14622-14626).
At present, WO is prepared3Main method include solid phase method, liquid phase method, the precipitation method (Akiyama M, Tamaki J,
Miura N,et a1.WO3based semiconductor sensor highly sensitive to NO and NO2,
Chem.Lett.,1991,9:1611-1616；Yang B,Barnes P R,Bertram W,et al.Strong
photoresponse of nanostructured tungsten trioxide films prepared via a sol-
gel route,J.Mater.Chem.,2007,17:2722-2729；Sanchez M D,Martinez-de C A,Lopez C
E,Photocatalytic properties of WO3nanoparticles obtained by precipitation in
presence of urea as complexing agent,Appl.Catal.:A,2011,398:179-186).Utilize these
Method can prepare the WO of different structure3, so that its photocatalysis performance is different.Research shows that catalyst pattern is different, its light
Catalytic performance is different, and pattern is influenceed larger (Cruz A M, Mart D S, Cuellar E L.Synthesis by experiment condition
and characterization of WO3nanoparticles prepared by the precipitation
method:Evaluation of photocatalytic activity under vis-irradiation, Solid
State Sci.,2010,12:88-94)；In addition, photocatalysis efficiency and surface organic group (such as hydroxyl, carboxyl, amino) number
Amount is relevant, because these groups can influence catalyst to absorption (Hao S Y, Hou J, the Aplea P, et of organic pollution
al.Amino-functionalized ceria with enhanced daylight photocatalytic
efficiency,Ceram.Int.,2016,42:7440-7446)。
By literature survey, in existing patent and periodical literature report, protected using addition surfactant mode
Stay WO3Surface organo-functional group and adjustment WO3The preparation method of pattern is less, and pertinent literature is as described above, Patents are as follows：
In CN105948127A " a kind of method for preparing white oxide tungsten ", disclose one kind by raw material of tungsten hexachloride,
NaNO3It is medium for conditioning agent, anhydrous normal butyl alcohol, the method that white oxide tungsten is prepared by hydro-thermal method；
In CN105923657A " a kind of preparation method of monoclinic form tungstic acid ", one kind is disclosed with soluble wolframic acid
Salt is raw material, and nitric acid is precipitating reagent, forms wolframic acid, the method that tungsten oxide is converted into by hydro-thermal reaction；
In CN105600825A " a kind of method that tungsten oxide pattern and size are adjusted by CNT ", disclose it is a kind of with
CNT is template and pattern conditioning agent, and ethylene glycol is dispersant, and tungstates is tungsten source, and different-shape is prepared by sedimentation
With the method for size tungsten oxide.
It is well known that adding surfactant the interface state of solution system can be made to occur significant change, so as to influence to close
Into the structure and performance of material.Polyvinylpyrrolidone (PVP, structure such as Fig. 1)：A kind of non-ionic macromolecule compound, be
Most characteristic fine chemicals in N vinylamide polymer, medication chemistry, food hygiene, surfactant,
Played a significant role in terms of catalyst synthesis.Due to containing N in PVP, protonated under certain acid condition is-NH+, with tungsten
Acid groupCombined by electrostatic attraction, so as to reach scattered predecessor and change the purpose of product property.Experimental result table
It is bright, this patent provide preparation method is simple, workable, cost of material is low and environmentally friendly, synthesized material is to related dye
It can be played a significant role with good photocatalysis efficiency, thus in terms of environmental protection.So far, there are not Patents also
And document report this method, therefore this patent has original creative and practicality.
The content of the invention
Related dye (is divided using rhodamine B, acid orange 7 as probe the technical problem to be solved in the present invention is to provide a kind of
Son) there is the brick-shaped monoclinic phase WO of high efficiency photocatalysis efficiency3Preparation method.
To solve the technical problem, the technical solution adopted by the present invention is as follows：
A kind of brick-shaped monoclinic phase WO3Preparation method, it is characterised in that comprise the following steps：
1st, the polyvinylpyrrolidone that 0.1-1.0g molecular weight is 40000-80000 is added in polytetrafluoroethyllining lining
(PVP) 10-60mL deionized water dissolving PVP, are taken, then add 5-15mL dense HCl to be acidified PVP solution, and are aged 2-6 hours；
2nd, 1-6g Na is weighed2WO4·2H2O is placed in beaker, adds 5-20mL deionized water dissolving Na2WO4, and shape
Into clear solution；
3rd, by Na2WO4Clear solution is added dropwise in PVP acid solutions dropwise, forms yellow suspension, and side edged magnetic force is stirred
Mix, be well mixed suspension, the magnetic agitation time is 20-50min；
4th, polytetrafluoroethyllining lining is placed in stainless steel cauldron, the hydro-thermal reaction 12- in 150-240 DEG C of baking oven
24h, after filtering, washing, absolute ethyl alcohol washing, 60-90 DEG C of drying, obtains pale yellow powder；
5th, pale yellow powder is calcined after 1-6h in 300-800 DEG C of tube furnace, obtains yellow WO3Powder.
In above-mentioned preparation process, a certain amount of PVP is dissolved in after deionized water, and it is entered with a certain amount of concentrated hydrochloric acid
Row acidifying.
In above-mentioned preparation process, ageing a period of time is needed after the acidifying of PVP solution, is become liquid crystal templated.
In above-mentioned preparation process, Na2WO4·2H2O solids are dissolved in after water, are added to dropwise in PVP acid solutions, in liquid crystal
Precipitation is formed in template.
In above-mentioned preparation process, brick-shaped monoclinic phase WO3Obtained by hydro-thermal reaction.
In the present invention, using PVP template effect, wolframic acid is deposited thereon, is easy to wolframic acid growth and development into rule
Crystal.In the present invention, by the use of hydrochloric acid as strong acid media, make after the N protonations in PVP, drawn with tungstate radicle by electrostatic
Power is combined, and strengthens the active force between template and precipitation, wolframic acid is precipitated oriented growth.In the present invention, Na2WO4·2H2O consolidates
Body is dissolved in after water, is added dropwise to dropwise in PVP acid solutions, and is stirred when being added dropwise, it is therefore an objective to be dispersed in predecessor
In system, under PVP effects, prevent product from reuniting.In the present invention, the purpose of hydro-thermal reaction is that the wolframic acid for making generation has been crystallized
It is kind.It was found from XRD (accompanying drawing 2a), WO3Main diffraction peak position appear in 2 θ for 23.1,23.6,24.4,34.2 degree etc.,
With monoclinic phase WO3(JCPDS 43-1035) standard card coincide substantially, and the corresponding crystal face of these diffraction maximums is respectively (002),
(020), (200), (202).Therefore, the product synthesized by the present invention is monoclinic phase.Understood according to SEM (accompanying drawing 2b), synthesized material
Material outward appearance is brick-shaped, and it is less to reunite.By infrared spectrum (referring to accompanying drawing 3) result, in synthetic product of the present invention
Hydroxy radical content is higher, because sample is in 1640cm-1Place has stronger infrared peak, and this peak is non-aqueous hydroxyl peak.With the brick of synthesis
Block monoclinic phase WO3For catalyst, photocatalysis is carried out to rhodamine B in waste water (RhB), as a result shown, synthesized product is to RhB
With excellent catalytic degradation efficiency：After illumination 35min, RhB degrades substantially (refers to accompanying drawing 4a) completely.In addition, passing through control
Experiment, without PVP in synthetic system, products therefrom substantially reduces to RhB catalytic degradation efficiency and (refers to accompanying drawing 4b).Go out
It is the reason for above-mentioned phenomenon now：Add after PVP, synthesized WO3Middle hydroxy radical content is high, improves adsorbance of the catalyst to RhB,
Thus high catalytic efficiency；In addition, forming brick-shaped product, be conducive to specific surface area to increase, can also improve Dye Adsorption amount.Pass through
Acid orange 7 (AO7) catalytic degradation is understood, the product that the present invention is synthesized also has good photocatalytic degradation effect (in detail to AO7
See accompanying drawing 5).
In summary, the brick-shaped monoclinic phase WO prepared by the present invention3Synthetic method is simple, cost is relatively low, environment-friendly,
There is efficient catalytic degradation to related dye, therefore, there is potential using value in terms of dye wastewater improvement.
Brief description of the drawings
The structural representation of Fig. 1 polyvinylpyrrolidones；
Fig. 2 WO3XRD (a) and SEM (b) figures；
Fig. 3 WO3FT-IR figure；
Under Fig. 4 ultraviolet-visible light irradiations, WO3Catalytic degradation efficiency (a) and additive PVP to RhB is to catalytic efficiency
Influenceing (b), (pH=6, catalyst quality is 0.05g, and dye strength is 0.05mg/L, and dye volume is 50mL, and action time is
1h)；
Under Fig. 5 ultraviolet-visible light irradiations, WO3To AO7 catalytic degradation efficiency (pH=5, catalyst quality is 0.05g,
Dye strength is 0.05mM, and dye volume is 50mL, and action time is 1h).
Embodiment
The preparation method of the present invention is described further below by embodiment, but the present invention is not limited to following implementation
Example.
Embodiment 1
The polyvinylpyrrolidone (PVP) that 0.1g molecular weight is 40000 is added in polytetrafluoroethyllining lining, takes 10mL to go
After ionized water dissolving, then add 5mL dense HCl to be acidified PVP solution, and be aged 2h；Weigh 1g Na2WO4·2H2O is placed in beaker
In, 5mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise in PVP acid solutions dropwise,
Yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 20min；By polytetrafluoroethyl-ne
Alkene liner is placed in stainless steel cauldron, the hydro-thermal reaction 12h in 150 DEG C of baking oven, washed through filtering, washing, absolute ethyl alcohol,
After 60 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow WO after calcining 1h in 300 DEG C of tube furnace3Powder
End.
Embodiment 2
The polyvinylpyrrolidone (PVP) that 0.1g molecular weight is 60000 is added in polytetrafluoroethyllining lining, takes 30mL to go
After ionized water dissolving, then add 10mL dense HCl to be acidified PVP solution, and be aged 4h；Weigh 4g Na2WO4·2H2O is placed in beaker
In, 15mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise to PVP acid solutions dropwise
In, yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 30min；By poly- four
PVF liner is placed in stainless steel cauldron, the hydro-thermal reaction 18h in 190 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol
After washing, 70 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow after calcining 4h in 500 DEG C of tube furnace
WO3Powder.
Embodiment 3
The polyvinylpyrrolidone (PVP) that 0.1g molecular weight is 80000 is added in polytetrafluoroethyllining lining, takes 60mL to go
After ionized water dissolving, then add 15mL dense HCl to be acidified PVP solution, and be aged 6h；Weigh 6g Na2WO4·2H2O is placed in beaker
In, 20mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise to PVP acid solutions dropwise
In, yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 50min；By poly- four
PVF liner is placed in stainless steel cauldron, the hydro-thermal reaction 24h in 240 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol
After washing, 90 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow after calcining 6h in 800 DEG C of tube furnace
WO3Powder.
Embodiment 4
The polyvinylpyrrolidone (PVP) that 0.5g molecular weight is 40000 is added in polytetrafluoroethyllining lining, takes 10mL to go
After ionized water dissolving, then add 5mL dense HCl to be acidified PVP solution, and be aged 2h；Weigh 1g Na2WO4·2H2O is placed in beaker
In, 5mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise in PVP acid solutions dropwise,
Yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 20min；By polytetrafluoroethyl-ne
Alkene liner is placed in stainless steel cauldron, the hydro-thermal reaction 12h in 150 DEG C of baking oven, washed through filtering, washing, absolute ethyl alcohol,
After 60 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow WO after calcining 1h in 300 DEG C of tube furnace3Powder
End.
Embodiment 5
The polyvinylpyrrolidone (PVP) that 0.5g molecular weight is 60000 is added in polytetrafluoroethyllining lining, takes 30mL to go
After ionized water dissolving, then add 10mL dense HCl to be acidified PVP solution, and be aged 4h；Weigh 4g Na2WO4·2H2O is placed in beaker
In, 15mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise to PVP acid solutions dropwise
In, yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 30min；By poly- four
PVF liner is placed in stainless steel cauldron, the hydro-thermal reaction 18h in 190 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol
After washing, 70 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow after calcining 4h in 500 DEG C of tube furnace
WO3Powder.
Embodiment 6
The polyvinylpyrrolidone (PVP) that 0.5g molecular weight is 80000 is added in polytetrafluoroethyllining lining, takes 60mL to go
After ionized water dissolving, then add 15mL dense HCl to be acidified PVP solution, and be aged 6h；Weigh 6g Na2WO4·2H2O is placed in beaker
In, 20mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise to PVP acid solutions dropwise
In, yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 50min；By poly- four
PVF liner is placed in stainless steel cauldron, the hydro-thermal reaction 24h in 240 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol
After washing, 90 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow after calcining 6h in 800 DEG C of tube furnace
WO3Powder.
Embodiment 7
The polyvinylpyrrolidone (PVP) that 1g molecular weight is 40000 is added in polytetrafluoroethyllining lining, take 10mL go from
After sub- water dissolving, then add 5mL dense HCl to be acidified PVP solution, and be aged 2h；Weigh 1g Na2WO4·2H2O is placed in beaker,
5mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise in PVP acid solutions dropwise, shape
Yellowly suspension, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 20min；By polytetrafluoroethylene (PTFE)
Liner is placed in stainless steel cauldron, the hydro-thermal reaction 12h in 150 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol washing, 60
DEG C drying after, obtain pale yellow powder；Pale yellow powder obtains yellow WO after calcining 1h in 300 DEG C of tube furnace3Powder.
Embodiment 8
The polyvinylpyrrolidone (PVP) that 1g molecular weight is 60000 is added in polytetrafluoroethyllining lining, take 30mL go from
After sub- water dissolving, then add 10mL dense HCl to be acidified PVP solution, and be aged 4h；Weigh 4g Na2WO4·2H2O is placed in beaker
In, 15mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise to PVP acid solutions dropwise
In, yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 30min；By poly- four
PVF liner is placed in stainless steel cauldron, the hydro-thermal reaction 18h in 190 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol
After washing, 70 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow after calcining 4h in 500 DEG C of tube furnace
WO3Powder.
Embodiment 9
The polyvinylpyrrolidone (PVP) that 1g molecular weight is 80000 is added in polytetrafluoroethyllining lining, take 60mL go from
After sub- water dissolving, then add 15mL dense HCl to be acidified PVP solution, and be aged 6h；Weigh 6g Na2WO4·2H2O is placed in beaker
In, 20mL deionized water dissolving is added, clear solution is formed；By Na2WO4Clear solution is added dropwise to PVP acid solutions dropwise
In, yellow suspension is formed, side edged magnetic agitation is well mixed suspension, and the magnetic agitation time is 50min；By poly- four
PVF liner is placed in stainless steel cauldron, the hydro-thermal reaction 24h in 240 DEG C of baking oven, through filtering, washing, absolute ethyl alcohol
After washing, 90 DEG C of drying, pale yellow powder is obtained；Pale yellow powder obtains yellow after calcining 6h in 800 DEG C of tube furnace
WO3Powder.
Claims (9)
1. a kind of brick-shaped monoclinic phase WO3Preparation method, it is characterised in that comprise the following steps：
1) polyvinylpyrrolidone (PVP) that 0.1-1.0g molecular weight is 40000-80000 is added in polytetrafluoroethyllining lining,
10-60mL deionized water dissolving PVP are taken, then add 5-15mL dense HCl to be acidified PVP solution, and are aged 2-6 hours；
2) 1-6g Na is weighed2WO4·2H2O is placed in beaker, adds 5-20mL deionized water dissolving Na2WO4, and form saturating
Bright solution；
3) by Na2WO4Clear solution is added dropwise in PVP acid solutions dropwise, forms yellow suspension, and side edged magnetic agitation makes
Suspension is well mixed, and the magnetic agitation time is 20-50min；
4) polytetrafluoroethyllining lining is placed in stainless steel cauldron, the hydro-thermal reaction 12-24h in 150-240 DEG C of baking oven, passed through
After filtering, washing, absolute ethyl alcohol washing, 60-90 DEG C of drying, pale yellow powder is obtained；
5) pale yellow powder is calcined after 1-6h in 300-800 DEG C of tube furnace, obtains yellow WO3Powder.
2. preparation method according to claim 1, it is characterised in that：It is to use PVP to be surface in above-mentioned preparation process
Activating agent, is dissolved in 10-60mL deionized water.
3. preparation method according to claim 1, it is characterised in that：In above-mentioned preparation process, PVP molecular weight is
40000-80000。
4. preparation method according to claim 1, it is characterised in that：In above-mentioned preparation process, PVP consumption is 0.1-
1.0g。
5. preparation method according to claim 1, it is characterised in that：It is to use after PVP dissolvings in above-mentioned preparation process
Concentrated hydrochloric acid carries out acidification to it, makes the N in PVP protonate to form-NH+。
6. preparation method according to claim 1, it is characterised in that：In above-mentioned preparation process, needed after the acidifying of PVP solution
Ageing 2-6 hours, becomes liquid crystal templated.
7. preparation method according to claim 1, it is characterised in that：In above-mentioned preparation process, the consumption of concentrated hydrochloric acid is
5-15mL。
8. preparation method according to claim 1, it is characterised in that：In above-mentioned preparation process, 1-6g Na2WO4It is molten
In after 5-20mL deionized water, it is added dropwise in PVP acid solutions, makes in solution dropwiseWith-the NH in PVP+Pass through
Electrostatic attraction is combined, so that PVP is fixed on pale yellow precipitate.
9. preparation method according to claim 1, it is characterised in that：In above-mentioned preparation process, mixed liquor is in 150-
Pale yellow powder is obtained in 240 DEG C of baking oven after hydro-thermal reaction 12-24h, pale yellow powder is forged in 300-800 DEG C of tube furnace
Burn after 1-6h, obtain yellow WO3Powder.
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Cited By (3)
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| CN109675641A (en) * | 2019-01-09 | 2019-04-26 | 太原理工大学 | A kind of polyvinylpyrrolidone cladding nanometer WO3And its preparation method and application |
| CN111348684A (en) * | 2020-03-10 | 2020-06-30 | 景德镇学院 | Preparation method and application of orthorhombic layered tungsten trioxide |
| CN116119719A (en) * | 2023-04-18 | 2023-05-16 | 崇义章源钨业股份有限公司 | Superfine platy tungsten oxide and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675641A (en) * | 2019-01-09 | 2019-04-26 | 太原理工大学 | A kind of polyvinylpyrrolidone cladding nanometer WO3And its preparation method and application |
| CN109675641B (en) * | 2019-01-09 | 2021-11-16 | 太原理工大学 | Polyvinylpyrrolidone coated nano WO3And preparation method and application thereof |
| CN111348684A (en) * | 2020-03-10 | 2020-06-30 | 景德镇学院 | Preparation method and application of orthorhombic layered tungsten trioxide |
| CN111348684B (en) * | 2020-03-10 | 2022-06-10 | 景德镇学院 | Preparation method and application of orthorhombic layered tungsten trioxide |
| CN116119719A (en) * | 2023-04-18 | 2023-05-16 | 崇义章源钨业股份有限公司 | Superfine platy tungsten oxide and preparation method thereof |
| CN116119719B (en) * | 2023-04-18 | 2023-06-27 | 崇义章源钨业股份有限公司 | Superfine platy tungsten oxide and preparation method thereof |
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