CN106975476A - A kind of efficient tungstic acid microsphere photocatalyst and preparation method thereof - Google Patents
A kind of efficient tungstic acid microsphere photocatalyst and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 20
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 5
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- 230000001699 photocatalysis Effects 0.000 claims abstract description 5
- -1 polyoxyethylene Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 13
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000012153 distilled water Substances 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910020350 Na2WO4 Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001126 phototherapy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/615—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
Abstract
The present invention relates to a kind of efficient tungstic acid microsphere photocatalyst and preparation method thereof, first monosaccharide solutions and tungsten source solution are well mixed, the mol ratio for obtaining monose and tungsten source in mixed solution A, mixed solution A is (1~3)：(1~2)；Then the surfactant solution for accounting for mixed solution A volume 1%~2% is added into mixed solution A, it is well mixed to obtain mixed solution B；Mixed solution B pH value is adjusted 3~7, homogeneous hydro-thermal reaction is carried out at 170~220 DEG C；Homogeneous hydro-thermal reaction is cooled to room temperature after terminating, and isolates product and washs drying, obtains dry powder material；Dry powder material is incubated 30~60min at 500~800 DEG C, efficient tungstic acid microsphere photocatalyst is obtained.The present invention is prepared for Tetragonal WO by hydro-thermal method3With monoclinic phase WO3Compound, pattern is microspheroidal, it is easy to synthesized, and photocatalysis efficiency and degradation rate are high.
Description
Technical field
The invention belongs to catalyst material field, and in particular to a kind of efficient tungstic acid microsphere photocatalyst and its preparation
Method.
Background technology
Tungstic acid (WO3) it is by WO6It is octahedra to be made up of common side or corner-sharing, mainly there is monoclinic phase, three monoclinic phases, orthogonal
Phase, Tetragonal, hexagonal phase and Emission in Cubic.Its energy gap is about 2.5-2.8eV, is a kind of n-type semiconductor, in ultraviolet light
Area and visible region have preferable absorption characteristic, can use photocatalyst [Zhen-Feng Huang, Jiajia Song, Lun
Pan,et al.Tungsten Oxides for Photocatalysis,Electrochemistry,and
Phototherapy[J].Advanced Materials,2015,27:5309-5327.].Extraneous stimulation (light, electricity, heat,
Inert atmosphere and reducing atmosphere) under, WO3Navy blue can be changed into by the yellow of itself： Therefore can be used as electrochromism, photochromic and gas-discoloration device [Jaehyun
Bae,Haekyoung Kim,Hong Chul Moon,et al.Low-voltage,simple WO3-based
electrochromic devices by directly incorporating an anodic species into the
electrolyte[J].Journal of Materials Chemistry C,2016,4:10887-10892.]。WO3Have
Excellent gas-sensitive property, it is to H2S、NO、NO2、NH3There is good sensitivity Deng gas, therefore be used frequently as gas sensitive device
[Zhang C.,Boudiba A.,Marco P.D.,et al.Room temperature responses of visible-
light illuminated WO3sensors to NO2in sub-ppm range[J].Sensors and Actuators
B,2013,181:395-401.].In addition, WO3There is larger hole path in crystal structure, Li can be made+Pass through, therefore can make
For lithium ion battery electrode material [Yang J.Q., Jiao L.F., Zhao Q.Q., et al.Facile preparation
and electrochemical properties of hierarchical chrysanthemum-like WO3·0.33H2O
[J].Journal of Materials Chemistry,2012,22:3699-3701.]。
At present, a variety of physics and the method for chemistry are used for WO3Synthesis, such as physical vaporous deposition, chemical vapor deposition
Area method, thermal evaporation, sol-gal process, hydro-thermal method, solvent-thermal method etc..In these methods, hydro-thermal method is due to simple to operate, instead
Answer condition easily controllable, the advantages of product purity is high has obtained extensive research, but because the limitation of band gap makes it in visible ray
In the range of utilization rate it is relatively low, it is not fine to make the degradation efficiency under its visible ray.
The content of the invention
It is an object of the invention to overcome problems of the prior art to be urged there is provided a kind of efficient tungstic acid microballoon light
Agent and preparation method thereof, obtained WO3Microballoon specific surface area is big, and photocatalysis performance is preferable.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
Comprise the following steps：
(1) monosaccharide solutions and tungsten source solution are well mixed, obtain monose and tungsten source in mixed solution A, mixed solution A
Mol ratio is (1~3)：(1~2)；Then the surface-active for accounting for mixed solution A volume 1%~2% is added into mixed solution A
Agent solution, it is well mixed to obtain mixed solution B；
(2) regulation mixed solution B pH value obtains mixed solution C 3~7；
(3) mixed solution C is subjected to homogeneous hydro-thermal reaction at 170~220 DEG C；
(4) homogeneous hydro-thermal reaction is cooled to room temperature after terminating, and isolates product and washs drying, obtains dry powder thing
Matter；
(5) dry powder material is incubated 30~60min at 500~800 DEG C, obtains efficient tungstic acid microballoon light and urge
Agent.
Further, the concentration of monosaccharide solutions is 0.5~1mol/L in step (1), the concentration of tungsten source solution for 0.5~
1mol/L, the concentration of surfactant solution is 0.01~0.05mol/L.
Further, monose uses C in step (1)6H12O6·H2O。
Further, tungsten source uses Na in step (1)2WO4·2H2O, surfactant uses polyoxyethylene fatty acid ester.
Further, it is to be well mixed by stirring 15~25min at 25~30 DEG C in step (1).
Further, pH value is adjusted using 2~3mol/L HCl solution in step (2).
Further, mixed solution C is poured into polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle in step (3), and volume is filled out
Fill than 30%~50%, then sealing polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle, be put into homogeneous hydro-thermal reaction instrument
Carry out homogeneous hydro-thermal reaction.
Further, the time of homogeneous hydro-thermal reaction is 20~28h in step (3).
Further, the drying in step (4) is to dry 6~10h in 60~80 DEG C of vacuum drying ovens.
One kind utilizes efficient tungstic acid microsphere photocatalyst, the grain of the photochemical catalyst made from preparation method as described above
Footpath is at 0.5~2 μm, and BET surfaces are 120~135m2/g。
Compared with prior art, the present invention has following beneficial technique effect：
The present invention prepares the WO of pure phase by one step hydro thermal method3, then by soak process, phase transition is produced,
Finally it is prepared for Tetragonal WO3With monoclinic phase WO3Compound, the combination product shows as microspheric pattern, and particle diameter about exists
1 μm or so, obtained product crystal property is good, and raw material is simple, and cost is than relatively low, it is easy to synthesize, and yield is high, is expected to be applied to
Factory mass produces.Compound one homojunction of formation prepared by the present invention, sets up built in field, promote light induced electron to
Same direction is constantly migrated, and photohole is moved in the opposite direction, drastically increases the mobility of carrier, so as to improve
Photocatalysis efficiency；Meanwhile, the WO synthesized by the present invention3Microballoon can provide more with bigger than surface for catalytic degradation reaction
Avtive spot, effectively improve the degradation rate of light-catalyzed reaction.
Further, monose is sugared using glucose in the present invention, it is easy to remove, and glucose removal process can generate hole knot
Structure, is conducive to the migration of electron hole pair.
WO synthesized by the present invention3Microspherulite diameter is at 0.5~2 μm, and BET surfaces are 120~135m2/ g, with preferable light
Catalytic performance, the light degradation methylene blue 60min under 1000W xenon lamp, degradation rate can reach 85~90%, relative commercial
P25 degradation rates lift one times；With good absorption property, 10 methylene blues of circulation absorption, adsorption rate remains to reach 80%
More than, show that the material is recyclable and be used for multiple times.
Brief description of the drawings
Fig. 1 is WO prepared by the embodiment of the present invention 13XRD spectrum.
Fig. 2 is microspheroidal WO prepared by the embodiment of the present invention 13SEM photograph under 25k multiplication factors.
Embodiment
The present invention is described in further details below in conjunction with the accompanying drawings.
1) 0.5~1M C is prepared6H12O6·H2O distilled water solutions, 0.5~1M Na2WO4·2H2O distilled water solutions with
And 0.01~0.05M polyoxyethylene fatty acid ester distilled water solution.
2) by above-mentioned solution C by volume6H12O6·H2O:Na2WO4·2H2O=(1~3):The ratio mixing of (1~2),
15~25min is stirred at 25~30 DEG C.Then the Polyoxyethylene fatty that volume ratio is 1%~2% is added into resulting solution
Acid esters distilled water solution, stirs 15~25min at 25~30 DEG C.
3) pH=3~7 of above-mentioned mixed solution are adjusted for 2~3M HCl solution with concentration.
4) well mixed solution is poured into polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle, keeps volume packing ratio to exist
30%~50%.
5) reactor of good seal is put into homogeneous hydro-thermal reaction instrument, it is 170~220 DEG C to set temperature parameter, reaction
Time is 20~28h.
6) reaction is cooled to room temperature after terminating, after end reaction thing is centrifuged, respectively with deionized water and anhydrous second
Alcohol respectively washing 3 times.Powder material after centrifuging, washing is put into 60~80 DEG C of vacuum drying ovens and dries 6~10h.
7) gained sample after drying is put into box high temperature resistance furnace, it is 500~800 DEG C to set temperature parameter, in sky
The gas atmosphere lower reaction time is 30~60min, that is, obtains final product.
Embodiment 1
1) 0.5M C is prepared6H12O6·H2O distilled water solutions, 0.5M Na2WO4·2H2O distilled water solutions and 0.01M
Polyoxyethylene aliphatic alcohol ether distilled water solution.
2) by above-mentioned solution C by volume6H12O6·H2O:Na2WO4·2H2O=1:1 ratio mixing, is stirred at 25 DEG C
Mix 25min.Then the polyoxyethylene aliphatic alcohol ether distilled water solution that volume ratio is 1% is added into resulting solution, at 25 DEG C
Stir 25min.
3) HCl solution for being 2M with concentration adjusts the pH=3 of above-mentioned mixed solution.
4) well mixed solution is poured into polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle, keeps volume packing ratio to exist
30%.
5) reactor of good seal is put into homogeneous hydro-thermal reaction instrument, it is 170 DEG C to set temperature parameter, and the reaction time is
28h。
6) reaction is cooled to room temperature after terminating, after end reaction thing is centrifuged, respectively with deionized water and anhydrous second
Alcohol respectively washing 3 times.Powder material after centrifuging, washing is put into 60 DEG C of vacuum drying ovens and dries 10h.
7) gained sample after drying is put into box high temperature resistance furnace, it is 500 DEG C to set temperature parameter, in air atmosphere
The lower reaction time will be 60min, that is, obtain final product.
As seen from Figure 1：Product prepared by the present invention is Tetragonal WO3With monoclinic phase WO3Compound.
As seen from Figure 2：The WO that the present invention is obtained3It is particle diameter about in 0.5~1 μm or so of micro-sphere structure.
The light degradation methylene blue 60min under 1000W xenon lamp, degradation rate can reach 90%, and its BET surface is 135m2/
G, with good absorption property, 10 methylene blues of circulation absorption, adsorption rate remains to reach more than 80%.
The degradation rates of commercialized P25 under the same conditions are 45%；Therefore, it is of the invention compared with commercialized P25, drop
Solution rate is greatly promoted.
Embodiment 2
1) 1M C is prepared6H12O6·H2O distilled water solutions, 1M Na2WO4·2H2O distilled water solutions and 0.05M's is poly-
Oxygen ethene fatty acid ester distilled water solution.
2) by above-mentioned solution C by volume6H12O6·H2O:Na2WO4·2H2O=3:2 ratio mixing, is stirred at 30 DEG C
Mix 15min.Then the polyoxyethylene fatty acid ester distilled water solution that volume ratio is 2% is added into resulting solution, at 30 DEG C
Stir 15min.
3) HCl solution for being 3M with concentration adjusts the pH=7 of above-mentioned mixed solution.
4) well mixed solution is poured into polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle, keeps volume packing ratio to exist
50%.
5) reactor of good seal is put into homogeneous hydro-thermal reaction instrument, it is 220 DEG C to set temperature parameter, and the reaction time is
20h。
6) reaction is cooled to room temperature after terminating, each with deionized water and absolute ethyl alcohol after end reaction thing is centrifuged
Washing 3 times.Powder material after centrifuging, washing is put into 80 DEG C of vacuum drying ovens and dries 6h.
7) gained sample after drying is put into box high temperature resistance furnace, it is 800 DEG C to set temperature parameter, in air atmosphere
The lower reaction time will be 30min, that is, obtain final product.
Obtained WO3Be particle diameter about in 1.5 μm or so of micro-sphere structure, its BET surface is 127m2/g。
The light degradation methylene blue 60min under 1000W xenon lamp, degradation rate can reach 85%.
Embodiment 3
1) 0.8M C is prepared6H12O6·H2O distilled water solutions, 0.8M Na2WO4·2H2O distilled water solutions and 0.03M
Polyoxyethylene fatty acid ester distilled water solution.
2) by above-mentioned solution C by volume6H12O6·H2O:Na2WO4·2H2O=2:1 ratio mixing, is stirred at 28 DEG C
Mix 20min.Then the polyoxyethylene fatty acid ester distilled water solution that volume ratio is 1.5% is added into resulting solution, at 28 DEG C
Lower stirring 20min.
3) HCl solution for being 2M with concentration adjusts the pH=5 of above-mentioned mixed solution.
4) well mixed solution is poured into polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle, keeps volume packing ratio to exist
40%.
5) reactor of good seal is put into homogeneous hydro-thermal reaction instrument, it is 180 DEG C to set temperature parameter, and the reaction time is
24h。
6) reaction is cooled to room temperature after terminating, each with deionized water and absolute ethyl alcohol after end reaction thing is centrifuged
Washing 3 times.Powder material after centrifuging, washing is put into 70 DEG C of vacuum drying ovens and dries 8h.
7) gained sample after drying is put into box high temperature resistance furnace, it is 650 DEG C to set temperature parameter, in air atmosphere
The lower reaction time will be 45min, that is, obtain final product.
Obtained WO3Be particle diameter about in 2 μm or so of micro-sphere structure, its BET surface is 120m2/g。
The light degradation methylene blue 60min under 1000W xenon lamp, degradation rate can reach 87%.
Comparative example 1
By template C6H12O6·H2O is substituted for others and is easily formed spherical template, such as PS microballoons, and three block is common
Polymers, SiO2Microballoon etc..But other templates are not as glucose is easily removed, and glucose removal process can generate hole knot
Structure, is conducive to the migration of electron hole pair.
Claims (10)
1. a kind of preparation method of efficient tungstic acid microsphere photocatalyst, it is characterised in that：Comprise the following steps：
(1) monosaccharide solutions and tungsten source solution are well mixed, obtain monose and mole in tungsten source in mixed solution A, mixed solution A
Than for (1~3)：(1~2)；Then into mixed solution A add account for mixed solution A volume 1%~2% surfactant it is molten
Liquid, it is well mixed to obtain mixed solution B；
(2) regulation mixed solution B pH value obtains mixed solution C 3~7；
(3) mixed solution C is subjected to homogeneous hydro-thermal reaction at 170~220 DEG C；
(4) homogeneous hydro-thermal reaction is cooled to room temperature after terminating, and isolates product and washs drying, obtains dry powder material；
(5) dry powder material is incubated 30~60min at 500~800 DEG C, obtains efficient tungstic acid microballoon photocatalysis
Agent.
2. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly the concentration of monosaccharide solutions is 0.5~1mol/L in (1), and the concentration of tungsten source solution is 0.5~1mol/L, surfactant solution
Concentration be 0.01~0.05mol/L.
3. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly monose uses C in (1)6H12O6·H2O。
4. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly tungsten source uses Na in (1)2WO4·2H2O, surfactant uses polyoxyethylene fatty acid ester.
5. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly it is well mixed by stirring 15~25min at 25~30 DEG C in (1).
6. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly pH value is adjusted using 2~3mol/L HCl solution in (2).
7. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly mixed solution C is poured into polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle in (3), and volume packing ratio is 30%~50%, so
Polytetrafluoroethyllining lining high-pressure hydrothermal reaction kettle is sealed afterwards, is put into homogeneous hydro-thermal reaction instrument and carries out homogeneous hydro-thermal reaction.
8. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly the time of homogeneous hydro-thermal reaction is 20~28h in (3).
9. a kind of preparation method of efficient tungstic acid microsphere photocatalyst according to claim 1, it is characterised in that：Step
Suddenly the drying in (4) is to dry 6~10h in 60~80 DEG C of vacuum drying ovens.
10. one kind is existed using efficient tungstic acid microsphere photocatalyst made from preparation method described in claim 1, its feature
In：The particle diameter of the photochemical catalyst is at 0.5~2 μm, and BET surfaces are 120~135m2/g。
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