CN105498745A - Nano acanthosphere-shaped zinc oxide photocatalyst and preparation method thereof - Google Patents
Nano acanthosphere-shaped zinc oxide photocatalyst and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 150000003751 zinc Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 deionized water compound Chemical class 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 4
- 235000013904 zinc acetate Nutrition 0.000 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 3
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000012266 salt solution Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 47
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 238000012360 testing method Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 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
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nano acanthosphere-shaped zinc oxide photocatalyst and a preparation method thereof, belongs to the field of photocatalytic materials, and particularly relates to a zinc oxide preparation method with zinci acetas dihydricus and cyclodextrin compounds and derivatives thereof serving as raw materials. The method comprises the following steps that firstly, a zinc salt solution is prepared from deionized water, and cyclodextrin is added to the zinc salt solution to form a mixed solution; after the mixed solution still stands for several hours, stirring is carried out, a sodium hydroxide solution is dropwise added slowly, and finally the mixture is contained in a high-pressure reaction container; after heating is carried out for several hours, the mixture is naturally cooled to room temperature, after precipitate is centrifugally washed, drying is carried out, and a target product is obtained. The process is simple and easy to operate, and obtained zinc oxide is formed by gathering and growing of nano acanthosphere-shaped zinc oxide around the sphere center, has the advantages of being small in particle size, good in dispersibility, large in specific surface area and the like, and is beneficial to application in the field of photocatalysis.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide, particularly relate to the nano zine oxide preparation that a kind of two water zinc acetates and cyclodextrin are raw material, can be applicable to photocatalytic pollutant degradation field.
Background technology
Zinc oxide is a kind of directly broad stopband II-VI race's oxide semiconductor material, nano zine oxide size is between cluster and Macroscopic particulates, there is the special nature that many macroscopic material such as the small-size effect of nano material, skin effect do not possess, nano zine oxide shows noticeable application prospect in light absorption, photocatalysis etc., can be widely used in photocatalysis, photoelectron and Optical Electro-Chemistry.
The preparation method of zinc oxide has vapor phase method, solid phase method, hydro-thermal method, the precipitation method, sol-gal process and physical evaporation etc., and pattern has spherical, bar-shaped, nano wire, nanobelt, three-dimensional order superstructure that is flower-shaped and that assembled by one dimension, two-dimensional nanostructure unit.Vapor phase method preparation needs high reaction temperature, condition of high vacuum degree usually, and equipment is complicated, expensive, and production cost is high.Chemical precipitation method preparation there will be secondary ion product, and there will be the problems such as washing difficulty, domain size distribution is wider, and after dry, particle is easily reunited.Sol-gal process affects comparatively large by the pH value of solution, concentration, reaction time, temperature, is unfavorable for the zinc oxide preparation of controllable appearance.Relative to additive method, zinc oxide prepared by hydro-thermal method has the features such as crystal morphology preparation temperature easy to control, relative is low, preparation method is simple, easy to operate.Therefore the present invention preferably uses water heat transfer zinc oxide, and for strengthening its photocatalysis performance by modification.
As everyone knows, pattern and the structure on performance of zinc oxide have significant impact, and improving Zinc oxide catalyzes activity can by reducing crystal grain or increase specific area to realize.Existing achievement in research is many based on above 2 modified zinc oxides, such as patent CN101249979A discloses a kind of prickly sphere zinc oxide atmospheric preparation method, the prickly sphere zinc oxide specific area that it synthesizes at ambient pressure is large, improves the contact probability with pollutant, finally improves rate of catalysis reaction.But in experimentation, strict regulation and control are needed to pH value; The raw material selected is zinc nitrate hexahydrate, very easily produces nitrate ion impurity, not easily isolates pure Zinc oxide powder.Patent CN102381726A discloses a kind of bell-shaped zinc oxide technology of preparing, and its zinc oxide structures prepared is novel, and preparation technology is simple.Shortcoming is that zinc oxide specific area is little, and photocatalysis performance is not ideal enough.A kind of preparation method of flower shape zinc oxide nanometer rods cluster disclosed in patent CN1033189443A, zinc oxide grain is of a size of nanoscale, there is the typical bulk effect of nano material, all improve a lot compared with typical die at light absorption, catalytic, but being limited to pattern is bar-shaped zinc oxide cluster, do not form the appearance structure of the acanthosphere shape similar with the present invention, thus specific area is little, and photocatalysis performance has no small gap with the present invention; And preparation method takes is chemical dissolution method, difficult to control operability poor.The prickly sphere zinc oxide adopting vapour deposition process to prepare in the article " the CVD growth of zinc oxide micrometer acanthosphere and the application in piezoelectric stress sensor thereof " that the people such as Liu Xin deliver is formed around centre of sphere growth by spiculation zinc oxide, but it is not tight that its thorn-like zinc oxide piles up arrangement, there is a big difference in specific area to gather the prickly sphere zinc oxide of growth with the present invention, and photocatalysis performance is limited.
There is following problem in the preparation method of existing zinc oxide in summary: as preparation method's difficulty, requirement for experiment condition is high, and the zinc oxide specific area of formation is little, and crystal grain is easily reunited, and photocatalysis effect is undesirable.
Summary of the invention
The technical problem that the present invention solves is: the nanometer prickly sphere zinc oxide photochemical catalyst and the preparation method that propose a kind of increasing specific surface area reduce crystallite dimension while.
In order to solve the problems of the technologies described above, the technical scheme that the present invention proposes is: a kind of preparation method of nanometer prickly sphere zinc oxide photochemical catalyst, and concrete steps are as follows:
(1) be the zinc solution of 0.01 ~ 0.2mol/L and concentration with deionized water compound concentration be respectively the sodium hydroxide solution of 0.1 ~ 1mol/L;
(2) in zinc solution, add the cyclodextrin of 5 ~ 100g/L, form mixed solution;
(3) get mixed solution, stir and slowly drip and press Zn
2+/ OH-is the sodium hydroxide solution of 1:1 ~ 10:1 ratio, continues stirring 10 ~ 40 minutes subsequently;
(4) load in high-pressure reaction vessel, be heated to 150 ~ 250 DEG C, isothermal reaction 8 ~ 24 hours;
(5) room temperature is naturally cooled to, by distilled water centrifuge washing sediment post-drying for several times.
Preferably, described zinc salt is two water zinc acetates.
Preferably, cyclodextrin comprises alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and derivative thereof.
Preferably, in described step (2), in mixed solution, the mol ratio of zinc ion and cyclodextrin is 1:1 ~ 1:5.
Preferably, described nanometer prickly sphere zinc oxide is formed around centre of sphere aggregation growth by nanoneedle thorn-like zinc oxide, and specific area is 110 ~ 300m
2/ g.
Beneficial effect:
The equipment that the preparation method of nanometer prickly sphere zinc oxide photochemical catalyst of the present invention uses is simple, and raw material easily obtains, and technique is concisely easy to operate, and preparation method's environmental friendliness can realize suitability for industrialized production.
The present invention adopts hydro-thermal method to prepare zinc oxide, and with two water zinc acetates and cyclodextrin compounds for raw material, cyclodextrin plays important regulating and controlling effect to zinc oxide acanthosphere shape special appearance.
The present invention utilizes cyclodextrin to have hydrophobic pocket and is easy to the characteristic that acetate forms inclusion complex, carrys out auxiliary synthesizing zinc oxide.Can effective controlled oxidization zinc pattern, form the spherical zinc oxide that a kind of nanometer thorn-like zinc oxide grows around the centre of sphere, grain size is little, its size uniformity, good dispersion, specific area is large, sphere is rich in hydroxyl, adsorbed water ability is strong, is easy to zinc oxide surface occurs in photohole reaction, and photocatalysis performance improves greatly.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is the XRD collection of illustrative plates of nanometer prickly sphere zinc oxide.
Fig. 2 is the SEM photo of nanometer prickly sphere zinc oxide.
Fig. 3 is nanometer prickly sphere zinc oxide rhodamine B degradation rate diagram.
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, without departing from the inventive concept of the premise, can also make some distortion and modification.These all belong to protection scope of the present invention.
Embodiment 1
Take 2.19g bis-water zinc acetate to be dissolved in the deionized water of 100mL, and add 48.65g alpha-cyclodextrin, get 10mL mixed solution and insert in the tank of polytetrafluoroethylene (PTFE); Magnetic stirring apparatus stirs 30 minutes, then the concentration slowly dripping 4mL is the sodium hydroxide solution of 1mol/L; The polytetrafluoroethylene (PTFE) filling mixed solution is loaded in stainless steel autoclave, in Muffle furnace, is heated to 180 DEG C, isothermal reaction 12 hours; Naturally cool to room temperature after taking-up, then with distilled water washing, after freeze drying, obtain nanometer Zinc oxide powder.Adopt X-ray diffractometer (XRD) characterizing sample, result as shown in Figure 1, be 31.65 °, 34.44 ° and 36.24 ° at 2 θ and locate appearance 3 strong peaks, (100), (002), (101) crystal face of corresponding zinc oxide respectively, analyzing known zinc oxide sample is six side's fibre ore structures, calculated by Scherrer formula (D=K λ/Bcos θ) and show, the zinc oxide average crystal grain of preparation is about 5nm, belongs to nanocrystalline ZnO.
Embodiment 2
Take 1.09g bis-water zinc acetate to be dissolved in the deionized water of 100mL, and add 11.35g beta-schardinger dextrin-, get 10mL mixed solution and insert in the tank of polytetrafluoroethylene (PTFE); Magnetic stirring apparatus stirs 30 minutes, then the concentration slowly dripping 4mL is the sodium hydroxide solution of 2.5mol/L; The polytetrafluoroethylene (PTFE) filling mixed solution is loaded in stainless steel autoclave, in Muffle furnace, is heated to 200 DEG C, isothermal reaction 8 hours; Naturally cool to room temperature after taking-up, then use distilled water centrifuge washing, after freeze drying, obtain Zinc oxide powder.Characterize zinc oxide with Scanning Electron microscope (SEM), as shown in Figure 2, to result prepared zinc oxide closely gather by six side's phase acicular type zinc oxides the spherical zinc oxide formed, and has the large 168.35m of specific area
2/ g, the features such as good dispersion.To there is the capture ability of stronger light induced electron, more photo-generate electron-hole pair can be produced, will higher photocatalysis performance be had.
Embodiment 3
Take 1.09g bis-water zinc acetate to be dissolved in the deionized water of 100mL, and add 12.97 gamma-cyclodextrins, get 10mL mixed solution and insert in the tank of polytetrafluoroethylene (PTFE); Magnetic stirring apparatus stirs 30 minutes, then the concentration slowly dripping 4mL is the sodium hydroxide solution of 0.25mol/L; The polytetrafluoroethylene (PTFE) filling mixed solution is loaded in stainless steel autoclave, in Muffle furnace, is heated to 180 DEG C, isothermal reaction 12 hours; Naturally cool to room temperature after taking-up, then with distilled water washing, after freeze drying, obtain nanometer Zinc oxide powder.With rhodamine B (12mg/L) the simulation printing and dyeing waste liquid of 50mL, test 40mg zinc oxide under ultraviolet lighting to the degradation capability of pollutant, every 10 minutes sampling and testings, data as shown in Figure 3, and compare for zinc oxide sample with common hydro-thermal legal system, the photocatalysis efficiency of this sample promotes about 20%.
The concrete technical scheme be not limited to described in above-described embodiment of the present invention, all employings are equal to replaces the protection domain that the technical scheme formed is application claims.
Claims (5)
1. a preparation method for nanometer prickly sphere zinc oxide photochemical catalyst, concrete steps are as follows:
(1) be the zinc solution of 0.01 ~ 0.2mol/L and concentration with deionized water compound concentration be respectively the sodium hydroxide solution of 0.1 ~ 1mol/L;
(2) in zinc solution, add the cyclodextrin of 5 ~ 100g/L, form mixed solution;
(3) get mixed solution, stir and slowly drip and press Zn
2+/ OH-is the sodium hydroxide solution of 1:1 ~ 10:1 ratio, continues stirring 10 ~ 40 minutes subsequently;
(4) load in high-pressure reaction vessel, be heated to 150 ~ 250 DEG C, isothermal reaction 8 ~ 24 hours;
(5) room temperature is naturally cooled to, by distilled water centrifuge washing sediment post-drying for several times.
2. the preparation method of nanometer prickly sphere zinc oxide photochemical catalyst according to claim 1, is characterized in that: described zinc salt is two water zinc acetates.
3. the preparation method of nanometer prickly sphere zinc oxide photochemical catalyst according to claim 1, cyclodextrin comprises alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and derivative thereof.
4. the preparation method of nanometer prickly sphere zinc oxide photochemical catalyst according to claim 1, is characterized in that: in described step (2), in mixed solution, the mol ratio of zinc ion and cyclodextrin is 1:1 ~ 1:5.
5. the nanometer prickly sphere zinc oxide prepared of the preparation method of nanometer prickly sphere zinc oxide photochemical catalyst according to claim 1, it is characterized in that: described nanometer prickly sphere zinc oxide is formed around centre of sphere aggregation growth by nanoneedle thorn-like zinc oxide, specific area is 110 ~ 300m
2/ g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046310A (en) * | 2018-08-22 | 2018-12-21 | 东莞理工学院 | A kind of zinc oxide photocatalysis film of two-layer composite and its preparation method and application |
| CN114956158A (en) * | 2022-06-13 | 2022-08-30 | 河北戴桥医药科技有限公司 | Preparation method of calamine powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249979A (en) * | 2008-04-01 | 2008-08-27 | 西南交通大学 | Atmospheric preparation method of prickly sphere zinc oxide |
| CN102381726A (en) * | 2010-08-31 | 2012-03-21 | 合肥学院 | Bell-shaped ZnO nanometer device material and preparation method thereof |
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