CN106423166B - A kind of synthetic method of cuprous oxide visible light catalyst - Google Patents
A kind of synthetic method of cuprous oxide visible light catalyst Download PDFInfo
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- CN106423166B CN106423166B CN201610912244.6A CN201610912244A CN106423166B CN 106423166 B CN106423166 B CN 106423166B CN 201610912244 A CN201610912244 A CN 201610912244A CN 106423166 B CN106423166 B CN 106423166B
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- cuprous oxide
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- light catalyst
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- -1 1- butyl -3- methyl imidazolium tetrafluoroborate Chemical compound 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000011805 ball Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006037 cell lysis Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/51—
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
Abstract
The invention discloses a kind of synthetic methods of hollow spheres cuprous oxide visible light catalyst, belong to the preparation technical field of catalysis material.Characterized by comprising the following steps: 0.1817 g Salicylaldoxime of precise is dispersed in 18 mL ethylene glycol, ultrasonic disperse forms bottle green clear solution.1.20-3.60 g 1- butyl -3- methyl imidazolium tetrafluoroborate is added thereto again, stirs 6-24 h, obtains blue suspension.Suspension is fully transferred in the stainless steel autoclave containing polytetrafluoroethyllining lining (25 mL of volume), kettle is sealed.Autoclave is placed in baking oven, 2-6 h is reacted at 100-180 DEG C.After reaction, product is centrifugated by cooled to room temperature, then is respectively cleaned 5 times with water, dehydrated alcohol respectively.The solid being collected into is placed in a vacuum drying oven, 60 DEG C of 12 h of drying can obtain hollow spheres cuprous oxide visible light catalyst.Operation of the present invention is simple, at low cost, and products therefrom has pure cubic structure, is a kind of synthetic method of effectively preparation hollow spheres cuprous oxide visible light catalyst.
Description
Technical field:
The invention belongs to the preparation technical fields of catalysis material, have been provided in particular in a kind of cuprous oxide visible light catalysis
The synthetic method of agent.
Background technique:
With the rapid development of industrial and agricultural production, environmental pollution and energy shortage have become two hang-ups of facing mankind.
In numerous pollutants, difficult for biological degradation, hardly possible are phenols, Polychlorinated biphenyls and polycyclic aromatic hydrocarbon etc. with the degradation of traditional wastewater facture
Macromolecular organic pollutant.Therefore, effective drop in relation to the big organic wastewater of such concentration height, difficult for biological degradation, bio-toxicity
Solution, has caused the extensive concern of countries in the world researcher.Utilize solar energy, photocatalysis degradation organic contaminant, it has also become solve
One of the effective ways of above-mentioned problem.Cuprous oxide is a kind of typical p-type semiconductor, and forbidden bandwidth is 2.0 eV-2.2 eV,
Belong to narrow gap semiconductor, there is unique optical property, light-catalyzed reaction can be caused under sunlight, be widely used in the sun
Energy battery, lithium ion battery, biosensor, photochemical cell and photocatalysis etc., have caused the attention of numerous researchers.
It is well known that the pattern of substance, crystal structure and surface characteristic etc. influence the performance of material, performance determines purposes.
The visible light catalyst of high activity and high stability in order to obtain, people have used microwave method, pulsed deposition method, collosol and gel
The methods of method, electrochemical deposition, for micro-nano materials of cuprous oxide such as nanosphere, nano wire, nano cubic block, octahedral structures
The synthesis of material.Such as any surfactant is not used in Y.-H. Tsai, at Cu (OAc)2, NaOH and N2H4In solution, pass through tune
The volume for saving hydrazine hydrate, obtains the cuprous nano material of different-shape, in catalytic cyclization addition reaction, has { 111 }
The octahedral figure cuprous oxide of crystal face shows preferable catalytic activity (Y.-H. Tsai, et as catalyst production highest
Al. Nanoscale, 2014,6 (15), 8704-8709.).S. Sun etc. is using complex as presoma, using treating different things alike
Method be prepared for cuprous oxide classifying nano ball, it is good that special pattern shows it to the photocatalytic degradation of methyl orange solution
Good catalytic activity and stability (S. Sun, et al. CrystEngComm, 2012,14 (10), 3545-3553.).
Y. Zhao etc. is prepared for cuprous oxide and is classified dendritic nano wire, and in photocatalysis hydrogenation reaction, energy conversion solar can be chemical energy
It carries out energy storage (Y. Zhao, et al. Nanoscale, 2014,6 (1), 195-198.).
Summary of the invention:
It is obtained the purpose of the present invention is to provide a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst
Hollow spheres cuprous oxide visible light catalyst be to be constructed by a large amount of nanoparticles as building block, the phase of nanoparticle
Mutually accumulation makes its surface have porous structure, helps to improve specific surface area.Hollow microsphere low, Surface Permeability with density
Well, the advantages that large specific surface area, strong visible light absorption capacity, interior ectosphere wall is used as active site, and organic pollutant is promoted to urge
Change degradation.Hollow microsphere constructed by a large amount of nanoparticles, is had the characteristics that nano-particles size is small, activity is high, is made
Empty spherical cuprous oxide has good visible light catalytic performance.
The technical solution adopted by the present invention is as follows a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst,
The following steps are included:
(1) 0.1817 g Salicylaldoxime of precise is dispersed in 18 mL ethylene glycol, and it is clear that ultrasonic disperse forms bottle green
Clear solution.
(2) 1.20-3.60 g 1- butyl -3- methyl imidazolium tetrafluoroborate is added into (1) described solution, stirs 6-
24 h obtain blue suspension.
(3) (2) described suspension is fully transferred to the stainless steel autoclave (25 mL of volume) containing polytetrafluoroethyllining lining
In, seal kettle.Autoclave is placed in baking oven, 2-6 h is reacted at 100-180 DEG C.After reaction, cooled to room temperature, will
Product centrifuge separation, then respectively cleaned 5 times with water, dehydrated alcohol respectively.The solid being collected into is placed in a vacuum drying oven, 60
DEG C dry 12 h, can obtain hollow spheres cuprous oxide visible light catalyst.
We utilize copper ion using solvent structure hollow spheres cuprous oxide visible light catalysts in the present invention
Interaction between glycol molecule is generated using 1- butyl -3- methyl imidazolium tetrafluoroborate as soft template in autoclave
Particular surroundings under, be finally prepared for hollow spheres cuprous oxide.
Further it is provided in:
In step 1, it is dispersed in Salicylaldoxime in ethylene glycol using ultrasonic method.
In step 2, into the clear solution described in step 1,1.20-3.60 g 1- butyl -3- methylimidazole tetrafluoro is added
Borate stirs 6-24 h.
In step 3, autoclave reaction temperature is 100-180 DEG C, and the reaction time is 2-6 h.
Hollow spheres cuprous oxide visible light catalyst prepared by the present invention, the catalyst are powder, and crystal phase is a cube knot
Structure, pattern be nanoparticle construct, the hollow microsphere with porous surface.Utilize scanning electron microscope (SEM, JEOL JSM-
6360LV, acceleration voltage are 20 kV) and X-ray diffractometer (XRD, Empyrean, Dutch PANalytical company) characterization institute
Obtain the pattern and crystal structure of product.Hollow spheres cuprous oxide visible light catalyst prepared by the present invention, has the characteristics that.
(1) ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate is added in reaction system, regulates and controls the pattern of product.
(2) preparation process method is simple to operation, and product is reproducible.
(3) hollow spheres cuprous oxide visible light catalyst prepared by the present invention is the hollow spheres with micron-scale
Structure, a large amount of nanoparticles are mutually accumulated, and so that the ball wall of hollow microsphere is had porous structure, and then improve specific surface area.Structure
The nanoparticle for building hollow sphere made from cuprous oxide has the characteristics that nano material size is small, activity is high, can effectively improve urging for material
Change activity.
(4) hollow spheres cuprous oxide visible light catalyst prepared by the present invention, compares with the cuprous oxide of purchase,
The cuprous oxide for being found to have hollow spheres structure imitates the photocatalytic degradation of persistent organic pollutants p-nitrophenol in water
Fruit is significant.
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Detailed description of the invention:
Fig. 1 a is scanning electron microscope (SEM) photo of the product prepared in embodiment 1；
Fig. 1 b is scanning electron microscope (SEM) photo of the product prepared in embodiment 1；
Fig. 2 is the X-ray diffractogram (XRD) of the product prepared in embodiment 1；
Fig. 3 is that the hollow spheres cuprous oxide prepared and the cuprous oxide of purchase are under visible light illumination, right in embodiment 1
The concentration versus time curve of nitrophenol.
Specific embodiment:
Embodiment 1: 0.1817 g Salicylaldoxime of precise is dispersed in 18 mL ethylene glycol, and ultrasonic disperse forms depth
Green clear solution.3.6 g 1- butyl -3- methyl imidazolium tetrafluoroborates are added thereto again, stir 6 h, it is outstanding to obtain blue
Turbid.Suspension is fully transferred in the stainless steel autoclave containing polytetrafluoroethyllining lining (25 mL of volume), kettle is sealed.Reaction
After, autoclave is placed in baking oven, 2 h are reacted at 170 DEG C, product is centrifugated by cooled to room temperature, then is divided
It is not cleaned respectively 5 times with water, dehydrated alcohol.The solid being collected into is placed in a vacuum drying oven, 60 DEG C of 12 h of drying can be obtained
Hollow spheres cuprous oxide visible light catalyst.It is about 1 μm -1.5 μm of size that SEM result (Fig. 1 a), which intuitively shows product,
Sphere, the SEM figure (Fig. 1 b) being further amplified confirms that ball interior is hollow structure, and wall thickness is about 300 nm, ball wall be by
Largely, unordered nanoparticle is constructed.XRD(Fig. 2) result and standard card (JCPDS No. 78-2076) coincide, show
Product is cubic phase Cu2O structure, belongs to cubic system.
In order to study the photocatalytic activity of prepared sample, using p-nitrophenol aqueous solution of degrading as model reaction, in order to
Compare, by etc. quality hollow spheres cuprous oxide and directly cuprous 50 mg of analysis pure zirconia that buys, be added 7.2 ×
10-4 mol·L-1In 100 mL of p-nitrophenyl phenol solution, ultrasonic disperse obtains suspension, places it in dark and stirs 30 min,
To reach adsorption equilibrium, then using 350 W xenon lamps as light source, 420 min of prolonged exposure, and sample at regular intervals, from
The heart separation after in clear solution use high performance liquid chromatograph (HPLC, U.S.'s Agilent, Agilent Technologies
1200 Series) it is detected.Operating condition are as follows: chromatographic column Alltech C18,4.6 mm × 250 mm；Mobile phase V
(CH3OH)/V(H2O)=58/42,1.0 mL/min of flow velocity；25 μ L of sampling volume.The change of the concentration of p-nitrophenol at any time
Change, as shown in Figure 3.From the figure 3, it may be seen that extension of the degradation rate of p-nitrophenyl phenol solution with light application time, presenting first quickly is reduced
The variation tendency gradually to tend towards stability again.Under identical experiment condition, using hollow spheres cuprous oxide as catalyst, illumination 60
Min can make the degradation rate of p-nitrophenyl phenol solution reach 50 %, and 240 min of illumination makes the degradation rate of p-nitrophenol reach 80
%, and using the cuprous oxide of purchase as catalyst, 240 min of illumination can only make the degradation rate of p-nitrophenyl phenol solution reach 40 %.
The data of photocatalysis experiment compare it is found that hollow spheres cuprous oxide is to p-nitrophenol organic pollutant difficult to degrade, performance
Better visible light catalytic performance out.
Embodiment 2-16:
Using the dosage and experiment condition of 1- butyl -3- methyl imidazolium tetrafluoroborate in table 1, according to described in embodiment 1
Preparation method, same available required hollow spheres cuprous oxide visible light catalyst.
The dosage and experiment condition of 1- butyl -3- methyl imidazolium tetrafluoroborate in table 1, embodiment 2-16
| Embodiment | 1- butyl -3- methyl imidazolium tetrafluoroborate dosage/g | Mixing time/h | Reaction temperature/DEG C | Reaction time/h |
| Embodiment 2 | 1.20 | 6 | 100 | 2 |
| Embodiment 3 | 1.20 | 6 | 100 | 4 |
| Embodiment 4 | 1.20 | 6 | 100 | 6 |
| Embodiment 5 | 2.40 | 12 | 140 | 2 |
| Embodiment 6 | 2.40 | 12 | 140 | 4 |
| Embodiment 7 | 2.40 | 12 | 140 | 6 |
| Embodiment 8 | 3.60 | 6 | 100 | 2 |
| Embodiment 9 | 3.60 | 6 | 100 | 4 |
| Embodiment 10 | 3.60 | 6 | 100 | 6 |
| Embodiment 11 | 3.60 | 12 | 140 | 2 |
| Embodiment 12 | 3.60 | 12 | 140 | 4 |
| Embodiment 13 | 3.60 | 12 | 140 | 6 |
| Embodiment 14 | 3.60 | 24 | 180 | 2 |
| Embodiment 15 | 3.60 | 24 | 180 | 4 |
| Embodiment 16 | 3.60 | 24 | 180 | 6 |
Application Example:
Hollow spheres cuprous oxide visible light catalyst prepared by embodiment 1-16 is respectively applied to catalysis to nitro
Phenol solution, and it is as shown in table 2 to count its effect.
The catalytic effect control of cuprous oxide visible light catalyst prepared by table 2, different embodiments
| Embodiment | Degradation rate/% of 60 min p-nitrophenol of illumination | Degradation rate/% of 240 min p-nitrophenol of illumination | Degradation rate/% of 420 min p-nitrophenol of illumination |
| Embodiment 1 | 49.79 | 79.88 | 84.44 |
| Embodiment 2 | 30.26 | 58.26 | 60.68 |
| Embodiment 3 | 32.68 | 62.36 | 64.21 |
| Embodiment 4 | 36.75 | 64.24 | 66.25 |
| Embodiment 5 | 32.78 | 60.24 | 62.25 |
| Embodiment 6 | 36.24 | 64.54 | 66.51 |
| Embodiment 7 | 40.25 | 68.51 | 70.84 |
| Embodiment 8 | 35.88 | 64.56 | 66.54 |
| Embodiment 9 | 38.61 | 68.28 | 70.68 |
| Embodiment 10 | 42.56 | 70.25 | 72.88 |
| Embodiment 11 | 44.56 | 73.51 | 76.12 |
| Embodiment 12 | 47.82 | 75.22 | 77.26 |
| Embodiment 13 | 48.68 | 77.25 | 79.22 |
| Embodiment 14 | 38.66 | 68.68 | 70.21 |
| Embodiment 15 | 42.26 | 71.48 | 73.28 |
| Embodiment 16 | 45.21 | 74.20 | 76.66 |
It is as shown in table 2:
Other conditions under the same conditions, with mentioning for -3 methyl imidazolium tetrafluoroborate dosage of ionic liquid 1- butyl
Height, product are presented the variation tendency gradually increased to the degradation rate of pollutant p-nitrophenol, illustrate the visible of p-nitrophenol
Photocatalytic activity enhances with the increase of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate dosage.
Other conditions under the same conditions, with the extension of mixing time, drop of the product to pollutant p-nitrophenol
The variation tendency gradually increased is presented in solution rate, this may be since mixing time is longer in preparation process, and presoma dispersibility is got over
Good, the size of hollow sphere is more uniform, and product dispersibility is better, and photocatalytic activity is also stronger.
Other conditions under the same conditions, with the raising of reaction temperature, drop of the product to pollutant p-nitrophenol
The presentation of solution rate first increases the variation tendency reduced again.When temperature is lower, product to the degradation rate of pollutant p-nitrophenol with
The raising of reaction temperature and increase, when reaction temperature is 170 DEG C, maximum is reached to the degradation rate of pollutant；With reaction temperature
Degree further increases, and reduces instead to the explanation rate of pollutant, this may be the ruler of hollow ball since reaction temperature is too high
Very little, surface texture homogeneity is deteriorated, and photocatalytic activity is caused to reduce instead.
Other conditions under the same conditions, with the extension of reaction time, drop of the product to pollutant p-nitrophenol
The variation tendency gradually increased is presented in solution rate, this may be since the reaction time is longer, and the inner space of hollow structure is more next, ball
The surface porosity factor of wall is higher, and specific surface area is bigger, and photocatalytic activity is stronger.
In conclusion optimum reaction condition are as follows: the dosage of 1- butyl -3- methyl imidazolium tetrafluoroborate is 3.6 g, stirring
6 h, reaction temperature are 170 DEG C, and the reaction time controls in 2 h.
Claims (2)
1. a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst, which comprises the following steps:
(1), precise 0.1817g Salicylaldoxime is dispersed in 18 mL ethylene glycol, and it is molten that ultrasonic disperse forms bottle green clarification
Liquid；
(2), 1.20-3.60 g 1- butyl -3- methyl imidazolium tetrafluoroborate is added into step (1) described solution, stirs 6-
24 h obtain blue suspension；
(3), step (2) described suspension is fully transferred in the stainless steel autoclave containing polytetrafluoroethyllining lining, seals kettle；It will
Autoclave is placed in baking oven, and 2-6 h is reacted at 100-180 DEG C；After reaction, cooled to room temperature, by product centrifugation point
From, then respectively cleaned 5 times with water, dehydrated alcohol respectively；The solid being collected into is placed in a vacuum drying oven, 60 DEG C of 12 h of drying,
Hollow spheres cuprous oxide visible light catalyst can be obtained.
2. a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst according to claim 1, feature exist
In: in step (1), it is dispersed in Salicylaldoxime in ethylene glycol using ultrasonic method.
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