CN106423166A - Compounding method for cuprous oxide visible photocatalyst - Google Patents
Compounding method for cuprous oxide visible photocatalyst Download PDFInfo
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- CN106423166A CN106423166A CN201610912244.6A CN201610912244A CN106423166A CN 106423166 A CN106423166 A CN 106423166A CN 201610912244 A CN201610912244 A CN 201610912244A CN 106423166 A CN106423166 A CN 106423166A
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- China
- Prior art keywords
- cuprous oxide
- visible light
- oxide visible
- hollow spheres
- 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 41
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 title abstract 5
- 238000013329 compounding Methods 0.000 title abstract 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- -1 1-butyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 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
- 238000001035 drying Methods 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
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000010189 synthetic method Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000011805 ball Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 238000006555 catalytic reaction Methods 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
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004005 microsphere 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
- 239000013078 crystal Substances 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 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
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction 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
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 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
- 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
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 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
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- 239000000126 substance Substances 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
-
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a compounding method for a cuprous oxide visible photocatalyst, belonging to the technical field of photocatalyst material preparation. The compounding method is characterized by comprising the following steps: accurately weighing 0.1817g of anhydrous copper acetate, dispersing anhydrous copper acetate in 18mL of glycol, ultrasonically dispersing and forming a dark green clear solution; adding 1.20-3.60g of 1-butyl-3-methylimidazolium tetrafluoroborate and stirring for 6-24h, thereby acquiring blue turbid liquid; transferring all the turbid liquid into a stainless steel high-pressure kettle containing a polytetrafluoroethylene liner (at 25mL volume) and sealing the kettle; putting the high-pressure kettle into an oven and reacting for 2-6h at 100-180 DEG C; after ending reaction, naturally cooling to room temperature, centrifugally separating the products and then washing with water and absolute ethyl alcohol for five times; putting the collected solid into a vacuum drying oven and drying for 12h at 60 DEG C, thereby acquiring a hollow spherical cuprous oxide visible photocatalyst. According to the compounding method, the operation is simple, the cost is low; the acquired product has a pure cubic structure; the compound method is used for effectively preparing the hollow spherical cuprous oxide visible photocatalyst.
Description
Technical field：
The invention belongs to the preparing technical field of catalysis material, it has been provided in particular in a kind of cuprous oxide visible light catalyst
Synthetic method.
Background technology：
Developing rapidly with industrial and agricultural production, environmental pollution and energy shortage have become two hang-ups of facing mankind.In crowd
In multi-pollutant, what difficult for biological degradation, hardly possible traditional wastewater facture were degraded is big point of phenols, Polychlorinated biphenyls and polycyclic aromatic hydrocarbon etc.
Sub- organic pollution.Therefore, about effective degraded of the big organic wastewater of such concentration height, difficult for biological degradation, bio-toxicity,
Cause the extensive concern of countries in the world researcher.Using solar energy, photocatalysis degradation organic contaminant, it has also become solve above-mentioned difficulty
One of effective ways of topic.Cuprous oxide is a kind of typical p-type semiconductor, and energy gap is 2.0 eV-2.2 eV, belongs to narrow
Gap semiconductor, has the optical property of uniqueness, can cause light-catalyzed reaction, be widely used in solar-electricity under sunshine
The aspects such as pond, lithium ion battery, biology sensor, photochemical cell and photocatalysis, have caused the attention of numerous researchers.
It is known that the pattern of material, crystal structure and surface characteristic etc. affect the performance of material, performance determines purposes.
In order to obtain the visible light catalyst of high activity and high stability, people have adopted microwave method, pulsed deposition method, collosol and gel
The methods such as method, electrochemical deposition, for the micro-nano material of the cuprous oxide such as nanosphere, nano wire, nano cubic block, octahedral structure
The synthesis of material.If Y.-H. Tsai etc. is not using any surfactant, at Cu (OAc)2, NaOH and N2H4In solution, by adjusting
The volume of section hydrazine hydrate, obtains the cuprous nano material of different-shape, in catalytic cyclization addition reaction, has { 111 }
The octahedral build cuprous oxide of crystal face, as catalyst production highest, shows preferable catalysis activity（Y.-H. Tsai, et
al. Nanoscale, 2014, 6 (15), 8704-8709.）.S. Sun etc. is with complex as presoma, using treating different things alike
Method be prepared for cuprous oxide classifying nano ball, it is good that special pattern makes it that photocatalytic degradation of methyl orange solution is shown
Good catalysis 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, in photocatalysis hydrogenation reaction, can conversion solar can be chemical energy
Carry out energy storage（Y. Zhao, et al. Nanoscale, 2014, 6 (1), 195-198.）.
Content of the invention：
It is an object of the invention to provide a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst, obtained in
Empty spherical cuprous oxide visible light catalyst is to be constructed as building block by a large amount of nanoparticles to form, the mutual heap of nano-particle
Amassing makes its surface have loose structure, is favorably improved specific surface area.Hollow microsphere has that density is low, Surface Permeability is good, ratio
The advantages of surface area is big, visible absorption ability is strong, interior ectosphere wall, all as avtive spot, promotes organic pollution catalysis fall
Solution.Hollow microsphere is to be constructed by a large amount of nano-particles to form, have nano-particles size little, active high the features such as, make hollow ball
Shape cuprous oxide has good visible light catalytic performance.
The technical scheme that the present invention takes is as follows, a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst,
Comprise the following steps：
（1）Precise 0.1817 g Salicylaldoxime is dispersed in 18 mL ethylene glycol, and it is molten that ultrasonic disperse forms bottle green clarification
Liquid.
（2）To（1）Add 1.20-3.60 g 1- butyl -3- methyl imidazolium tetrafluoroborate in described solution, stir 6-
24 h, obtain blue suspension.
（3）Will（2）Described suspension is fully transferred to stainless steel autoclave containing teflon-lined（Volume 25 mL）
In, seal kettle.Autoclave is placed in baking oven, at 100-180 DEG C, reacts 2-6 h.After reaction terminates, naturally cool to room temperature, will
Product centrifugation, respectively clean 5 times with water, absolute ethyl alcohol respectively.The solid collected is placed in vacuum drying chamber, 60
DEG C drying 12 h, you can hollow spheres cuprous oxide visible light catalyst.
In the present invention, we adopt solvent structure hollow spheres cuprous oxide visible light catalysts, using copper ion
Interaction and glycol molecule between, with 1- butyl -3- methyl imidazolium tetrafluoroborate as soft template, produces in autoclave
Particular surroundings under, be finally prepared for hollow spheres cuprous oxide.
Further it is provided in：
In step 1, Salicylaldoxime is made to be dispersed in ethylene glycol using ultrasonic method.
In step 2, in the settled solution described in step 1, add 1.20-3.60 g 1- butyl -3- methylimidazole tetrafluoro
Borate, stirs 6-24 h.
In step 3, autoclave reaction temperature is 100-180 DEG C, and the reaction time is 2-6 h.
The hollow spheres cuprous oxide visible light catalyst of present invention preparation, this catalyst is powder, and crystalline phase is a cube knot
Structure, the hollow microsphere of porous surface is constructed, had to pattern for nano-particle.Using SEM（SEM, JEOL JSM-
6360LV, accelerating potential is 20 kV）And X-ray diffractometer（XRD, Empyrean, Dutch PANalytical company）Characterize institute
Obtain pattern and the crystal structure of product.The hollow spheres cuprous oxide visible light catalyst of present invention preparation, has the characteristics that.
（1）Ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, the pattern of regulation and control product is added in reaction system.
（2）Preparation process method is simple to operation, and product is reproducible.
（3）The hollow spheres cuprous oxide visible light catalyst of present invention preparation, is the hollow spheres with micron-scale
Structure, a large amount of nano-particles are mutually piled up, and make the ball wall of hollow microsphere have loose structure, and then improve specific surface area.Structure
Build hollow sphere made from cuprous oxide nano-particle have nano material size little, active high the features such as, urging of material can be effectively improved
Change activity.
（4）The hollow spheres cuprous oxide visible light catalyst of present invention preparation, is contrasted with the cuprous oxide bought,
Find that there is the photocatalytic degradation effect to persistent organic pollutants p-nitrophenol in water for the cuprous oxide of hollow spheres structure
Fruit is notable.
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Brief description：
Fig. 1 a is the SEM of the product of preparation in embodiment 1（SEM）Photo；
Fig. 1 b is the SEM of the product of preparation in embodiment 1（SEM）Photo；
Fig. 2 is the X-ray diffractogram of the product of preparation in embodiment 1（XRD）；
Fig. 3 be embodiment 1 in preparation hollow spheres cuprous oxide and buy cuprous oxide under visible light illumination, to nitro
The concentration versus time curve of phenol.
Specific embodiment：
Embodiment 1：Precise 0.1817 g Salicylaldoxime is dispersed in 18 mL ethylene glycol, and ultrasonic disperse forms bottle green
Settled solution.It is added thereto to 3.6 g 1- butyl -3- methyl imidazolium tetrafluoroborate again, stirs 6 h, obtain blue suspended
Liquid.Suspension is fully transferred to stainless steel autoclave containing teflon-lined（Volume 25 mL）In, seal kettle.Reaction knot
Shu Hou, autoclave is placed in baking oven, reacts 2 h, naturally cool to room temperature at 170 DEG C, by product centrifugation, then distinguishes
Respectively clean 5 times with water, absolute ethyl alcohol.The solid collected is placed in vacuum drying chamber, 60 DEG C of drying 12 h, you can in obtaining
Empty spherical cuprous oxide visible light catalyst.SEM result（Fig. 1 a）Intuitively presenting product is about 1 μm -1.5 μm of size
Spheroid, the SEM figure amplifying further（Fig. 1 b）Confirmation ball interior is hollow structure, and wall thickness is about 300 nm, and ball wall is by big
Amount, unordered nano-particle are constructed and are formed.XRD（Fig. 2）Result and standard card（JCPDS No. 78-2076）It coincide, show to produce
Thing is Emission in Cubic Cu2O structure, belongs to cubic system.
In order to study the photocatalytic activity of prepared sample, with the p-nitrophenol aqueous solution of degrading as model reaction, in order to
Contrasted, by etc. quality hollow spheres cuprous oxide and directly buy cuprous 50 mg of analysis pure zirconia, addition 7.2 ×
10-4mol·L-1In p-nitrophenyl phenol solution 100 mL, ultrasonic disperse obtains suspension, is placed in dark and stirs 30 min,
To reach adsorption equilibrium, then using 350 W xenon lamps as light source, prolonged exposure 420 min, and sample at set intervals, from
The heart uses high performance liquid chromatograph in settled solution after separating（HPLC, U.S.'s Agilent, Agilent Technologies
1200 Series）Detected.Operating condition is：Chromatographic column Alltech C18,4.6 mm × 250 mm；Mobile phase V
(CH3OH)/V(H2O)=58/42, flow velocity 1.0 mL/min；Sampling volume 25 μ L.The change in time of the concentration of p-nitrophenol
Change, as shown in Figure 3.From the figure 3, it may be seen that the degradation rate of p-nitrophenyl phenol solution is with the prolongation of light application time, assume first quick reduction
The variation tendency gradually tending towards stability again.Under identical experiment condition, with hollow spheres cuprous oxide as catalyst, illumination 60
Min can make the degradation rate of p-nitrophenyl phenol solution reach 50 %, and illumination 240 min makes the degradation rate of p-nitrophenol reach 80
%, and with the cuprous oxide of purchase as catalyst, illumination 240 min can only make the degradation rate of p-nitrophenyl phenol solution reach 40 %.
Knowable to the data of photocatalysis experiment compares, the p-nitrophenol organic pollution to difficult degradation for the hollow spheres cuprous oxide, performance
Go out more preferable visible light catalytic performance.
Embodiment 2-16：
Using the consumption of 1- butyl -3- methyl imidazolium tetrafluoroborate and experiment condition in table 1, according to the system described in embodiment 1
Preparation Method, equally can obtain required hollow spheres cuprous oxide visible light catalyst.
The consumption of 1- butyl -3- methyl imidazolium tetrafluoroborate and experiment condition in table 1, embodiment 2-16
| Embodiment | 1- butyl -3- methyl imidazolium tetrafluoroborate consumption/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：
By embodiment 1-16 preparation hollow spheres cuprous oxide visible light catalyst, be respectively applied to be catalyzed p-nitrophenol
Solution, and it is as shown in table 2 to count its effect.
Table 2, the catalytic effect comparison of the cuprous oxide visible light catalyst of different embodiment preparation
| Embodiment | Degradation rate/the % of illumination 60 min p-nitrophenol | Degradation rate/the % of illumination 240 min p-nitrophenol | Degradation rate/the % of illumination 420 min p-nitrophenol |
| 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 |
As shown in table 2：
Under the conditions of other condition identicals, with the raising of ionic liquid 1- butyl -3 methyl imidazolium tetrafluoroborate consumption,
Product assumes, to the degradation rate of pollutant p-nitrophenol, the variation tendency being gradually increased, and illustrates that the visible ray of p-nitrophenol is urged
Change activity to strengthen with the increase of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate consumption.
Under the conditions of other condition identicals, with the prolongation of mixing time, the fall to pollutant p-nitrophenol for the product
Solution rate assumes the variation tendency being gradually increased, and this is likely due to, and mixing time in preparation process is longer, and presoma dispersiveness is got over
Good, the size of hollow ball is more homogeneous, and product dispersiveness is better, and photocatalytic activity is also stronger.
Under the conditions of other condition identicals, with the raising of reaction temperature, the fall to pollutant p-nitrophenol for the product
Solution rate presents first increases the variation tendency reducing again.When temperature is relatively low, product to the degradation rate of pollutant p-nitrophenol with
The rising of reaction temperature and increase, when reaction temperature be 170 DEG C when, maximum is reached to the degradation rate of pollutant；With reaction temperature
Degree raises further, the explanation rate of pollutant is reduced on the contrary, this is likely due to, and reaction temperature is too high, the chi of hollow ball
Very little, surface texture homogeneity is deteriorated, and leads to photocatalytic activity to reduce on the contrary.
Under the conditions of other condition identicals, with the prolongation in reaction time, the fall to pollutant p-nitrophenol for the product
Solution rate assumes the variation tendency being gradually increased, and this is likely due to, and the reaction time is longer, and the inner space of hollow-core construction is more next, ball
The surface porosity factor of wall is higher, and specific surface area is bigger, and photocatalytic activity is stronger.
In sum, optimum reaction condition is：The consumption of 1- butyl -3- methyl imidazolium tetrafluoroborate is 3.6 g, stirring
6 h, reaction temperature is 170 DEG C, and the reaction time controls in 2 h.
Claims (4)
1. a kind of synthetic method of hollow spheres cuprous oxide visible light catalyst is it is characterised in that comprise the following steps：
（1）, precise 0.1817g Salicylaldoxime be dispersed in 18 mL ethylene glycol, ultrasonic disperse formed bottle green clarification molten
Liquid；
（2）, to step（1）Add 1.20-3.60 g 1- butyl -3- methyl imidazolium tetrafluoroborate in described solution, stir 6-
24 h, obtain blue suspension；
（3）, by step（2）Described suspension is fully transferred in stainless steel autoclave containing teflon-lined, seals kettle；Will
Autoclave is placed in baking oven, reacts 2-6 h at 100-180 DEG C；After reaction terminates, naturally cool to room temperature, by product centrifugation point
From, respectively clean 5 times with water, absolute ethyl alcohol respectively；The solid collected is placed in vacuum drying chamber, 60 DEG C of drying 12 h,
Hollow spheres cuprous oxide visible light catalyst.
2. the synthetic method of a kind of hollow spheres cuprous oxide visible light catalyst according to claim 1, its feature exists
In：Step（1）In, so that Salicylaldoxime is dispersed in ethylene glycol using ultrasonic method.
3. the synthetic method of a kind of hollow spheres cuprous oxide visible light catalyst according to claim 1, its feature exists
In：After adding 1.20-3.60g 1- butyl -3- methyl imidazolium tetrafluoroborate, stir 6-24h.
4. the synthetic method of a kind of hollow spheres cuprous oxide visible light catalyst according to claim 1, its feature exists
In；Reaction temperature is 100-180 DEG C, and the reaction time is 2-6h.
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