CN106944074A - A kind of visible-light response type composite photo-catalyst and its preparation method and application - Google Patents
A kind of visible-light response type composite photo-catalyst and its preparation method and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 89
- 230000004044 response Effects 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000013049 sediment Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 235000012208 gluconic acid Nutrition 0.000 claims description 14
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 13
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000174 gluconic acid Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000041 non-steroidal anti-inflammatory agent Substances 0.000 claims description 6
- 229940021182 non-steroidal anti-inflammatory drug Drugs 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 abstract description 41
- 229960001259 diclofenac Drugs 0.000 abstract description 41
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000001788 irregular Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000001429 visible spectrum Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 71
- 238000001179 sorption measurement Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 229910052724 xenon Inorganic materials 0.000 description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
-
- B01J35/40—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
A kind of visible-light response type composite photo-catalyst of the present invention and its preparation method and application, the visible-light response type composite photo-catalyst is CuBi2O4/β‑Bi2O3, CuBi in the visible-light response type composite photo-catalyst2O4For hollow sub-microsphere,β‑Bi2O3For irregular nano particle, and CuBi2O4Withβ‑Bi2O3Between be in close contact.Visible-light response type composite photo-catalyst prepared by the present invention has stronger absorption in whole limit of visible spectrum, and compares pureβ‑Bi2O3Cyclic utilization rate with more preferable photocatalysis performance and Geng Gao.By 0.4 g CuBi2O4/β‑Bi2O3（1:2.25, wt%）For handling Diclofenac organic wastewater with difficult degradation thereby, it is seen that the h of light irradiation 3, the clearance to the mg/L diclofenac solutions of 1 L 5 is 89.02%, is reused the 7th time, is 78.43% to diclofenac solution clearance.
Description
Technical field
The present invention relates to photocatalysis technology field, more particularly to a kind of visible-light response type composite photo-catalyst and its preparation
Methods and applications.
Background technology
In recent years, continuing to develop for economic society and deepening continuously for process of industrialization, result in a large amount of emerging organic
The discharge of pollutant waste water, but municipal sewage system is difficult to completely remove it at present, so as to cause these emerging organic
Pollutant is in surface water, underground water, be even detected in potable water system.And these emerging organic pollutions, such as antiphen
Acid etc., under trace concentration, if exposure wherein also can be by serious harm for a long time for the mankind and animals and plants.Therefore, give up
The removal of emerging organic pollution is still the emphasis and difficult point of current field of environment protection in water.
Photocatalysis oxidation technique has the advantages such as reaction condition is gentle, reaction speed is fast, mineralization rate is high, secondary pollution is few.
EPA is classified as most promising environmentally friendly new and high technology.TiO2Base semiconductor catalysis material is currently to grind both at home and abroad
Study carefully most commonly used photochemical catalyst, but the greater band gap of the material（3.2 eV）, and only in ultraviolet light（Only account for solar radiation
Total amount 4%）Irradiation is lower to produce photocatalytic activity, and which greatly limits its application.Therefore, cheap sunshine can efficiently be utilized
Visible-light-responsive photocatalyst development turns into the focus in current photocatalysis oxidation technique field.
Bismuth oxide（Bi2O3）It is a kind of visible-light response type semi-conducting material, due to its unique optics and electric property,
Have widely studied in terms of gas sensor, photovoltaic cell, optical coating, fuel cell, super capacitor.In addition, Bi2O3
The internal polarization of Bi 6s tracks lone pair electrons induction in structure contributes to separation and the carrier of photo-generate electron-hole pair
Transmission so that Bi2O3With certain photocatalysis.Bi2O3It is primarily presentα、β、γ、δFour kinds of crystalline structures, whereinα-Bi2O3Stable under normal temperature, energy gap is about 2.8 eV（The eV of conduction band 0.33, the eV of valence band 3.13）, rung as visible ray
Answer the existing numerous studies of type photochemical catalyst.But, althoughβ-Bi2O3Energy gap be 2.4 eV, with thanα-Bi2O3It is stronger
Visible absorption ability, stillβ-Bi2O3Three aspect problems are still had as the research of photochemical catalyst：（1）β-Bi2O3
Easily it is transformed into photocatalytic processα-Bi2O3, and and CO2Reaction generation carbonate, causes photocatalytic activity to decline；（2）β-Bi2O3
The quantum efficiency of photocatalytic system is low, causes its photocatalytic activity poor；（3）β-Bi2O3Conduction band be less than H+/H2Reduction electricity
Position, causes light induced electron easily compound with photohole, so as to influence photocatalysis efficiency.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of visible-light response type composite photocatalyst
Agent and its preparation method and application, it is intended to solve existingβ-Bi2O3As there is above-mentioned technological deficiency in the research of photochemical catalyst
Problem.
Technical scheme is as follows：
A kind of visible-light response type composite photo-catalyst, wherein, the visible-light response type composite photo-catalyst is CuBi2O4/β-Bi2O3, CuBi in the visible-light response type composite photo-catalyst2O4For hollow sub-microsphere,β-Bi2O3For irregular nanometer
Grain, and CuBi2O4Withβ-Bi2O3Between be in close contact.
Described visible-light response type composite photo-catalyst, wherein, CuBi2O4/β-Bi2O3In, CuBi2O4Withβ-Bi2O3's
Mass ratio is 1：（0.5-20）.
As above a kind of preparation method of any described visible-light response type composite photo-catalyst, wherein, including following step
Suddenly：
（1）CuBi2O4Preparation：By Bi (NO3)3·5H2O is dissolved in dense HNO3In, stir to being completely dissolved, add Cu
(NO3)2·3H20.5-2 mol/L alkaline sedimentation agent solution is then added dropwise to well mixed in O, stirring dropwise, and by after dropwise addition
Solution dilutes, and continues to stir after 0.5-2 h, the solution is transferred in reactor, and rise temperature reacts 18- to 80-150 DEG C
30 h, question response kettle is cooled to after room temperature, and the sediment that reaction is obtained is washed, and by centrifuging, is then dried in vacuo,
Grinding, sieving, produce CuBi2O4；
（2）CuBi2O4@C preparation：By step（1）In prepared CuBi2O4It is scattered in gluconic acid solution, ultrasonic 10-
After 50 min, mixed liquor is moved in reactor, rise temperature is to 150-250 DEG C, and question response kettle is naturally cooled to after room temperature,
The sediment that reaction is obtained is reclaimed by centrifuging, and sediment is washed, is then dried in vacuo, is ground, sieves, produce
CuBi2O4@C；
（3）CuBi2O4/β-Bi2O3Preparation：By step（2）In prepared CuBi2O4@C are scattered in HNO3In solution, ultrasound
10-50 min, obtain solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, 30-120 min are stirred vigorously at room temperature,
Obtain solution B；Subcarbonate is dissolved in ultra-pure water, 10-50 min is stirred, obtains solution C；First by solution A and solution B
Magnetic agitation 10-50 min after mixing, then solution C is added dropwise dropwise thereto, continue to stir 10-50 min, will react what is produced
Sediment is washed, and collects sediment by centrifuging；Sediment after washing is put into temperature programming stove, program liter is set
Warm stove is warming up to 300-800 DEG C in 10-60 min, and reacts 2-10 h in temperature programming stove, treats that temperature programming stove is natural
It is cooled to after room temperature, collects solid sediment, you can obtain CuBi2O4/β-Bi2O3。
The preparation method of described visible-light response type composite photo-catalyst, wherein, step（1）In, the alkaline sedimentation
Alkaline precipitating agent in agent solution is the one or more in NaOH, potassium hydroxide and ammoniacal liquor.
The preparation method of described visible-light response type composite photo-catalyst, wherein, step（2）In, the gluconic acid
The volume of glucose in solutions acid is 0.04-0.8 mL.
The preparation method of described visible-light response type composite photo-catalyst, wherein, step（3）In, the Bi (NO3)3·
5H2The mole that O is added is 0.1-3.6 mmol.
The preparation method of described visible-light response type composite photo-catalyst, wherein, step（3）In, the basic carbonate
Salt and Bi (NO3)3·5H2The ratio between O mole is（1-10）:1.
The preparation method of described visible-light response type composite photo-catalyst, wherein, step（3）In, described program heating
The temperature of stove is increased to 300-800 DEG C.
The preparation method of described visible-light response type composite photo-catalyst, wherein, step（3）In, described program heating
The reaction time of stove is 2-10 h.
A kind of application of visible-light response type composite photo-catalyst, wherein, by as above any described visible-light response type
Composite photo-catalyst is applied to waste water of the processing containing non-steroid anti-inflammatory drug.
Beneficial effect：Compare pureβ-Bi2O3, the visible-light response type composite photo-catalyst prepared by the present invention has visible
The advantages of optical absorption intensity is higher, photocatalysis performance is more preferable, cyclic utilization rate is higher.
Brief description of the drawings
Fig. 1 is CuBi in the embodiment of the present invention 12O4/β-Bi2O3Scanning electron microscope diagram.
Fig. 2 is CuBi in the embodiment of the present invention 12O4/β-Bi2O3X ray diffracting spectrum.
Fig. 3 is CuBi in the embodiment of the present invention 12O4/β-Bi2O3UV-Vis DRS spectrogram.
Fig. 4 is CuBi in the embodiment of the present invention 12O4/β-Bi2O3Photocatalysis performance schematic diagram.
Fig. 5 is CuBi in the embodiment of the present invention 92O4/β-Bi2O3Reuse performance schematic diagram.
Embodiment
The present invention provides a kind of visible-light response type composite photo-catalyst and its preparation method and application, to make the present invention's
Purpose, technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that this place is retouched
The specific embodiment stated only to explain the present invention, is not intended to limit the present invention.
To improveβ-Bi2O3Photocatalytic activity, itself and other semiconductors couplings with appropriate band structure are constructed multiple
Closing light catalyst is a kind of effective technological means.On the one hand, using the different band structure difference institute shape of two kinds of semiconductors
Into new band structure feature, improve composite photocatalyst system in photo-generate electron-hole Transport, so as to reduce photoproduction
The recombination rate of electron-hole, is improvedβ-Bi2O3Photocatalytic activity；On the other hand, can also be steady by the chemistry of other semiconductors
It is qualitative to improveβ-Bi2O3Structural stability.CuBi2O4It is excellent that semiconductor has visible light-responded strong, chemical stability good etc.
Gesture, and its conduction band positions is higher, and its light induced electron has stronger reducing power.In addition, comparingβ-Bi2O3, CuBi2O4's
Conduction band and valence band potential energy are relatively born, and both semiconductors couplings will certainly change the photocatalysis performance of whole reaction system.Therefore,
The present invention is by by CuBi2O4Withβ-Bi2O3It is compound to construct composite photocatalyst to improveβ-Bi2O3Photocatalytic activity and knot
Structure stability.
Specifically, the present invention provides a kind of visible-light response type composite photo-catalyst, wherein, the visible-light response type is answered
Closing light catalyst is CuBi2O4/β-Bi2O3, CuBi in the visible-light response type composite photo-catalyst2O4For hollow sub-microsphere,β-Bi2O3For irregular nano particle, and CuBi2O4Withβ-Bi2O3Between be in close contact.Visible-light response type i.e. of the present invention
Composite photo-catalyst is CuBi2O4/β-Bi2O3, the CuBi2O4/β-Bi2O3It is by hollow sub-microsphere CuBi2O4With irregularly receiving
Rice grainβ-Bi2O3Composite photo-catalyst formed by close contact.
CuBi of the present invention2O4/β-Bi2O3In, CuBi2O4Withβ-Bi2O3Mass ratio be 1：（0.5-20）.Preferably,
CuBi2O4Withβ-Bi2O3Mass ratio be 1:（1-15）.It is highly preferred that CuBi2O4Withβ-Bi2O3Mass ratio be 1:（1.5-
10）.More preferably, CuBi2O4Withβ-Bi2O3Mass ratio be 1：（1.8-5）.Still further preferably, CuBi2O4Withβ-Bi2O3
Mass ratio be 1：（2-3）, for example, CuBi2O4Withβ-Bi2O3Mass ratio be 1:2.25.
The present invention also provides the preparation method of a kind of as above any described visible-light response type composite photo-catalyst, and it is wrapped
Include following steps：
（1）CuBi2O4Preparation：By Bi (NO3)3·5H2O is dissolved in dense HNO3In, stir to being completely dissolved, add Cu
(NO3)2·3H20.5-2 mol/L alkaline sedimentation agent solution is then added dropwise to well mixed in O, stirring dropwise, and by after dropwise addition
Solution dilutes, and continues to stir after 0.5-2 h, the solution is transferred in reactor, and rise temperature reacts 18- to 80-150 DEG C
30 h, question response kettle is cooled to after room temperature, and the sediment that reaction is obtained is washed, and by centrifuging, is then dried in vacuo,
Grinding, sieving, produce CuBi2O4。
Above-mentioned steps（1）In, the alkaline precipitating agent in the alkaline sedimentation agent solution can be NaOH, potassium hydroxide
With the one or more in ammoniacal liquor.
Above-mentioned steps of the present invention（1）The uniform CuBi of appearance structure is prepared using hydro-thermal method2O4.Above-mentioned steps（1）Specifically
For by the Bi (NO of 0.04 molar part3)3·5H2O is dissolved in the dense HNO of 2-6 mL3In, preferably 2-5 mL, further preferred 2.5-4
mL（Such as 3 mL）, stirring is completely dissolved it, adds the Cu (NO of the molar parts of 20 mL 0.023)2·3H2O, stirring mixes it
Close uniform, the alkaline precipitating agent of 0.5-2 mol/L alkaline sedimentation agent solution, preferably 0.8-1.5 mol/L is then added dropwise dropwise
Solution, further preferred 1-1.4 mol/L（Such as 1.2 mol/L）Alkaline sedimentation agent solution, and solution after dropwise addition is diluted to
50-100 mL, preferably 60-80 mL（Such as 70 mL）, continue to stir 0.5-2 h, preferably stir after 0.8-1.5 h, by the solution
It is transferred in autoclave, rise temperature is to 80-150 DEG C, preferably 90-110 DEG C（Such as 100 DEG C）, 18-30 h are reacted, it is excellent
Select 22-26 h（Such as 24 h）, question response kettle naturally cooled to after room temperature, will be reacted obtained sediment and is washed（It is preferred to use super
Pure water supersound washing repeatedly）, and by centrifuging（Rotating speed preferably uses 5000-7000 r/min）, then it is dried in vacuo（It is preferred that
6-18 h, such as 12 h are dried in 40-80 DEG C of vacuum drying chamber）, grinding, sieving（It is preferred that 60-120 mesh sieves are crossed, such as 80 mesh
Sieve）, produce CuBi2O4。
（2）CuBi2O4/β-Bi2O3Preparation：By step（1）In prepared CuBi2O4It is scattered in gluconic acid solution
In, after ultrasonic 10-50 min, mixed liquor is moved in reactor, rise temperature to 150-250 DEG C, question response kettle natural cooling
To room temperature, the sediment that reaction is obtained is reclaimed by centrifuging, and sediment is washed, is then dried in vacuo, grinding, mistake
Sieve, produces CuBi2O4@C。
Step（2）In, the volume of gluconic acid is 0.04-0.8 mL, preferably 0.1-0.6 in the gluconic acid solution
ML, further preferred 0.2-0.4 mL.
Above-mentioned steps of the present invention（2）CuBi is prepared using hydro-thermal method2O4@C.Above-mentioned steps（2）Specifically, by step（1）In
Prepared CuBi2O4It is scattered in 70 mL gluconic acid solutions（Volume containing gluconic acid is 0.04-0.8 mL, preferably
0.1-0.6 mL, further preferred 0.2-0.4 mL, such as 0.3 mL）, ultrasonic 10-50 min, preferably 20-40 min（Such as 30
min）, mixed liquor is moved in 100 mL autoclaves, rise temperature is to 150-250 DEG C, preferably 160-200 DEG C（Such as 180
℃）, react 2-10 h, still further preferably preferably 2.5-6 h, 3-5 h（Such as 4 h）, question response kettle naturally cooled to after room temperature,
It is 4000-10000 r/min, preferably 5000-7000 r/min by rotating speed（Such as 6000 r/min）Centrifuge separation
The solid sediment that reaction is obtained is reclaimed, and solid sediment is washed（It is preferred that with ultra-pure water supersound washing repeatedly）, Ran Houzhen
Sky is dried（It is preferred that drying 6-18 h in 40-80 DEG C of vacuum drying chamber, 12 h are dried such as in 60 DEG C of vacuum drying chambers）, grind
Mill, sieving（It is preferred that crossing 60-120 mesh sieves, 80 mesh sieves are such as crossed）, produce CuBi2O4@C。
（3）CuBi2O4/β-Bi2O3Preparation：By step（2）In prepared CuBi2O4@C are scattered in HNO3In solution,
Ultrasonic 10-50 min, obtain solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, 30-120 is stirred vigorously at room temperature
Min, obtains solution B；Subcarbonate is dissolved in ultra-pure water, 10-50 min is stirred, obtains solution C；First by solution A and
Magnetic agitation 10-50 min after solution B mixing, then solution C is added dropwise dropwise thereto, continue to stir 10-50 min, reaction is produced
Raw sediment washing, and collect sediment by centrifuging；Sediment after washing is put into temperature programming stove, journey is set
Sequence heating furnace is warming up to 300-800 DEG C in 10-60 min, and reacts 2-10 h in temperature programming stove, treats temperature programming stove
Naturally cool to after room temperature, collect solid sediment, you can obtain CuBi2O4/β-Bi2O3。
Step（3）In, the Bi (NO3)3·5H2The mole that O is added is 0.1-3.6 mmol, preferably 0.2-2.5
Mmol, further preferred 0.25-1.5 mmol, further preferably 0.3-1.0 mmol, more preferably 0.35-0.5 mmol.
Step（3）In, the subcarbonate is the one or more in sodium carbonate, potassium carbonate and ammonium carbonate.
Step（3）In, the subcarbonate and Bi (NO3)3·5H2The ratio between O mole is（1-10）:1, preferably（3-
8）:1, further preferably（5-7）:1.
Step（3）In, the temperature of described program heating furnace is increased to 300-800 DEG C, preferably 400-700 DEG C, further
It is preferred that 500-650 DEG C.
Step（3）In, the reaction time of described program heating furnace is 2-10 h, preferably 3-7 h, further preferred 4-6 h.
Above-mentioned steps of the present invention（3）The technology being combined using liquid phase synthesis-calcining prepares CuBi2O4/β-Bi2O3.It is above-mentioned
Step（3）Specifically, by step（2）In prepared CuBi2O4@C are scattered in 20 mL HNO3Solution（Wherein HNO3Concentration
For 0.5-4 mol/L, preferably 0.6-2 mol/L, such as further preferred 0.8-1.5 mol/L, 1.0 mol/L）In, ultrasonic 10-
50 min, preferably 20-40 min（Such as 30 min）, obtain solution A；By 0.1-3.6 mmol, preferably 0.2-2.5 mmol, enter one
Preferred 0.25-1.5 mmol are walked, further preferably 0.3-1.0 mmol, more preferably 0.35-0.5 mmol（Such as 0.39 mmol）Bi
(NO3)3·5H2O is added to 20 mL HNO3Solution（Wherein HNO3Concentration be 0.5-4 mol/L, preferably 0.6-2 mol/L, enter
The preferred 0.8-1.5 mol/L of one step, such as 1.0 mol/L）In, 30-120 min, preferably 40-90 min are stirred vigorously at room temperature
（Such as 60 min）, obtain solution B；By the subcarbonate of certain molar weight（Subcarbonate and Bi (NO3)3·5H2O mole
Amount the ratio between be（1-10）:1, preferably（3-8）:1, further preferably（5-7）:1, such as 6:1）It is added in 40 mL ultra-pure waters, stirs
10-50 min, preferably 20-40 min（Such as 30 min）, obtain solution C.Magnetic agitation 10- after first mixing solution A and solution B
50 min, preferably 20-40 min（Such as 30 min）, then solution C is added dropwise dropwise thereto, a large amount of white precipitates can be now produced,
Continue to stir 10-50 min, preferably 20-40 min（Such as 30 min）, it is 4000-10000 r/min by rotating speed, preferably
5000-7000 r/min（Such as 6000 r/min）The obtained solid sediment of centrifuge separation and recovery reaction, and will be solid
Body sediment is washed（It is preferred that with the supersound washing repeatedly of absolute ethyl alcohol and ultra-pure water）.Sediment after washing is put into temperature programming
Stove, sets temperature programming stove in 10-60 min, preferably 20-40 min（Such as 30 min）300-800 DEG C is inside warming up to, preferably
400-700 DEG C, further preferred 500-650 DEG C（Such as 600 DEG C）, and the reaction 2-10 h, preferably 3-7 in temperature programming stove
H, further preferred 4-6 h（Such as 5 h）, after temperature programming stove naturally cools to room temperature, collect solid sediment, you can obtain
CuBi2O4/β-Bi2O3。
The present invention also provides a kind of application of visible-light response type composite photo-catalyst, wherein, will be as above any described
Visible-light response type composite photo-catalyst contains non-steroid anti-inflammatory drug applied to processing（Such as Diclofenac）Waste water.
The application process of the visible-light response type composite photo-catalyst of the present invention is to the mould containing non-steroid anti-inflammatory drug
Intend waste water（Such as the Diclofenac aqueous solution）It is middle to add visible-light response type composite photo-catalyst, i.e. CuBi2O4/β-Bi2O3, it is advanced
Visible ray illumination is carried out after the dark adsorption reaction of row, balance to be achieved.It is measured by sampling and gives up by intervals in application process
Non-steroid anti-inflammatory drug in water（Such as Diclofenac）Concentration.
Preferably, in the application, CuBi2O4/β-Bi2O3Consumption be：Contained non-steroid anti-inflammatory drug in waste water（Such as
Diclofenac）With CuBi2O4/β-Bi2O3Mass ratio be 1:（10-150）, preferably 1:（50-120）, further preferred 1:
（70-100）, such as 1:80.
The present invention prepares that appearance structure is uniform, stable chemical nature visible-light response type half first with hydrothermal synthesis method
Conductor CuBi2O4With core shell structure CuBi2O4@C, on this basis, the technology being combined by liquid phase synthesis-calcining is in program
CuBi is obtained under conditions of heating2O4/β-Bi2O3.Compare pureβ-Bi2O3, the visible-light response type complex light prepared by the present invention
Catalyst has the advantages that visible absorption intensity is higher, photocatalysis performance is more preferable, cyclic utilization rate is higher.
Below by embodiment, the present invention is described in detail.
Embodiment 1
The preparation of visible-light response type composite photo-catalyst：
（1）, first appearance structure uniform CuBi is prepared using hydro-thermal method2O4, i.e., by the Bi (NO of 0.04 molar part3)3·5H2O
It is dissolved in the dense HNO of 3 mL3In, stirring is completely dissolved it, adds the Cu (NO of the molar parts of 20 mL 0.023)2·3H2O, is stirred
Mixing is well mixed it, the mol/L of 20 mL 1.2 NaOH is then added dropwise dropwise, and the mixed liquor after dropwise addition is diluted into 70
ML, continues to stir after 1 h, the mixed liquor is transferred in autoclave, and rise temperature reacts 24 h to 100 DEG C, treats anti-
Kettle is answered to naturally cool to after room temperature, the sediment ultra-pure water supersound washing repeatedly that reaction is obtained, and 6000 r/min's
Centrifuged under rotating speed, 12 h are then dried in 60 DEG C of vacuum drying chambers, ground, cross 80 mesh sieves, produce CuBi2O4。
（2）, further using hydro-thermal method prepare CuBi2O4@C.Accurately weigh 0.1 g steps（1）In it is prepared
CuBi2O4It is scattered in 70 mL gluconic acid solutions（Contain 0.3 mL gluconic acids）, after ultrasonic 30 min, mixed liquor is moved to
In 100 mL autoclaves, rise temperature reacts 4 h, question response kettle is naturally cooled to after room temperature, by sediment to 180 DEG C
Centrifuge, then done in 60 DEG C of vacuum drying chambers with ultra-pure water supersound washing repeatedly, and under 6000 r/min rotating speed
Dry 12 h, grinds, crosses 80 mesh sieves, and it is 1 to produce mass ratio:1.4 CuBi2O4@C。
（3）, finally the technology that is combined using liquid phase synthesis-calcining prepare CuBi2O4/β-Bi2O3.Accurately weigh 0.1 g
Step（2）In prepared CuBi2O4@C are scattered in 20 mL HNO3Solution（1 mol/L）In, ultrasonic 30 min makes it fully divide
Dissipate, obtain solution A；By 0.39 mmol Bi (NO3)3·5H2O is added to 20 mL HNO3Solution（1 mol/L）In, at room temperature
Being stirred vigorously 1 h is completely dissolved it, obtains solution B；By 2.34 mmol Na2CO3It is added in 40 mL ultra-pure waters, stirring 30
Min, obtains solution C.The min of magnetic agitation 30 after first mixing solution A and solution B, is well mixed it, then thereto dropwise
Solution C is added dropwise, a large amount of white precipitates can be now produced, continues to stir after 30 min, washs heavy with absolute ethyl alcohol and deionized water
Starch.The sediment after washing is then put into temperature programming stove, sets temperature programming stove to be warming up to 600 DEG C in 30 min,
And 5 h are reacted at 600 DEG C, after temperature programming stove naturally cools to room temperature, you can it is 1 to obtain mass ratio:2.25
CuBi2O4/β-Bi2O3.Obtained CuBi2O4/β-Bi2O3SEM（Scanning electron microscope diagram）、XRD（X ray diffracting spectrum）、
UV-Vis（UV-Vis DRS spectrum）Characterization result is shown in Fig. 1 to Fig. 3 respectively.By SEM it can be seen that, it is seen that photoresponse type answer
CuBi in closing light catalyst2O4For hollow sub-microsphere,β-Bi2O3For irregular nano particle, and demonstrate through XRD analysis visible
The composition of photoresponse type composite photo-catalyst is mainly CuBi2O4Withβ-Bi2O3, UV-Vis collection of illustrative plates then can see, CuBi2O4/β-Bi2O3There is higher optical absorption intensity in whole limit of visible spectrum.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and Diclofenac residual concentration in supernatant is determined, the photocatalysis performance of the visible-light response type composite photo-catalyst is as schemed
4.From test result, it is seen that photoresponse type composite photo-catalyst is 89.02% to the removal efficiency of Diclofenac, much high
Yu Chunβ-Bi2O3To the removal efficiency of Diclofenac（60.19%）.
Embodiment 2
Preparing for visible-light response type composite photo-catalyst is same as Example 1.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.2 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and determine Diclofenac residual concentration in supernatant.From test result, it is seen that photoresponse type composite photo-catalyst is to double
The removal efficiency of the fragrant acid of chlorine is 80.49%.
Embodiment 3
Preparing for visible-light response type composite photo-catalyst is same as Example 1, simply gluconic acid in gluconic acid solution
Volume is 0.6 mL.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and determine Diclofenac residual concentration in supernatant.From test result, it is seen that photoresponse type composite photo-catalyst is to double
The removal efficiency of the fragrant acid of chlorine is 78.62%.
Embodiment 4
The preparation of visible-light response type composite photo-catalyst：
（1）、CuBi2O4Prepare it is same as Example 1.
（2）、CuBi2O4Preparing for@C is same as Example 1.
（3）, it is last, the technology being combined using liquid phase synthesis-calcining prepares CuBi2O4/β-Bi2O3.Accurately weigh 0.1
G steps（2）In prepared CuBi2O4@C are scattered in 20 mL HNO3Solution（1 mol/L）In, ultrasonic 30 min makes its abundant
It is scattered, obtain solution A；By 1.29 mmol Bi (NO3)3·5H2O is added to 20 mL HNO3Solution（1 mol/L）In, room temperature
Under be stirred vigorously 1 h and be completely dissolved it, obtain solution B；By 7.74 mmol Na2CO3It is added in 40 mL ultra-pure waters, stirs
30 min, obtain solution C.The min of magnetic agitation 30 after first mixing solution A and solution B, is well mixed it, then thereto by
Solution C is added dropwise in drop, can now produce a large amount of white precipitates, continues to stir after 30 min, is washed with absolute ethyl alcohol and deionized water
Sediment.The sediment after washing is then put into temperature programming stove, sets temperature programming stove to be warming up to 600 in 30 min
DEG C, and 5 h are reacted at 600 DEG C, after temperature programming stove naturally cools to room temperature, you can it is 1 to obtain mass ratio:6
CuBi2O4/β-Bi2O3。
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and determine Diclofenac residual concentration in supernatant.From test result, it is seen that photoresponse type composite photo-catalyst is to double
The removal efficiency of the fragrant acid of chlorine is 81.36%.
Embodiment 5
Preparing for visible-light response type composite photo-catalyst is same as Example 1, and simply the reaction temperature of temperature programming stove is 500
℃。
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and determine Diclofenac residual concentration in supernatant.From test result, it is seen that photoresponse type composite photo-catalyst is to double
The removal efficiency of the fragrant acid of chlorine is 85.27%.
Embodiment 6
Preparing for visible-light response type composite photo-catalyst is same as Example 3, and simply the reaction temperature of temperature programming stove is 700
℃。
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and determine Diclofenac residual concentration in supernatant.From test result, it is seen that photoresponse type composite photo-catalyst is to double
The removal efficiency of the fragrant acid of chlorine is 83.78%.
Embodiment 7
Preparing for visible-light response type composite photo-catalyst is same as Example 1, and simply the reaction time of temperature programming stove is 3
h。
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/L of 1 L 5
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out and reaches
To after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid point is made by centrifugation after terminating
From, and determine Diclofenac residual concentration in supernatant.From test result, it is seen that photoresponse type composite photo-catalyst is to double
The removal efficiency of the fragrant acid of chlorine is 75.92%.
Embodiment 8
Preparing for visible-light response type composite photo-catalyst is same as Example 1.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal：In the mg/ of 1 L 20
In L diclofenac solutions, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, the dark min of adsorption reaction 30 is first carried out
Reach after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, test and solid-liquid is made by centrifugation after terminating
Separation, and Diclofenac residual concentration in supernatant is determined, from test result, it is seen that photoresponse type composite photo-catalyst pair
The removal efficiency of Diclofenac is 72.46%.
Embodiment 9：
Preparing for visible-light response type composite photo-catalyst is same as Example 1.
Visible-light response type composite photo-catalyst is repeatedly applied to remove the performance test of Organic substance in water：In 1 L 5
In mg/L diclofenac solutions, the above-mentioned visible-light response type composite photo-catalysts of 0.4 g are added, dark adsorption reaction 30 is first carried out
Min is reached after adsorption equilibrium, then the h of light-catalyzed reaction 3 under the conditions of the irradiation of 300 W xenon lamps, and experiment is made solid by centrifugation after terminating
Liquid is separated, and determines Diclofenac residual concentration in supernatant.The visible-light response type composite photo-catalyst of recovery is through ultra-pure water
Washing after drying, is ground for several times, in 60 DEG C of vacuum drying chambers, crosses 80 mesh sieves, again applied to Diclofenac wastewater treatment,
Ibid, it reuses efficiency as shown in figure 5, from test result to processing procedure, it is seen that photoresponse type composite photo-catalyst
When reusing the 7th time, its degradation efficiency to Diclofenac is 78.43%.
In summary, a kind of visible-light response type composite photo-catalyst that the present invention is provided and its preparation method and application,
The present invention prepares that appearance structure is uniform, stable chemical nature visible-light response type semiconductor first with hydrothermal synthesis method
CuBi2O4With core shell structure CuBi2O4@C, on this basis, the technology being combined by liquid phase synthesis-calcining is in temperature programming
Under conditions of obtain CuBi2O4/β-Bi2O3.Visible-light response type composite photo-catalyst prepared by the present invention is in whole visible ray
There is stronger absorption in spectral limit, and compare pureβ-Bi2O3Cyclic utilization rate with more preferable photocatalysis performance and Geng Gao.Will
0.4 g CuBi2O4/β-Bi2O3（1:2.25, wt%）For handling Diclofenac organic wastewater with difficult degradation thereby, it is seen that light irradiation 3
H, the clearance to the mg/L diclofenac solutions of 1 L 5 is 89.02%, reuses the 7th time, diclofenac solution is removed
Rate is 78.43%.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
1. a kind of visible-light response type composite photo-catalyst, it is characterised in that the visible-light response type composite photo-catalyst is
CuBi2O4/β-Bi2O3, CuBi in the visible-light response type composite photo-catalyst2O4For hollow sub-microsphere,β-Bi2O3Not advise
Then nano particle, and CuBi2O4Withβ-Bi2O3Between be in close contact.
2. visible-light response type composite photo-catalyst according to claim 1, it is characterised in that CuBi2O4/β-Bi2O3In,
CuBi2O4Withβ-Bi2O3Mass ratio be 1：（0.5-20）.
3. a kind of preparation method of visible-light response type composite photo-catalyst as described in claim 1-2 is any, its feature exists
In comprising the following steps：
（1）CuBi2O4Preparation：By Bi (NO3)3·5H2O is dissolved in dense HNO3In, stir to being completely dissolved, add Cu
(NO3)2·3H20.5-2 mol/L alkaline sedimentation agent solution is then added dropwise to well mixed in O, stirring dropwise, and by after dropwise addition
Solution dilutes, and continues to stir after 0.5-2 h, solution is transferred in reactor, and rise temperature reacts 18-30 to 80-150 DEG C
H, question response kettle is cooled to after room temperature, and the sediment that reaction is obtained is washed, and by centrifuging, is then dried in vacuo, is ground
Mill, sieving, produce CuBi2O4；
（2）CuBi2O4@C preparation：By step（1）In prepared CuBi2O4It is scattered in gluconic acid solution, ultrasonic 10-50
After min, mixed liquor is moved in reactor, rise temperature is to 150-250 DEG C, and question response kettle is naturally cooled to after room temperature, is passed through
Centrifuge and reclaim the sediment that reaction is obtained, and sediment is washed, be then dried in vacuo, grind, sieve, produce
CuBi2O4@C；
（3）CuBi2O4/β-Bi2O3Preparation：By step（2）In prepared CuBi2O4@C are scattered in HNO3In solution, ultrasound
10-50 min, obtain solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, 30-120 min are stirred vigorously at room temperature,
Obtain solution B；Subcarbonate is dissolved in ultra-pure water, 10-50 min is stirred, obtains solution C；First by solution A and solution B
Magnetic agitation 10-50 min after mixing, then solution C is added dropwise dropwise thereto, continue to stir 10-50 min, will react what is produced
Sediment is washed, and collects sediment by centrifuging；Sediment after washing is put into temperature programming stove, program liter is set
Warm stove is warming up to 300-800 DEG C in 10-60 min, and reacts 2-10 h in temperature programming stove, treats that temperature programming stove is natural
It is cooled to after room temperature, collects solid sediment, you can obtain CuBi2O4/β-Bi2O3。
4. the preparation method of visible-light response type composite photo-catalyst according to claim 3, it is characterised in that step
（1）In, the alkaline precipitating agent in the alkaline sedimentation agent solution is one kind or many in NaOH, potassium hydroxide and ammoniacal liquor
Kind.
5. the preparation method of visible-light response type composite photo-catalyst according to claim 3, it is characterised in that step
（2）In, the volume of gluconic acid is 0.04-0.8 mL in the gluconic acid solution.
6. the preparation method of visible-light response type composite photo-catalyst according to claim 3, it is characterised in that step
（3）In, the Bi (NO3)3·5H2The mole that O is added is 0.1-3.6 mmol.
7. the preparation method of visible-light response type composite photo-catalyst according to claim 3, it is characterised in that step
（3）In, the subcarbonate and Bi (NO3)3·5H2The ratio between O mole is（1-10）:1.
8. the preparation method of visible-light response type composite photo-catalyst according to claim 3, it is characterised in that step
（3）In, the temperature of described program heating furnace is increased to 300-800 DEG C.
9. the preparation method of visible-light response type composite photo-catalyst according to claim 3, it is characterised in that step
（3）In, the reaction time of described program heating furnace is 2-10 h.
10. a kind of application of visible-light response type composite photo-catalyst, it is characterised in that will be as described in claim 1-2 is any
Visible-light response type composite photo-catalyst be applied to processing the waste water containing non-steroid anti-inflammatory drug.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108585111A (en) * | 2018-05-12 | 2018-09-28 | 辽宁大学 | The method that semi-conducting material Zinc Tungstate is catalyzed ultrasonotomography Meloxicam |
| WO2020042125A1 (en) * | 2018-08-30 | 2020-03-05 | 南通纺织丝绸产业技术研究院 | Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof |
| CN111068715A (en) * | 2019-12-26 | 2020-04-28 | 西安理工大学 | Ag/Bi2O3/CuBi2O4Preparation method of nanofiber composite photocatalyst |
| CN111744504A (en) * | 2020-07-02 | 2020-10-09 | 重庆大学 | Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst |
| CN112536039A (en) * | 2020-12-03 | 2021-03-23 | 浙江大学 | Preparation method of visible light catalytic material of composite oxide with hierarchical structure |
| CN113731430A (en) * | 2021-09-26 | 2021-12-03 | 辽宁大学 | Double Z type CuO/CuBi2O4/Bi2O3Composite photocatalyst and preparation method and application thereof |
| CN115055187A (en) * | 2022-05-20 | 2022-09-16 | 石家庄循环化工研究院 | Copper doped beta-Bi 2 O 3 Preparation method of crystal catalyst and benzene series wastewater purification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703948A (en) * | 2009-12-02 | 2010-05-12 | 淮北煤炭师范学院 | Novel method for preparing compound high-activity photocatalyst |
| CN105233837A (en) * | 2015-10-29 | 2016-01-13 | 苏州首户电气有限公司 | Modified copper bismuthate photocatalyst and preparation method thereof |
| CN106486656A (en) * | 2016-09-20 | 2017-03-08 | 华中科技大学 | A kind of lithium ion battery, its negative material and preparation method and application |
-
2017
- 2017-03-17 CN CN201710160064.1A patent/CN106944074B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703948A (en) * | 2009-12-02 | 2010-05-12 | 淮北煤炭师范学院 | Novel method for preparing compound high-activity photocatalyst |
| CN105233837A (en) * | 2015-10-29 | 2016-01-13 | 苏州首户电气有限公司 | Modified copper bismuthate photocatalyst and preparation method thereof |
| CN106486656A (en) * | 2016-09-20 | 2017-03-08 | 华中科技大学 | A kind of lithium ion battery, its negative material and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 田玉 等: "水热法制备β-Bi2O3纳米片及其光催化性能的研究", 《江汉大学学报(自然科学版)》 * |
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| CN108585111A (en) * | 2018-05-12 | 2018-09-28 | 辽宁大学 | The method that semi-conducting material Zinc Tungstate is catalyzed ultrasonotomography Meloxicam |
| CN108585111B (en) * | 2018-05-12 | 2021-04-30 | 辽宁大学 | Method for degrading meloxicam by catalyzing and ultrasonically degrading zinc tungstate serving as semiconductor material |
| WO2020042125A1 (en) * | 2018-08-30 | 2020-03-05 | 南通纺织丝绸产业技术研究院 | Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof |
| CN111068715A (en) * | 2019-12-26 | 2020-04-28 | 西安理工大学 | Ag/Bi2O3/CuBi2O4Preparation method of nanofiber composite photocatalyst |
| CN111068715B (en) * | 2019-12-26 | 2022-12-20 | 西安理工大学 | Ag/Bi 2 O 3 /CuBi 2 O 4 Preparation method of nanofiber composite photocatalyst |
| CN111744504A (en) * | 2020-07-02 | 2020-10-09 | 重庆大学 | Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst |
| CN112536039A (en) * | 2020-12-03 | 2021-03-23 | 浙江大学 | Preparation method of visible light catalytic material of composite oxide with hierarchical structure |
| CN112536039B (en) * | 2020-12-03 | 2021-09-17 | 浙江大学 | Preparation method of visible light catalytic material of composite oxide with hierarchical structure |
| CN113731430A (en) * | 2021-09-26 | 2021-12-03 | 辽宁大学 | Double Z type CuO/CuBi2O4/Bi2O3Composite photocatalyst and preparation method and application thereof |
| CN113731430B (en) * | 2021-09-26 | 2023-11-10 | 辽宁大学 | Double Z-type CuO/CuBi 2 O 4 /Bi 2 O 3 Composite photocatalyst, preparation method and application thereof |
| CN115055187A (en) * | 2022-05-20 | 2022-09-16 | 石家庄循环化工研究院 | Copper doped beta-Bi 2 O 3 Preparation method of crystal catalyst and benzene series wastewater purification method |
| CN115055187B (en) * | 2022-05-20 | 2023-07-18 | 石家庄循环化工研究院 | Copper doped beta-Bi 2 O 3 Preparation method of crystal catalyst and benzene series wastewater purification method |
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