CN106944074B - 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
- Publication number
- CN106944074B CN106944074B CN201710160064.1A CN201710160064A CN106944074B CN 106944074 B CN106944074 B CN 106944074B CN 201710160064 A CN201710160064 A CN 201710160064A CN 106944074 B CN106944074 B CN 106944074B
- Authority
- CN
- China
- Prior art keywords
- visible
- cubi
- response type
- type composite
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000004044 response Effects 0.000 title claims abstract description 87
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 77
- 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 5
- 230000001788 irregular Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000013049 sediment Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 15
- 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
- 235000012208 gluconic acid Nutrition 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
- 239000003054 catalyst 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
- 239000007787 solid Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000002156 mixing 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
- 238000004064 recycling Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 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 5
- 125000004122 cyclic group Chemical group 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
- 238000001179 sorption measurement Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 238000012360 testing method Methods 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
- 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
- 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
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 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
- 238000011160 research Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 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 2
- 238000002441 X-ray diffraction Methods 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
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000985 reflectance spectrum 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
- 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
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 150000005323 carbonate salts Chemical class 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 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
- 238000007873 sieving Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 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
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/76—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 invention and its preparation method and application, the visible-light response type composite photo-catalyst are 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 entire limit of visible spectrum, and compares pureβ‑Bi2O3With better photocatalysis performance and higher cyclic utilization rate.By the CuBi of 0.4 g2O4/β‑Bi2O3(1:2.25, wt%) is for handling Diclofenac organic wastewater with difficult degradation thereby, it is seen that light irradiates 3 h, and the removal rate to 1 L, 5 mg/L diclofenac solution is 89.02%, reuses the 7th time, is 78.43% to diclofenac solution removal rate.
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 preparations
Methods and applications.
Background technique
In recent years, the continuous development of economic society and process of industrialization deepen continuously, and result in a large amount of emerging organic
The discharge of pollutant waste water, but municipal sewage system is difficult to be completely removed at present, it is emerging organic so as to cause these
Pollutant in surface water, underground water, be even detected in potable water system.And these emerging organic pollutants, such as antiphen
Acid etc., even if under trace concentration, if exposure wherein also will receive serious harm for a long time for the mankind and animals and plants.Therefore, it gives up
The removal of emerging organic pollutant is still the key points and difficulties of current field of environment protection in water.
Photocatalysis oxidation technique has the advantages such as reaction condition is mild, reaction speed is fast, mineralization rate is high, secondary pollution is few.
U.S.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 (3.2 eV) of the material, and only (only accounts for solar radiation in ultraviolet light
Total amount 4%) the lower generation photocatalytic activity of irradiation, which greatly limits its applications.Therefore, cheap sunlight can efficiently be utilized
Visible-light-responsive photocatalyst development becomes the hot spot in current photocatalysis oxidation technique field.
Bismuth oxide (Bi2O3) it is a kind of visible-light response type semiconductor material, due to its unique optics and electric property,
Gas sensor, photovoltaic cell, optical coating, fuel cell, in terms of have extensive research.In addition, Bi2O3
The internal polarization field of Bi 6s track lone pair electrons induction in structure facilitates separation and the carrier of photo-generate electron-hole pair
Transmitting, to make Bi2O3With certain photocatalysis.Bi2O3It is primarily presentα、β、γ、δFour kinds of crystalline structures, whereinα-Bi2O3Stablize under room temperature, forbidden bandwidth is about 2.8 eV(conduction band, 0.33 eV, 3.13 eV of valence band), it is rung as visible light
Type photochemical catalyst is answered to have numerous studies.Although however,β-Bi2O3Forbidden bandwidth be 2.4 eV, have thanα-Bi2O3It is stronger
Visible light absorption capacity, stillβ-Bi2O3Research as photochemical catalyst still has three aspect problems: (1)β-Bi2O3?
Easily it is transformed into photocatalytic processα-Bi2O3, and and CO2Reaction generates carbonate, and photocatalytic activity is caused to decline；(2)β-Bi2O3
The quantum efficiency of photocatalytic system is low, causes its photocatalytic activity poor；(3)β-Bi2O3Conduction band be lower than H+/H2Reduction electricity
Position, causes light induced electron easily compound with photohole, to influence photocatalysis efficiency.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of visible-light response type composite photocatalysts
Agent and its preparation method and application, it is intended to solve existingβ-Bi2O3As there are above-mentioned technological deficiencies 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-Bi2O3Not advise
Then nano particle, and CuBi2O4Withβ-Bi2O3Between be in close contact.
The visible-light response type composite photo-catalyst, wherein CuBi2O4/β-Bi2O3In, CuBi2O4Withβ-Bi2O3's
Mass ratio is 1:(0.5-20).
The preparation method of a kind of as above any visible-light response type composite photo-catalyst, wherein including following step
It is rapid:
(1) CuBi2O4Preparation: by Bi (NO3)3·5H2O is dissolved in dense HNO3In, it stirs to being completely dissolved, adds Cu
(NO3)2·3H2The alkaline sedimentation agent solution of 0.5-2 mol/L is then added dropwise to being uniformly mixed in O, stirring dropwise, and will be after dropwise addition
Solution dilution continues after stirring 0.5-2 h, which is transferred in reaction kettle, increases temperature to 80-150 DEG C, reacts 18-
30 h, after reaction kettle is cooled to room temperature, the sediment that reaction is obtained is washed, and by centrifuge separation, is then dried in vacuo,
It is ground up, sieved to get CuBi2O4；
(2) CuBi2O4The preparation of@C: by CuBi prepared in step (1)2O4It is scattered in gluconic acid solution, ultrasound
After 10-50 min, mixed liquor is moved in reaction kettle, increases temperature to 150-250 DEG C, to reaction kettle cooled to room temperature
Afterwards, the sediment obtained by centrifuge separation recycling reaction, and sediment is washed, it is then dried in vacuo, is ground up, sieved, i.e.,
Obtain CuBi2O4@C；
(3) CuBi2O4/β-Bi2O3Preparation: by CuBi prepared in step (2)2O4@C is scattered in HNO3In solution,
Ultrasonic 10-50 min, obtains solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, it is vigorously stirred 30-120 at room temperature
Min obtains solution B；Subcarbonate is dissolved in ultrapure 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 sediment is collected by centrifuge separation；Sediment after washing is put into temperature programming furnace, journey is set
Sequence heating furnace is warming up to 300-800 DEG C in 10-60 min, and 2-10 h is reacted in temperature programming furnace, to temperature programming furnace
After cooled to room temperature, solid sediment is collected, CuBi can be obtained2O4/β-Bi2O3。
The preparation method of the visible-light response type composite photo-catalyst, wherein in step (1), the alkaline sedimentation
Alkaline precipitating agent in agent solution is one of sodium hydroxide, potassium hydroxide and ammonium hydroxide or a variety of.
The preparation method of the visible-light response type composite photo-catalyst, wherein in step (2), the gluconic acid
The volume of glucose in solutions acid is 0.04-0.8 mL.
The preparation method of the visible-light response type composite photo-catalyst, wherein in step (3), the Bi (NO3)3·
5H2The mole that O is added is 0.1-3.6 mmol.
The preparation method of the visible-light response type composite photo-catalyst, wherein in step (3), the basic carbonate
Salt and Bi (NO3)3·5H2The ratio between mole of O is (1-10): 1.
The preparation method of the visible-light response type composite photo-catalyst, wherein in step (3), described program heating
The temperature of furnace is increased to 300-800 DEG C.
The preparation method of the visible-light response type composite photo-catalyst, wherein in step (3), described program heating
The reaction time of furnace is 2-10 h.
A kind of application of visible-light response type composite photo-catalyst, wherein by as above any visible-light response type
Composite photo-catalyst is applied to waste water of the processing containing non-steroid anti-inflammatory drug.
The utility model has the advantages that comparing pureβ-Bi2O3, the present invention prepared by visible-light response type composite photo-catalyst have it is visible
The advantages that optical absorption intensity is higher, photocatalysis performance is more preferable, cyclic utilization rate is higher.
Detailed description of the invention
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-Bi2O3Ultraviolet-visible diffuse reflectance spectrum figure.
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.
Specific embodiment
The present invention provides a kind of visible-light response type composite photo-catalyst and its preparation method and application, of the invention to make
Purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that this place is retouched
The specific embodiment stated is only used to explain the present invention, is not intended to limit the present invention.
To improveβ-Bi2O3Photocatalytic activity, it is constructed with other semiconductors couplings with appropriate band structure multiple
Light combination 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
At new band structure feature, improve composite photocatalyst system in photo-generate electron-hole Transport, to reduce photoproduction
The recombination rate of electron-hole improvesβ-Bi2O3Photocatalytic activity；It on the other hand, can also be steady by the chemistry of other semiconductors
It is qualitative to improveβ-Bi2O3Structural stability.CuBi2O4Semiconductor have it is visible light-responded it is strong, that chemical stability is good etc. is excellent
Gesture, and its conduction band positions is higher, and light induced electron has stronger reducing power.In addition, comparingβ-Bi2O3, CuBi2O4's
Conduction band and valence band potential energy are relatively negative, both semiconductors couplings will certainly change the photocatalysis performance of entire 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 multiple
Light combination 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 receive
Rice grainβ-Bi2O3The composite photo-catalyst for being in close contact and being formed.
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 visible-light response type composite photo-catalyst, packets
Include following steps:
(1) CuBi2O4Preparation: by Bi (NO3)3·5H2O is dissolved in dense HNO3In, it stirs to being completely dissolved, adds Cu
(NO3)2·3H2The alkaline sedimentation agent solution of 0.5-2 mol/L is then added dropwise to being uniformly mixed in O, stirring dropwise, and will be after dropwise addition
Solution dilution continues after stirring 0.5-2 h, which is transferred in reaction kettle, increases temperature to 80-150 DEG C, reacts 18-
30 h, after reaction kettle is cooled to room temperature, the sediment that reaction is obtained is washed, and by centrifuge separation, is then dried in vacuo,
It is ground up, sieved to get CuBi2O4。
In above-mentioned steps (1), the alkaline precipitating agent in the alkaline sedimentation agent solution can be sodium hydroxide, potassium hydroxide
One or more of with ammonium hydroxide.
Above-mentioned steps (1) of the present invention prepare the uniform CuBi of appearance structure using hydro-thermal method2O4.Above-mentioned steps (1) are specific
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 makes it completely dissolved, and adds the Cu (NO of 20 mL, 0.02 molar part3)2·3H2O, stirring keep it mixed
It closes uniformly, the alkaline sedimentation agent solution of 0.5-2 mol/L, the preferably alkaline precipitating agent of 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, after preferably stirring 0.8-1.5 h, by the solution
It is transferred in autoclave, increases temperature to 80-150 DEG C, preferably 90-110 DEG C (such as 100 DEG C), react 18-30 h, it is excellent
Select 22-26 h(such as 24 h), after reaction kettle cooled to room temperature, the sediment washing that reaction is obtained is (preferably using super
Pure water supersound washing repeatedly), and by centrifuge separation (revolving speed preferably uses 5000-7000 r/min), it is then dried in vacuo (preferably
The dry 6-18 h in 40-80 DEG C of vacuum oven, such as 12 h), is ground up, sieved and (preferably crosses 60-120 mesh, such as 80 mesh
Sieve) to get CuBi2O4。
(2) CuBi2O4/β-Bi2O3Preparation: by CuBi prepared in step (1)2O4It is scattered in gluconic acid solution
In, after ultrasonic 10-50 min, mixed liquor is moved in reaction kettle, increases temperature to 150-250 DEG C, to reaction kettle natural cooling
To room temperature, the sediment obtained by centrifuge separation recycling reaction, and sediment is washed, it is then dried in vacuo, grinding, mistake
Sieve is to get CuBi2O4@C。
In step (2), 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 (2) of the present invention prepare CuBi using hydro-thermal method2O4@C.Above-mentioned steps (2) are specifically, by step (1)
Prepared CuBi2O4Be scattered in 70 mL gluconic acid solutions (volume containing gluconic acid be 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 being moved in 100 mL autoclaves, raising temperature is to 150-250 DEG C, and preferably 160-200 DEG C (such as 180
DEG C), react 2-10 h, preferably 2.5-6 h, still further preferably 3-5 h(such as 4 h), after reaction kettle cooled to room temperature,
It is the centrifuge centrifuge separation of 4000-10000 r/min, preferably 5000-7000 r/min(such as 6000 r/min) by revolving speed
The solid sediment that recycling reaction obtains, and solid sediment is washed into (preferably with ultrapure water supersound washing repeatedly), then very
Sky is dried (dries 6-18 h, dry 12 h) such as in 60 DEG C of vacuum ovens, grinds preferably in 40-80 DEG C of vacuum oven
Mill, sieving (preferably crossing 60-120 mesh, such as cross 80 meshes) are to get CuBi2O4@C。
(3) CuBi2O4/β-Bi2O3Preparation: by CuBi prepared in step (2)2O4@C is scattered in HNO3In solution,
Ultrasonic 10-50 min, obtains solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, it is vigorously stirred 30-120 at room temperature
Min obtains solution B；Subcarbonate is dissolved in ultrapure 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 sediment is collected by centrifuge separation；Sediment after washing is put into temperature programming furnace, journey is set
Sequence heating furnace is warming up to 300-800 DEG C in 10-60 min, and 2-10 h is reacted in temperature programming furnace, to temperature programming furnace
After cooled to room temperature, solid sediment is collected, CuBi can be obtained2O4/β-Bi2O3。
In step (3), 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 preferable 0.35-0.5 mmol.
In step (3), the subcarbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
In step (3), the subcarbonate and Bi (NO3)3·5H2The ratio between mole of O is (1-10): 1, preferably (3-
8): 1, further preferred (5-7): 1.
In step (3), 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.
In step (3), the reaction time of described program heating furnace is 2-10 h, preferably 3-7 h, further preferred 4-6 h.
The technology preparation CuBi that above-mentioned steps (3) of the present invention are combined using liquid phase synthesis-calcining2O4/β-Bi2O3.It is above-mentioned
Step (3) is specifically, by CuBi prepared in step (2)2O4@C is scattered in 20 mL HNO3Solution (wherein HNO3Concentration
For 0.5-4 mol/L, preferably 0.6-2 mol/L, further preferred 0.8-1.5 mol/L, in 1.0 mol/L), 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, into one
Preferred 0.25-1.5 mmol is walked, further preferably 0.3-1.0 mmol, more preferable 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, into
The preferred 0.8-1.5 mol/L of one step is vigorously stirred 30-120 min, preferably 40-90 min in 1.0 mol/L) at room temperature
(such as 60 min), obtain solution B；By subcarbonate (subcarbonate and the Bi (NO of certain molar weight3)3·5H2Mole of O
The ratio between amount is (1-10): 1, preferably (3-8): 1, further preferred (5-7): 1, such as 6:1) be added in 40 mL ultrapure waters, it 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 generated at this time,
Continue to stir 10-50 min, preferably 20-40 min(such as 30 min), it is 4000-10000 r/min by revolving speed, preferably
5000-7000 r/min(such as 6000 r/min) the obtained solid sediment of centrifuge centrifuge separation recycling reaction, and will consolidate
Body sediment washing (preferably with dehydrated alcohol and ultrapure water supersound washing repeatedly).Sediment after washing is put into temperature programming
Temperature programming furnace is arranged in 10-60 min, preferably 20-40 min(such as 30 min in furnace) it is interior be warming up to 300-800 DEG C, preferably
It is 400-700 DEG C, 500-650 DEG C further preferred (such as 600 DEG C), and 2-10 h, preferably 3-7 are reacted in temperature programming furnace
H, further preferred 4-6 h(such as 5 h), after temperature programming furnace cooled to room temperature, collect solid sediment, can be obtained
CuBi2O4/β-Bi2O3。
The present invention also provides a kind of applications of visible-light response type composite photo-catalyst, wherein will be as above any described
Visible-light response type composite photo-catalyst is applied to the waste water that processing contains non-steroid anti-inflammatory drug (such as Diclofenac).
The application method of visible-light response type composite photo-catalyst of the invention is to the mould containing non-steroid anti-inflammatory drug
Visible-light response type composite photo-catalyst, i.e. CuBi are added in quasi- waste water (such as Diclofenac aqueous solution)2O4/β-Bi2O3, advanced
The dark adsorption reaction of row carries out visible light illumination after balance to be achieved.It is measured by sampling in application process by certain time interval useless
The concentration of non-steroid anti-inflammatory drug (such as Diclofenac) in water.
Preferably, in the application, CuBi2O4/β-Bi2O3Dosage be: non-steroid anti-inflammatory drug contained in waste water is (such as
Diclofenac) and CuBi2O4/β-Bi2O3Mass ratio be 1:(10-150), preferably 1:(50-120), further preferred 1:
(70-100), such as 1:80.
The invention firstly uses the hydrothermal synthesis method preparation visible-light response types that appearance structure is uniform, chemical property is stable half
Conductor CuBi2O4With core-shell structure CuBi2O4@C, on this basis, the technology combined by liquid phase synthesis-calcining is in program
CuBi is obtained under conditions of heating2O4/β-Bi2O3.It compares pureβ-Bi2O3, the present invention prepared by visible-light response type complex light
Catalyst has many advantages, such as 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), the uniform CuBi of appearance structure is prepared using hydro-thermal method first2O4, i.e., by the Bi (NO of 0.04 molar part3)3·
5H2O is dissolved in the dense HNO of 3 mL3In, stirring makes it completely dissolved, and adds the Cu (NO of 20 mL, 0.02 molar part3)2·3H2O,
Stirring is uniformly mixed it, the NaOH of 20 mL, 1.2 mol/L is then added dropwise dropwise, and the mixed liquor after dropwise addition is diluted to 70
ML continues after stirring 1 h, which is transferred in autoclave, increases temperature to 100 DEG C, 24 h is reacted, to anti-
After answering kettle cooled to room temperature, the sediment ultrapure water supersound washing repeatedly that reaction is obtained, and 6000 r/min's
It is centrifugated under revolving speed, then dry 12 h in 60 DEG C of vacuum ovens, grinding cross 80 meshes to get CuBi2O4。
(2), CuBi is further prepared using hydro-thermal method2O4@C.Prepared by accurately weighing in 0.1 g step (1)
CuBi2O4It is scattered in 70 mL gluconic acid solutions (containing 0.3 mL gluconic acid), after 30 min of ultrasound, mixed liquor is moved to
In 100 mL autoclaves, temperature is increased to 180 DEG C, 4 h are reacted, after reaction kettle cooled to room temperature, by sediment
It with ultrapure water supersound washing repeatedly, and is centrifugated under the revolving speed of 6000 r/min, is then done in 60 DEG C of vacuum ovens
The CuBi that 80 meshes are 1:1.4 to get mass ratio is crossed in dry 12 h, grinding2O4@C。
(3), the technology preparation CuBi finally combined using liquid phase synthesis-calcining2O4/β-Bi2O3.Accurately weigh 0.1 g
Prepared CuBi in step (2)2O4@C is scattered in 20 mL HNO3In solution (1 mol/L), 30 min of ultrasound divide it sufficiently
It dissipates, obtains solution A；By 0.39 mmol Bi (NO3)3·5H2O is added to 20 mL HNO3In solution (1 mol/L), at room temperature
It is vigorously stirred 1 h to make it completely dissolved, obtains solution B；By 2.34 mmol Na2CO3It is added in 40 mL ultrapure waters, stirring 30
Min obtains solution C.30 min of magnetic agitation after first mixing solution A and solution B, is uniformly mixed it, then thereto dropwise
Solution C is added dropwise, a large amount of white precipitates can be generated at this time, continues after stirring 30 min, it is heavy to be washed with dehydrated alcohol and deionized water
Starch.The sediment after washing is then put into temperature programming furnace, setting temperature programming furnace is warming up to 600 DEG C in 30 min,
And in 600 DEG C of 5 h of reaction, after temperature programming furnace cooled to room temperature, it is 1:2.25's that mass ratio, which can be obtained,
CuBi2O4/β-Bi2O3.Obtained CuBi2O4/β-Bi2O3SEM(scanning electron microscope diagram), XRD(X x ray diffraction map),
UV-Vis(ultraviolet-visible diffuse reflectance 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 is multiple
CuBi in light combination catalyst2O4For hollow sub-microsphere,β-Bi2O3For irregular nano particle, and demonstrate through XRD analysis visible
The ingredient of photoresponse type composite photo-catalyst is mainly CuBi2O4Withβ-Bi2O3, UV-Vis map then can see, CuBi2O4/β-Bi2O3There is higher optical absorption intensity in entire limit of visible spectrum.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal: in 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and Diclofenac residual concentration in supernatant is measured, the photocatalysis performance of the visible-light response type composite photo-catalyst is as schemed
4.It is much high by test result it is found that visible-light response type composite photo-catalyst is 89.02% to the removal efficiency of Diclofenac
Yu Chunβ-Bi2O3To the removal efficiency (60.19%) of Diclofenac.
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 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.2 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and measure Diclofenac residual concentration in supernatant.By test result it is found that visible-light response 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, only glucose in gluconic acid solution
The volume of acid is 0.6 mL.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal: in 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and measure Diclofenac residual concentration in supernatant.By test result it is found that visible-light response 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), finally, preparing CuBi using the technology that liquid phase synthesis-calcining combines2O4/β-Bi2O3.Accurately weigh 0.1
Prepared CuBi in g step (2)2O4@C is scattered in 20 mL HNO3In solution (1 mol/L), 30 min of ultrasound make it sufficiently
Dispersion, obtains solution A；By 1.29 mmol Bi (NO3)3·5H2O is added to 20 mL HNO3In solution (1 mol/L), room temperature
Under be vigorously stirred 1 h and make it completely dissolved, obtain solution B；By 7.74 mmol Na2CO3It is added in 40 mL ultrapure waters, stirs
30 min, obtain solution C.30 min of magnetic agitation after first mixing solution A and solution B is uniformly mixed it, then thereto by
Solution C is added dropwise in drop, can generate a large amount of white precipitates at this time, continues after stirring 30 min, is washed with dehydrated alcohol and deionized water
Sediment.The sediment after washing is then put into temperature programming furnace, setting temperature programming furnace is warming up to 600 in 30 min
DEG C, and in 600 DEG C of 5 h of reaction, after temperature programming furnace cooled to room temperature, it is 1:6's that mass ratio, which can be obtained,
CuBi2O4/β-Bi2O3。
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal: in 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and measure Diclofenac residual concentration in supernatant.By test result it is found that visible-light response 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, only the reaction temperature of temperature programming furnace
It is 500 DEG C.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal: in 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and measure Diclofenac residual concentration in supernatant.By test result it is found that visible-light response 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, only the reaction temperature of temperature programming furnace
It is 700 DEG C.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal: in 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and measure Diclofenac residual concentration in supernatant.By test result it is found that visible-light response 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, only the reaction time of temperature programming furnace
For 3 h.
Visible-light response type composite photo-catalyst is applied to go the performance test of Diclofenac in water removal: in 1 L, 5 mg/L
In diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark 30 min of adsorption reaction is first carried out and reaches
To after adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid point is made by centrifugation after experiment
From, and measure Diclofenac residual concentration in supernatant.By test result it is found that visible-light response 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 1 L, 20 mg/
In L diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, first carries out dark 30 min of adsorption reaction
After reaching adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, solid-liquid is made by centrifugation after experiment
Separation, and Diclofenac residual concentration in supernatant is measured, by test result it is found that visible-light response 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 the performance test of removal Organic substance in water: in 1 L 5
In mg/L diclofenac solution, the above-mentioned visible-light response type composite photo-catalyst of 0.4 g is added, dark adsorption reaction 30 is first carried out
After min reaches adsorption equilibrium, then 3 h of light-catalyzed reaction under 300 W xenon lamp irradiation conditions, made admittedly after experiment by centrifugation
Liquid separation, and measure Diclofenac residual concentration in supernatant.The visible-light response type composite photo-catalyst of recycling is through ultrapure water
Washing after drying, is ground for several times, in 60 DEG C of vacuum ovens, is crossed 80 meshes, is applied to Diclofenac wastewater treatment again,
Treatment process is same as above, and reuses efficiency as shown in figure 5, by test result it is found that visible-light response type composite photo-catalyst
When reusing the 7th time, the degradation efficiency to Diclofenac is 78.43%.
In conclusion a kind of visible-light response type composite photo-catalyst provided by the invention and its preparation method and application,
The invention firstly uses the hydrothermal synthesis method preparation visible-light response type semiconductors that appearance structure is uniform, chemical property is stable
CuBi2O4With core-shell structure CuBi2O4@C, on this basis, the technology combined by liquid phase synthesis-calcining is in temperature programming
Under conditions of obtain CuBi2O4/β-Bi2O3.Visible-light response type composite photo-catalyst is in entire visible light prepared by the present invention
There is stronger absorption in spectral limit, and compares pureβ-Bi2O3With better photocatalysis performance and higher cyclic utilization rate.It will
The CuBi of 0.4 g2O4/β-Bi2O3(1:2.25, wt%) is for handling Diclofenac organic wastewater with difficult degradation thereby, it is seen that light irradiation 3
H, the removal rate to 1 L, 5 mg/L diclofenac solution are 89.02%, reuse the 7th time, remove to diclofenac solution
Rate is 78.43%.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (8)
1. a kind of preparation method of visible-light response type composite photo-catalyst, which is characterized in that the visible-light response type is compound
Photochemical 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, CuBi2O4/β-Bi2O3In, CuBi2O4Withβ-Bi2O3Mass ratio be 1:(0.5-20)；The preparation method comprises the following steps:
(1) CuBi2O4Preparation: by Bi (NO3)3·5H2O is dissolved in dense HNO3In, it stirs to being completely dissolved, adds Cu
(NO3)2·3H2The alkaline sedimentation agent solution of 0.5-2 mol/L is then added dropwise to being uniformly mixed in O, stirring dropwise, and will be after dropwise addition
Solution dilution continues after stirring 0.5-2 h, solution is transferred in reaction kettle, increases temperature to 80-150 DEG C, reacts 18-30
H, after reaction kettle is cooled to room temperature, the sediment that reaction is obtained is washed, and by centrifuge separation, is then dried in vacuo, is ground
Mill is sieved to get CuBi2O4；
(2) CuBi2O4The preparation of@C: by CuBi prepared in step (1)2O4It is scattered in gluconic acid solution, ultrasonic 10-50
After min, mixed liquor is moved in reaction kettle, temperature is increased to 150-250 DEG C, after reaction kettle cooled to room temperature, passes through
The obtained sediment of centrifuge separation recycling reaction, and sediment is washed, is then dried in vacuo, be ground up, sieved to get
CuBi2O4@C；
(3) CuBi2O4/β-Bi2O3Preparation: by CuBi prepared in step (2)2O4@C is scattered in HNO3In solution, ultrasound
10-50 min, obtains solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, it is vigorously stirred 30-120 min at room temperature,
Obtain solution B；Subcarbonate is dissolved in ultrapure 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, reaction is generated
Sediment washing, and sediment is collected by centrifuge separation；Sediment after washing is put into temperature programming furnace, program liter is set
Warm furnace is warming up to 300-800 DEG C in 10-60 min, and 2-10 h is reacted in temperature programming furnace, natural to temperature programming furnace
After being cooled to room temperature, solid sediment is collected, CuBi can be obtained2O4/β-Bi2O3。
2. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step
(1) in, the alkaline precipitating agent in the alkaline sedimentation agent solution is one of sodium hydroxide, potassium hydroxide and ammonium hydroxide or more
Kind.
3. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step
(2) in, the volume of gluconic acid is 0.04-0.8 mL in the gluconic acid solution.
4. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step
(3) in, the Bi (NO3)3·5H2The mole that O is added is 0.1-3.6 mmol.
5. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step
(3) in, the subcarbonate and Bi (NO3)3·5H2The ratio between mole of O is (1-10): 1.
6. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step
(3) in, the temperature of described program heating furnace is increased to 300-800 DEG C.
7. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step
(3) in, the reaction time of described program heating furnace is 2-10 h.
8. a kind of application of visible-light response type composite photo-catalyst, which is characterized in that will be as claimed in claim 1
The visible-light response type composite photo-catalyst that preparation method is prepared is applied to waste water of the processing containing non-steroid anti-inflammatory drug.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710160064.1A CN106944074B (en) | 2017-03-17 | 2017-03-17 | A kind of visible-light response type composite photo-catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710160064.1A CN106944074B (en) | 2017-03-17 | 2017-03-17 | A kind of visible-light response type composite photo-catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106944074A CN106944074A (en) | 2017-07-14 |
| CN106944074B true CN106944074B (en) | 2019-07-09 |
Family
ID=59473095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710160064.1A Expired - Fee Related CN106944074B (en) | 2017-03-17 | 2017-03-17 | A kind of visible-light response type composite photo-catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106944074B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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 |
|---|
| 水热法制备β-Bi2O3纳米片及其光催化性能的研究;田玉 等;《江汉大学学报(自然科学版)》;20131031;第41卷(第5期);第44页摘要 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106944074A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| Cheng et al. | One-step microwave hydrothermal preparation of Cd/Zr-bimetallic metal–organic frameworks for enhanced photochemical properties | |
| Yuan et al. | In-situ synthesis of 3D microsphere-like In2S3/InVO4 heterojunction with efficient photocatalytic activity for tetracycline degradation under visible light irradiation | |
| CN107088434B (en) | A kind of g-C3N4-Cu2The preparation method and applications of O catalyst | |
| CN108479759B (en) | Visible light response type lanthanum-doped bismuth tungstate catalyst and preparation method thereof | |
| CN104801328B (en) | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature | |
| CN105032468A (en) | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof | |
| CN106944043B (en) | A kind of micro-nano hetero-junctions visible light composite photocatalyst and its preparation method and application | |
| CN103599802A (en) | Preparation method of silver phosphate/graphene nanocomposite | |
| CN103191725B (en) | BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof | |
| CN109364933A (en) | A kind of copper-bismuth/composite bismuth vanadium photocatalyst preparation and application | |
| CN107159273A (en) | A kind of preparation method of BiOCl nano-photocatalysts and obtained photochemical catalyst and application | |
| CN108355669B (en) | Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof | |
| CN109174082A (en) | It is a kind of to prepare BiVO4/MnO2The method of composite photocatalyst oxidant | |
| CN109985618A (en) | A kind of H occupies BiVO4The catalysis material of-OVs, preparation method and applications | |
| CN106362742B (en) | A kind of Ag/ZnO nano-complex and its preparation method and application | |
| CN106693996B (en) | Preparation method and application of bismuth sulfide-bismuth ferrite composite visible-light-driven photocatalyst | |
| CN102671674A (en) | Magnetically supported silver bromide photochemical catalysis material and preparation method thereof | |
| CN111686770B (en) | Metal ion co-doped BiOBr microsphere, preparation method and application thereof | |
| CN107626297B (en) | A kind of tiny balloon shape bismuth/composite bismuth vanadium photocatalyst and its preparation method and application | |
| CN104148100B (en) | A kind of novel vanadium phosphate catalysis material and its preparation method and application | |
| Wu et al. | Self-floating biomass charcoal supported flower-like plasmon silver/carbon, nitrogen co-doped defective TiO2 as robust visible light photocatalysts | |
| Sun et al. | Modulating charge transport behavior across the interface via g-C3N4 surface discrete modified BiOI and Bi2MoO6 for efficient photodegradation of glyphosate | |
| CN104549222A (en) | Preparation method and application of visible-light-induced photocatalyst chromium chromate | |
| CN109382088A (en) | SnO2/ α~Bi2O3/ β~Bi2O3Composite material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190709 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |