CN106944043A - A kind of micro-nano hetero-junctions visible light composite photocatalyst and its preparation method and application - Google Patents
A kind of micro-nano hetero-junctions visible light composite photocatalyst and its preparation method and application Download PDFInfo
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- CN106944043A CN106944043A CN201710159909.5A CN201710159909A CN106944043A CN 106944043 A CN106944043 A CN 106944043A CN 201710159909 A CN201710159909 A CN 201710159909A CN 106944043 A CN106944043 A CN 106944043A
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 83
- 239000000654 additive Substances 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- XRRONFCBYFZWTM-UHFFFAOYSA-N octadecanoic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCC(O)=O XRRONFCBYFZWTM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000013049 sediment Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 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
- 239000006259 organic additive Substances 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 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 44
- 229960001259 diclofenac Drugs 0.000 abstract description 44
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000012901 Milli-Q water Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 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
- 238000002604 ultrasonography 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
A kind of micro-nano hetero-junctions visible light composite photocatalyst of the present invention and its preparation method and application, the micro-nano hetero-junctions visible light composite photocatalyst is CuBi2O4/Ag3PO4, CuBi in the micro-nano hetero-junctions visible light composite photocatalyst2O4For micrometer structure, Ag3PO4For nanostructured, and CuBi2O4With Ag3PO4Close contact forms hetero-junctions.Compare pure Ag3PO4, the micro-nano hetero-junctions visible light composite photocatalyst prepared by the present invention is respectively provided with the advantages of visible absorption intensity is high, photocatalysis performance is good, anti-light corrosivity is strong.By 0.5 g using stearic acid sodium CuBi made from additive2O4/Ag3PO4（1:1, wt%）Applied to processing Diclofenac organic wastewater with difficult degradation thereby, 240 minutes diclofenac solution clearances to the mg/L of 1 L 10 are reused the 5th time up to 88.73%, are 73.69% to diclofenac solution clearance.
Description
Technical field
The present invention relates to photocatalysis technology field, more particularly to a kind of micro-nano hetero-junctions visible light composite photocatalyst and its
Preparation method and application.
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.
Silver orthophosphate（Ag3PO4）It is a kind of visible-light response type catalyst found in recent years, can absorb wavelength and be less than 520 nm
Sunshine.Under the irradiation of sunshine, the catalyst quantum yield is high, Photocatalytic oxidation activity is strong.But in pure Ag3PO4Light is urged
Change in reaction system, due to Ag3PO4There is certain microsolubility in the solution（Solubility is 0.02 g/L）, and Ag/Ag+'s
Electrode potential is higher than Ag3PO4Conduction band potential, final Ag+In Ag3PO4Surface is reduced into metal Ag0, induce photoetch effect.
And the generation of photoetch effect, then Ag can be destroyed step by step3PO4Stability, reduce Ag3PO4Photocatalytic activity, finally lead
Cause Ag3PO4Loss of catalytic activity.
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 micro-nano hetero-junctions visible ray complex light
Catalyst and its preparation method and application, it is intended to solve existing Ag3PO4Photochemical catalyst is easy to the problem of photoetch, stability are poor,
And Ag is further enhanced on this basis3PO4Visible absorption intensity and photocatalytic activity.
Technical scheme is as follows：
A kind of micro-nano hetero-junctions visible light composite photocatalyst, wherein, the micro-nano hetero-junctions visible light composite photocatalyst is
CuBi2O4/Ag3PO4, CuBi in the micro-nano hetero-junctions visible light composite photocatalyst2O4For micrometer structure, Ag3PO4For nanometer
Structure, and CuBi2O4With Ag3PO4It is in close contact and constitutes heterojunction structure.
Described micro-nano hetero-junctions visible light composite photocatalyst, wherein, CuBi2O4/Ag3PO4In, CuBi2O4With Ag3PO4
Mass ratio be 1：（0.1-9）.
As above a kind of preparation method of any described micro-nano hetero-junctions visible light composite photocatalyst, wherein, including with
Lower step：
（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/Ag3PO4Preparation：By step（1）In prepared CuBi2O4It is scattered in ultra-pure water, ultrasonic 10-50
After min, the aqueous solution for being dissolved with additive is added, magnetic agitation 1-4 h are added dropwise and are dissolved with AgNO3The aqueous solution, after
Continuous stirring 25-35 min, are finally added dropwise and are dissolved with the phosphatic aqueous solution dropwise, after stirring 0.5-3 h, by centrifuging back
The sediment that reaction is obtained is received, and sediment is washed, is then dried in vacuo, is ground, sieves, produce CuBi2O4/Ag3PO4。
The preparation method of described micro-nano hetero-junctions visible light composite photocatalyst, wherein, step（1）In, the alkalescence
Alkaline precipitating agent in precipitant solution is the one or more in NaOH, potassium hydroxide and ammoniacal liquor.
The preparation method of described micro-nano hetero-junctions visible light composite photocatalyst, wherein, step（2）In, the addition
Agent is organic additive, and the organic additive is sodium citrate or stearic acid sodium.
The preparation method of described micro-nano hetero-junctions visible light composite photocatalyst, wherein, step（2）In, the phosphoric acid
Salt is one kind in sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate.
The preparation method of described micro-nano hetero-junctions visible light composite photocatalyst, wherein, step（2）In, addition
AgNO3Mole with add CuBi2O4The ratio between mole is（1-15）:1.
The preparation method of described micro-nano hetero-junctions visible light composite photocatalyst, wherein, step（2）In, the addition
The mole of agent and the AgNO added3The ratio between mole be（0.2-3）:1.
The preparation method of described micro-nano hetero-junctions visible light composite photocatalyst, wherein, step（2）In, it is described to add
AgNO3Mole and the ratio between the phosphatic mole that adds be 10:（3-7）.
A kind of application of micro-nano hetero-junctions visible light composite photocatalyst, wherein, as above any described micro-nano is heterogeneous
Tie visible light composite photocatalyst and be applied to waste water of the processing containing non-steroid anti-inflammatory drug.
Beneficial effect：Compare pure Ag3PO4, the micro-nano hetero-junctions visible light composite photocatalyst prepared by the present invention has can
See the advantages of optical absorption intensity is high, photocatalysis performance is good, anti-light corrosivity is strong.
Brief description of the drawings
Fig. 1 is CuBi in the embodiment of the present invention 12O4/Ag3PO4Scanning electron microscope diagram.
Fig. 2 is CuBi in the embodiment of the present invention 22O4/Ag3PO4Scanning electron microscope diagram.
Fig. 3 is CuBi in Example 1 and Example 2 of the present invention2O4/Ag3PO4X ray diffracting spectrum.
Fig. 4 is CuBi in Example 1 and Example 2 of the present invention2O4/Ag3PO4UV-Vis DRS spectrogram.
Fig. 5 is CuBi in Example 1 and Example 2 of the present invention2O4/Ag3PO4Photocatalysis performance schematic diagram.
Fig. 6 is CuBi in Example 1 and Example 2 of the present invention2O4/Ag3PO4Recycling performance schematic diagram.
Embodiment
The present invention provides a kind of micro-nano hetero-junctions visible light composite photocatalyst and its preparation method and application, to send out this
Bright 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 herein
Described specific embodiment only to explain the present invention, is not intended to limit the present invention.
Heterojunction semiconductor is in the face superior performance such as rectification, photovoltaic property and fiber waveguide effect side so that hetero-junctions light
Lotus separating power is sent a telegraph far above single semiconductor；In addition, heterojunction structure is various, morphology controllable, Ag is improved available for optimization3PO4
The structure of base catalyst, improves Ag3PO4The catalytic performance and stability of based photocatalyst.CuBi2O4, can although quantum energy is low
See that photoresponse is strong, chemical stability is good, and its conduction band positions is higher, with stronger reducing power.Therefore, the present invention passes through
By Ag3PO4With CuBi2O4It is compound to construct hetero-junctions composite photocatalyst, so as to give full play to the advantage of this two classes material, i.e.,
Ag3PO4The stronger oxidability of valence band hole and CuBi2O4The stronger reducing power of conduction band electron, and two kinds of materials collaboration
Act on improving the photocatalytic activity and stability of composite.
Specifically, the present invention provides a kind of micro-nano hetero-junctions visible light composite photocatalyst, wherein, the micro-nano hetero-junctions
Visible light composite photocatalyst is CuBi2O4/Ag3PO4, CuBi in the micro-nano hetero-junctions visible light composite photocatalyst2O4For
Micrometer structure, Ag3PO4For nanostructured, and CuBi2O4With Ag3PO4It is in close contact and constitutes heterojunction structure.It is i.e. of the present invention
Micro-nano hetero-junctions visible light composite photocatalyst is CuBi2O4/Ag3PO4, the CuBi2O4/Ag3PO4It is CuBi2O4With Ag3PO4
It is in close contact the visible light composite photocatalyst of the heterojunction structure formed.
CuBi of the present invention2O4/Ag3PO4In, CuBi2O4With Ag3PO4Mass ratio be 1：（0.1-9）.Preferably, CuBi2O4
With Ag3PO4Mass ratio be 1：（0.2-6）.It is highly preferred that CuBi2O4With Ag3PO4Mass ratio be 1：（0.5-4）.Further preferably
Ground, CuBi2O4With Ag3PO4Mass ratio be 1：（0.8-3）.Still further preferably, CuBi2O4With Ag3PO4Mass ratio be 1：
（0.8-2.5）, for example, CuBi2O4With Ag3PO4Mass ratio be 1:1 or 1:2.33.
The present invention also provides the preparation method of a kind of as above any described micro-nano hetero-junctions visible light composite photocatalyst,
It comprises 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, 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/Ag3PO4Preparation：By step（1）In prepared CuBi2O4It is scattered in ultra-pure water, ultrasound
After 10-50 min, the aqueous solution for being dissolved with additive is added, magnetic agitation 1-4 h are added dropwise and are dissolved with AgNO3Water
Solution, continues to stir 25-35 min, is finally added dropwise dropwise and is dissolved with the phosphatic aqueous solution, after stirring 0.5-3 h, by from
The sediment that heart separation and recovery reaction is obtained, and sediment is washed, then it is dried in vacuo, grinds, sieves, produce CuBi2O4/
Ag3PO4。
Step（2）In, the additive is organic additive, and the organic additive can be sodium citrate or stearic acid
Sodium etc..
Step（2）In, the phosphate can be optional sodium or the phosphate of potassium, for example, sodium dihydrogen phosphate, phosphoric acid hydrogen two
Sodium, sodium phosphate or dipotassium hydrogen phosphate.
Step（2）In, the AgNO of addition3Mole with add CuBi2O4The ratio between mole is（1-15）:1, preferably
For（2-10）:1, more preferably（3-9）:1, much further preferably from（3.5-8.5）:1.
Step（2）In, the mole of the additive and the AgNO added3The ratio between mole be（0.2-3）:1, preferably
For（0.5-2）:1, more preferably（0.8-1.5）:1, much further preferably from（0.9-1.2）:1.
Step（2）In, the AgNO3Mole and the ratio between the phosphatic mole that adds be 10:（3-7）, preferably
For 10:（3.2-6）, more preferably 10:（3.3-4）.
Above-mentioned steps of the present invention（2）Micro-nano hetero-junctions visible light composite photocatalyst is prepared using in situ Precipitation
CuBi2O4/Ag3PO4, above-mentioned steps（2）Specifically, by step（1）In prepared CuBi2O4It is scattered in 40 mL ultra-pure waters,
Ultrasonic 10-50 min, preferably 20-40 min（Such as 30 min）Afterwards, the aqueous solution that 10 mL are dissolved with additive is added, magnetic force is stirred
Mix 1-4 h, preferably 1.5-3 h（Such as 2 h）, add dropwise 10 mL and be dissolved with AgNO3The aqueous solution, continue stir 25-35
Min (preferably 30 min), is finally added dropwise 20 mL and is dissolved with the phosphatic aqueous solution, stir 0.5-3 h, preferably 1-2 h dropwise
Afterwards, it is 4000-10000 r/min, preferably 5000-7000 r/min by rotating speed（Such as 6000 r/min）Centrifuge point
The solid sediment obtained from recovery reaction, and solid sediment is washed（It is preferred that repeatedly ultrasonic with absolute ethyl alcohol and ultra-pure water
Washing）, then it is dried in vacuo（It is preferred that 6-18 h are dried in 40-80 DEG C of vacuum drying chamber, such as in 60 DEG C of vacuum drying chambers
Dry 12 h）, grinding, sieving（It is preferred that crossing 60-120 mesh sieves, 80 mesh sieves are such as crossed）, produce CuBi2O4/Ag3PO4。
The present invention also provides a kind of application of micro-nano hetero-junctions visible light composite photocatalyst, wherein, will as above any institute
The micro-nano hetero-junctions visible light composite photocatalyst stated contains non-steroid anti-inflammatory drug applied to processing（Such as Diclofenac）It is useless
Water.
The application process of the micro-nano hetero-junctions visible light composite photocatalyst of the present invention is to containing non-steroid anti-inflammatory drug
Simulated wastewater（Such as the Diclofenac aqueous solution）Middle addition micro-nano hetero-junctions visible light composite photocatalyst, i.e. CuBi2O4/
Ag3PO4, first carry out carrying out visible ray illumination after dark adsorption reaction, balance to be achieved.Intervals are pressed in application process
Non-steroid anti-inflammatory drug in waste water is measured by sampling（Such as Diclofenac）Concentration.
Preferably, in the application, CuBi2O4/Ag3PO4Consumption be：Contained non-steroid anti-inflammatory drug in waste water（It is such as double
The fragrant acid of chlorine）With CuBi2O4/Ag3PO4Mass ratio be 1:（10-100）, preferably 1:（20-70）, further preferred 1:（40-
60）, such as 1:50.
The present invention prepares that appearance structure is uniform, stable chemical nature visible-light response type half first with hydrothermal synthesis method
Conductor CuBi2O4, then using in situ Precipitation, it is made what different-shape, heterogeneity were constituted in different additive reaction system
Micro-nano hetero-junctions visible light composite photocatalyst CuBi2O4/Ag3PO4.Compare pure Ag3PO4, the present invention prepared by micro-nano it is heterogeneous
Knot visible light composite photocatalyst is respectively provided with the advantages of visible absorption intensity is high, photocatalysis performance is good, anti-light corrosivity is strong.
Below by embodiment, the present invention is described in detail.
Embodiment 1
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：
（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, 20 mL1.2 mol/L 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 micro-nano hetero-junctions CuBi prepared using in situ Precipitation2O4/Ag3PO4, i.e., accurately weigh 0.2 mmol
Step（1）In prepared CuBi2O4It is scattered in 40 mL ultra-pure waters, and ultrasonic 30 min, then add 10 mL and be dissolved with
The aqueous solution of 1.8 mmol sodium citrate additives, the h of magnetic agitation 2 adds dropwise 10 mL and is dissolved with 1.8 mmol's
AgNO3Solution, continues to stir 30 min, the Na that 20 mL are dissolved with 0.6 mmol is finally added dropwise dropwise2HPO4·12H2O solution,
1.5 h are stirred, solid sediment are separated and recovered for 6000 r/min centrifuge by rotating speed, and solid sediment is used
The supersound washing repeatedly of absolute ethyl alcohol and ultra-pure water, then dries 12 h in 60 DEG C of vacuum drying chambers, grinds, crosses 80 mesh sieves, i.e.,
Obtain CuBi2O4And Ag3PO4Mass ratio is 1:2.33 CuBi2O4/Ag3PO4.Wherein pure Ag3PO4Preparation process and CuBi2O4/
Ag3PO4It is similar, simply do not add CuBi2O4.Obtained CuBi2O4/Ag3PO4SEM, XRD, UV-Vis characterization result difference
See Fig. 1, Fig. 3 and Fig. 4.By SEM it can be seen that, CuBi in micro-nano hetero-junctions visible light composite photocatalyst2O4For micrometer structure,
Ag3PO4For nanostructured, and CuBi2O4And Ag3PO4Between be in close contact and form hetero-junctions, and demonstrate micro-nano through XRD analysis
The composition of hetero-junctions visible light composite photocatalyst；UV-Vis collection of illustrative plates then can see, CuBi2O4/Ag3PO4In visible-range
Photon absorbing intensity compare pure Ag3PO4It is significantly improved.
Micro-nano hetero-junctions visible light composite photocatalyst is applied to go the performance test of Diclofenac in water removal：In 1 L 10
In mg/L diclofenac solutions, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.5 g are added, dark adsorption reaction is first carried out
30 min are reached after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, and experiment passes through after terminating
Centrifugation makes separation of solid and liquid, and determines Diclofenac residual concentration in supernatant, the micro-nano hetero-junctions visible light composite photocatalyst
And the photocatalysis performance of silver orthophosphate such as Fig. 5.From test result, the min of illumination 240, micro-nano hetero-junctions visible ray complex light is urged
Agent is 81.95% to the removal efficiency of Diclofenac, higher than removal efficiency of the pure phosphoric acid silver to Diclofenac（74.18%）, and
And in micro-nano hetero-junctions visible light composite photocatalyst silver orthophosphate consumption it is relatively low, reduce cost.
Embodiment 2
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：
（1）、CuBi2O4Prepare it is same as Example 1.
（2）, further micro-nano hetero-junctions CuBi prepared using in situ Precipitation2O4/Ag3PO4, i.e., accurately weigh 0.2
Mmol steps（1）In prepared CuBi2O4It is scattered in 40 mL ultra-pure waters, and ultrasonic 30 min, then add 10 mL dissolvings
There is the aqueous solution of 0.72 mmol stearic acid sodium additives, the h of magnetic agitation 2 adds dropwise 10 mL and is dissolved with 0.72 mmol
AgNO3Solution, continues to stir 30 min, the Na that 20 mL are dissolved with 0.24 mmol is finally added dropwise dropwise2HPO4·12H2O is molten
Liquid, stirs 1.5 h, separates and recovers solid sediment by rotating speed for 6000 r/min centrifuge, and solid is precipitated
The supersound washing repeatedly of thing absolute ethyl alcohol and ultra-pure water, then dries 12 h in 60 DEG C of vacuum drying chambers, grinds, crosses 80 mesh
Sieve, produces CuBi2O4And Ag3PO4Mass ratio is 1:1 CuBi2O4/Ag3PO4.Wherein pure Ag3PO4Preparation process with
CuBi2O4/Ag3PO4It is similar, simply do not add CuBi2O4.Obtained CuBi2O4/Ag3PO4SEM, XRD, UV-Vis characterize
As a result Fig. 2, Fig. 3 and Fig. 4 are seen respectively.By SEM it can be seen that, micro-nano hetero-junctions visible light composite photocatalyst is into nucleocapsid micro-nano knot
Structure, Ag3PO4It is attached to CuBi2O4Surface forms hetero-junctions, and demonstrates micro-nano hetero-junctions visible ray complex light through XRD analysis and urge
The composition of agent, UV-Vis collection of illustrative plates then can see, CuBi2O4/Ag3PO4Compared in the photon absorbing intensity of visible-range pure
Ag3PO4It is significantly improved.
Micro-nano hetero-junctions visible light composite photocatalyst is applied to go the performance test of Diclofenac in water removal：In 1 L 10
In mg/L diclofenac solutions, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.5 g are added, dark absorption are first carried out anti-
30 min are answered to reach after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, test and lead to after terminating
Crossing centrifugation makes separation of solid and liquid, and determines Diclofenac residual concentration in supernatant, the micro-nano hetero-junctions visible ray composite photocatalyst
The photocatalysis performance of agent and silver orthophosphate such as Fig. 5.From test result, the min of illumination 240, composite is gone to Diclofenac
Except efficiency is 88.73%, higher than removal efficiency of the pure phosphoric acid silver to Diclofenac（79.64%）, and silver orthophosphate in composite
Consumption it is relatively low, reduce cost.
Embodiment 3：
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：
（1）、CuBi2O4Prepare it is same as Example 1.
（2）, further micro-nano hetero-junctions CuBi prepared using in situ Precipitation2O4/Ag3PO4, i.e., accurately weigh 0.2
Mmol steps（1）In prepared CuBi2O4It is scattered in 40 mL ultra-pure waters, and ultrasonic 30 min, then add 10 mL dissolvings
There is the aqueous solution of 0.72 mmol sodium citrate additives, the h of magnetic agitation 2 adds dropwise 10 mL and is dissolved with 0.72 mmol
AgNO3Solution, continues to stir 30 min, the Na that 20 mL are dissolved with 0.24 mmol is finally added dropwise dropwise2HPO4·12H2O
Solution, stirs 1.5 h, separates and recovers solid sediment by rotating speed for 6000 r/min centrifuge, and solid is sunk
The supersound washing repeatedly of starch absolute ethyl alcohol and ultra-pure water, then dries 12 h in 60 DEG C of vacuum drying chambers, grinds, crosses 80
Mesh sieve, produces CuBi2O4And Ag3PO4Mass ratio is 1:1 CuBi2O4/Ag3PO4。
Micro-nano hetero-junctions visible light composite photocatalyst is applied to go the performance test of Diclofenac in water removal：In 1 L 10
In mg/L diclofenac solutions, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.5 g are added, dark adsorption reaction is first carried out
30 min are reached after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, and experiment passes through after terminating
Centrifugation makes separation of solid and liquid, and determines Diclofenac residual concentration in supernatant, from test result, micro-nano hetero-junctions visible ray
Composite photo-catalyst is 77.32% to the removal efficiency of Diclofenac.
Embodiment 4
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：The preparation process of micro-nano hetero-junctions visible light composite photocatalyst
It is same as Example 1.
Micro-nano hetero-junctions visible light composite photocatalyst is applied to go the performance test of Diclofenac in water removal：In 1 L 50
In mg/L diclofenac solutions, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.5 g are added, dark adsorption reaction is first carried out
30 min are reached after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, and experiment passes through after terminating
Centrifugation makes separation of solid and liquid, and determines Diclofenac residual concentration in supernatant, from test result, micro-nano hetero-junctions visible ray
Composite photo-catalyst is 70.38% to the removal efficiency of Diclofenac.
Embodiment 5
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：The preparation process of micro-nano hetero-junctions visible light composite photocatalyst
It is same as Example 2.
Micro-nano hetero-junctions visible light composite photocatalyst is applied to go the performance test of Diclofenac in water removal：In 1 L 50
In mg/L diclofenac solutions, the above-mentioned composite photo-catalysts of 0.5 g are added, the dark min of adsorption reaction 30 is first carried out and reaches that absorption is flat
After weighing apparatus, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, test and separation of solid and liquid is made by centrifugation after terminating, and
Diclofenac residual concentration in supernatant is determined, from test result, micro-nano hetero-junctions visible light composite photocatalyst is to double
The removal efficiency of the fragrant acid of chlorine is 75.49%.
Embodiment 6
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：The preparation process of micro-nano hetero-junctions visible light composite photocatalyst
It is same as Example 2.
Micro-nano hetero-junctions visible light composite photocatalyst is applied to go the performance test of Diclofenac in water removal：In 1 L 10
In mg/L diclofenac solutions, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.2 g are added, dark adsorption reaction is first carried out
30 min are reached after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, and experiment passes through after terminating
Centrifugation makes separation of solid and liquid, and determines Diclofenac residual concentration in supernatant, from test result, micro-nano hetero-junctions visible ray
Composite photo-catalyst is 80.64% to the removal efficiency of Diclofenac.
Embodiment 7
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：The preparation process of micro-nano hetero-junctions visible light composite photocatalyst
It is same as Example 1.
Micro-nano hetero-junctions visible light composite photocatalyst is repeatedly applied to the performance test of Diclofenac in water removal：1
In the mg/L diclofenac solutions of L 10, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.5 g are added, are first secretly inhaled
The min of reaction enclosure 30 is reached after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, and experiment terminates
Separation of solid and liquid is made by centrifugation afterwards, and determines Diclofenac residual concentration in supernatant.The visible recovery of micro-nano hetero-junctions of recovery
Closing light catalyst after drying, is ground for several times, in 60 DEG C of vacuum drying chambers through milli-Q water, is crossed 80 mesh sieves, is applied to again
Diclofenac wastewater treatment, ibid, it reuses efficiency as shown in fig. 6, from test result, complex light is urged to processing procedure
When agent reuses the 5th time, its degradation efficiency to Diclofenac is 65.03%.
Embodiment 8
The preparation of micro-nano hetero-junctions visible light composite photocatalyst：The preparation process of micro-nano hetero-junctions visible light composite photocatalyst
It is same as Example 2.
Micro-nano hetero-junctions visible light composite photocatalyst is repeatedly applied to the performance test of Diclofenac in water removal：1
In the mg/L diclofenac solutions of L 10, the above-mentioned micro-nano hetero-junctions visible light composite photocatalysts of 0.5 g are added, are first secretly inhaled
The min of reaction enclosure 30 is reached after adsorption equilibrium, then the min of light-catalyzed reaction 240 under the conditions of the irradiation of 300 W xenon lamps, and experiment terminates
Separation of solid and liquid is made by centrifugation afterwards, and determines Diclofenac residual concentration in supernatant.The visible recovery of micro-nano hetero-junctions of recovery
Closing light catalyst after drying, is ground for several times, in 60 DEG C of vacuum drying chambers through milli-Q water, is crossed 80 mesh sieves, is applied to again
Diclofenac wastewater treatment, ibid, it reuses efficiency as shown in fig. 6, from test result, micro-nano is heterogeneous to processing procedure
Knot visible light composite photocatalyst is when reusing the 5th time, and its degradation efficiency to Diclofenac is 73.69%.
In summary, a kind of micro-nano hetero-junctions visible light composite photocatalyst for providing of the present invention and preparation method thereof and should
Prepare that appearance structure is uniform, stable chemical nature visible-light response type semiconductor first with hydrothermal synthesis method with, the present invention
CuBi2O4, then using in situ Precipitation, different-shape, the micro-nano of heterogeneity composition are made in different additive reaction system
Hetero-junctions visible light composite photocatalyst CuBi2O4/Ag3PO4.Compare pure Ag3PO4, the micro-nano hetero-junctions prepared by the present invention can
See that photoreactivation photochemical catalyst is respectively provided with the advantages of visible absorption intensity is high, photocatalysis performance is good, anti-light corrosivity is strong.By 0.5
G is using stearic acid sodium CuBi made from additive2O4/Ag3PO4（1:1, wt%）Applied to processing Diclofenac difficult degradation organic waste
Water, 240 minutes diclofenac solution clearances to the mg/L of 1 L 10 are reused the 5th time, to Diclofenac up to 88.73%
Solution clearance is 73.69%.
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 micro-nano hetero-junctions visible light composite photocatalyst, it is characterised in that the micro-nano hetero-junctions visible ray complex light
Catalyst is CuBi2O4/Ag3PO4, CuBi in the micro-nano hetero-junctions visible light composite photocatalyst2O4For micrometer structure,
Ag3PO4For nanostructured, and CuBi2O4With Ag3PO4Close contact forms hetero-junctions.
2. micro-nano hetero-junctions visible light composite photocatalyst according to claim 1, it is characterised in that CuBi2O4/Ag3PO4
In, CuBi2O4With Ag3PO4Mass ratio be 1：（0.1-9）.
3. a kind of preparation method of micro-nano hetero-junctions visible light composite photocatalyst as described in claim 1-2 is any, it is special
Levy and be, comprise 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/Ag3PO4Preparation：By step（1）In prepared CuBi2O4It is scattered in ultra-pure water, ultrasonic 10-50
After min, the aqueous solution for being dissolved with additive is added, magnetic agitation 1-4 h are added dropwise and are dissolved with AgNO3The aqueous solution, after
Continuous stirring 25-35 min, are finally added dropwise and are dissolved with the phosphatic aqueous solution dropwise, after stirring 0.5-3 h, by centrifuging back
The sediment that reaction is obtained is received, and sediment is washed, is then dried in vacuo, is ground, sieves, produce CuBi2O4/Ag3PO4。
4. the preparation method of micro-nano hetero-junctions visible light composite photocatalyst according to claim 3, it is characterised in that step
Suddenly（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 micro-nano hetero-junctions visible light composite photocatalyst according to claim 3, it is characterised in that step
Suddenly（2）In, the additive is organic additive, and the organic additive is sodium citrate or stearic acid sodium.
6. the preparation method of micro-nano hetero-junctions visible light composite photocatalyst according to claim 3, it is characterised in that step
Suddenly（2）In, the phosphate is one kind in sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate.
7. the preparation method of micro-nano hetero-junctions visible light composite photocatalyst according to claim 3, it is characterised in that step
Suddenly（2）In, the AgNO of addition3Mole with add CuBi2O4The ratio between mole is（1-15）:1.
8. the preparation method of micro-nano hetero-junctions visible light composite photocatalyst according to claim 3, it is characterised in that step
Suddenly（2）In, the mole of the additive and the AgNO added3The ratio between mole be（0.2-3）:1.
9. the preparation method of micro-nano hetero-junctions visible light composite photocatalyst according to claim 3, it is characterised in that step
Suddenly（2）In, the AgNO3Mole and the ratio between the phosphatic mole that adds be 10:（3-7）.
10. a kind of application of micro-nano hetero-junctions visible light composite photocatalyst, it is characterised in that will be as any such as claim 1-2
Described micro-nano hetero-junctions visible light composite photocatalyst is applied to waste water of the processing containing non-steroid anti-inflammatory drug.
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| CN108246306A (en) * | 2018-02-08 | 2018-07-06 | 秦英皓 | One pot process has visible light-responded photochemical catalyst CuBi2O4/Bi2WO6Nanosphere and its application |
| CN109019685A (en) * | 2018-09-12 | 2018-12-18 | 西南科技大学 | A kind of synthesis CuBi2O4The method of base colloidal materials |
| CN109148593A (en) * | 2018-07-16 | 2019-01-04 | 复旦大学 | A kind of ternary p-type CuBi2O4Thin film transistor (TFT) and preparation method thereof |
| CN110227517A (en) * | 2019-06-03 | 2019-09-13 | 河北地质大学 | CuBi2O4/BiPO4P-n junction heterojunction photocatalyst, preparation method and applications |
| CN111468138A (en) * | 2020-05-27 | 2020-07-31 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| 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 |
| CN112547101A (en) * | 2020-11-30 | 2021-03-26 | 佛山科学技术学院 | Visible light catalytic composite material and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108246306A (en) * | 2018-02-08 | 2018-07-06 | 秦英皓 | One pot process has visible light-responded photochemical catalyst CuBi2O4/Bi2WO6Nanosphere and its application |
| CN108246306B (en) * | 2018-02-08 | 2020-07-24 | 秦英皓 | One-pot synthesis of photocatalyst CuBi with visible light response2O4/Bi2WO6Nanosphere and application thereof |
| CN109148593A (en) * | 2018-07-16 | 2019-01-04 | 复旦大学 | A kind of ternary p-type CuBi2O4Thin film transistor (TFT) and preparation method thereof |
| CN109019685A (en) * | 2018-09-12 | 2018-12-18 | 西南科技大学 | A kind of synthesis CuBi2O4The method of base colloidal materials |
| CN110227517A (en) * | 2019-06-03 | 2019-09-13 | 河北地质大学 | CuBi2O4/BiPO4P-n junction heterojunction photocatalyst, preparation method and applications |
| CN111468138A (en) * | 2020-05-27 | 2020-07-31 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| CN111468138B (en) * | 2020-05-27 | 2021-11-30 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| CN112547101A (en) * | 2020-11-30 | 2021-03-26 | 佛山科学技术学院 | Visible light catalytic composite material and preparation method and application thereof |
| 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 |
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