CN109046388B - Method for removing antibiotics in water body by using copper sulfide/bismuth vanadate heterojunction photocatalyst - Google Patents
Method for removing antibiotics in water body by using copper sulfide/bismuth vanadate heterojunction photocatalyst Download PDFInfo
- Publication number
- CN109046388B CN109046388B CN201811106908.5A CN201811106908A CN109046388B CN 109046388 B CN109046388 B CN 109046388B CN 201811106908 A CN201811106908 A CN 201811106908A CN 109046388 B CN109046388 B CN 109046388B
- Authority
- CN
- China
- Prior art keywords
- bismuth vanadate
- copper sulfide
- bismuth
- nitrate
- heterojunction photocatalyst
- 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.)
- Active
Links
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 205
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 203
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 198
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 42
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 42
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 57
- 239000000725 suspension Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 22
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000013032 photocatalytic reaction Methods 0.000 claims description 15
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 13
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 description 28
- 230000015556 catabolic process Effects 0.000 description 21
- 238000006731 degradation reaction Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 229910000397 disodium phosphate Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000004298 light response Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical group [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for removing antibiotics in a water body by utilizing a copper sulfide/bismuth vanadate heterojunction photocatalyst. The method can be carried out at normal temperature and normal pressure, can mineralize antibiotics (such as ciprofloxacin) into water and carbon dioxide, can effectively carry out solid-liquid separation, has no secondary pollution, has the advantages of simple operation, no need of large-scale equipment, low cost and the like, has wide application range, high treatment efficiency, good treatment effect, strong reusability, environmental friendliness, can efficiently degrade the antibiotics in the water body, and has good application value and application prospect.
Description
Technical Field
The invention belongs to the field of advanced oxidation treatment of environmental pollutants, relates to a method for removing antibiotics in a water body, and particularly relates to a method for removing antibiotics in a water body by using a copper sulfide/bismuth vanadate heterojunction photocatalytic material.
Background
With the continuous development of medicine and pharmacology and the increasing demand of people on medical supplies such as medicines and the like, more and more pharmaceutical factories are in charge. Among the produced medicines, antibiotics are widely used for treating bacterial infection, but in the production process thereof, waste water containing antibiotics is discharged into rivers and lakes due to improper management of the discharged waste water by factories, and then aquatic organisms are harmed by accumulation of pollutants in water environment. Ciprofloxacin, for example, is a typical antibiotic-type recalcitrant pollutant. Although the ciprofloxacin concentration in the wastewater water body in the nature is low, if the organic wastewater containing ciprofloxacin is discharged into rivers, lakes and oceans, the water body is seriously polluted, toxic action is generated on microorganisms in the water body, and the microorganisms are dead. In addition, the ciprofloxacin has extremely high stability, the natural degradation of the ciprofloxacin is difficult to realize, and the human health is seriously damaged.
Aiming at the current situation of antibiotic pollution in water, a plurality of methods are applied to removing antibiotics in water, including microbial degradation, photo-Fenton oxidation and charcoal adsorption, but all the methods have some disadvantages, such as complex process operation, secondary pollution and high cost, and when the ciprofloxacin is degraded by a microbial method, the ciprofloxacin can also inhibit the growth of bacteria. Therefore, the search for a green and environment-friendly treatment method capable of efficiently degrading antibiotics is a big problem in the current society.
The photocatalysis technology is one of advanced oxidation methods which are developed rapidly in recent years, utilizes natural solar energy to convert into chemical energy to further degrade pollutants, and belongs to the reinforcement of the traditional chemical method. The principle of adopting the photocatalysis technology to degrade organic pollutants is that a semiconductor photocatalysis material can absorb sunlight, when the absorbed energy is larger than the forbidden bandwidth, a photoproduction electron-hole pair is generated, the photoproduction electron-hole pair reacts with oxygen or water/hydroxyl through the reducibility and the oxidability of the electron-hole pair to generate a superoxide radical or a hydroxyl radical, the generated active group is utilized to react with the pollutants adsorbed on the surface of a catalyst, the organic pollutants which are difficult to degrade are degraded into small molecular substances, and finally the small molecular substances are mineralized into water and carbon dioxide. The photocatalysis technology has the advantages of being carried out at normal temperature and normal pressure, high degradation efficiency, strong oxidability, no secondary pollution and the like, the core of the photocatalysis technology is a photocatalyst, however, the existing photocatalyst has the defects of narrow visible light response range, high rate of photon-generated electron-hole recombination, insufficient photocatalytic activity and the like, for example, the composite material of cadmium sulfide and bismuth vanadate has the problems of narrow visible light absorption range, high carrier recombination efficiency, insufficient photocatalytic activity and the like; for example, the preparation process of the copper sulfide/bismuth vanadate heterojunction has the following problems: in the preparation process of the composite material, the use amount of bismuth vanadate too much or too little can seriously affect the photocatalytic performance of the composite material; in the preparation process of the composite material, if the method for preparing copper sulfide is different from the adopted raw materials, the formation of the copper sulfide/bismuth vanadate heterojunction can be seriously influenced, so that the copper sulfide has no photocatalytic activity, and further the copper sulfide/bismuth vanadate heterojunction can not be formed, so that the problems can be caused because different preparation methods have different requirements on reaction conditions and raw materials, and different reaction conditions and raw materials have important influences on the formation of the copper sulfide/bismuth vanadate heterojunction, for example, different copper salts, bismuth salts or thiosulfate can change the conditions such as the pH value of the system, so that the copper sulfide/bismuth vanadate heterojunction catalyst can not be formed; the conventional conditions are harsh, and the temperature is strictly required, so that the cost is increased. The existence of the above problems severely limits the practical application range of the photocatalytic technology. In addition, the following problems still exist when the existing photocatalysis technology is adopted to remove antibiotics (such as ciprofloxacin) in the water body: (1) with the extension of the illumination time, the service life of the photocatalyst is continuously weakened, so that the removal rate is reduced; (2) when inorganic salt ions are contained in the water body, the inorganic salt ions can have certain influence on the degradation of the ciprofloxacin. Therefore, the method for effectively removing the antibiotics in the water body, which is simple to operate, low in treatment cost, wide in application range, high in treatment efficiency, good in treatment effect, strong in reusability and environment-friendly, has very important practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the method for removing the antibiotics in the water body by using the copper sulfide/bismuth vanadate heterojunction photocatalyst, which has the advantages of simple operation, low treatment cost, wide application range, high treatment efficiency, good treatment effect, strong reusability and environmental friendliness.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for removing antibiotics in a water body by using a copper sulfide/bismuth vanadate heterojunction photocatalyst is disclosed, wherein the method adopts the copper sulfide/bismuth vanadate heterojunction photocatalyst to treat the antibiotics in the water body; the copper sulfide/bismuth vanadate heterojunction photocatalyst comprises copper sulfide and bismuth vanadate, and the copper sulfide is attached to the bismuth vanadate.
In the method, the mass ratio of copper sulfide to bismuth vanadate in the copper sulfide/bismuth vanadate heterojunction photocatalyst is 1-11: 33; the bismuth vanadate is blocky; the thickness of the bismuth vanadate is 1-2 μm; the copper sulfide is granular.
In the above method, a further improvement is provided, in which the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst comprises the following steps:
s1, preparing bismuth vanadate and copper nitrate trihydrate into a suspension of bismuth vanadate and copper nitrate;
s2, mixing the suspension of bismuth vanadate and copper nitrate prepared in the step S1 with sodium thiosulfate pentahydrate to prepare a suspension of bismuth vanadate, copper nitrate and sodium thiosulfate;
and S3, performing water bath reaction on the suspension of bismuth vanadate, copper nitrate and sodium thiosulfate prepared in the step S2 to obtain the copper sulfide/bismuth vanadate heterojunction photocatalyst.
In the above method, in a further improvement, in step S1, the method for preparing bismuth vanadate includes the following steps:
(1) preparing bismuth nitrate pentahydrate and ammonium metavanadate into a suspension of bismuth nitrate and ammonium metavanadate;
(2) and (2) mixing the suspension of bismuth nitrate and ammonium metavanadate prepared in the step (1) with urea for reaction, and cleaning and drying the obtained reaction product to obtain bismuth vanadate.
In the above method, further improvement is that in the step (1), the preparation method of the suspension of bismuth nitrate and ammonium metavanadate comprises the following steps: dissolving pentahydrate bismuth nitrate in a nitric acid solution to prepare a bismuth nitrate solution; mixing ammonium metavanadate with a bismuth nitrate solution to obtain a suspension of bismuth nitrate and ammonium metavanadate; the proportion of the bismuth nitrate pentahydrate, the ammonium metavanadate and the nitric acid solution is 3 mmol: 16 mL; the concentration of the nitric acid solution is 1 mol/L.
In a further improvement of the above method, in the step (2), the ratio of the suspension of bismuth nitrate and ammonium metavanadate to urea is 32 mL: 3 g; the mixing is carried out under stirring conditions; the stirring time is 10min to 30 min; the reaction is carried out at a temperature of 70-80 ℃; the reaction time is 23-24 h; the cleaning is respectively cleaning for 4 to 6 times by adopting water and ethanol; the drying is carried out at a temperature of 50-70 ℃; the drying time is 20-24 h.
In the above method, further improvement, in step S1, the method for preparing the suspension of bismuth vanadate and copper nitrate includes the following steps: ultrasonically dispersing bismuth vanadate in ethanol to obtain bismuth vanadate suspension; mixing the bismuth vanadate suspension with copper nitrate trihydrate to obtain a suspension of bismuth vanadate and copper nitrate; the ratio of the bismuth vanadate to the ethanol is 0.3 g: 40 mL-50 mL; the mass ratio of the bismuth vanadate to the copper nitrate trihydrate is 0.3: 0.0233-0.0746; the ultrasonic dispersion time is 30-60 min; the mixing is carried out under stirring conditions; the stirring time is 50-60 min.
In the above method, further improvement is that in step S2, the molar ratio of sodium thiosulfate pentahydrate to copper nitrate trihydrate in the suspension of bismuth vanadate, copper nitrate and sodium thiosulfate is 1: 1-1.2; the mixing is carried out under stirring conditions; the stirring time is 10 min-30 min.
In a further improvement of the above method, in step S3, the water bath reaction is performed at a temperature of 60 ℃ to 70 ℃; the water bath reaction time is 3-24 h; the method also comprises the following steps after the water bath reaction is finished: washing and drying a product obtained after the water bath reaction; the washing is respectively 4-6 times by adopting water and ethanol; the drying is carried out at a temperature of 50-70 ℃; the drying time is 20-24 h.
In a further refinement of the above method, the method comprises the steps of: mixing the copper sulfide/bismuth vanadate heterojunction photocatalyst with water containing antibiotics, stirring under a dark condition, carrying out photocatalytic reaction under an illumination condition after reaching adsorption-desorption balance, and finishing the treatment of the antibiotics in the water.
In the method, the addition amount of the copper sulfide/bismuth vanadate heterojunction photocatalyst is further improved, and 0.5 g-1 g of the copper sulfide/bismuth vanadate heterojunction photocatalyst is added in each liter of water containing antibiotics.
In the method, the antibiotics in the water body containing the antibiotics are ciprofloxacin and/or tetracycline; the initial concentration of the antibiotics in the water body containing the antibiotics is 8 mg/L-10 mg/L; the pH value of the water body containing the antibiotics is 5-6.
In the method, the stirring time is further improved to be 30-60 min; the photocatalytic reaction is carried out under visible light with the wavelength of 400 nm-760 nm; the photocatalytic reaction is carried out at the rotating speed of 550-600 r/min; the time of the photocatalytic reaction is 0-90 min.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a method for removing antibiotics in a water body by utilizing a copper sulfide/bismuth vanadate heterojunction photocatalyst, which can realize the efficient degradation of ciprofloxacin in the water body by mixing the copper sulfide/bismuth vanadate heterojunction photocatalyst with the water body containing the antibiotics for photocatalytic reaction. The method is a novel advanced oxidation technology (photocatalysis), takes ciprofloxacin as an example, and has the degradation principle of antibiotics in water bodies as shown in formulas (1) to (3), and specifically comprises the following steps: the method comprises the steps of utilizing a copper sulfide/bismuth vanadate heterojunction photocatalyst to generate electron-hole pairs under the irradiation of visible light, transferring holes to a valence band of copper sulfide through an energy band difference of the copper sulfide and the bismuth vanadate, further reacting with pollutants adsorbed on the surface of the catalyst, and degrading antibiotics (ciprofloxacin) into small molecular substances until finally degrading the antibiotics (ciprofloxacin) into water and carbon dioxide, so that efficient degradation of the ciprofloxacin is realized. The method for removing the antibiotics in the water body can be carried out at normal temperature and normal pressure, can mineralize the antibiotics (such as ciprofloxacin) into water and carbon dioxide, can effectively carry out solid-liquid separation, has no secondary pollution, has the advantages of simple operation, no need of large-scale equipment, low cost and the like, has wide application range, high treatment efficiency, good treatment effect, strong reusability, environmental friendliness, can efficiently degrade the antibiotics in the water body, and has good application value and application prospect.
2. In the method, the copper sulfide/bismuth vanadate heterojunction photocatalyst comprises copper sulfide and bismuth vanadate, wherein the copper sulfide is attached to the bismuth vanadate. According to the invention, bismuth vanadate is used as a main material and has a positive valence band position, holes can be generated on the valence band by absorbing light energy, the holes have strong oxidizing capability and can directly oxidize refractory organic pollutants adsorbed on the surface of the material, and meanwhile, the holes can also react with water or hydroxyl to generate hydroxyl radicals which can oxidize most of the refractory organic pollutants. Copper sulfide is used as a modification material, the forbidden band width is narrow, the visible light absorption range is wide, the pollutant degradation capability is strong, and the semiconductor photocatalytic material is excellent in performance. On the basis, the copper sulfide is a p-type semiconductor, the bismuth vanadate is an n-type semiconductor, the copper sulfide and the bismuth vanadate have matched energy band positions, a heterojunction is formed by attaching the copper sulfide to the bismuth vanadate, electrons on the copper sulfide are transferred to the bismuth vanadate by attaching the copper sulfide to the bismuth vanadate, holes on the bismuth vanadate are transferred to the copper sulfide until Fermi level balance is achieved, finally, an internal electric field is formed at a contact surface, and under the action of the internal electric field, electrons and holes of the photo-generated electron-hole pairs are respectively transferred to a conduction band of the bismuth vanadate and a valence band of the copper sulfide, so that effective separation of the photo-generated electron-hole pairs is achieved, and photocatalytic activity is improved. In the invention, the copper sulfide and the bismuth vanadate form a p-n heterojunction, the copper sulfide has more negative conduction band positions, the bismuth vanadate has more positive valence band positions, electrons are transferred from the conduction band of the copper sulfide to the conduction band of the bismuth vanadate, and holes are transferred from the valence band of the bismuth vanadate to the valence band of the copper sulfide, so that the effective separation of photon-generated carriers is realized. In addition, since the conduction band of bismuth vanadate is more positive than the redox potential of oxygen and the valence band of copper sulfide is more negative than the redox potential of water, neither superoxide radical nor hydroxyl radical can be generated, and holes accumulated on the valence band of copper sulfide can react with the refractory organic pollutants adsorbed on the surface of the material, so that the refractory organic pollutants can be finally degraded into water and carbon dioxide. According to the invention, copper sulfide is attached to bismuth vanadate to form a heterojunction photocatalyst, so that photo-generated electron hole pairs can be effectively separated, the absorption range of the bismuth vanadate to visible light can be effectively widened, and the photocatalytic activity of the composite material is greatly improved. Therefore, the copper sulfide/bismuth vanadate heterojunction photocatalyst has the advantages of wide visible light response range, high quantum efficiency, high photocatalytic activity and the like, is a novel semiconductor photocatalytic material, and has good application value and application prospect.
3. In the method of the invention, the repeated utilization rate of the material in the copper sulfide/bismuth vanadate heterojunction photocatalyst is another standard for measuring the practical application of the copper sulfide/bismuth vanadate heterojunction photocatalyst. The copper sulfide/bismuth vanadate heterojunction photocatalyst compositely constructed by the copper sulfide and the bismuth vanadate is exposed to visible light to continuously treat water containing ciprofloxacin for 4 times, the catalytic effect is basically unchanged and still reaches 83 percent, and the catalytic effect is maintained at a higher level. Therefore, the copper sulfide/bismuth vanadate heterojunction photocatalyst has the advantages of good stability, strong reusability, simple recovery, high recovery rate and the like, and is a visible light response semiconductor photocatalytic material with wide application prospect.
4. In the method, bismuth vanadate is a visible light semiconductor catalyst in the copper sulfide/bismuth vanadate heterojunction photocatalyst, has a wide response range to visible light, exposes (040) crystal faces, and can provide tetragonal polyatomic center BiV (BiV) due to the (040) crystal faces4And bismuth is positioned in the center of the square, so that the (040) crystal face can provide more active sites and generate multi-electron transfer in the reaction process, and further the photocatalytic activity of the bismuth vanadate is improved.
5. In the method, in the copper sulfide/bismuth vanadate heterojunction photocatalyst, bismuth vanadate is a bismuth-system semiconductor, wherein bismuth is a heavy metal element with low toxicity and low radioactivity, and can be called as a green element, and the reserve quantity of bismuth resources in China is the first world (accounting for 70% of the total reserve quantity in the world). And the other semiconductor copper sulfide has simple preparation method and can realize industrial production. Compared with the traditional photocatalyst titanium dioxide, the precursor required in the preparation of the copper sulfide/bismuth vanadate heterojunction photocatalyst has wide sources and low price, and better meets the standards of modern scientific technology of environmental protection, high quality and low price. Therefore, the copper sulfide/bismuth vanadate heterojunction photocatalyst does not cause harm to the environment, has wide raw material sources, is economical and practical, and is a green, environment-friendly and economical semiconductor photocatalytic material.
6. In the invention, the copper sulfide/bismuth vanadate heterojunction photocatalyst used can also show higher photocatalytic activity when degrading antibiotics (such as ciprofloxacin) in the presence of various anions and cations, and has wide application prospect in the aspect of environmental pollutant degradation.
7. According to the method, the copper sulfide/bismuth vanadate heterojunction photocatalyst with high photocatalytic activity can be prepared by taking sodium thiosulfate and copper nitrate as precursor raw materials and bismuth vanadate as a carrier material through a simple water bath method. Compared with other conventional methods, the catalyst prepared by the preparation method disclosed by the invention is high in crystallization degree, no impurity is generated in the preparation process, and the preparation method disclosed by the invention has the advantages of simple process, mild reaction conditions, convenience in operation, cleanness, no pollution and the like, is suitable for large-scale preparation, and is convenient for industrial utilization.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a scanning electron microscope image of a copper sulfide/bismuth vanadate heterojunction photocatalyst prepared in example 1 of the present invention.
FIG. 2 is an EDS energy spectrum of the copper sulfide/bismuth vanadate heterojunction photocatalyst prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of the copper sulfide/bismuth vanadate heterojunction photocatalyst prepared in example 1 of the present invention.
FIG. 4 shows copper sulfide/bismuth vanadate heterojunction photocatalysts (A1, A2, A3 and A4) and bismuth vanadate (BiVO) prepared in example 1 of the present invention4) And the ultraviolet diffuse reflectance pattern of copper sulfide (CuS).
FIG. 5 shows copper sulfide/bismuth vanadate heterojunction photocatalysts (A1, A2, A3 and A4) and bismuth vanadate (BiVO) in example 1 of the present invention4) And a graph of the degradation effect of copper sulfide (CuS) on ciprofloxacin.
Fig. 6 is a graph showing the effect of the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 3) on the cyclic degradation of ciprofloxacin in example 1 of the present invention.
Fig. 7 is a graph showing the degradation effect of the copper sulfide/bismuth vanadate heterojunction photocatalyst on ciprofloxacin in the presence of different coexisting ions in example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of three or more repeated experiments.
Example 1
A method for removing antibiotics in a water body by using a copper sulfide/bismuth vanadate heterojunction photocatalyst comprises the following steps of:
weighing bismuth vanadate (BiVO)4) 100mg of copper sulfide (CuS) and copper sulfide/bismuth vanadate heterojunction photocatalysts (A1, A2, A3 and A4) are respectively added into 100mL of ciprofloxacin solution and 10mg/L of ciprofloxacin solution (the pH value of the ciprofloxacin solution is 5.6), magnetic stirring is carried out for 30min under the dark condition, so that adsorption-desorption balance between ciprofloxacin and photocatalysts is achieved, then photocatalytic reaction is carried out for 90min under visible light with the wavelength of 400-760 nm, wherein the photocatalytic reaction is carried out at the magnetic stirring rotating speed of 550 r/min, and the removal treatment of ciprofloxacin in the water body is completed.
Blank group: a100 mL, 10mg/L ciprofloxacin solution was treated under the same conditions without adding any photocatalyst, and this was used as a control.
In this embodiment, the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1) used includes bismuth vanadate and copper sulfide, and the copper sulfide is attached to the bismuth vanadate to form a heterojunction material. The mass ratio of the copper sulfide to the bismuth vanadate in the copper sulfide/bismuth vanadate heterojunction photocatalyst (A1) is 3: 97. The bismuth vanadate is blocky and has the thickness of 1-2 mu m; the copper sulfide is in the form of particles.
In this embodiment, the method for preparing the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1) includes the following steps:
(1) dissolving 6 mmol of pentahydrate bismuth nitrate in 32mL of nitric acid solution with the concentration of 1mol/L, and performing ultrasonic treatment for 10min to obtain bismuth nitrate solution; adding 6 mmol of ammonium metavanadate into the bismuth nitrate solution, and magnetically stirring for one hour to obtain a suspension of bismuth nitrate and ammonium metavanadate; 3g of urea was added to the suspension of bismuth nitrate and ammonium metavanadate, the mixture was stirred for 10min, and the resulting suspension was reacted in an oil bath at 80 ℃ for 24 hours. After the reaction is finished, the reaction solution is added,naturally cooling the reaction product solution to room temperature, filtering to obtain bright yellow precipitates, washing the bright yellow precipitates with ultrapure water and absolute ethyl alcohol for 4 times respectively, placing the washed solids in an oven, and drying at 60 ℃ for 24 hours to obtain bismuth vanadate (BiVO)4）。
(2) Dispersing 0.3g of bismuth vanadate prepared in the step (1) in 40mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain a bismuth vanadate suspension; 0.0233g of copper nitrate trihydrate were added to the suspension of bismuth vanadate and the mixture was magnetically stirred for 60min to completely dissolve the copper nitrate trihydrate, resulting in a suspension of bismuth vanadate and copper nitrate. 0.0239g of sodium thiosulfate pentahydrate were added to the suspension of bismuth vanadate and copper nitrate, and magnetic stirring was carried out for 10min to obtain a suspension of bismuth vanadate, copper nitrate and sodium thiosulfate. And reacting the suspension of bismuth vanadate, copper nitrate and sodium thiosulfate for 4 hours in a water bath at 70 ℃. After the water bath reaction is finished, naturally cooling the reaction product solution to room temperature, filtering to obtain solid substances, washing the obtained solid substances with ultrapure water and absolute ethyl alcohol for 5 times respectively, placing the washed solid substances in an oven, and drying at 70 ℃ for 24 hours to obtain the copper sulfide/bismuth vanadate heterojunction photocatalyst (CuS/BiVO)4) And the number is A1.
In this example, the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 2) used was substantially the same as the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1), except that: the mass ratio of the copper sulfide to the bismuth vanadate in the copper sulfide/bismuth vanadate heterojunction photocatalyst (A2) is 1: 19.
In this embodiment, the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 2) is basically the same as the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1), and the differences are only that: preparation method of copper sulfide/bismuth vanadate heterojunction photocatalyst (A2) in step (2), the amounts of copper nitrate trihydrate and sodium thiosulfate pentahydrate used were 0.0397g and 0.0408g, respectively.
In this example, the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) used was substantially the same as the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1), except that: the mass ratio of the copper sulfide to the bismuth vanadate in the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) is 7: 93.
In this embodiment, the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) is basically the same as the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1), and the differences are only that: the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) comprises the following steps of respectively using 0.0568g of copper nitrate trihydrate and 0.083g of sodium thiosulfate pentahydrate in the step (2).
In this example, the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 4) used was substantially the same as the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1), except that: the mass ratio of the copper sulfide to the bismuth vanadate in the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) is 9: 91.
In this embodiment, the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 4) is basically the same as the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1), and the differences are only that: preparation method of copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) in step (2), the amounts of copper nitrate trihydrate and sodium thiosulfate pentahydrate used were 0.0746g and 0.0767g, respectively.
In this embodiment, the method for preparing bismuth vanadate includes the following steps: dissolving 6 mmol of pentahydrate bismuth nitrate in 32mL of nitric acid solution with the concentration of 1mol/L, and performing ultrasonic treatment for 10min to obtain bismuth nitrate solution; adding 6 mmol of ammonium metavanadate into the bismuth nitrate solution, and magnetically stirring for one hour to obtain a suspension of bismuth nitrate and ammonium metavanadate; 3g of urea was added to the suspension of bismuth nitrate and ammonium metavanadate, the mixture was stirred for 10min, and the resulting suspension was reacted in an oil bath at 80 ℃ for 24 hours. After the reaction is finished, naturally cooling the reaction product solution to room temperature, filtering to obtain bright yellow precipitates, cleaning the bright yellow precipitates for 4 times respectively by using ultrapure water and absolute ethyl alcohol, placing the solids obtained after cleaning in an oven, and drying for 24 hours at 60 ℃ to obtain bismuth vanadate (BiVO)4）。
In this embodiment, the method for preparing copper sulfide includes the following steps: dissolving 2mmol of copper nitrate trihydrate in 40mL of absolute ethanol solution, magnetically stirring for 10min, adding 2mmol of sodium thiosulfate pentahydrate, and reacting the obtained suspension for 4h in a water bath at 70 ℃. And after the reaction is finished, naturally cooling the reaction product solution to room temperature, filtering to obtain solid substances, respectively washing the solid substances for 4 times by using ultrapure water and absolute ethyl alcohol, and placing the washed solid substances in an oven to dry the solid substances for 24 hours at 70 ℃ to obtain copper sulfide (CuS).
FIG. 1 is a scanning electron microscope image of a copper sulfide/bismuth vanadate heterojunction photocatalyst prepared in example 1 of the present invention. As can be seen from FIG. 1, the bismuth vanadate has irregular lumps with exposed (040) crystal faces on the irregular lumps, has a thickness of 1 μm to 2 μm, has a rough surface, and has many copper sulfide particles adhered thereto. Namely, in the copper sulfide/bismuth vanadate heterojunction photocatalyst, copper sulfide is granular and is attached to the massive bismuth vanadate.
FIG. 2 is an EDS energy spectrum of the copper sulfide/bismuth vanadate heterojunction photocatalyst prepared in example 1 of the present invention. As can be seen from FIG. 2, the composite material contains Bi, V, O, Cu, S.
FIG. 3 is an X-ray diffraction pattern of the copper sulfide/bismuth vanadate heterojunction photocatalyst prepared in example 1 of the present invention. As can be seen from fig. 3, the copper sulfide/bismuth vanadate heterojunction photocatalyst only shows the characteristic peak of bismuth vanadate, but the peak of copper sulfide does not appear, and the possible reasons are that: the strength of the XRD characteristic peak is related to the content of the material, whereas in the composite material of example 1, when the mass ratio of copper sulfide to bismuth vanadate is 7: 93, the content of copper sulfide is too small, and thus the characteristic peak of copper sulfide is not shown.
FIG. 4 shows copper sulfide/bismuth vanadate heterojunction photocatalysts (A1, A2, A3 and A4) and bismuth vanadate (BiVO) prepared in example 1 of the present invention4) And the ultraviolet diffuse reflectance pattern of copper sulfide (CuS). From fig. 4, it is known that both copper sulfide and bismuth vanadate respond to visible light, and the response range of the copper sulfide/bismuth vanadate heterojunction photocatalyst to visible light increases with the increase of the content of copper sulfide.
During the photocatalytic reaction, one sample was taken every 15 min. Centrifuging the sample to achieve solid-liquid separation effect, collecting the supernatant, measuring the concentration change with an ultraviolet-visible spectrophotometer to obtain the removal rate of ciprofloxacin by different materials, and the result is shown in figure 5.
FIG. 5 shows copper sulfide/bismuth vanadate heterojunction photocatalysts (A1, A2, A3 and A4) and bismuth vanadate (BiVO) in example 1 of the present invention4) And a graph of the degradation effect of copper sulfide (CuS) on ciprofloxacin. As can be seen from FIG. 5, the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) has the best effect of removing ciprofloxacin, the removal rate of ciprofloxacin within 90min reaches 86.7%, and the removal rates of copper sulfide and bismuth vanadate for ciprofloxacin are 8.1% and 54.1% respectively. Along with the reduction of the content of the copper sulfide, the removal rate of ciprofloxacin by the copper sulfide/bismuth vanadate heterojunction photocatalyst is reduced, because when the content of the copper sulfide is low, insufficient copper sulfide and bismuth vanadate form a heterojunction, and the removal efficiency is reduced. For example, when the mass ratio of copper sulfide to bismuth vanadate is 3: 97, the removal rate of ciprofloxacin by the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 1) within 90min is 76.3%, which is smaller than the removal rate of ciprofloxacin by the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3), but still a better removal rate is obtained. In addition, with the continuous increase of the content of copper sulfide, the photocatalytic performance of the composite material is continuously improved, and when the ratio of the copper sulfide to the copper sulfide reaches 7: 93, the ciprofloxacin removal effect is the best, because the copper sulfide to the copper sulfide and the copper sulfide form a high-efficiency heterojunction structure, the formation of the heterojunction structure is favorable for improving the separation efficiency of a photon-generated carrier, and the response range of bismuth vanadate to visible light can be widened, so that the ciprofloxacin removal efficiency is improved. However, when the mass ratio of copper sulfide to bismuth vanadate is greater than 7: 93, more copper sulfide is exposed and cannot form an effective heterojunction with bismuth vanadate, the photocatalytic effect of the copper sulfide alone is far lower than that of bismuth vanadate, and the recombination efficiency of photo-generated carriers of the copper sulfide is high, so that the catalytic effect of the composite material is remarkably reduced, for example, when the mass ratio of copper sulfide to bismuth vanadate is 9: 91, the degradation efficiency of the copper sulfide/bismuth vanadate heterojunction photocatalyst (A4) to ciprofloxacin within 90min is 77.8%, and the degradation efficiency is smaller than that of the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) to ciprofloxacinThe removal efficiency of the ciprofloxacin is high, but the ciprofloxacin in the water body can be well removed. According to the invention, when the mass ratio of bismuth ferrite to bismuth tungstate is 1-11: 33, the copper sulfide/bismuth vanadate heterojunction photocatalyst has a good removal effect on ciprofloxacin in a water body, and particularly, when the mass ratio of copper sulfide to bismuth vanadate is 7: 93, the removal effect of the copper sulfide/bismuth vanadate heterojunction photocatalyst on ciprofloxacin is optimal.
The ciprofloxacin solution was treated repeatedly with the copper sulfide/bismuth vanadate heterojunction photocatalyst (a 3) prepared in example 1, and the results are shown in fig. 6. Fig. 6 is a graph showing the cyclic degradation effect of the copper sulfide/bismuth vanadate heterojunction photocatalyst on ciprofloxacin in example 1 of the present invention. As can be seen from fig. 6, the copper sulfide/bismuth vanadate heterojunction photocatalyst compositely constructed by the copper sulfide and the bismuth vanadate of the present invention is exposed to visible light to continuously treat water containing ciprofloxacin for 4 times, the catalytic effect is basically unchanged and still reaches as high as 83%, and is maintained at a higher level, and the copper sulfide/bismuth vanadate heterojunction photocatalyst compositely constructed by the copper sulfide and the bismuth vanadate of the present invention shows excellent photostability, so that the heterojunction compositely constructed by the copper sulfide and the bismuth vanadate can significantly improve the repeated utilization rate of the material, and the recovery method of the composite material after use is simpler, most of the material can be obtained only by centrifugation, and the loss rate of the material is lower. Therefore, the copper sulfide/bismuth vanadate heterojunction photocatalyst has the advantages of good stability, strong reusability, simple recovery, high recovery rate and the like, and is a visible light response semiconductor photocatalytic material with wide application prospect.
Example 2
The method for investigating the degradation effect of the copper sulfide/bismuth vanadate heterojunction photocatalyst on ciprofloxacin in the presence of different coexisting ions comprises the following steps of:
5 parts of the copper sulfide/bismuth vanadate heterojunction photocatalyst (A3) prepared in example 1 was weighed out, 100mg of the photocatalyst was added to 100mL of a 10mg/L ciprofloxacin solution (pH 5.6) and 4 parts of the rhodamine B solution were added with Na as a coexisting ion3PO4、Na2HPO4、NaH2PO4And CaCl2And the other part does not add any coexisting ions. And magnetically stirring for 30min under a dark condition to ensure that adsorption-desorption balance is achieved between the ciprofloxacin and the copper sulfide/bismuth vanadate heterojunction photocatalyst, and then carrying out photocatalytic reaction for 90min under visible light with the wavelength of 400-760 nm, wherein the photocatalytic reaction is carried out at the magnetic stirring rotating speed of 550 r/min, so that the degradation treatment of the ciprofloxacin in the water body is completed.
During the photocatalytic reaction, one sample was taken every 15 min. Centrifuging the sample to separate solid from liquid, collecting the supernatant, measuring the concentration change with an ultraviolet-visible spectrophotometer to obtain the removal rate of the copper sulfide/bismuth vanadate heterojunction photocatalyst to the ciprofloxacin under the condition of different coexisting ions, and the result is shown in fig. 7.
Fig. 7 is a graph showing the degradation effect of the copper sulfide/bismuth vanadate heterojunction photocatalyst on ciprofloxacin in the presence of different coexisting ions in example 2 of the present invention. As can be seen from FIG. 7, in Na3PO4、Na2HPO4、NaH2PO4And CaCl2Under the condition of coexistence of ions, the copper sulfide/bismuth vanadate heterojunction photocatalyst still has a high degradation effect on ciprofloxacin in a water body, and the material is proved to have a high degradation effect under the coexistence of a plurality of ions. Comparing four coexisting anions, Na3PO4、Na2HPO4、NaH2PO4Have different degrees of influence on the catalytic effect, which is due to Na3PO4Can capture generated holes under the irradiation of visible light and convert the holes into Na2HPO4And NaH2PO4Then Na2HPO4Further consumption of photogenerated holes to convert NaH2PO4. Compared with Na3PO4Conversion to Na2HPO4，Na2HPO4Conversion of NaH2PO4More difficult, therefore, Na2HPO4、NaH2PO4There is only a slight inhibition of the photocatalytic effect. CaCl2To catalytic effectThe fruit produces an inhibitory effect due to Ca2+The metal complex can be formed with the ciprofloxacin, so that the ciprofloxacin can not be degraded, and the generated intermediate product can compete with the ciprofloxacin for active sites, so that the photocatalysis effect is further reduced.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. A method for removing antibiotics in a water body by using a copper sulfide/bismuth vanadate heterojunction photocatalyst is characterized in that the method adopts the copper sulfide/bismuth vanadate heterojunction photocatalyst to treat the antibiotics in the water body; the copper sulfide/bismuth vanadate heterojunction photocatalyst comprises copper sulfide and bismuth vanadate, and the copper sulfide is attached to the bismuth vanadate; the mass ratio of the copper sulfide to the bismuth vanadate in the copper sulfide/bismuth vanadate heterojunction photocatalyst is 1-11: 33; the bismuth vanadate is blocky; the thickness of the bismuth vanadate is 1-2 μm; the copper sulfide is granular; the preparation method of the copper sulfide/bismuth vanadate heterojunction photocatalyst comprises the following steps:
s1, ultrasonically dispersing bismuth vanadate in ethanol to obtain bismuth vanadate suspension; mixing the bismuth vanadate suspension with copper nitrate trihydrate to obtain a suspension of bismuth vanadate and copper nitrate;
s2, mixing the suspension of bismuth vanadate and copper nitrate prepared in the step S1 with sodium thiosulfate pentahydrate to prepare a suspension of bismuth vanadate, copper nitrate and sodium thiosulfate;
and S3, performing water bath reaction on the suspension of bismuth vanadate, copper nitrate and sodium thiosulfate prepared in the step S2 to obtain the copper sulfide/bismuth vanadate heterojunction photocatalyst.
2. The method according to claim 1, wherein in step S1, the method for preparing bismuth vanadate comprises the following steps:
(1) preparing bismuth nitrate pentahydrate and ammonium metavanadate into a suspension of bismuth nitrate and ammonium metavanadate;
(2) and (2) mixing the suspension of bismuth nitrate and ammonium metavanadate prepared in the step (1) with urea for reaction, and cleaning and drying the obtained reaction product to obtain bismuth vanadate.
3. The method according to claim 2, wherein in the step (1), the preparation method of the suspension of bismuth nitrate and ammonium metavanadate comprises the following steps: dissolving pentahydrate bismuth nitrate in a nitric acid solution to prepare a bismuth nitrate solution; mixing ammonium metavanadate with a bismuth nitrate solution to obtain a suspension of bismuth nitrate and ammonium metavanadate; the proportion of the bismuth nitrate pentahydrate, the ammonium metavanadate and the nitric acid solution is 3 mmol: 16 mL; the concentration of the nitric acid solution is 1 mol/L;
in the step (2), the ratio of the suspension of bismuth nitrate and ammonium metavanadate to urea is 32 mL: 3 g; the mixing is carried out under stirring conditions; the stirring time is 10min to 30 min; the reaction is carried out at a temperature of 70-80 ℃; the reaction time is 23-24 h; the cleaning is respectively cleaning for 4 to 6 times by adopting water and ethanol; the drying is carried out at a temperature of 50-70 ℃; the drying time is 20-24 h.
4. The method according to claim 1, wherein in the step S1, the ratio of the bismuth vanadate to the ethanol is 0.3 g: 40 mL-50 mL; the mass ratio of the bismuth vanadate to the copper nitrate trihydrate is 0.3: 0.0233-0.0746; the ultrasonic dispersion time is 30-60 min; the mixing is carried out under stirring conditions; the stirring time is 50 min-60 min;
the molar ratio of the sodium thiosulfate pentahydrate to the copper nitrate trihydrate is 1: 1-1.2;
in the step S2, the mixing is performed under stirring conditions; the stirring time is 10min to 30 min;
in the step S3, the water bath reaction is carried out at the temperature of 60-70 ℃; the water bath reaction time is 3-24 h; the method also comprises the following steps after the water bath reaction is finished: washing and drying a product obtained after the water bath reaction; the washing is respectively 4-6 times by adopting water and ethanol; the drying is carried out at a temperature of 50-70 ℃; the drying time is 20-24 h.
5. A method according to any one of claims 1 to 4, characterized in that the method comprises the steps of: mixing the copper sulfide/bismuth vanadate heterojunction photocatalyst with water containing antibiotics, stirring under a dark condition, carrying out photocatalytic reaction under an illumination condition after reaching adsorption-desorption balance, and finishing the treatment of the antibiotics in the water.
6. The method according to claim 5, wherein the addition amount of the copper sulfide/bismuth vanadate heterojunction photocatalyst is 0.5-1 g per liter of water containing antibiotics.
7. The method according to claim 6, wherein the antibiotic in the antibiotic-containing water body is ciprofloxacin and/or tetracycline; the initial concentration of the antibiotics in the water body containing the antibiotics is 8 mg/L-10 mg/L; the pH value of the water body containing the antibiotics is 5-6.
8. The method according to claim 6 or 7, characterized in that the stirring time is 30-60 min; the photocatalytic reaction is carried out under visible light with the wavelength of 400 nm-760 nm; the photocatalytic reaction is carried out at the rotating speed of 550-600 r/min; the time of the photocatalytic reaction is 0-90 min and is not 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811106908.5A CN109046388B (en) | 2018-09-21 | 2018-09-21 | Method for removing antibiotics in water body by using copper sulfide/bismuth vanadate heterojunction photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811106908.5A CN109046388B (en) | 2018-09-21 | 2018-09-21 | Method for removing antibiotics in water body by using copper sulfide/bismuth vanadate heterojunction photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109046388A CN109046388A (en) | 2018-12-21 |
| CN109046388B true CN109046388B (en) | 2020-03-17 |
Family
ID=64763459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811106908.5A Active CN109046388B (en) | 2018-09-21 | 2018-09-21 | Method for removing antibiotics in water body by using copper sulfide/bismuth vanadate heterojunction photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109046388B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530479B (en) * | 2020-04-29 | 2023-06-20 | 清华大学深圳国际研究生院 | Preparation method of bismuth tungstate and copper sulfide composite material |
| CN113231084A (en) * | 2021-05-21 | 2021-08-10 | 北京理工大学 | Copper tungstate/copper sulfide photocatalyst, preparation method and application |
| CN116371432B (en) * | 2023-03-24 | 2023-10-03 | 深圳市罗湖区城市管理和综合执法局 | Composite photocatalytic nano material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112896B (en) * | 2013-02-06 | 2014-12-24 | 长安大学 | Method for preparing octahedral nano bismuth vanadate photocatalyst by microwave process |
| CN106064093B (en) * | 2016-05-20 | 2018-09-07 | 辽宁石油化工大学 | A kind of preparation method of fabricated in situ CuS/WO3 heterojunction photocatalysts |
| CN106311283B (en) * | 2016-08-15 | 2019-02-05 | 河南师范大学 | A kind of p-n heterojunction BiVO4/MoS2Composite photo-catalyst and preparation method thereof |
| CN108543539B (en) * | 2018-03-14 | 2021-05-25 | 福建工程学院 | BiVO4/AgIO3Heterojunction nano photocatalytic material and preparation method and application thereof |
-
2018
- 2018-09-21 CN CN201811106908.5A patent/CN109046388B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109046388A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927176B (en) | Copper sulfide/bismuth vanadate heterojunction photocatalyst and preparation method thereof | |
| Gao et al. | Solar photocatalytic abatement of tetracycline over phosphate oxoanion decorated Bi2WO6/polyimide composites | |
| CN111530466B (en) | Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries | |
| CN109046388B (en) | Method for removing antibiotics in water body by using copper sulfide/bismuth vanadate heterojunction photocatalyst | |
| Mafa et al. | Synthesis of Bi5O7I-MoO3 photocatalyst via simultaneous calcination of BiOI and MoS2 for visible light degradation of ibuprofen | |
| CN109317183B (en) | Boron nitride quantum dot/ultrathin porous carbon nitride composite photocatalytic material and preparation method and application thereof | |
| CN108816265B (en) | Bismuth vanadate/nitrogen-doped carbon quantum dot/cuprous oxide double-Z-type photocatalyst and preparation method and application thereof | |
| Izzudin et al. | Simultaneous remediation of hexavalent chromium and organic pollutants in wastewater using period 4 transition metal oxide-based photocatalysts: a review | |
| CN108067267B (en) | Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof | |
| CN103801284A (en) | Method for preparing pucherite-graphene composite photocatalyst | |
| CN112844484B (en) | Boron nitride quantum dot/porous metal organic framework composite photocatalytic material and preparation method and application thereof | |
| CN109999844B (en) | MoS2Composite Fenton catalyst of/Schweitermann stone, preparation method and application | |
| Xing et al. | Efficient degradation of tetracycline over vacancy-modified Cu-doped Bi2O2S via peroxymonosulfate activation and photocatalysis | |
| Qiu et al. | Designing a novel dual Z-scheme Bi2S3-ZnS/MoSe2 photocatalyst for photocatalytic reduction of Cr (VI) | |
| Yang et al. | An inorganic-organic hybrid indium tin selenide featuring a two-dimensional layered structure for high efficient photocatalytic Cr (VI) reduction | |
| Basaleh et al. | Novel visible light heterojunction CdS/Gd2O3 nanocomposites photocatalysts for Cr (VI) photoreduction | |
| CN110787826B (en) | Ag-loaded WO3Nano fiber-porous carbon photocatalysis material and preparation method thereof | |
| CN110075929B (en) | Preparation method of polyacid intercalation 3D-LDHs photo-Fenton catalyst | |
| CN111604083A (en) | Graphite type carbon nitride composite photocatalytic material with oxygen vacancy bismuth tungstate/oxygen-enriched structure and preparation method and application thereof | |
| CN109482209B (en) | Method for removing antibiotics by using silver phosphate/bismuth sulfide/bismuth oxide double-Z-type photocatalyst | |
| CN109092333B (en) | Nano composite catalyst, preparation and application thereof | |
| Wu et al. | Recent advances of semiconductor photocatalysis for water pollutant treatment: mechanisms, materials and applications | |
| CN110624574B (en) | Double Bi4O5I2Preparation method of photocatalytic material and application of photocatalytic material in degrading MC-LR | |
| CN111151238B (en) | Bismuth vanadate heterojunction BiVO4/Bi25VO40Material, preparation method and application thereof | |
| CN106256430B (en) | A kind of bismuth oxychloride/graphene composite photocatalyst preparation method of tin dope |
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 |