CN113956473B - Halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater by photocatalysis and preparation method thereof - Google Patents
Halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater by photocatalysis and preparation method thereof Download PDFInfo
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- CN113956473B CN113956473B CN202110945763.3A CN202110945763A CN113956473B CN 113956473 B CN113956473 B CN 113956473B CN 202110945763 A CN202110945763 A CN 202110945763A CN 113956473 B CN113956473 B CN 113956473B
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- halloysite
- halloysite nanotube
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- silver phosphate
- silver
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- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 64
- 239000002071 nanotube Substances 0.000 title claims abstract description 60
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 21
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 239000002351 wastewater Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 title abstract description 11
- 238000007146 photocatalysis Methods 0.000 title description 7
- 229920000767 polyaniline Polymers 0.000 claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 16
- 229940019931 silver phosphate Drugs 0.000 claims abstract description 16
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- 239000002114 nanocomposite Substances 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims abstract description 4
- 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 claims abstract 2
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract 2
- 238000011065 in-situ storage Methods 0.000 claims abstract 2
- 239000011734 sodium Substances 0.000 claims abstract 2
- 229910052708 sodium Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 5
- 235000019800 disodium phosphate Nutrition 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 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 description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 229960003405 ciprofloxacin Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 1
- 229960001193 diclofenac sodium Drugs 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000003814 drug Substances 0.000 abstract description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 9
- 230000003115 biocidal effect Effects 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 10
- 229960001680 ibuprofen Drugs 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 229940079593 drug Drugs 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001259 diclofenac Drugs 0.000 description 1
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000010826 pharmaceutical waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil 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
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater and a preparation method thereof, and the halloysite nanotube composite material comprises the following components: firstly, enabling halloysite nanotubes to react with silver nitrate and sodium hydrophosphate to form a silver phosphate-halloysite nanotube photocatalyst-adsorbent system, so as to obtain silver phosphate grafted halloysite nanotubes; and then, coating polyaniline on the halloysite nanotube grafted with silver phosphate by an in-situ soap-free emulsion polymerization method to prepare the polyaniline-coated silver phosphate-halloysite nanotube nanocomposite. The adopted halloysite nanotubes can adsorb antibiotic molecules to the surface and the cavity of the halloysite nanotubes with high selectivity; silver phosphate is used as a photocatalyst, so that the removal efficiency of the medicine is improved, and the toxicity of the product is degraded; the introduction of polyaniline makes the material utilize long wave light more effectively, raise photocatalytic capacity and improve physical, mechanical and electric performance. The halloysite nanotube composite material of the antibiotic can be recycled for multiple times, has good biodegradability, is safe and nontoxic, and is environment-friendly.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater and a preparation method thereof.
Background
The increase in global drug production has led to an increase in drug pollutants in our water body. The occurrence of pharmaceutical compounds in the natural environment has caused a new problem. Antibiotics in particular are widely used in the treatment of diseases in human and veterinary animals, and large amounts of drugs, which may constitute a series of threat to the environmental system and human health, are discharged, even in low concentrations of residues, eventually contaminating surface and ground water. Typical examples of these drugs detected in surface and groundwater include ibuprofen, diclofenac, ciprofloxacin, and tetracycline, which are antibiotics that are difficult to biodegrade due to their durability in the environment. Conventional contaminated water treatment techniques have been reported to reduce only a small fraction of the drug contaminants present in the water. Conventional contaminated water treatment techniques for pharmaceutical waste can only be partially degraded by strong oxidants such as hydrogen peroxide, permanganate and ozone. The use of these oxidants can produce toxic secondary byproducts. Furthermore, these antibiotics are commonly found in agricultural soils when the waters are used to irrigate farmlands. Thus, degradation of antibiotics in the environment is an urgent problem.
Oxidation, adsorption, electrolytic degradation, biological degradation and photocatalytic degradation are conventional methods for treating antibiotics in wastewater. In view of economy and environment, the adsorption method is considered as a promising method for removing antibiotics, which uses adsorbents such as natural minerals, metal oxides, carbon, and molecular imprinting polymers. Carbon materials are generally adopted, have high specific surface area, rich surface groups and high stability, have better adsorption performance, are the first choice materials for wastewater treatment, but have the defects of high cost, complex synthesis process, small capacity, slow dynamics characteristic and the like, so that the large-scale application of the carbon materials is limited. In recent years, halloysite nanotubes have been widely used in various fields, and have the advantages of naturally occurring property, biocompatibility, high dispersibility, non-toxicity, easy availability, relatively low cost compared with carbon nanotubes, and the like.
In addition to adsorption, semiconductor photocatalytic technology has received extensive attention from many researchers as an efficient, green solution for degrading environmental pollutants. Photocatalysis is mainly dependent on the semiconductor material and the efficiency of the light source. At present, the traditional photocatalyst TiO2 is difficult to absorb rich visible light, and limits practical application. Therefore, it is necessary to explore novel visible light-induced photocatalysts such as silver-based materials, bismuth-based materials, polymeric materials, and the like.
Polyaniline has been widely used in the field of photocatalysis due to its conjugated pi system, a wide absorption range under the induction of visible light, and unique electron and hole transport characteristics. In addition, polyaniline is relatively inexpensive and easy to prepare compared to doped noble metals. So far, many published studies indicate that the binding of polyaniline to a semiconductor can improve the transfer efficiency of carriers between polyaniline and a semiconductor. Polyaniline is often combined with other inorganic components to form nanocomposite materials to improve physical, mechanical, and electrical properties, such as enhanced solubility, conductivity, magnetic and optoelectronic properties, and the like. In recent years, the encapsulation of inorganic nanomaterials within polyaniline shells has become the hottest and most interesting research direction in nanocomposite synthesis. However, the adsorption capacity is a problem to be solved by related technical workers in the field at present.
Therefore, if a green and low-cost multielement adsorption degradation material with high adsorption effect can be developed, the photocatalyst can be uniformly dispersed, and the visible light region absorbed by the photocatalyst can be enlarged, so that the photocatalytic degradation of antibiotics can be carried out, the treatment of medicine wastewater can be greatly improved, and the harm to human bodies and the environment can be reduced. The halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater can provide important technical support for the development of treatment of drug wastewater in the future, and has very important significance.
Disclosure of Invention
In order to achieve the aim of the invention, the invention provides the following technical scheme:
compared with the prior art, the invention has the beneficial effects that:
1. the semiconductor photocatalyst for degrading the antibiotics adsorbed by the material in the invention isSilver phosphate not only has visible light activity, but also has good oxidizing ability, and can oxidize a small amount of water and release O 2 Has better oxidative degradation capability to partial antibiotics and less toxicity of degradation products.
2. The halloysite nanotube is a naturally occurring aluminosilicate clay nanotube, is mainly composed of multi-wall nano tubular crystals, has the characteristic of high specific surface area, and enhances the adsorption capacity of materials. Halloysite nanotubes are rolled tubular structures, the outer surfaces of the halloysite nanotubes are slightly negatively charged, and the inner surfaces of the cavities of the halloysite nanotubes are slightly positively charged. This change in halloysite nanotube surface charge characteristics enables it to efficiently adsorb various positively and negatively charged antibiotic molecules to its surface and into its cavity.
3. The silver phosphate-halloysite nanotube photocatalyst-adsorbent system consisting of the silver phosphate photocatalyst and the halloysite nanotubes is used in the invention, the efficiency of removing medicines and proteins is improved through photocatalysis and adsorption processes, and meanwhile, the dispersibility of the synthesized silver phosphate in the composite material can be improved through the addition of the halloysite nanotubes.
4. The introduction of polyaniline in the invention is helpful to expand the light absorption area, and the long-wave light is more effectively utilized, thereby improving the photocatalysis capability. The invention can be applied to some protein solutions containing antibiotics, can avoid the denaturation of proteins when adsorbing antibiotics, and can keep the original protein nature. In addition, polyaniline is coated on the surface of halloysite nanotubes to form a nanocomposite, and physical, mechanical and electrical properties such as conductivity, magnetism and photoelectric properties can be improved.
Drawings
FIG. 1 is a graph showing the effect of ibuprofen solution and degradation products on E.coli growth. FIG. (a) shows E.coli colonies grown on agar plates coated with an ibuprofen solution, and FIG. (b) shows E.coli colonies grown on agar plates coated with an ibuprofen-degrading solution.
Detailed Description
The invention is further illustrated by the following description of specific embodiments.
Example 1
A halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater by photocatalysis and a preparation method thereof specifically comprise the following preparation steps:
(1) 3.3g halloysite nanotubes were dispersed in 100mL of 0.03mol/L silver nitrate and sonicated for 40min, then 150mL of 0.2mol/L sodium hydrogen phosphate was added and the solution was stirred continuously for 30 min to form a bright yellow precipitate. And centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nano particles, washing the collected particles with deionized water, centrifuging again, repeating the centrifuging operation for three times, and drying the particles at 70 ℃ to obtain the silver phosphate grafted halloysite nano tube.
(2) Prior to soap-free emulsion polymerization, 3g of silver branched phosphate halloysite nanotubes, 1mL of aniline, and 80mL of 0.8mol/L HCl were mixed into 450mL of water to prepare halloysite nanotubes with surface adsorbed aniline chloride. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 min to obtain a colloid mixture. Then 80mL of an aqueous acidic ammonium persulfate solution was added dropwise to the colloidal mixture under ice-water bath and magnetic stirring for 30 minutes, and magnetic stirring was continued for 12 hours. And (3) centrifugally separating the polymerized mixture to obtain dark green powder, washing the dark green powder with clear water for several times until the washing liquid is neutral, and drying the dark green powder overnight at 40 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 1wt% of silver phosphate.
Example 2
(1) 3.75g halloysite nanotubes were dispersed in 150mL of 0.05mol/L silver nitrate and sonicated for 40min, then 150mL of 0.2mol/L sodium hydrogen phosphate was added and the solution was stirred continuously for 40min to form a bright yellow precipitate. And centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nano particles, washing the collected particles with deionized water, centrifuging again, repeating the centrifuging operation for three times, and drying the particles at 70 ℃ to obtain the silver phosphate grafted halloysite nano tube.
(2) Prior to soap-free emulsion polymerization, 3.5g of silver branched phosphate halloysite nanotubes, 1.5mL of aniline, and 60mL of 1.0mol/L HCl were mixed into 450mL of water to prepare halloysite nanotubes with surface adsorbed aniline chloride. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 min to obtain a colloid mixture. Then, 90ml of an aqueous acidic ammonium persulfate solution was dropwise added to the colloidal mixture under ice-water bath and magnetic stirring for 30 minutes, followed by magnetic stirring for 12 hours. And (3) centrifugally separating the polymerized mixture to obtain dark green powder, washing the dark green powder with clear water for several times until the washing liquid is neutral, and drying the dark green powder overnight at 50 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 2wt% of silver phosphate.
Example 3
(1) 1.67g halloysite nanotubes were dispersed in 250mL silver nitrate at 0.05mol/L and sonicated for 40min, then 150mL sodium hydrogen phosphate at 0.2mol/L was added and the solution was stirred continuously for 30-60min to form a bright yellow precipitate. And centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nano particles, washing the collected particles with deionized water, centrifuging again, repeating the centrifuging operation for three times, and drying the particles at 70 ℃ to obtain the silver phosphate grafted halloysite nano tube.
(2) Prior to soap-free emulsion polymerization, 1.5g of silver branched phosphate halloysite nanotubes, 1mL of aniline, and 50mL of 1.0mol/L HCl were mixed into 450mL of water to prepare halloysite nanotubes with surface adsorbed aniline chloride. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 min to obtain a colloid mixture. 110mL of an aqueous acidic ammonium persulfate solution was then added dropwise to the colloidal mixture under magnetic stirring with an ice-water bath for 30 minutes, and magnetic stirring was continued for 12 hours. And (3) centrifugally separating the polymerized mixture to obtain dark green powder, washing the dark green powder with clear water for several times until the washing liquid is neutral, and drying the dark green powder overnight at 50 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 3wt% of silver phosphate.
Example 4
(1) 1.38g halloysite nanotubes were dispersed in 300mL of 0.05mol/L silver nitrate and sonicated for 40min, then 200mL of 0.2mol/L sodium hydrogen phosphate was added and the solution was stirred continuously for 40min to form a bright yellow precipitate. And centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nano particles, washing the collected particles with deionized water, centrifuging again, repeating the centrifuging operation for three times, and drying the particles at 70 ℃ to obtain the silver phosphate grafted halloysite nano tube.
(2) Prior to soap-free emulsion polymerization, 5g of silver branched phosphate halloysite nanotubes, 1mL of aniline, and 40mL of 1.0mol/L HCl were mixed into 450mL of water to prepare halloysite nanotubes with surface adsorbed aniline chloride. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 min to obtain a colloid mixture. 120ml of an aqueous acidic ammonium persulfate solution was then added dropwise to the colloidal mixture under ice-water bath and magnetic stirring for 30 minutes, followed by magnetic stirring for 12 hours. And (3) centrifugally separating the polymerized mixture to obtain dark green powder, washing the dark green powder with clear water for several times until the washing liquid is neutral, and drying the dark green powder overnight at 50 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 4wt% of silver phosphate.
Each test was performed on a halloysite nanotube composite material that adsorbs and degrades antibiotics in wastewater as described in examples 1-4 above:
1. photocatalyst addition to antibiotic degradation Rate test (in the case of ibuprofen) 300mg of photocatalyst was added to 300mL of 5mg/L ibuprofen solution the photocatalytic experiment was performed in a jacketed glass reactor equipped with a 26W visible light lamp before the photocatalytic experiment the ibuprofen and halloysite nanotube composite mixture was stirred in the dark for 30 minutes.
The photocatalytic degradation rate of ibuprofen by the materials prepared in examples 1-4 shown in the following table is 62.7%, 67.4%, 73.0% and 81.4%.
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Degradation rate (%) | 62.7 | 67.4 | 73.0 | 81.4 |
2. Toxicity evaluation of antibiotic degradation products (ibuprofen for example): toxicity of degradation products to E.coli was investigated.
Control group: coating with ibuprofen-containing solution which is not adsorbed and degraded by the material.
The two groups of agar plates obtained were incubated at 37℃for 24h, and toxicity was assessed by observing the number of surviving colonies.
Experimental group: 200. Mu.L of the diluted E.coli was dispersed in 0.5mL of the ibuprofen degrading solution. After 10min of reaction, 500. Mu.L of the above solution was added to 4mL of sterilized brine (NaCl, 85%) to give a mixture. 200. Mu.L of the solution was spread on an agar plate.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
1. The preparation method of the halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater is characterized by comprising the following steps of:
firstly dispersing halloysite nanotubes in silver nitrate solution for ultrasonic action, and then adding sodium hydrophosphate to form a silver phosphate-halloysite nanotube photocatalyst-adsorbent system to obtain a halloysite nanotube grafted with silver phosphate; under the condition that ammonium persulfate is used as an oxidant, adopting an in-situ soap-free emulsion polymerization method to coat polyaniline on the surface of the halloysite nanotube grafted with silver phosphate, and preparing the polyaniline-coated silver phosphate-halloysite nanotube nanocomposite.
2. The method of manufacturing according to claim 1, characterized in that: the method comprises the following steps:
(1) Dispersing 1-5g halloysite nanotubes in 100-300mL of 0.01-0.05 mol/L silver nitrate, performing ultrasonic action for 20-60 min, then adding 80-200mL of 0.2mol/L sodium hydrogen phosphate, and continuously stirring the solution for 30-60min to form a bright yellow precipitate;
centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nano particles, washing the collected particles with deionized water, centrifuging again, repeating the centrifuging operation for three times, and drying the particles at 60-80 ℃ to obtain the silver phosphate grafted halloysite nano tube;
(2) 3-5g of halloysite nanotube with silver branch phosphate, 1-3mL of aniline and 0.8-1.2mol/L HCl of 50-100 mL are mixed into 450mL of water to prepare halloysite nanotube with surface adsorbing aniline chloride;
stirring or ultrasonic irradiating for 30 min by using a magnetic stirrer to obtain a colloid mixture;
then taking 80-120ml of acidic ammonium persulfate aqueous solution, dropwise adding the aqueous solution into the colloid mixture in 30 minutes under the conditions of ice water bath and magnetic stirring, and continuously magnetically stirring for 12-24 h;
and (3) centrifugally separating the polymerized mixture to obtain dark green powder, washing the dark green powder with clear water for several times until the washing liquid is neutral, and drying the dark green powder overnight at 40-60 ℃ under vacuum to obtain the polyaniline-coated halloysite nanotube composite material with the capability of adsorbing and degrading antibiotics in wastewater.
3. The preparation method according to claim 2, characterized in that: the preparation method of the acidic ammonium persulfate solution in the step (2) comprises the following steps: slowly dripping 0.75-1.5mL of hydrochloric acid into 100-200mL of 5-8wt% ammonium persulfate solution, and magnetically stirring for 30-60min to obtain an acidic ammonium persulfate solution.
4. The preparation method according to claim 2, characterized in that: the halloysite nanotube composite material synthesized in the step (2) is an application for adsorbing and degrading ciprofloxacin, tetracycline and diclofenac sodium antibiotics in boiling water.
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