CN113956473A - 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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- CN113956473A CN113956473A CN202110945763.3A CN202110945763A CN113956473A CN 113956473 A CN113956473 A CN 113956473A CN 202110945763 A CN202110945763 A CN 202110945763A CN 113956473 A CN113956473 A CN 113956473A
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- halloysite nanotube
- halloysite
- silver phosphate
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- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 63
- 239000002071 nanotube Substances 0.000 title claims abstract description 59
- 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 53
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 20
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 230000000593 degrading effect Effects 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 title abstract description 11
- 238000007146 photocatalysis Methods 0.000 title abstract description 8
- 229920000767 polyaniline Polymers 0.000 claims abstract description 18
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229940019931 silver phosphate Drugs 0.000 claims abstract description 18
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 claims abstract description 15
- 239000004332 silver Substances 0.000 claims abstract description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000397 disodium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019800 disodium phosphate Nutrition 0.000 claims abstract description 7
- 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
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 238000000576 coating method Methods 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
- 239000000243 solution Substances 0.000 claims description 25
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- 239000000203 mixture Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 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
- 238000007720 emulsion polymerization reaction Methods 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
- 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
- 239000000084 colloidal system Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 229960001193 diclofenac sodium Drugs 0.000 claims 1
- 238000002156 mixing Methods 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
- 239000011941 photocatalyst Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 230000003115 biocidal effect Effects 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 7
- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 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 12
- 229960001680 ibuprofen Drugs 0.000 description 12
- 229940079593 drug Drugs 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011780 sodium chloride 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
- 238000004065 wastewater treatment 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
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000006065 biodegradation reaction Methods 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
- 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
- 238000005119 centrifugation Methods 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
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- 238000011109 contamination Methods 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
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- 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
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 239000002048 multi walled nanotube 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
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- 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
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- 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
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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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Abstract
The invention discloses a halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater and a preparation method thereof, wherein the halloysite nanotube composite material comprises the following steps: firstly, reacting a halloysite nanotube with silver nitrate and sodium hydrogen phosphate to form a silver phosphate-halloysite nanotube photocatalyst-adsorbent system, so as to obtain a silver phosphate grafted halloysite nanotube; and then coating the polyaniline on the halloysite nanotube grafted with the silver phosphate by using an in-situ soap-free emulsion polymerization method to prepare the polyaniline-coated silver phosphate-halloysite nanotube nanocomposite. The adopted halloysite nanotube can adsorb antibiotic molecules to the surface and the cavity of the halloysite nanotube with high selectivity; the silver phosphate is used as the photocatalyst, so that the removal efficiency of the medicine is improved, and the toxicity of the product is degraded; the introduction of polyaniline can make the material more effectively utilize long-wave light, raise photocatalysis capacity and improve physical, mechanical and electrical properties. The halloysite nanotube composite material of the antibiotic can be recycled for multiple times, has good biodegradability, is safe and nontoxic, and is green and 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 contamination in our water. 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 even in low concentrations of residues, large amounts of drugs are emitted which can constitute a series of threats to the prescription and consumption of the public on the environmental system and human health, eventually contaminating surface and ground water. Typical examples of these drugs detected in surface and groundwater include ibuprofen, diclofenac, ciprofloxacin, and tetracycline, which are difficult to biodegrade antibiotics due to their durability in the environment. Conventional contaminated water treatment techniques have been reported to reduce only a small fraction of the pharmaceutical contaminants present in the water. Conventional contaminated water treatment technologies for pharmaceutical waste can only be partially degraded by strong oxidants such as hydrogen peroxide, permanganate and ozone. The use of these oxidants generates toxic secondary by-products. Furthermore, these antibiotics are commonly found in agricultural soils when the water areas are used for irrigating farmlands. Thus, degradation of antibiotics in the environment is an urgent problem.
The oxidation, adsorption, electrolysis, biodegradation and photocatalytic degradation are conventional methods for treating antibiotics in wastewater. In view of economy and environment, adsorption is considered as a promising method for removing antibiotics using adsorbents such as natural minerals, metal oxides, carbon, and molecularly imprinted polymers. Generally, carbon materials are mostly adopted, have high specific surface area, abundant surface groups, high stability and good adsorption performance, are the first choice materials for wastewater treatment, but have the defects of high cost, complex synthesis process, small capacity, slow dynamic property 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 advantages of natural existence, biocompatibility, high dispersibility, non-toxicity, easy availability, and relatively low cost compared to carbon nanotubes.
In addition to adsorption, semiconductor photocatalysis has received much attention from many researchers as an efficient and green solution for degrading environmental pollutants. Photocatalysis is primarily dependent on the efficiency of the semiconductor material and the light source. At present, the traditional photocatalyst TiO2 is difficult to absorb abundant visible light, so that the practical application of the photocatalyst is limited. Therefore, it is necessary to search for novel visible light-induced photocatalysts such as silver-based materials, bismuth-based materials, polymer materials, and the like.
Polyaniline is widely used in the field of photocatalysis due to its conjugated pi system, wide absorption range under the induction of visible light, and unique electron and hole transport characteristics. Furthermore, polyaniline is relatively inexpensive and easy to prepare compared to doped noble metals. To date, many published studies have shown that the combination of polyaniline and a semiconductor can improve the efficiency of carrier transfer between polyaniline and a semiconductor. Polyaniline is often combined with other inorganic components to form nanocomposites to improve physical, mechanical, and electrical properties, such as enhanced solubility, electrical conductivity, magnetic, and optoelectronic properties. In recent years, encapsulation of inorganic nanomaterials in polyaniline shells has become the hottest and most interesting direction of research in nanocomposite synthesis. But the adsorption capacity is the problem which needs to be solved by the relevant technologists in the field at present.
Therefore, if a green and cheap multielement adsorption degradation material which has high adsorption effect, can uniformly disperse the photocatalyst and simultaneously can expand the visible light absorption area of the photocatalyst so as to carry out photocatalytic degradation on antibiotics can be developed, the treatment of the pharmaceutical 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 provides important technical support for the development of future drug wastewater treatment, and has very important significance.
Disclosure of Invention
In order to realize the purpose of the invention, the invention provides the following technical scheme:
compared with the prior art, the invention has the beneficial effects that:
1. the antibiotic semiconductor photocatalyst for degrading the antibiotic adsorbed by the material is silver phosphate, has visible light activity and good oxidizing ability, and can oxidize a small amount of water and release O2And the composite has better oxidative degradation capability on part of antibiotics, and the toxicity of degradation products is lower.
2. The halloysite nanotube is a naturally-occurring aluminosilicate clay nanotube, mainly consists of multi-wall nanotube crystals, has the characteristic of high specific surface area, and enhances the adsorption capacity of the material. The halloysite nanotube is a rolled tubular structure, the outer surface of the halloysite nanotube is slightly negatively charged, and the inner surface of the tube cavity is slightly positively charged. This change in the surface charge characteristics of halloysite nanotubes enables them to efficiently adsorb various positively and negatively charged antibiotic molecules to their surfaces and cavities.
3. The silver phosphate-halloysite nanotube photocatalyst-adsorbent system consisting of the silver phosphate photocatalyst and the halloysite nanotubes is used in the invention, so that the removal efficiency of drugs and proteins is improved through the photocatalysis and adsorption processes, and meanwhile, the dispersibility of the synthesized silver phosphate in the composite material can be improved by adding the halloysite nanotubes.
4. The introduction of polyaniline in the invention is beneficial to enlarging a light absorption area and more effectively utilizing long-wave light, thereby improving the photocatalytic capacity. The invention can be applied to protein solutions containing antibiotics, can avoid the denaturation of proteins when adsorbing the antibiotics, and keeps the original protein nature. In addition, the polyaniline is coated on the surface of the halloysite nanotube to form a nano composite material, 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 the colonies of E.coli grown on agar plates coated with ibuprofen solution, and FIG. (b) shows the colonies of E.coli grown on agar plates coated with ibuprofen-degrading solution.
Detailed Description
The present invention will be further illustrated by the following examples.
Example 1
A halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater by photocatalysis and a preparation method thereof are disclosed, and the preparation method comprises the following specific 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 then centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nanoparticles, 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 halloysite nanotube grafted with silver phosphate.
(2) Prior to soap-free emulsion polymerization, 3g of silver phosphate-branched halloysite nanotubes, 1mL of aniline, and 80mL of 0.8mol/L HCl were mixed into 450mL of water to prepare halloysite nanotubes with aniline chloride adsorbed on the surface. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 minutes to obtain a colloidal mixture. Then 80mL of an aqueous acidic ammonium persulfate solution was added dropwise to the colloidal mixture over 30 minutes with magnetic stirring in an ice-water bath and magnetic stirring for 12 h. And centrifugally separating the polymerized mixture to obtain dark green powder, washing the powder for several times by using clear water until the washing liquid is neutral, and drying the powder overnight at 40 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 1 wt% 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 then centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nanoparticles, 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 halloysite nanotube grafted with silver phosphate.
(2) Prior to soap-free emulsion polymerization, 3.5g of silver phosphate-branched 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 minutes to obtain a colloidal mixture. Then 90ml of an aqueous acidic ammonium persulfate solution was added dropwise to the colloidal mixture over 30 minutes under magnetic stirring in an ice-water bath, and magnetic stirring was continued for 12 hours. And centrifugally separating the polymerized mixture to obtain dark green powder, washing the powder for several times by using clear water until the washing liquid is neutral, and drying the powder overnight in vacuum at 50 ℃ to obtain the polyaniline-coated halloysite nanotube composite material containing 2 wt% of silver phosphate.
Example 3
(1) 1.67g of halloysite nanotubes were dispersed in 250mL 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 30-60min to form a bright yellow precipitate. And then centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nanoparticles, 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 halloysite nanotube grafted with silver phosphate.
(2) Prior to soap-free emulsion polymerization, a mixture of 1.5g of silver phosphate-branched halloysite nanotubes, 1mL of aniline, and 50mL of 1.0mol/L HCl was mixed into 450mL of water to prepare halloysite nanotubes with surface adsorbed aniline chloride. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 minutes to obtain a colloidal mixture. Then 110mL of an aqueous acidic ammonium persulfate solution was added dropwise to the colloidal mixture over 30 minutes with magnetic stirring in an ice-water bath and magnetic stirring for 12 h. And centrifugally separating the polymerized mixture to obtain dark green powder, washing the powder for several times by using clear water until the washing liquid is neutral, and drying the powder overnight at 50 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 3 wt% 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 then centrifuging the obtained bright yellow solution, collecting silver phosphate-halloysite nanoparticles, 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 halloysite nanotube grafted with silver phosphate.
(2) 5g of silver phosphate-branched halloysite nanotubes, 1mL of aniline, and 40mL of 1.0mol/L HCl were mixed into 450mL of water to prepare halloysite nanotubes with aniline chloride adsorbed on the surface prior to soap-free emulsion polymerization. Stirring with a magnetic stirrer or ultrasonic irradiation for 30 minutes to obtain a colloidal mixture. 120ml of an aqueous acidic ammonium persulfate solution was then added dropwise to the colloidal mixture over 30 minutes with magnetic stirring in an ice-water bath and magnetic stirring for 12 hours. And centrifugally separating the polymerized mixture to obtain dark green powder, washing the powder for several times by using clear water until the washing liquid is neutral, and drying the powder overnight at 50 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material containing 4 wt% of silver phosphate.
The following tests were conducted on a halloysite nanotube composite adsorbing and degrading antibiotics in wastewater of examples 1-4 above:
1. photocatalyst addition test for antibiotic degradation rate (in the case of ibuprofen): 300mg of photocatalyst was added to 300mL of a 5mg/L ibuprofen solution, the photocatalytic experiment was performed in a jacketed glass reactor equipped with a 26W visible light lamp, the ibuprofen and halloysite nanotube composite mixture was stirred in the dark for 30 minutes prior to the photocatalytic experiment, this was done to reach the adsorption-degradation equilibrium, a specific volume (2mL) of visible light illuminated ibuprofen photocatalyst mixture was sampled at a specific time, the powdered photocatalyst was removed from the sampled volume by centrifugation at 6000rpm for 5 minutes, the concentration of ibuprofen in the sampled volume was estimated by measuring absorbance using a UVevis spectrophotometer, the degradation rate was calculated using 3 experiments and averaged.
The photocatalytic degradation rates of ibuprofen for the materials prepared in examples 1-4 are 62.7%, 67.4%, 73.0%, and 81.4% as shown in the following tables.
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Degradation Rate (%) | 62.7 | 67.4 | 73.0 | 81.4 |
2. Evaluation of toxicity of antibiotic degradation products (ibuprofen for example): the toxicity of the degradation products to E.coli was investigated.
Control group: the solution containing ibuprofen is coated without adsorptive degradation of 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 groups: 200. mu.L of the diluted E.coli was dispersed in 0.5mL of ibuprofen degradation solution. After 10min of reaction, 500. mu.L of the above solution was added to 4mL of sterile saline (NaCl, 85%) to obtain a mixture. 200 μ L of the suspension was spread on agar plates.
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 attributes 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. A preparation method of a halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater is characterized by comprising the following steps:
firstly, dispersing a halloysite nanotube in a silver nitrate solution, performing ultrasonic action, and then adding sodium hydrogen phosphate to form a silver phosphate-halloysite nanotube photocatalyst-adsorbent system to obtain a silver phosphate grafted halloysite nanotube; and under the condition that ammonium persulfate is used as an oxidant, coating polyaniline on the surface of the silver phosphate grafted halloysite nanotube by adopting an in-situ soap-free emulsion polymerization method to prepare the polyaniline-coated silver phosphate-halloysite nanotube nanocomposite.
2. The method of claim 1, wherein: the method comprises the following steps:
(1) dispersing 1-5g of halloysite nanotubes in 300mL of 0.01-0.05mol/L silver nitrate, performing ultrasonic action for 20-60min, 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 nanoparticles, washing the collected particles with deionized water, centrifuging again, repeating the centrifuging operation for three times, and drying the particles at the temperature of 60-80 ℃ to obtain the halloysite nanotubes grafted with silver phosphate;
(2) before soap-free emulsion polymerization, mixing 3-5g of a halloysite nanotube with silver phosphate branches, 1-3mL of aniline and 50-100mL of 0.8-1.2mol/L HCl into 450mL of water to prepare the halloysite nanotube with aniline chloride adsorbed on the surface; stirring with a magnetic stirrer or performing ultrasonic irradiation for 30 minutes to obtain a colloid mixture; then 80-120ml of acidic ammonium persulfate aqueous solution is taken and is dripped into the colloid mixture within 30 minutes under the conditions of ice water bath and magnetic stirring, and the magnetic stirring is continued for 12-24 hours; and centrifugally separating the polymerized mixture to obtain dark green powder, washing the powder with clear water for several times until the washing liquid is neutral, and drying the powder overnight at 40-60 ℃ in vacuum to obtain the polyaniline-coated halloysite nanotube composite material with the capability of adsorbing and degrading antibiotics in wastewater.
3. The method of claim 2, wherein: the preparation method of the acidic ammonium persulfate solution in the step (2) comprises the following steps: 0.75-1.5mL of hydrochloric acid is slowly dropped into 200mL of 5-8 wt% ammonium persulfate solution with 100-.
4. The method of claim 2, wherein: the halloysite nanotube composite material synthesized in the step (2) is applied to adsorption and degradation of antibiotics such as ciprofloxacin, tetracycline, diclofenac sodium and the like in boiling water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114873681A (en) * | 2022-05-25 | 2022-08-09 | 扬州大学 | Method for treating alizarin red wastewater by combining adsorption and photocatalysis |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080249221A1 (en) * | 2007-04-06 | 2008-10-09 | Naturalnano Research, Inc. | Polymeric adhesive including nanoparticle filler |
| CN102935385A (en) * | 2012-11-02 | 2013-02-20 | 常州大学 | Efficient and stable visible light polyaniline group nanometer silver phosphate compound photocatalyst and preparation method thereof |
| CN103934008A (en) * | 2014-04-17 | 2014-07-23 | 常州大学 | Preparation method of halloysite loading phosphoric acid Silverlight catalyst |
| US20160144349A1 (en) * | 2013-06-25 | 2016-05-26 | Council Of Scientific & Industrial Research | Reduced graphene oxide-silver phosphate (rgo-agp) and a process for the preparation thereof for the photodegradation of organic dyes |
| CN107163573A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of halloysite nanotubes and polyaniline compound oil absorption material |
| CN107789995A (en) * | 2017-10-25 | 2018-03-13 | 太原理工大学 | A kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation method and application |
| CN110227557A (en) * | 2019-05-20 | 2019-09-13 | 湖南大学 | Silver orthophosphate and the pucherite Three-element composite photocatalyst of polyaniline modified synergic and its preparation method and application |
| CN112142971A (en) * | 2020-08-17 | 2020-12-29 | 兰州理工大学 | Polyaniline/halloysite/barium ferrite electromagnetic composite material and preparation method thereof |
| CN112892504A (en) * | 2021-03-17 | 2021-06-04 | 常新园 | Adsorbent for industrial sewage treatment and preparation method thereof |
-
2021
- 2021-08-16 CN CN202110945763.3A patent/CN113956473B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080249221A1 (en) * | 2007-04-06 | 2008-10-09 | Naturalnano Research, Inc. | Polymeric adhesive including nanoparticle filler |
| CN102935385A (en) * | 2012-11-02 | 2013-02-20 | 常州大学 | Efficient and stable visible light polyaniline group nanometer silver phosphate compound photocatalyst and preparation method thereof |
| US20160144349A1 (en) * | 2013-06-25 | 2016-05-26 | Council Of Scientific & Industrial Research | Reduced graphene oxide-silver phosphate (rgo-agp) and a process for the preparation thereof for the photodegradation of organic dyes |
| CN103934008A (en) * | 2014-04-17 | 2014-07-23 | 常州大学 | Preparation method of halloysite loading phosphoric acid Silverlight catalyst |
| CN107163573A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of halloysite nanotubes and polyaniline compound oil absorption material |
| CN107789995A (en) * | 2017-10-25 | 2018-03-13 | 太原理工大学 | A kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation method and application |
| CN110227557A (en) * | 2019-05-20 | 2019-09-13 | 湖南大学 | Silver orthophosphate and the pucherite Three-element composite photocatalyst of polyaniline modified synergic and its preparation method and application |
| CN112142971A (en) * | 2020-08-17 | 2020-12-29 | 兰州理工大学 | Polyaniline/halloysite/barium ferrite electromagnetic composite material and preparation method thereof |
| CN112892504A (en) * | 2021-03-17 | 2021-06-04 | 常新园 | Adsorbent for industrial sewage treatment and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114873681A (en) * | 2022-05-25 | 2022-08-09 | 扬州大学 | Method for treating alizarin red wastewater by combining adsorption and photocatalysis |
| CN114873681B (en) * | 2022-05-25 | 2023-04-25 | 扬州大学 | Method for treating alizarin red wastewater by combining adsorption and photocatalysis |
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