CN113979509A - Application of ultrathin sheet metal hydroxide in antibiotic degradation - Google Patents
Application of ultrathin sheet metal hydroxide in antibiotic degradation Download PDFInfo
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- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 54
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 54
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 31
- 230000015556 catabolic process Effects 0.000 title claims abstract description 29
- 238000005286 illumination Methods 0.000 claims abstract description 28
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims abstract description 26
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 19
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 17
- 238000005070 sampling Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 11
- 239000012984 antibiotic solution Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000009775 high-speed stirring Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000004098 Tetracycline Substances 0.000 claims description 3
- 229960002180 tetracycline Drugs 0.000 claims description 3
- 229930101283 tetracycline Natural products 0.000 claims description 3
- 235000019364 tetracycline Nutrition 0.000 claims description 3
- 150000003522 tetracyclines Chemical class 0.000 claims description 3
- 238000011002 quantification Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011282 treatment Methods 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000010936 titanium Substances 0.000 description 17
- 238000004088 simulation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910020517 Co—Ti Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 230000007674 genetic toxicity Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- 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 relates to the technical field of catalytic degradation, in particular to application of ultrathin sheet metal hydroxide in antibiotic degradation. The application of the ultrathin sheet metal hydroxide in the degradation of antibiotics comprises the following steps: (a) mixing the water dispersion of the ultrathin sheet metal hydroxide with an antibiotic solution, and carrying out mixed adsorption in a dark environment; (b) and (3) placing the mixed and adsorbed system under simulated illumination for reaction, sampling at regular time and determining the ultraviolet absorption value. The ultrathin sheet metal hydroxide is used for degrading the antibiotics, the experimental method is simple, the accuracy is high, the ultrathin sheet metal hydroxide has excellent photocatalytic degradation performance on the antibiotics such as tetracycline hydrochloride, the antibiotic residual quantity is low after the reaction is finished, and the degradation rate is high; the method can be used for simulating photocatalytic degradation of antibiotics, researching the degradation behavior rule of the antibiotics, performing antibiotic environmental pollution prevention and treatment according to the rule, and the like, and has important significance.
Description
Technical Field
The invention relates to the technical field of catalytic degradation, in particular to application of ultrathin sheet metal hydroxide in antibiotic degradation.
Background
With the rapid development of the pharmaceutical industry, the problem of water pollution is becoming more serious, and the water pollution has adverse effect on human life. Wastewater containing antibiotic drugs not only has genetic toxicity, but also can cause antibiotic resistance. Traditional treatments such as adsorption, membrane filtration, and biological treatment have been used in recent years to eliminate antibiotic compounds. However, these treatment methods are inefficient due to secondary pollution caused by adsorption and membrane filtration. Also, antibiotic compounds are toxic and difficult to degrade and are not amenable to biological treatment. Therefore, there is an urgent need to develop a new technology for eliminating antibiotic compounds in wastewater from pharmaceutical industry. In contrast, photocatalysis has received much attention because of its environmental friendliness. Specifically, in the photocatalysis process, the pollutant is degraded by utilizing the photogenerated charges with oxidation and reduction capabilities, and secondary pollution is avoided. Therefore, the development of an effective photocatalyst is crucial to pharmaceutical wastewater treatment.
Photochemical degradation of pesticides is one of the major modes of environmental degradation of pesticides. At present, the principle of the photocatalytic technology is mainly explained by the solid semiconductor energy band theory. In the solid band theory, a Conduction Band (CB) having no high energy of electrons and a Valence Band (VB) having low energy of electrons constitute an electron band of a semiconductor, and a forbidden band exists between them, and its Eg depends on the difference between the lowest value of the conduction band and the highest value of the valence band. When a solar photon (hv ≧ Eg) with sufficient energy is absorbed by the semiconductor, an electron in its valence band is excited to the conduction band to generate a photogenerated electron, and a photogenerated hole is generated in the valence band. The photoproduction holes have strong oxidizing ability, the photoproduction electrons have strong reducing ability, and the photoproduction holes and the photoproduction electrons can migrate to different positions on the surface of the semiconductor and generate oxidation-reduction reaction with pollutants adsorbed on the surface, so that the chemical reaction is driven to be carried out, and the conversion from solar energy to chemical energy is completed.
However, the existing catalysts for antibiotic degradation have few types, complex preparation process and high cost, and the photocatalytic activity of the catalyst for antibiotic degradation is low.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide application of ultrathin sheet metal hydroxide in antibiotic degradation.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the application of the ultrathin sheet metal hydroxide in the degradation of antibiotics comprises the following steps:
(a) mixing the water dispersion of the ultrathin sheet metal hydroxide with an antibiotic solution, and carrying out mixed adsorption in a dark environment;
(b) and (3) placing the mixed and adsorbed system under simulated illumination for reaction, sampling at regular time and determining the ultraviolet absorption value.
In a specific embodiment of the present invention, the method further comprises: the time t of the simulated illumination is taken as an abscissa, -In (C/C)0) As an ordinate, -In (C/C) is plotted0) The slope of a relation curve with t is taken as an apparent reaction rate constant of the photocatalytic degradation reaction; c is the concentration of residual antibiotic corresponding to the simulated illumination time t, C0The concentration of the residual antibiotic at the end of the adsorption was determined in a dark environment.
In a specific embodiment of the present invention, the method further comprises: and determining the content of the residual antibiotic by comparing the ultraviolet light absorption value with a standard curve of the content of the antibiotic.
In a specific embodiment of the present invention, the method for timing sampling comprises: sampling once every 10-15 min, filtering the sample, and collecting filtrate. Furthermore, the number of the timing samples is 6-8, and the total testing time is preferably 1.5-2 h.
In a specific embodiment of the invention, the simulated illumination is visible light. Furthermore, the intensity of the simulated illumination is 4500-5000 mW cm–2。
In a specific embodiment of the present invention, the time for mixing and adsorbing in the dark environment is 30-40 min.
In a specific embodiment of the present invention, in the step (a), the concentration of the antibiotic solution is 10 to 100 mg/L.
In a specific embodiment of the present invention, the amount of the ultrathin flaky metal hydroxide in the system is 0.2 to 1.5g/L in terms of wet amount.
In a specific embodiment of the present invention, the method for quantifying ultrathin flaky metal hydroxide comprises:
(i) weighing the same flaky metal hydroxide wet samples with different masses, and recording the wet samples as wet weights;
(ii) drying each wet sample under the same condition to constant weight, and recording the mass of each dried sample as the dry weight;
(iii) and drawing a relation curve of the wet weight and the dry weight by taking the dry weight as an ordinate and the wet weight as an abscissa, and taking the relation curve as a standard curve.
In a particular embodiment of the invention, the antibiotic is an agricultural antibiotic. Preferably, the antibiotic is an antibiotic of the tetracycline family. Further, the antibiotic is tetracycline hydrochloride.
In a specific embodiment of the present invention, the preparation method of the ultra-thin flake metal hydroxide comprises: mixing and reacting aqueous solution containing metal ions and ammonia water solution under high-speed stirring, and collecting solid; wherein the metal ion comprises Zn2+、Ti4+、Ni2+、Fe3+、Mg2+、Cu2+、Co2+And Al3+Two or three of them. Further, the metal ions include Zn2 +And Ti4+。
The existing LDH preparation is mainly synthesized by a urea method, the synthesis method is relatively complex, and the accumulation of the synthesized LDH sheets is relatively thick. The LDH sheets synthesized by the method are hardly accumulated, can reach a nanometer level, and has simpler operation and mild conditions.
In an embodiment of the present invention, the molar ratio of the metal ions in the aqueous solution containing metal ions at high valence to the metal ions at low valence is 1: 2.5 to 3.5.
The coprecipitation method for preparing the ultrathin flake metal hydroxide has higher selectivity on cations, and when the metal ions wrapComprises Ti4+When the molar ratio is regulated to be within the range, the LDH nano-sheets can be effectively formed.
In an embodiment of the invention, the concentration of the high valence metal ions in the aqueous solution containing metal ions is 35 to 40mmol/L, such as 37.5 mmol/L.
In a specific embodiment of the present invention, the mass fraction of the aqueous ammonia solution is 2% to 3%.
In a specific embodiment of the present invention, the volume ratio of the aqueous solution containing metal ions to the aqueous ammonia solution is 1: 0.8 to 1.2.
In a specific embodiment of the invention, the high-speed stirring speed is 1000-1600 rpm.
In a specific embodiment of the present invention, the mixing reaction under high speed stirring comprises: and simultaneously dripping the aqueous solution containing the metal ions and the ammonia water solution into the high-speed stirring system, and continuing to stir at high speed for 10-30 min after finishing dripping.
In a specific embodiment of the invention, the collecting the solids comprises: and carrying out centrifugal separation on the materials after the mixed reaction, and washing the solid product with deionized water for 3-5 times.
In a particular embodiment of the invention, the solid is kept wet. To prevent LDH from piling up after drying, resulting in performance degradation.
Compared with the prior art, the invention has the beneficial effects that:
the ultrathin flaky metal hydroxide is used for degrading antibiotics, has excellent photocatalytic degradation performance on antibiotics such as tetracycline hydrochloride, has high reaction activity, can be used for simulating photocatalytic degradation of antibiotics, researching antibiotic degradation behavior rules, performing antibiotic environmental pollution control according to the rules, and the like, and has important significance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a standard curve of 355nm UV absorption of tetracycline hydrochloride according to the present invention versus its content;
FIG. 2 is a transmission electron micrograph of a ultrathin flaky metal hydroxide prepared in example 4 of the present invention;
FIG. 3 is a pseudo-first order kinetic fit curve of the catalytic degradation reaction corresponding to the simulation experiments of model Nos. 1#, 2#, and 3# of the present invention;
FIG. 4 is a UV spectrum of tetracycline hydrochloride concentration change at different times in the 3# simulation experiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The application of the ultrathin sheet metal hydroxide in the degradation of antibiotics comprises the following steps:
(a) mixing the water dispersion of the ultrathin sheet metal hydroxide with an antibiotic solution, and carrying out mixed adsorption in a dark environment;
(b) and (3) placing the mixed and adsorbed system under simulated illumination for reaction, sampling at regular time and determining the ultraviolet absorption value.
In a specific embodiment of the present invention, the method further comprises: the time t of the simulated illumination is taken as an abscissa, -In (C/C)0) As a ordinatedrawing-In (C/C)0) The slope of a relation curve with t is taken as an apparent reaction rate constant of the photocatalytic degradation reaction, namely the degradation rate; c is the concentration of residual antibiotic corresponding to the simulated illumination time t, C0The concentration of the residual antibiotic at the end of the adsorption was determined in a dark environment.
In a specific embodiment of the present invention, the method further comprises: and determining the content of the residual antibiotic by comparing the ultraviolet absorption value with a standard curve of the content of the antibiotic. For example, tetracycline hydrochloride, the UV absorbance at 355nm is used to plot a standard curve.
In a specific embodiment of the present invention, the method for timing sampling comprises: sampling once every 10-15 min, filtering the sample, and collecting filtrate. Furthermore, the number of the timing sampling is 6-8, preferably 6. The total time of the test is 1.5-2 h.
In a specific embodiment of the invention, the simulated illumination is visible light. Furthermore, the intensity of the simulated illumination is 4500-5000 mW cm–2。
As in various embodiments, the intensity of the simulated illumination may be 4500mW · cm–2、4600mW·cm–2、4700mW·cm–2、4800mW·cm–2、4900mW·cm–2、5000mW·cm–2And so on.
In actual operation, under simulated illumination, the system is kept at temperature through external regulation and control, and the temperature is not increased due to the influence of illumination.
In a specific embodiment of the invention, the temperature of the system in a dark environment is 25 +/-2 ℃; the temperature of the system under simulated illumination was 25 + -2 deg.C.
In a specific embodiment of the present invention, the time for mixing and adsorbing in the dark environment is 30-40 min. Further, the mixed adsorption is performed under stirring conditions.
In actual operation, sampling can be carried out every 10-15 min, filtering by a filter membrane with the aperture of 0.22 mu m, collecting filtrate, measuring the ultraviolet absorption value, when the ultraviolet absorption value is basically unchanged, indicating that the adsorption is sufficient in a dark environment, finishing the dark reaction, and carrying out subsequent simulated illumination treatment.
In a specific embodiment of the present invention, in the step (a), the concentration of the antibiotic solution is 10 to 100mg/L, preferably 40 to 60 mg/L.
In a specific embodiment of the present invention, the amount of the ultrathin flaky metal hydroxide in the system is 0.2 to 1.5g/L, preferably 0.2 to 0.4g/L, in terms of a wet sample amount.
Because the catalytic activity is related to the concentration of the residual antibiotics in the system, the concentration of the antibiotics is reduced too fast when the performance is extremely strong, and the degradation rate of the antibiotics cannot be accurately judged, the residual antibiotics in the system is controlled to be 10-40 mg/L, preferably 15-35 mg/L when the reaction is finished by regulating and controlling the using amount of the ultrathin flaky metal hydroxide, so that the accuracy of the regular determination of the degradation behavior is ensured.
In a specific embodiment of the present invention, the method for quantifying ultrathin flaky metal hydroxide comprises:
(i) weighing the same flaky metal hydroxide wet samples with different masses, and recording the wet samples as wet weights;
(ii) drying each wet sample under the same condition to constant weight, and recording the mass of each dried sample as the dry weight;
(iii) and drawing a relation curve of the wet weight and the dry weight by taking the dry weight as an ordinate and the wet weight as an abscissa, and taking the relation curve as a standard curve.
In actual operation, the ultrathin sheet metal hydroxide wet sample is directly used, and for accurate sampling, when the ultrathin sheet metal hydroxide with certain wet weight is pre-fetched, the corresponding dry weight can be calculated through a standard curve, and the sampling is directly carried out, so that the comparative analysis is also convenient.
In a specific embodiment of the invention, the drying temperature is 60 +/-5 ℃, and the drying time is 48-52 h.
In actual practice, the sample was not changed in mass after drying at the above-mentioned drying temperature for 48 hours, and was considered to be completely dried to a constant weight.
In a particular embodiment of the invention, the antibiotic comprises an antibiotic of the tetracycline family. Further, the antibiotic is tetracycline hydrochloride.
In a specific embodiment of the present invention, the preparation method of the ultra-thin flake metal hydroxide comprises: mixing and reacting aqueous solution containing metal ions and ammonia water solution under high-speed stirring, and collecting solid; wherein the metal ion comprises Zn2+、Ti4+、Ni2+、Fe3+、Mg2+、Cu2+、Co2+And Al3+Two or three of them.
In a particular embodiment of the invention, the metal ion comprises Zn2+And Ti4+、Ni2+And Fe3+、Co2+And Ti4 +、Co2+And Al3+、Mg2+And Al3+、Ni2+And Ti4+Or Mg2+、Cu2+And Al3+The combination of (1). Further, the metal ions include Zn2+And Ti4+。
The existing LDH preparation is mainly synthesized by a urea method, the synthesis method is relatively complex, and the accumulation of the synthesized LDH sheets is relatively thick. The LDH sheets synthesized by the method are hardly accumulated, can reach a nanometer level, and has simpler operation and mild conditions.
In practice, the metal ions are derived from soluble metal salts, such as nitrates, chlorides, etc. of the metal ions.
In a specific embodiment of the present invention, the molar ratio of the metal ions in the aqueous solution containing metal ions at high valence to the metal ions at low valence is 1: 3 (2.5 to 3.5), preferably 1: 3.
As in the various embodiments, the aqueous solution containing metal ions may contain metal ions in a higher valence state, such as Ti4+Or Al3+With a metal ion of lower valence Co2+、Zn2+Or Ni2+The molar ratios can be 1: 2.5, 1: 2.6, 1: 2.7, 1: 2.8, 1: 2.9, 1: 3, 1: 3.1, 1: 3.2, 1: 3.3, 1: 3.4, 1: 3.5, etc.
The coprecipitation method of the invention for preparing the ultrathin flake metal hydroxide has higher selectivity to cations,when the metal ion comprises Ti4+When the molar ratio is regulated to be within the range, the LDH nano-sheets can be effectively formed.
In an embodiment of the invention, the concentration of the high valence metal ions in the aqueous solution containing metal ions is 35 to 40mmol/L, such as 37.5 mmol/L.
In one embodiment of the present invention, deionized water is used as a solvent for the aqueous solution containing metal ions and the aqueous ammonia solution. In another embodiment of the present invention, decarburized deionized water is used as a solvent for the aqueous solution containing metal ions and the aqueous ammonia solution.
In practical operation, the preparation of the ammonia solution comprises: and diluting ammonia water to a preset concentration by adopting deionized water or decarburized deionized water. The ammonia water is commercial strong ammonia water, and the mass fraction is 25-28%.
In a specific embodiment of the present invention, the mass fraction of the aqueous ammonia solution is 2% to 3%.
In a specific embodiment of the present invention, the volume ratio of the aqueous solution containing metal ions to the aqueous ammonia solution is 1: 0.8 to 1.2.
As in the different embodiments, the volume ratio of the metal ion containing aqueous solution to the aqueous ammonia solution can be 1: 0.8, 1: 0.9, 1: 1, 1: 1.1, 1: 1.2, etc.
In a specific embodiment of the invention, the high-speed stirring speed is 1000-1600 rpm.
In a specific embodiment of the present invention, the mixing reaction under high speed stirring comprises: and simultaneously dripping the aqueous solution containing the metal ions and the ammonia water solution into the high-speed stirring system, and continuing to stir at high speed for 10-30 min after finishing dripping.
In the specific embodiment of the invention, after the dropwise addition is finished, high-speed stirring is continued for 15-20 min.
In a specific embodiment of the invention, the dropping speed is 20-30 μ L/s.
In a specific embodiment of the invention, the collecting the solids comprises: and carrying out centrifugal separation on the materials after the mixed reaction, and washing the solid product with deionized water for 3-5 times. In practice, the washing may be performed with decarburized deionized water.
In a specific embodiment of the invention, the rotation speed of the centrifugal separation is 4000 +/-500 rpm, and the time of the centrifugal separation is 5-10 min.
In a particular embodiment of the invention, the solid is kept wet. To prevent LDH from piling up after drying, resulting in performance degradation.
The decarburized deionized water used in the following examples was prepared as follows:
and (3) taking deionized water, introducing nitrogen into the deionized water for enough time, boiling the deionized water, and filling the boiled deionized water into a container with a sealing function to obtain decarburized deionized water for later use.
Example 1
This example provides a method for preparing a ultrathin flaky metal hydroxide, comprising the following steps:
(1) as metal ion Zn2+With Ti4+The molar ratio of (3) to (1) zinc nitrate and titanium tetrachloride were weighed and dissolved in 200mL of decarburized deionized water to prepare Zn2+With Ti4+Aqueous solution containing metal ions with the concentrations of 112.5mmol/L and 37.5mmol/L respectively; and uniformly mixing commercially available 25% -28% ammonia water and decarbonized deionized water according to the volume ratio of 1: 9 to obtain 200mL ammonia water solution.
(2) Simultaneously dropwise adding the aqueous solution containing the metal ions and the ammonia water solution prepared in the step (1) into a three-neck flask with a high-speed stirring magneton at a speed of 25 mu L/s; and after the dropwise addition, continuously stirring at the stirring speed of 1000-1600 rpm for 15min, then carrying out centrifugal separation at 4000rpm for 5min, pouring out the supernatant, and carrying out centrifugal washing on the separated solid product for 5 times by using decarburized deionized water, wherein the centrifugal speed is 4000rpm, and the centrifugal time is 5min, so as to obtain the ultrathin flaky metal hydroxide wet sample. The wet samples were stored in centrifuge tubes and kept moist.
Example 2
This example refers to the preparation of the ultrathin flaky metal hydroxide of example 1The preparation method is different only in that the aqueous solution containing the metal ions is different; in this embodiment, the preparation of the aqueous solution containing metal ions includes: according to metal ion Ni2+With Ti4+The molar ratio of (3) to (1) was determined by weighing nickel nitrate and titanium tetrachloride, respectively, and dissolving them in 200mL of decarburized deionized water to prepare Ni2+With Ti4+The concentration of the aqueous solution containing metal ions is 112.5mmol/L and 37.5mmol/L respectively.
Example 3
This example refers to the preparation method of the ultra-thin flake metal hydroxide of example 1, differing only in that the aqueous solution containing the metal ion; in this embodiment, the preparation of the aqueous solution containing metal ions includes: according to the metal ion Co2+With Ti4+The molar ratio of cobalt nitrate to titanium tetrachloride was 3: 1, and the cobalt nitrate and titanium tetrachloride were dissolved in 200mL of decarburized deionized water to prepare Co2+With Ti4+The concentration of the aqueous solution containing metal ions is 112.5mmol/L and 37.5mmol/L respectively.
Example 4
This example refers to the preparation method of the ultra-thin flake metal hydroxide of example 1, differing only in that the aqueous solution containing the metal ion; in this embodiment, the preparation of the aqueous solution containing metal ions includes: according to the metal ion Co2+With Al3+The molar ratio of cobalt nitrate to aluminum nitrate was 3: 1, and the cobalt nitrate and aluminum nitrate were dissolved in 200mL of decarburized deionized water to prepare Co2+With Al3+The concentration of the aqueous solution containing metal ions is 112.5mmol/L and 37.5mmol/L respectively.
Example 5
The embodiment provides a method for catalytic degradation of antibiotics under simulated illumination, which comprises the following steps:
(a) adding the ultrathin sheet metal hydroxide wet sample into 50mL of deionized water, and performing ultrasonic dispersion to obtain an ultrathin sheet metal hydroxide aqueous dispersion; prepare 100mg/L tetracycline hydrochloride aqueous solution. Mixing the above water dispersion with 50mL of 100mg/L tetracycline hydrochloride aqueous solution, stirring at room temperature for 30min in dark environment (collecting filtrate by filtering with 0.22 μm filter membrane every 15min for ultraviolet absorption value detection to obtain 3mL sample), and terminating dark reaction.
(b) Placing the system subjected to the dark reaction in the step (a) under visible light for removing far ultraviolet and infrared, wherein the illumination intensity is 4700mW cm–2And meanwhile, keeping the temperature of the system unchanged (room temperature), collecting 3mL of sample every 15min, filtering the collected filtrate through a filter membrane with the aperture of 0.22 mu m, detecting the ultraviolet absorption value, totaling 6 sampling points, and carrying out illumination reaction for 90 min.
(c) According to a relation standard curve of the ultraviolet absorption value and the tetracycline hydrochloride content, as shown in figure 1, determining the corresponding content of the sample at different simulated illumination time; with the time t of the simulated illumination as the abscissa, -In (C/C)0) As an ordinate, -In (C/C) is plotted0) And (3) a curve of the relation with t, wherein the slope is used as an apparent reaction rate constant of the photocatalytic degradation reaction. Wherein C is the concentration of tetracycline hydrochloride in the system residue (in the sampled filtrate) corresponding to the simulated illumination time t (min), C0The concentration of tetracycline hydrochloride remained in the system (in the filtrate from the sampling) at the end of the adsorption of the mixture in a dark environment.
The types and the amounts of the ultrathin flaky metal hydroxides in each set of simulation experiments, the apparent reaction rate constant of the photocatalytic degradation reaction and the like are shown in table 1.
The method for quantifying the ultrathin flaky metal hydroxide comprises the following steps:
(i) weighing wet samples of the same kind of ultrathin sheet metal hydroxides with different masses, and recording the wet samples as wet weights;
(ii) drying each wet sample under the same condition to constant weight, and recording the mass of each dried sample as the dry weight;
(iii) and drawing a relation curve of the wet weight and the dry weight by taking the dry weight as an ordinate and the wet weight as an abscissa, and taking the relation curve as a standard curve.
In the above simulation experiment, the wet sample of ultrathin sheet metal hydroxide was used directly, and the corresponding dry weight was calculated from the standard curve corresponding to ultrathin sheet metal hydroxide.
Wherein, the relationship curves of the wet weight and the dry weight of the ultrathin flaky metal hydroxide of the examples 1 to 4 are respectively as follows:
x is the wet sample weight and y is the dry sample weight;
example 1: Zn-Ti: y is 0.0929x +0.0006
Example 2: Ni-Ti: 0.0822x-0.0033
Example 3: Co-Ti: y is 0.1367x-0.0043
Example 4: Co-Al: y 0.1526 x-0.0082.
Table 1 information of different simulation experiments
Wherein the k value is an apparent reaction rate constant of the photocatalytic degradation reaction and is a slope value of a pseudo-first order kinetic fitting curve of the photocatalytic degradation reaction. Because the catalytic activity is related to the concentration of the residual tetracycline hydrochloride in the system, when the performance is extremely strong, the concentration of the tetracycline hydrochloride is reduced too fast, and the degradation rate of the tetracycline hydrochloride cannot be accurately judged, the residual tetracycline hydrochloride in the system is controlled to be 10-40 mg/L at the end of the reaction by regulating the dosage of the ultrathin flaky metal hydroxide, and the accuracy of the determination of the degradation behavior rule is ensured.
FIG. 2 is a transmission electron micrograph of the ultrathin flaky metal hydroxide prepared in example 4 of the present invention. The irregular ultra-thin flake metal hydroxides obtained in examples 1 and 2 were prepared. The irregular ultra-thin sheet-like structure formed in example 1 may be one of the factors that may make it have strong degradation performance.
Fig. 3 is a pseudo first order kinetic fitting curve of the catalytic degradation reaction corresponding to simulation experiments 1#, 2#, and 3 #.
FIG. 4 is a UV spectrum of tetracycline hydrochloride concentration change at different times in the 3# simulation experiment.
From the above, the ultrathin flaky metal hydroxide prepared in the embodiment 1 of the present invention can effectively degrade tetracycline hydrochloride, and has high reaction activity; the ultrathin flaky metal hydroxide of example 2 can effectively degrade tetracycline hydrochloride, but cannot be further degraded when the concentration of tetracycline hydrochloride solution is still at a higher level; the ultra-thin flake metal hydroxide of the embodiment 3 has strong adsorbability, but the tetracycline hydrochloride solution has little change in concentration and has slow degradation speed on tetracycline hydrochloride; the ultra-thin flake metal hydroxide of example 4 has strong adsorbability but has little degradation property to tetracycline hydrochloride, and the tetracycline hydrochloride concentration rises after the completion of the photoreaction, which is caused by the shedding of the tetracycline hydrochloride adsorbed thereon.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The application of the ultrathin sheet metal hydroxide in the degradation of antibiotics is characterized by comprising the following steps:
(a) mixing the water dispersion of the ultrathin sheet metal hydroxide with an antibiotic solution, and carrying out mixed adsorption in a dark environment;
(b) and (3) placing the mixed and adsorbed system under simulated illumination for reaction, sampling at regular time and determining the ultraviolet absorption value.
2. The use according to claim 1, further comprising: the time t of the simulated illumination is taken as an abscissa, -In (C/C)0) As an ordinate, -In (C/C) is plotted0) The slope of a relation curve with t is taken as an apparent reaction rate constant of the photocatalytic degradation reaction; c is the concentration of residual antibiotic corresponding to the simulated illumination time t, C0The concentration of the corresponding residual antibiotics at the end of the mixed adsorption in a dark environment;
preferably, the method for timing sampling comprises: sampling once every 10-15 min, filtering the sample, and collecting filtrate.
3. Use according to claim 1, wherein the simulated illumination is visible light;
preferably, the intensity of the simulated illumination is 4500-5000 mW cm–2。
4. The use according to claim 1, wherein the time of mixed adsorption in a dark environment is 30-40 min;
preferably, the temperature of the system in a dark environment is 25 +/-2 ℃; the temperature of the system under simulated illumination was 25 + -2 deg.C.
5. The use according to claim 1, wherein in step (a), the concentration of the antibiotic solution is 10-100 mg/L.
6. The use according to claim 1, wherein the amount of the ultrathin flaky metal hydroxide in the system is 0.2 to 1.5g/L in terms of a wet sample.
7. Use according to claim 6, characterized in that the method of quantification of ultrathin flaky metal hydroxide comprises:
(i) weighing the same flaky metal hydroxide wet samples with different masses, and recording the wet samples as wet weights;
(ii) drying each wet sample under the same condition to constant weight, and recording the mass of each dried sample as the dry weight;
(iii) and drawing a relation curve of the wet weight and the dry weight by taking the dry weight as an ordinate and the wet weight as an abscissa, and taking the relation curve as a standard curve.
8. The use according to claim 1, wherein the antibiotic is an agricultural antibiotic;
preferably, the agricultural antibiotic is a tetracycline family antibiotic;
preferably, the antibiotic is tetracycline hydrochloride.
9. The method of claim 1The application is characterized in that the preparation method of the ultrathin flake metal hydroxide comprises the following steps: mixing and reacting aqueous solution containing metal ions and ammonia water solution under high-speed stirring, and collecting solid; wherein the metal ion comprises Zn2+、Ti4+、Ni2+、Fe3+、Mg2+、Cu2+、Co2+And Al3+Two or three of them.
10. The use according to claim 9, wherein the molar ratio of the metal ions in the aqueous solution containing metal ions at high valence to the metal ions at low valence is 1: 2.5 to 3.5;
preferably, in the aqueous solution containing metal ions, the concentration of the metal ions in a high valence state is 35-40 mmol/L;
preferably, the mass fraction of the ammonia water solution is 2-3%;
preferably, the volume ratio of the aqueous solution containing metal ions to the aqueous ammonia solution is 1: 1 (0.8 to 1.2).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370374A (en) * | 2014-09-06 | 2015-02-25 | 湘潭大学 | Method for denitrogenation and phosphorus-removal of town sewage through efficient immobilized algae bacterial symbiosis system |
| CN106466605A (en) * | 2016-08-03 | 2017-03-01 | 广西大学 | A kind of Fe3O4@SiO2The preparation method of@ZnO magnetic nanometer photocatalyst |
| CN108855099A (en) * | 2018-07-20 | 2018-11-23 | 常州大学 | A kind of preparation method and its photochemical catalyst of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst |
| CN113231096A (en) * | 2021-05-19 | 2021-08-10 | 湘潭大学 | g-C3N4Metal hydroxide composite photocatalyst and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370374A (en) * | 2014-09-06 | 2015-02-25 | 湘潭大学 | Method for denitrogenation and phosphorus-removal of town sewage through efficient immobilized algae bacterial symbiosis system |
| CN106466605A (en) * | 2016-08-03 | 2017-03-01 | 广西大学 | A kind of Fe3O4@SiO2The preparation method of@ZnO magnetic nanometer photocatalyst |
| CN108855099A (en) * | 2018-07-20 | 2018-11-23 | 常州大学 | A kind of preparation method and its photochemical catalyst of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst |
| CN113231096A (en) * | 2021-05-19 | 2021-08-10 | 湘潭大学 | g-C3N4Metal hydroxide composite photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周浩 等: ""Mg-M(Al,Fe)层状双氢氧化物光催化降解环丙沙星试验研究"" * |
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