CN113979509B - 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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- CN113979509B CN113979509B CN202111304501.5A CN202111304501A CN113979509B CN 113979509 B CN113979509 B CN 113979509B CN 202111304501 A CN202111304501 A CN 202111304501A CN 113979509 B CN113979509 B CN 113979509B
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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
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 28
- 230000015556 catabolic process Effects 0.000 title claims abstract description 26
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 17
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 30
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 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 25
- 238000005286 illumination Methods 0.000 claims abstract description 25
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 238000005070 sampling Methods 0.000 claims abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 11
- 230000031700 light absorption Effects 0.000 claims abstract description 9
- 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 53
- 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 16
- 238000001035 drying Methods 0.000 claims description 10
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000010936 titanium Substances 0.000 description 19
- 239000011701 zinc Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004088 simulation Methods 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000007146 photocatalysis Methods 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000007674 genetic toxicity Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000007789 sealing Methods 0.000 description 1
- 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
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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 degradation of antibiotics. The application of the ultrathin sheet metal hydroxide in the degradation of antibiotics comprises the following steps: (a) Mixing the ultrathin sheet metal hydroxide aqueous dispersion with an antibiotic solution, and mixing and adsorbing in a dark environment; (b) And (3) placing the mixed adsorption system under simulated illumination for reaction, sampling at regular time and measuring the ultraviolet light absorption value. The invention uses the ultrathin sheet metal hydroxide in the degradation of antibiotics, has simple experimental method, high accuracy, excellent photocatalytic degradation performance on antibiotics such as tetracycline hydrochloride, low antibiotic residue after the reaction is finished, and quick degradation rate; the method can be used for simulating photocatalytic degradation of antibiotics, researching degradation behavior rules of the antibiotics, preventing and controlling environmental pollution of the antibiotics according to the rules, 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 degradation of antibiotics.
Background
With the rapid development of the pharmaceutical industry, the problem of water pollution is increasingly serious, and the life of human beings is adversely affected. The wastewater containing antibiotic medicines has genetic toxicity and can also lead to antibiotic resistance. Traditional treatments such as adsorption, membrane filtration, and biological treatments have been used in recent years to eliminate antibiotic compounds. However, these treatments are inefficient due to secondary pollution caused by adsorption and membrane filtration. Meanwhile, since antibiotic compounds are toxic and difficult to degrade, biological treatment is not suitable. Therefore, there is an urgent need to develop a new technology for eliminating antibiotic compounds in the waste water of the pharmaceutical industry. In contrast, photocatalysis has received much attention because of its environmental friendliness. In particular, in the photocatalysis process, the photo-generated charges with oxidation and reduction capability are utilized to degrade pollutants, so that secondary pollution is not caused. Therefore, the development of an effective photocatalyst is critical to pharmaceutical wastewater treatment.
Photochemical degradation of pesticides is one of the main modes of degradation of the pesticide environment. At present, the principle of the photocatalysis technology is mainly explained by solid semiconductor energy band theory. In solid band theory, a Conduction Band (CB) without high energy of electrons and a Valence Band (VB) with low energy of electrons form an electron band of a semiconductor, and a forbidden band exists between the conduction band and the valence band, and the value Eg of the forbidden band depends on the difference between the lowest value of the conduction band and the highest value of the valence band. When solar photons (hv. Gtoreq.eg.) with enough energy are absorbed by the semiconductor, electrons in the valence band are excited to the conduction band, generating photogenerated electrons, and simultaneously generating photogenerated holes in the valence band. The photo-generated holes have strong oxidizing capability and the photo-generated electrons have strong reducing capability, so that the photo-generated holes can migrate to different positions on the surface of the semiconductor and generate oxidation-reduction reaction with pollutants adsorbed on the surface, thereby driving chemical reaction to be carried out and completing conversion from solar energy to chemical energy.
However, the existing catalysts for antibiotic degradation have few types, complex preparation process, high cost and low photocatalytic activity.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide the application of ultrathin sheet metal hydroxide in antibiotic degradation.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the application of the ultrathin sheet metal hydroxide in the degradation of antibiotics comprises the following steps:
(a) Mixing the ultrathin sheet metal hydroxide aqueous dispersion with an antibiotic solution, and mixing and adsorbing in a dark environment;
(b) And (3) placing the mixed adsorption system under simulated illumination for reaction, sampling at regular time and measuring the ultraviolet light absorption value.
In a specific embodiment of the present invention, further comprising: taking the time t of the simulated illumination as the abscissa, -In (C/C) 0 ) On the ordinate, draw-In (C/C 0 ) A relation curve with t, wherein the slope is used as an apparent reaction rate constant of the photocatalytic degradation reaction; c is the concentration of residual antibiotics corresponding to the simulated illumination time t, C 0 The concentration of the residual antibiotics corresponding to the end of the mixed adsorption in the dark environment.
In a specific embodiment of the present invention, further comprising: and determining the content of the residual antibiotics by comparing the ultraviolet light absorption value with a standard curve of the content of the antibiotics.
In a specific embodiment of the present invention, the method for timing sampling includes: sampling every 10-15 min, filtering the sample, and collecting filtrate. Further, the number of the timing samples is 6-8, and the total duration of the test is preferably 1.5-2 h.
In a specific embodiment of the present invention, the simulated illumination is visible light. Further, the intensity of the simulated illumination is 4500-5000 mW.cm –2 。
In a specific embodiment of the present invention, the time of the mixed adsorption in the dark environment is 30 to 40 minutes.
In a specific embodiment of the present invention, in step (a), the concentration of the antibiotic solution is 10 to 100mg/L.
In a specific embodiment of the present invention, the amount of the ultrathin sheet metal hydroxide used in the system is 0.2 to 1.5g/L in terms of wet sample.
In a specific embodiment of the present invention, the method for quantifying an ultrathin sheet metal hydroxide comprises:
(i) Weighing wet samples of the same sheet metal hydroxide with different masses, and recording the wet samples as wet weights;
(ii) Drying each wet sample to constant weight under the same condition, and recording the mass of each dried sample as dry weight;
(iii) And drawing a relation curve of wet weight and dry weight by taking dry weight as an ordinate and wet weight as an abscissa, and taking the relation curve as a standard curve.
In a specific embodiment of the invention, the antibiotic is an agricultural antibiotic. Preferably, the antibiotic is a tetracycline antibiotic. Further, the antibiotic is tetracycline hydrochloride.
In a specific embodiment of the present invention, the method for preparing an ultrathin sheet metal hydroxide comprises: mixing the aqueous solution containing metal ions with an ammonia water solution under high-speed stirring for reaction, and collecting solids; wherein the metal ion comprises Zn 2+ 、Ti 4+ 、Ni 2+ 、Fe 3+ 、Mg 2+ 、Cu 2+ 、Co 2+ And Al 3+ Two or three of the above. Further, the metal ion includes Zn 2 + And Ti is 4+ 。
The existing LDH preparation is mainly synthesized by a urea method, the synthesis method is relatively complex, and the synthesized LDH sheets are thicker in accumulation. The synthesized LDH sheets are hardly accumulated, can reach the nanometer level, and have simpler operation and mild conditions.
In a specific embodiment of the present invention, the molar ratio of the metal ion in the higher valence state to the metal ion in the lower valence state in the metal ion-containing aqueous solution is 1: (2.5 to 3.5).
The coprecipitation method of the invention prepares ultrathin sheet metal hydroxide with higher selectivity to cations when the metal ions comprise Ti 4+ When the molar ratio is regulated within the range, LDH nanosheets can be effectively formed.
In a specific embodiment of the present invention, the concentration of the metal ion in the higher valence state in the aqueous solution containing metal ions is 35 to 40mmol/L, such as 37.5mmol/L.
In the specific embodiment of the invention, the mass fraction of the ammonia water solution is 2% -3%.
In a specific embodiment of the present invention, the volume ratio of the metal ion-containing aqueous solution to the aqueous ammonia solution is 1: (0.8 to 1.2).
In a specific embodiment of the present invention, the high speed stirring has a rotational speed of 1000 to 1600rpm.
In a specific embodiment of the present invention, the mixing reaction under high-speed stirring includes: and simultaneously dropwise adding the aqueous solution containing metal ions and the ammonia water solution into the high-speed stirring system, and continuously stirring at a high speed for 10-30 min after the dropwise adding is finished.
In a specific embodiment of the present invention, the collecting solids comprises: and (3) centrifugally separating the materials after the mixed reaction, and washing the solid product with deionized water for 3-5 times.
In a specific embodiment of the invention, the solid is kept wet. To prevent the LDH from piling up after drying, resulting in reduced performance.
Compared with the prior art, the invention has the beneficial effects that:
the ultrathin sheet metal hydroxide is used for degrading antibiotics, has excellent photocatalytic degradation performance on the antibiotics such as tetracycline hydrochloride, has higher reactivity, can be used for simulating photocatalytic degradation of the antibiotics, researching the degradation behavior rule of the antibiotics, preventing and controlling environmental pollution of the antibiotics according to the rule, 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 that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the relationship between 355nm ultraviolet absorbance and the content of tetracycline hydrochloride in the present invention;
FIG. 2 is a transmission electron microscope image of an ultrathin sheet metal hydroxide prepared in example 4 of the invention;
FIG. 3 is a pseudo first order kinetic fitting curve of catalytic degradation reactions corresponding to simulation experiments of # 1, # 2 and # 3 of the present invention;
FIG. 4 is a graph of ultraviolet light spectrum of tetracycline hydrochloride concentration variation corresponding to different times in the 3# simulation experiment of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The application of the ultrathin sheet metal hydroxide in the degradation of antibiotics comprises the following steps:
(a) Mixing the ultrathin sheet metal hydroxide aqueous dispersion with an antibiotic solution, and mixing and adsorbing in a dark environment;
(b) And (3) placing the mixed adsorption system under simulated illumination for reaction, sampling at regular time and measuring the ultraviolet light absorption value.
In a specific embodiment of the present invention, further comprising: taking the time t of the simulated illumination as the abscissa, -In (C/C) 0 ) On the ordinate, draw-In (C/C 0 ) A relation curve between the slope and t is used as an apparent reaction rate constant of photocatalytic degradation reaction, namely degradation rate; c is the concentration of residual antibiotics corresponding to the simulated illumination time t, C 0 The concentration of the residual antibiotics corresponding to the end of the mixed adsorption in the dark environment.
In a specific embodiment of the present invention, further comprising: and determining the content of the residual antibiotics by comparing the ultraviolet light absorption value with a standard curve of the content of the antibiotics. For example, using tetracycline hydrochloride, a standard curve was drawn with UV absorbance at 355 nm.
In a specific embodiment of the present invention, the method for timing sampling includes: sampling every 10-15 min, filtering the sample, and collecting filtrate. Further, the number of the timing samples is 6 to 8, preferably 6. The total duration of the test is 1.5-2 h.
In a specific embodiment of the present invention, the simulated illumination is visible light. Further, the intensity of the simulated illumination is 4500-5000 mW.cm –2 。
The intensity of the simulated illumination may be 4500mW cm, as in various embodiments –2 、4600mW·cm –2 、4700mW·cm –2 、4800mW·cm –2 、4900mW·cm –2 、5000mW·cm –2 Etc.
In actual operation, under simulated illumination, the system is kept at the temperature through external regulation and control, and the temperature is not influenced by illumination to rise.
In a specific embodiment of the invention, the temperature of the system in a dark environment is 25+ -2deg.C; the temperature of the system under simulated light was 25±2℃.
In a specific embodiment of the present invention, the time of the mixed adsorption in the dark environment is 30 to 40 minutes. Further, the mixed adsorption is performed under stirring.
In actual operation, sampling can be carried out every 10-15 min, filtering and collecting filtrate through a 0.22 mu m aperture filter membrane, measuring an ultraviolet light absorption value, when the ultraviolet light absorption value is basically unchanged, indicating that the absorption is sufficient in a dark environment, ending the dark reaction, and carrying out subsequent simulated illumination treatment.
In a specific embodiment of the present invention, in step (a), the concentration of the antibiotic solution is 10 to 100mg/L, preferably 40 to 60mg/L.
In a specific embodiment of the present invention, the ultra-thin sheet metal hydroxide is used in an amount of 0.2 to 1.5g/L, preferably 0.2 to 0.4g/L, based on the wet sample.
Because the catalytic activity is related to the concentration of the residual antibiotics in the system, the concentration of the antibiotics can be reduced too quickly when the performance is extremely strong, and the degradation rate cannot be accurately judged, the residual antibiotics in the system at the end of the reaction can be controlled to be 10-40 mg/L, preferably 15-35 mg/L by regulating and controlling the dosage of the ultrathin sheet metal hydroxide, so that the accuracy of determining the degradation behavior rule is ensured.
In a specific embodiment of the present invention, the method for quantifying an ultrathin sheet metal hydroxide comprises:
(i) Weighing wet samples of the same sheet metal hydroxide with different masses, and recording the wet samples as wet weights;
(ii) Drying each wet sample to constant weight under the same condition, and recording the mass of each dried sample as dry weight;
(iii) And drawing a relation curve of wet weight and dry weight by taking dry weight as an ordinate and 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 when the ultrathin sheet metal hydroxide with a certain wet weight is pre-taken for accurate sampling, the corresponding dry weight can be calculated through a standard curve, and the ultrathin sheet metal hydroxide wet sample is directly sampled, so that the comparison analysis is convenient.
In a specific embodiment of the invention, the drying temperature is 60+/-5 ℃ and the drying time is 48-52 hours.
In practice, the sample was considered to be thoroughly dried to constant weight when the mass was no longer changed after drying at the above drying temperature for 48 hours.
In a specific embodiment of the invention, the antibiotic comprises a tetracycline antibiotic. Further, the antibiotic is tetracycline hydrochloride.
In a specific embodiment of the present invention, the method for preparing an ultrathin sheet metal hydroxide comprises: mixing the aqueous solution containing metal ions with an ammonia water solution under high-speed stirring for reaction, and collecting solids; wherein the metal ion comprises Zn 2+ 、Ti 4+ 、Ni 2+ 、Fe 3+ 、Mg 2+ 、Cu 2+ 、Co 2+ And Al 3+ Two or three of the above.
In a specific embodiment of the present invention, the metal ion comprises Zn 2+ And Ti is 4+ 、Ni 2+ And Fe (Fe) 3+ 、Co 2+ And Ti is 4 + 、Co 2+ And Al 3+ 、Mg 2+ And Al 3+ 、Ni 2+ And Ti is 4+ Or Mg (Mg) 2+ 、Cu 2+ And Al 3+ Is combined with the combination of the above. Further, the metal ion includes Zn 2+ And Ti is 4+ 。
The existing LDH preparation is mainly synthesized by a urea method, the synthesis method is relatively complex, and the synthesized LDH sheets are thicker in accumulation. The synthesized LDH sheets are hardly accumulated, can reach the nanometer level, and have simpler operation and mild conditions.
In practice, the metal ions are derived from soluble metal salts, such as nitrate, chloride salts, etc. of the metal ions.
In a specific embodiment of the present invention, the molar ratio of the metal ion in a higher valence state to the metal ion in a lower valence state in the metal ion-containing aqueous solution is 1: (2.5 to 3.5), preferably 1:3.
In the aqueous solution containing metal ions, as in various embodiments, metal ions of a higher valence state, such as Ti 4+ Or Al 3+ With metal ions Co of low valence state 2+ 、Zn 2+ Or Ni 2+ The molar ratio of (3) may 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 prepares ultrathin sheet metal hydroxide with higher selectivity to cations when the metal ions comprise Ti 4+ When the molar ratio is regulated within the range, LDH nanosheets can be effectively formed.
In a specific embodiment of the present invention, the concentration of the metal ion in the higher valence state in the aqueous solution containing metal ions is 35 to 40mmol/L, such as 37.5mmol/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, decarbonized deionized water is used as a solvent for the aqueous solution containing metal ions and the aqueous ammonia solution.
In actual operation, the preparation of the ammonia solution comprises the following steps: and diluting ammonia water to a preset concentration by adopting deionized water or decarbonized deionized water. The ammonia water is commercial strong ammonia water, and the mass fraction is 25% -28%.
In the specific embodiment of the invention, the mass fraction of the ammonia water solution is 2% -3%.
In a specific embodiment of the present invention, the volume ratio of the metal ion-containing aqueous solution to the aqueous ammonia solution is 1: (0.8 to 1.2).
As in the various embodiments, the volume ratio of the metal ion-containing aqueous solution to the aqueous ammonia solution may be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, etc.
In a specific embodiment of the present invention, the high speed stirring has a rotational speed of 1000 to 1600rpm.
In a specific embodiment of the present invention, the mixing reaction under high-speed stirring includes: and simultaneously dropwise adding the aqueous solution containing metal ions and the ammonia water solution into the high-speed stirring system, and continuously stirring at a high speed for 10-30 min after the dropwise adding is finished.
In a specific embodiment of the present invention, after the dripping is completed, stirring is continued for 15 to 20 minutes at a high speed.
In a specific embodiment of the present invention, the dropping speed is 20 to 30. Mu.L/s.
In a specific embodiment of the present invention, the collecting solids comprises: and (3) centrifugally separating 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 decarbonized deionized water.
In a specific embodiment of the invention, the rotational speed of the centrifugal separation is 4000.+ -.500 rpm, and the time of the centrifugal separation is 5-10 min.
In a specific embodiment of the invention, the solid is kept wet. To prevent the LDH from piling up after drying, resulting in reduced performance.
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
The embodiment provides a preparation method of ultrathin sheet metal hydroxide, which comprises the following steps:
(1) According to metal ion Zn 2+ With Ti 4+ The molar ratio of zinc nitrate and titanium tetrachloride is respectively weighed according to the ratio of 3:1, and the zinc nitrate and titanium tetrachloride are dissolved in 200mL decarburized deionized water to prepare Zn 2+ With Ti 4+ Aqueous solutions containing metal ions at concentrations of 112.5mmol/L and 37.5mmol/L, respectively; the commercial 25% -28% ammonia water and decarbonized deionized water are uniformly mixed according to the volume ratio of 1:9 to obtain 200mL ammonia water solution.
(2) Simultaneously dropwise adding the aqueous solution containing metal ions and the ammonia water solution prepared in the step (1) into a three-neck flask with a high-speed stirring magnet, wherein the dropwise adding speed is 25 mu L/s; after the dripping is finished, stirring for 15min at a stirring speed of 1000-1600 rpm, then centrifugally separating for 5min at 4000rpm, pouring supernatant, centrifugally washing the separated solid product with decarburized deionized water for 5 times, and obtaining the ultrathin sheet metal hydroxide wet sample at a centrifugal speed of 4000rpm for 5 min. The wet sample was stored in a centrifuge tube and kept wet.
Example 2
This example is different from the method for producing an ultrathin sheet metal hydroxide of example 1 only in that the aqueous solution containing metal ions is different; in this example, the preparation of the metal ion-containing aqueous solution includes: according to metal ion Ni 2+ With Ti 4+ The molar ratio of nickel nitrate and titanium tetrachloride is respectively weighed according to the ratio of 3:1, and the nickel nitrate and titanium tetrachloride are dissolved in 200mL of decarbonized deionized water to prepare Ni 2+ With Ti 4+ Aqueous solutions containing metal ions at concentrations of 112.5mmol/L and 37.5mmol/L, respectively.
Example 3
This example is different from the method for producing an ultrathin sheet metal hydroxide of example 1 only in that the aqueous solution containing metal ions is different; in this example, the preparation of the metal ion-containing aqueous solution includes: according to the goldIon Co of genus 2+ With Ti 4+ Cobalt nitrate and titanium tetrachloride are respectively weighed according to the mol ratio of 3:1 and dissolved in 200mL decarburized deionized water to prepare Co 2+ With Ti 4+ Aqueous solutions containing metal ions at concentrations of 112.5mmol/L and 37.5mmol/L, respectively.
Example 4
This example is different from the method for producing an ultrathin sheet metal hydroxide of example 1 only in that the aqueous solution containing metal ions is different; in this example, the preparation of the metal ion-containing aqueous solution includes: according to metal ion Co 2+ With Al 3+ The molar ratio of cobalt nitrate and aluminum nitrate is respectively weighed according to the ratio of 3:1, and the cobalt nitrate and the aluminum nitrate are dissolved in 200mL decarburized deionized water to prepare Co 2+ With Al 3+ Aqueous solutions containing metal ions at concentrations of 112.5mmol/L and 37.5mmol/L, respectively.
Example 5
The embodiment provides a method for catalytic degradation of antibiotics under simulated illumination, comprising the following steps:
(a) Adding the ultrathin sheet metal hydroxide wet sample into 50mL of deionized water, and performing ultrasonic dispersion to obtain ultrathin sheet metal hydroxide aqueous dispersion; preparing 100mg/L tetracycline hydrochloride aqueous solution. Mixing the aqueous dispersion with 50mL of 100mg/L tetracycline hydrochloride aqueous solution, stirring at room temperature under dark environment for 30min (3 mL of sample is taken every 15min, filtrate is collected through a 0.22 mu m aperture filter membrane, and ultraviolet absorption value detection is carried out), and ending dark reaction.
(b) The system with dark reaction finished in the step (a) is placed under visible light without far ultraviolet and infrared, and the light intensity is 4700mW cm –2 Meanwhile, the temperature of the system is kept unchanged (room temperature), 3mL of sample is taken every 15min and filtered through a filter membrane with the aperture of 0.22 mu m, the ultraviolet absorption value is detected, and the total of 6 sampling points is taken for total illumination reaction for 90min.
(c) Determining the corresponding content of the sample at different simulated illumination time according to a relation standard curve of the ultraviolet light absorption value and the tetracycline hydrochloride content as shown in figure 1; takes the time t of the simulated illumination as the abscissa, -In (C/C) 0 ) On the ordinate, draw-In (C/C 0 ) The slope of the curve as a function of t is used as the apparent reaction rate constant for the photocatalytic degradation reaction. Wherein C is the concentration of tetracycline hydrochloride remained in the system (in the sampled filtrate) corresponding to the simulated illumination time t (min), C 0 The concentration of tetracycline hydrochloride was the corresponding system residue (in the sampled filtrate) at the end of the mixed adsorption in dark environment.
The types and amounts of the ultrathin sheet metal hydroxides in each group of simulation experiments, apparent reaction rate constants of photocatalytic degradation reactions, and the like are shown in Table 1.
The method for quantifying the ultrathin sheet metal hydroxide comprises the following steps:
(i) Weighing the same ultrathin sheet metal hydroxide wet samples with different masses, and recording the wet samples as wet weights;
(ii) Drying each wet sample to constant weight under the same condition, and recording the mass of each dried sample as dry weight;
(iii) And drawing a relation curve of wet weight and dry weight by taking dry weight as an ordinate and wet weight as an abscissa, and taking the relation curve as a standard curve.
In the simulation experiment, the ultrathin sheet metal hydroxide wet sample is directly used, and the corresponding dry weight is calculated according to a standard curve corresponding to the ultrathin sheet metal hydroxide.
Wherein, the relationship curves of the wet weight and the dry weight of the ultrathin sheet metal hydroxides of examples 1-4 are respectively as follows:
x is the wet sample weight and y is the dry sample weight;
example 1: zn-Ti: y=0.0929x+0.0006
Example 2: ni-Ti: y= 0.0822x-0.0033
Example 3: co-Ti: y= 0.1367x-0.0043
Example 4: co-Al: y= 0.1526x-0.0082.
TABLE 1 information on different simulation experiments
Wherein, the k value is the apparent reaction rate constant of the photocatalytic degradation reaction, which is the pseudo first order dynamics fitting curve slope value of the photocatalytic degradation reaction. As the catalytic activity is related to the concentration of the residual tetracycline hydrochloride in the system, the concentration of the tetracycline hydrochloride can be reduced too fast when the performance is extremely strong, and the degradation rate cannot be accurately judged, the residual tetracycline hydrochloride in the system is controlled to be 10-40 mg/L when the reaction is finished by regulating and controlling the dosage of the ultrathin sheet metal hydroxide, so that the accuracy of determining the degradation behavior rule is ensured.
FIG. 2 is a transmission electron microscopic image of an ultrathin sheet metal hydroxide prepared in example 4 of the invention. Irregular ultrathin sheet metal hydroxides prepared in example 1 and example 2. Whereas the irregular ultrathin sheet structure formed in example 1 may be one of the factors that make it very degradable.
FIG. 3 is a pseudo first order kinetic fit curve of catalytic degradation reactions corresponding to simulation experiments # 1, # 2, and # 3.
FIG. 4 is a graph of ultraviolet light spectrum of tetracycline hydrochloride concentration variation corresponding to different times in the model 3.
From the above, the ultrathin sheet metal hydroxide prepared in the embodiment 1 of the invention can effectively degrade tetracycline hydrochloride, and has higher reactivity; the ultrathin sheet metal hydroxide of example 2 was effective in degrading tetracycline hydrochloride, but was not further degraded at higher levels of tetracycline hydrochloride solution; the ultrathin sheet metal hydroxide of the embodiment 3 has stronger adsorptivity, but the concentration of the tetracycline hydrochloride solution is not changed greatly, and the degradation speed of the tetracycline hydrochloride is slower; the ultrathin sheet metal hydroxide of example 4 had strong adsorptivity, but had little degradation property for tetracycline hydrochloride, and the tetracycline hydrochloride concentration increased after the end of the photoreaction, which was caused by the shedding of tetracycline hydrochloride adsorbed thereon.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The application of the ultrathin sheet metal hydroxide in the degradation of antibiotics is characterized by comprising the following steps:
(a) Mixing the ultrathin sheet metal hydroxide aqueous dispersion with an antibiotic solution, and mixing and adsorbing in a dark environment;
(b) Placing the mixed and adsorbed system under simulated illumination for reaction, sampling at regular time and measuring the ultraviolet light absorption value;
the antibiotic is tetracycline hydrochloride;
the preparation method of the ultrathin sheet metal hydroxide comprises the following steps: mixing the aqueous solution containing metal ions with an ammonia water solution under high-speed stirring for reaction, and collecting solids; wherein the metal ion comprises Zn 2+ And Ti is 4+ 、Ni 2+ And Ti is 4+ 、Co 2+ And Ti is 4+ Any combination mode of the two components;
in the aqueous solution containing metal ions, the molar ratio of the metal ions in a high valence state to the metal ions in a low valence state is 1: (2.5-3.5);
in the aqueous solution containing metal ions, the concentration of the metal ions in a high valence state is 35-40 mmol/L;
the mass fraction of the ammonia water solution is 2% -3%;
the volume ratio of the aqueous solution containing metal ions to the aqueous ammonia solution is 1: (0.8-1.2).
2. The use according to claim 1, further comprising: taking the time t of the simulated illumination as the abscissa, -In (C/C) 0 ) On the ordinate, draw-In (C/C 0 ) A relation curve with t, wherein the slope is used as an apparent reaction rate constant of the photocatalytic degradation reaction; c is the concentration of residual antibiotics corresponding to the simulated illumination time t, C 0 The concentration of the residual antibiotics corresponding to the end of the mixed adsorption in the dark environment.
3. The use of claim 1, wherein the method of timing sampling comprises: sampling every 10-15 min, filtering the sample, and collecting filtrate.
4. The use according to claim 1, wherein the simulated illumination is visible light;
the intensity of the simulated illumination is 4500-5000 mW cm –2 。
5. The use according to claim 1, wherein the time of the mixed adsorption in the dark environment is 30-40 min.
6. The use according to claim 1, wherein the temperature of the mixed adsorption in a dark environment is 25±2 ℃; the temperature of the system under simulated light was 25±2℃.
7. The use according to claim 1, wherein in step (a), the concentration of the antibiotic solution is 10-100 mg/L.
8. The use according to claim 1, wherein the ultra-thin sheet metal hydroxide is used in an amount of 0.2 to 1.5g/L in terms of wet sample.
9. The use according to claim 8, wherein the method for quantifying the ultrathin sheet metal hydroxide comprises:
(i) Weighing wet samples of the same sheet metal hydroxide with different masses, and recording the wet samples as wet weights;
(ii) Drying each wet sample to constant weight under the same condition, and recording the mass of each dried sample as dry weight;
(iii) And drawing a relation curve of wet weight and dry weight by taking dry weight as an ordinate and wet weight as an abscissa, and taking the relation curve as a standard curve.
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