CN116713014B - Co/Ti 3 C 2 T x Fenton-like catalyst and preparation method and application thereof - Google Patents
Co/Ti 3 C 2 T x Fenton-like catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN116713014B CN116713014B CN202310542126.0A CN202310542126A CN116713014B CN 116713014 B CN116713014 B CN 116713014B CN 202310542126 A CN202310542126 A CN 202310542126A CN 116713014 B CN116713014 B CN 116713014B
- Authority
- CN
- China
- Prior art keywords
- solution
- use according
- stirring
- teta
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 98
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 37
- 239000004098 Tetracycline Substances 0.000 claims description 17
- 229960002180 tetracycline Drugs 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- 229940079593 drug Drugs 0.000 claims description 10
- 239000003814 drug Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 206010059866 Drug resistance Diseases 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000002064 nanoplatelet Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 36
- 238000006731 degradation reaction Methods 0.000 abstract description 36
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 110
- 239000000243 solution Substances 0.000 description 28
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 229930101283 tetracycline Natural products 0.000 description 15
- 235000019364 tetracycline Nutrition 0.000 description 15
- 150000003522 tetracyclines Chemical class 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 229910001429 cobalt ion Inorganic materials 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000011529 RT qPCR Methods 0.000 description 2
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000003753 real-time PCR Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 238000012408 PCR amplification Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001083492 Trapa Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000013612 plasmid Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The invention discloses a Co/Ti 3 C 2 T x Fenton-like catalyst, preparation method and application thereof, co/Ti 3 C 2 T x The material is Co distributed in the flake Ti 3 C 2 T x The surface of the material. Co/Ti 3 C 2 T x The preparation method of the material comprises the following steps: ti is mixed with 3 AlC 2 Mixing lithium fluoride and hydrochloric acid to obtain a first solution, stirring the first solution for at least 12h, centrifuging to collect precipitate, washing to neutrality, and drying to obtain multilayer Ti 3 C 2 T x Multilayer Ti 3 C 2 T x Dispersing into glycol water solution to obtain second solution, and ultrasonically treating the second solution under nitrogen or inert gas for at least 0.5 hr to obtain ultrathin Ti 3 C 2 T x Dripping cobalt chloride solution into ultrathin Ti 3 C 2 T x Stirring the nano-sheet dispersion liquid, carrying out ultrasonic treatment in a nitrogen or inert gas environment, centrifugally collecting precipitate, washing and drying to obtain Co/Ti 3 C 2 T x Material, co/Ti obtained by the preparation method of the invention 3 C 2 T x The material has the advantages of high efficiency, energy conservation and environmental protection, the adsorption rate of the material to ARG can reach more than 3-log, and the degradation rate to ARG can reach 0.9min ‑1 And has good stability and environmental factor interference resistance.
Description
Technical Field
The invention belongs to the technical field of purification of drug-resistant gene polluted water, and in particular relates to a Co/Ti 3 C 2 T x Fenton-like catalyst and its preparation method and application are provided.
Background
Antibiotic Resistance Genes (ARGs) are fragments of genes encoding antibiotic resistance proteins that can migrate through various environmental mediators and amplify in host microorganisms, play a critical role in the formation of pathogenic superbacteria, and have been listed as an emerging contaminant. Some sewage treatment plants have become breeding sites and point sources for ARGs. However, conventional wastewater treatment techniques, such as chlorination and ultraviolet disinfection, are not effective in inactivating or mineralizing ARGs.
Advanced oxidation processes hold good promise for controlling ARGs pollution by generating various Reactive Oxygen Species (ROS) in situ. Among them, fenton-like advanced oxidation processes based on Peroxomonosulphate (PMS) are receiving attention because of their high efficiency, low cost and ease of operation. The single-atom catalyst with unique electronic properties and high atom utilization rate is applied to PMS activation degradation of organic pollutants difficult to degrade, and breaks through the limitation of heterogeneous catalysts in terms of dynamics and catalytic activity. However, due to the lower concentration of ARGs in the wastewater and the shorter ROS half-life, ROS utilization and ARGs removal are lower.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a Co/Ti 3 C 2 T x A material.
Another object of the present invention is to provide the Co/Ti composition 3 C 2 T x Preparation method of material, co/Ti 3 C 2 T x The material has dual reaction sites.
Another object of the present invention is to provide the Co/Ti composition 3 C 2 T x The material is used as Fenton-like catalyst for removing drug resistance genes in wastewater.
The aim of the invention is achieved by the following technical scheme.
Co/Ti 3 C 2 T x Material Co is distributed in flake Ti 3 C 2 T x The surface of the material.
In the technical proposal, the Co is smaller than Ti 3 C 2 T x 1.8wt% of the material, preferably Co is Ti 3 C 2 T x 0.4 to 0.5wt% or 1.3 to 1.4wt% of the material.
Co/Ti 3 C 2 T x The preparation method of the material comprises the following steps:
step 1, ti is mixed with 3 AlC 2 Mixing lithium fluoride and hydrochloric acid to obtain a first solution, stirring the first solution for at least 12h, centrifuging to collect precipitate, washing to neutrality, and drying to obtain multilayer Ti 3 C 2 T x Wherein Ti in the first solution 3 AlC 2 The concentration of lithium fluoride in the first solution is 30-70 g/L;
in the step 1, ultrapure water is used for the washing.
In the step 1, the concentration of the hydrochloric acid is 5 to 15M, preferably 9M.
In the step 1, the temperature of the stirring is 25 to 60 ℃, preferably 35 ℃.
In the step 1, the stirring time is 12 to 30 hours, preferably 24 hours.
Step 2, multilayer Ti 3 C 2 T x Dispersing into glycol water solution to obtain second solution, and ultrasonically treating the second solution under nitrogen or inert gas for at least 0.5 hr to obtain ultrathin Ti 3 C 2 T x A nanoplatelet dispersion, wherein the second solution comprises multiple layers of Ti 3 C 2 T x The concentration of (3) to (7) g/L;
in the step 2, the concentration of ethylene glycol in the ethylene glycol aqueous solution is 1-3M.
In the step 2, the time of the ultrasonic wave is 0.5 to 2 hours, preferably 1 hour.
In said step 2, the second solution is sonicated at 0-25 ℃, preferably 0 ℃.
Step 3, dripping cobalt chloride solution into the ultrathin Ti 3 C 2 T x Stirring the nano-sheet dispersion liquid, carrying out ultrasonic treatment in a nitrogen or inert gas environment, centrifugally collecting precipitate, washing and drying to obtain Co/Ti 3 C 2 T x The material comprises cobalt and ultrathin Ti in cobalt chloride solution in parts by weight 3 C 2 T x In the nano-sheet dispersionMultilayer Ti 3 C 2 T x The ratio of (1) is (0.005-0.02): 1.
in the step 3, the concentration of cobalt chloride in the cobalt chloride solution is 0.4-0.6M.
In the above technical scheme, the cobalt chloride solution is a mixture of cobalt chloride and ethylene glycol.
In the step 3, the stirring time is 20-40 min, and the stirring temperature is room temperature.
In the step 3, the temperature of the ultrasonic wave is 0 to 25 ℃, preferably 0 ℃, and the time of the ultrasonic wave is 0.5 to 2 hours, preferably 1 hour.
In the step 3, absolute ethanol and ultrapure water are used for the washing.
In the steps 1 and 3, the drying is freeze drying.
Co/Ti obtained by the preparation method 3 C 2 T x A material.
Co/Ti as described above 3 C 2 T x The material is used as Fenton-like catalyst for removing drug resistance genes in wastewater.
In the technical proposal, co/Ti 3 C 2 T x The material activates PMS to perform advanced oxidation to remove drug resistance genes in wastewater.
In the above technical scheme, the drug-resistant gene is a tetracycline resistance gene (tetA) and contains 214 base pairs in total.
In the above technical scheme, the Co/Ti 3 C 2 T x The addition amount of the materials is 50-250 mg/L, the temperature of the wastewater is 20-30 ℃, and the preferable temperature is 25 ℃.
In the technical scheme, the method for removing the drug resistance genes in the wastewater comprises the following steps: co/Ti addition to wastewater 3 C 2 T x The material is oscillated to reach adsorption equilibrium, PMS is added, and the material is oscillated to perform advanced oxidation reaction.
In the technical scheme, the concentration of PMS in the wastewater is 50-300 mg/L, preferably 200mg/L.
Co/Ti obtained by the preparation method of the invention 3 C 2 T x The material has the advantages of high efficiency, energy conservation and environmental protection, the adsorption capacity of the material to ARG can reach more than 3-log, and the degradation rate of the material to ARG can reach 0.9min -1 And has good stability and environmental factor interference resistance. Co/Ti 3 C 2 T x The rich Ti site on the material can coordinate with PO of ARG phosphate skeleton through Ti-O-P coordination 4 3- And by combining, the high-efficiency degradation of the drug-resistant gene is realized. Co/Ti 3 C 2 T x Co-O on materials 3 The site can activate PMS to form hydroxyl radical with surface bond, and degrade ARGs into inactive micromolecular organic matter and NO in situ 3 - . Co/Ti obtained by the preparation method of the invention 3 C 2 T x The material can still keep high-efficiency removal of drug-resistant genes in actual wastewater and different pH ranges, and Co/Ti 3 C 2 T x The leaching amount of cobalt ions of the material is lower than the standard requirement of water quality, no secondary pollution is caused, and the material has the characteristic of environmental friendliness.
Drawings
FIG. 1 is Co/Ti obtained by the preparation method of example 1 3 C 2 T x AFM of the material;
FIG. 2 is Co/Ti obtained by the preparation method in example 1 3 C 2 T x TEM (left) and HAADF-STEM (right) plots of the material;
FIG. 3 is Co/Ti as prepared in example 1 3 C 2 T x Material (upper curve) and comparative example 1 to obtain Ti 3 C 2 T x XRD of the material (lower curve);
FIG. 4 is Co/Ti as prepared in example 1 3 C 2 T x XPS (left) and XANES profile (right) of the material;
FIG. 5 is Co/Ti as prepared in example 1 3 C 2 T x Materials and comparative example 1 obtaining Ti 3 C 2 T x The material is respectively used as a catalyst to resist the degradation effect of the tetracycline resistance gene within 20min after PMS is added;
FIG. 6 shows the Co/Ti ratios obtained by the preparation of examples 1 to 4 3 C 2 T x Materials and comparative example 1 obtaining Ti 3 C 2 T x The material is respectively used as a catalyst to resist the adsorption quantity (left axis) and degradation rate (right axis) of the tetracycline resistance gene (tetA);
FIG. 7 is Co/Ti as prepared in example 1 3 C 2 T x The adsorption capacity (left axis) and degradation rate (right axis) of the material to tetA under different catalyst addition amounts;
FIG. 8 is Co/Ti as prepared in example 1 3 C 2 T x Adsorption capacity (left axis) and degradation rate (right axis) of the material to tetA under different pH conditions;
FIG. 9 is Co/Ti as prepared in example 1 3 C 2 T x The adsorption capacity (left axis) and degradation rate (right axis) of the material to tetA in different water bodies;
FIG. 10 is Co/Ti as prepared in example 1 3 C 2 T x Cobalt ion concentration of the material leaked during the PMS activation process;
FIG. 11 is Co/Ti as prepared in example 1 3 C 2 T x Cycling testing of the material against tetracycline resistance gene (tetA) degradation;
FIG. 12 is Co/Ti as prepared in example 1 3 C 2 T x Nitrate concentration in the system during the process of degrading the tetracycline resistance gene by the material.
Detailed Description
Ti 3 C 2 T x (T x Is a surface functional group) is used as a novel two-dimensional transition metal carbide, and is an ideal carrier of a single metal active site in PMS activation due to the large specific surface area, excellent conductivity, high reducing capability, hydrophilic surface and strong mechanical stability. Compared with other nonmetallic two-dimensional materials, ti 3 C 2 T x Ti ions on the surface are expected to form strong chelation with the phosphate main chain of ARGs, so that the high-efficiency adsorption of the ARGs is realized. Anchoring atomically dispersed Co to Ti 3 C 2 T x The construction of ARGs adsorption and PMS activation double reaction sites on the nanosheets is expected to effectively solve the problem of low ARGs removal rate.
The technical scheme of the invention is further described below with reference to specific embodiments.
The sources of the drugs involved in the examples below are as follows: ti (Ti) 3 AlC 2 (99%, jilin 11 technologies Co., ltd.), lithium fluoride (99%, allatin), hydrochloric acid (36%, peak), ethylene glycol (98%, microphone), cobalt chloride (99%, allatin).
The drug-resistant gene is anti-tetracycline drug-resistant gene (tetA) and contains 214 base pairs, and the method for obtaining the drug-resistant gene is shown in DOI:10.1016/j.cej.2016.10.107, and is summarized as follows: the plasmid extracted from the tetracycline-resistant bacteria (collected in the river mouth of the sea and added with tetracycline for screening in LB liquid medium) is subjected to PCR amplification to obtain tetA, which contains 214 base pairs in total, and has the sequence:
5′-GATTGCTACATCCTGCTTGCCTTCGCGACACGGGGATGGATGGCGTTCCCGATC ATGGTCCTGCTTGCTTCGGGTGGCATCGGAATGCCGGCGCTGCAAGCAATGTTGTC CAGGCAGGTGGATGAGGAACGTCAGGGGCAGCTGCAAGGCTCACTGGCGGCGCTC ACCAGCCTGACCTCGATCGTCGGACCCCTCCTCTTCACGGCGATCTATG-3′。
the types of instruments involved in the following examples are as follows: stirrer (type 85-1), water bath (type HH-1), freeze dryer (LGJ-10C), ultrasonic cleaner (KQ-300 DE), centrifuge (TDZ 4-WS/TDZ4 WS), refrigerated centrifuge (TGL-20M).
Examples 1 to 4
Co/Ti 3 C 2 T x The preparation method of the material comprises the following steps:
step 1, ti is mixed with 3 AlC 2 Mixing lithium fluoride and 9M hydrochloric acid (hydrochloric acid aqueous solution) to obtain a first solution, stirring the first solution in a water bath at 35deg.C for 24 hr, centrifuging to collect precipitate, washing the precipitate with ultrapure water to neutrality, and lyophilizing to obtain multilayer Ti 3 C 2 T x Wherein Ti in the first solution 3 AlC 2 The concentration of lithium fluoride in the first solution is 50g/L;
step 2, multilayer Ti 3 C 2 T x Dispersing into glycol water solution to obtain second solution, and performing ice bath ultrasonic treatment on the second solution at 0 ℃ for 1h under argon environment to obtain ultrathin Ti 3 C 2 T x Nanosheet dispersion, wherein the second solution comprises multiple layers of Ti 3 C 2 T x The concentration of the ethylene glycol in the ethylene glycol aqueous solution is 5g/L, and the concentration of the ethylene glycol in the ethylene glycol aqueous solution is 2M;
step 3, dropwise adding cobalt chloride solution into the ultrathin Ti 3 C 2 T x Stirring the nanosheet dispersion liquid at room temperature of 20-25 ℃ for 30min, carrying out ice bath ultrasound at 0 ℃ for 1h under an argon environment, centrifuging by a refrigerated centrifuge to collect precipitate (the temperature is 10 ℃ and the centrifuging time is 30 min), washing by sequentially adopting absolute ethyl alcohol and ultrapure water, and freeze-drying to obtain Co/Ti 3 C 2 T x The material comprises cobalt chloride solution which is a mixture of cobalt chloride and ethylene glycol, and cobalt and ultrathin Ti in the cobalt chloride solution in parts by weight 3 C 2 T x Multilayer Ti in nanosheet dispersion 3 C 2 T x The ratio of (2) is X, and the concentration of cobalt chloride in the cobalt chloride solution is 0.5M. X is shown in Table 1.
TABLE 1
| Examples | X | Numbering device |
| Example 1 | 0.01:1 | Co-1％/Ti 3 C 2 T x Catalyst |
| Example 2 | 0.005:1 | Co-0.5％/Ti 3 C 2 T x Catalyst |
| Example 3 | 0.015:1 | Co-1.5％/Ti 3 C 2 T x Catalyst |
| Example 4 | 0.02:1 | Co-2％/Ti 3 C 2 T x Catalyst |
Co/Ti prepared in examples 1-4 were tested with an inductively coupled plasma Mass Spectrometry 3 C 2 T x The cobalt content of the material was 0.45wt%, 0.86wt%, 1.35wt% and 1.78wt%, respectively.
Comparative example 1
Ti (titanium) 3 C 2 T x A method of preparing a material comprising: ultra-thin Ti 3 C 2 T x Stirring the nanosheet dispersion liquid at room temperature of 20-25 ℃ for 30min, carrying out ice bath ultrasound at 0 ℃ for 1h under an argon environment, centrifugally collecting precipitate (at 25 ℃ for 30 min) by a refrigerated centrifuge, washing with anhydrous ethanol and ultrapure water in sequence, and freeze-drying to obtain Ti 3 C 2 T x Material, wherein, ultra-thin Ti 3 C 2 T x Nanoplatelet dispersions with ultra-thin Ti in example 1 3 C 2 T x The nanosheet dispersion is the same.
AFM electron microscopy photograph as shown in FIG. 1 shows Co/Ti 3 C 2 T x The thickness of the material was 1.8nm.
TEM and HAADF-STEM electron micrographs of FIG. 2 show that Co/Ti can be observed 3 C 2 T x Two-dimensional nano-sheet structure of material, and atomically dispersed cobalt is loaded on Ti 3 C 2 T x The nanosheet surface was free of cobalt particles.
XRD pattern of FIG. 3 shows Co/Ti 3 C 2 T x Crystal structure of materialWith Ti 3 C 2 T x The materials are similar, and have no characteristic peak of Co, which further explains Co/Ti 3 C 2 T x Co nanoparticles were not present.
XPS and XANES Specifications of FIG. 4 Co/Ti 3 C 2 T x The valence state of Co in the material is +2 and +3.
Method for testing the effect of a catalyst against the degradation of a tetracycline resistance gene (tetA): adding tetA into ultrapure water to prepare the initial concentration of tetA to be 10 12 The preparation method comprises the steps of (1) adding a catalyst into a tetA aqueous solution with the temperature of 25 ℃ and the pH value of 6.6 through a test, oscillating for 30 minutes to reach adsorption balance to obtain a mixed solution, taking a certain amount of the mixed solution into a centrifuge tube, centrifuging to precipitate the catalyst, quantitatively analyzing tetA in supernatant by using a real-time quantitative PCR (qPCR) instrument to obtain a cycle threshold (Ct), converting according to a standard curve to obtain the gene copy number, and obtaining the difference between the gene copy number in the supernatant after adsorption balance and the initial gene copy number (12-log) as the adsorption amount of the catalyst to tetA. And (3) adding PMS after adsorption equilibrium, and oscillating the system to perform advanced oxidation reaction. Sampling every 5 minutes, quantitatively analyzing tetA in reaction liquid (uniformly mixed) by using a real-time quantitative PCR (qPCR) instrument to obtain a period threshold value, converting according to a standard curve to obtain a gene copy number, wherein the difference value between the gene copy number at the time t and the gene copy number at the initial time (12-log) is the degradation effect of the catalyst on the tetA, and performing first-order dynamics fitting on a degradation curve according to the degradation effect to obtain an apparent rate constant (k) which represents the degradation rate of the catalyst on the tetA. Wherein the catalyst addition amount is 200mg/L, and the catalyst is Co/Ti prepared by the examples 1-4 3 C 2 T x Materials and comparative example 1 obtaining Ti 3 C 2 T x One of the materials, PMS is added in an amount of 200mg/L.
As shown in FIG. 5, ti prepared in comparative example 1 was prepared at a time point of PMS addition after adsorption equilibrium of 0min 3 C 2 T x The material removed 0.5-log of tetA in 20min, co/Ti prepared in example 1 3 C 2 T x The material can remove 7.2-log tetA in 20 min.
As shown in FIG. 6, the adsorption amount of the catalyst to tetA is not substantially affected by the cobalt atom loading, and can reach an adsorption amount of 3-log or more. The degradation rate of the catalyst to tetA is affected by the cobalt content, when the cobalt content is below 1wt% (comparative example 1 and example 2), the degradation rate of tetA increases with increasing cobalt content, when the cobalt content exceeds 1wt% (example 3 and example 4), the degradation rate of tetA no longer increases, so Co/Ti at a cobalt content of 1wt% 3 C 2 T x The material is the optimal catalyst, and the apparent rate constant (k) of the material for tetA removal reaches 0.94min -1 。
Test example 1 preparation of Co/Ti 3 C 2 T x The adsorption capacity and degradation rate of the material to tetA under different catalyst addition amounts are basically the same as the method for testing the effect of the catalyst on the tetracycline resistance gene (tetA) degradation, except that the catalyst is prepared by using only example 1 3 C 2 T x The addition amount of the material and the catalyst is 50mg/L, 100mg/L, 150mg/L, 200mg/L and 250 mg/L. The test results are shown in fig. 7, and the catalyst addition amount affects the adsorption amount and degradation rate of tetA. When the catalyst addition amount was less than 200mg/L, co/Ti was prepared in example 1 as the catalyst addition amount was increased 3 C 2 T x The adsorption capacity and degradation rate of the material to tetA are both increased, and when the catalyst addition amount exceeds 200mg/L, co/Ti is prepared in example 1 3 C 2 T x The adsorption and degradation rate of the material to tetA were no longer increased, so 200mg/L was used for the preparation of Co/Ti according to example 1 3 C 2 T x Optimal addition of material.
Test example 1 preparation of Co/Ti 3 C 2 T x Adsorption capacity and degradation rate of the material to tetA at different pH values. The test method is substantially the same as the aforementioned "method for testing a catalyst for its effect against the degradation of a tetracycline resistance gene (tetA)" except that the pH of the aqueous tetA solution is adjusted to 5.5, 6.0, 6.6, 7.6 or 8.1 "before the catalyst is added. The test results are shown in FIG. 8, example 1 for Co/Ti production 3 C 2 T x The adsorption and degradation rates of the material to tetA in the pH range of 5.5-8.1 are both slowly reduced with the increase of pH, but example 1 prepared Co/Ti 3 C 2 T x The adsorption capacity of the material to tetA is still higher than 3-log, and the degradation rate to tetA is 0.8min -1 The pH value change of the water body does not obviously inhibit Co/Ti 3 C 2 T x Removal effect of material on tetA.
Test example 1 preparation of Co/Ti 3 C 2 T x The adsorption capacity and degradation rate of the material to tetA in three actual water bodies of river water, lake water and secondary effluent are basically the same as the method for testing the effect of the catalyst on resisting the degradation of the tetracycline resistance gene (tetA), the only difference is that the tetA is added into the actual water body, and the initial concentration of the tetA is configured to be 10 12 The actual water body of the cobies/mL tetA aqueous solution is ultrapure water, river water (sea river, tianjin), lake water (water chestnut lake of university of south China, tianjin) or secondary effluent discharged by sewage treatment plants (sewage treatment plants of university of south China, tianjin), and the catalyst is prepared Co/Ti according to the method of the embodiment 1 3 C 2 T x Materials. The test results are shown in FIG. 9, example 1 for Co/Ti production 3 C 2 T x The adsorption capacity and degradation rate of the material to tetA in three actual water bodies of river water, lake water and secondary effluent are slightly reduced, but the adsorption capacity to tetA is higher than 3-log, and the degradation rate to tetA is 0.6min -1 Above, therefore Co/Ti 3 C 2 T x The material has excellent removing effect on tetA in actual water body.
To test the amount of cobalt ions leaked from the catalyst during PMS activation, the Co/Ti preparation of example 1 of the present invention was examined 3 C 2 T x Leakage of cobalt ions during 20min PMS activation of the material. Specifically, co/Ti was prepared according to example 1 3 C 2 T x The material is added into a tetA aqueous solution (the preparation method is the same as the method for testing the degradation effect of a catalyst on a tetracycline resistance gene (tetA)), PMS is added, and the system is vibrated to perform advanced oxidation reaction. Preparation of Co/Ti by addition to example 1 3 C 2 T x The time point of the material was 0min, samples were taken every 5 min, and the Co ion concentration was measured with an inductively coupled plasma mass spectrometer. EXAMPLE 1 Co/Ti preparation 3 C 2 T x The material dosage is 200mg/L, the PMS dosage is 200mg/L, the temperature of the tetA aqueous solution is 25 ℃, and the pH value of the tetA aqueous solution before adding the catalyst is 6.6. The test results are shown in FIG. 10, example 1 for Co/Ti production 3 C 2 T x The highest concentration of cobalt ions leaked by the material in the PMS activating process is 0.2mg/L and is far lower than the allowable limit (1 mg/L) specified by the national standard of China (GB 25467-2010), thus Co/Ti 3 C 2 T x The cobalt ions leaked from the material in the PMS activating process can not cause secondary pollution.
To test catalyst reusability Co/Ti was prepared using example 1 3 C 2 T x The material was subjected to 5 times according to the method of testing the effect of the catalyst against the degradation of the tetracycline resistance gene (tetA). After each pass, co/Ti is recovered by filtration 3 C 2 T x The material was washed with absolute ethanol and ultra-pure water in an ultrasonic cleaner. The test results are shown in FIG. 11, co/Ti after 5 cycles 3 C 2 T x The degradation effect and adsorption capacity of the material on tetA are slightly reduced, but the adsorption capacity on tetA is still more than 2.8-log, and the degradation effect on tetA exceeds 5.2-log, which shows that the Co/Ti of the invention 3 C 2 T x Has excellent stability and reusability.
To test the degree of mineralization of the bases during degradation of tetA Co/Ti was prepared using example 1 3 C 2 T x Materials tested NO during the reaction 3 - Concentration of ions. Specifically, co/Ti was prepared according to example 1 3 C 2 T x The material was added to the aqueous tetA solution (the method of configuration was essentially the same as the "method of testing the effect of the catalyst on resistance to tetracycline resistance gene (tetA)" except that the initial concentration of tetA in the aqueous tetA solution was 10 13 cobies/mL "), PMS was added, and the system was shaken to carry out advanced oxidation. Sampling at a specific time, measuring with ion chromatographNO in test sample 3 - Ion concentration. EXAMPLE 1 Co/Ti preparation 3 C 2 T x The material addition amount is 200mg/L, the PMS addition amount is 200mg/L, the temperature of the tetA aqueous solution is 25 ℃, and Co/Ti is added 3 C 2 T x The pH of the aqueous solution of tetA before the material was 6.6. The test results are shown in FIG. 12 for Co/Ti preparation with addition of example 1 3 C 2 T x The time point of the material is 0min, and NO in the sample is increased along with the extension of the reaction time 3 - The ion concentration gradually increases. After 60min of treatment, NO in the sample 3 - The ion concentration reaches 0.85mg/L, which indicates that 91.4% of nitrogen in tetA is mineralized, and the base of the tetracycline resistance gene is mineralized into nitrate. Thus Co/Ti 3 C 2 T x tetA can be inactivated deeply.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (18)
1. Co/Ti 3 C 2 T x The application of material activated PMS advanced oxidation to remove drug resistance genes in wastewater is characterized in that,
Co/Ti 3 C 2 T x the material is Co distributed in the flake Ti 3 C 2 T x Surface of material, co/Ti 3 C 2 T x The preparation method of the material comprises the following steps:
step 1, ti is mixed with 3 AlC 2 Mixing lithium fluoride and hydrochloric acid to obtain a first solution, stirring the first solution for at least 12h, centrifuging to collect precipitate, washing to neutrality, and drying to obtain multilayer Ti 3 C 2 T x Wherein Ti in the first solution 3 AlC 2 The concentration of lithium fluoride in the first solution is 30-70 g/L;
step 2, multilayer Ti 3 C 2 T x Dispersing into glycol water for dissolvingIn the solution, a second solution is obtained, and the second solution is subjected to ultrasonic treatment for at least 0.5h under the environment of nitrogen or inert gas to obtain ultrathin Ti 3 C 2 T x A nanoplatelet dispersion, wherein the second solution comprises multiple layers of Ti 3 C 2 T x The concentration of (3) to (7) g/L;
step 3, dripping cobalt chloride solution into the ultrathin Ti 3 C 2 T x Stirring the nano-sheet dispersion liquid, carrying out ultrasonic treatment in a nitrogen or inert gas environment, centrifugally collecting precipitate, washing and drying to obtain Co/Ti 3 C 2 T x The material comprises cobalt and ultrathin Ti in cobalt chloride solution in parts by weight 3 C 2 T x Multilayer Ti in nanosheet dispersion 3 C 2 T x The ratio of (1) is (0.005-0.02): 1.
2. the use according to claim 1, wherein Co is less than Ti 3 C 2 T x 1.8% by weight of material.
3. The use according to claim 1, wherein Co is Ti 3 C 2 T x 0.4 to 0.5 weight percent of the material.
4. The use according to claim 1, wherein Co is Ti 3 C 2 T x 1.3 to 1.4 weight percent of the material.
5. The use according to claim 1, wherein the drug-resistant gene is an anti-tetracycline drug-resistant gene.
6. The use according to claim 1, characterized in that the Co/Ti 3 C 2 T x The adding amount of the material is 50-250 mg/L, and the temperature of the wastewater is 20-30 ℃.
7. The use according to claim 1, wherein the method for removing drug resistance genes from wastewater comprises the following steps: to wasteCo/Ti is added into water 3 C 2 T x And (3) vibrating the material to reach adsorption balance, adding PMS, and vibrating to perform advanced oxidation reaction, wherein the concentration of PMS in the wastewater is 50-300 mg/L.
8. The use according to claim 1, wherein in said step 1, said washing is performed with ultra-pure water.
9. The use according to claim 1, wherein in step 1, the temperature of the stirring is 25 to 60 ℃ and the time of the stirring is 12 to 30 hours.
10. The use according to claim 1, wherein in step 2 the concentration of ethylene glycol in the aqueous ethylene glycol solution is 1-3M.
11. The use according to claim 1, wherein in step 2, the time of the ultrasound is between 0.5 and 2 hours.
12. The use according to claim 1, characterized in that in step 2 the second solution is sonicated at 0-25 ℃.
13. The use according to claim 1, wherein in step 3 the cobalt chloride solution is a mixture of cobalt chloride and ethylene glycol, the concentration of cobalt chloride in the cobalt chloride solution being between 0.4 and 0.6M.
14. The use according to claim 1, wherein in step 3, the stirring time is 20 to 40min and the stirring temperature is room temperature.
15. The use according to claim 1, wherein in step 3, the temperature of the ultrasound is between 0 and 25 ℃ and the time of the ultrasound is between 0.5 and 2 hours.
16. The use according to claim 1, wherein in said step 3, said washing is performed with absolute ethanol and ultra-pure water.
17. The use according to claim 1, wherein in step 1 and step 3, the drying is freeze-drying.
18. The use according to claim 1, wherein in step 1 the concentration of the hydrochloric acid is 5-15M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310542126.0A CN116713014B (en) | 2023-05-15 | 2023-05-15 | Co/Ti 3 C 2 T x Fenton-like catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310542126.0A CN116713014B (en) | 2023-05-15 | 2023-05-15 | Co/Ti 3 C 2 T x Fenton-like catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116713014A CN116713014A (en) | 2023-09-08 |
| CN116713014B true CN116713014B (en) | 2023-12-15 |
Family
ID=87865131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310542126.0A Active CN116713014B (en) | 2023-05-15 | 2023-05-15 | Co/Ti 3 C 2 T x Fenton-like catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116713014B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417406A (en) * | 2018-01-30 | 2018-08-17 | 哈尔滨工业大学 | A kind of Ti3C2MXene-Co composite material and preparation methods |
| CN113697930A (en) * | 2021-09-04 | 2021-11-26 | 河海大学 | Method for removing pollutants in water |
| CN114054059A (en) * | 2021-12-15 | 2022-02-18 | 陈雪文 | Method for degrading sulfamethoxazole in wastewater by activating persulfate through magnetic two-dimensional Mxene/CuFeO2 catalyst |
-
2023
- 2023-05-15 CN CN202310542126.0A patent/CN116713014B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417406A (en) * | 2018-01-30 | 2018-08-17 | 哈尔滨工业大学 | A kind of Ti3C2MXene-Co composite material and preparation methods |
| CN113697930A (en) * | 2021-09-04 | 2021-11-26 | 河海大学 | Method for removing pollutants in water |
| CN114054059A (en) * | 2021-12-15 | 2022-02-18 | 陈雪文 | Method for degrading sulfamethoxazole in wastewater by activating persulfate through magnetic two-dimensional Mxene/CuFeO2 catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Activating two-dimensional Ti3C2Tx-MXene with single-atom cobalt for efficient CO2 photoreduction;Yi-Hong Chen et al;Cell Reports Physical Science;第2页 第10页 Supplemental information * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116713014A (en) | 2023-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106076335B (en) | A kind of preparation method and application of heterogeneous Fenton catalyst | |
| CN106881059B (en) | A kind of preparation method of iron/carbon composite | |
| CN107626335B (en) | Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof | |
| CN104069879A (en) | Preparation method for titanium dioxide/hydroxyapatite composite photocatalyst | |
| CN106517341B (en) | A kind of method and its application for preparing manganese dioxide nano catalyst | |
| CN106830121A (en) | A kind of domestic sewage treating compound and preparation method thereof | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| US11850664B2 (en) | Silicified modified zero-valent iron and its preparation method and application | |
| CN111635025B (en) | Method for treating dye wastewater by using patina/glucose-glucose oxidase catalytic oxidation system | |
| CN110639592A (en) | Boron and nitrogen doped carbon porous nanosheet supported transition metal nanoparticle material catalyst and preparation method and application thereof | |
| CN106986396A (en) | A kind of modification of chitosan and preparation method thereof | |
| CN106434621A (en) | Method for immobilizing laccase on polyacrylamide-coated magnetic nano particles and application of method | |
| CN103816903B (en) | The synthetic method of iron-base magnetic nanoneedle iron ore | |
| CN111533237A (en) | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material | |
| CN114291992B (en) | Preparation combination for removing municipal sludge antibiotic resistance genes and application | |
| CN116713014B (en) | Co/Ti 3 C 2 T x Fenton-like catalyst and preparation method and application thereof | |
| CN107051392A (en) | The functionalization aeroge and preparation method acted on heavy metal ion adsorption desorption | |
| CN107686156B (en) | A kind of Fenton method of efficient degradation organic pollutants | |
| CN109158078A (en) | A kind of porous phosphorus removing material and its preparation method and application suitable for decentralized wastewater processing | |
| CN107159175B (en) | It is a kind of using sub- titanium oxide as the catalytic ozonization water treatment method of catalyst | |
| CN110357223B (en) | Zinc-bismuth cooperatively modified cerium oxide composite electrode and preparation method and application thereof | |
| CN106698378A (en) | Preparation method and application of novel organic modified porous nanomaterial | |
| CN109592748A (en) | A kind of iron carbon composite and preparation method | |
| CN109985600A (en) | A kind of modified meerschaum and its application in the treatment of waste water | |
| CN107265663A (en) | A kind of town dweller's domestic sewage treating compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |