CN117599621A - Pollution-resistant composite modified ceramic membrane and preparation method and application thereof - Google Patents
Pollution-resistant composite modified ceramic membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN117599621A CN117599621A CN202311529025.6A CN202311529025A CN117599621A CN 117599621 A CN117599621 A CN 117599621A CN 202311529025 A CN202311529025 A CN 202311529025A CN 117599621 A CN117599621 A CN 117599621A
- Authority
- CN
- China
- Prior art keywords
- membrane
- composite modified
- cobalt
- pollution
- modified ceramic
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 84
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 31
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 150000001868 cobalt Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 3
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 3
- 229960000623 carbamazepine Drugs 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229960005489 paracetamol Drugs 0.000 claims description 3
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960004306 sulfadiazine Drugs 0.000 claims description 3
- 229960002135 sulfadimidine Drugs 0.000 claims description 3
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims description 3
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 3
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 claims description 3
- 229960001544 sulfathiazole Drugs 0.000 claims description 3
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- -1 bisphenol a Chemical compound 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229910002500 C-N-Co Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910002514 Co–Co Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/05—Cermet materials
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A pollution-resistant composite modified ceramic membrane and its preparation method and application are provided. The invention belongs to the technical field of water recycling and water purification membrane treatment. The invention aims to solve the technical problems of membrane pollution and poor retention rate of small molecular organic matters in the existing ceramic membrane separation technology. The composite modified ceramic membrane comprises a ceramic substrate membrane and a single-atom cobalt/nitrogen Co-doped multi-wall carbon nano tube layer (Co 1 NC). Co is prepared by the invention 1 NC is loaded on the ceramic substrate film to form a catalytic film, so that the agglomeration effect of the material can be reduced, the reaction substances are concentrated, the transfer path is shortened, and the mass transfer efficiency of the surface dominant reaction is enhanced. Meanwhile, due to the hydrophilic characteristic of the nitrogen-doped multiwall carbon nanotube, the problem that the existing carbon-based material and metal nano material block the ceramic substrate membrane pores is solved, the flux of the composite membrane is ensured, and the membrane pollution is relieved. Can be used for activating persulfate to selectively enhance the degradation of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of water recycling and water purification membrane treatment, and particularly relates to a pollution-resistant composite modified ceramic membrane, and a preparation method and application thereof.
Background
Ceramic ultrafiltration membranes have excellent mechanical sieving properties in the entrapment of suspended particles, macromolecular organics, microorganisms and colloids, and are therefore widely used in the field of water treatment. However, there are two key problems with current ultrafiltration processes that limit their practical application: the interception effect of the emerging organic pollutants is poor, and the membrane pollution caused by natural organic matters is also a problem. The advanced oxidation technology coupled with ceramic membrane filtration technology can effectively solve the problems. Among them, the cobalt-based heterogeneous catalyst activated Persulfate (PMS) oxidation system has been receiving attention because of its high reactivity and simple separation. However, the coordination structure of metal atoms in conventional heterogeneous catalysts is poorly tunable, affecting the catalytic performance. In contrast, the single-atom cobalt catalyst (Co-SACs) is a heterogeneous catalyst with atomic dispersed metal active sites, can make up the defects of the traditional catalyst, and has stronger activity in removing refractory organic pollutants. In addition, the Co-SACs/PMS system can regulate the non-radical oxidation pathway with higher tolerance and selectivity to water matrix. However, it has been reported in the past that activation of PMS in monoatomic dispersions degrades single microcontaminants. The defect is that the material is easy to generate agglomeration effect and affects the catalytic performance. Therefore, there is a need to develop a pollution resistant ceramic membrane to meet the practical demands of future water treatment.
Disclosure of Invention
The invention aims to solve the technical problems of membrane pollution and poor retention rate of small molecular organic matters in the existing ceramic membrane separation technology, and provides a pollution-resistant composite modified ceramic membrane, a preparation method and application thereof, which can reduce the agglomeration effect of nano catalytic materials, have higher mass transfer and activation efficiency, and can cooperatively realize the selective enhanced degradation of emerging organic pollutants and the pollution alleviation of ceramic membranes.
The technical scheme of the invention is realized by the following steps:
one of the purposes of the invention is to provide a pollution-resistant composite modified ceramic membrane, which comprises a ceramic substrate membrane and a single-atom cobalt/nitrogen co-doped multi-wall carbon nano tube layer loaded on the ceramic substrate membrane.
Preferably, the ceramic base film includes one or more of oxides, carbides and nitrides of titanium, zirconium, and aluminum.
Preferably, the ceramic substrate membrane has a membrane pore size of 20-600nm.
Preferably, the doping amount of the monoatomic cobalt in the monoatomic cobalt/nitrogen co-doped multiwall carbon nanotube layer relative to the multiwall carbon nanotube is 0.5-3.0wt.%.
Preferably, the loading amount of the single-atom cobalt/nitrogen co-doped multi-wall carbon nano tube in the composite modified ceramic membrane is 0.1-0.3mg/cm 2 。
The second object of the invention is to provide a preparation method of the pollution-resistant composite modified ceramic membrane, which comprises the following steps:
(1) Adding cobalt salt and citric acid into deionized water, and performing ultrasonic treatment until the cobalt salt and the citric acid are completely dissolved to obtain a cobalt salt solution;
(2) Adding multi-wall carbon nano tube dispersion liquid and melamine into cobalt salt solution, carrying out ultrasonic treatment until the dispersion is uniform, stirring and drying in an oil bath pot, and calcining at high temperature to obtain single-atom cobalt/nitrogen co-doped multi-wall carbon nano tubes;
(3) And ultrasonically dispersing the monoatomic cobalt/nitrogen co-doped multiwall carbon nanotube into deionized water, then press-filtering the monoatomic cobalt/nitrogen co-doped multiwall carbon nanotube onto the surface of a ceramic substrate membrane under constant pressure, and washing and drying the ceramic substrate membrane to obtain the pollution-resistant composite modified ceramic membrane.
Preferably, the cobalt salt in the step (1) is one of nitrate, sulfate, acetate or chloride.
Preferably, the molar ratio of cobalt salt to citric acid in step (1) is 1:1.
Preferably, the multiwall carbon nanotubes in step (2) have a diameter of 30-50nm and a length of 10 μm.
Preferably, in the step (2), the mass ratio of the multiwall carbon nanotubes to the melamine is 1: (2-4).
Preferably, the temperature of the oil bath in step (2) is 90-120 ℃.
Preferably, the calcining atmosphere in the step (2) is nitrogen or argon, the heating rate is 2-5 ℃/min, the calcining temperature is 700-800 ℃, and the heat preservation time is 1-3h.
Preferably, the constant pressure in step (3) is 0.06-0.1Mpa.
The invention further aims to provide an application of the pollution-resistant composite modified ceramic membrane in selective enhanced degradation of organic pollutants by activating persulfate.
Preferably, the organic pollutant comprises one or more of phenol, bisphenol A, bisphenol F, 2, 4-dichlorophenol, acetaminophen, sulfamethoxazole, sulfathiazole, sulfadiazine, sulfadimidine, atrazine and carbamazepine.
Preferably, the persulfate is added in an amount of 0.1 to 0.5mM.
Compared with the prior art, the invention has the remarkable effects that:
(1) The composite modified ceramic membrane prepared by the invention has the performance of quickly activating PMS, and the preparation method has the advantages of short period, simple procedure and low cost. In the operation process of the catalytic film, cobalt ion leaching is not detected, and the chemical stability is strong.
(2) The composite modified ceramic membrane prepared by the invention can generate various free radicals and rich singlet oxygen when PMS is activated, can realize the rapid degradation of phenols and sulfonamides organic micro-pollutants, and shows high selectivity and tolerance of complex water matrix. When the secondary effluent is treated, the catalytic membrane has excellent anti-pollution performance, the flux of the membrane is slowly reduced, and the membrane pollution is effectively reduced.
(3) The composite modified ceramic membrane prepared by the invention is prepared by mixing Co with the following components in percentage by weight 1 NC is loaded on the ceramic substrate film to form a catalytic film, so that the agglomeration effect of the material can be reduced, the reaction substances are concentrated, the transfer path is shortened, and the mass transfer efficiency of the surface dominant reaction is enhanced. Meanwhile, due to the hydrophilic characteristic of the nitrogen-doped multiwall carbon nanotube, the problem that the existing carbon-based material and metal nano material block the ceramic substrate membrane pores is solved, so that the flux of the composite membrane is ensured, and the membrane pollution is relieved.
Drawings
FIG. 1 is a flow chart of a process for preparing a single-atom cobalt/nitrogen co-doped multiwall carbon nanotube according to the present invention;
FIG. 2 shows a composite modified ceramic film (Co 1 NC-CM);
FIG. 3 shows a composite modified ceramic film (Co 1 NC-CM) SEM and EDS maps;
FIG. 4 is an XRD pattern of the surface layer of the composite modified ceramic membrane prepared in example 1;
FIG. 5 is a Co k-edge FT-EXAFS spectrum of the surface layer of the composite modified ceramic membrane prepared in example 1;
FIG. 6 is a graph showing the wavelet transform of synchrotron radiation of the surface layer of the composite modified ceramic membrane prepared in example 1;
FIG. 7 is an XPS chart of the composite modified ceramic film prepared in example 1; (a) represents XPS holomography and (b) represents C1s;
FIG. 8 is a diagram of a ceramic membrane filtration device;
FIG. 9 is a graph comparing flux and fouling resistance values of the membranes obtained in example 1 with those of comparative examples 1 to 3; (a) Represents the flux of the membrane, (b) represents the fouling resistance value of the membrane;
FIG. 10 shows the phenol removal effect of the composite modified ceramic membranes prepared in examples 1-2 with different cobalt monoatomic doping amounts;
FIG. 11 shows the different Co's prepared in examples 1-3 1 NC-loaded ceramic membrane has phenol removal effect;
FIG. 12 shows the results of EPR characterization of active species in the composite modified ceramic membrane catalyst system prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
Reference to "one embodiment" or "an embodiment" of the present invention means that a particular feature, structure, or characteristic may be included in at least one implementation of the present invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1: the preparation method of the pollution-resistant composite modified ceramic membrane comprises the following steps:
step 1: 100mg of multi-walled carbon nanotubes were uniformly dispersed in 50mL of 30wt.% dilute nitric acid and kept in an oil bath at 100℃for 2 hours to remove metal impurities. Washed to neutrality with deionized water and dried in an oven at 60 ℃.
Step 2: and dispersing the dried multi-wall carbon nano tube in 100mL of 30wt.% methanol aqueous solution, and carrying out ultrasonic treatment to obtain a uniformly dispersed multi-wall carbon nano tube dispersion liquid.
Step 3: 21.11mg of cobalt acetate tetrahydrate and 17.80mg of citric acid monohydrate were added to 20ml of deionized water, and the mixture was sonicated until complete dissolution, to give a cobalt salt solution.
Step 4: 300mg of melamine, the multiwall carbon nanotube dispersion obtained in the step 2 and 1mL of the cobalt salt solution obtained in the step 3 are treated by ultrasonic until the dispersion is uniform, and the mixture is stirred in an oil bath pot at the temperature of 100 ℃ until the mixture is dried.
Step 5: the dried mixture was ground and then calcined using a tube furnace under argon atmosphere at a heating rate of 5 ℃/min to 700 ℃ for 1 hour. Followed by washing with 1mol/L dilute sulfuric acid at 60℃for 4 hours to remove surface metal impurities. Washing with deionized water to neutrality, and drying in oven at 60deg.C to obtain single atom cobalt/nitrogen Co-doped multiwall carbon nanotubes (flow chart see FIG. 1), denoted as Co 1 NC (wherein the doping amount of the monoatomic cobalt is 0.5wt% with respect to the multiwall carbon nanotube).
Step 6: 3.47mg of Co 1 NC is added into deionized water, a cell disruption instrument is subjected to ultrasonic dispersion, then the mixture is subjected to pressure filtration on the surface of a ceramic substrate membrane (made of zirconium titanium metal material with the thickness of 2.5 mm, the diameter of 47 mm and the aperture of 20-50 nm) under the constant pressure of 0.1MPa, repeatedly washed by deionized water for several times, and finally dried overnight in a vacuum drying boxObtaining the pollution-resistant composite modified ceramic film, which is marked as Co 1 NC-CM in which Co 1 NC loading of 0.2mg/cm 2 A photograph of the real object is shown in fig. 2. Microscopic characterization of the composite modified ceramic membranes is shown in fig. 3.
FIGS. 4-7 show that Co-Co metal bonds and Co-O bonds are not present in the composite modified ceramic film, but rather the bonded form of C-N-Co, indicating that cobalt in the composite modified ceramic film is present in the form of a single atom.
Example 2:
a composite modified ceramic membrane was prepared according to the procedure of example 1, except that: in the step 4, 2mL and 6mL of cobalt salt solution are respectively added to prepare the composite modified ceramic membrane with different monoatomic cobalt doping amounts. Respectively recorded as 1.0% Co 1 NC and 3.0% Co 1 NC。
Example 3:
a composite modified ceramic membrane was prepared according to the procedure of example 1, except that: in step 6, 1.73mg and 5.20mg of Co were loaded 1 NC to prepare a load of 0.1mg/cm 2 And 0.3mg/cm 2 Is a composite modified ceramic membrane.
Comparative example 1:
the ceramic substrate film used in example 1 was cleaned with deionized water alone without any modification treatment.
Comparative example 2:
a composite modified ceramic membrane was prepared according to the procedure of example 1, except that: and (3) omitting the step (3) and adding no cobalt salt solution in the step (4) to obtain the multi-wall carbon nano tube catalytic ceramic membrane doped with nitrogen element, namely NCNT-CM.
Comparative example 3:
a composite modified ceramic membrane was prepared according to the procedure of example 1, except that: in the step 4, melamine is not added, and the multi-wall carbon nano tube catalytic ceramic membrane doped with cobalt nano particles, namely the CoCNT-CM, is obtained.
The leaching amount of cobalt ions in the materials obtained in example 1 and comparative examples 1 to 3 was measured by ICP, and the results are shown in Table 1. The cobalt ion leaching rate of the composite modified ceramic membrane prepared in the embodiment 1 in the application process is lower than the detection lower limit of an instrument by 0.001mg/L, which indicates that the composite modified ceramic membrane has strong stability and lower risk of heavy metal leakage. The higher leaching rate of the CoCNT-CM prepared in the comparative example 3 shows that the cobalt nanoparticle modified catalytic film has poor stability and hidden danger of metal leakage.
Application example:
the catalytic ceramic membranes prepared using example 1 and comparative examples 1-3 were run in the apparatus shown in FIG. 8, and the specific flux values after filtration of 120mL of secondary effluent (from Wenchang sewage treatment plant based on anaerobic/aerobic process in Harbin city, 6 months 2023) at a PMS dosage of 0.3mM and a constant pressure of 0.06MPa are shown in Table 1. The results show a significant increase in the specific flux value for example 1, demonstrating a mitigation of membrane fouling. In addition, the film contamination resistance value in example 1 was also significantly reduced as compared to comparative examples 1-3, confirming effective alleviation of film contamination. The complete results of the flux decline curve and membrane fouling resistance are shown in fig. 9, indicating that the catalytic ceramic membrane has anti-fouling properties and can maintain a stable high flux.
The catalytic ceramic membranes prepared using example 1 and comparative examples 1-3 were run in the apparatus shown in fig. 8, with different organic contaminant water solutions having ph=7 being filtered separately at a constant pressure of 0.06 MPa. Wherein, the dosage of phenol, bisphenol A, bisphenol F, 2, 4-dichlorophenol, acetaminophen, sulfamethoxazole, sulfathiazole, sulfadiazine and sulfadimidine is respectively 10mg/L, and the dosage of atrazine and carbamazepine is respectively 5mg/L. The removal rates of each contaminant are listed in table 1. The results show that the catalytic ceramic membrane prepared in example 1 has extremely high selectivity removal rate (more than 91 percent) of phenolic and sulfonamide organic pollutants. And the removal effect on all the emerging organic pollutants is obviously better than the results of comparative examples 1-3.
TABLE 1
The catalytic ceramic membranes prepared using examples 1-2 were run in the apparatus shown in fig. 8 with PMS dosing of 0.3mm and phenol concentration of 10mg/L by filtration of aqueous phenol solution at ph=7 at constant pressure of 0.06 mpa. The removal rate results are shown in FIG. 10. The results show that 0.5 to 3.0wt.% monoatomic cobalt doping levels can achieve 100% phenol removal quickly.
The catalytic ceramic membranes prepared using examples 1, 3 were run in the apparatus shown in fig. 8 with PMS addition of 0.3mm and a phenol concentration of 10mg/L by filtration of an aqueous phenol solution at ph=7 at a constant pressure of 0.06 mpa. The removal rate results are shown in FIG. 11. The results showed that 0.1-0.3mg/cm 2 Under the load, the fast removal of refractory organic phenol can be realized.
Active species in the system were characterized by EPR using the catalytic ceramic membrane prepared in example 1. As shown in FIG. 12, hydroxyl radicals and sulfate radicals (.OH and SO) were detected 4 ·- ) Indicating the presence of free radicals in the degradation reaction. In contrast, the non-radical pathway-singlet oxygen 1 O 2 ) The characteristic signal of (2) is strongest, in the description system 1 O 2 The highest content is the root cause of the complex water matrix resistance of the catalytic membrane filtration system and the selective and efficient removal of phenols and sulfonamides organic micro-pollutants.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The pollution-resistant composite modified ceramic membrane is characterized by comprising a ceramic substrate membrane and a single-atom cobalt/nitrogen co-doped multi-wall carbon nano tube layer loaded on the ceramic substrate membrane.
2. The pollution-resistant composite modified ceramic membrane according to claim 1, wherein the ceramic substrate membrane comprises one or more of oxides, carbides and nitrides of titanium, zirconium and aluminum, and the membrane pore size of the ceramic substrate membrane is 20-600nm.
3. The contamination resistant composite modified ceramic membrane of claim 1, wherein the doping amount of the monoatomic cobalt in the monoatomic cobalt/nitrogen co-doped multiwall carbon nanotube layer is 0.5 to 3.0wt.% relative to the multiwall carbon nanotubes.
4. The pollution-resistant composite modified ceramic membrane according to claim 1, wherein the loading amount of the single-atom cobalt/nitrogen co-doped multi-wall carbon nanotubes in the composite modified ceramic membrane is 0.1-0.3mg/cm 2 。
5. The method for preparing the pollution-resistant composite modified ceramic membrane according to any one of claims 1 to 4, comprising the following steps:
(1) Adding cobalt salt and citric acid into deionized water, and performing ultrasonic treatment until the cobalt salt and the citric acid are completely dissolved to obtain a cobalt salt solution;
(2) Adding multi-wall carbon nano tube dispersion liquid and melamine into cobalt salt solution, carrying out ultrasonic treatment until the dispersion is uniform, stirring and drying in an oil bath pot, and calcining at high temperature to obtain single-atom cobalt/nitrogen co-doped multi-wall carbon nano tubes;
(3) And ultrasonically dispersing the monoatomic cobalt/nitrogen co-doped multiwall carbon nanotube into deionized water, then press-filtering the monoatomic cobalt/nitrogen co-doped multiwall carbon nanotube onto the surface of a ceramic substrate membrane under constant pressure, and washing and drying the ceramic substrate membrane to obtain the pollution-resistant composite modified ceramic membrane.
6. The method of claim 5, wherein the cobalt salt in step (1) is one of a nitrate, sulfate, acetate or chloride salt, and the molar ratio of cobalt salt to citric acid is 1:1.
7. The method of claim 5, wherein the mass ratio of the multiwall carbon nanotubes to the melamine in step (2) is 1: (2-4), the temperature of the oil bath is 90-120 ℃.
8. The method according to claim 5, wherein the constant pressure in step (3) is 0.06-0.1Mpa.
9. Use of the pollution-resistant composite modified ceramic membrane according to any one of claims 1-4 for the selective enhanced degradation of organic pollutants by activated persulfates.
10. The use according to claim 9, wherein the organic contaminant comprises one or more of phenol, bisphenol a, bisphenol F, 2, 4-dichlorophenol, acetaminophen, sulfamethoxazole, sulfathiazole, sulfadiazine, sulfadimidine, atrazine and carbamazepine, and the persulfate is added in an amount of 0.1-0.5mM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311529025.6A CN117599621B (en) | 2023-11-16 | 2023-11-16 | Pollution-resistant composite modified ceramic membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311529025.6A CN117599621B (en) | 2023-11-16 | 2023-11-16 | Pollution-resistant composite modified ceramic membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117599621A true CN117599621A (en) | 2024-02-27 |
| CN117599621B CN117599621B (en) | 2024-07-05 |
Family
ID=89952672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311529025.6A Active CN117599621B (en) | 2023-11-16 | 2023-11-16 | Pollution-resistant composite modified ceramic membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117599621B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070029195A1 (en) * | 2005-08-03 | 2007-02-08 | Changming Li | Polymer/nanoparticle composites, film and molecular detection device |
| CN109745984A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | A kind of preparation method of the monatomic doped carbon nanometer pipe of metal |
| CN112808235A (en) * | 2020-12-31 | 2021-05-18 | 华南理工大学 | Co @ NCNT material prepared by reduction-oxidation-reduction strategy and preparation method thereof |
| CN115888405A (en) * | 2022-09-15 | 2023-04-04 | 三峡大学 | Preparation method and application of in-situ grown cobalt-carbon nanotube filtering membrane |
-
2023
- 2023-11-16 CN CN202311529025.6A patent/CN117599621B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070029195A1 (en) * | 2005-08-03 | 2007-02-08 | Changming Li | Polymer/nanoparticle composites, film and molecular detection device |
| CN109745984A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | A kind of preparation method of the monatomic doped carbon nanometer pipe of metal |
| CN112808235A (en) * | 2020-12-31 | 2021-05-18 | 华南理工大学 | Co @ NCNT material prepared by reduction-oxidation-reduction strategy and preparation method thereof |
| CN115888405A (en) * | 2022-09-15 | 2023-04-04 | 三峡大学 | Preparation method and application of in-situ grown cobalt-carbon nanotube filtering membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117599621B (en) | 2024-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Changing conventional blending photocatalytic membranes (BPMs): Focus on improving photocatalytic performance of Fe3O4/g-C3N4/PVDF membranes through magnetically induced freezing casting method | |
| Lu et al. | An overview of nanomaterials for water and wastewater treatment | |
| US9486747B2 (en) | Nanocomposite membranes with advanced antifouling properties under visible light irradiation | |
| Sheoran et al. | Recent advances of carbon-based nanomaterials (CBNMs) for wastewater treatment: Synthesis and application | |
| Masheane et al. | Synthesis of Fe-Ag/f-MWCNT/PES nanostructured-hybrid membranes for removal of Cr (VI) from water | |
| Zhu et al. | Hierarchical porous ceramic membrane with energetic ozonation capability for enhancing water treatment | |
| JP2009509762A (en) | Water purifier and method incorporating activated carbon particles and surface carbon nanofilaments | |
| CN107376673B (en) | Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof | |
| Miao et al. | Continuous and complete conversion of high concentration p‐nitrophenol in a flow‐through membrane reactor | |
| He et al. | Synthesis and lead absorption properties of sintered activated carbon supported zero-valent iron nanoparticle | |
| Li et al. | Self-cleaning photocatalytic PVDF membrane loaded with NH2-MIL-88B/CDs and Graphene oxide for MB separation and degradation | |
| CN111715254A (en) | Preparation method of nitrogen-modified porous carbon-coated cobalt nanoparticle catalyst | |
| Yun et al. | Reduction of nitrate in secondary effluent of wastewater treatment plants by Fe 0 reductant and Pd–Cu/graphene catalyst | |
| US11433375B2 (en) | Photocatalytic carbon filter | |
| Reddy et al. | Graphene-based nanomaterials for the removal of pharmaceuticals in drinking water sources | |
| CN115193469B (en) | Preparation method, application and water treatment method of photocatalytic ceramic membrane | |
| CN113262787A (en) | Preparation method of iron-based composite catalyst for catalytic ozonation treatment of coal chemical wastewater | |
| Mehdi et al. | Adsorption of cadmium ions on silica coated metal organic framework | |
| Hou et al. | Reactive seeding growth of cobalt-doped MIL-88B (Fe) on Al2O3 membrane for phenol removal in a photocatalytic membrane reactor | |
| Liu et al. | Polysulfone Ultrafiltration Membrane Promoted by Brownmillerite SrCu x Co1–x O3− λ-Deposited MCM-41 for Industrial Wastewater Decontamination: Catalytic Oxidation and Antifouling Properties | |
| El-Sabban et al. | PPy-NTs/C/TiO2/poly (ether sulfone) porous composite membrane: Efficient ultrafiltration of Evans blue dye from industrial wastewater | |
| Zhang et al. | Catalytic membrane with multiscale iron-based catalysts anchored on 2D/2D hybrid g-C3N4/layered clay for pollutant removal | |
| CN117599621B (en) | Pollution-resistant composite modified ceramic membrane and preparation method and application thereof | |
| WO2016197397A1 (en) | Preparation method and use of photocatalytic degradation-adsorption material | |
| CN116099384A (en) | Preparation method of spinel nanoparticle modified ceramic membrane |
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 |