CN109647525B - Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst - Google Patents
Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst Download PDFInfo
- Publication number
- CN109647525B CN109647525B CN201910048721.2A CN201910048721A CN109647525B CN 109647525 B CN109647525 B CN 109647525B CN 201910048721 A CN201910048721 A CN 201910048721A CN 109647525 B CN109647525 B CN 109647525B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal organic
- framework photocatalyst
- photocatalyst
- mil
- 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
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 135
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 130
- 230000002950 deficient Effects 0.000 title claims abstract description 59
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 40
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000013206 MIL-53 Substances 0.000 claims abstract description 3
- 230000007547 defect Effects 0.000 claims description 41
- 239000004098 Tetracycline Substances 0.000 claims description 32
- 229960002180 tetracycline Drugs 0.000 claims description 32
- 229930101283 tetracycline Natural products 0.000 claims description 32
- 235000019364 tetracycline Nutrition 0.000 claims description 32
- 150000003522 tetracyclines Chemical class 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000000593 degrading effect Effects 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000009471 action Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 27
- 239000013078 crystal Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000013255 MILs Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for photocatalytic degradation of organic pollutants by using a defective metal organic framework photocatalyst, which is characterized in that the defective metal organic framework photocatalyst is used for photocatalytic degradation of the organic pollutants, wherein the defective metal organic framework photocatalyst is prepared by taking ferric trichloride hexahydrate and terephthalic acid as raw materials and N, N-dimethylformamide as a solvent through a solvothermal reaction under the action of an acid regulator; the defective metal organic framework photocatalyst is a defective MIL-53 metal organic framework photocatalyst. The method for photocatalytic degradation of organic pollutants by using the defective metal organic framework photocatalyst has the advantages of simple process, convenience in operation, low cost, easiness in recycling, high treatment efficiency, high degradation rate and the like, can realize effective and rapid degradation of the organic pollutants, and has good application prospect in actual treatment of organic pollutant wastewater.
Description
Technical Field
The invention belongs to the field of application of photocatalysis, and relates to a method for degrading organic pollutants by using defect type metal organic framework photocatalyst.
Background
The photocatalysis technology is a green technology with important application prospect in the fields of energy and environment. In recent years, research and development of photocatalysis application technology are rapid, the novel technology has the advantages of low energy consumption, simple operation process, mild reaction conditions and the like, organic matters in water, air and soil can be completely oxidized into nontoxic and harmless substances at room temperature, and secondary pollution is avoided. Especially has outstanding performance in the aspect of degrading organic pollutants, and can effectively degrade various organic wastewater including antibiotic pharmaceutical wastewater, sulfur-containing fuel wastewater, fermentation production wastewater, fine chemical wastewater and the like so as to reach the discharge standard.
In recent years, Metal Organic Frameworks (MOFs) have attracted much attention as a class of crystalline porous materials having a periodic network structure formed by connecting inorganic metal centers (metal ions or metal clusters) and bridged organic ligands to each other through self-assembly. MILs series (Laweschil framework materials) are MOF materials synthesized by Laweschil research working group including Ferey at France Versailles university with trivalent metal ions (aluminum (Al), iron (Fe), vanadium (V), chromium (Cr) and terephthalic acid and other carboxylic acid ligands, crystals synthesized based on different metal centers have the same crystal structure, MIL-53 is a member of MIL family, is MOF with Fe (III) as a central metal ion and composed of octahedron Fe (III) and 1, 4-terephthalic acid, the forbidden band width is 2.72eV, and the visible light response characteristic is achieved, however, due to the faster recombination of photo-generated electrons and holes, the photocatalytic activity of MIL-53 is still poor.2O2) Sulfate Persulfate (PS), persulfate Peroxinoosulfonate (PMS) and the like are taken as electron acceptors; the second is to construct a heterojunction structure, such as MIL-53/AgI, MIL-53/Ag3PO4MIL-53/CdS, MIL-53/SnS, etc. However, the technology of adding the electron acceptor has poor treatment effect, complex preparation and potential harm to the environment; the heterojunction photocatalysis is easy to generate the phenomenon of light corrosion, toxic metal ions are easy to dissolve out, and the environmental hazard and the damage to the environment are possibly causedSecondary pollution. Therefore, it is necessary to develop a novel metal organic framework material with a uniform mesoporous structure, a high specific surface area, a wide light absorption range, a small forbidden bandwidth, a large photocurrent, a small impedance, and a high photocatalytic activity, which is very important for effectively degrading organic pollutants in the environment.
Disclosure of Invention
The defect metal organic framework photocatalyst has the advantages of uniform mesoporous structure, high specific surface area, wide light absorption range, small forbidden bandwidth, large photocurrent, small impedance and high photocatalytic activity, and particularly has an obvious effect of photocatalytic degradation of organic pollutants.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for degrading organic pollutants by using defect metal organic framework photocatalyst, wherein the method adopts the defect metal organic framework photocatalyst to carry out photocatalytic degradation on the organic pollutants; the defect type metal organic framework photocatalyst is prepared by taking ferric trichloride hexahydrate and terephthalic acid as raw materials and N, N-dimethylformamide as a solvent through a solvothermal reaction under the action of an acid regulator; the defect type metal organic framework photocatalyst is a defect type MIL-53 metal organic framework photocatalyst.
In the above method, a further improvement is provided, and the preparation method of the defective metal organic framework photocatalyst comprises the following steps:
(1) dissolving ferric trichloride hexahydrate and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution A;
(2) adding an acid regulator into the mixed solution A obtained in the step (1) to obtain a mixed solution B;
(3) and (3) carrying out solvent thermal reaction on the mixed solution B obtained in the step (2), cleaning, filtering and drying to obtain the defective metal organic framework photocatalyst.
In a further improvement of the above process, in the step (1), the molar ratio of ferric trichloride hexahydrate, terephthalic acid and N, N-dimethylformamide is 1: 280.
In the step (2), the ratio of the mixed solution A to the acid regulator is 56 mL: 10 μ L-56 mL: 100 μ L; the acid regulator is HCl solution; the concentration of the HCl solution is 1-5 mol/L.
In the step (2), the ratio of the mixed solution A to the acid regulator is 56 mL: 10 μ L-56 mL: 30 μ L.
In a further improvement of the above method, in the step (3), the temperature of the solvothermal reaction is 150-170 ℃; the solvothermal reaction time is 15-24 h.
In the method, a defect metal organic framework photocatalyst is adopted to carry out photocatalytic degradation on organic pollutants in a water body, and the method comprises the following steps: the defect type metal organic framework photocatalyst is mixed with organic pollutant water to carry out dark reaction, and photocatalytic degradation reaction is carried out after adsorption and desorption balance is achieved, so that photocatalytic degradation of the organic pollutants in the water is completed.
In the method, the addition amount of the defective metal organic framework photocatalyst is 0.3-0.5 g per liter of organic pollutant water.
In the method, the organic pollutant water body is antibiotic wastewater; the antibiotic in the antibiotic wastewater is tetracycline; the concentration of the organic pollutants in the organic pollutant water body is 10 mg/L-40 mg/L.
In the method, the dark reaction is carried out under the dark condition; the dark reaction time is 30-60 min; the photocatalytic degradation reaction is carried out under the condition of visible light with the wavelength lambda being more than 420; the time of the photocatalytic degradation reaction is 120-150 min.
The main innovation points of the invention are as follows:
the method is completely different from the traditional method for adding an electron acceptor and constructing a heterojunction, the invention creatively provides a novel method for regulating and controlling the metal organic framework photocatalyst, the defect type metal organic framework photocatalyst is prepared by adopting an acid regulation strategy for the first time, and the photocatalytic activity of the defect type metal organic framework photocatalyst is researched for the first time, so that reference and basic work are provided for modifying the photocatalytic activity of the metal organic framework by using the acid regulation strategy. In the invention, defects are introduced in the synthesis process of the metal organic framework photocatalyst by adopting an acid regulation strategy, the defects mainly mean that the periodic arrangement of metal organic framework photocatalyst crystals is damaged due to the deletion or the offset of atoms or ions in the metal organic framework photocatalyst, and the defects introduced in the metal organic framework photocatalyst have a plurality of advantages, such as: the catalytic capability of the metal organic framework photocatalyst is improved; the adsorption capacity of the metal organic framework photocatalyst to gas is improved, probably because the cluster of the metal organic framework photocatalyst is not closed any more due to defects, and the molecular diffusion is facilitated; the charge transfer capacity or the photocatalytic hydrogen production capacity is improved; the extended fluorescence lifetime and the properties of the semiconductor give it the ability to degrade dyes efficiently. Therefore, the defect type metal organic framework photocatalyst prepared by the acid regulation strategy has a high specific surface area, a uniform mesoporous structure, a rough surface, a wide light absorption range and a narrow forbidden band width, can effectively inhibit the recombination of photo-generated electrons and holes, has excellent optical properties such as high photocurrent and small impedance, simultaneously has high photocatalytic activity, and can effectively degrade organic pollutants.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for photocatalytic degradation of organic pollutants by using a defective metal organic framework photocatalyst, which can effectively remove the organic pollutants by using the defective metal organic framework photocatalyst to carry out photocatalytic degradation on the organic pollutants, has the advantages of simple process, convenient operation, low cost, easy recovery and reuse, high treatment efficiency, high degradation rate and the like, can effectively and quickly degrade the organic pollutants, and has good application prospect in the actual treatment of organic pollutant (such as tetracycline) wastewater.
(2) In the method, the defect type metal organic framework photocatalyst is prepared by taking ferric trichloride hexahydrate and terephthalic acid as raw materials and N, N-dimethylformamide as a solvent through a solvothermal reaction under the action of an acid regulator, and the prepared defect type MIL-53 metal organic framework photocatalyst has the advantages of uniform mesoporous structure, high specific surface area, wide light absorption range, small forbidden bandwidth, large photocurrent, small impedance, high photocatalytic activity and the like, is a novel visible-light catalyst with novel morphological structure and excellent photocatalytic performance, and has good use value and application prospect.
(3) In the method of the present invention, the defective metal-organic framework photocatalyst is used, and the specific surface area of the defective metal-organic framework photocatalyst is from 10.201cm by introducing defects in terms of crystal structure2Increase in the amount of/g to 130.958cm2In terms of pore structure, the pore structure of the perfect MIL-53 metal organic framework photocatalyst (MIL-53) is a microporous structure, the pore structure of the defective metal organic framework photocatalyst is a mesoporous structure, and in terms of optical properties, the resistance of the perfect MIL-53 metal organic framework photocatalyst (MIL-53) is 1.0 × 105ohm, the electrical resistance of the defective metal organic framework photocatalyst is 0.5 × 105And (4) ohm. The photocurrent intensity of the perfect MIL-53 metal organic framework photocatalyst (MIL-53) is 0.05 muA/cm2The photocurrent of the defective metal-organic framework photocatalyst was increased to 0.20. mu.A/cm2The photocurrent was increased by 4 times. In the aspect of photocatalytic degradation of dyes, the photocatalytic degradation rate of a perfect MIL-53 metal-organic framework photocatalyst (MIL-53) is 59%, and the photocatalytic degradation rate of a defective metal-organic framework photocatalyst is 90%, and is improved by about 1.5 times compared with that of MIL-53. It can be seen that the defective metal organic framework photocatalysis of the present invention has excellent photocatalytic activity, unique crystal structure, excellent optical properties, and the excellent photocatalytic activity may be related to its unique crystal structure and excellent optical properties.
(4) In the method, the defect type metal organic framework photocatalyst is prepared by adopting an acid regulation strategy for the first time, namely the defect type metal organic framework photocatalyst with novel appearance structure and excellent photocatalytic performance is prepared by taking ferric trichloride hexahydrate and terephthalic acid as raw materials and carrying out solvothermal reaction under the action of an acid regulator. Particularly, in the aspect of degrading organic pollutants, the photocatalytic degradation rate of MIL-53 can be improved by 1.5 times, and the photocatalytic efficiency of the defective metal organic framework photocatalyst on the organic pollutants is 90%.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a photo-current diagram of defective metal organic framework photocatalysts (D-1 and D-4) and perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention.
FIG. 2 is a graph showing the impedance of the defective metal organic framework photocatalyst (D-1, D-4) and the perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention.
FIG. 3 is a UV diffuse reflectance graph of defective metal organic framework photocatalysts (D-1 and D-4) and perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention.
FIG. 4 is a diagram showing the band structure of the defective metal organic framework photocatalyst (D-1, D-4) and the perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention.
FIG. 5 is a graph showing the effect of defective MOFs photocatalyst (D-1, D-2, D-3, D-4, D-5, D-10) and perfect MIL-53 MOFs photocatalyst (MIL-53) on the photocatalytic degradation of tetracycline under the condition of λ > 420nm in visible light in example 1 of the present invention.
FIG. 6 is a graph showing the effect of the defective metal-organic framework photocatalyst (D-1) in example 2 on the photocatalytic degradation of tetracycline at different concentrations under visible light with a wavelength λ > 420 nm.
FIG. 7 is a graph showing the cyclic degradation effect of the defective metal-organic framework photocatalyst (D-1) in example 3 of the present invention in photocatalytic degradation of tetracycline under visible light with a wavelength λ > 420 nm.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples of the present invention, unless otherwise specified, materials and instruments used are commercially available, processes used are conventional, apparatuses used are conventional, and the obtained data are average values of three or more repeated experiments.
Example 1:
a method for photocatalytic degradation of organic pollutants by using a defective metal organic framework photocatalyst, in particular to photocatalytic degradation of tetracycline in a water body by using a defective MIL-53 metal organic framework photocatalyst, which comprises the following steps:
respectively adding 50mg of defective metal organic framework photocatalyst (D-1, D-2, D-3, D-4, D-5 and D-10) and perfect MIL-53 metal organic framework photocatalyst (MIL-53) into 100mL of tetracycline solution with the concentration of 20mg/L, carrying out ultrasonic uniformity, reacting for 60min under the condition of no light (magnetic stirring), illuminating for 150min under the condition of visible light with the wavelength lambda being more than 420nm after adsorption and desorption balance is achieved, and carrying out photocatalytic degradation reaction to finish the photocatalytic degradation of tetracycline in the water body.
In this embodiment, the defect type metal organic framework photocatalyst (D-1, D-2, D-3, D-4, D-5, D-10), specifically the defect type MIL-53 metal organic framework photocatalyst, is prepared by using ferric trichloride hexahydrate and terephthalic acid as raw materials and N, N-dimethylformamide as a solvent through a solvothermal reaction under the action of an acid regulator, and comprises the following steps:
(1) dissolving ferric trichloride hexahydrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 1: 280 to the ferric trichloride hexahydrate, the terephthalic acid and the N, N-dimethylformamide, and uniformly mixing to form a bright yellow clear solution, namely a mixed solution A.
(2) mu.L, 20. mu.L, 30. mu.L, 40. mu.L, 50. mu.L and 100. mu.L of 1mol/L HCl solutions were added to 56mL of the mixed solution A obtained in step (1), respectively, and the mixture was mixed uniformly to obtain a mixed solution B.
(3) And (3) placing the mixed solution B obtained in the step (2) into a reaction kettle, carrying out a solvothermal reaction 24 at the temperature of 170 ℃, respectively cleaning the obtained crystal with DMF and methanol for three times, filtering, and drying at 60 ℃ for 12 hours to obtain an orange crystal, namely the defective metal organic framework photocatalyst. Wherein the dosage of the HCl solution is 10 muL, 20 muL, 30 muL, 40 muL, 50 muL and 100 muL corresponding defect type metal organic framework photocatalyst which is named as D-1, D-2, D-3, D-4, D-5 and D-10.
In this embodiment, the preparation method of the perfect MIL-53 metal organic framework photocatalyst comprises the following steps:
(a) dissolving ferric trichloride hexahydrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 1: 280 to the ferric trichloride hexahydrate, the terephthalic acid and the N, N-dimethylformamide, and uniformly mixing to form a bright yellow clear solution, namely a mixed solution A.
(b) And (b) placing the mixed solution A obtained in the step (a) into a reaction kettle, carrying out a solvothermal reaction 24 at the temperature of 170 ℃, respectively cleaning the obtained crystal with DMF and methanol for three times, filtering, and drying at 60 ℃ for 12 hours to obtain an orange yellow crystal, namely the perfect metal organic framework photocatalyst, which is named as MIL-53.
FIG. 1 is a photo-current diagram of defective metal organic framework photocatalysts (D-1 and D-4) and perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention. As can be seen from FIG. 1, the photocurrent intensity of the perfect MIL-53 metal organic framework photocatalyst (MIL-53) was 0.05. mu.A/cm2The photocurrent of the defective metal-organic framework photocatalyst (D-1) was 0.18. mu.A/cm2It can be seen that the photocurrent of the defective metal-organic framework photocatalyst (D-1) is significantly increased, probably because the defects can effectively inhibit the recombination of photo-generated electrons and holes. However, the photocurrent of the defective metal-organic framework photocatalyst (D-4) was reduced compared to the perfect MIL-53 metal-organic framework photocatalyst (MIL-53), probably due to excessive acid affecting the crystal structure, resulting in crystal plane changes, photo-generated electron and hole separation, and further affecting the photocurrent intensity。
FIG. 2 is a graph showing the impedance of the defective metal organic framework photocatalyst (D-1, D-4) and the perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention. As can be seen from FIG. 2, the impedances of the defective metal-organic framework photocatalysts (D-1 and D-4) are uniformly distributed, on both sides of the perfect MIL-53 metal organic framework photocatalyst (MIL-53), the impedance of the defective MIL-53 metal organic framework photocatalyst (MIL-53) is smaller than that of the perfect MIL-53 metal organic framework photocatalyst (MIL-53), the impedance of the defective metal-organic framework photocatalyst (D-4) is larger than that of the perfect MIL-53 metal-organic framework photocatalyst (MIL-53), it is likely that defects due to low (10 μ L) amounts of hydrochloric acid coordinator (acid regulator) favour the separation and transport of electrons and holes, while high amounts (40 μ L) of hydrochloric acid coordinator (acid regulator) may affect the crystal structure and not favour the separation of electrons and holes.
FIG. 3 is a UV diffuse reflectance graph of defective metal organic framework photocatalysts (D-1 and D-4) and perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention. As can be seen from FIG. 3, the perfect MIL-53 metal organic framework photocatalyst (MIL-53) has an absorption peak at 445nm, which shows that the photocatalyst has absorption to visible light and is a potential semiconductor material. The defect metal organic framework photocatalysts (D-1 and D-4) also have absorption peaks at 445nm, the absorption peak of the defect metal organic framework photocatalyst (D-1) is stronger than that of the perfect MIL-53 metal organic framework photocatalyst (MIL-53), and the absorption peak of the defect metal organic framework photocatalyst (D-4) is weaker than that of the perfect MIL-53 metal organic framework photocatalyst (MIL-53), possibly due to different crystal structures caused by different acid dosages, and possibly related to the photocatalytic activity.
FIG. 4 is a diagram showing the band structure of the defective metal organic framework photocatalyst (D-1, D-4) and the perfect MIL-53 metal organic framework photocatalyst (MIL-53) prepared in example 1 of the present invention. As can be seen from FIG. 4, the valence band VB of the perfect MIL-53 MOF photocatalyst (MIL-53) was 2.10eV, and the valence band VB of the defective MOF photocatalysts (D-1 and D-4) was slightly changed to 2.00eV, which was smaller than E (OH)-/·OH)2.16eV, not and OH-OH is generated by the reaction. The conduction band CB of the perfect MIL-53 metal organic framework photocatalyst (MIL-53) is positioned at-0.56 eV and is less than E (O)2/·O2 -) 0.33eV, possibly in combination with O2Reaction to form O2 -，·O2 -Participate in the photocatalytic degradation reaction of tetracycline. The positions of conduction band CB of the defective metal organic framework photocatalysts (D-1 and D-4) are slightly changed and are respectively moved to-0.58 eV and-0.68 eV which are less than E (O)2/·O2 -) 0.33eV, possibly in combination with O2Reaction to form O2 -，·O2 -Participate in the photocatalytic degradation reaction of tetracycline. It can be seen that different band structures may be associated with different amounts of hydrochloric acid.
In the example, 3mL of sample was taken every 30min, the characteristic peak of tetracycline in the solution was measured by an ultraviolet-visible spectrophotometer and converted to concentration, and the degradation rate was calculated
FIG. 5 is a graph showing the effect of defective MOFs photocatalyst (D-1, D-2, D-3, D-4, D-5, D-10) and perfect MIL-53 MOFs photocatalyst (MIL-53) on the photocatalytic degradation of tetracycline under the condition of λ > 420nm in visible light in example 1 of the present invention. As shown in FIG. 5, the degradation rates of D-1, D-2, D-3, MIL-53, D-4, D-5 and D-10 for tetracycline were 90.17%, 79.8%, 69%, 59%, 52%, 42.7% and 39%, respectively. In the dark reaction stage, several materials have adsorption effect on tetracycline, because several materials have porous structures, which are beneficial to adsorption. The photocatalysis efficiency of a perfect MIL-53 metal organic framework photocatalyst (MIL-53) is 59 percent, which shows that the MIL-53 is a photocatalyst for potential degradation of organic dye wastewater. The degradation rate of acid-regulated defective metal organic framework photocatalysts (D-1, D-2 and D-3) to tetracycline is 90.17%, 79.8% and 69%, and the photocatalytic activity of MIL-53 can be improved, which indicates that the acid regulation strategy is feasible for improving the photocatalytic activity of the metal organic framework. However, the degradation rates of the defective metal organic framework photocatalysts (D-4, D-5 and D-10) on tetracycline are respectively 52%, 42.7% and 39%, which are lower than MIL-53, and the defect indicates that the excessive acid can influence the crystal structure and reduce the photocatalytic activity. Thus, in the acid-conditioning strategy, the amount of acid has a significant effect on the photocatalytic activity, and the appropriate amount of acid needs to be selected.
Example 2:
a method for photocatalytic degradation of organic pollutants by using a defective metal organic framework photocatalyst, in particular to photocatalytic degradation of tetracycline water bodies with different concentrations by using a defective MIL-53 metal organic framework photocatalyst, which comprises the following steps:
taking 4 parts of the defective metal organic framework photocatalyst (D-1) prepared in the example 1, adding 50mg of the defective metal organic framework photocatalyst into tetracycline solutions (the volume is 100mL) with the concentrations of 10mg/L, 20mg/L, 30mg/L and 40mg/L respectively, carrying out ultrasonic uniform reaction for 60min (magnetic stirring) under the condition of no light, illuminating for 150min under the condition of visible light with the wavelength lambda being more than 420nm after adsorption and desorption balance is achieved, and carrying out photocatalytic degradation reaction to complete photocatalytic degradation of tetracycline in the water body.
Sampling 3mL every 30min, measuring the characteristic peak value of tetracycline in the solution by using an ultraviolet-visible spectrophotometer, converting the characteristic peak value into concentration, and calculating the degradation rate.
FIG. 6 is a graph showing the effect of the defective metal-organic framework photocatalyst (D-1) in example 2 on the photocatalytic degradation of tetracycline at different concentrations under visible light with a wavelength λ > 420 nm. As shown in FIG. 6, the degradation rates of the defective metal-organic framework photocatalyst (D-1) to tetracycline solutions with initial concentrations of 10mg/L, 20mg/L, 30mg/L and 40mg/L were 96.93%, 90.17%, 84.51% and 79.0%, respectively, which indicates that the photocatalytic effect of the defective metal-organic framework photocatalyst (D-1) decreases with the increase of tetracycline concentration; meanwhile, the defect type metal organic framework photocatalyst (D-1) can treat tetracycline solution with higher concentration.
Example 3:
a method for degrading organic pollutants by using defect metal organic framework photocatalyst photocatalysis, in particular to a method for circularly degrading tetracycline by using defect MIL-53 metal organic framework photocatalyst, which comprises the following steps:
(1) adding 50mg of the defective metal organic framework photocatalyst (D-1) prepared in the example 1 into 100mL of tetracycline solution with the concentration of 20mg/L, carrying out ultrasonic uniform reaction for 60min (magnetic stirring) under a dark condition, illuminating for 150min under a visible light condition with the wavelength lambda being more than 420nm after adsorption and desorption balance is achieved, and carrying out photocatalytic degradation reaction to complete photocatalytic degradation of tetracycline in a water body.
(2) And (2) after the photocatalytic degradation reaction in the step (1) is finished, collecting the residual sample, drying, and carrying out photocatalytic degradation on the tetracycline water body under the same experimental conditions for 4 times in total.
Sampling 3mL every 30min, measuring the characteristic peak value of tetracycline in the solution by using an ultraviolet-visible spectrophotometer, converting the characteristic peak value into concentration, and calculating the degradation rate of different cycles.
FIG. 7 is a graph showing the cyclic degradation effect of the defective metal-organic framework photocatalyst (D-1) in example 3 of the present invention in photocatalytic degradation of tetracycline under visible light with a wavelength λ > 420 nm. As shown in FIG. 7, the degradation rates of tetracycline by four-cycle degradation are respectively 90.17%, 88.64%, 84.42% and 75.24%, which indicates that the defect type metal organic framework photocatalyst (D-1) has good reusability and can be used in practical water bodies.
In conclusion, the defect type metal organic framework photocatalyst has a good crystal structure, a high specific surface area and a uniform mesoporous structure, is responsive to visible light, has good separation and migration efficiency of a photon-generated carrier, is a photocatalyst with high photocatalytic activity, can quickly and efficiently degrade organic pollutants, meets the requirements of practical application, and has good use value and application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (7)
1. A method for degrading organic pollutants by using defect metal organic framework photocatalyst is characterized in that the method adopts the defect metal organic framework photocatalyst to carry out photocatalytic degradation on the organic pollutants; the preparation method of the defect type metal organic framework photocatalyst comprises the following steps:
(1) dissolving ferric trichloride hexahydrate and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution A;
(2) adding an acid regulator into the mixed solution A obtained in the step (1) to obtain a mixed solution B; the ratio of the mixed solution A to the acid regulator is 56mL to 10 mu L-56 mL to 30 mu L; the acid regulator is HCl solution; the concentration of the HCl solution is 1-5 mol/L;
(3) carrying out solvent thermal reaction on the mixed solution B obtained in the step (2), cleaning, filtering and drying to obtain a defective metal organic framework photocatalyst; the defect type metal organic framework photocatalyst is a defect type MIL-53 metal organic framework photocatalyst.
2. The process according to claim 1, wherein in the step (1), the molar ratio of ferric trichloride hexahydrate, terephthalic acid and N, N-dimethylformamide is 1: 280.
3. The method according to claim 1, wherein in the step (3), the temperature of the solvothermal reaction is 150-170 ℃; the solvothermal reaction time is 15-24 h.
4. The method according to any one of claims 1 to 3, wherein the method is used for photocatalytic degradation of organic pollutants in a water body by using a defective metal organic framework photocatalyst, and comprises the following steps: the defect type metal organic framework photocatalyst is mixed with organic pollutant water to carry out dark reaction, and photocatalytic degradation reaction is carried out after adsorption and desorption balance is achieved, so that photocatalytic degradation of the organic pollutants in the water is completed.
5. The method according to claim 4, wherein the addition amount of the defective metal organic framework photocatalyst is 0.3-0.5 g per liter of organic pollutant water.
6. The method of claim 5, wherein the body of organic contaminant water is antibiotic wastewater; the antibiotic in the antibiotic wastewater is tetracycline; the concentration of the organic pollutants in the organic pollutant water body is 10 mg/L-40 mg/L.
7. The method according to claim 5 or 6, wherein the dark reaction is stirring under dark conditions; the dark reaction time is 30-60 min; the photocatalytic degradation reaction is carried out under the condition of visible light with the wavelength lambda being more than 420; the time of the photocatalytic degradation reaction is 120-150 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910048721.2A CN109647525B (en) | 2019-01-18 | 2019-01-18 | Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910048721.2A CN109647525B (en) | 2019-01-18 | 2019-01-18 | Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109647525A CN109647525A (en) | 2019-04-19 |
| CN109647525B true CN109647525B (en) | 2020-08-28 |
Family
ID=66120184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910048721.2A Active CN109647525B (en) | 2019-01-18 | 2019-01-18 | Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109647525B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899559B (en) * | 2017-11-29 | 2020-07-31 | 中南大学 | Defect MI L-53 (Al) metal organic framework and preparation method and application thereof |
| CN110095420B (en) * | 2019-05-08 | 2022-02-11 | 国家纳米科学中心 | Method for detecting concentration of hydrogen peroxide and application thereof |
| CN110244016B (en) * | 2019-07-16 | 2020-06-05 | 中国矿业大学(北京) | Method and device for measuring degradation rate of organic pollutants |
| CN110668547A (en) * | 2019-08-08 | 2020-01-10 | 天津大学 | Method for treating metronidazole wastewater by utilizing photocatalytic oxidation technology |
| CN111992253A (en) * | 2020-03-17 | 2020-11-27 | 武汉纺织大学 | Organic-metal framework catalyst for catalytic degradation of antibiotics and preparation method thereof |
| CN111659468B (en) * | 2020-06-17 | 2023-06-20 | 南京师范大学 | MoS (MoS) 2 Composite catalyst of defective MIL-101 (Fe), preparation method and application |
| CN111790405B (en) * | 2020-07-09 | 2022-04-12 | 湖南大学 | Photocatalyst capable of degrading antibiotics and preparation method and application thereof |
| CN112657555B (en) * | 2020-12-01 | 2022-06-17 | 南昌航空大学 | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof |
| CN112877714B (en) * | 2021-01-27 | 2022-04-08 | 浙江大学衢州研究院 | Double-defect ultrathin metal organic framework nanosheet catalyst and preparation method and application thereof |
| CN113145174B (en) * | 2021-04-15 | 2022-06-07 | 中南林业科技大学 | Coordination modulator modified iron-based metal organic framework porous composite material and preparation method and application thereof |
| CN113318791B (en) * | 2021-06-30 | 2022-06-14 | 武汉大学 | Preparation method and application of amino-modified Fe/Cu-MOF photocatalyst |
| CN113559936A (en) * | 2021-07-30 | 2021-10-29 | 陕西科技大学 | Defective UiO-66 photocatalytic material and preparation method and application thereof |
| CN114957693B (en) * | 2022-05-26 | 2023-06-20 | 东莞理工学院 | Preparation and application of defective iron-based metal organic framework for enhancing active point exposure |
| CN115007215A (en) * | 2022-07-23 | 2022-09-06 | 南京信息工程大学 | Preparation method of uniform MIL-101(Fe) icosahedral photocatalyst |
-
2019
- 2019-01-18 CN CN201910048721.2A patent/CN109647525B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109647525A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109647525B (en) | Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst | |
| CN112892611B (en) | Fish scale tubular carbon nitride and preparation method and application thereof | |
| Wang et al. | Photocatalytic MOF membranes with two-dimensional heterostructure for the enhanced removal of agricultural pollutants in water | |
| Li et al. | ZIF-derived non-bonding Co/Zn coordinated hollow carbon nitride for enhanced removal of antibiotic contaminants by peroxymonosulfate activation: Performance and mechanism | |
| CN106492847B (en) | Cellulose nanometer fibril aeroge of negative photocatalyst-bearing and preparation method thereof | |
| CN109201121B (en) | Bimetal load type magnetic visible light composite catalytic material and preparation method and application thereof | |
| CN109847801B (en) | Defective metal organic framework photocatalyst and preparation method thereof | |
| CN106693996B (en) | Preparation method and application of bismuth sulfide-bismuth ferrite composite visible-light-driven photocatalyst | |
| Yang et al. | Two-dimensional layered organic hybrid selenidostannate coupled with polyaniline for high efficient photocatalytic Cr (VI) reduction | |
| CN109569732B (en) | Method for preparing MIL-100(Fe)/BiOCl composite photocatalyst by one-pot method | |
| Li et al. | Bimetallic (Cu, Zn) ZIF-derived S-scheme heterojunction for efficient remediation of aqueous pollutants in visible light/peroxymonosulfate system | |
| CN112718009A (en) | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof | |
| Guo et al. | Precise regulation of defect concentration in MOF and its influence on photocatalytic overall water splitting | |
| CN109999917B (en) | Covalent organic framework-based composite photocatalyst for degrading organic pollutants in water and preparation method thereof | |
| Ma et al. | Cerium-cobalt bimetallic metal–organic frameworks with the mixed ligands for photocatalytic degradation of methylene blue | |
| CN111085215B (en) | alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst | |
| Nguyen et al. | Bimetallic Co/Zn-ZIF as an efficient photocatalyst for degradation of indigo carmine | |
| CN113289685A (en) | Bismuth molybdate/modified MIL-88A-Fe composite photocatalyst and preparation method thereof | |
| CN110180572B (en) | N-doped BiVO 4 -OVs/GO nano composite structured photocatalytic material and application thereof | |
| CN107570212B (en) | Metal oxide catalyst with composite material as carrier and preparation method and application thereof | |
| CN113522330B (en) | Magnetic ZIF-8 coated Fe3O4/g-C3N4Composite catalyst, preparation method and application | |
| CN110586139B (en) | Fe (III) cluster/bismuth oxyiodate composite photocatalytic material and preparation method and application thereof | |
| CN114849762A (en) | g-C 3 N 4 /BiOI/Ag 2 CrO 4 Preparation method and application of ternary heterojunction photocatalyst | |
| CN113751033A (en) | MOF modified zeolite loaded BiOX/TiO2Photocatalytic material and preparation method thereof | |
| CN112371147A (en) | Fe3O4Quantum dot modified Bi2O4/g-C3N4Preparation method and application of composite photocatalyst |
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 |