CN112076796A - Preparation method and application of magnetic Cu-MOF-based photocatalyst - Google Patents
Preparation method and application of magnetic Cu-MOF-based photocatalyst Download PDFInfo
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- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 90
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000013110 organic ligand Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 24
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960003506 piperazine hexahydrate Drugs 0.000 claims abstract description 18
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 18
- XRSQZFJLEPBPOZ-UHFFFAOYSA-N 4-amino-2-methylbenzoic acid Chemical compound CC1=CC(N)=CC=C1C(O)=O XRSQZFJLEPBPOZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- 238000003828 vacuum filtration Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000004753 textile Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 229910017135 Fe—O Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
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- 239000013505 freshwater Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IAZJBPYVKVBVSI-UHFFFAOYSA-N phenyl-(2-phenylphenyl)diazene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1C1=CC=CC=C1 IAZJBPYVKVBVSI-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
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- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
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Abstract
The invention discloses a preparation method of a magnetic Cu-MOF-based photocatalyst, which comprises the following steps: under closed conditions, copper nitrate trihydrate Cu (N)O3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 4.0-6.0, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst. The material has an absorption wavelength range of 475-800nm to visible light, and shows excellent visible light response capability; the magnetic Cu-MOF-based photocatalyst has good thermal stability, can keep the stability of a framework below 265 ℃, and shows good photocatalytic degradation efficiency, water stability and recyclable performance when active deep blue K-R in water is degraded by photocatalysis.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a preparation method of a magnetic Cu-MOF-based photocatalyst, and application of the magnetic Cu-MOF-based photocatalyst.
Background
About 2/3 people live in water-deficient areas, and water pollution further aggravates the shortage of fresh water. According to statistics, about 80 million tons of dye are produced in the world every year, 10-15% of dye can enter environmental water body in the production and dyeing process, and hundreds of millions of tons of high-toxicity high-carcinogenicity/mutagenicity wastewater are generated. Approximately 3000 million tons of textiles are consumed by human beings every year, most of the textiles need to be dyed, the dyes are approximately 75% of azo (phenylazobenzene) structures, and most of the dyes are reactive dyes which have extremely high stability (for example, the hydrolysis half-life of reactive blue 19 is approximately 46 years) and cannot be naturally degraded. Therefore, the treatment of dyeing wastewater has attracted high attention from governments, industries and academia of various countries in the world. As the first textile kingdom in the world, the research on how to solve the important environmental problem has great significance for strengthening ecological environment protection and building an environment-friendly society which is put forward in the 'thirteen-five' planning of China.
The photocatalytic degradation has attracted attention due to high economy, thorough treatment, simple operation, environmental friendliness and the ability to utilize solar energy. Metal oxide photocatalyst TiO2ZnO and the like can be used for photocatalytic degradation of dyes, but are easy to run off and difficult to recover in practical useThe utilization rate of visible light is low. Metal sulfide CdS, In2S3The visible light has high utilization rate, but is easily polluted by heavy metal caused by photo-corrosion, and the surface energy is high, so that the visible light is easy to agglomerate and lose efficacy. The metal-organic framework (MOFs) material is a crystalline solid porous hybrid material formed by orderly assembling metal nodes and organic ligands through coordination bonds. Semiconductor quantum dots (metal nodes) or light absorption antennas (aromatic organic ligands) which are isolated, uniformly and orderly distributed can generate a charge separation excited state on MOFs under the action of light excitation, so that a photocatalytic reaction is driven to be carried out, and the designability of the MOFs is far superior to that of inorganic semiconductors and other porous materials. The MOFs is improved through post-modification to obtain high visible light responsiveness and magnetism, so that efficient visible light catalytic degradation of the MOFs composite material on reactive dyes can be realized, rapid separation from a water body environment can be realized, and the recyclable performance of the MOFs composite material is remarkably improved.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic Cu-MOF-based photocatalyst, and the Cu-MOF-based photocatalyst has good thermal stability and good photocatalytic degradation efficiency.
The invention also aims to provide application of the magnetic Cu-MOF-based photocatalyst in degrading active deep blue K-R in water.
The technical scheme adopted by the invention is that a preparation method of a magnetic Cu-MOF-based photocatalyst comprises the following steps: under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 4.0-6.0, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst.
The present invention is also characterized in that,
copper nitrate trihydrate, organic ligand H3L, piperazine hexahydrate and Fe3O4The molar ratio of the nano particles is 2-4: 1: 0.2-0.5: 1-3; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5：1-3。
The temperature of the solvothermal reaction is 65-85 ℃, and the required reaction time is 24-72 hours.
Triangular organic ligands H3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, performing vacuum filtration to remove DMF and distilled water by using a Buchner funnel after 30min, namely washing and performing vacuum filtration by using distilled water and methanol in sequence, drying the obtained white solid at the drying temperature of 70 ℃ for 8H to obtain the organic ligand H3L。
The invention adopts another technical scheme that the magnetic Cu-MOF-based photocatalyst is used for carrying out photocatalytic degradation on dye active deep blue K-R for textile industry in water.
The beneficial effect of the invention is that,
the invention adopts transition metal copper ions and a triangular organic ligand H3L、Fe3O4The magnetic Cu-MOF-based photocatalyst is constructed by coordination self-assembly of the nano particles, and the material has an absorption wavelength range of 475-800nm to visible light, thereby showing excellent visible light response capability; the magnetic Cu-MOF-based photocatalyst has good thermal stability, can keep the stability of a framework below 265 ℃, and shows good photocatalytic degradation efficiency, water stability and recyclable performance when active deep blue K-R in water is degraded by photocatalysis. In addition, the preparation method is simple and is applied to the reaction of photocatalytic degradationMild condition, easy recovery and no secondary pollution.
Drawings
FIG. 1 is a graph of the thermal weight loss of the prepared magnetic Cu-MOF-based photocatalyst;
FIG. 2 shows the Cu-MOF, magnetic Cu-MOF based photocatalyst and Fe prepared3O4An infrared spectrum of the nanoparticles;
FIG. 3 shows the Cu-MOF, magnetic Cu-MOF based photocatalysts and Fe prepared3O4Single crystal X-ray powder diffraction simulated patterns (theoretical values) of nanoparticles and actual test X-ray powder diffraction patterns (actual values) of a large number of crystal samples;
FIG. 4 is a scanning electron microscope image of the prepared magnetic Cu-MOF-based photocatalyst;
FIG. 5 is a UV-VIS diffuse reflectance spectrum of the prepared magnetic Cu-MOF based photocatalyst;
FIG. 6 is a graph of the UV-VIS absorption spectra of active deep blue K-R liquids in water at different concentrations.
FIG. 7 is a standard curve of absorbance Y of UV-VIS absorption spectrum of active deep blue K-R liquid with different concentrations in water and corresponding concentration X.
FIG. 8 is a diagram of the ultraviolet-visible absorption spectrum of an aqueous solution of active deep blue K-R with the initial concentration of 34.02mg/L in photocatalytic degradation water by using a magnetic Cu-MOF photocatalytic material.
FIG. 9 is a graph of the concentration ratio C/C corresponding to the UV-VIS spectrum of the active deep blue K-R liquid of FIG. 80Curve over time t, wherein C0Initial concentration, C real-time concentration.
FIG. 10 is a graph of the concentration ratio C/C corresponding to the UV-VIS absorption spectrum of the active deep blue K-R liquid of FIG. 80Is plotted against time t.
FIG. 11 is a graph of the photocatalytic degradation efficiency of the prepared magnetic Cu-MOF photocatalytic material in 5 consecutive cycles of photocatalytic degradation of an aqueous solution of active deep blue K-R of 34.02 mg/L.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a magnetic Cu-MOF-based photocatalyst, which comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 4.0-6.0, and reacting under a solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst;
copper nitrate trihydrate, organic ligand H3L, piperazine hexahydrate and Fe3O4The molar ratio of the nano particles is 2-4: 1: 0.2-0.5: 1-3; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 1-3; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 65-85 ℃, and the required reaction time is 24-72 hours;
more preferably, copper nitrate trihydrate and organic ligand H3L, piperazine hexahydrate and Fe as template agent3O4The molar ratio of the nanoparticles is 2: 1: 0.2: 1, and the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 3, specifically 0.02mmol (12.22mg) of organic ligand H per 0.04mmol (7.18mg) of copper nitrate trihydrate3L, 0.004mmol (0.78mg) of piperazine hexahydrate and 0.02mmol (4.63mg) of Fe3O4Corresponding to 5mL of N, N-dimethylformamide and 3mL of absolute ethanol; the temperature of the solvothermal reaction is 75 ℃, and the reaction time is 48 h;
triangular organic ligands H3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H3L；
The drying temperature is 70 ℃, and the drying time is 8 hours;
organic ligand H3The route of the synthesis reaction of L is as follows:
the magnetic Cu-MOF-based photocatalyst is used for carrying out photocatalytic degradation on active deep blue K-R of a dye for textile industry in a water body; the method specifically comprises the following steps: pouring a dye solution containing active deep blue K-R into a quartz tube reactor, adding a magnetic Cu-MOF-based photocatalyst, continuously stirring for 1-3h in a dark box under the condition of light isolation to ensure that the dye and the catalyst reach adsorption-desorption balance, and then continuously stirring for 2-16h under the irradiation of a 300W xenon lamp until the photocatalytic degradation is finished.
Further preferably, the concentration of active deep blue K-R in the dye aqueous solution is controlled to be 0.5-80mg/L, and 5-20mg of magnetic Cu-MOF-based photocatalyst is added into 60mL of the dye aqueous solution with the concentration; after the photocatalytic degradation is finished, the magnetic Cu-MOF-based photocatalyst is separated by magnet attraction and recycled according to the method.
The magnetic Cu-MOF-based photocatalyst provided by the invention has three important conditions of high-efficiency visible light catalytic degradation of active deep blue K-R in water under visible light irradiation simulated by a xenon lamp: firstly, an ultraviolet-visible diffuse reflection (UV-Vis DRS) spectrogram of the magnetic photocatalyst shows that the absorption wavelength range of the magnetic photocatalyst to visible light is 475-; secondly, the Cu-MOF framework of the magnetic photocatalyst has a three-dimensional structure which is inserted and nested in a double way, and the deprotonated aromatic H in the framework3Highly ordered rows of L ligandsIn addition, the method is beneficial to enhancing the light absorption and pi electron supply effect, promoting the generation and transfer of photo-generated electrons, improving the separation efficiency of photo-generated electrons and holes and improving the photocatalysis efficiency. Thirdly, the Fe3O4The widely fused Fe-O metal cluster exists in the basic magnetic Cu-MOF photocatalyst, so that visible light can be directly absorbed, energy is transferred to a Cu-MOF framework, and the visible light catalysis efficiency is improved; fe3O4The existence of the nano particles enables the solid photocatalyst to be quickly separated from a water system under the action of the magnet, so that the loss of the catalyst is avoided, and the recycling capability is improved.
Infrared spectroscopy tests related to the present invention: uniformly mixing and grinding a magnetic Cu-MOF-based photocatalyst and potassium bromide powder according to a mass ratio of 1:100, pressing into a sheet, and testing on an infrared spectrometer.
The invention relates to a test of a thermal weight loss curve: weighing 8-20 mg of naturally-dried magnetic Cu-MOF-based photocatalyst, placing the weighed magnetic Cu-MOF-based photocatalyst into an alumina crucible, and testing on a thermal weight loss analyzer.
The photocatalytic degradation test related to the present invention: after the magnetic Cu-MOF-based photocatalyst reaches adsorption-desorption balance in a dye solution with active deep blue K-R, taking out supernatant liquid at intervals under the irradiation of a 300W xenon lamp, placing the supernatant liquid in a cuvette, and testing on an ultraviolet-visible spectrophotometer.
Example 1
Organic ligand H3L(0.04mmol，24.44mg)、Cu(NO3)2·3H2O (0.08mmol, 14.36mg), piperazine hexahydrate (0.008mmol, 1.56mg) and 0.04mmol (9.26mg) Fe3O4After being uniformly mixed with 8.0mL of a mixed solution of N, N-dimethylformamide and absolute ethyl alcohol (volume ratio: 5: 3), a 65% by mass concentrated nitric acid solution was added dropwise thereto, the pH of the reaction system was adjusted to 5.0, and the mixture was sealed in a 25mL glass vial. And carrying out solvothermal reaction for 48 hours at 75 ℃, and naturally cooling to room temperature to obtain the magnetic Cu-MOF-based photocatalyst.
FIG. 1 is a graph showing the thermogravimetric plot of the prepared magnetic Cu-MOF-based photocatalyst, and it can be seen that under flowing nitrogen, the temperature is raised at 10 ℃/min, and the magnetic Cu-MOF-based photocatalyst undergoes 2 main weight loss stages within the temperature range of 30-800 ℃; a weight loss rate of about 47.63% between 30 ℃ and 190 ℃ resulting from the leaving of small guest molecules and coordinated DMF molecules within the magnetic Cu-MOF-based photocatalyst cavity; between 191 ℃ and 543 ℃, the weight loss rate of 28.75 percent comes from the collapse of the magnetic Cu-MOF-based photocatalyst framework and the decomposition of part of organic ligands; the remaining 12.27% of the mass was undecomposed ligand, ash and oxides of Cu, Fe, indicating that the magnetic Cu-MOF based photocatalyst has good thermal stability.
By the method of the invention, Fe is not added3O4Under the condition of magnetic nano particles, preparing Cu-MOF according to the same process; FIG. 2 shows the Cu-MOF, magnetic Cu-MOF based photocatalyst and Fe prepared3O4Infrared spectrum of the nanoparticles. The spectrum of FIG. 2 shows 3270cm-1The nearby characteristic peaks are caused by stretching vibration of amide groups on organic ligands of Cu-MOF and magnetic Cu-MOF based photocatalysts; 1387cm-1Nearby stretching vibration peaks are attributed to asymmetric stretching vibration of carbonyl groups on the aromatic rings of the Cu-MOF and magnetic Cu-MOF based photocatalysts. Magnetic Cu-MOF-based photocatalyst is 561cm-1The characteristic peak comes from Fe in Cu-MOF cavity/pore channel3O4Stretching vibration of Fe-O bond in nano particle, while in pure Fe3O4The characteristic peak of the Fe-O bond in the nano particle appears at 568cm-1To (3).
FIG. 3 shows the Cu-MOF, magnetic Cu-MOF based photocatalysts and Fe prepared3O4Single crystal X-ray powder diffraction patterns (theoretical values) for the nanoparticles and actual test X-ray powder diffraction patterns (actual values) for a large number of crystal samples. The spectrum of fig. 3 shows that the actual values (namely 2 theta angle values) of diffraction peaks of X-ray powder diffraction spectra of a large number of samples of the Cu-MOF and magnetic Cu-MOF based photocatalysts are basically consistent with the theoretical values obtained by a Cu-MOF single crystal diffraction test, and the spatial structures of the large number of synthesized Cu-MOF and magnetic Cu-MOF based photocatalysts are consistent with the spatial structure of a single crystal used by the single crystal test, and the difference of the intensities of the individual diffraction peaks is related to the preferred orientation of the samples. In addition, the magnetic Cu-MOF-based photocatalyst is 62.6 degrees, 57.2 degrees and 43.3 degreesDiffraction peak positions at 35.6 DEG, 30.4 DEG and Fe3O4Diffraction peak positions of the nano particles at 62.4 degrees, 57.4 degrees, 43.1 degrees, 35.4 degrees and 30.3 degrees are almost completely consistent, which indicates that magnetic Fe exists in a cavity/pore channel of the magnetic Cu-MOF-based photocatalyst3O4Nanoparticles.
FIG. 4 is a scanning electron microscope image of the prepared magnetic Cu-MOF-based photocatalyst. The spectrum of FIG. 4 shows that the appearance of the magnetic Cu-MOF photocatalyst crystal is in a multi-edge octahedral shape, and the size of a single crystal is about 300X 300 μm3。
FIG. 5 is a UV-VIS diffuse reflectance spectrum of the prepared magnetic Cu-MOF based photocatalyst; the ultraviolet-visible diffuse reflection curve in FIG. 5 shows that, with white barium sulfate white plate as the blank control, the absorption wavelength of the magnetic Cu-MOF-based photocatalyst to visible light within the range of 200-800 nm is 475-800 nm.
When the magnetic Cu-MOF-based photocatalyst prepared in example 1 is used for catalyzing and degrading active dark blue K-R by visible light, the concentration range of the dye aqueous solution is 0.1 mg/L-50 mg/L.
Preparing 8 active deep blue K-R aqueous solutions with the concentrations of 0.1, 1, 5, 10, 20, 30, 40 and 50mg/L by using distilled water as an experimental group, and using the distilled water as a blank control, and respectively testing the absorbance values of the active deep blue K-R aqueous solutions with different concentrations at the position of 571nm of the maximum absorption wavelength of the active deep blue K-R aqueous solutions by using an ultraviolet-visible spectrophotometer, wherein as shown in figure 6, the absorbance values at the position of 571nm are increased along with the gradual increase of the concentration of the prepared dye active deep blue K-R; and drawing a standard curve by taking the concentration of the active deep blue K-R aqueous solution as an X axis and the corresponding absorbance value as a Y axis, wherein a standard linear function relation curve is presented between the absorbance value Y of the dye and the concentration X, and R is shown in figure 72Is 0.9997.
The magnetic Cu-MOF-based photocatalyst prepared in example 1 is used for catalyzing and degrading active deep blue K-R with the concentration of 34.02mg/L by visible light;
weighing 10mg of the magnetic Cu-MOF-based photocatalyst prepared in example 1, placing the magnetic Cu-MOF-based photocatalyst in a 100mL quartz tube reactor, and pouring 60mL of active deep blue with a certain concentration into the quartz tube reactorAnd transferring the K-R aqueous solution into a dark box at room temperature, and placing the solution for about 1h under magnetic stirring until adsorption-desorption equilibrium is achieved between the dye molecules and the photocatalyst. Taking out 4mL of active deep blue K-R supernatant to test the absorbance value, determining the concentration of the active deep blue K-R supernatant to be 34.02mg/L through a standard curve, then starting a 300W xenon lamp for irradiation under magnetic stirring, setting 34.02mg/L of active deep blue K-R aqueous solution without adding other photocatalysts as a blank control sample, taking out 4mL of supernatant at regular intervals (quickly pouring the supernatant into a quartz tube after the test is finished), and testing an ultraviolet-visible absorption spectrogram of the active deep blue K-R by using an ultraviolet-visible spectrophotometer, wherein as shown in figure 8, the absorbance value of the active deep blue K-R at 571nm is quickly reduced along with the extension of the illumination time, and the characteristic absorption peak almost completely disappears after 16 hours. The change of the concentration of active deep blue K-R with time, at which the concentration C and the initial concentration C were compared, was read through the standard curve of FIG. 70Ratio of C/C0The photocatalytic degradation efficiency of the magnetic Cu-MOF-based photocatalyst on the active deep blue K-R is obtained by taking the time as an X axis and a Y axis, as shown in figure 9, within 16h, the visible light catalytic degradation efficiency of the magnetic Cu-MOF-based photocatalyst on the active deep blue K-R is 87.6%; in the blank control sample without adding the photocatalyst, the concentration of the dye is only slightly and negligibly changed, which shows that the magnetic Cu-MOF-based photocatalyst has remarkable visible light photocatalytic degradation efficiency on active deep blue K-R. In addition, as shown in FIG. 10, in ln (C/C)0) Plotted as Y-axis and time as X-axis, the resulting photocatalytic degradation rate constant (i.e., the slope of the line in FIG. 10) was 0.122h-1(R2＝0.995)。
Continuously circulating visible light catalytic degradation is carried out on the active dark blue K-R by circularly utilizing the magnetic Cu-MOF photocatalyst; attracting the magnetic Cu-MOF-based photocatalyst at the bottom of the quartz tube by a magnet, pouring out the dye aqueous solution residual liquid in the quartz tube, separating the photocatalyst and repeating the photocatalytic degradation experiment operation again. As shown in fig. 11, in the next 4 continuous photocatalytic degradation cycle experiments, the photocatalytic degradation efficiency of the cyclically used magnetic Cu-MOF-based photocatalyst on the active deep blue K-R is 83.4%, 80.2%, 78.1% and 75.1%, respectively, and the experimental results show that the magnetic Cu-MOF-based photocatalyst is stable in the process of catalytically degrading the active deep blue K-R by visible light and has a good catalytic degradation effect.
Example 2
The invention relates to a preparation method of a magnetic Cu-MOF-based photocatalyst, which comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 4.0, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst;
copper nitrate trihydrate, organic ligand H3L, piperazine hexahydrate and Fe3O4The molar ratio of the nanoparticles is 2: 1: 0.2: 1; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 1; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 65 ℃, and the required reaction time is 24 hours;
triangular organic ligands H3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step 1.1 within 15min, dripping triethylamine into the mixed solution within 10min, reacting in an ice-water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H3L；
The drying temperature is 70 ℃, and the drying time is 8 hours;
example 3
The invention relates to a preparation method of a magnetic Cu-MOF-based photocatalyst, which comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 6.0, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst;
copper nitrate trihydrate, organic ligand H3L, piperazine hexahydrate and Fe3O4The molar ratio of the nanoparticles is 3: 1: 0.3: 2; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 2; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 70 ℃, and the required reaction time is 30 hours;
triangular organic ligands H3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step 1.1 within 15min, dripping triethylamine into the mixed solution within 10min, reacting in an ice-water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H3L；
The drying temperature is 70 ℃, and the drying time is 8 hours;
example 4
The invention relates to a preparation method of a magnetic Cu-MOF-based photocatalyst, which comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 4.5, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst;
copper nitrate trihydrate, organic ligand H3L, piperazine hexahydrate and Fe3O4The molar ratio of the nanoparticles is 4: 1: 0.4: 1.5; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 1; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 80 ℃, and the required reaction time is 40 hours;
triangular organic ligands H3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step 1.1 within 15min, dripping triethylamine into the mixed solution within 10min, reacting in an ice-water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H3L；
The drying temperature is 70 ℃, and the drying time is 8 hours;
example 5
The invention relates to a preparation method of a magnetic Cu-MOF-based photocatalyst, which comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 6.0, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst;
copper nitrate trihydrate, organic ligand H3L, piperazine hexahydrate and Fe3O4The molar ratio of the nanoparticles is 4: 1: 0.5: 3; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 3; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 85 ℃, and the required reaction time is 72 hours;
triangular organic ligands H3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step 1.1 within 15min, dripping triethylamine into the mixed solution within 10min, reacting in an ice-water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H3L；
The drying temperature is 70 ℃, and the drying time is 8 h.
Claims (5)
1. A preparation method of a magnetic Cu-MOF-based photocatalyst is characterized by comprising the following steps: under closed conditions, copper nitrate trihydrate Cu (NO)3)2·3H2O and organic ligand H3L、Fe3O4Uniformly mixing magnetic nanoparticles, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol, continuously stirring, dropwise adding concentrated nitric acid solution to adjust the pH of a reaction system to 4.0-6.0, and reacting under the solvothermal condition to obtain the magnetic Cu-MOF-based photocatalyst.
2. The method of claim 1, wherein the copper nitrate trihydrate and organic ligand H are present in the form of a magnetic Cu-MOF-based photocatalyst3L, piperazine hexahydrate and Fe3O4The molar ratio of the nano particles is 2-4: 1: 0.2-0.5: 1-3; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5: 1-3.
3. The method of claim 1, wherein the temperature of the solvothermal reaction is 65-85 ℃ and the reaction time is 24-72 hours.
4. The method of claim 1, wherein the triangular organic ligand H is selected from the group consisting of3The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, performing vacuum filtration to remove DMF and distilled water by using a Buchner funnel after 30min, namely washing and performing vacuum filtration by using distilled water and methanol in sequence, drying the obtained white solid at the drying temperature of 70 ℃ for 8H to obtain the organic ligand H3L。
5. The magnetic Cu-MOF-based photocatalyst prepared by the method of any one of claims 1 to 4, wherein the magnetic Cu-MOF-based photocatalyst is used for photocatalytic degradation of dye active deep blue K-R for textile industry in a water body.
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| CN115814838A (en) * | 2022-09-21 | 2023-03-21 | 上海婴鸟环保科技集团有限公司 | Supported catalyst for catalytic combustion of dichloroethane |
| CN115722212A (en) * | 2022-11-29 | 2023-03-03 | 浙江工业大学 | Magnetic metal-organic framework material and preparation method and application thereof |
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