CN113893852A - Preparation method and application of copper metal organic framework derived porous carbon composite material - Google Patents
Preparation method and application of copper metal organic framework derived porous carbon composite material Download PDFInfo
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- CN113893852A CN113893852A CN202111054918.0A CN202111054918A CN113893852A CN 113893852 A CN113893852 A CN 113893852A CN 202111054918 A CN202111054918 A CN 202111054918A CN 113893852 A CN113893852 A CN 113893852A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 claims abstract description 231
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 230000015556 catabolic process Effects 0.000 claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 30
- 239000011941 photocatalyst Substances 0.000 claims abstract description 24
- -1 copper metal organic framework compound Chemical class 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000001782 photodegradation Methods 0.000 claims abstract description 14
- 239000000975 dye Substances 0.000 claims description 67
- 239000011259 mixed solution Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 28
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 229940043267 rhodamine b Drugs 0.000 claims description 27
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 26
- 229940012189 methyl orange Drugs 0.000 claims description 26
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
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- 238000010000 carbonizing Methods 0.000 abstract 1
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- 239000000126 substance Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000007865 diluting Methods 0.000 description 10
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 239000013110 organic ligand Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention discloses a preparation method and application of a copper metal organic framework derived porous carbon composite material, wherein the preparation method comprises the following steps: 1) preparing a copper metal organic framework compound MOF; 2) carbonizing a copper metal organic framework compound MOF at high temperature to generate a copper metal organic framework derived porous carbon composite material; the copper metal organic framework derived porous carbon composite material prepared by the preparation method is used as a photocatalyst to be applied to the photodegradation reaction of organic dye. The preparation method has the advantages of sufficient raw material sources and low production cost, is suitable for expanded production requirements, and is convenient for industrial production; the copper metal organic framework derived porous carbon composite material prepared by the preparation method is applied to the photodegradation reaction of organic dye as a photocatalyst, the copper metal organic framework derived porous carbon composite material has strong catalytic degradation capability on the organic dye methyl violet, and the copper metal organic framework derived porous carbon composite material has good recycling capability and good stability.
Description
Technical Field
The invention relates to the technical field of preparation and application of photocatalysts, in particular to a preparation method and application of a porous carbon composite material derived from a copper metal organic framework.
Background
The industrial dye waste water is a main source of water pollution, wherein triphenylmethane dye is widely used as industrial dye due to the characteristics of bright color, high fixation rate, good dyeing fastness and the like, and the dosage is very large, but the dye waste water has high chroma, strong toxicity, is difficult to degrade and is easy to cause cancer, thus becoming one of the waste water which is urgently needed to be treated at present. Methyl violet as a triphenylmethane derivative has good water solubility, is widely applied to dyeing of silk, acrylic fiber, hemp, paper and leather, pigment, stamp-pad ink, printing ink and the like, and has very high toxicity to organisms when directly discharged into water. Various methods are used for removing organic dyeing, including adsorption, electrochemical methods and the like, but the traditional method is not economical and environment-friendly, can cause secondary pollution and cannot thoroughly degrade organic matters. There is therefore an urgent need to develop an economical and environmentally friendly method for photocatalytic degradation which can overcome the above problems, but there is still a need to develop a photocatalytic system having high catalytic activity.
Metal-Organic Frameworks (MOFs) materials have a wide variety of topological structure types and have excellent performance and potential application values in the fields of fluorescence, sensing, gas storage and separation and the like, and thus have been widely paid attention to by chemists and materials scientists in the last two decades. The MOF material is made of metal ions or goldThe metal ion cluster forms a structure infinitely expanded in a three-dimensional space through the connection of organic ligands, thereby having the advantages of both inorganic and organic materials. To receive TiO2Inspired by research on photocatalytic performance of semiconductor materials, attempts to apply MOF materials to the field of photocatalysis have been increasing in recent years. Organic ligands with electron-rich or large-pi conjugated structures tend to have strong absorption in the uv-vis region. In addition, Cu in the ligand field2+Electronic transitions between the d orbitals of the plasma also bring about absorption of the MOF material in the visible region.
The porous carbon material refers to a carbon material having a structure from nano-scale micro-pores to micro-scale pores, and can be classified into micro-porous, mesoporous and macroporous carbon materials due to different pore sizes. The ordered porous carbon material means a material having a uniform pore size distribution therein or having a specific pore structure. The ordered porous material has high chemical stability and good conductivity, and has high specific surface area and adjustable pore size due to the existence of the porous structure, so that the ordered porous material has wide application in the aspects of adsorption, catalysis, electrochemistry, energy storage and the like.
At present, the porous carbon material with regular pore size distribution prepared by calcining a metal organic framework compound serving as a precursor is applied to the photodegradation reaction of organic dye in a few reports.
Disclosure of Invention
The invention aims to solve the technical problems that aiming at the defects in the prior art, the preparation method and the application of the copper metal organic framework derived porous carbon composite material are provided, the preparation method is simple and easy to industrialize, the copper metal organic framework derived porous carbon composite material prepared by the preparation method is applied to the photodegradation reaction of organic dye as a photocatalyst, the copper metal organic framework derived porous carbon composite material has strong catalytic degradation capability on organic dye methyl violet, and the copper metal organic framework derived porous carbon composite material has good recycling capability and good stability.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a copper metal organic framework derived porous carbon composite material comprises the following steps:
1) dissolving 4-21 ligand and copper trifluoromethanesulfonate (II) in acetonitrile in sequence, stirring at room temperature for 15-25min to form a mixed solution A, dropwise adding triethylamine into the mixed solution A, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven for reacting for 22-26h, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (3) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace for high-temperature carbonization, and cooling to room temperature after calcination to obtain the copper metal organic framework derivative porous carbon composite material.
As a preferred embodiment, the molar ratio between the 4-21 ligand and the copper (II) trifluoromethanesulfonate in step 1) is 1: 2.
as a preferable scheme, in the step 1), during the reaction in which the vial containing the mixed solution B is placed in a drying oven, the temperature of the drying oven is maintained at 80 ℃.
As a preferable scheme, in the step 2), in the high-temperature carbonization process, the calcination temperature of the tubular muffle furnace is 800-1100 ℃.
As a preferable scheme, the calcination time is 2-8 h.
As a preferable scheme, the temperature rise rate of the tubular muffle furnace in the high-temperature carbonization process in the step 2) is 5 ℃/min.
As a preferable scheme, nitrogen is introduced during the high-temperature carbonization in the step 2), and the introduction rate of the nitrogen is 60 mL/min.
An application of the copper metal organic framework-derived porous carbon composite material, which is prepared by the preparation method of the copper metal organic framework-derived porous carbon composite material, as a photocatalyst in the photodegradation reaction of organic dye methyl violet.
As a preferable scheme, the copper metal organic framework derived porous carbon composite material has catalytic degradation capability on methylene blue, methyl orange, rhodamine B and methyl violet, wherein the catalytic degradation capability of the copper metal organic framework derived porous carbon composite material on methyl violet is strongest.
The invention has the beneficial effects that: the preparation method of the copper metal organic framework derived porous carbon composite material is simple, the raw material source is sufficient, the production cost is low, the requirements of expanded production are met, and the industrial production is facilitated; the copper metal organic framework derived porous carbon composite material prepared by the preparation method is applied to the photodegradation reaction of organic dye as a photocatalyst, the copper metal organic framework derived porous carbon composite material has strong catalytic degradation capability on the organic dye methyl violet, and the copper metal organic framework derived porous carbon composite material has good recycling capability and good stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of copper metal organic framework derivatized porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4 and Cu @ C-1100-4;
FIG. 2 is an X-ray diffraction pattern of copper metal organic framework derivatized porous carbon composite materials Cu @ C-1000-2, Cu @ C-1000-4 and Cu @ C-1000-8;
FIG. 3 is a Raman spectrum of copper metal organic framework derivatized porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4 and Cu @ C-1100-4;
FIG. 4 is a Raman spectrum of Cu metal organic framework derivatized porous carbon composite materials Cu @ C-1000-2, Cu @ C-1000-4 and Cu @ C-1000-8;
FIG. 5 is a drawing showing nitrogen adsorption stripping of copper metal organic framework derivatized porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4 and Cu @ C-1100-4;
FIG. 6 is a drawing showing the nitrogen adsorption stripping of copper metal organic framework derivatized porous carbon composite materials Cu @ C-1000-2, Cu @ C-1000-4 and Cu @ C-1000-8;
FIG. 7 is a plot of the pore size distribution of copper metal organic framework derivatized porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4 and Cu @ C-1100-4;
FIG. 8 is a plot of the pore size distribution of the copper metal organic framework derivatized porous carbon composite materials Cu @ C-1000-2, Cu @ C-1000-4 and Cu @ C-1000-8;
FIG. 9 is a scanning electron micrograph of copper metal organic framework derivatized porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4 and Cu @ C-1100-4;
FIG. 10 is a scanning electron micrograph of copper metal organic framework derivatized porous carbon composite materials Cu @ C-1000-2, Cu @ C-1000-4 and Cu @ C-1000-8;
FIG. 11 is a UV diffuse reflectance plot of copper metal organic framework derivatized porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2, and Cu @ C-1000-8;
FIG. 12 is O of Cu organometallic framework derivatized porous carbon composite Cu @ C-1000-42 -A free radical trapping pattern;
FIG. 13 is a-OH radical trapping diagram for a copper metal organic framework derivatized porous carbon composite Cu @ C-1000-4;
FIG. 14 is a graph of the photocatalytic performance of copper metal organic framework derivatized porous carbon composite Cu @ C-1000-4 for different dyes;
FIG. 15 is a graph of the photocatalytic performance of different copper metal organic framework derivatized porous carbon composites on Methyl Violet (MV) dye;
FIG. 16 is a graph of the photocatalytic performance of copper metal organic framework-derived porous carbon composite material Cu @ C-1000-4 versus Methyl Violet (MV) dye at different dosages;
FIG. 17 is a graph of the photocatalytic performance of copper metal organic framework derivatized porous carbon composite Cu @ C-1000-4 for different concentrations of Methyl Violet (MV) dye;
FIG. 18 is a graph of the photocatalytic performance of copper metal organic framework derivatized porous carbon composite Cu @ C-1000-4 for Methyl Violet (MV) dyes at different pH values;
FIG. 19 is a diagram of the study of the photocatalytic mechanism of copper metal organic framework-derived porous carbon composite material Cu @ C-1000-4 on Methyl Violet (MV) dye;
FIG. 20 is a graph of the photocatalytic stability of copper metal organic framework derivatized porous carbon composite Cu @ C-1000-4 versus Methyl Violet (MV) dye.
Detailed Description
The structural and operational principles of the present invention are explained in further detail below with reference to the accompanying drawings.
Example 1
Preparation of copper metal organic framework derived porous carbon composite material Cu @ C-800-4
1) Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven at the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (2) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace, calcining for 4 hours at the calcining temperature of 800 ℃, wherein the heating rate of the tubular muffle furnace is kept at 5 ℃/min in the heating process, introducing nitrogen in the working process of the tubular muffle furnace, keeping the introduction rate of the nitrogen at 60mL/min, and cooling to room temperature to obtain the copper metal organic framework derivative porous carbon composite material Cu @ C-800-4.
Example 2
Preparation of copper metal organic framework derived porous carbon composite material Cu @ C-900-4
1) Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven at the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (2) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace, calcining for 4 hours at the calcining temperature of 900 ℃, wherein the heating rate of the tubular muffle furnace is kept at 5 ℃/min in the heating process, introducing nitrogen in the working process of the tubular muffle furnace, keeping the introduction rate of the nitrogen at 60mL/min, and cooling to room temperature to obtain the copper metal organic framework derivative porous carbon composite material Cu @ C-900-4.
Example 3
Preparation of copper metal organic framework derived porous carbon composite material Cu @ C-1000-4
1) Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven at the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (2) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace, calcining for 4 hours at the calcining temperature of 1000 ℃, wherein the heating rate of the tubular muffle furnace is kept at 5 ℃/min in the heating process, introducing nitrogen in the working process of the tubular muffle furnace, keeping the introduction rate of the nitrogen at 60mL/min, and cooling to room temperature to obtain the copper metal organic framework derivative porous carbon composite material Cu @ C-1000-4.
Example 4
Preparation of copper metal organic framework derived porous carbon composite material Cu @ C-1100-4
1) Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven at the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (2) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace, calcining for 4 hours at the calcining temperature of 1100 ℃, wherein the heating rate of the tubular muffle furnace is kept at 5 ℃/min in the heating process, introducing nitrogen in the working process of the tubular muffle furnace, keeping the introduction rate of the nitrogen at 60mL/min, and cooling to room temperature to obtain the copper metal organic framework derivative porous carbon composite material Cu @ C-1100-4.
Comparative example 1
Preparation of copper metal organic framework derived porous carbon composite material Cu @ C-1000-2
1) Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven at the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (2) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace, calcining for 2h at the calcining temperature of 1000 ℃, wherein the heating rate of the tubular muffle furnace is kept at 5 ℃/min in the heating process, introducing nitrogen in the working process of the tubular muffle furnace, keeping the introduction rate of the nitrogen at 60mL/min, and cooling to room temperature to obtain the copper metal organic framework derivative porous carbon composite material Cu @ C-1000-2.
Comparative example 2
Preparation of copper metal organic framework derived porous carbon composite material Cu @ C-1000-8
1) Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven at the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (2) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace, calcining for 8 hours at the calcining temperature of 1000 ℃, wherein the heating rate of the tubular muffle furnace is kept at 5 ℃/min in the heating process, introducing nitrogen in the working process of the tubular muffle furnace, keeping the introduction rate of the nitrogen at 60mL/min, and cooling to room temperature to obtain the copper metal organic framework derivative porous carbon composite material Cu @ C-1000-8.
Comparative example 3
Preparation of copper metal organic framework compound MOF
Dissolving 0.05mmol of 4-21 ligand and 0.10mol of copper (II) trifluoromethanesulfonate in 10mL of acetonitrile in sequence, stirring at room temperature for 20min to form a mixed solution A, then adding 20 mu L of triethylamine into the mixed solution A dropwise, and uniformly shaking to obtain a mixed solution B; and (3) placing the small bottle filled with the mixed solution B into a drying oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain the copper metal organic framework compound MOF.
The 4-21 ligand used in examples 1-6 and comparative examples 1-3 above was prepared by comparative example 4, and the 4-21 ligand was a fluorescent compound, to which reference is specifically made below (patent No. 201710344393.1, entitled novel fluorescent compound and use thereof).
Comparative example 4
Preparation of 4-21 ligands
1) Fully dissolving 5g of resorcinol and 2.8mL of acetaldehyde in 30mL of ethanol with the volume concentration of 95% to form a mixture A;
2) freezing the mixture A, and dropwise adding 9mL of hydrochloric acid with the volume concentration of 37% to the frozen mixture A to form a mixture B;
3) heating the mixture B to room temperature, heating for 24 hours at the temperature of 80 ℃, and adding 30mL of deionized water into the mixture B after cooling to room temperature to obtain a mixed solution;
4) standing the mixed solution at-20 deg.C for 24 hr, and filtering to obtain yellow solid;
5) the yellow solid was placed in a mixture of ethanol and water at a ratio of 1: 1, washing the obtained glacial ethanol aqueous solution until the pH of the waste liquid is neutral to obtain a light yellow solid;
6) the pale yellow solid was dried under vacuum at 100 ℃ for 16 hours to give 4-21 ligand.
The copper metal organic framework-derived porous carbon composite material Cu @ C-800-4 used in the following experiments 1-13 was prepared from example 1, the copper metal organic framework-derived porous carbon composite material Cu @ C-900-4 was prepared from example 2, the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-4 was prepared from example 3, the copper metal organic framework-derived porous carbon composite material Cu @ C-1100-4 was prepared from example 4, the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-2 was prepared from comparative example 1, the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-8 was prepared from comparative example 2, and the copper metal organic framework compound MOF was prepared from comparative example 3.
P-XRD experiment
The experimental steps are as follows: x-ray diffractometry is respectively carried out on copper metal organic framework derived porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2 and Cu @ C-1000-8 by using an X-ray diffractometer.
The experimental results are as follows: as shown in fig. 1 and 2.
Raman shift experiment
The experimental steps are as follows: raman spectroscopy is respectively carried out on copper metal organic framework derived porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2 and Cu @ C-1000-8 by using a Raman spectrometer.
The experimental results are as follows: as shown in fig. 3 and 4.
Adsorption experiment of specific surface area
The experimental steps are as follows: specific surface area and pore size determination are respectively carried out on copper metal organic framework derived porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2 and Cu @ C-1000-8 by using a specific surface area adsorption instrument.
The experimental results are as follows: as shown in fig. 5, 6, 7 and 8.
Scanning electron microscope experiment
The experimental steps are as follows: respectively carrying out appearance determination on Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2 and Cu @ C-1000-8 of the porous carbon composite material derived from the copper metal organic framework by using a scanning electron microscope.
The experimental results are as follows: as shown in fig. 9, a is a 5 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-800-4, b is a 1 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-800-4, C is a 5 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-900-4, d is a 1 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-900-4, e is a 5 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-4, f is a 1 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-4, and g is a 5 μm electron microscope picture of the copper metal organic framework-derived porous carbon composite material Cu @ C-1100-4, h is a 1-micrometer electron microscope image of the copper metal organic framework derived porous carbon composite material Cu @ C-1100-4; as shown in fig. 10, i is a 5 μm electron microscope image of the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-2, j is a 1 μm electron microscope image of the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-2, k is a 5 μm electron microscope image of the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-8, and l is a 1 μm electron microscope image of the copper metal organic framework-derived porous carbon composite material Cu @ C-1000-8.
Ultraviolet diffuse reflection experiment
The experimental steps are as follows: an ultraviolet diffuse reflection instrument is used for respectively measuring copper metal organic framework derived porous carbon composite materials Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2 and Cu @ C-1000-8.
The experimental results are as follows: as shown in fig. 11.
Free radical trapping experiments
The experimental steps are as follows: o is carried out on the porous carbon composite material Cu @ C-1000-4 derived from the copper metal organic framework by using a free radical trapping instrument2 -and-OH radical capture assay.
The experimental results are as follows: as shown in fig. 12 and 13.
Photocatalytic experiment of copper metal organic framework derived porous carbon composite material Cu @ C-1000-4 on different dyes
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Are all 4 × 10-5Putting four dyes of Methyl Orange (MO), rhodamine B (RhB), Methylene Blue (MB) and Methyl Violet (MV) in a 100ml beaker in mol/L, and weighing 30mg of Cu @ C-1000-4 are respectively added into the dye solution, a beaker is wrapped with tinfoil and placed in a dark environment for magnetic stirring for 60min to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. In the reaction process, 7mL of solution is taken out of the reaction system every 10min, and then centrifuged for 5min by using a centrifuge (model H1850R, Hunan instrument laboratory development Co., Ltd., Hunan province) with the revolution number of 12000 r/min to obtain Methyl Orange (MO) supernatant, rhodamine B (RhB) supernatant, Methylene Blue (MB) supernatant and Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Orange (MO) standard substance, dissolving in 50ml of water to prepare 200mg/L of standard solution, diluting with water to obtain Methyl Orange (MO) standard solutions with the concentrations of 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L, measuring the absorbance of the Methyl Orange (MO) standard solution at 463nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Majieda apparatus Co., Ltd.), recording data, and drawing a Methyl Orange (MO) standard curve;
3) weighing 10mg of rhodamine B (RhB) standard substance, dissolving the rhodamine B (RhB) standard substance in 50ml of water to prepare 200mg/L standard solution, then diluting the standard solution with water into rhodamine B (RhB) standard solution with the concentration of 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L respectively, measuring the absorbance of the rhodamine B (RhB) standard solution at 554nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mei Banda Instrument Co., Ltd.), recording data, and drawing a rhodamine B (RhB) standard curve;
4) weighing 10mg of Methylene Blue (MB) standard substance, dissolving the 10mg of Methylene Blue (MB) standard substance in 50ml of water to prepare 200mg/L of standard solution, then diluting the standard solution with water into Methylene Blue (MB) standard solution with the concentration of 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L respectively, measuring the absorbance of the Methylene Blue (MB) standard solution at 662nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Co., Ltd.), recording data, and drawing a Methylene Blue (MB) standard curve;
5) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solutions, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Meida instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
6) measuring absorbance at 463nm of the supernatant of Methyl Orange (MO), absorbance at 554nm of the supernatant of rhodamine B (RhB), absorbance at 662nm of the supernatant of Methylene Blue (MB) and absorbance at 583nm of the supernatant of Methyl Violet (MV) obtained in step 1) with an ultraviolet spectrophotometer (model UV-650, Shanghai Meidsda instruments, Ltd.), and respectively comparing the Methyl Orange (MO) standard curve, the rhodamine B (RhB) standard curve, the Methylene Blue (MB) standard curve and the Methyl Violet (MV) standard curve to obtain the Methyl Orange (MO) concentration of the Methyl Orange (MO) supernatant, the rhodamine B (RhB) concentration of the rhodamine B (RhB) supernatant, the Methylene Blue (MB) concentration of the Methylene Blue (MB) supernatant and the Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then according to a degradation rate formula.
（C0Denotes the initial concentration of the dye, CtIndicating the concentration of the dye at the time t), calculating the degradation rate, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 14, the concentration was 4X 10-5In four dye solutions of Methyl Orange (MO), rhodamine B (RhB), Methylene Blue (MB) and Methyl Violet (MV) in mol/L, the catalytic degradation capability of 30mg of photocatalyst Cu @ C-1000-4 to Methyl Violet (MV) is strongest, and the degradation capability of 30mg of photocatalyst Cu @ C-1000-4 to other three dyes is arranged from strong to weak: methylene Blue (MB)>Methyl Orange (MO)>Rhodamine b (rhb).
Photocatalytic experiment of porous carbon composite material derived from different copper metal organic frameworks on Methyl Violet (MV) dye
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Are all 4 × 10-5Putting a mol/L Methyl Violet (MV) dye into a 100ml beaker, weighing 30mg of MOF, Cu @ C-800-4, Cu @ C-900-4, Cu @ C-1000-4, Cu @ C-1100-4, Cu @ C-1000-2 and Cu @ C-1000-8 which are copper metal organic framework compounds, respectively adding into the dye solution, wrapping a beaker with tinfoil, and magnetically stirring for 60min in a dark environment to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. In the reaction process, taking out 7mL of solution from the reaction system every 10min, and then centrifuging for 5min by using a centrifuge (model H1850R, Hunan instrument laboratory development Co., Ltd., Producer) with the revolution number of 12000 r/min to obtain Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solution, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mayda instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
3) measuring absorbance of the Methyl Violet (MV) supernatant obtained in step 1) at 583nm with an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Ltd.), comparing with a Methyl Violet (MV) standard curve, determining Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then obtaining the Methyl Violet (MV) concentration according to a degradation rate formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at time t), calculating the degradation rate, and calculating the degradation rate according to a first-order kinetic formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at the time t, and k is an apparent first-order kinetic rate constant), calculating to obtain a k value, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 15, the concentration was 4X 10-5In mol/L Methyl Violet (MV) dye solution, 30mg of Cu @ C-1000-4 has the strongest catalytic degradation capability on Methyl Violet (MV), and k =0.0512min-1。
Experiment 9
Photocatalytic experiment of copper metal organic framework derived porous carbon composite material Cu @ C-1000-4 p-Methyl Violet (MV) dye with different feeding amounts
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Are all 4 × 10-5Putting the mol/L Methyl Violet (MV) dye into a 100ml beaker, weighing 10mg, 15mg, 20mg, 25mg and 30mg of Cu @ C-1000-4 photocatalyst respectively, adding the photocatalyst into the dye solution, wrapping the beaker with tinfoil, and magnetically stirring the beaker in a dark environment for 60min to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. In the reaction process, taking out 7mL of solution from the reaction system every 10min, and then centrifuging for 5min by using a centrifuge (model H1850R, Hunan instrument laboratory development Co., Ltd., Producer) with the revolution number of 12000 r/min to obtain Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solution, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mayda instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
3) measuring the nail obtained in step 1) with an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Ltd.)The absorbance of the Methyl Violet (MV) supernatant at 583nm is compared with the Methyl Violet (MV) standard curve to obtain the Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then the formula of degradation rate is used
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at time t), calculating the degradation rate, and calculating the degradation rate according to a first-order kinetic formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at the time t, and k is an apparent first-order kinetic rate constant), calculating to obtain a k value, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 16, the concentration was 4X 10-5In mol/L Methyl Violet (MV) dye solution, when the feeding amount is 25mg, the catalytic degradation capability of Cu @ C-1000-4 to Methyl Violet (MV) is strongest, and k =0.0920min-1The catalytic degradation capacity of the photocatalyst Cu @ C-1000-4 with the feeding amount of less than 25mg to Methyl Violet (MV) is enhanced along with the increase of the feeding amount.
Photocatalytic experiment of copper metal organic framework derived porous carbon composite material Cu @ C-1000-4 on Methyl Violet (MV) dyes with different concentrations
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Are respectively 2X 10-5mol/L、3×10-5 mol/L、4×10-5mol/L、5×10-5mol/L and 6X 10-5Putting a mol/L Methyl Violet (MV) dye into a 100ml beaker, weighing 25mg of Cu @ C-1000-4 photocatalyst, respectively adding the Cu @ C-1000-4 photocatalyst into the dye solution, wrapping the beaker with tinfoil, and magnetically stirring the beaker in a dark environment for 60min to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. Taking out from the reaction system every 10min in the reaction processDischarging 7mL of the solution, and centrifuging for 5min at a rotation number of 12000 r/min by using a centrifuge (model H1850R, Hunan instrument laboratory Instrument development Co., Ltd., Hunan province) to obtain Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solution, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mayda instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
3) measuring absorbance of the Methyl Violet (MV) supernatant obtained in step 1) at 583nm with an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Ltd.), comparing with a Methyl Violet (MV) standard curve, determining Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then obtaining the Methyl Violet (MV) concentration according to a degradation rate formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at time t), calculating the degradation rate, and calculating the degradation rate according to a first-order kinetic formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at the time t, and k is an apparent first-order kinetic rate constant), calculating to obtain a k value, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 17, the Methyl Violet (MV) concentration was 4X 10-5When mol/L is adopted, the catalytic degradation capacity of 25mg of Cu @ C-1000-4 to methyl violet is the strongest, and k =0.0920min-1(ii) a The dosage of the photocatalyst Cu @ C-1000-4 is 25mg, and the concentration of Methyl Violet (MV) is less than 4 multiplied by 10-5At mol/L, the catalytic degradation capacity of Cu @ C-1000-4 to methyl violet is enhanced with the increase of the concentration of Methyl Violet (MV).
Experiment 11
Photocatalytic experiment of copper metal organic framework derived porous carbon composite material Cu @ C-1000-4 on Methyl Violet (MV) dyes with different pH values
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Is 4 x 10-5Putting a mol/L Methyl Violet (MV) dye into a 100ml beaker, adjusting the pH value of the Methyl Violet (MV) by adopting a 1M HCl solution and a 0.1M NaOH solution to ensure that the initial pH value of the Methyl Violet (MV) is respectively 4, 5, 6 and 7, weighing 25mg of Cu @ C-1000-4 photocatalyst, adding the Cu @ C-1000-4 photocatalyst into the dye solution, wrapping tin foil in the beaker, and magnetically stirring for 60min in a dark environment to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. In the reaction process, taking out 7mL of solution from the reaction system every 10min, and then centrifuging for 5min by using a centrifuge (model H1850R, Hunan instrument laboratory development Co., Ltd., Producer) with the revolution number of 12000 r/min to obtain Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solution, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mayda instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
3) measuring absorbance of the Methyl Violet (MV) supernatant obtained in step 1) at 583nm with an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Ltd.), comparing with a Methyl Violet (MV) standard curve, determining Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then obtaining the Methyl Violet (MV) concentration according to a degradation rate formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at time t), calculating the degradation rate, and calculating the degradation rate according to a first-order kinetic formula 
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at the time t, and k is an apparent first-order kinetic rate constant), calculating to obtain a k value, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 18, the Methyl Violet (MV) concentration was 4X 10-5When the mol/L is that the feeding amount of the photocatalyst Cu @ C-1000-4 is 25mg and the pH value of a Methyl Violet (MV) solution is 6, the catalytic degradation capacity of the Cu @ C-1000-4 to the Methyl Violet (MV) is the strongest, and k =0.0920min-1At a Methyl Violet (MV) concentration of 4X 10-5When the mol/L is that the feeding amount of the photocatalyst Cu @ C-1000-4 is 25mg and the pH value of the Methyl Violet (MV) solution is less than 6, the catalytic degradation capacity of the Cu @ C-1000-4 to the Methyl Violet (MV) is enhanced along with the increase of the pH value of the Methyl Violet (MV) solution.
Experiment 12
Photocatalysis mechanism experiment of copper metal organic framework derived porous carbon composite material Cu @ C-1000-4 p-Methyl Violet (MV) dye
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Is 4 x 10-5Putting a mol/L Methyl Violet (MV) dye into a 100ml beaker, adopting a 1M HCl solution and a 0.1M NaOH solution to ensure that the initial pH value of the Methyl Violet (MV) is 6, weighing 25mg of Cu @ C-1000-4 photocatalyst, adding the Cu @ C-1000-4 photocatalyst into the dye solution, respectively adding 10mg of Ammonium Oxalate (AO), 10mg of p-Benzoquinone (BQ) and 2ml of tert-butyl alcohol (TBA), and respectively capturing cavities h+O free radicals2-And OH. Wrapping the beaker with tinfoil, and magnetically stirring in dark environment for 60min to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. During the reaction, 7mL of the solution was taken out of the reaction system every 10min, and then centrifuged at 5m at a rotation number of 12000 r/min by using a centrifuge (model H1850R, Hunan instrument laboratory Ltd., Hunan Ltd.) (a Biotech Co., Ltd.)in to obtain Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solution, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mayda instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
3) measuring absorbance of the Methyl Violet (MV) supernatant obtained in step 1) at 583nm with an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Ltd.), comparing with a Methyl Violet (MV) standard curve, determining Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then obtaining the Methyl Violet (MV) concentration according to a degradation rate formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at time t), calculating the degradation rate, and calculating the degradation rate according to a first-order kinetic formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at the time t, and k is an apparent first-order kinetic rate constant), calculating to obtain a k value, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 19, the Methyl Violet (MV) concentration was 4X 10-5At mol/L, pH 6, photocatalyst Cu @ C-1000-4 loading of 25mg, OH is the predominant active oxidizing radical in the Methyl Violet (MV) photolysis system.
Experiment 13
Photocatalytic stability experiment of copper metal organic framework derived porous carbon composite material on Methyl Violet (MV) dye
The experimental steps are as follows:
1) first, 50ml of an initial concentration C was taken0Is 4 x 10-5The Methyl Violet (MV) dye in mol/L was placed in a 100ml beaker and dissolved in 1M HClThe initial pH value of Methyl Violet (MV) is adjusted to 6 by the solution and 0.1M NaOH solution, 25mg of Cu @ C-1000-4 photocatalyst is weighed and added into the dye solution, a beaker is wrapped by tinfoil and placed in a dark environment for magnetic stirring for 60min to achieve adsorption-desorption balance. After 60min, the reaction system is transferred to a 500W Xe lamp and a cut-off filter as the illumination environment of a visible light source, and the reaction solution is placed at a position 10cm away from the light source for photodegradation reaction. In the reaction process, taking out 7mL of solution from the reaction system every 10min, and then centrifuging for 5min by using a centrifuge (model H1850R, Hunan instrument laboratory development Co., Ltd., Producer) with the revolution number of 12000 r/min to obtain Methyl Violet (MV) supernatant;
2) weighing 10mg of Methyl Violet (MV) standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L and 35mg/L Methyl Violet (MV) standard solution, measuring the absorbance of the Methyl Violet (MV) standard solution at 583nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mayda instruments, Ltd.), recording data, and drawing a Methyl Violet (MV) standard curve;
3) measuring absorbance of the Methyl Violet (MV) supernatant obtained in step 1) at 583nm with an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral instruments, Ltd.), comparing with a Methyl Violet (MV) standard curve, determining Methyl Violet (MV) concentration of the Methyl Violet (MV) supernatant, and then obtaining the Methyl Violet (MV) concentration according to a degradation rate formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at time t), calculating the degradation rate, and calculating the degradation rate according to a first-order kinetic formula
（C0Denotes the initial concentration of the dye, CtRepresenting the concentration of the dye at the time t, and k is an apparent first-order kinetic rate constant), calculating to obtain a k value, recording data, and drawing to obtain an experimental result.
4) Centrifuging the reaction solution left after the reaction in the step 1) by using a centrifuge (model H1850R, Hunan instrument laboratory Instrument development Co., Ltd., Producer, Hunan province) at the revolution number of 12000 r/min for 5min, washing the solution for 3 times by using deionized water to obtain a solid material, and then mixing the solid material with deionized water according to the proportion of 1: 1 ethylene glycol: soaking in ethanol mixture, and magnetically stirring overnight. Washing with ethanol and deionized water for 3 times, respectively, vacuum drying at 60 deg.C, and storing;
5) using the solid material recovered in the step 4) in the reaction of the step 1), and then calculating the degradation rate according to the step 3)
% and first order kinetic k values. And recording data and drawing to obtain an experimental result.
6) Repeating the step 5) for three times, and calculating the degradation rate
% and first order kinetic k values. And recording data and drawing to obtain an experimental result.
The experimental results are as follows: as can be seen from FIG. 20, the Methyl Violet (MV) concentration was 4X 10-5The photocatalyst Cu @ C-1000-4 exhibited good stability at a mol/L, pH value of 6 and a Cu @ C-1000-4 charge of 25 mg.
The above description is only a preferred embodiment of the present invention, and all the minor modifications, equivalent changes and modifications made to the above embodiment according to the technical solution of the present invention are within the scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a copper metal organic framework derived porous carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving 4-21 ligand and copper trifluoromethanesulfonate (II) in acetonitrile in sequence, stirring at room temperature for 15-25min to form a mixed solution A, dropwise adding triethylamine into the mixed solution A, and uniformly shaking to obtain a mixed solution B; placing the small bottle filled with the mixed solution B in a drying oven for reacting for 22-26h, naturally cooling, filtering out crystals C by using filter paper, and naturally drying at room temperature to obtain a copper metal organic framework compound MOF;
2) and (3) putting the crucible filled with the copper metal organic framework compound MOF into a tubular muffle furnace for high-temperature carbonization, and cooling to room temperature after calcination to obtain the copper metal organic framework derivative porous carbon composite material.
2. The preparation method of the porous carbon composite material derived from the copper metal organic framework, according to claim 1, is characterized in that: the molar ratio of the 4-21 ligand to the copper (II) trifluoromethanesulfonate in the step 1) is 1: 2.
3. the preparation method of the porous carbon composite material derived from the copper metal organic framework, according to claim 1, is characterized in that: in step 1), the temperature of the drying oven is kept at 80 ℃ during the reaction in the drying oven in which the vial containing the mixed solution B is placed.
4. The preparation method of the porous carbon composite material derived from the copper metal organic framework, according to claim 1, is characterized in that: and 2) in the high-temperature carbonization process, the calcining temperature of the tubular muffle furnace is 800-1100 ℃.
5. The preparation method of the copper metal organic framework-derived porous carbon composite material according to claim 4, characterized in that: the calcination time is 2-8 h.
6. The preparation method of the porous carbon composite material derived from the copper metal organic framework, according to claim 1, is characterized in that: in the step 2), the temperature rise rate of the tubular muffle furnace is 5 ℃/min in the high-temperature carbonization process.
7. The preparation method of the copper metal organic framework-derived porous carbon composite material according to claim 6, characterized in that: and 2) introducing nitrogen in the high-temperature carbonization process in the step 2), wherein the introduction rate of the nitrogen is 60 mL/min.
8. The application of the porous carbon composite material derived from the copper metal organic framework is characterized in that: the use of the copper metal organic framework-derived porous carbon composite material prepared by the method of preparing a copper metal organic framework-derived porous carbon composite material according to any one of claims 1 to 7 as a photocatalyst in the photodegradation reaction of organic dyes.
9. Use of the copper metal organic framework derived porous carbon composite material according to claim 8, characterized in that: the copper metal organic framework derived porous carbon composite material has catalytic degradation capability on methylene blue, methyl orange, rhodamine B and methyl violet, wherein the copper metal organic framework derived porous carbon composite material has the strongest catalytic degradation capability on the methyl violet.
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| CN108421531A (en) * | 2018-02-10 | 2018-08-21 | 广东医科大学 | A kind of preparation method and applications of copper metal organic framework compounds |
| CN110624508A (en) * | 2019-08-14 | 2019-12-31 | 广东医科大学 | Preparation method and application of metal organic framework derived porous carbon material |
| CN112076794A (en) * | 2020-09-04 | 2020-12-15 | 西安工程大学 | Cu-MOF material based on triangular organic ligand, and preparation method and application thereof |
| US20210046447A1 (en) * | 2019-08-15 | 2021-02-18 | Numat Technologies Inc. | Water stable copper paddlewheel metal organic framework (mof) compositions and processes using the mofs |
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| CN108421531A (en) * | 2018-02-10 | 2018-08-21 | 广东医科大学 | A kind of preparation method and applications of copper metal organic framework compounds |
| CN110624508A (en) * | 2019-08-14 | 2019-12-31 | 广东医科大学 | Preparation method and application of metal organic framework derived porous carbon material |
| US20210046447A1 (en) * | 2019-08-15 | 2021-02-18 | Numat Technologies Inc. | Water stable copper paddlewheel metal organic framework (mof) compositions and processes using the mofs |
| CN112076794A (en) * | 2020-09-04 | 2020-12-15 | 西安工程大学 | Cu-MOF material based on triangular organic ligand, and preparation method and application thereof |
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