CN113477270B - Preparation method of copper-iron bimetal confined nitrogen-doped carbon nano tube composite material - Google Patents
Preparation method of copper-iron bimetal confined nitrogen-doped carbon nano tube composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 35
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 35
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 239000000243 solution Substances 0.000 claims description 34
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
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- 238000000197 pyrolysis Methods 0.000 claims description 11
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- 239000011261 inert gas Substances 0.000 claims description 6
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000034 method Methods 0.000 abstract description 27
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- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
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- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a preparation method of a copper-iron bimetal confined nitrogen doped carbon nano tube composite material. The catalyst obtained by the invention anchors the monoatomic iron and copper nano particles on the carbon nano tube through coordination, has high catalytic site density, large specific surface area and good conductivity, and shows excellent performance and wide application prospect in the fields of adsorption separation, catalysis, energy storage and the like; the preparation method has the advantages of simple process, low cost and wide application prospect and practical value.
Description
Technical Field
The invention relates to the field of inorganic catalyst preparation, in particular to a preparation method of a copper-iron bimetallic finite field nitrogen doped carbon nano tube composite material.
Background
The transition metal finite field nitrogen doped carbon nano tube composite material becomes a catalyst material with prospect in the aspects of electrochemical catalysis, energy environmental catalysis and the like due to the excellent specific surface area, surface physical and chemical properties, unique metal carbon bond and similar d-state density of noble metal approaching to fermi energy level. However, the synthesis of the conventional nitrogen-doped carbon nanotube material often has the defects of complicated preparation process, higher energy consumption, low yield and the like, so that the method is not suitable for large-scale industrialized production. In recent years, metal organic framework materials are used as precursors for preparing transition metal finite field nitrogen doped carbon nanotube materials, and compared with the traditional preparation method, the preparation method is simple, has the structure with the controllability and the finite field property, has larger specific surface area and higher catalytic efficiency and stability, so that more and more research teams are concerned.
The conventional preparation method of the metal organic framework material used as the precursor is a hydrothermal method, a solvothermal method, a microwave method, a liquid phase diffusion method and the like. The hydrothermal method is to carry out the reaction in a closed pressure vessel at high temperature and high pressure, the method has harsh use conditions, needs a high-pressure reaction kettle, a corrosion-resistant lining and the like, and has a higher difficulty coefficient in large-scale preparation; the solvothermal method is developed by the establishment of a hydrothermal method, has a great improvement in yield compared with a diffusion method, still requires high-pressure reaction equipment and higher reaction temperature, and is difficult to synthesize in batches; the microwave method is an emerging preparation technology in recent years, and can produce the metal organic frame material with high quality and high yield in a short time, however, the process flow of the method needs high-boiling-point chemical substances as solvents, the solvents are difficult to recover, the energy consumption is high, the equipment cost is high, and the method is difficult to apply to actual production; the liquid phase diffusion method is a method of mixing the dissolved organic ligand and the metal particles according to a certain proportion and gradually precipitating crystals, and compared with the above methods, the method has mild reaction conditions and high quality of the synthesized crystals, and is one of the most common methods for synthesizing metal-organic frame materials at present. However, the synthesized precursor has poor conductivity and low catalytic activity, and is not suitable for being directly used as a catalyst material. One approach to solve the above problems is to mix and assemble the precursor and the secondary highly conductive self-support, but this method can severely clog its micropores, limiting its effective mass transfer during the electrocatalytic process. In recent years, the removal or conversion of organic ligands to carbon by high temperature calcination of precursors, which can convert low activity precursors to highly active metal compounds or metal-carbon complexes, has attracted considerable attention.
Recent studies have shown that the coating of the transition metal on the nitrogen-doped carbon composite (M@N-C, m=fe, co, ni, etc.) exhibits excellent performance in the catalytic field due to the synergistic effect between the transition metal and nitrogen. Patent number CN 111635535A discloses a preparation method of a magnetic metal-organic framework composite material,the method comprises the steps of adding ferrous salt, ferric salt, zinc salt and organic ligand 2-methylimidazole into deionized water, continuously stirring, and finally separating in an external magnetic field to obtain Fe 2 O 3 Coordinated metal organic framework composite materials, however, the ferric salt added in the method easily replaces Zn in the metal organic framework structure 2+ Resulting in structural distortion. Theoretical calculation shows that, in the non-noble metal transition metal, since copper is positioned at the top of a volcanic diagram and is close to Pt, the activity is highest, and patent number CN 111916769A discloses a preparation method of a Cu doped hollow hexagonal metal organic framework material, which comprises the steps of firstly preparing a precursor by a solution diffusion method, then treating with tannic acid to obtain a hollow metal organic framework, mixing the hollow metal organic framework with copper salt to obtain the precursor, and finally mixing the precursor with g-C 3 N 4 The Cu doped hollow hexagonal metal organic framework material is obtained by grinding and pyrolysis in a tube furnace, and the method has the advantages of complex preparation process, high energy consumption, large Cu ion diffusion coefficient, easy occurrence of self aggregation, surface oxidation and the like in the pyrolysis process. Compared with a single metal-organic framework, the bimetal metal-organic framework has higher electron transfer efficiency and better stability, and the bimetal site can regulate and control the electronic state of the catalyst and couple the characteristics of the two metals. In addition, the synergistic effect of the bimetal can improve the catalytic performance of the metal organic framework, and the bimetal has been widely applied to oxidation, hydrogenation, dehydrogenation and other reactions at present. More importantly, the performance of the alloy can be regulated by regulating the proportion of the bimetal, and the alloy exhibits high plasticity. Patent number CN 109126885A discloses a preparation method of a copper-cobalt bimetal organic frame/nanofiber composite material, which comprises the steps of firstly preparing the copper-cobalt bimetal organic frame by a solvothermal method, then mixing the copper-cobalt bimetal organic frame with a high polymer, and preparing the copper-cobalt bimetal organic frame/nanofiber composite material by an electrostatic spinning method.
Based on the method, the copper-iron bimetal limited-domain nitrogen doping is prepared by adopting the copper-iron bimetal coordination metal organic framework precursor through a one-step calcination methodCarbon nanotube composite material by nano-scale FeN x And CuN x The synergistic effect of the double active sites can regulate the structure and property of the carbon-based material, and promote the catalytic activity of the nitrogen-doped carbon composite material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of a copper-iron bimetallic confined nitrogen-doped carbon nano tube composite material, which aims to solve the technical problems that: 1. a proper carbon carrier is selected to solve the problem of uneven distribution of active sites of the catalyst; 2. solves the problems of complex preparation process, harsh experimental conditions and incapability of large-scale production of the bimetal metal organic framework material.
The invention adopts the following technical scheme to solve the technical problems:
the preparation method of the copper-iron bimetal confined nitrogen doped carbon nano tube composite material comprises the following steps:
(1) Uniformly stirring ferric acetylacetonate, acid-washed copper foil and 2-methylimidazole in a methanol solution at room temperature, and carrying out ultrasonic treatment for 1h to obtain solution A; zn (NO) 3 ) 2 ·6H 2 O is stirred uniformly in methanol solution at room temperature to obtain solution B; then pouring the solution B into the solution A and stirring uniformly at room temperature, centrifuging, washing and drying the obtained mixed solution to obtain a precursor;
(2) And (3) transferring the precursor obtained in the step (1) into a tube furnace under the protection of inert gas, and calcining and pyrolyzing to obtain the copper-iron bimetallic confined nitrogen doped carbon nanotube composite material.
Preferably, in the step (1), the acid-washed copper foil is acid-washed with hydrochloric acid having a concentration of 2 to 4M for 12 to 48 hours.
Preferably, in the step (1), the dosage ratio of the ferric acetylacetonate, the copper foil subjected to acid washing, the 2-methylimidazole and the methanol in the solution A is 0.1-3 g:0.1-3 g:4-10 g:40-320 mL.
Preferably, in the step (1), zn (NO 3 ) 2 ·6H 2 The dosage ratio of O to methanol is 1 g-9 g:20160mL。
Preferably, in the step (1), the stirring time after pouring the liquid B into the liquid A is 18 to 30 hours.
Preferably, in the step (1), the drying is performed at 50 to 70 ℃ for 8 to 16 hours.
Preferably, in the step (2), the inert gas is at least one of argon and nitrogen, and the flow rate of the inert gas is 0.1-5 mL/min.
Preferably, in the step (2), the temperature of the calcination pyrolysis is 950-1050 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-2 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention establishes a preparation method of the copper-iron bimetal confined nitrogen doped carbon nano tube, realizes that metal nano particles and specific organic ligands form a specific bimetal organic frame, and obtains the copper-iron bimetal confined nitrogen doped carbon nano tube composite material through high-temperature carbonization treatment, thereby fully playing the structural characteristics of large specific surface area, high porosity and modifiable property of the metal organic frame material.
2. Compared with a hydrothermal method, a solvothermal method and a microwave method, the preparation method has the advantages of simplicity, low energy consumption and universality for the preparation of various metal-organic frame compound materials, and is suitable for large-scale and industrial production; the invention synthesizes the copper-iron bimetallic confined nitrogen doped carbon nano tube composite material by a simple in-situ pyrolysis method, solves the problem of low catalytic activity of a metal organic framework precursor, has low cost, simple operation steps and easy regulation and control of reaction process conditions compared with the mixed assembly of a metal organic framework material and a secondary high-conductivity self-supporting body, and is particularly suitable for preparing the bimetallic catalyst derived from the metal organic framework with high specific surface area.
3. According to the method for preparing the copper-iron bimetal confined nitrogen doped carbon nano tube composite material, iron and copper atoms are uniformly dispersed in the precursor skeleton, and the sample is presented due to high-temperature volatilization of zinc through high-temperature pyrolysisPorous structure, rich micropores and mesopores, and can make the residual iron and copper form FeN with nitrogen x And CuN x An active site. After pyrolysis, the monoatomic iron and copper nano-particles are limited in the carbon nano-tubes, so that the monoatomic iron and copper nano-particles are prevented from being oxidized into metal oxides in the pyrolysis process.
4. Due to Fe 3+ Easy to replace Zn in metal organic frame structure 2+ The invention introduces Fe by using copper foil through simple ion reaction, which leads to obvious distortion of structure 2+ And Cu 2+ The Fe of the metal organic frame in the growth process is reduced 2+ Oxidized to Fe 3+ The preparation method of the copper-iron bimetal confined nitrogen doped carbon nano tube composite material is simple, raw materials are simple and easy to obtain, the cost is low, the yield is high, the stability is good, and the industrial large-scale application can be realized.
Drawings
FIG. 1 is an SEM image of a Cu-Fe bimetallic finite field nitrogen doped carbon nanotube composite material prepared in example 1 of the present invention;
fig. 2 is a TEM image of a copper-iron bi-metal confinement nitrogen-doped carbon nanotube composite material prepared in example 1 of the present invention.
Detailed Description
The following describes in detail the examples of the present invention, which are carried out on the premise of the technical proposal of the present invention, and give detailed embodiments and specific operation procedures, but the scope of the present invention is not limited to the following examples
Example 1
(1) The preparation process of the precursor comprises the following steps: a predetermined amount of concentrated hydrochloric acid was prepared into 20mL of a hydrochloric acid solution (3M concentration), and a copper foil (2X 2 cm) 2 ) Immersing in hydrochloric acid solution for cleaning for 24 hours to remove oxide layer on the surface of the copper foil, and then washing the copper foil treated with hydrochloric acid with deionized water and methanol in sequence. 6.5g of 2-methylimidazole and 0.44g of ferric acetylacetonate were weighed and dispersed in 80mL of a methanol solution with stirring, and then 2.9g of copper foil after acid washing treatment was added to the above solution and sonicated for 1 hour to obtain solution A. Next, 6.0g of Zn was stirred vigorouslyNO 3 ) 2 ·6H 2 O was dissolved in 40mL of methanol to obtain solution B. And then pouring the solution B into the solution A rapidly, stirring for 24 hours at 25 ℃, centrifugally collecting a precursor precipitate of the copper-iron bimetal metal organic framework, cleaning the precursor precipitate with methanol for three times, and then placing the precursor precipitate in a 60 ℃ oven for drying to obtain a precursor.
(2) Carbonization: the precursor obtained in the step (1) is placed in a tube furnace for direct pyrolysis (pyrolysis temperature is 950 ℃, pyrolysis time is 1h, and heating rate is 5 ℃ for min) -1 ，N 2 The air flow rate is 0.2 mL/min), and the copper-iron bimetal confined nitrogen doped carbon nano tube composite material is obtained.
Fig. 1 is an SEM image of a copper-iron bi-metal confinement nitrogen-doped carbon nanotube composite material prepared in this embodiment, and it can be seen from the figure that the material has a carbon nanotube structure.
Fig. 2 is a TEM image of the copper-iron bi-metal confinement nitrogen-doped carbon nanotube composite material prepared in this example, in which no Fe nanoparticles could be observed, indicating that the nitrogen-doped carbon nanotubes obtained by high temperature carbonization can effectively prevent aggregation of metal nanoparticles.
The catalytic performance of the copper-iron bimetallic confined nitrogen doped carbon nanotube composite material prepared in the embodiment is tested according to the following method: preparing 20mg/L of gold orange II solution simulated organic pollutant wastewater (V=1000 mL) and 10mg/L of hexavalent chromium solution simulated heavy metal wastewater (V=1000 mL) respectively, adding 20mg of oxidant hydrogen sulfate and 2mL of reducing agent formic acid respectively, pumping the pollutant solutions into a catalytic reaction device respectively by using a sewage conveying pump, and degrading by using a copper-iron bimetal coordination metal organic frame derived nitrogen doped carbon nano tube composite material. Through tests, the degradation rate of organic pollutants gold orange II and heavy metal pollutants hexavalent chromium reaches 100%.
Example 2
In this example, a copper-iron bimetallic confined nitrogen doped carbon nanotube composite material was prepared in the same manner as in example 1, except that: the pyrolysis temperature was 1050 ℃.
Through tests, the composite material prepared by the embodiment is in a carbon nano tube structure, and the bimetallic copper iron is highly dispersed in the metal organic framework derived nitrogen doped carbon nano tube, so that the catalytic activity is high.
The composite material prepared in this example was tested for catalytic performance in the same manner as in example 1. Through tests, the degradation rate of organic pollutants gold orange II and heavy metal pollutants hexavalent chromium reaches 100%.
Example 3
In this example, a copper-iron bimetallic confined nitrogen doped carbon nanotube composite material was prepared in the same manner as in example 1, except that: in the precursor preparation process, the dosage of the methanol solution A is 40mL, and the dosage of the methanol solution B is 20mL.
Through tests, the composite material prepared by the embodiment is in a carbon nano tube structure, and the bimetallic copper iron is highly dispersed in the metal organic framework derived nitrogen doped carbon nano tube, so that the catalytic activity is high.
The composite material prepared in this example was tested for catalytic performance in the same manner as in example 1. Through tests, the degradation rate of organic pollutants gold orange II and heavy metal pollutants hexavalent chromium reaches 100%.
Example 4
In this example, a copper-iron bimetallic confined nitrogen doped carbon nanotube composite material was prepared in the same manner as in example 1, except that: in the precursor preparation process, the dosage of the methanol solution A is 160mL, and the dosage of the methanol solution B is 80mL.
Through tests, the composite material prepared by the embodiment is in a carbon nano tube structure, and the bimetallic copper iron is highly dispersed in the metal organic framework derived nitrogen doped carbon nano tube, so that the catalytic activity is high.
The composite material prepared in this example was tested for catalytic performance in the same manner as in example 1. Through tests, the degradation rate of organic pollutants gold orange II and heavy metal pollutants hexavalent chromium reaches 100%.
Example 5
In this example, a copper-iron bimetallic confined nitrogen doped carbon nanotube composite material was prepared in the same manner as in example 1, except that: in the precursor preparation process, the dosage of the solution A and the dosage of the solution B are 320mL and 160mL respectively.
Through tests, the composite material prepared by the embodiment is in a carbon nano tube structure, and the bimetallic copper iron is highly dispersed in the metal organic framework derived nitrogen doped carbon nano tube, so that the catalytic activity is high.
The composite material prepared in this example was tested for catalytic performance in the same manner as in example 1. Through tests, the degradation rate of organic pollutants gold orange II and heavy metal pollutants hexavalent chromium reaches 100%.
The foregoing is illustrative only and is not intended to limit the present invention, and any modifications, equivalents, improvements and modifications falling within the spirit and principles of the invention are intended to be included within the scope of the present invention.
Claims (8)
1. The preparation method of the copper-iron bimetal confined nitrogen doped carbon nano tube composite material is characterized by comprising the following steps of:
(1) Uniformly stirring ferric acetylacetonate, acid-washed copper foil and 2-methylimidazole in a methanol solution at room temperature, and carrying out ultrasonic treatment for 1h to obtain solution A; zn (NO) 3 ) 2 ·6H 2 O is stirred uniformly in methanol solution at room temperature to obtain solution B; then pouring the solution B into the solution A and stirring uniformly at room temperature, centrifuging, washing and drying the obtained mixed solution to obtain a precursor;
(2) And (3) transferring the precursor obtained in the step (1) into a tube furnace under the protection of inert gas, and calcining and pyrolyzing to obtain the copper-iron bimetallic confined nitrogen doped carbon nanotube composite material.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the acid-washed copper foil is subjected to acid washing treatment by adopting hydrochloric acid with the concentration of 2-4M, and the acid washing time is 12-48 hours.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the dosage ratio of the ferric acetylacetonate, the copper foil subjected to acid washing treatment, the 2-methylimidazole and the methanol in the solution A is 0.1-3 g:0.1-3 g:4-10 g:40-320 mL.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), zn (NO 3 ) 2 ·6H 2 The dosage ratio of O to methanol is 1 g-9 g:20-160 mL.
5. The method of manufacturing according to claim 1, characterized in that: in the step (1), the stirring time after the solution B is poured into the solution A is 18-30 h.
6. The method of manufacturing according to claim 1, characterized in that: in the step (1), the drying is performed at 50-70 ℃ for 8-16 hours.
7. The method of manufacturing according to claim 1, characterized in that: in the step (2), the inert gas is at least one of argon and nitrogen, and the flow rate of the inert gas is 0.1-5 mL/min.
8. The method of manufacturing according to claim 1, characterized in that: in the step (2), the temperature of the calcination pyrolysis is 950-1050 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-2 hours.
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