CN113477270A - Preparation method of copper-iron bimetal confined nitrogen doped carbon nanotube composite material - Google Patents
Preparation method of copper-iron bimetal confined nitrogen doped carbon nanotube composite material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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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
Abstract
The invention discloses a preparation method of a copper-iron bimetal confinement nitrogen-doped carbon nanotube composite material. The catalyst obtained by the invention anchors the monatomic iron and copper nanoparticles on the carbon nanotube 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 preparation process, low cost, wide application prospect and high 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 bimetal limited-area nitrogen-doped carbon nanotube composite material.
Background
The transition metal confined nitrogen doped carbon nanotube composite material has excellent specific surface area, surface physical and chemical properties, unique metal carbon bond and similar d-state density of noble metal close to Fermi level, so that the composite material becomes a catalyst material with prospect in the aspects of electrochemical catalysis, energy source environment catalysis and the like. However, the synthesis of the conventional nitrogen-doped carbon nanotube material often has the defects of complicated preparation process, high energy consumption, low yield and the like, so that the method is not suitable for large-scale and industrial production. In recent years, metal organic framework materials are used as precursors to prepare transition metal confinement nitrogen-doped carbon nanotube materials, and compared with the traditional preparation method, the preparation method is simple, and the structure has controllability and confinement, larger specific surface area, higher catalytic efficiency and stability, so that more and more research teams pay attention to the preparation method.
The conventional preparation methods commonly used for the metal organic framework material as a precursor include a hydrothermal method, a solvothermal method, a microwave method, a liquid phase diffusion method and the like. The hydrothermal method is a reaction in a closed pressure vessel at high temperature and high pressure, has harsh use conditions, needs a high-pressure reaction kettle, a corrosion-resistant lining and the like, and has a high difficulty coefficient in scale preparation; the solvent thermal method is developed from the establishment of a hydrothermal method, has greatly improved yield compared with a diffusion method, still needs high-pressure reaction equipment and higher reaction temperature, and is difficult to synthesize in batches; the microwave method is a new preparation technology in recent years, can produce the metal organic framework material with high quality and high yield in a short time, but the process flow needs high-boiling-point chemical substances as a solvent, the solvent is difficult to recover, the energy consumption is high, the equipment cost is high, and the application to practical production is difficult; the liquid phase diffusion method is a method for gradually precipitating crystals by mixing dissolved organic ligands and metal particles according to a certain proportion, and compared with the methods, the method has the advantages of mild reaction conditions and high quality of synthesized crystals, and is one of the most common methods for synthesizing metal organic framework 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 of the methods to solve the above problems is to mix and assemble the precursor and the secondary highly conductive self-supporting body, but the method can severely block the micropores, and limit the effective mass transfer in the electrocatalytic process. In recent years, a precursor having low activity can be converted into a metal compound or a metal-carbon composite having high activity by removing or converting an organic ligand into carbon by calcining the precursor at high temperature, and thus has attracted much attention.
Recent studies have shown that nitrogen-doped carbon composites (M @ N-C, M ═ Fe, Co, Ni, etc.) coated with transition metals exhibit excellent performance in the catalytic field due to the synergistic effect between the transition metals and nitrogen. Patent No. CN 111635535A discloses a preparation method of a magnetic metal organic framework composite material, which 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 Fe2O3The coordination metal organic framework composite material, however, the trivalent ferric salt added in the method is easy to replace Zn in the metal organic framework structure2+Resulting in structural distortion. Theoretical calculation shows that in non-noble metal transition metal, as the position of copper is at the top of volcanic diagram and close to Pt, the activity is highest, and patent number CN 111916769A discloses a preparation method of Cu-doped hollow hexagonal metal organic framework material3N4The Cu-doped hollow hexagonal metal organic framework material is obtained by grinding and pyrolyzing the material 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 problems of self-aggregation, surface oxidation and the like in the pyrolysis process. Compared with a single metal organic framework, the double metal organic framework has higher electron transfer efficiency and better stability, and the double metal sites can regulate and control the electronic state of the catalyst and couple the characteristics of two metals. In addition, the synergistic effect of the bimetal can improve the catalytic performance of the metal organic framework, and the bimetal can be widely applied to oxidation and hydrogen at presentAnd (4) reactions such as conversion and dehydrogenation. More importantly, the performance of the bimetal can be adjusted by adjusting the proportion of the bimetal, and high plasticity is shown. Patent No. CN 109126885A discloses a preparation method of a copper-cobalt bimetallic organic framework/nanofiber composite material, the invention firstly adopts a solvothermal method to prepare the copper-cobalt bimetallic organic framework, and then the copper-cobalt bimetallic organic framework is mixed with a high molecular polymer to prepare the copper-cobalt bimetallic organic framework/nanofiber composite material through an electrostatic spinning method.
Based on the method, the copper-iron bimetal coordination metal organic framework precursor is adopted to prepare the copper-iron bimetal confinement nitrogen-doped carbon nanotube composite material by a one-step calcination method, and the nano-scale FeN is usedxAnd CuNxThe structure and the property of the carbon-based material are adjusted by the synergistic effect of the double active sites, and the catalytic activity of the nitrogen-doped carbon composite material is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a copper-iron bimetal confinement nitrogen-doped carbon nanotube composite material, which aims to solve the technical problems that: 1. selecting a proper carbon carrier to solve the problem of uneven distribution of active sites of the catalyst; 2. the problems that the preparation process of the bimetallic metal organic framework material is complicated, the experimental conditions are harsh, and the scale production cannot be realized are solved.
In order to solve the technical problem, the invention adopts the following technical scheme:
the preparation method of the copper-iron bimetal confined nitrogen doped carbon nanotube composite material comprises the following steps:
(1) uniformly stirring iron acetylacetonate, the copper foil subjected to acid cleaning treatment and 2-methylimidazole in a methanol solution at room temperature, and carrying out ultrasonic treatment for 1h to obtain solution A; adding Zn (NO)3)2·6H2Stirring the solution O in methanol solution at room temperature to obtain solution B; then, pouring the solution B into the solution A, stirring uniformly at room temperature, centrifuging, washing and drying the obtained mixed solution to obtain a precursor;
(2) and (3) under the protection of inert gas, transferring the precursor obtained in the step (1) to a tube furnace for calcination and pyrolysis to obtain the copper-iron bimetal confined nitrogen-doped carbon nanotube composite material.
Preferably, in the step (1), the copper foil subjected to acid washing treatment is subjected to acid washing treatment by using hydrochloric acid with the concentration of 2-4M, and the acid washing time is 12-48 h.
Preferably, in the step (1), the using amount ratio of the iron acetylacetonate, the copper foil subjected to acid cleaning, the 2-methylimidazole and the methanol in the solution A is 0.1-3 g: 4-10 g: 40-320 mL.
Preferably, in the step (1), Zn (NO) is contained in the solution B3)2·6H2The dosage ratio of the O to the methanol is 1 g-9 g: 20-160 mL.
Preferably, in the step (1), the stirring time after the liquid B is poured into the liquid A is 18-30 h.
Preferably, in the step (1), the drying is carried out at 50-70 ℃ for 8-16 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 a specific organic ligand form a specific bimetal organic framework, and obtains the copper-iron bimetal confined nitrogen-doped carbon nano tube composite material through high-temperature carbonization treatment, and fully exerts the structural characteristics of large specific surface area, high porosity and repairability of the metal organic framework material.
2. Compared with a hydrothermal method, a solvothermal method and a microwave method, the method has the advantages of simple preparation process, low energy consumption, universality for preparation of various metal organic framework compound materials and suitability for large-scale and industrial production; the copper-iron bimetallic confined nitrogen-doped carbon nanotube composite material is synthesized by a simple in-situ pyrolysis method, the problem of low catalytic activity of a metal-organic framework precursor is solved, and compared with the method of mixing and assembling the metal-organic framework material and a secondary high-conductivity self-supporting body, the method has the advantages of low cost, simple operation steps and easily regulated reaction process conditions, and is particularly suitable for preparing the high-specific-surface-area metal-organic framework derived bimetallic catalyst.
3. The method for preparing the copper-iron bimetal limited-domain nitrogen-doped carbon nanotube composite material is adopted, so that iron and copper atoms are uniformly dispersed in a precursor framework, a sample presents a porous structure due to high-temperature volatilization of zinc through high-temperature pyrolysis, and simultaneously has rich micropores and mesopores, and the residual iron, copper and nitrogen form FeNxAnd CuNxAn active site. And after high-temperature pyrolysis, the monatomic iron and copper nanoparticles are confined in the carbon nanotube, so that the oxidation to metal oxide in the high-temperature pyrolysis process is avoided.
4. Due to Fe3+Easy to replace Zn in metal organic framework structure2+Leading the structure to generate obvious distortion, the invention utilizes the copper foil to introduce Fe through simple ion reaction2+And Cu2+Reducing Fe in the growth process of the metal organic framework2+Is oxidized into Fe3+The preparation method of the copper-iron bimetal confined nitrogen doped carbon nanotube composite material is simple, the raw materials are simple and easy to obtain, the price 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 domain-limited N-doped carbon nanotube composite material prepared in example 1 of the present invention;
fig. 2 is a TEM image of the cu-fe bimetallic confinement nitrogen-doped carbon nanotube composite material prepared in example 1 of the present invention.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, 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: preparing 20mL hydrochloric acid solution (3M concentration) from a certain amount of concentrated hydrochloric acid, and processing copper foil (2 × 2 cm)2) The copper foil treated with hydrochloric acid was washed by soaking in a hydrochloric acid solution for 24 hours to remove an oxide layer on the surface of the copper foil, and then the copper foil treated with hydrochloric acid was washed with deionized water and methanol in this order. 6.5g of 2-methylimidazole and 0.44g of iron acetylacetonate were weighed out and dispersed in 80mL of a methanol solution with constant stirring, and then 2.9g of an acid-washed copper foil was added to the above solution and subjected to ultrasonic treatment for 1 hour to obtain solution A. Next, 6.0g of Zn (NO) was added under vigorous stirring3)2·6H2O was dissolved in 40mL of methanol to obtain solution B. And then quickly pouring the solution B into the solution A, stirring for 24 hours at 25 ℃, centrifuging to collect the precipitate of the precursor of the copper-iron bimetallic metal organic frame, cleaning with methanol for three times, and drying in a 60 ℃ drying oven to obtain the precursor.
(2) And (3) carbonization: putting the precursor obtained in the step (1) into a tubular furnace for direct pyrolysis (the pyrolysis temperature is 950 ℃, the pyrolysis time is 1h, and the heating rate is 5 ℃ for min-1，N2The air flow rate is 0.2mL/min), and the copper-iron bimetal confinement nitrogen-doped carbon nanotube composite material is obtained.
Fig. 1 is an SEM image of the cu-fe bimetallic confinement nitrogen-doped carbon nanotube composite material prepared in this example, which shows that the material has a carbon nanotube structure.
Fig. 2 is a TEM image of the cu-Fe bimetallic confinement nitrogen-doped carbon nanotube composite material prepared in this example, in which Fe nanoparticles cannot be observed, which indicates that the nitrogen-doped carbon nanotube 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 golden orange II solution simulated organic pollutant wastewater (V is 1000mL) and 10mg/L of hexavalent chromium solution simulated heavy metal wastewater (V is 1000mL), respectively adding 20mg of hydrogen peroxymonosulfate serving as an oxidant and 2mL of formic acid serving as a reducing agent, respectively pumping the pollutant solutions into a catalytic reaction device by using a sewage delivery pump, and degrading by using a copper-iron bimetal coordination metal organic framework derived nitrogen-doped carbon nanotube composite material. Tests show that the degradation rate of organic pollutant orange II and heavy metal pollutant hexavalent chromium reaches 100 percent.
Example 2
This example prepares a copper-iron bimetallic confined nitrogen doped carbon nanotube composite 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 nanotube structure, and the bimetallic copper and iron are highly dispersed in the nitrogen-doped carbon nanotube derived from the metal organic framework, so that the catalytic activity is high.
The composite material obtained in this example was tested for its catalytic performance in the same manner as in example 1. Tests show that the degradation rate of organic pollutant orange II and heavy metal pollutant hexavalent chromium reaches 100 percent.
Example 3
This example prepares a copper-iron bimetallic confined nitrogen doped carbon nanotube composite in the same manner as in example 1, except that: in the precursor preparation process, the dosage of the methanol in the solution A is 40mL, and the dosage of the methanol in the solution B is 20 mL.
Through tests, the composite material prepared by the embodiment is in a carbon nanotube structure, and the bimetallic copper and iron are highly dispersed in the nitrogen-doped carbon nanotube derived from the metal organic framework, so that the catalytic activity is high.
The composite material obtained in this example was tested for its catalytic performance in the same manner as in example 1. Tests show that the degradation rate of organic pollutant orange II and heavy metal pollutant hexavalent chromium reaches 100 percent.
Example 4
This example prepares a copper-iron bimetallic confined nitrogen doped carbon nanotube composite 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 80 mL.
Through tests, the composite material prepared by the embodiment is in a carbon nanotube structure, and the bimetallic copper and iron are highly dispersed in the nitrogen-doped carbon nanotube derived from the metal organic framework, so that the catalytic activity is high.
The composite material obtained in this example was tested for its catalytic performance in the same manner as in example 1. Tests show that the degradation rate of organic pollutant orange II and heavy metal pollutant hexavalent chromium reaches 100 percent.
Example 5
This example prepares a copper-iron bimetallic confined nitrogen doped carbon nanotube composite in the same manner as in example 1, except that: in the precursor preparation process, the dosage of the methanol in the solution A is 320mL, and the dosage of the methanol in the solution B is 160 mL.
Through tests, the composite material prepared by the embodiment is in a carbon nanotube structure, and the bimetallic copper and iron are highly dispersed in the nitrogen-doped carbon nanotube derived from the metal organic framework, so that the catalytic activity is high.
The composite material obtained in this example was tested for its catalytic performance in the same manner as in example 1. Tests show that the degradation rate of organic pollutant orange II and heavy metal pollutant hexavalent chromium reaches 100 percent.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a copper-iron bimetal confined nitrogen doped carbon nanotube composite material is characterized by comprising the following steps:
(1) uniformly stirring iron acetylacetonate, the copper foil subjected to acid cleaning treatment and 2-methylimidazole in a methanol solution at room temperature, and carrying out ultrasonic treatment for 1h to obtain solution A; adding Zn (NO)3)2·6H2Stirring the solution O in methanol solution at room temperature to obtain solution B; then, pouring the solution B into the solution A, stirring uniformly at room temperature, centrifuging, washing and drying the obtained mixed solution to obtain a precursor;
(2) and (3) under the protection of inert gas, transferring the precursor obtained in the step (1) to a tube furnace for calcination and pyrolysis to obtain the copper-iron bimetal confined nitrogen-doped carbon nanotube composite material.
2. The method of claim 1, wherein: in the step (1), the copper foil subjected to acid washing treatment is subjected to acid washing treatment by using hydrochloric acid with the concentration of 2-4M, and the acid washing time is 12-48 h.
3. The method of claim 1, wherein: in the step (1), the dosage ratio of the iron acetylacetonate, the copper foil subjected to acid cleaning, the 2-methylimidazole and the methanol in the solution A is 0.1-3 g: 4-10 g: 40-320 mL.
4. The method of claim 1, wherein: in the step (1), Zn (NO) in the solution B3)2·6H2The dosage ratio of the O to the methanol is 1 g-9 g: 20-160 mL.
5. The method of claim 1, wherein: in the step (1), the stirring time of the solution B after the solution A is poured into the solution B is 18-30 h.
6. The method of claim 1, wherein: in the step (1), the drying is carried out for 8-16 hours at 50-70 ℃.
7. The method of claim 1, wherein: 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 claim 1, wherein: 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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