CN110237813B - Preparation method and application of carbon/manganese dioxide composite nanofiber with hollow structure - Google Patents
Preparation method and application of carbon/manganese dioxide composite nanofiber with hollow structure Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention relates to a preparation method and application of a carbon/manganese dioxide composite nanofiber with a hollow structure. The prepared composite nanofiber membrane has long and continuous fibers and good mechanical strength, can avoid the problem of agglomeration of manganese dioxide nanoparticles in the application process, is easy to separate and recycle after use, and improves the operability and practical applicability of the manganese dioxide material to the maximum extent. The carbon/manganese dioxide composite nanofiber membrane with the hollow structure has a good application prospect in the aspect of adsorption and application of heavy metal ions in water.
Description
Technical Field
The invention belongs to the technical field of environment nano new functional materials, and particularly relates to manganese dioxide modified carbon nanofiber with a multilevel structure and a hollow structure, a preparation method thereof and application thereof in heavy metal ion adsorption
Background
With the rapid increase of global industrial activities such as electronics, chemical engineering, mechanical manufacturing and mining, the problem of heavy metal pollution in wastewater has attracted extensive attention from countries all over the world. In recent years, nano metal oxide adsorbents have been widely used for removing heavy metal ions (copper, lead, zinc, tin, nickel, cobalt, chromium, cobalt, etc.) in sewage, and these nano particles include iron oxide (Fe)2O3) Aluminum oxide (Al)2O3) Cerium oxide (CeO)2) Zinc oxide (ZnO) and manganese oxide (MnO)2). Ultra-fine MnO in comparison with other metal oxide particles2The nano particles have the advantages of large specific surface area, high-efficiency adsorption capacity and the like, and an effective way is provided for removing various toxic heavy metal ions. However, nano MnO2The particles tend to agglomerate during adsorption due to their high surface energy; furthermore, a nano MnO2The particles are easily suspended in water and are difficult to separate from a large amount of water, limiting operability and practical applicability.
Electrostatic spinning is an effective method for preparing a continuous fiber membrane with an adjustable structure. The prepared nanofiber membrane has the advantages of high specific surface area, high porosity, small size of pores among fibers and the like, and can provide more adsorption sites for the adsorption process. The electrostatic spinning technology can be used for preparing various composite nanofiber adsorbents, the prepared electrospun fibers have good flexibility and mechanical strength, and the composite adsorbents can be easily separated from a solution. The composite nano-fiber membrane material solves the problems of the nano-materials and can promote the further application of the nano-materials.
Based on the introduction of the background, the invention provides a preparation method of carbon/manganese dioxide composite nanofibers with hollow structures. The flexible carbon nanofiber membrane is prepared by an electrostatic spinning technology and a post-calcining method, and is prepared by taking the flexible carbon nanofiber membrane as a precursor template through a simple hydrothermal reaction process. The reaction principle is that carbon is used as a reducing agent to reduce KMnO4. When the carbon nano-fiber contacts with KMnO4When in solution, atMnO is formed on the surface of the carbon fiber2And (3) consumption of the nano-crystal and the carbon nano-fiber through oxidation-reduction reaction gradually forms a hollow structure. In hydrothermal process, nanocrystalline MnO2Will be used as an active nucleation center, and the reactant KMnO increases with the increase of hydrothermal temperature4Decomposition to MnO in equivalent2And continuously depositing on the nucleation center to gradually form manganese dioxide nano-sheets uniformly covering the surface of the carbon nano-fiber with the hollow structure. The prepared composite nanofiber membrane can avoid the problem of agglomeration of nano particles in the using process, and can be easily separated and recycled after being used. In addition, by changing the hydrothermal reaction conditions, the mass ratio of carbon to manganese dioxide in the obtained carbon/manganese dioxide composite fiber membrane with the hollow structure is continuously changed, and the structure types of the material are greatly enriched. Due to the physical and chemical properties of manganese dioxide and the structural characteristics of the nanofiber membrane, the obtained carbon/manganese dioxide composite nanofiber membrane with the hollow structure has a very good application prospect in the aspect of adsorption and application of heavy metal ions in water.
Disclosure of Invention
The invention aims to provide a preparation method of carbon/manganese dioxide composite nanofiber with a hollow structure, and aims to solve the problems that a manganese dioxide nanomaterial is agglomerated in the using process and is not easy to separate and recycle after being used. Simultaneously explores the adsorption application of the prepared composite nanofiber membrane to heavy metal ions in water.
In order to achieve the above purpose, the preparation method of the carbon/manganese dioxide composite nanofiber membrane with a hollow structure of the invention comprises the following steps: the preparation method comprises the steps of firstly preparing a flexible carbon nanofiber membrane by an electrostatic spinning technology and a post-calcining method, taking the flexible carbon nanofiber membrane as a precursor template, and converting the flexible carbon nanofiber membrane into a carbon/manganese dioxide composite nanofiber membrane with a hollow structure by a hydrothermal reaction process.
The preparation method comprises the following specific steps:
(1) dissolving the selected polymer in N, N-Dimethylformamide (DMF), stirring until the polymer is completely dissolved (heating and dissolving are carried out if necessary), and preparing a polymer solution with the mass fraction of 8-12 wt%;
(2) putting the electrostatic spinning solution into a spinning nozzle of spinning equipment, wherein the inner diameter of a tube head of a glass spinning nozzle is 0.5-2 mm, the working voltage of the electrospinning equipment is 15-30 kV, an aluminum sleeve is used as an anode, an aluminum foil is used as a cathode for receiving, and the distance between the two electrodes is 10-30 cm; carrying out electrostatic spinning to obtain an organic polymer fiber membrane;
(3) and (3) carrying out pre-oxidation and carbonization processes on the organic polymer fiber membrane obtained in the step (2) to obtain the flexible carbon nanofiber membrane. The pre-oxidation temperature is increased to 240-300 ℃ from room temperature at a heating rate of 1-5 ℃/min, and is kept at the highest temperature for 2 hours to achieve the purpose of pre-oxidation; and carbonizing in a tubular muffle furnace, raising the temperature to 400-600 ℃ at a rate of 1-3 ℃/min in a nitrogen atmosphere, then raising the temperature to 800-1200 ℃ at a rate of 3-8 ℃/min, and calcining for 2-6 h at the highest temperature to obtain the carbon nanofiber with good mechanical properties.
(4) Placing 0.02-0.1 g of the flexible carbon nanofiber membrane obtained in the step (3) in 50mL of 1-5 mmol of KMnO4And after the fiber membrane is completely soaked in the solution, putting the mixed solution into a closed hydrothermal reaction kettle, carrying out hydrothermal reaction for 4-8 h at 70-160 ℃, repeatedly washing the obtained product with water and ethanol, and drying in a vacuum oven at 60 ℃ to finally obtain the carbon/manganese dioxide composite nanofiber membrane.
The polymer in the step (1) is polyacrylonitrile, polyvinylpyrrolidone and polystyrene.
The preparation of the carbon/manganese dioxide composite nanofiber with the hollow structure and the adsorption application of the carbon/manganese dioxide composite nanofiber to heavy metal ions in water are characterized in that: the composite nanofiber membrane can effectively remove Cu in wastewater2+、Pb2+And Cd2+The heavy metal ions are equal, the fiber membrane can be recycled, and the antibiotic removal rate can reach 89.6-98.5%.
The test method for the adsorption performance of the heavy metal ion adsorption film on heavy metal ions in water comprises the following steps: and testing the heavy metal ions with different concentrations by using an ICP-8000 type inductively coupled plasma emission spectrometer so as to determine the concentration of the heavy metal ions in the water.
Has the advantages that:
(1) the carbon/manganese dioxide nanofiber membrane with the hollow structure prepared by adopting the electrostatic spinning technology has long and continuous fibers and good mechanical strength, can avoid the agglomeration problem of nano particles in the using process, can be easily separated and recovered after being used, and improves the operability and the practical applicability of the manganese dioxide material to the maximum extent;
(2) the preparation method has universality, and is prepared by taking the flexible electrospun carbon nanofiber membrane as a precursor template through simple hydrothermal reaction. The reaction principle is that carbon is used as a reducing agent to reduce KMnO4. When the carbon nano-fiber contacts with KMnO4When in solution, MnO is formed on the surface of the carbon fiber2And the carbon nano fiber is consumed through oxidation-reduction reaction to become the carbon/manganese dioxide composite nano fiber membrane with a hollow structure.
(3) The surface of the carbon/manganese dioxide nano fiber with the hollow structure obtained by the invention is uniformly grown with a layer of nano flaky single crystal MnO2The specific surface area of the material is increased, and the adsorption capacity of the fiber is greatly improved;
(4) the carbon/manganese dioxide nanofiber membrane with the hollow structure is easy to obtain raw materials, simple to operate, environment-friendly, low in cost and easy to realize industrial production.
Drawings
FIG. 1: isothermally fitted curve of the carbon/manganese dioxide composite nanofiber membrane having a hollow structure obtained in example 1;
FIG. 2: the kinetic adsorption curve of the carbon/manganese dioxide composite nanofiber membrane with a hollow structure obtained in example 2 on lead ions in water;
FIG. 3: a scanning electron micrograph of the carbon/manganese dioxide composite nanofiber membrane having a hollow structure was obtained in example 3.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples, and should not be construed as limiting the scope of the present invention.
Example 1:
(1) dissolving polyacrylonitrile in N, N-dimethylformamide, heating and stirring at 65 ℃ until the polyacrylonitrile is completely dissolved, and preparing a polyacrylonitrile solution with the mass fraction of 11 wt%;
(2) putting the electrostatic spinning solution into a spinning nozzle of spinning equipment, wherein the inner diameter of a tube head of a glass spinning nozzle is 1.5mm, the working voltage of the electrospinning equipment is 20kV, an aluminum sleeve is used as an anode, an aluminum foil is used as a cathode for receiving, and the distance between the two electrodes is 10 cm; carrying out electrostatic spinning to obtain a polyacrylonitrile fiber membrane;
(3) raising the temperature of the polyacrylonitrile fiber membrane obtained in the step (2) from room temperature to 260 ℃ at the speed of 2 ℃/min in the air atmosphere, and pre-oxidizing for two hours; placing the fiber membrane obtained by pre-oxidation into a tubular furnace, heating to 500 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, calcining for 3h after the temperature reaches 800 ℃ at a heating speed of 4 ℃/min to obtain a flexible carbon nanofiber membrane;
(4) placing 0.02g of the flexible carbon nanofiber membrane obtained in the step (3) in 50mL of 1mmol of KMnO4And after the fiber membrane is completely soaked in the solution, putting the mixed solution into a closed hydrothermal reaction kettle, carrying out hydrothermal reaction for 4 hours at 100 ℃, repeatedly washing the obtained product with water and ethanol, and drying in a vacuum oven at 60 ℃ to finally obtain the carbon/manganese dioxide composite nanofiber membrane with a hollow structure. The nanofiber membrane has an initial concentration of 100mg/L of Pb in water at room temperature2+The removal rate of (2) was 96.3%. The adsorbed nanofiber membrane was regenerated with 0.05M HCl solution. After five times of desorption, the nanofiber membrane has good response to Pb2+The adsorption capacity of the adsorbent can reach 92.3 percent of the primary adsorption capacity.
Example 2:
(1) dissolving polyacrylonitrile in N, N-dimethylformamide, heating and stirring at 70 ℃ until the polyacrylonitrile is completely dissolved, and preparing a polyacrylonitrile solution with the mass fraction of 8.5 wt%;
(2) putting the electrostatic spinning solution into a spinneret tube of spinning equipment, wherein the inner diameter of a tube head of a glass spinneret tube is 1mm, the working voltage of the electrospinning equipment is 15kV, an aluminum sleeve is used as an anode, an aluminum foil is used as a cathode for receiving, and the distance between the two electrodes is 15 cm; carrying out electrostatic spinning to obtain a polyacrylonitrile fiber membrane;
(3) raising the temperature of the polyacrylonitrile fiber membrane obtained in the step (2) from room temperature to 280 ℃ at the speed of 4 ℃/min in the air atmosphere, and pre-oxidizing for two hours; placing the fiber membrane obtained by pre-oxidation into a tubular furnace, heating to 400 ℃ at a speed of 3 ℃/min in a nitrogen atmosphere, and calcining for 2h after the temperature reaches 1000 ℃ at a heating speed of 6 ℃/min to obtain a flexible carbon nanofiber membrane;
(4) placing 0.05g of the flexible carbon nanofiber membrane obtained in the step (3) in 50mL of 2mmol KMnO4And after the fiber membrane is completely soaked in the solution, putting the mixed solution into a closed hydrothermal reaction kettle, carrying out hydrothermal reaction for 4 hours at 140 ℃, repeatedly washing the obtained product with water and ethanol, and drying in a vacuum oven at 60 ℃ to finally obtain the carbon/manganese dioxide composite nanofiber membrane with a hollow structure. The nanofiber membrane has an initial concentration of 100mg/L of Pb in water at room temperature2+The removal rate of (2) was 98.5%. The adsorbed nanofiber membrane was regenerated with 0.05M HCl solution. After five times of desorption, the nanofiber membrane has good response to Pb2+The adsorption capacity of the adsorbent can reach 93.5 percent of the primary adsorption capacity.
Example 3:
(1) dissolving polystyrene in N, N-dimethylformamide, heating and stirring at 65 ℃ until the polystyrene is completely dissolved, and preparing a polyacrylonitrile solution with the mass fraction of 12 wt%;
(2) putting the electrostatic spinning solution into a spinneret tube of spinning equipment, wherein the inner diameter of a tube head of a glass spinneret tube is 2mm, the working voltage of the electrospinning equipment is 25kV, an aluminum sleeve is used as an anode, an aluminum foil is used as a cathode for receiving, and the distance between the two electrodes is 20 cm; carrying out electrostatic spinning to obtain a polyacrylonitrile fiber membrane;
(3) raising the temperature of the polyacrylonitrile fiber membrane obtained in the step (2) from room temperature to 280 ℃ at the speed of 1 ℃/min in the air atmosphere, and pre-oxidizing for two hours; placing the fiber membrane obtained by pre-oxidation into a tubular furnace, heating to 500 ℃ at a speed of 2 ℃/min in a nitrogen atmosphere, calcining for 3h after the temperature reaches 800 ℃ at a heating speed of 5 ℃/min to obtain a flexible carbon nanofiber membrane;
(4) placing 0.08g of the flexible carbon nanofiber membrane obtained in the step (3) in 50mL of a membrane with the thickness of 3mmol KMnO4And after the fiber membrane is completely soaked in the solution, putting the mixed solution into a closed hydrothermal reaction kettle, carrying out hydrothermal reaction for 5 hours at 120 ℃, repeatedly washing the obtained product with water and ethanol, and drying in a vacuum oven at 60 ℃ to finally obtain the carbon/manganese dioxide composite nanofiber membrane with a hollow structure. The nanofiber membrane has an initial concentration of 100mg/L of Cu in water at room temperature2+The removal rate of (3) was 93.6%. The adsorbed nanofiber membrane was regenerated with 0.05M HCL solution. After five desorption, the nanofiber membrane is aligned to Cu2+The adsorption capacity of the adsorbent can reach 90.6 percent of the primary adsorption capacity.
Example 4:
(1) dissolving polyvinylpyrrolidone in N, N-dimethylformamide, stirring at room temperature until the polyvinylpyrrolidone is completely dissolved, and preparing a polyacrylonitrile solution with the mass fraction of 10 wt%;
(2) putting the electrostatic spinning solution into a spinneret tube of spinning equipment, wherein the inner diameter of a tube head of a glass spinneret tube is 1mm, the working voltage of the electrospinning equipment is 15kV, an aluminum sleeve is used as an anode, an aluminum foil is used as a cathode for receiving, and the distance between the two electrodes is 15 cm; carrying out electrostatic spinning to obtain a polyacrylonitrile fiber membrane;
(3) raising the temperature of the polyacrylonitrile fiber membrane obtained in the step (2) from room temperature to 270 ℃ at the speed of 2 ℃/min in the air atmosphere, and pre-oxidizing for two hours; placing the fiber membrane obtained by pre-oxidation into a tubular furnace, heating to 500 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, calcining for 3h after the temperature reaches 1200 ℃ at a heating speed of 6 ℃/min, and obtaining the flexible carbon nanofiber membrane;
(4) placing 0.05g of the flexible carbon nanofiber membrane obtained in the step (3) in 50mL of 2mmol KMnO4And after the fiber membrane is completely soaked in the solution, putting the mixed solution into a closed hydrothermal reaction kettle, carrying out hydrothermal reaction for 6 hours at 80 ℃, repeatedly washing the obtained product with water and ethanol, and drying in a vacuum oven at 60 ℃ to finally obtain the carbon/manganese dioxide composite nanofiber membrane with a hollow structure. The nanofiber membrane has an initial concentration of 100mg/L of Cd in water at room temperature2+The removal rate of (2) was 89.6%. The adsorbed nanofiber membrane was regenerated with 0.05M HCl solution. After five times of desorption, the nanometerFibrous membrane for Cd2+The adsorption capacity of the adsorbent can reach 85.4 percent of the primary adsorption capacity.
Claims (5)
1. A preparation method of a carbon/manganese dioxide composite nanofiber membrane with a hollow structure is characterized by comprising the following steps: the flexible electrospun carbon nanofiber membrane is used as a precursor template, and is converted into a carbon/manganese dioxide nanofiber membrane with a hollow structure through a hydrothermal reaction process; the method comprises the following specific steps:
(1) dissolving the selected polymer in N, N-dimethylformamide, stirring or heating until the polymer is completely dissolved, and preparing a polymer solution with the mass fraction of 8-12 wt%;
(2) putting the electrostatic spinning solution prepared in the step (1) into a spinning pipe of spinning equipment for electrostatic spinning so as to obtain a polymer nanofiber membrane;
(3) carrying out pre-oxidation and carbonization processes on the organic polymer fiber membrane obtained in the step (2) to obtain a flexible carbon nanofiber membrane; the pre-oxidation temperature is 1-5 ℃ from room temperatureoThe temperature rise rate of C/min is increased to 240-300oC, keeping for 2 hours to achieve the aim of pre-oxidation; the carbonization is carried out in a muffle furnace in a nitrogen atmosphere by 1-3oThe rate of C/min is increased to 400-600oC, then 3 to 8oThe temperature rise rate of C/min reaches 800-1200oC, calcining for 2-6 hours to obtain carbon nanofibers with good mechanical properties;
(4) placing 0.02-0.1 g of the flexible carbon nanofiber membrane obtained in the step (3) in 50mL of 1-5 mmol of KMnO4After the fiber membrane is completely soaked in the solution, placing the mixed solution into a closed hydrothermal reaction kettle at 70-160 DEGoAnd C, carrying out hydrothermal reaction for 4-8 h, repeatedly washing the obtained product with water and ethanol, and drying in a vacuum oven to finally obtain the carbon/manganese dioxide composite nanofiber membrane with the hollow structure.
2. The method for preparing a carbon/manganese dioxide composite nanofiber membrane with a hollow structure according to claim 1, wherein the method comprises the following steps: the polymer in the step (1) is one of polyacrylonitrile, polyvinylpyrrolidone or polystyrene.
3. The method for preparing a carbon/manganese dioxide composite nanofiber membrane with a hollow structure according to claim 1, wherein the method comprises the following steps: the inner diameter of the tube head of the spinneret in the step (2) is 0.5-2 mm, the working voltage of the electric spinning equipment is 15-30 kV, the aluminum sleeve is used as an anode, the aluminum foil is used as a cathode, and the distance between the two electrodes is 10-30 cm.
4. The method for preparing a carbon/manganese dioxide composite nanofiber membrane with a hollow structure according to claim 1, wherein the method comprises the following steps: the carbon/manganese dioxide composite nanofiber membrane with the hollow structure is characterized in that the average diameter of fibers is 300-600 nm.
5. The application of the nanofiber membrane obtained by the preparation method of the carbon/manganese dioxide composite nanofiber membrane with the hollow structure according to claim 1 is characterized in that: the carbon/manganese dioxide composite nanofiber membrane can effectively remove Cu in wastewater2+、Pb2+And Cd2+And the fiber membrane can be repeatedly used, and the ion removal rate can reach 89.6-98.5%.
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