CN109133962B - Electrostatic spinning nanofiber composite carbon aerogel and preparation method thereof - Google Patents
Electrostatic spinning nanofiber composite carbon aerogel and preparation method thereof Download PDFInfo
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Abstract
The patent provides a preparation method of nanofiber composite carbon aerogel, and belongs to the field of nanofiber carbon aerogel. The method comprises the following steps: adopting an electrostatic spinning-support dispersion liquid receiving mode to obtain a composite dispersion liquid of the nanofiber and the support body; and (3) obtaining fluffy carbon aerogel through freeze drying, pre-oxidation and carbonization treatment. The method for directly receiving the electrostatic spinning nano-fiber by the support dispersion liquid can ensure that the support body is simultaneously diffused into a fiber network in the spinning process, thereby avoiding the step of mechanically dispersing and then crosslinking the fiber membrane in most preparation methods and improving the problem of uneven dispersion of the additive. The composite carbon aerogel prepared by the invention has an open pore structure formed by assembling the nano fibers and the support body, and has excellent mechanical properties and compression resilience. The carbon aerogel can be applied to the aspect of environmental management and has good application prospect in the field of electrode materials of super capacitors.
Description
Technical Field
The invention discloses an electrostatic spinning nanofiber composite carbon aerogel and a preparation method thereof, belonging to the field of nanofiber carbon aerogels.
Background
The carbon aerogel is a three-dimensional light porous carbon material and has the characteristics of high specific surface area, ultralow density, good conductivity and the like; can be used as adsorbent, catalyst carrier and electrode material, and is applied to adsorption, catalysis and electrocatalysis treatment of pollutants in water; the lithium ion battery is also an ideal electrode material of a new energy battery and an electric double layer super capacitor, has good application prospect in the aspect of hydrogen storage, and is one of the research hotspots in recent years. The types of carbon aerogels at present mainly comprise biochar, carbon nanotubes, graphene and carbon nanofiber-based carbon aerogels. The biological carbon aerogel is limited by the structure of the raw material, and the microstructure of the material is not easy to regulate and control; the preparation of carbon nanotubes or graphene-based carbon aerogels requires high bulk density of raw materials, a corresponding increase in material cost, and general mechanical properties. In contrast, the carbon nanofiber is simple to prepare, flexible in structure regulation and high in strength, and is an excellent carbon aerogel basic construction unit.
The electrostatic spinning technology is a method for simply and rapidly preparing the one-dimensional nano fiber. Under the action of electrostatic field force, the spinning solution is charged, and simultaneously, an electric field force opposite to the surface tension direction of the liquid is generated; when the electric field force is larger than the surface tension, the charged spinning solution forms a jet flow at a spinneret orifice; the jet stream moves in the air, evaporates the solvent, solidifies the fibers, and deposits on the collection device. The electrostatic spinning technology can select corresponding raw materials according to requirements, wherein the raw materials comprise different polymers, inorganic matters and polymer/inorganic matter composites; in addition, the parameters of the spinning process are flexible and controllable, and fibers with different structures such as uniform fibers, beads, porous fibers and the like can be obtained, so that the technology is widely applied to the preparation of two-dimensional nanofiber membranes.
At present, the construction of three-dimensional structures by using electrospinning technology has been partially studied. For example, a three-dimensional nanofiber block is prepared by a liquid phase receiving method in document 1 (Novel wet electrospinning system for manufacturing of spinning nanofiber 3-dimensional fabric, Yokoyama, Yoshiro et al, Materials Letters, volume 63, page 754-. The preparation method is simple and effective, but the material has poor mechanical property due to the lack of a three-dimensional structure stabilizing step, so that the practical application of the material is limited. Patent 1 (dingbin, dawn, shanyang, gejialong, huangmeiling, juJie, shujiangong, a three-dimensional carbon fiber-based aerogel and a preparation method thereof, CN 103265010A) and document 2 (Ultralight nanofiber-associated cellular aerogels with super elasticity and multifunctionality, Bin Ding et al, Nature Communication, volume 5, page 5802) disperse continuous fibers to obtain a fiber suspension with micro-nanometer length, and then, the fiber suspension is subjected to subsequent curing and shaping to reconstruct a three-dimensional structure, and then, short fibers are subjected to crosslinking and heat treatment to obtain the three-dimensional carbon fiber-based aerogel. The method can improve the mechanical property of the aerogel, but the preparation process is complex, and the short fibers need to be crosslinked again in the three-dimensional structure reconstruction. In addition, studies have shown that the mechanical properties of the aerogel can be improved by compounding a one-Dimensional material with a two-Dimensional material, as disclosed in patent 2 (Liu bang, huang yunpo, muo yue, zhang yu, lewy, ruheng, a Carbon nanofiber-Graphene composite aerogel and a cooperative assembly preparation method, CN 105161312 a), document 3 (Elastic Carbon elastomers reinforced from electron fibers and Graphene as Three-Dimensional network Matrix for Efficient Energy Storage/Conversion, volume 6, page 31541), a flat sheet membrane is prepared by using a conventional flat sheet or roller as a receiver, and then is homogenized, then assembled with Graphene oxide, and further subjected to freeze drying and high temperature carbonization to prepare the Carbon nanofiber/Graphene composite aerogel. In the method, the long fibers in the two-dimensional fiber membrane also need to be homogenized and dispersed, so that a continuous fiber network is damaged, the mechanical strength of the nano fibers is reduced, and a large amount of support body materials are required to be added in the process of forming the micron-sized fiber dispersion liquid into the three-dimensional aerogel. Patent 3 (bellbin, zhengyuming, populus, three-dimensional oil-water separation material based on electrostatic spinning technology and preparation method thereof, CN 104674384B) adopts liquid receiving to prepare nanofibers, then adds substances for enhancing mechanical properties into nanofiber dispersion liquid, and then obtains three-dimensional material through freeze drying and heat treatment. In the carbon aerogel obtained by the preparation method, the nano fibers are a continuous network, but because the fiber blocks form a closely-packed fiber network in the spinning process, the problem that substances are difficult to diffuse into the fiber blocks exists in the subsequent operation of adding the substances for enhancing the mechanical properties, the phenomenon that the additives are not uniformly distributed in the fiber networks is further caused, and the practical application of the additives is limited. Therefore, how to simply, controllably and effectively compound the electrospun one-dimensional nanofiber material with the two-dimensional material still needs to be further researched.
Disclosure of Invention
Aiming at the problems of uncontrollable structure, general mechanical property, complex preparation method, high raw material stacking density, uneven dispersion of a support body and the like of the carbon aerogel, the invention provides a nano-fiber composite carbon aerogel and a preparation method thereof. The method is simple and feasible, and the process parameters are controllable; the microstructure and the macrostructure of the material can be regulated and controlled; the required bulk density of the raw materials is greatly reduced, and the supporting bodies can be uniformly distributed in the materials; the prepared material is an open pore network formed by assembling one-dimensional nanofibers and a two-dimensional support body on the microstructure, and has excellent mechanical properties and compression resilience.
The invention provides a preparation method of a nanofiber composite carbon aerogel with an open pore structure, which comprises the following specific steps:
(1) preparing an electrostatic spinning polymer solution;
(2) adopting a supporter dispersion liquid to receive the electrostatic spinning nano-fiber and preparing a nano-fiber/supporter uniform dispersion liquid;
(3) placing the mixed dispersion liquid prepared in the step (2) into a container with a specific shape for freeze forming, and then placing the container into a freeze dryer for drying to obtain a fluffy nanofiber/support body composite block;
(4) and (4) pre-oxidizing and carbonizing the block prepared in the step (3) to obtain the ultralight elastic nanofiber composite carbon aerogel.
The electrostatic spinning polymer liquid in the step (1) comprises one or more of polyacrylonitrile, polymethyl methacrylate, polyamic acid, polycarbonate, polyurethane, polyvinyl chloride, polyvinylidene fluoride, polyethylene and the like.
The electrostatic spinning technology in the step (2) has the process parameters as follows: the spinning voltage is 5-30 kV of positive voltage and minus 30-5 kV of negative voltage; the feeding flow rate of the solution is 0.1-5 mL/h; the distance between the spinning nozzle and the receiving liquid level is 5-30 cm. The support body is one or more of graphene, graphene oxide, black scales, boron nitride nanosheets, manganese dioxide nanosheets, molybdenum disulfide nanosheets and the like, which have a two-dimensional lamellar structure on a micro-nano scale; the solution of the dispersion support is a liquid with the infiltration work larger than 0 when the nano-fiber is infiltrated, namely the contact angle between the nano-fiber and the receiving solution is smaller than 90 degrees.
The freeze drying process parameters in the step (3) are as follows: the freezing temperature is-50 to-20 ℃, the freezing time is 6 to 12 hours, and the time of a freeze dryer is 12 to 72 hours.
The parameters of the pre-oxidation process in the step (4) are as follows: the pre-oxidation temperature is 150-300 ℃, and the pre-oxidation time is 30-180 min; the parameters of the carbonization process are as follows: the inert atmosphere is nitrogen or argon, the temperature is raised at a rate of 1-10 ℃/min, the carbonization temperature is 500-1000 ℃, the carbonization time is 1-5 h, and the temperature is lowered at a rate of 1-3 ℃/min.
The principle and method of the invention:
the invention adopts the method of electrostatic spinning/supporter dispersion liquid receiving to prepare the nano-fiber composite carbon aerogel. In the preparation process, the charged spinning solution forms a jet flow at a spinning nozzle, moves in the air, and reaches the liquid level of the receiving solution after solvent volatilization and fiber solidification; the required wetting work when the receiving liquid wets the nano-fiber is the product of the surface energy of the receiving liquid and the contact angle between the nano-fiber and the receiving liquid, and when the wetting work is larger than zero, namely the contact angle between the nano-fiber and the receiving solution is smaller than 90 degrees, the nano-fiber can be wetted by the receiving liquid. The support body gradually diffuses into the fiber network along with the process of immersing the nano fibers into liquid, and is self-assembled with the one-dimensional nano fibers to form an open pore structure. Because the dispersion liquid of the support body synchronously diffuses into the fiber network, the fluffy nanofiber-support body composite block with uniform internal structure can be obtained after freeze drying. In the subsequent heat treatment process, the nano-fibers are further converted into carbon nano-fibers, and finally the composite carbon aerogel with a microscopically open pore structure can be obtained. The macroscopic shape of the three-dimensional block depends mainly on the setting shape of the dispersion when frozen.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the nanofiber composite carbon aerogel prepared by the method has a uniform internal structure. The method of directly receiving the electrostatic spinning nano-fiber by using the support dispersion liquid overcomes the defect that the sheet material is difficult to uniformly disperse into the interior of the fiber block in the existing method;
(2) the nanofiber composite carbon aerogel prepared by the method has a continuous fiber network and the support bodies can be uniformly distributed in the fiber network, so that the addition proportion of the support bodies required by the construction of the three-dimensional aerogel structure is low, the bulk density of raw materials is greatly reduced, and the material cost is reduced;
(3) the continuous nanofiber network in the nanofiber composite carbon aerogel prepared by the method is cooperatively assembled with the two-dimensional lamellar material to form an open pore structure, so that the material has excellent mechanical properties and compression resilience;
(4) the preparation method of the electrostatic spinning nanofiber composite carbon aerogel has the advantages of simple operation, mild conditions, controllable volume and shape of the carbon aerogel, and capability of being adjusted according to actual application requirements;
(5) in the preparation method of the electrostatic spinning nanofiber composite carbon aerogel, the microstructure of the nanofiber is controllable, and composite carbon aerogels with different microstructures can be obtained through selection and matching of raw materials and regulation and control of preparation parameters;
(6) the preparation method of the electrostatic spinning nanofiber composite carbon aerogel has wide application range. The two-dimensional support can be selected according to practical application; the dispersion liquid can be selected according to the wettability of the dispersion liquid to the nano fibers, namely, the wetting power, and the larger the wetting power is, the better the wetting effect is; the source of raw materials for preparing the nano-fiber is very wide.
Description of the drawings:
FIG. 1 is an SEM photograph of PAN/GO composite carbon aerogel in example 1
FIG. 2 is a TEM image of PAN/GO composite carbon aerogel in example 1
FIG. 3 is a graph of uniaxial compressive stress strain for PAN/GO composite carbon aerogel in example 1
FIG. 4 is an SEM image of PAN/PMMA/GO composite porous carbon aerogel in example 3
FIG. 5 is TEM image of PAN/PMMA/GO composite porous carbon aerogel in example 3
FIG. 6 is an optical photograph of PAN/GO composite carbon aerogel in various shapes as in example 6
FIG. 7 is a graph showing the change of the adsorption amount of PAN/GO composite carbon aerogel in tetracycline-containing wastewater treatment with time in example 8
The specific implementation mode is as follows:
a nanofiber composite carbon aerogel and a method for preparing the same according to the present invention will be described below by way of specific embodiments, it being understood that the following specific embodiments are illustrative and not limiting to the scope of the invention, which is defined by the claims. It will be apparent to those skilled in the art that various changes in the materials selected and in the control parameters of the preparation of these embodiments can be made without departing from the spirit and scope of the invention.
Example 1
Preparing a nano-fiber composite carbon aerogel material by using Polyacrylonitrile (PAN) and Graphene Oxide (GO) as raw materials:
(1) preparing a spinning solution: weighing 2 g of PAN polymer powder, adding the PAN polymer powder into Dimethylformamide (DMF), and stirring the mixture in a water bath at 60 ℃ until the PAN polymer powder is dissolved to obtain PAN spinning solution with the mass fraction of 10%;
(2) preparation of nanofiber/support dispersion: and (2) transferring the spinning solution obtained in the step (1) into an injector, connecting the injector with an automatic sample injector, and connecting a needle with a high-voltage power supply to carry out electrostatic spinning, wherein the receiving solution is 0.2 mg/mL GO water dispersion. Spinning conditions are as follows: the spinning voltage is 20 kV and 10 kV, the flow rate of the spinning solution is 1 mL/h, the distance between the needle head and the surface of the receiving liquid is 15 cm, and the fiber density is 2 mg/mL;
(3) preparing a nanofiber/support composite block: transferring the PAN nanofiber/GO composite dispersion liquid prepared in the step (2) into a 100 mL beaker, placing the beaker into a refrigerator at-20 ℃ for 6 hours, and transferring the beaker into a freeze dryer for drying for 48 hours;
(4) and (4) placing the block dried in the step (3) into a forced air drying oven for pre-oxidation at the temperature of 300 ℃ for 60 min. And then transferring the carbon aerogel to a tubular furnace, heating to 500 ℃ at the speed of 5 ℃/min under the protection of nitrogen, keeping for 1 h, and cooling to room temperature at the speed of 3 ℃/min to obtain the nanofiber graphene oxide composite carbon aerogel.
Example 2
With PAN and manganese dioxide nanosheets (MnO)2) Preparing a nano-fiber composite carbon aerogel material by using the following raw materials:
(1) preparing a spinning solution: weighing 2 g of PAN polymer powder, adding the PAN polymer powder into DMF, and stirring in a water bath at 60 ℃ until the PAN polymer powder is dissolved to obtain a PAN spinning solution with the mass fraction of 10%;
(2) preparation of nanofiber/support dispersion: transferring the spinning solution obtained in the step (1) into a syringe, connecting the syringe to an automatic sample injector, and connecting a needle to a high-voltage power supply to carry out electrostatic spinning, wherein the receiving solution is 0.5 mg/mL MnO 2/50% tert-butyl alcohol/water dispersion solution. Spinning conditions are as follows: the spinning voltage is 15 kV and-5 kV, the flow rate of the spinning solution is 2 mL/h, the distance between the needle head and the surface of the receiving liquid is 20 cm, and the fiber density is 2 mg/mL;
(3) preparing a nanofiber/support composite block: transferring the PAN nanofiber/MnO 2 dispersion liquid prepared in the step (2) into a 100 mL beaker, placing the beaker into a refrigerator at-30 ℃ for 8 h, and transferring the beaker into a freeze dryer for drying for 72 h;
(4) and (4) placing the block dried in the step (3) into a forced air drying oven for pre-oxidation at the temperature of 300 ℃ for 120 min. And then transferring the carbon aerogel to a tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min under the protection of nitrogen, keeping for 1 h, and cooling to room temperature at the speed of 2 ℃/min to obtain the nano-fiber manganese dioxide composite carbon aerogel.
Example 3
Preparing a nano-fiber composite carbon aerogel material by using PAN, polymethyl methacrylate (PMMA) and GO as raw materials:
(1) preparing a spinning solution: weighing 2 g of PAN and 1 g of PMMA polymer powder, adding the PAN and PMMA polymer powder into DMF, and placing the mixture in a water bath at 60 ℃ to stir until the mixture is dissolved to obtain a mixed spinning solution with the mass fraction of 15%;
(2) preparation of nanofiber/support dispersion: and (2) transferring the spinning solution obtained in the step (1) into an injector, connecting the injector with an automatic sample injector, and connecting a needle with a high-voltage power supply to carry out electrostatic spinning, wherein the receiving solution is 0.2 mg/mL GO/50% ethanol/water dispersion solution. Spinning conditions are as follows: the spinning voltage is 30 kV, -5 kV, the flow rate of the spinning solution is 0.5 mL/h, the distance between the needle head and the surface of the receiving liquid is 20 cm, and the fiber density is 1 mg/mL;
(3) preparing a nanofiber/support composite block: transferring the PAN/PMMA nanofiber/GO dispersion liquid prepared in the step (2) into a 100 mL beaker, placing the beaker into a refrigerator at-20 ℃ for 6 hours, and transferring the beaker into a freeze dryer for drying for 48 hours;
(4) and (4) placing the block dried in the step (3) into a forced air drying oven for pre-oxidation at the temperature of 280 ℃ for 30 min. And then transferring the carbon aerogel to a tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min under the protection of argon, keeping for 2 hours, and cooling to room temperature at the speed of 3 ℃/min to obtain the porous nanofiber graphene oxide composite carbon aerogel.
Example 4
Preparing a nano-fiber composite carbon aerogel material by using PAN, PMMA and graphene as raw materials:
(1) preparing a spinning solution: weighing 2 g of PAN and 0.5 g of PMMA polymer powder, adding the PAN and PMMA polymer powder into DMF, and placing the mixture in a water bath at 60 ℃ to stir until the mixture is dissolved to obtain a mixed spinning solution with the mass fraction of 15%;
(2) preparation of nanofiber/support dispersion: and (2) transferring the spinning solution obtained in the step (1) into an injector, connecting the injector to an automatic sample injector, and connecting a needle to a high-voltage power supply for electrostatic spinning, wherein the receiving solution is 0.5 mg/mL graphene/tert-butyl alcohol dispersion solution. Spinning conditions are as follows: the spinning voltage is 15 kV, -15 kV, the flow rate of the spinning solution is 1 mL/h, the distance between the needle head and the surface of the receiving liquid is 30 cm, and the fiber density is 2 mg/mL;
(3) preparing a nanofiber/support composite block: transferring the PAN/PMMA nanofiber/graphene dispersion liquid prepared in the step (2) into a 100 mL beaker, placing the beaker into a refrigerator at-30 ℃ for 4 hours, and transferring the beaker into a freeze dryer for drying for 48 hours;
(4) and (4) placing the block dried in the step (3) into a forced air drying oven for pre-oxidation at the temperature of 200 ℃ for 60 min. And then transferring the carbon aerogel to a tubular furnace, heating to 800 ℃ at the speed of 10 ℃/min under the protection of argon, keeping for 2 hours, and cooling to room temperature at the speed of 3 ℃/min to obtain the porous nanofiber graphene composite carbon aerogel.
Example 5
Preparing a nano-fiber composite carbon aerogel material by using PAN, PMMA and boron Nitride (NB) as raw materials:
(1) preparing a spinning solution: weighing 2 g of PAN and 0.5 g of PMMA polymer powder, adding the PAN and PMMA polymer powder into DMF, and placing the mixture in a water bath at 60 ℃ to stir until the mixture is dissolved to obtain a mixed spinning solution with the mass fraction of 20%;
(2) preparation of nanofiber/support dispersion: and (2) transferring the spinning solution obtained in the step (1) into an injector, connecting the injector with an automatic sample injector, and connecting a needle with a high-voltage power supply to carry out electrostatic spinning, wherein the receiving solution is 0.25 mg/mL NB/tert-butyl alcohol dispersion solution. Spinning conditions are as follows: the spinning voltage is 20 kV and 10 kV, the flow rate of the spinning solution is 0.5 mL/h, the distance between the needle head and the surface of the receiving liquid is 10 cm, and the fiber density is 1 mg/mL;
(3) preparing a nanofiber/support composite block: placing the PAN/PMMA nanofiber/NB dispersion liquid prepared in the step (2) in a refrigerator at the temperature of 50 ℃ below zero for 6 hours, and then transferring the PAN/PMMA nanofiber/NB dispersion liquid to a freeze dryer for drying for 48 hours;
(4) and (4) placing the block dried in the step (3) into a forced air drying oven for pre-oxidation at the temperature of 280 ℃ for 1 h. And then transferring the carbon aerogel to a tubular furnace, heating to 1000 ℃ at the speed of 5 ℃/min under the protection of nitrogen, keeping for 1 h, and cooling to room temperature at the speed of 3 ℃/min to obtain the porous nanofiber boron nitride composite carbon aerogel.
Example 6
Preparing nanofiber composite carbon aerogel materials with various shapes by taking PAN and GO as raw materials:
(1) preparing a spinning solution: weighing 2 g of PAN polymer powder, adding the PAN polymer powder into DMF, and stirring in a water bath at 60 ℃ until the PAN polymer powder is dissolved to obtain a PAN spinning solution with the mass fraction of 15%;
(2) preparation of nanofiber/support dispersion: and (3) transferring the spinning solution obtained in the step (1) into an injector, connecting the injector with an automatic sample injector, and connecting a needle with a high-voltage power supply to carry out electrostatic spinning, wherein the receiving solution is 1 mg/mL GO water dispersion. Spinning conditions are as follows: the spinning voltage is 5 kV, -30 kV, the flow rate of the spinning solution is 1.5 mL/h, the distance between the needle head and the surface of the receiving liquid is 15 cm, and the fiber density is 4 mg/mL;
(3) preparing a nanofiber/support composite block: transferring the PAN nanofiber/GO dispersion liquid prepared in the step (2) into containers of different shapes (cuboid, water drop type and heart shape), placing the containers in a refrigerator at-20 ℃ for 12 hours, and transferring the containers to a freeze dryer for drying for 12 hours;
(4) and (4) placing the block dried in the step (3) into a forced air drying oven for pre-oxidation at the temperature of 280 ℃ for 180 min. And then transferring the carbon aerogel to a tubular furnace, heating to 600 ℃ at the speed of 2 ℃/min under the protection of nitrogen, keeping for 1 h, and cooling to room temperature at the speed of 3 ℃/min to obtain the nanofiber graphene oxide composite carbon aerogel with various shapes.
Example 7
With polyamic acid (PAA) and molybdenum disulfide (MoS)2) Preparing a nano-fiber composite carbon aerogel material by using the following raw materials:
(1) preparing a spinning solution: weighing 2 g of PAA, adding the PAA into DMF, and stirring in a water bath at 60 ℃ until the PAA is dissolved to obtain a PAA spinning solution with the mass fraction of 15%;
(2) preparation of nanofiber/support dispersion: transferring the spinning solution obtained in the step (1) into an injector, connecting the injector with an automatic sample injector, and connecting a needle with a high-voltage power supply to carry out electrostatic spinning, wherein the receiving solution is 1 mg/mL MoS2/50% ethanol/water dispersion. Spinning conditions are as follows: the spinning voltage is 5 kV, -30 kV, the flow rate of the spinning solution is 1.5 mL/h, the distance between the needle head and the surface of the receiving liquid is 15 cm, and the fiber density is 5 mg/mL;
(3) preparing a nanofiber-support composite block: putting the PAA nanofiber/MoS 2 dispersion liquid prepared in the step (2) in a refrigerator at-20 ℃ for 5h, and then transferring the PAA nanofiber/MoS 2 dispersion liquid to a freeze dryer for drying for 48 h;
(4) and (4) placing the block dried in the step (3) into an air drying oven for pre-oxidation at the temperature of 280 ℃ for 180min, and performing PAA thermal imidization to generate Polyimide (PI). And then transferring the carbon aerogel to a tubular furnace, heating to 600 ℃ at the speed of 2 ℃/min under the protection of nitrogen, keeping for 1 h, and cooling to room temperature at the speed of 3 ℃/min to obtain the nanofiber molybdenum disulfide oxide composite carbon aerogel.
Example 8
The nanofiber graphene oxide composite carbon aerogel prepared in example 1 is applied to adsorption treatment of tetracycline-containing wastewater:
0.01 g of nano-fiber graphene oxide composite carbon aerogel is taken, a 50 mg/L tetracycline solution is taken as a model to degrade pollutants, and the nano-fiber graphene oxide composite carbon aerogel is oscillated at 150 r.p.m under the conditions of pH =6 and 30 ℃ in a dark place to carry out static adsorption. As shown in FIG. 7, the adsorption amount of tetracycline by the material under these conditions reached 53 mg/g.
Example 9
Loading iron-manganese oxide by taking the nanofiber graphene oxide composite carbon aerogel prepared in the example 1 as a carrier to prepare an electrode material:
(1) soaking 0.01 g of nanofiber graphene oxide composite carbon aerogel in 0.1 mol/L permanganate solution for 12 hours;
(2) putting the soaked blocks into a boiling ferrous sulfate solution of 0.5 mol/L, and slowly adding a sodium hydroxide solution of 5 mol/L;
(3) after the reaction is finished, the material is washed by clear water, freeze-dried and aged to obtain the iron-manganese oxide loaded nanofiber graphene oxide composite carbon aerogel.
Example 10
Taking the nanofiber graphene oxide composite carbon aerogel prepared in the example 1 as a carrier to load gold nanoparticles, and preparing a catalytic material:
(1) soaking 0.01 g of nanofiber graphene oxide composite carbon aerogel in water;
(2) adding 0.01 g of chloroauric acid into the solution, simultaneously adding a proper amount of sodium borohydride, and uniformly stirring;
(3) and after the reaction is finished, washing the material with clear water, and freeze-drying to obtain the gold nanoparticle-loaded nanofiber graphene oxide composite carbon aerogel.
Claims (9)
1. A preparation method of electrostatic spinning nanofiber composite carbon aerogel is characterized by comprising the following steps:
(1) preparing an electrostatic spinning polymer solution;
(2) in the electrostatic spinning process, the dispersion liquid with the support body with the two-dimensional lamellar structure is used as receiving liquid, the nano fiber is directly received, and the nano fiber/support body uniformly-mixed dispersion liquid is prepared; the receiving liquid is liquid with the infiltration work larger than 0 when the nano-fibers are infiltrated, namely the contact angle between the nano-fibers and the receiving solution is smaller than 90 degrees;
(3) freezing and shaping the mixed dispersion liquid prepared in the step (2) in a container with a specific shape, and then drying in a freeze dryer to obtain a fluffy nanofiber-support body composite block;
(4) and (4) pre-oxidizing and carbonizing the block prepared in the step (3) to obtain the nanofiber composite carbon aerogel.
2. The method for preparing the nanofiber composite carbon aerogel according to claim 1, wherein the support in the step (2) is one or more of graphene, graphene oxide, black scales, boron nitride nanosheets, manganese dioxide nanosheets and molybdenum disulfide nanosheets with a two-dimensional lamellar structure on a micro-nano scale.
3. The method for preparing nanofiber composite carbon aerogel according to claim 1, wherein the electrospinning and the support compounding in the step (2) are performed simultaneously, so that the support with a two-dimensional lamellar structure can be simultaneously diffused into the fiber network during the spinning process and cooperatively assembled with the nanofibers, thereby achieving the uniform compounding of the nanofibers and the support.
4. The method for preparing nanofiber composite carbon aerogel according to claim 1, wherein the electrospun polymer solution in the step (1) comprises one or more of polyacrylonitrile, polymethyl methacrylate, polyamic acid, polycarbonate, polyurethane, polyvinyl chloride, polyvinylidene fluoride, and polyethylene.
5. The method of claim 1, wherein the nanofibers can be solid, hollow, or multi-hollow by adjusting the ratio of different polymer solutes in the electrospinning solution and subsequent preparation parameters.
6. The method for preparing the nanofiber composite carbon aerogel according to claim 1, wherein the specific steps in the steps (3) and (4) are to transfer the nanofiber/support uniform dispersion liquid into a container with a specific shape, place the container in a refrigerator for freezing for 6-12 h, and then transfer the container to a freeze dryer for drying for 12-72 h to obtain a fluffy nanofiber-support composite block; placing the composite nanofiber-support body block in an oven at the temperature of 150-300 ℃, and pre-oxidizing for 30-180 min; and then, in a carbonization furnace, heating to 500-1000 ℃ at the speed of 1-10 ℃/min under the protection of inert atmosphere, keeping for 1-5 h, and then cooling to room temperature at the speed of 1-3 ℃/min to obtain the nanofiber composite carbon aerogel.
7. The ultra-light elastic nanofiber composite carbon aerogel prepared by the preparation method of any one of claims 1-6, wherein the carbon aerogel has an internal structure of an open pore network formed by the cooperative assembly of the nanofibers and a two-dimensional support, can bear 20-80% of strain, and has good compression resilience; the addition ratio of the two-dimensional support during the preparation of the carbon aerogel is lower than 1/2 for the mass of the fiber.
8. The ultra-light elastic nanofiber composite carbon aerogel prepared by the preparation method of any one of claims 1 to 6, which can be used as an adsorption material, a catalyst carrier and an electrode material for adsorption, catalysis and electrocatalysis removal treatment of pollutants in water; can also be used as electrode materials of new energy batteries and electric double layer super capacitors.
9. The ultra-light elastic nanofiber composite carbon aerogel prepared by the preparation method of any one of claims 1 to 6, which is characterized in that the ultra-light elastic nanofiber composite carbon aerogel can be filled into a filter column when being used as an adsorption material, and pollutants in water can be removed by adopting a dynamic adsorption mode.
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| CN110079876A (en) * | 2019-04-30 | 2019-08-02 | 苏州大学 | A kind of preparation method and application of high oil-absorbing nanofiber aeroge |
| CN112624738B (en) * | 2020-12-02 | 2022-05-24 | 江苏奥尼韦尔自动化科技有限公司 | Preparation method of ceramic fiber material |
| CN113073423A (en) * | 2021-02-24 | 2021-07-06 | 东华大学 | Method for preparing micro-nanofiber three-dimensional network by expansion method |
| CN113149655B (en) * | 2021-04-01 | 2021-09-21 | 哈尔滨工业大学 | Method for preparing three-dimensional nanofiber ceramic aerogel through eddy current field assisted-electrostatic spinning |
| CN113774524A (en) * | 2021-08-19 | 2021-12-10 | 南京理工大学 | Carbon fiber gel material and preparation method and application thereof |
| CN114560709B (en) * | 2021-11-19 | 2023-05-02 | 东华大学 | Ceramic nanofiber aerogel with hinged structure and preparation method thereof |
| CN115124363B (en) * | 2022-06-29 | 2023-01-31 | 航天特种材料及工艺技术研究所 | High-temperature-resistant ultra-light ceramic fiber porous elastomer material and preparation method and application thereof |
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