CN113201858A - Preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots - Google Patents
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Abstract
The invention discloses a preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots. The preparation method comprises the following steps: firstly, dissolving a high molecular polymer carbon source in a solvent, sequentially adding a metal salt and a pore-forming agent, uniformly mixing to prepare a stable precursor solution, and then carrying out electrostatic spinning on the precursor solution to obtain a precursor nanofiber membrane; calcining the obtained precursor nanofiber membrane in an air atmosphere to obtain a pre-oxidized fiber membrane; and carbonizing the obtained pre-oxidized fiber film at high temperature in an inert atmosphere to obtain the highly-dispersed flexible superfine porous carbon nanofiber film loaded with the oxide quantum dots. The preparation method of the flexible ultrafine porous carbon nanofiber-loaded oxide quantum dot provided by the invention is simple in process, and the prepared oxide quantum dot is small in particle size and high in loading rate, is highly uniformly dispersed in the ultrafine porous carbon nanofiber, and has a wide application prospect in the fields of flexible electronics, energy and catalysis.
Description
Technical Field
The invention relates to a preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots, and belongs to the technical field of new materials and chemical engineering.
Background
Quantum Dots (QDs) are a class of quasi-zero-dimensional nanomaterials consisting of a small number of atoms and generally having a spherical or spheroidal appearance. Due to the characteristics of small size, large specific surface area, easy stress relaxation and the like, quantum dot materials attract extensive attention in the field of alkali metal ion battery electrode materials. The small size is beneficial to shortening the ion diffusion path, the large specific surface area is beneficial to increasing the contact area of the electrode/electrolyte, the storage capacity can be increased through the double electric layer capacitance and the surface redox reaction, and the stress relaxation is beneficial to relieving the stress generated by the volume change of the electrode material in the charging and discharging process.
Despite the many advantages of quantum dots, the development of quantum dots has been limited. First, quantum dots have a large surface energy and tend to self-polymerize into larger particles, losing the advantage of the size effect. Secondly, the high specific surface area of quantum dots is often accompanied by high reactivity, reducing the chemical stability of the quantum dots. These all limit the scale-up applications of quantum dots. Studies have shown that the combination of quantum dots with porous carbon materials is one of the major routes to solve the above problems. The porous carbon-loaded quantum dot not only inherits the characteristics of wide carbon material source and stable physicochemical properties, but also shows the characteristics of unique quantum size effect, semiconductor effect, edge effect, fluorescence effect and the like. The small pore diameter of the porous carbon can prevent the quantum dots from agglomerating, and the large specific surface area is favorable for providing a large number of energy storage active sites, so that the porous carbon shows great development potential in the fields of electrochemical energy storage materials, catalysis and the like. However, there are few reports on porous carbon nanofiber-supported oxide quantum dot composites, the synthesis process is complex, the yield is low, toxic raw materials and reagents are required, and the prepared composites have brittleness. Therefore, the universal and simple preparation method of the flexible porous carbon nanofiber-loaded oxide quantum dot is developed, and has important significance for the practical application of the flexible porous carbon nanofiber-loaded oxide quantum dot in the fields of flexible electronics, energy and catalysis.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in the prior art, the synthesis process of the central porous carbon nanofiber load oxide quantum dot composite material is complex, the yield is low, toxic raw materials and reagents are needed, and the prepared composite material has the problems of brittleness and the like.
In order to solve the technical problem, the invention discloses a preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots, which comprises the following steps:
step 1: preparing an electrostatic spinning precursor solution, wherein the precursor solution consists of a high-molecular polymer carbon source, a solvent, a pore-forming agent and metal salt; the purpose of adding the high molecular polymer carbon source into the precursor solution is to control the hydrolytic complexation of the metal salt in the solvent by utilizing the hydrogen bond and physical entanglement between the high molecular polymer carbon source and the metal salt colloidal particles so that the salt colloidal particles are uniformly distributed in the solution;
step 2: performing electrostatic spinning on the obtained mixed solution to obtain a precursor nanofiber membrane;
and step 3: calcining the obtained precursor nanofiber membrane in an air atmosphere to obtain a pre-oxidized fiber membrane;
and 4, step 4: and heating and carbonizing the obtained pre-oxidized fiber film in an inert atmosphere to obtain the flexible superfine porous carbon nanofiber film uniformly loaded with the oxide quantum dots.
Preferably, in the precursor solution of step 1, the weight ratio of the high molecular polymer carbon source to the solvent is 1: 3-1: 20, the weight ratio of the high molecular polymer carbon source to the pore-forming agent is 1: 0.1-1: 5.
preferably, the step 1 specifically comprises: dissolving a high molecular polymer carbon source in a solvent at 20-100 ℃, stirring for 30-480 min, then sequentially adding a metal salt and a pore-forming agent at 25-80 ℃, and stirring for 10-360 min to obtain a uniform and stable precursor solution.
Preferably, the high molecular polymer carbon source in step 1 is at least one of polyvinylpyrrolidone, polyvinyl alcohol and polyethylene oxide.
Preferably, the pore-forming agent in step 1 is at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene and polyethylene glycol.
Preferably, the solvent in step 1 is at least one of water, ethanol and glacial acetic acid.
Preferably, the metal salt in step 1 is at least one of a zirconium salt and a silicon salt; the zirconium salt is zirconium oxychloride octahydrate, zirconium acetylacetonate, zirconium chloride or zirconium acetate; the silicate is tetraethyl silicate or tetrabutyl silicate.
Preferably, the electrostatic spinning in step 2 has the following process parameters: the environment temperature is 25-55 ℃, the temperature of the receiving device is 25-55 ℃, the rotating speed of the receiving device is 20-100 r/min, the relative humidity is 20-70%, the filling speed is 0.5-90 mL/h, the voltage is 10-50 kV, and the distance between the receiving device and a spinning nozzle is 10-30 cm; the receiving device is a metal roller.
Preferably, the calcination in step 3 comprises: heating the temperature from room temperature to 150-300 ℃ at a heating rate of 2-5 ℃/min, and keeping the temperature at 150-300 ℃ for 30-180 min; the carbonization in the step 4 comprises: heating the temperature from room temperature to 600-1300 ℃ at a heating rate of 2-5 ℃/min, keeping the temperature at 600-1300 ℃ for 30-360 min, and then naturally cooling.
The invention also provides the flexible superfine porous carbon nanofiber membrane loaded with the oxide quantum dots, which is prepared by the preparation method of the flexible superfine porous carbon nanofiber loaded with the zirconia quantum dots, wherein the average diameter of the oxide quantum dots loaded by the material is 2-6 nm, and the content of the loaded oxide quantum dots is 5-50%; the porous carbon nanofiber membrane in the material has the aperture of 0.5-150 nm and the specific surface area of 300-1800 m2A thickness of 20 to 300 mu m and a softness of 10 to 70mN, and containsThe average diameter of the fiber(s) is 50 to 200 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides an in-situ preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots, which is simple and convenient in equipment and simple in steps, so that the production cost is reduced; the invention is environment-friendly and efficient, is suitable for large-scale production, and has good commercial application prospect;
2. the oxide quantum dots obtained by the method have small particle size and high load rate, and are highly dispersed uniformly in the superfine porous carbon nanofiber;
3. the porous carbon nanofiber prepared by the method has the advantages of small diameter, high porosity and flexibility, provides sufficient space and continuous conductive channels for material transmission, and has potential application prospects in the fields of flexible electronics, energy and catalysis.
Drawings
Fig. 1 is a diagram of a flexible ultrafine porous carbon nanofiber-loaded zirconia quantum dot prepared in example 1;
FIG. 2 is an SEM image of the flexible ultrafine porous carbon nanofiber-supported zirconia quantum dot prepared in example 1;
FIG. 3 is a TEM spectrum of the flexible ultrafine porous carbon nanofiber-supported zirconia quantum dots prepared in example 1;
fig. 4 is an XRD spectrum of the flexible ultrafine porous carbon nanofiber-supported zirconia quantum dot prepared in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The starting materials used in the following examples are, unless otherwise specified, commercially available products.
Example 1
A preparation method of flexible ultrafine porous carbon nanofiber-loaded zirconia quantum dots comprises the following specific steps:
(1) preparing a precursor solution consisting of a high-molecular polymer carbon source, a solvent, a pore-forming agent and metal salt: dissolving 0.9g of polyvinylpyrrolidone (avastin, PVP, molecular weight 1300000) in 5.1g of distilled water at room temperature, stirring for 240min to prepare a polyvinylpyrrolidone solution with the mass fraction of 10%, then adding 0.01 mol of zirconium acetate (avastin) into the PVP solution, stirring for 180min, finally adding 3g of polytetrafluoroethylene emulsion (purchased from Xingwang plastic raw materials Co., Ltd., solid content of 60%, particle size of 0.2 μm) into the solution, and stirring to form a uniformly mixed precursor solution.
(2) Carrying out electrostatic spinning on the obtained precursor solution, wherein under the action of an electric field, the repulsion force of the surface charges of the charged droplets exceeds the surface tension thereof, a jet flow is formed from the surface, and the jet flow is finally deposited on a receiving substrate through a series of processes of stretching, solvent volatilization, polymer solution jet flow solidification and the like to obtain a precursor nanofiber membrane, wherein during electrostatic spinning, a constant-temperature thermal field of 25 ℃ is applied in a spinning interval, and the temperature of a receiving device is controlled to be 25 ℃; the parameters of electrostatic spinning are as follows: the relative humidity is 40%, the filling speed is 1mL/h, the voltage is 22kV, the distance between the receiving device and the spinning nozzle is 20cm, the rotating speed of the receiving device is 60r/min, and the receiving device is a metal roller.
(3) And calcining the obtained precursor nanofiber membrane in an air atmosphere to prepare a pre-oxidized fiber membrane, wherein the calcining refers to gradually increasing the temperature from room temperature (25 ℃) to 250 ℃, the temperature increase rate is 5 ℃/min, and the temperature is kept for 180min at 250 ℃.
(4) And (2) carbonizing the obtained pre-oxidized fiber film at high temperature in an inert atmosphere to obtain the flexible superfine porous carbon nanofiber film loaded with the zirconia quantum dots, wherein the carbonization refers to gradually increasing the temperature from room temperature (25 ℃) to 1000 ℃, the heating rate is 2 ℃/min, keeping the temperature at 1000 ℃ for 120min, and then naturally cooling and cooling in the inert atmosphere. The prepared zirconia quantum dots are observed by a high-magnification transmission electron microscope, and are highly and uniformly dispersed in the porous carbon fibers.
The prepared flexible superfine porous carbon nanofiber membrane loaded with the zirconia quantum dots is measured and analyzed by a transmission electron microscope (JEM-2010F), and the average diameter of the loaded zirconia quantum dots is 4 nm; according to thermogravimetric analyzer (SDT Q600) test analysis, the content of the loaded zirconia quantum dots is 36%; according to the scanningThrough electron microscope (Hitachi, S-4800) test analysis, the average diameter of the fibers in the porous carbon nanofiber membrane is 84nm, and the relative standard deviation is 1-5%; the pore diameter of the fiber membrane is 65nm and the specific surface area is 1244m according to the specific surface area and pore diameter analyzer (ASAP 2460)2(ii)/g, the thickness of the fiber membrane measured by a thickness gauge (CHY-C2) was 160 μm; the softness of the fiber film was measured to be 30mN according to a fiber softness meter (RRY-1000).
The prepared flexible superfine porous carbon nanofiber membrane loaded with the zirconia quantum dots is photographed, and the photograph is shown in figure 1. as can be seen from figure 1, the membrane material prepared in example 1 is uniform and complete, can be self-supported and has certain flexibility.
SEM test of the prepared flexible superfine porous carbon nanofiber membrane loaded with the zirconia quantum dots shows that the porous carbon nanofiber has a small diameter and an average diameter of 150nm as shown in figure 2.
The result of TEM test on the prepared flexible superfine porous carbon nanofiber membrane loaded with zirconia quantum dots is shown in fig. 3, and it can be seen from the figure that a large amount of uniformly dispersed zirconia quantum dot particles are loaded in the superfine porous carbon nanofiber membrane, and the porous carbon fiber has rich pore structure.
XRD (X-ray diffraction) testing is carried out on the prepared flexible superfine porous carbon nanofiber membrane loading the zirconia quantum dots, the obtained spectrogram is shown in figure 4, and as can be seen from figure 4, the porous carbon nanofiber membrane loads the monoclinic phase zirconia quantum dots.
Example 2
A preparation method of flexible ultrafine porous carbon nanofiber-loaded silicon oxide quantum dots comprises the following specific steps:
(1) preparing a precursor solution consisting of a high-molecular polymer carbon source, a solvent, a pore-forming agent and metal salt: dissolving 0.9g of polyvinylpyrrolidone (avastin, PVP, molecular weight 1300000) in 5.1g of distilled water at room temperature, stirring for 240min to prepare a polyvinylpyrrolidone solution with the mass fraction of 10%, then adding 5g of tetraethyl silicate (avastin) and 0.05g of phosphoric acid (avastin) into the PVP solution, stirring for 180min, finally adding 3g of polytetrafluoroethylene emulsion (purchased from Xingwang plastic raw materials Co., Ltd., solid content of 60%, particle size of 0.2 μm) into the solution, and stirring to form a precursor solution which is uniformly mixed.
(2) Carrying out electrostatic spinning on the obtained precursor solution, wherein under the action of an electric field, the repulsion force of the surface charges of the charged droplets exceeds the surface tension thereof, a jet flow is formed from the surface, and the jet flow is finally deposited on a receiving substrate through a series of processes of stretching, solvent volatilization, polymer solution jet flow solidification and the like to obtain a precursor nanofiber membrane, wherein during electrostatic spinning, a constant-temperature thermal field of 25 ℃ is applied in a spinning interval, and the temperature of a receiving device is controlled to be 25 ℃; the parameters of electrostatic spinning are as follows: the relative humidity is 40%, the filling speed is 1mL/h, the voltage is 22kV, the distance between the receiving device and the spinning nozzle is 20cm, the rotating speed of the receiving device is 60r/min, and the receiving device is a metal roller.
(3) And calcining the obtained precursor nanofiber membrane in an air atmosphere to prepare a pre-oxidized fiber membrane, wherein the calcining refers to gradually increasing the temperature from room temperature (25 ℃) to 250 ℃, the temperature increasing rate is 5 ℃/min, and the temperature is kept for 180min at 250 ℃.
(4) And (2) carbonizing the obtained pre-oxidized fiber film at high temperature in an inert atmosphere to obtain the flexible superfine porous carbon nanofiber film loaded with the silicon oxide quantum dots, wherein the carbonization refers to gradually increasing the temperature from room temperature (25 ℃) to 1000 ℃, the heating rate is 2 ℃/min, keeping the temperature at 1000 ℃ for 120min, and then naturally cooling in the inert atmosphere.
The prepared flexible superfine porous carbon nanofiber-loaded silicon oxide quantum dots are measured and analyzed by a transmission electron microscope (JEM-2010F), and the average diameter of the loaded silicon oxide quantum dots is 5 nm; according to the test analysis of a thermogravimetric analyzer (SDT Q600), the content of the loaded silicon oxide quantum dots is 35 percent; according to the test analysis of a scanning electron microscope (Hitachi, S-4800), the average diameter of fibers in the porous carbon nanofiber membrane is 120nm, and the relative standard deviation is 1-5%; the fiber had a pore size of 60nm and a specific surface area of 1022m, as measured by a specific surface area and pore size Analyzer (ASAP 2460)2(ii)/g, the thickness of the fiber membrane measured by a thickness gauge (CHY-C2) was 176 μm; the softness of the fiber film was 32mN as measured by a fiber softness meter (RRY-1000).
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.
Claims (10)
1. A preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots is characterized by comprising the following steps:
step 1: preparing an electrostatic spinning precursor solution, wherein the precursor solution consists of a high-molecular polymer carbon source, a solvent, a pore-forming agent and metal salt;
step 2: performing electrostatic spinning on the obtained mixed solution to obtain a precursor nanofiber membrane;
and step 3: calcining the obtained precursor nanofiber membrane in an air atmosphere to obtain a pre-oxidized fiber membrane;
and 4, step 4: and heating and carbonizing the obtained pre-oxidized fiber film in an inert atmosphere to obtain the flexible superfine porous carbon nanofiber film uniformly loaded with the oxide quantum dots.
2. The method for preparing the flexible ultrafine porous carbon nanofiber supported oxide quantum dot according to claim 1, wherein in the precursor solution of the step 1, the weight ratio of the high molecular polymer carbon source to the solvent is 1: 3-1: 20, the weight ratio of the high molecular polymer carbon source to the pore-forming agent is 1: 0.1-1: 5.
3. the method for preparing the flexible ultrafine porous carbon nanofiber-supported oxide quantum dot according to claim 1, wherein the step 1 specifically comprises: dissolving a high molecular polymer carbon source in a solvent at 20-100 ℃, stirring for 30-480 min, then sequentially adding a metal salt and a pore-forming agent at 25-80 ℃, and stirring for 10-360 min to obtain a uniform and stable precursor solution.
4. The method for preparing the flexible ultrafine porous carbon nanofiber supported oxide quantum dot according to claim 1, wherein the high molecular polymer carbon source in step 1 is at least one of polyvinylpyrrolidone, polyvinyl alcohol and polyethylene oxide.
5. The method for preparing the flexible ultrafine porous carbon nanofiber supported oxide quantum dot as claimed in claim 1, wherein the pore-forming agent in step 1 is at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene and polyethylene glycol.
6. The method for preparing the flexible ultrafine porous carbon nanofiber supported oxide quantum dot according to claim 1, wherein the solvent in the step 1 is at least one of water, ethanol and glacial acetic acid.
7. The method for preparing the flexible ultrafine porous carbon nanofiber supported oxide quantum dot according to claim 1, wherein the metal salt in the step 1 is at least one of zirconium salt and silicon salt; the zirconium salt is zirconium oxychloride octahydrate, zirconium acetylacetonate, zirconium chloride or zirconium acetate; the silicate is tetraethyl silicate or tetrabutyl silicate.
8. The method for preparing the flexible ultrafine porous carbon nanofiber supported oxide quantum dot according to claim 1, wherein the electrostatic spinning in the step 2 has the following process parameters: the environment temperature is 25-55 ℃, the temperature of the receiving device is 25-55 ℃, the rotating speed of the receiving device is 20-100 r/min, the relative humidity is 20-70%, the filling speed is 0.5-90 mL/h, the voltage is 10-50 kV, and the distance between the receiving device and a spinning nozzle is 10-30 cm; the receiving device is a metal roller.
9. The method for preparing the flexible ultrafine porous carbon nanofiber-supported zirconia quantum dot as claimed in claim 1, wherein the calcination in the step 3 comprises: heating the temperature from room temperature to 150-300 ℃ at a heating rate of 2-5 ℃/min, and keeping the temperature at 150-300 ℃ for 30-180 min; the carbonization in the step 4 comprises: heating the temperature from room temperature to 600-1300 ℃ at a heating rate of 2-5 ℃/min, keeping the temperature at 600-1300 ℃ for 30-360 min, and then naturally cooling.
10. The flexible ultrafine porous carbon nanofiber membrane loaded with the oxide quantum dots, prepared by the preparation method of the flexible ultrafine porous carbon nanofiber loaded with the zirconia quantum dots according to any one of claims 1 to 9, is characterized in that the average diameter of the oxide quantum dots loaded with the material is 2 to 6nm, and the content of the loaded oxide quantum dots is 5 to 50%; the porous carbon nanofiber membrane in the material has the aperture of 0.5-150 nm and the specific surface area of 300-1800 m2Per g, the thickness is 20 to 300 mu m, the softness is 10 to 70mN, and the average diameter of the contained fiber is 50 to 200 nm.
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|---|---|---|---|---|
| CN114318664A (en) * | 2021-12-23 | 2022-04-12 | 南通大学 | Flexible carbon nanofiber membrane with oriented structure and preparation method thereof |
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| CN114318664B (en) * | 2021-12-23 | 2023-11-14 | 南通大学 | Flexible carbon nanofiber membrane with orientation structure and preparation method thereof |
| CN114351357A (en) * | 2022-01-12 | 2022-04-15 | 大连民族大学 | Flexible bactericidal nanofiber membrane and preparation method and application thereof |
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