阅读说明：本技术 一种碳纤维基纳米复合材料的制备方法及其应用 (Preparation method and application of carbon fiber-based nano composite material ) 是由 周俊宏 邓洪祥 于 2021-07-29 设计创作，主要内容包括：本发明公开了一种碳纤维基纳米复合材料的制备方法及其应用,具体涉及纳米材料领域,该设计经过一系列的加工步骤：基底、备用溶液一、前驱体材料、备用溶液二、样品材料的获取,最后经过退火处理,制备得到碳纤维基纳米复合材料。本发明中制备的碳纤维基纳米复合材料采用碳纤维作为基底,通过特定的工艺技术将催化剂均匀地分散于碳纤维材料中,形成含有特有纳米三维结构材料的复合体系,孔隙率和比表面积高,具备优异的性能,同时,使用了水热法来合成氧化镍和钛酸锶纳米材料,使其具有低温合成的可能性,对工艺的要求简单易操作。(The invention discloses a preparation method and application of a carbon fiber-based nano composite material, and particularly relates to the field of nano materials, wherein the design is carried out through a series of processing steps: and finally, annealing treatment is carried out to prepare the carbon fiber-based nanocomposite material. The carbon fiber-based nano composite material prepared by the invention adopts carbon fibers as a substrate, and the catalyst is uniformly dispersed in the carbon fiber material through a specific process technology to form a composite system containing a specific nano three-dimensional structure material, so that the porosity and the specific surface area are high, the excellent performance is achieved, meanwhile, a hydrothermal method is used for synthesizing the nickel oxide and strontium titanate nano material, the possibility of low-temperature synthesis is achieved, and the process requirement is simple and easy to operate.)

1. The preparation method of the carbon fiber-based nano composite material is characterized by comprising the following steps of:

s1, preparing a standby substrate: taking a proper amount of carbon fiber raw materials without impurities as a carbon fiber substrate, and carrying out ultrasonic cleaning treatment on the carbon fibers to obtain a standby substrate;

s2, obtaining a first standby solution: dissolving metatitanic acid with a certain mass in deionized water, immediately introducing protective gas for 20min, adding strontium hydroxide with a certain mass into the metatitanic acid solution, and magnetically stirring for 1h to obtain a standby solution I;

s3, preparation of a precursor material: taking a proper amount of a standby substrate and a standby solution I, placing the standby substrate and the standby solution I in a reaction container, and carrying out hydrothermal reaction to obtain a precursor material;

s4, obtaining a second standby solution: dissolving nickel chloride with certain mass in deionized water, performing magnetic stirring, alternately performing stirring operation clockwise and anticlockwise, and slowly adding sodium hydroxide solution with certain molar mass in the stirring process to obtain a standby solution II;

s5, preparation of a sample material: adding the prepared precursor material into the standby solution II, placing the precursor material into a reaction container, and carrying out hydrothermal reaction for a period of time to obtain a sample material;

s6, placing the sample material before annealing in a tubular furnace for annealing treatment to prepare the carbon fiber-based nano composite material.

2. The method for preparing a carbon fiber-based nanocomposite as claimed in claim 1, wherein in the step S1, the cleaning method is as follows:

placing a carbon fiber raw material in a sodium hydroxide solution with a certain molar mass, soaking for two hours, washing with deionized water and absolute ethyl alcohol to be neutral, placing the carbon fiber raw material in an air-blast drying oven at 70 ℃ and keeping the drying time for 12 hours; and (2) placing the dried carbon fiber raw material in a nitric acid solution with a certain molar mass for soaking for two hours, then washing the carbon fiber raw material to be neutral by using deionized water and absolute ethyl alcohol, placing the carbon fiber raw material in an air-blast drying oven at 70 ℃ and keeping the drying time for 12 hours, thereby obtaining the standby substrate.

3. The method for preparing a carbon fiber-based nanocomposite material as claimed in claim 1, wherein: the ultrasonic cleaning in step S1 is to place the carbon fiber raw material in a beaker, add deionized water and absolute ethanol, and clean in an ultrasonic cleaning machine.

4. The method for preparing a carbon fiber-based nanocomposite material as claimed in claim 1, wherein: wherein the shielding gas in step S2 is specifically argon.

5. The method for preparing a carbon fiber-based nanocomposite material as claimed in claim 1, wherein: in the steps S2 and S4, magnetic stirring is performed on a constant temperature heating magnetic stirring platform.

6. The method for preparing a carbon fiber-based nanocomposite material as claimed in claim 1, wherein: in the steps S3 and S5, the reaction vessel is a polytetrafluoroethylene-lined high-pressure reaction kettle, wherein the hydrothermal reaction is carried out in a way that the reaction vessel is placed in an electric heating blowing dry box for keeping the temperature of 200 ℃ for 12 hours.

7. The method for preparing a carbon fiber-based nanocomposite material as claimed in claim 1, wherein: in the step S6, the temperature of the vacuum drying is 500 ℃, and the time of the vacuum drying is 2 hours.

8. The application of the carbon fiber-based nano composite material is characterized in that: the carbon fiber-based nanocomposite prepared by the preparation method of any one of the 1-7 is applied to treatment of industrial wastewater.

9. Use according to claim 8, characterized in that: and putting the carbon fiber nano composite material and industrial wastewater into a reaction device according to a set proportion, and carrying out catalytic degradation on the industrial wastewater.

Technical Field

The invention relates to the field of nano materials, in particular to a preparation method and application of a carbon fiber-based nano composite material.

Background

Nanotechnology, also known as nanotechnology, is a technique for investigating the properties and applications of materials with structure sizes in the range of 1-100 nm. Nanoscience technology is a scientific technology based on many modern advanced scientific technologies, which is a product of the combination of dynamic science (dynamic mechanics) and modern science (chaotic physics, intelligent quantum, quantum mechanics, mesoscopic physics, molecular biology) with modern technology (computer technology, microelectronics and scanning tunneling microscopy, nuclear analysis technology), and which in turn will lead to a series of new scientific technologies, such as: nano-physics, nano-biology, nano-chemistry, nano-electronics, nano-fabrication techniques, nano-metrology, and the like.

The nano material is a material which has at least one dimension in a three-dimensional space in a nano size (1-100nm) or is formed by taking the nano size and the nano material as a basic unit, and the nano material is about equivalent to the dimension of closely arranging 10-1000 atoms.

The preparation method of the nano nickel oxide mainly comprises the following steps: solid phase reaction method, sol-gel method, liquid phase method, micro-emulsion method, hydrothermal method. The nano nickel oxide can be used as a photocatalyst for degrading organic pollutants in industrial wastewater. But the single nano nickel oxide catalyst has low degradation rate on organic pollutants in industrial wastewater.

The existing preparation methods of strontium titanate are many, and mainly comprise the following steps: sol-gel methods, chemical precipitation methods, high temperature solid phase methods, microwave synthesis methods, plasma methods, and hydrothermal methods. Strontium titanate materials prepared by different methods will have different shapes, sizes and spatial structures. The hydrothermal method has the advantages that the particle size of the prepared strontium titanate powder particles can reach the nanometer level, the reaction temperature is low, and the requirement on the preparation process is not very high. Strontium titanate has piezoelectric effect under ultrasonic vibration, and can greatly improve the degradation rate of the catalyst on organic pollutants in industrial wastewater when the strontium titanate is cooperated with a semiconductor catalyst.

The carbon fiber has the characteristics of common carbon materials, such as high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like, but is different from the common carbon materials in that the carbon fiber has obvious anisotropy and softness in appearance, can be processed into various fabrics, shows high strength along the fiber axis direction, and is favorable for solving the problem of secondary pollution caused when industrial wastewater is treated by using the carbon fiber as a carrier of a nano composite material.

Disclosure of Invention

In order to overcome the above defects in the prior art, embodiments of the present invention provide a method for preparing a carbon fiber-based nanocomposite material and an application thereof, so as to solve the problems in the background art.

In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the carbon fiber-based nano composite material is characterized by comprising the following steps of:

s1, preparing a standby substrate: taking a proper amount of carbon fiber raw materials without impurities, and carrying out ultrasonic cleaning treatment on the carbon fibers to obtain a standby substrate;

s2, obtaining a first standby solution: dissolving metatitanic acid with a certain mass in deionized water, immediately introducing protective gas for 20min, adding strontium hydroxide with a certain mass into the metatitanic acid solution, and magnetically stirring for 1h to obtain a standby solution I;

s3, preparation of a precursor material: taking a proper amount of a standby substrate and a standby solution I, placing the standby substrate and the standby solution I in a reaction container, and carrying out hydrothermal reaction to obtain a precursor material;

s4, obtaining a second standby solution: dissolving nickel chloride with certain mass in deionized water, performing magnetic stirring, alternately performing stirring operation clockwise and anticlockwise, and slowly adding sodium hydroxide solution with certain molar mass in the stirring process to obtain a standby solution II;

s5, preparation of a sample material: adding the prepared precursor material into the standby solution II, placing the precursor material into a reaction container, and carrying out hydrothermal reaction for a period of time to obtain a sample material;

s6, placing the sample material before annealing in a tubular furnace for annealing treatment to prepare the carbon fiber-based nano composite material.

In a preferred embodiment, in step S1, the cleaning method is as follows:

placing a carbon fiber raw material in a sodium hydroxide solution with a certain molar mass, soaking for two hours, washing with deionized water and absolute ethyl alcohol to be neutral, placing the carbon fiber raw material in an air-blast drying oven at 70 ℃ and keeping the drying time for 12 hours; and (2) placing the dried carbon fiber raw material in a nitric acid solution with a certain molar mass for soaking for two hours, then washing the carbon fiber raw material to be neutral by using deionized water and absolute ethyl alcohol, placing the carbon fiber raw material in an air-blast drying oven at 70 ℃ and keeping the drying time for 12 hours, thereby obtaining the standby substrate.

In a preferred embodiment, the ultrasonic cleaning in step S1 is to place the carbon fiber raw material in a beaker, add deionized water and absolute ethanol, and clean in an ultrasonic cleaning machine.

In a preferred embodiment, the protective gas in step S2 is specifically argon.

In a preferred embodiment, in the steps S2 and S4, the magnetic stirring is performed on a constant temperature heating magnetic stirring platform.

In a preferred embodiment, in the steps S3 and S5, the reaction vessel is a polytetrafluoroethylene-lined high-pressure reaction kettle, and the hydrothermal reaction is carried out by placing the reaction vessel in an electric hot-blast air drying oven at 200 ℃ for 12 h.

In a preferred embodiment, in the step S6, the temperature of the vacuum drying is 500 ℃, and the time of the vacuum drying is 2 hours.

In a preferred embodiment, the application of the carbon fiber-based nanocomposite comprises the carbon fiber-based nanocomposite prepared by the preparation method of any one of the above 1-7, and the carbon fiber-based nanocomposite is applied to the treatment of industrial wastewater.

In a preferred embodiment, the carbon fiber nano composite material and industrial wastewater are put into a reaction device according to a set proportion, and the industrial wastewater is subjected to catalytic degradation.

The invention has the technical effects and advantages that:

the carbon fiber-based nano composite material prepared by the invention adopts carbon fibers as a substrate, and the catalyst is uniformly dispersed in the carbon fiber material through a specific process technology to form a composite system containing a specific nano three-dimensional structure material, so that the porosity and the specific surface area are high, the excellent performance is achieved, meanwhile, a hydrothermal method is used for synthesizing the nickel oxide and strontium titanate nano material, the possibility of low-temperature synthesis is achieved, and the process requirement is simple and easy to operate.

Drawings

Fig. 1 schematically shows a flow chart of the preparation of the carbon fiber-based composite nano material.

Fig. 2 schematically shows a carbon fiber nanocomposite.

FIG. 3 schematically shows a Scanning Electron Microscope (SEM) image of a standby substrate at low magnification.

Fig. 4 schematically shows a high-power Scanning Electron Microscope (SEM) image of the standby substrate.

Figure 5 schematically shows a low power Scanning Electron Microscope (SEM) image of the composite material.

Figure 6 schematically shows a high power Scanning Electron Microscope (SEM) image of the composite material.

Fig. 7 is a schematic diagram showing the effect of processing methyl blue by the carbon fiber-based composite nano material.

Fig. 8 is a graph schematically showing experimental data of the degradation rate of the carbon fiber-based nanocomposite applied to methyl blue.

Wherein, 1, a carbon fiber substrate; 2. an ultrasonic cleaning machine; 3. a beaker; 4. an air-blast drying oven; 5. preparing a first solution; 6. a polytetrafluoroethylene lining high-pressure reaction kettle; 7. a precursor material; 8. a second solution is prepared; 9. a tube furnace; 10. sample material before annealing; 11. carbon fiber-based nanocomposites.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example one

The carbon fiber is used as a substrate of the nano composite material, and the modifier is uniformly dispersed in the carbon fiber substrate material to form a composite system containing a specific nano three-dimensional structure material, so that the nano composite material has more excellent performance.

Example two

Referring to fig. 1 and 2, a simple and environmentally friendly method for preparing carbon fiber-based nanocomposites suitable for catalytic degradation of wastewater is proposed according to an inventive improvement of the present invention.

Specifically, the preparation method of the carbon fiber-based nano composite material comprises the following steps: and carrying out ultrasonic cleaning treatment on the carbon fibers to obtain a standby substrate.

And then dissolving a certain mass of metatitanic acid in deionized water, introducing protective gas for 20min, adding a certain mass of strontium hydroxide into the metatitanic acid solution, and magnetically stirring for 1h to obtain a first standby solution.

And then, placing the standby substrate and the standby solution I in a reaction container, and carrying out hydrothermal reaction to obtain a precursor material.

And then, dissolving nickel chloride with certain mass in deionized water, carrying out magnetic stirring, and slowly adding sodium hydroxide solution with certain molar mass in the stirring process to obtain a standby solution II.

And then, adding the prepared precursor material into the second standby solution, placing the mixture into a reaction container, and carrying out hydrothermal reaction to obtain a sample material.

And finally, annealing the sample material to prepare the carbon fiber-based nano composite material.

In the design of the invention, a hydrothermal method is used for synthesizing the nickel oxide and strontium titanate nano composite material, so that the nickel oxide and strontium titanate nano composite material has the possibility of low-temperature synthesis, and the requirements on the process are simple and easy to operate.

The carbon fiber has the characteristics of high porosity and specific surface area, can provide rich landing sites for the nano composite material, and is beneficial to the growth of the nano composite material.

EXAMPLE III

In this embodiment, in order to obtain a brand-new crystal structure with the optimal shape and size for degradation and catalysis, research and design are performed on the preparation method of the carbon fiber-based nanocomposite material, and experimental limitations are performed on each step mode.

Firstly, soaking carbon fibers in a sodium hydroxide solution with a certain molar mass for two hours, then washing the carbon fibers to be neutral in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and drying the carbon fibers in a drying oven at 70 ℃ for 12 hours; soaking the dried carbon fibers in a nitric acid solution with a certain molar mass for two hours, cleaning the carbon fibers to be neutral in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and drying the carbon fibers in a drying oven at 70 ℃ for 12 hours to obtain the standby substrate.

Referring to fig. 2 and 3, fig. 2 is a low power scanning electron microscope image of a spare substrate, and fig. 3 is a high power scanning electron microscope image of a spare substrate, it can be obtained from fig. 2 and 3 that carbon fibers are porous carbon materials. The surface of the nano-material is beneficial to the attachment of the nano-material.

Dissolving metatitanic acid with a certain mass in deionized water, introducing protective gas for 20min, adding strontium hydroxide with a certain mass into the metatitanic acid solution, and magnetically stirring for 1h to obtain a first standby solution.

Wherein the protective gas is argon, and the aeration rate of the argon is kept at 50 sccm.

And then, placing the standby substrate and the standby solution I in a reaction container, and carrying out hydrothermal reaction to obtain a precursor material.

And then, dissolving nickel chloride with certain mass in deionized water, carrying out magnetic stirring, and slowly adding sodium hydroxide solution with certain molar mass in the stirring process to obtain a standby solution II.

And then, adding the prepared precursor material into the second standby solution, placing the mixture into a reaction container, and carrying out hydrothermal reaction to obtain a sample material.

Wherein, the reaction vessel is a polytetrafluoroethylene lining high-pressure reaction kettle, the reaction kettle is kept at the constant temperature of 200 ℃ for 12 hours in an electric heating blowing dry box, and is cooled to the room temperature.

And finally, annealing the sample material, and putting the sample material into a tubular furnace to anneal for 2 hours at 500 ℃ to prepare the carbon fiber-based nano composite material.

Example four

In this example, the carbon fiber-based nanocomposite prepared according to the method of the above example was applied to the treatment of industrial wastewater, and a sample of the industrial wastewater was obtained from a municipal wastewater treatment plant.

Specifically, the carbon fiber-based nano composite material and the industrial wastewater are placed into a beaker according to a set proportion of 15mg/mL, and then the beaker is placed into an ultrasonic cleaning machine to perform catalytic degradation on the industrial wastewater.

Referring to fig. 8, the carbon fiber-based nanocomposite prepared by the method was taken as a 3mg/mL material with methyl blue of 40mg/L as a treatment object, and the degradation rate thereof was measured using UV.

The result shows that the degradation rate reaches 94.6 percent within 30 min.

In the description above, references to "one embodiment," "an embodiment," "one example," "an example," etc., indicate that the embodiment or example so described may include a particular feature, structure, characteristic, property, element, or limitation, but every embodiment or example does not necessarily include the particular feature, structure, characteristic, property, element, or limitation. Moreover, repeated use of the phrase "in accordance with an embodiment of the present application" although it may possibly refer to the same embodiment, does not necessarily refer to the same embodiment.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.