Carbon fiber cloth-moo3-FeOOH composite material and preparation method thereof

Abstract

The present application relates to a kind of carbon fiber cloth MoO3 FeOOH composite material and its preparation method, comprising: a. carbon fiber cloth is arranged in dielectric barrier discharge equipment under processing a certain time for standby;B. one molybdenum acetylacetone is added to ethylene glycol, stirring, nitric acid is added to adjust the pH of solution, continue to stir, solution is reacted at constant temperature, cool to room temperature, separate, the obtained powder is washed, the obtained powder is dried, obtain white MoO3 Powder;C. the carbon fiber cloth after dielectric barrier discharge processing is fixed in hot evaporation film machine cabin, white MoO3 Powder is placed in hot evaporation film machine, MoO3 Nanoparticle is plated on the surface of carbon fiber cloth, obtain carbon fiber cloth MoO3 Material;D. iron sulfate and hexamethylenetetramine are sequentially dissolved in the mixed solution of ethylene glycol and water, stirring, form solution A;Then solution A and carbon fiber cloth MoO3 are mixed, react, obtain carbon cloth MoO3 FeOOH composite material.Product size is uniform, size is adjustable, dispersion is good, can be applied to photocatalysis, gas sensitive, adsorption and other fields.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of photocatalytic nanomaterials, its preparation process and application, and relates to a preparation method of a carbon fiber cloth@MoO3@FeOOH composite material. BACKGROUND

[0002] The activated carbon fiber has a large specific surface area and pore volume, a small pore size and a uniform pore size. The activated carbon fiber has a good adsorption capacity for water-soluble organic matters containing oxygen, chlorine and aromatic rings. The activated carbon fiber can not only enrich the pollutants on the surface of the catalyst to improve the quantum yield of the photocatalyst, but also effectively adsorb by-products in the photocatalytic reaction process, so that the pollutants are continuously degraded until completely mineralized into small molecular inorganic matters. The rate of the adsorption-migration-photodegradation reaction process is much higher than that of the process in which the single catalyst directly adsorbs the organic matters from the solution and degrades the organic matters, thereby improving the photocatalytic reaction efficiency of the single catalyst. The preparation method of the composite photocatalyst with the carbon fiber material as the base and the application of the composite photocatalyst in the photocatalytic degradation of organic pollutants have become the main research direction.

[0003] China has rich molybdenum resources, and main compounds thereof include molybdenum trioxide and sodium molybdate. The molybdenum trioxide is a transition metal oxide that attracts much attention, and has three structure types: hexagonal phase (h-MoO3), monoclinic phase (β-MoO3) and orthorhombic phase (α-MoO3). The h-MoO3 has good photoelectricity and is an n-type semiconductor material, and has a band gap of 2.8-3.2 eV and excellent performance in the photodegradation of pollutants, and has a good prospect in the photocatalytic technology.

[0004] According to the crystal type, the hydroxyl iron oxide mainly includes four polymorphs: α-FeOOH, β-FeOOH, γ-FeOOH and δ-FeOOH. Among them, the α-FeOOH has an orthorhombic or rhombic structure, and each unit cell contains 4 FeOOH, has a length of 10-30 nm and a width of about 4 nm, and is yellow in the powder state. The β-FeOOH has a tetragonal structure, and each unit cell contains 8 FeOOH, and exists less in nature. The β-FeOOH is not a pure phase due to containing chlorine ions (Cl, 6.2%, by weight), and is usually obtained by hydrolysis of a Fe salt solution containing Cl or fluorine ions (F), and has a color of brown to bright yellow.

[0005] Under light, the ·HO produced in the photocatalytic reaction of FeOOH in aqueous solution has extremely strong oxidizing property and can oxidize organic matters in water bodies without selectivity. Under visible light irradiation, the valence band electrons of FeOOH undergo interband transition to produce photo-generated electrons (e) and holes (h). O2 adsorbed on the surface of the photocatalyst captures the electrons to form superoxide anion (·O), and then the holes oxidize hydroxyl ions (OH) and water (H2O) adsorbed on the surface of the photocatalyst into hydroxyl radicals (·HO). ·HO has very strong oxidizing ability and can oxidize most organic matters, finally converting them into CO2, H2O and inorganic salts, etc., to promote the harmless treatment of most organic pollutants. However, the photocatalytic efficiency of the above-mentioned material needs to be further improved. SUMMARY

[0006] The primary technical problem to be solved by the present application is to provide a preparation method of carbon fiber cloth@MoO3@FeOOH composite material, which has the advantages of cheap and easy-to-obtain raw materials, simple synthesis process, low cost, short reaction period, firm combination, and long-lasting and efficient catalytic effect.

[0007] A preparation method of carbon fiber cloth@MoO3@FeOOH composite material, comprising the following steps:

[0008] a. The carbon fiber cloth is sequentially placed in acetone, ethanol and deionized water for ultrasonic soaking for a certain time, and then the bamboo charcoal fiber cloth is placed in a constant temperature drying oven for drying at a certain temperature, and then the carbon fiber cloth is placed in a dielectric barrier discharge device for treatment for a certain time for standby;

[0009] b. A certain amount of molybdenum acetylacetonate is added to ethylene glycol, magnetically stirred, nitric acid is added to adjust the pH of the solution, stirring is continued, the solution is moved to a hydrothermal reaction kettle, reacts at a constant temperature for a certain time, naturally cools to room temperature, centrifuged, the precipitate is washed with water and ethanol for several times, and the obtained powder is placed in a drying oven for drying at a constant temperature for a certain time to obtain white MoO3 powder;

[0010] c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of a thermal evaporation film machine, white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuum is drawn, the evaporation rate is controlled by setting current, a layer of MoO3 nanoparticles with a certain thickness is plated on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material;

[0011] d. A certain amount of iron sulfate and hexamethylenetetramine are sequentially dissolved in a mixed solution of ethylene glycol and water (in a certain proportion), stirred for a certain time to form solution A; then solution A and carbon cloth@MoO3 are moved to a reaction kettle, reacted at a constant temperature for a certain time, naturally cooled to room temperature, centrifuged, dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0012] Further, the soaking ultrasonic time of step a is 5-60 minutes, the drying temperature is 30-80℃, and the treatment time of dielectric barrier discharge is 10-60 minutes.

[0013] Further, the amount of acetylacetone molybdenum of step b is 0.0328-3.28g, the amount of ethylene glycol is 1-150ml, the pH is 0.5-5, the reaction temperature is 100-200℃, and the reaction time is 6-15h.

[0014] Further, the vacuum degree of thermal evaporation of step c is 10 -2 -10 -5 Pa, the rate is

[0015] Further, the amount of iron sulfate of step d is 0.04-4.0g, the amount of hexamethyl tetramine is 0.02-2.0g, the amount of ethylene glycol is 10-120ml, and the amount of water is 0.5-5ml.

[0016] The reaction temperature of step d is stage heating: the first stage is heated to 100-120℃, the reaction time is 1-2 hours, the second stage is heated to 140-160℃, the reaction time is 2-3 hours, and the third stage is heated to 180-200℃, the reaction time is 6-18 hours.

[0017] The temperature treatment of steps b and d is closed treatment in a hydrothermal reaction kettle.

[0018] A carbon fiber cloth@MoO3@FeOOH composite material prepared by the above preparation method, characterized in that: the MoO3@FeOOH thickness of the surface of the carbon fiber cloth@MoO3@FeOOH composite material is 150nm-500nm; wherein the average thickness of MoO3 is 20-50nm, and the thickness of FeOOH is 100-480nm; the FeOOH is a porous nanosheet structure.

[0019] The carbon fiber cloth@MoO3@FeOOH composite material prepared by the method has the advantages that the preparation method is simple and controllable. The combination degree of the nanomaterial and the carrier (carbon fiber cloth) can be significantly improved by the medium barrier discharge and the heat evaporation technology, so that the stability of the material is improved, the catalytic effect is persistent, and the catalytic efficiency is improved. In addition, the surface FeOOH is assembled into a porous nanosheet, which can effectively increase the contact area and further improve the adsorption and catalytic effect. The stepwise heating can make the FeOOH particles slowly generate on the MoO3 surface at the beginning, so as to improve the combination degree, and the high temperature in the later stage can effectively accelerate the generation of the nanosheet. The prepared carbon fiber cloth@MoO3@FeOOH composite material is uniform in size, adjustable in size, and well dispersed, and can be applied to the fields of photocatalysis, gas sensitivity, adsorption and the like. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The scanning electron microscope photos of the carbon fiber cloth@MoO3@FeOOH composite material prepared in the application. DETAILED DESCRIPTION

[0021] The method described in the application is further described by specific examples, but it does not mean that the application is limited to these examples.

[0022] Example 1:

[0023] A preparation method of a carbon fiber cloth@MoO3@FeOOH composite material, which comprises the following steps: a. sequentially immersing carbon fiber cloth in acetone, ethanol and deionized water for ultrasonic treatment for 15 min, then drying the carbon fiber cloth in a constant temperature drying box at 60 DEG C, and then treating the carbon fiber cloth in a medium barrier discharge device for 30 min for standby; b. adding 0.652 g of molybdenum acetylacetate to 120 ml of ethylene glycol, magnetically stirring, adding nitric acid to adjust the PH of the solution to 3, continuously stirring, moving the solution to a hydrothermal reaction kettle, reacting at 180 DEG C for 8 hours, naturally cooling to room temperature, centrifuging, and drying to obtain white MoO3 powder; c. fixing the carbon fiber cloth treated by the medium barrier discharge in a heat evaporation film machine cabin, placing the white MoO3 powder in an evaporation boat of the heat evaporation film machine, vacuumizing to 10 -4 Pa, setting the current control evaporation rate to carbon fiber cloth is placed in a constant temperature drying oven at 60°C for drying, and then the carbon fiber cloth is placed under a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652 g of molybdenum acetylacetonate is added to 120 ml of ethylene glycol, and the solution is magnetically stirred, and nitric acid is added to adjust the pH of the solution to 3, and the stirring is continued, and the solution is moved to a hydrothermal reaction kettle, and the solution is reacted at 180°C for 8 hours, and the solution is naturally cooled to room temperature, and centrifuged, and dried, and white MoO3 powder is obtained; c. The carbon fiber cloth treated by the dielectric barrier discharge is fixed in a thermal evaporation film machine cabin, and the white MoO3 powder is placed in an evaporation boat of the thermal evaporation film machine, and vacuum is drawn to 10 Figure 1 As shown in FIG. 2, the carbon cloth @ MoO3@ FeOOH composite material with a continuous porous nanosheet assembled surface is obtained in the present application. The thickness of MoO3@ FeOOH on the surface is 330 nm; the average thickness of MoO3 is 30 nm, and the average thickness of FeOOH is 280 nm; and the FeOOH is a porous nanosheet structure.

[0024] Example 2

[0025] The difference between this example and example 1 is that the soaking ultrasonic time in step a is changed to 5, 30, 50, and 60 minutes, and the other steps are the same as those in example 1, and the specific steps are as follows: a. The carbon fiber cloth is sequentially soaked in acetone, ethanol, and deionized water for 5, 30, 50, and 60 minutes under ultrasonic, and then the carbon fiber cloth is placed in a constant temperature drying oven at 60°C for drying, and then the carbon fiber cloth is placed under a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652 g of molybdenum acetylacetonate is added to 120 ml of ethylene glycol, and the solution is magnetically stirred, and nitric acid is added to adjust the pH of the solution to 3, and the stirring is continued, and the solution is moved to a hydrothermal reaction kettle, and the solution is reacted at 180°C for 8 hours, and the solution is naturally cooled to room temperature, and centrifuged, and dried, and white MoO3 powder is obtained; c. The carbon fiber cloth treated by the dielectric barrier discharge is fixed in a thermal evaporation film machine cabin, and the white MoO3 powder is placed in an evaporation boat of the thermal evaporation film machine, and vacuum is drawn to 10 -4 Pa, and the current control evaporation rate is set to carbon fiber cloth is placed in a constant temperature drying oven at 60°C for drying, and then the carbon fiber cloth is placed under a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652 g of molybdenum acetylacetonate is added to 120 ml of ethylene glycol, and the solution is magnetically stirred, and nitric acid is added to adjust the pH of the solution to 3, and the stirring is continued, and the solution is moved to a hydrothermal reaction kettle, and the solution is reacted at 180°C for 8 hours, and the solution is naturally cooled to room temperature, and centrifuged, and dried, and white MoO3 powder is obtained; c. The carbon fiber cloth treated by the dielectric barrier discharge is fixed in a thermal evaporation film machine cabin, and the white MoO3 powder is placed in an evaporation boat of the thermal evaporation film machine, and vacuum is drawn to 10

[0026] Example 3:

[0027] The difference between this embodiment and embodiment 1 is that the drying temperature in step a is changed to 30, 80℃, and the others are the same as embodiment 1, which are as follows: a. The carbon fiber cloth is sequentially immersed in acetone, ethanol, and deionized water for 15 min, and then dried in a constant temperature drying oven at 30, 80℃, and then placed in a dielectric barrier discharge device for 30 min for standby; b. 0.652 g of molybdenum acetylacetone is added to 120 ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the PH of the solution to 3, continuously stirred, and then the solution is moved to a hydrothermal reaction kettle, reacted at 180℃ for 8 hours, naturally cooled to room temperature, centrifuged, and dried to obtain white MoO3 powder; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of a thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuumized to 10 -4 Pa, and the evaporation rate is controlled by setting the current to A layer of MoO3 nanoparticles is plated on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2 g of ferric sulfate and 0.2 g of hexamethylenetetramine are sequentially dissolved in a mixed solution of 100 ml of ethylene glycol and 20 ml of water, continuously stirred to form solution A; then solution A and carbon cloth@MoO3 are moved to a reaction kettle for staged heating: the first stage is to heat to 110℃ for 2 hours, the second stage is to heat to 150℃ for 2 hours, and the third stage is to heat to 180℃ for 12 hours, and then naturally cooled to room temperature, centrifuged, and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0028] Embodiment 4:

[0029] The difference between this embodiment and embodiment 1 is that the dielectric barrier discharge time in step a is changed to 10, 60 minutes, and the others are the same as embodiment 1, which are as follows: a. The carbon fiber cloth is sequentially immersed in acetone, ethanol, and deionized water for 15 min, and then dried in a constant temperature drying oven at 60℃, and then placed in a dielectric barrier discharge device for 10, 60 minutes for standby; b. 0.652 g of molybdenum acetylacetone is added to 120 ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the PH of the solution to 3, continuously stirred, and then the solution is moved to a hydrothermal reaction kettle, reacted at 180℃ for 8 hours, naturally cooled to room temperature, centrifuged, and dried to obtain white MoO3 powder; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of a thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuumized to 10 -4 Pa, and the evaporation rate is controlled by setting the current to carbon fiber cloth is placed in a medium resistance discharge equipment for treatment for 30 minutes for standby; b. A corresponding amount of molybdenum acetylacetone is added into 120 ml of ethylene glycol, and is magnetically stirred. Nitric acid is added to adjust the PH of the solution to 3. The solution is continuously stirred and is moved to a hydrothermal reaction kettle. The solution is reacted at 180℃ for 8 hours. The solution is naturally cooled to room temperature, is centrifuged, and is dried to obtain white MoO3 powder; c. The carbon fiber cloth treated by the medium resistance discharge is fixed in a hot vapor deposition film machine cabin. The white MoO3 powder is placed in an evaporation boat of the hot vapor deposition film machine. The hot vapor deposition film machine is vacuumized to 10 Pa. The evaporation rate is controlled by an electric current. The carbon fiber cloth is treated by hot vapor deposition for 30 minutes to obtain a carbon fiber cloth@MoO3 material.

[0030] Example 5

[0031] The difference between this example and example 1 is that the amount of molybdenum acetylacetone in step b is changed to 0.0328g, 0.978g, 2.18g, 3.28g, and the other steps are the same as those in example 1. The specific steps are as follows: a. The carbon fiber cloth is sequentially placed in acetone, ethanol, and deionized water for ultrasonic immersion for 15 minutes. Then, the carbon fiber cloth is placed in a constant temperature drying oven for drying at 60℃. Subsequently, the carbon fiber cloth is placed in a medium resistance discharge equipment for treatment for 30 minutes for standby; b. A corresponding amount of molybdenum acetylacetone is added into 120 ml of ethylene glycol, and is magnetically stirred. Nitric acid is added to adjust the PH of the solution to 3. The solution is continuously stirred and is moved to a hydrothermal reaction kettle. The solution is reacted at 180℃ for 8 hours. The solution is naturally cooled to room temperature, is centrifuged, and is dried to obtain white MoO3 powder; c. The carbon fiber cloth treated by the medium resistance discharge is fixed in a hot vapor deposition film machine cabin. The white MoO3 powder is placed in an evaporation boat of the hot vapor deposition film machine. The hot vapor deposition film machine is vacuumized to 10 Pa. The evaporation rate is controlled by an electric current. The carbon fiber cloth is treated by hot vapor deposition for 30 minutes to obtain a carbon fiber cloth@MoO3 material. -4 Pa, and the evaporation rate is controlled by an electric current to be carbon fiber cloth is placed in a medium resistance discharge equipment for treatment for 30 minutes for standby; b. A corresponding amount of molybdenum acetylacetone is added into 120 ml of ethylene glycol, and is magnetically stirred. Nitric acid is added to adjust the PH of the solution to 3. The solution is continuously stirred and is moved to a hydrothermal reaction kettle. The solution is reacted at 180℃ for 8 hours. The solution is naturally cooled to room temperature, is centrifuged, and is dried to obtain white MoO3 powder; c. The carbon fiber cloth treated by the medium resistance discharge is fixed in a hot vapor deposition film machine cabin. The white MoO3 powder is placed in an evaporation boat of the hot vapor deposition film machine. The hot vapor deposition film machine is vacuumized to 10 Pa. The evaporation rate is controlled by an electric current. The carbon fiber cloth is treated by hot vapor deposition for 30 minutes to obtain a carbon fiber cloth@MoO3 material.

[0032] Example 6

[0033] The embodiment is different from example 1 in that the PH in step b is changed to 0.5, 2, 4, 5, and the others are the same as example 1, as follows: a. The carbon fiber cloth is sequentially placed in acetone, ethanol, deionized water for 15 min respectively, and then the carbon fiber cloth is placed in a constant temperature drying oven at 60℃ for drying, and then the carbon fiber cloth is placed in a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652g molybdenum acetylacetone is added to 120ml ethylene glycol, magnetic stirring, adding nitric acid to adjust the PH of the solution to 0.5, 2, 4, 5, continuous stirring, the solution is moved to the hydrothermal reaction kettle, reaction at 180℃ for 8 hours, natural cooling to room temperature, centrifugal, drying, white MoO3 powder is obtained; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of the thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuum to 10 -4 Pa, set the current control evaporation rate to A layer of MoO3 nanoparticles is plated on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine are sequentially dissolved in a mixed solution of 100ml ethylene glycol and 20ml water, continuous stirring, forming solution A; then solution A and carbon cloth@MoO3 are moved to the reaction kettle for staged heating: the first stage is heating to 110℃, the reaction time is 2 hours, the second stage is heating to 150℃, the reaction time is 2 hours, the third stage is heating to 180℃, the reaction time is 12 hours, natural cooling to room temperature, centrifugal, drying, to obtain carbon cloth@MoO3@FeOOH composite material.

[0034] Example 7:

[0035] The embodiment is different from example 1 in that the reaction temperature in step b is changed to 100℃, 150℃, 200℃, and the others are the same as example 1, as follows: a. The carbon fiber cloth is sequentially placed in acetone, ethanol, deionized water for 15 min respectively, and then the carbon fiber cloth is placed in a constant temperature drying oven at 60℃ for drying, and then the carbon fiber cloth is placed in a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652g molybdenum acetylacetone is added to 120ml ethylene glycol, magnetic stirring, adding nitric acid to adjust the PH of the solution to 0.5, 2, 4, 5, continuous stirring, the solution is moved to the hydrothermal reaction kettle, reaction at 180℃ for 8 hours, natural cooling to room temperature, centrifugal, drying, white MoO3 powder is obtained; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of the thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuum to 10 -4 Pa, set the current control evaporation rate to A layer of MoO3 nanoparticles was deposited on the surface of carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine were dissolved sequentially in a mixed solution of 100ml of ethylene glycol and 20ml of water, and stirred continuously to form solution A; then solution A and carbon cloth@MoO3 were transferred to a reaction vessel and subjected to staged heating: the first stage was heated to 110℃ and the reaction time was 2 hours, the second stage was heated to 150℃ and the reaction time was 2 hours, and the third stage was heated to 180℃ and the reaction time was 12 hours. After naturally cooling to room temperature, the mixture was centrifuged and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0036] Example 8:

[0037] The difference between this embodiment and Embodiment 1 is that the reaction time in step b is changed to 6, 12, and 15 hours, while the rest is the same as Embodiment 1, as follows: a. The carbon fiber cloth is soaked in acetone, ethanol, and deionized water for 15 minutes each, then dried in a constant temperature drying oven at 60°C, and then treated under a dielectric barrier discharge device for 30 minutes for later use; b. 0.652g of molybdenum acetylacetonate is added to 120ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the pH of the solution to 3. The solution is continuously stirred, and the solution is transferred to a hydrothermal reactor and reacted at 180°C for 6, 12, and 15 hours. After naturally cooling to room temperature, it is centrifuged and dried to obtain white MoO3 powder; c. The carbon fiber cloth treated with dielectric barrier discharge is fixed in the chamber of a thermal evaporation coating machine, and the white MoO3 powder is placed in the evaporation boat of the thermal evaporation coating machine. The vacuum is then drawn to 10°C. -4 Pa, the current is set to control the evaporation rate. A layer of MoO3 nanoparticles was deposited on the surface of carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine were dissolved sequentially in a mixed solution of 100ml of ethylene glycol and 20ml of water, and stirred continuously to form solution A; then solution A and carbon cloth@MoO3 were transferred to a reaction vessel and subjected to staged heating: the first stage was heated to 110℃ and the reaction time was 2 hours, the second stage was heated to 150℃ and the reaction time was 2 hours, and the third stage was heated to 180℃ and the reaction time was 12 hours. After naturally cooling to room temperature, the mixture was centrifuged and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0038] Example 9:

[0039] The difference between this embodiment and Embodiment 1 is that the vacuum level in step c is changed to 10. -3Pa, other same as example 1, as follows: a. carbon fiber cloth is placed in acetone, ethanol, deionized water respectively for 15 min, then the carbon fiber cloth is placed in constant temperature drying oven at 60℃ for drying, then the carbon fiber cloth is placed in dielectric barrier discharge device for 30 minutes for standby; b. 0.652g molybdenum acetylacetone is added into 120ml ethylene glycol, magnetic stirring, adding nitric acid to adjust the PH of the solution to 3, continue to stir, move the solution to hydrothermal reactor, react at 180℃ for 8 hours, natural cooling to room temperature, centrifugal, drying, white MoO3 powder is obtained; c. the carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of thermal evaporation film machine, white MoO3 powder is placed in the evaporation boat of thermal evaporation film machine, vacuum to 10 -3 Pa, set the current control evaporation rate to 0.2, 0.6, 1, A layer of MoO3 nanoparticles is plated on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g iron sulfate and 0.2g hexamethylenetetramine are sequentially dissolved in 100ml ethylene glycol and 20ml water mixed solution, continuous stirring, forming solution A; then solution A and carbon cloth@MoO3 are moved to the reactor for staged heating: the first stage is heating to 110℃, the reaction time is 2 hours, the second stage is heating to 150℃, the reaction time is 2 hours, the third stage is heating to 180℃, the reaction time is 12 hours, natural cooling to room temperature, centrifugal, drying, carbon cloth@MoO3@FeOOH composite material is obtained.

[0040] Example 10:

[0041] The difference between this example and example 1 is that the evaporation rate in step c is changed to 0.2, 0.6, 1, Other same as example 1, as follows: a. carbon fiber cloth is placed in acetone, ethanol, deionized water respectively for 15 min, then the carbon fiber cloth is placed in constant temperature drying oven at 60℃ for drying, then the carbon fiber cloth is placed in dielectric barrier discharge device for 30 minutes for standby; b. 0.652g molybdenum acetylacetone is added into 120ml ethylene glycol, magnetic stirring, adding nitric acid to adjust the PH of the solution to 3, continue to stir, move the solution to hydrothermal reactor, react at 180℃ for 8 hours, natural cooling to room temperature, centrifugal, drying, white MoO3 powder is obtained; c. the carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of thermal evaporation film machine, white MoO3 powder is placed in the evaporation boat of thermal evaporation film machine, vacuum to 10 -4 Pa, set the current control evaporation rate to 0.2, 0.6, 1, A layer of MoO3 nanoparticles was deposited on the surface of carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine were dissolved sequentially in a mixed solution of 100ml of ethylene glycol and 20ml of water, and stirred continuously to form solution A; then solution A and carbon cloth@MoO3 were transferred to a reaction vessel and subjected to staged heating: the first stage was heated to 110℃ and the reaction time was 2 hours, the second stage was heated to 150℃ and the reaction time was 2 hours, and the third stage was heated to 180℃ and the reaction time was 12 hours. After naturally cooling to room temperature, the mixture was centrifuged and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0042] Example 11:

[0043] The difference between this embodiment and Embodiment 1 is that the ferric sulfate in step d is changed to 0.04, 1.8, 2.1, and 4.0 g, respectively. The rest is the same as Embodiment 1, as follows: a. The carbon fiber cloth is sequentially immersed in acetone, ethanol, and deionized water for 15 min each. Then, the carbon fiber is dried in a constant temperature drying oven at 60°C. Subsequently, the carbon fiber is treated under a dielectric barrier discharge device for 30 minutes for later use. b. 0.652 g of molybdenum acetylacetonate is added to 120 ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the pH of the solution to 3. The solution is continuously stirred, transferred to a hydrothermal reactor, and reacted at 180°C for 8 hours. After natural cooling to room temperature, it is centrifuged and dried to obtain white MoO3 powder. c. The carbon fiber cloth treated with dielectric barrier discharge is fixed in the thermal evaporation coating chamber. The white MoO3 powder is placed in the evaporation boat of the thermal evaporation coating machine, and a vacuum is drawn to 10... -4 Pa, set the current to control the evaporation rate. A layer of MoO3 nanoparticles was deposited on the surface of carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 0.04, 1.8, 2.1, 4.0 g of ferric sulfate and 0.2 g of hexamethylenetetramine were dissolved sequentially in a mixed solution of 100 ml of ethylene glycol and 20 ml of water, and stirred continuously to form solution A; then solution A and carbon cloth@MoO3 were transferred to a reaction vessel and subjected to staged heating: the first stage was heated to 110℃ and the reaction time was 2 hours, the second stage was heated to 150℃ and the reaction time was 2 hours, and the third stage was heated to 180℃ and the reaction time was 12 hours. After naturally cooling to room temperature, centrifugation and drying were performed to obtain carbon cloth@MoO3@FeOOH composite material.

[0044] Example 12:

[0045] The embodiment is different from example 1 in that the amount of hexamethyl tetramine in step d is changed to 0.02, 0.4, 1.1, 2.0 g, and the others are the same as example 1, as follows: a. The carbon fiber cloth is sequentially placed in acetone, ethanol, deionized water for 15 min respectively, and then the carbon fiber cloth is placed in a constant temperature drying oven at 60℃ for drying, and then the carbon fiber cloth is placed in a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652 g of molybdenum acetylacetone is added to 120 ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the PH of the solution to 3, continuously stirred, the solution is moved to a hydrothermal reaction kettle, reacted at 180℃ for 8 hours, naturally cooled to room temperature, centrifuged, dried, and white MoO3 powder is obtained; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of the thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuumized to 10 -4 Pa, the evaporation rate is controlled by setting the current to A layer of MoO3 nanoparticles is plated on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2 g of iron sulfate and 0.02, 0.4, 1.1, 2.0 g of hexamethyl tetramine are sequentially dissolved in a mixed solution of 100 ml of ethylene glycol and 20 ml of water, continuously stirred to form solution A; then solution A and carbon cloth@MoO3 are moved to the reaction kettle for staged heating: the first stage is to heat to 110℃ for 2 hours, the second stage is to heat to 150℃ for 2 hours, and the third stage is to heat to 180℃ for 12 hours, and then naturally cooled to room temperature, centrifuged, dried, and carbon cloth@MoO3@FeOOH composite material is obtained.

[0046] Example 13:

[0047] The embodiment is different from example 1 in that the amount of ethylene glycol and water in step d is changed to 60 ml and 60 ml, and the others are the same as example 1, as follows: a. The carbon fiber cloth is sequentially placed in acetone, ethanol, deionized water for 15 min respectively, and then the carbon fiber cloth is placed in a constant temperature drying oven at 60℃ for drying, and then the carbon fiber cloth is placed in a dielectric barrier discharge device for treatment for 30 minutes for standby; b. 0.652 g of molybdenum acetylacetone is added to 120 ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the PH of the solution to 3, continuously stirred, the solution is moved to a hydrothermal reaction kettle, reacted at 180℃ for 8 hours, naturally cooled to room temperature, centrifuged, dried, and white MoO3 powder is obtained; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of the thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuumized to 10 -4 Pa, the evaporation rate is controlled by setting the current to A layer of MoO3 nanoparticles was deposited on the surface of carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine were dissolved sequentially in a mixed solution of 60ml of ethylene glycol and 60ml of water, and stirred continuously to form solution A; then solution A and carbon cloth@MoO3 were transferred to a reaction vessel and subjected to staged heating: the first stage was heated to 110℃ and the reaction time was 2 hours, the second stage was heated to 150℃ and the reaction time was 2 hours, and the third stage was heated to 180℃ and the reaction time was 12 hours. After natural cooling to room temperature, the mixture was centrifuged and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0048] Example 14:

[0049] The difference between this embodiment and Embodiment 1 is that the reaction temperature in step d is changed to 100-120°C for 1 hour in the first stage, 140-160°C for 3 hours in the second stage, and 190-200°C for 6-18 hours in the third stage. The rest is the same as Embodiment 1, specifically as follows: a. The carbon fiber cloth is sequentially immersed in acetone, ethanol, and deionized water for 15 minutes each. Then, the carbon fiber is dried in a constant temperature drying oven at 60°C. Subsequently, the carbon fiber is arranged in a medium... a. Treat the carbon fiber cloth treated with dielectric barrier discharge for 30 minutes and set aside; b. Add 0.652g of molybdenum acetylacetonate to 120ml of ethylene glycol, stir magnetically, add nitric acid to adjust the pH of the solution to 3, continue stirring, transfer the solution to a hydrothermal reactor, react at 180℃ for 8 hours, cool naturally to room temperature, centrifuge, and dry to obtain white MoO3 powder; c. Fix the carbon fiber cloth treated with dielectric barrier discharge in the chamber of a thermal evaporation coating machine, place the white MoO3 powder in the evaporation boat of the thermal evaporation coating machine, and evacuate to 10℃. -4 Pa, set the current to control the evaporation rate. A layer of MoO3 nanoparticles was deposited on the surface of carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine were dissolved in a mixed solution of 100ml of ethylene glycol and 20ml of water, and stirred continuously to form solution A; then solution A and carbon cloth@MoO3 were transferred to a reaction vessel and reacted at the corresponding temperature for a certain number of hours, naturally cooled to room temperature, centrifuged, and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0050] Example 15:

[0051] The embodiment is different from embodiment 1 in that the reaction time in step d is changed to 8, 20 hours, and the others are the same as embodiment 1, as follows: a. The carbon fiber cloth is sequentially placed in acetone, ethanol, and deionized water for 15 min, and then placed in a constant temperature drying oven at 60℃ for drying, and then placed in a dielectric barrier discharge device for 30 min for standby; b. 0.652g of molybdenum acetylacetonate is added to 120ml of ethylene glycol, magnetically stirred, and nitric acid is added to adjust the PH of the solution to 3, continuously stirred, and the solution is moved to a hydrothermal reaction kettle, reacted at 180℃ for 8 hours, naturally cooled to room temperature, centrifuged, and dried to obtain white MoO3 powder; c. The carbon fiber cloth treated by dielectric barrier discharge is fixed in the cabin of a thermal evaporation film machine, the white MoO3 powder is placed in the evaporation boat of the thermal evaporation film machine, vacuumized to 10 -4 Pa, and the evaporation rate is controlled by current A layer of MoO3 nanoparticles is plated on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material; d. 1.2g of ferric sulfate and 0.2g of hexamethylenetetramine are sequentially dissolved in a mixed solution of 100ml of ethylene glycol and 20ml of water, continuously stirred to form solution A; then solution A and carbon cloth@MoO3 are moved to a reaction kettle, reacted at 180℃ for 8 hours, naturally cooled to room temperature, centrifuged, and dried to obtain carbon cloth@MoO3@FeOOH composite material.

[0052] Comparative example 1

[0053] The method of embodiment 1 is selected to prepare carbon cloth, carbon cloth@MoO3, carbon cloth@FeOOH, and MoO3@FeOOH composite material on a glass substrate, respectively.

[0054] Comparative example 2

[0055] The method of embodiment 1 is selected to prepare carbon cloth@MoO3@FeOOH composite material, without using stage heating in step d, and one-step heating: directly heating to 180℃, and two-step heating: first heating to 150℃, and then heating to 180℃, are used respectively. The others are the same as embodiment 1.

[0056] The catalytic effect of the above-mentioned embodiments 1-15 and comparative examples is characterized, which shows that the catalytic efficiency of embodiments 1-15 is higher than that of comparative example 1 in various cases. The catalytic cycle firm stability of embodiments 1-15 and comparative examples is characterized, which shows that the catalytic cycle firm stability of embodiments 1-15 is higher than that of comparative example 1 in various cases.

Claims

1. A method for preparing a carbon fiber cloth@MoO3@FeOOH composite material, characterized in that, Includes the following steps: a. Soak carbon fiber cloth in acetone, ethanol, and deionized water sequentially, then sonicate for a certain time. Dry the carbon fiber cloth at a certain temperature, and then place the carbon fiber cloth under a dielectric barrier discharge device for a certain time for later use. b. Add a certain amount of molybdenum acetylacetonate to ethylene glycol, stir, add nitric acid to adjust the pH of the solution, continue stirring, react the solution at a constant temperature for a certain time, cool to room temperature, separate, wash the precipitate, and dry the resulting powder for a certain time to obtain white MoO3 powder. c. Place the carbon fiber cloth treated with dielectric barrier discharge into the chamber of a thermal evaporation coating machine and fix it. Place the white MoO3 powder into the evaporation boat of the thermal evaporation coating machine, evacuate, set the current to control the evaporation rate, and deposit a layer of MoO3 nanoparticles of a certain thickness on the surface of the carbon fiber cloth to obtain carbon fiber cloth@MoO3 material. d. A certain amount of ferric sulfate and hexamethylenetetramine were dissolved sequentially in a mixed solution of ethylene glycol and water, and stirred for a certain time to form solution A; then solution A was mixed with carbon fiber cloth@MoO3, reacted at a constant temperature for a certain time, naturally cooled to room temperature, centrifuged, and dried to obtain carbon fiber cloth@MoO3@FeOOH composite material.

2. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The ultrasonic soaking time in step a is 5-60 minutes, and the drying temperature is 30-80℃.

3. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The dielectric barrier discharge treatment time in step a is 10-60 minutes.

4. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: In step b, the amount of molybdenum acetylacetone is 0.0328-3.28g, the amount of ethylene glycol is 1-150ml, and the pH is 0.5-5.

5. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The reaction temperature in step b is 100-200℃, and the reaction time is 6-15h.

6. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The vacuum degree of thermal evaporation in step c is 10. -2 -10 -5 Pa, speed is 7. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The amount of ferric sulfate in step d is 0.04-4.0g; the amount of hexamethylenetetramine is 0.02-2.0g; the amount of ethylene glycol is 10-120ml; and the amount of water is 5-50ml.

8. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The reaction temperature in step d is increased in stages: the first stage is to raise the temperature to 100-120℃ and the reaction time is 1-2 hours; the second stage is to raise the temperature to 140-160℃ and the reaction time is 2-3 hours; and the third stage is to raise the temperature to 180-200℃ and the reaction time is 6-18 hours.

9. The method for preparing the carbon fiber cloth@MoO3@FeOOH composite material as described in claim 1, characterized in that: The temperature treatment in steps b and d is carried out in a closed hydrothermal reactor.

10. A carbon fiber cloth@MoO3@FeOOH composite material prepared by the preparation method according to any one of claims 1-9, characterized in that: The thickness of MoO3@FeOOH on the surface of the carbon fiber cloth@MoO3@FeOOH composite material is 150nm-500nm; wherein MoO3 is 20-50nm and FeOOH is 100-480nm thick; the FeOOH is a porous nanosheet structure.

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