CN108047806B - graphene/Ag-carbon microsphere aerogel coating and preparation method and application thereof - Google Patents
graphene/Ag-carbon microsphere aerogel coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene/Ag-carbon microsphere aerogel coating as well as a preparation method and application thereof, and belongs to the technical field of new coating materials. The preparation steps of the coating are as follows: firstly, preparing nano Ag-carbon microspheres, and then mixing the nano Ag-carbon microspheres with AgNO3Mixing the solutions, and stirring, centrifugally separating, washing and ultrasonically dispersing to obtain uniform nano Ag-carbon microspheres; then adding graphene oxide into the nano Ag-carbon microsphere solution, adding 5-10 wt% of cysteine, and stirring to obtain a hydrogel mixture; and finally, placing the hydrogel mixture in hot oil at the temperature of 75-85 ℃ for 8-10h, washing, performing aftertreatment by adopting a freeze-drying method to obtain graphene/Ag-carbon microsphere aerogel, and adding the graphene/Ag-carbon microsphere aerogel serving as an additive into the coating to obtain the graphene/Ag-carbon microsphere aerogel coating. The coating disclosed by the invention has ultrahigh VOCs (volatile organic compounds) adsorption performance and self-degradation capability, is good in anti-haze effect and has a potential application prospect.
Description
Technical Field
The invention belongs to the technical field of new coating materials, and particularly relates to a graphene/Ag-carbon microsphere aerogel coating as well as a preparation method and application thereof.
Background
With the continuous increase of national economy and the continuous improvement of the living standard of people in China, environmental protection becomes a main melody for people to pursue healthy and green life. With the higher requirements of people on the indoor and outdoor decoration coatings, more people pay more attention to the haze-resistant environment-friendly coatings in the process of selecting the functional coatings, and more people pursue 'fresh air close to nature and in the shape of a forest', so that the research and development of the coatings with the haze-resistant effect are of great significance.
Graphene, the thinnest and strongest material known to man, contains a single layer of carbon atoms connected in a honeycomb arrangement, the thickness of graphene is only one carbon atom in diameter, and the carbon atom diameter D is 0.14 nm. The graphene sheet layer prepared in the experiment is limited by the preparation method and conditions, and a two-dimensional graphene sheet layer with an infinite area cannot be prepared. The largest graphene lamellar layer prepared in the current experiment is a Geim-led research group of Manchester university, and the maximum width of the graphene prepared by a mechanical stripping method can reach 10 mu m. Even the graphene sheet prepared in the current laboratory has a much higher specific surface area than most other substances, so that the application of the graphene in the modified coating is widely concerned by researchers at home and abroad.
At present, the graphene coating is industrialized in korea, europe, the united states and other developed countries, but not a lot, the industrialization of the graphene-based heavy-duty anticorrosive coating for protecting wind power equipment, which is mainly developed by enterprises such as the Changzhou sixth element science and technology limited company and is mainly based on graphene, is realized, and meanwhile, patent reports about the graphene modified coating are disclosed more. For example, chinese patent 201610813904.5 discloses a graphene conductive anticorrosive paint, which is an organic-inorganic composite primer using water-based epoxy resin and potash water glass as film forming substances and using graphene oxide and tin dioxide nanoparticles as main fillers. The application effectively improves the conductivity and hardness of the coating, has good corrosion resistance, and is suitable for the corrosion-resistant coating of various metal pipelines and metal components. For another example, chinese patent 201510208892.9 discloses a graphene-modified thermal conductive coating, which can make the coating contact with the substrate more tightly by adding graphene into the coating, and can effectively improve the friction resistance and thermal conductivity of the coating.
However, the graphene modified coating is mainly focused on the application fields of corrosion resistance, conductive coating and the like at present, and the industrial research and application in the field of haze-resistant environment protection are less. With the increasing haze pollution, the PM2.5 air pollutants are one of the main components of haze, which has posed a serious challenge to the environment in which humans depend for survival, and the Volatile Organic Compounds (VOCs) which are the cause of PM2.5 become one of the major air pollutants recognized in the world. Therefore, the research and development of the graphene-based coating with high VOCs adsorption capacity has important environmental protection significance and wide application prospect.
Relevant patents on the application of graphene in haze prevention are published after retrieval.
For example, chinese patent 201410722672.3 discloses a graphene-based haze-preventing mask filter material and a method for preparing the same, in which a graphene aqueous solution is added with a crosslinking agent such as ascorbic acid, and graphene sheets are self-assembled by a hydrothermal reaction to obtain porous spongy three-dimensional graphite. For another example, chinese patent 201410219506.1 discloses a filter material composition for an anti-haze mask, which comprises, by weight, 4-6 parts of cinnamaldehyde diethylacetal, 9-11 parts of nanoscale tourmaline, 55-65 parts of activated carbon fiber, 15-25 parts of straw particles, 0.9-1.1 parts of nano silver, 0.9-1.1 parts of graphene, and 1.5-2.5 parts of a drying agent. Both the above-mentioned two applications can improve the filtering quality of antifog haze gauze mask to a certain extent, but its range of application is limited, and its antifog haze performance is waited to further improve.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defect that the existing coating is relatively poor in haze-resistant effect, and provides a graphene/Ag-carbon microsphere aerogel coating and a preparation method and application thereof. The aerogel coating disclosed by the invention has ultrahigh VOCs (volatile organic compounds) adsorption performance and self-degradation capability, is good in anti-haze effect, simple in preparation process and low in cost, and is convenient to popularize and apply.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the preparation method of the graphene/Ag-carbon microsphere aerogel coating comprises the following steps:
step one, preparation of nano Ag-carbon microspheres
Adding AgNO into carbon microsphere suspension with mass concentration of 0.3-0.5 wt%3The solution is mixed to obtain a mixed solution, and the obtained mixed solution is respectively subjected to magnetic stirring, centrifugal separation, washing and ultrasonic dispersion treatment to obtain uniform nano Ag-carbon microspheres;
step two, preparation of graphene/Ag-carbon microsphere aerogel
Adding the graphene oxide suspension into the nano Ag-carbon microsphere solution, uniformly mixing, adding cysteine, and stirring to obtain a hydrogel mixture; placing the hydrogel mixture in hot oil at 75-85 ℃ for 8-10h, then washing to remove the 3D structure, and processing the blocky hydrogel by adopting a freeze-drying method to obtain the graphene/Ag-carbon microsphere aerogel;
step three, preparation of the coating
And adding the obtained aerogel serving as an additive into the coating to obtain the graphene/Ag-carbon microsphere aerogel coating.
Furthermore, the addition amount of the graphene/Ag-carbon microsphere aerogel in the obtained coating is 5-10% of the total weight of the coating.
Furthermore, the carbon microsphere-AgNO obtained in the step one3Ag in the mixed solution+The concentration of the carbon microspheres is 1-1.5 mol/L, the carbon microspheres are of hollow structures, and the specific surface area of the carbon microspheres is 1800-2200 m2/g 。
Furthermore, the size of the nano silver ions in the nano Ag-carbon microspheres obtained in the step one is 50-200 nm.
Furthermore, in the step one, carbon microsphere-AgNO is added3And stirring the mixed solution by a magnetic rotor at 180-220 rpm for 20-24 h, centrifuging at 2800-3000 rpm for 10-15 min to remove redundant silver ions, washing the obtained nano Ag-carbon microspheres by distilled water and alcohol, and dispersing by ultrasonic waves for 45-60 min again to obtain the uniform nano Ag-carbon microspheres.
Furthermore, the preparation method of the carbon microspheres in the step one comprises the following steps:
(1) uniformly dispersing cellulose in deionized water according to the amount of 5-8 g/100ml, then placing the mixture into a hydrothermal reaction kettle, keeping the temperature constant at 200-220 ℃ for 6-8 h, and naturally cooling to room temperature;
(2) performing suction filtration on substances on the lower layer in the hydrothermal reaction kettle, washing the substances with absolute ethyl alcohol and distilled water, and drying the substances at the temperature of 100-110 ℃ for 10-12 hours;
(3) putting the dried substance obtained in the step (2) and a KOH solution into a crucible according to the dipping ratio of KOH/C (1.3-1.5), then putting the crucible into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 600-800W, and the activation time is 8-11 min;
(4) adding dilute HCl into the obtained activated product to be neutral, and then drying at 100-110 ℃ to obtain the activated product with the specific surface area of 1800-2200 m2Carbon microspheres per gram.
Furthermore, in the second step, the concentration of graphene oxide contained in the graphene oxide suspension is 3-5 mg/ml, and the addition amount of cysteine is 5-10% of the total amount of the nano Ag-carbon microsphere solution.
Secondly, the graphene/Ag-carbon microsphere aerogel coating prepared by the method is adopted.
Thirdly, the graphene/Ag-carbon microsphere aerogel composite anti-haze coating disclosed by the invention is applied to the field of indoor and outdoor decoration.
Furthermore, when the coating is used as an indoor and outdoor decoration coating, the coating is directly applied to the surface of a substrate, or is applied to the surface of other coatings as a functional top coating.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) according to the preparation method of the graphene/Ag-carbon microsphere aerogel coating, graphene oxide and nano Ag-carbon microspheres are compounded, so that the graphene/Ag-carbon microsphere aerogel is prepared, the obtained aerogel is added into the coating as an additive, and the graphene/Ag-carbon microsphere aerogel coating is obtained.
(2) According to the preparation method of the graphene/Ag-carbon microsphere aerogel coating, disclosed by the invention, the preparation technology of the hollow carbon microspheres has the characteristics of simplicity in operation, no pollution, rich raw material sources and the like, the reaction can be completed in one step, the specific surface area of the prepared carbon microspheres is large, and the adsorption performance of the obtained aerogel coating is further ensured.
(3) According to the graphene/Ag-carbon microsphere aerogel coating, the graphene/Ag-carbon microsphere aerogel is used as an additive of the coating, the graphene/Ag-carbon microsphere aerogel is of a cylindrical multi-branch complex three-dimensional network structure, and has an abundant microporous structure inside, so that the specific surface area and the pore volume rate of the graphene/Ag-carbon microsphere aerogel are much higher than those of common materials, and the graphene/Ag-carbon microsphere aerogel coating has super-strong adsorption capacity on organic solvents and organic substances, particularly VOCs (volatile organic compounds), so that the haze resistance of the coating can be remarkably improved by adding the graphene/Ag-carbon microsphere aerogel coating, and the problem that the existing indoor and outdoor decoration coating is poor in haze resistance is solved.
(4) Compared with the existing product, the graphene/Ag-carbon microsphere aerogel composite anti-haze coating has the advantages that the adsorption performance is improved by 2 times, the viscosity is as high as or above a CPS (mPa & s), the adhesive force is good, the performance is stable, and the service life is long; meanwhile, the method is economic and environment-friendly, low in cost, strong in competitive advantage and has a huge application prospect.
(5) According to the application of the graphene/Ag-carbon microsphere aerogel composite anti-haze coating, the anti-haze coating is directly coated on the surface of a base material, or is coated on the surface of other coatings as a functional surface coating, so that the anti-haze capability of the coating can be effectively improved, and the operation is simple.
Drawings
FIG. 1 is a scanned image of the carbon microspheres obtained in the present invention;
FIG. 2 is a scanning image of graphene oxide obtained according to the present invention;
FIG. 3 is a schematic diagram of a preparation process of the graphene/Ag-carbon microsphere aerogel composite anti-haze coating;
FIG. 4 is a process flow diagram of a preparation method of the graphene/Ag-carbon microsphere aerogel composite anti-haze coating.
Detailed Description
Because the anti-haze coating has huge market and wide indoor and outdoor application, and the requirements on environmental protection are higher and higher along with national policies, the control on VOCs is stricter and stricter in the future, and therefore, the research and development of new anti-haze coatings are of great significance. Graphene, the thinnest and strongest material known to man, comprises a single layer of carbon atoms connected in a honeycomb arrangement having a specific surface area of up to 2630m2The coating has rich mesoporous structure, so that a large-area protective layer can be formed by a thin coating after the coating is uniformly dispersed in the coating, and the most important is that the coating loaded with graphene has strong adsorption performance. However, it is well known that ideal graphene is a perfect two-dimensional network structure, and its adsorption to molecules is generally a weak physical adsorption. In order to realize excellent adsorption performance of the graphene-based material on gas molecules, the hollow-structure carbon microspheres with smooth and homogeneous surfaces and high adsorption performance are compounded with graphene, and dispersion force can be generated on single-layer interfaces of the carbon microspheres and the graphene due to intercalation of graphene oxide, so that the coating is ensured to have high adsorption performance. Meanwhile, the graphene aerogel obtained by the invention has the characteristics of graphene and aerogel, and has high porosity, ultra-light density, high mechanical strength, and good thermal conductivity and electrical conductivity. In addition, the nano silver ions are loaded on the surface of the carbon microsphere firstly and then are perfectly compounded with the graphene, so that catalysis can be achievedAnd haze decomposition effect.
Although research and development reports of graphene/carbon microsphere aerogel exist abroad, related patents of graphene/carbon microsphere composite materials also exist domestically, for example, Chinese patent 201310235331.9 discloses a preparation method of a graphene/carbon microsphere composite material, and the application takes water-soluble starch and graphite oxide as raw materials, and the graphene/carbon microsphere composite material with excellent electrochemical properties is prepared by sequentially hydrolyzing starch, ultrasonically dispersing the graphite oxide, synthesizing carbon microspheres by two-step heating, and then carbonizing and activating. However, the existing graphene/carbon microsphere composite material is mainly prepared in order to improve the electrochemical performance of the carbon microspheres, and cannot be effectively applied to the anti-haze coating. According to the invention, the graphene/carbon microsphere aerogel is formed by self-assembling the carbon microspheres with high adsorption capacity and graphene oxide, and the nano silver ions are added to enable the graphene/carbon microsphere aerogel to have a catalytic sterilization effect, and meanwhile, the addition amount of each component and specific preparation process parameters are optimized and designed through a large number of experiments, so that the graphene/carbon microsphere aerogel with low cost and excellent VOCs (volatile organic compounds) adsorption performance can be prepared, and the haze resistance of the coating can be obviously improved by using the aerogel as an additive.
Specifically, the graphene/Ag-carbon microsphere aerogel coating is prepared by the following steps:
step one, preparation of nano Ag-carbon microspheres
Adding AgNO into carbon microsphere suspension with mass concentration of 0.3-0.5 wt%3The solution is mixed to obtain a mixed solution, and Ag is contained in the mixed solution+The concentration of (A) is 1-1.5 mol/L, and the obtained carbon microsphere-AgNO is subjected to3And stirring the mixed solution by a magnetic rotor at 180-220 rpm for 20-24 h, centrifuging at 2800-3000 rpm for 10-15 min to remove redundant silver ions, washing the obtained nano Ag-carbon microspheres by distilled water and alcohol, and dispersing by ultrasonic waves for 45-60 min again to obtain the uniform nano Ag-carbon microspheres. The carbon microsphere is of a hollow structure, and the specific surface area of the carbon microsphere is 1800-2200 m2And g, the size of the nano silver ions in the obtained nano Ag-carbon microspheres is 50-200 nm. The preparation method of the carbon microspheres comprises the following steps:
(1) uniformly dispersing cellulose in deionized water according to the amount of 5-8 g/100ml, then placing the mixture into a hydrothermal reaction kettle, keeping the temperature constant at 200-220 ℃ for 6-8 h, and naturally cooling to room temperature;
(2) performing suction filtration on substances on the lower layer in the hydrothermal reaction kettle, washing the substances with absolute ethyl alcohol and distilled water, and drying the substances at the temperature of 100-110 ℃ for 10-12 hours;
(3) putting the dried substance obtained in the step (2) and a KOH solution into a crucible according to the dipping ratio of KOH/C (1.3-1.5), then putting the crucible into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 600-800W, and the activation time is 8-11 min;
(4) adding dilute HCl into the obtained activated product to be neutral, and then drying at 100-110 ℃ to obtain the activated product with the specific surface area of 1800-2200 m2Carbon microspheres per gram.
Step two, preparation of graphene/Ag-carbon microsphere aerogel
Adding 6-10 ml of graphene oxide suspension (the concentration of graphene oxide is 3-5 mg/ml) into the nano Ag-carbon microsphere solution, uniformly mixing, adding cysteine accounting for 5-10% of the total amount of the nano Ag-carbon microsphere solution, and stirring to obtain a hydrogel mixture; and (3) placing the hydrogel mixture in hot oil at 75-85 ℃ for 8-10h, washing to remove the 3D structure, and treating blocky hydrogel by adopting a freeze-drying method to obtain the graphene/Ag-carbon microsphere aerogel. The obtained graphene/Ag-carbon microsphere aerogel is a cylindrical multi-branch complex three-dimensional network structure, and contains a large number of microporous structures inside, so that the specific surface area and the pore volume rate of the aerogel are much higher than those of common materials, and the aerogel has super-strong adsorption capacity on organic solvents and organic substances, particularly VOCs (volatile organic compounds), so that the anti-haze performance of the coating can be remarkably improved by adding the aerogel, and the problem that the existing indoor and outdoor decoration coating is poor in anti-haze performance is solved. The graphene oxide can be obtained commercially or prepared by the following method:
(1) mixing 10-15 g of natural graphite and 230-250 ml of concentrated H2SO4And 5 to 10g of NaNO3Mixing the powders, placing in ice-water bath, stirring at 3-4 deg.C for 0.5 hr while stirring3-5 g of KMnO is added in several times43g in total, after the addition is finished, carrying out heat preservation reaction for 1.5-2 h to complete low-temperature reaction; (2) raising the temperature of the system to 35 ℃, and keeping the temperature for reaction for 3 hours to finish the medium-temperature reaction; (3) raising the temperature of the system to 100 ℃, dripping distilled water by using a constant pressure funnel, and reacting for 1h to finish high-temperature reaction; (4) after the reaction is finished, adding 70mL of distilled water and 10mL of hydrogen peroxide, continuously stirring for 15min, and adjusting the product to be neutral by adopting dilute HCl and distilled water; and finally, dispersing the obtained graphite oxide in water, carrying out ultrasonic treatment for 8 hours, and placing the graphite oxide in a vacuum drying oven for drying for later use.
Step three, preparation of the coating
And adding the obtained aerogel serving as an additive into the coating to obtain the graphene/Ag-carbon microsphere aerogel coating.
According to the invention, graphene oxide and nano Ag-carbon microspheres are compounded to prepare the graphene/Ag-carbon microsphere aerogel, the obtained aerogel has ultrahigh VOCs adsorption performance and self-degradation capability, the anti-haze capability of the coating can be effectively improved by adding the aerogel serving as an additive into the coating, and the addition amount of the graphene/Ag-carbon microsphere aerogel in the coating accounts for 5-10% of the total weight of the coating. The preparation technology of the hollow carbon microspheres has the characteristics of simplicity in operation, no pollution, rich raw material sources and the like, can be completely reacted in one step, has large specific surface area, uniform spherical shape and smooth surface, further ensures the adsorption performance of the obtained aerogel, and lays a foundation for uniformly loading the carbon microspheres on graphene to prepare a graphene/carbon microsphere aerogel (G/CS hybrid aerogel) functional coating. Meanwhile, the adsorption performance of the obtained graphene/carbon microsphere aerogel can be further ensured by reasonably controlling the process parameters, and the antibacterial and catalytic performances of the graphene/carbon microsphere aerogel are improved by adding nano silver ions.
For a further understanding of the present invention, reference will now be made to the following examples.
Example 1
The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to the embodiment is shown in fig. 3 and 4, and includes the following steps:
(1) preparing carbon microspheres: the cellulose is used as raw material, and the carbon microsphere is prepared by a hydrothermal carbonization method.
Specifically, 0.8g of cellulose is weighed into a 20mL sample bottle, 15mL of deionized water is added, magnetic stirring is carried out for 30min at the rotating speed of 30r/min, the cellulose is uniformly dispersed in the solution, and then the solution is placed into a 25mL hydrothermal reaction kettle. Sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a muffle furnace, keeping the temperature for 7 hours at 220 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature in the muffle furnace. And (3) carrying out suction filtration on the lower-layer substances in the hydrothermal reaction kettle, washing with absolute ethyl alcohol and distilled water, and drying at 110 ℃ for 12 h. Putting the carbon microspheres into a crucible according to the impregnation ratio of KOH/C of 1.3, then putting the carbon microspheres into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 700W, and the activation time is 10 min; then adding dilute HCl into the obtained product to be neutral, drying at the temperature of 110 ℃, and finally obtaining the product with the specific surface area of 1800-2200 m2The scanning picture of the carbon microspheres is shown in figure 1.
(2) Preparation of nano Ag-carbon microsphere
0.4 wt% of carbon microspheres are taken and poured into 15ml of distilled water, and then AgNO is added3Solution, mixing Ag in solution+The concentration of the mixed solution is 1mol/L, the mixed solution is shaken up and stirred by a magnetic rotor at 200rpm for 24 hours; separating for 15min at 3000rpm by using a centrifuge to remove redundant silver ions, washing the obtained nano Ag-carbon microspheres (AgCS) by using distilled water and alcohol, and dispersing for 1h by using ultrasonic waves again to obtain uniform nano Ag-carbon microspheres, wherein the specific surface area of the carbon microspheres is 2000-2100 m2And g, the size of the nano silver ions in the obtained nano Ag-carbon microspheres is 50-150 nm.
(3) Preparation of graphene/Ag-carbon microsphere aerogel
Adding 5ml of graphene oxide suspension (the concentration of graphene oxide is 3mg/ml) into 10ml of AgCS solution, uniformly mixing, adding cysteine accounting for 5% of the total amount of the nano Ag-carbon microsphere solution, performing ultrasonic treatment for 1h to convert 2D graphene oxide sheets into 3D graphene hydrogel to obtain a hydrogel mixture, and then putting the hydrogel mixture into hot oil at 80 ℃ for 9 h. And finally, washing the 3D structure by adopting ultra-pure water. The remaining block-shaped hydrogel is converted into aerogel by adopting a freeze-drying method until the aerogel is ready for use.
(4) Adding the obtained aerogel serving as an additive into the coating to obtain the anti-haze composite coating of the embodiment, wherein the addition amount of the graphene/Ag-carbon microsphere aerogel in the coating accounts for 7% of the total weight of the coating.
Be used for indoor outer fitment with the aerogel coating that this embodiment obtained, during the specific use, directly coat in the substrate surface with gained coating, or coat in other coating surfaces as functional top coat with it and use can, have the effect of good catalytic decomposition haze, and easy operation. Compared with the existing product, the adsorption performance of the graphene composite coating can be effectively improved by 2 times, the cost of the product is basically unchanged, and the technical indexes are as follows: (a) adsorption performance: the adsorption rate reaches 80% or more; (b) viscosity: 40000 or above CPS (mPas); (c) adhesion force: the 3M 600 transparent adhesive tape is pasted and rapidly peeled off in the direction of 90 degrees after standing for more than 1min, and the adhesive tape has the advantages of no carbon particles basically, good adhesive force, stable performance and long service life, thereby having strong competitive advantage and huge application prospect.
Example 2
The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to the embodiment is shown in fig. 3 and 4, and includes the following steps:
(1) preparing carbon microspheres: the cellulose is used as raw material, and the carbon microsphere is prepared by a hydrothermal carbonization method.
Specifically, 0.8g of cellulose is weighed into a 20mL sample bottle, 10mL of deionized water is added, magnetic stirring is carried out for 20min at the rotating speed of 40r/min, the cellulose is uniformly dispersed in the solution, and then the solution is placed into a 25mL hydrothermal reaction kettle. And sealing the hydrothermal reaction kettle, putting the sealed hydrothermal reaction kettle into a muffle furnace, keeping the temperature of the sealed hydrothermal reaction kettle constant at 200 ℃ for 8 hours, and naturally cooling the sealed hydrothermal reaction kettle to room temperature in the muffle furnace. And (3) carrying out suction filtration on the lower-layer substances in the hydrothermal reaction kettle, washing with absolute ethyl alcohol and distilled water, and drying at 105 ℃ for 11 h. Putting the carbon microspheres into a crucible according to the impregnation ratio of KOH/C of 1.5, then putting the carbon microspheres into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 600W, and the activation time is 11 min; then adding dilute HCl to the obtained product to be neutral, drying at the temperature of 100 ℃, and finally obtaining the product which is the carbon microsphere with high specific surface area, wherein the scanning picture of the product is shown in figure 1.
(2) Preparation of nano Ag-carbon microsphere
0.3 wt% of carbon microspheres are taken and poured into 15ml of distilled water, and then AgNO is added3Solution, mixing Ag in solution+The concentration of the mixed solution is 1.3mol/L, the mixed solution is shaken up and stirred by a magnetic rotor at 180rpm for 20 hours; separating for 12min by adopting a centrifugal machine at the rotating speed of 2800rpm to remove redundant silver ions, then washing the obtained nano Ag-carbon microspheres (AgCS) by adopting distilled water and alcohol, and dispersing for 45min by adopting ultrasonic waves again to obtain uniform nano Ag-carbon microspheres, wherein the specific surface area of the carbon microspheres is 1900-2000 m2And g, the size of the nano silver ions in the obtained nano Ag-carbon microspheres is 100-170 nm.
(3) Preparation of graphene/Ag-carbon microsphere aerogel
Adding 5ml of graphene oxide suspension (the concentration of graphene oxide is 5mg/ml) into 10ml of AgCS solution, uniformly mixing, adding cysteine accounting for 10% of the total amount of the nano Ag-carbon microsphere solution, performing ultrasonic treatment for 40min to obtain a hydrogel mixture, and then putting the hydrogel mixture into hot oil at 75 ℃ for 10 h. And finally, washing the 3D structure by adopting ultra-pure water. The remaining block-shaped hydrogel is converted into aerogel by adopting a freeze-drying method until the aerogel is ready for use. In this embodiment, natural graphite is prepared into graphite oxide by a Hummer chemical oxidation method, the obtained graphite oxide is dispersed in water, ultrasonic treatment is performed for 8 hours, and then the graphite oxide is placed in a vacuum drying oven for drying and standby, and a scanning picture of the obtained graphene oxide is shown in fig. 2.
(4) Adding the obtained aerogel serving as an additive into the coating to obtain the anti-haze composite coating of the embodiment, wherein the addition amount of the graphene/Ag-carbon microsphere aerogel in the coating accounts for 10% of the total weight of the coating. When being used for indoor and outdoor decoration with this embodiment aerogel coating, its anti haze effect is comparatively close with embodiment 1.
Example 3
The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to the embodiment is shown in fig. 3 and 4, and includes the following steps:
(1) preparing carbon microspheres: the cellulose is used as raw material, and the carbon microsphere is prepared by a hydrothermal carbonization method.
Specifically, 0.5g of cellulose is weighed into a 20mL sample bottle, 10mL of deionized water is added, magnetic stirring is carried out for 40min at the rotating speed of 35r/min, the cellulose is uniformly dispersed in the solution, and then the solution is placed into a 25mL hydrothermal reaction kettle. Sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a muffle furnace, keeping the temperature constant at 215 ℃ for 6h, and naturally cooling the hydrothermal reaction kettle to room temperature in the muffle furnace. And (3) carrying out suction filtration on the lower layer of substances in the hydrothermal reaction kettle, washing with absolute ethyl alcohol and distilled water, and drying at 100 ℃ for 10 h. Putting the carbon microspheres into a crucible according to the impregnation ratio of KOH/C of 1.4, then putting the carbon microspheres into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 650W, and the activation time is 9 min; then adding dilute HCl to the obtained product to be neutral, drying at 105 ℃, and finally obtaining the product which is the carbon microsphere with high specific surface area, wherein the scanning picture of the product is shown in figure 1.
(2) Preparation of nano Ag-carbon microsphere
0.5 wt% of carbon microspheres are taken and poured into 15ml of distilled water, and then AgNO is added3Solution, mixing Ag in solution+The concentration of the mixed solution is 1.5mol/L, the mixed solution is shaken up and stirred for 21 hours by adopting a magnetic rotor at 190 rpm; and (3) separating by adopting a centrifuge at the rotating speed of 2900rpm for 10min to remove redundant silver ions, then washing the obtained nano Ag-carbon microspheres (AgCS) by adopting distilled water and alcohol, and dispersing for 55min by adopting ultrasonic waves again to obtain the uniform nano Ag-carbon microspheres. Wherein the specific surface area of the carbon microspheres is 2100-2200 m2And g, the size of the nano silver ions in the obtained nano Ag-carbon microspheres is 130-200 nm.
(3) Preparation of graphene/Ag-carbon microsphere aerogel
Adding 5ml of graphene oxide suspension (the concentration of graphene oxide is 4mg/ml) into 10ml of AgCS solution, uniformly mixing, adding cysteine accounting for 8% of the total amount of the nano Ag-carbon microsphere solution, performing ultrasonic treatment for 50min to obtain a hydrogel mixture, and then putting the hydrogel mixture into hot oil at 85 ℃ for 8 h. And finally, washing the 3D structure by adopting ultra-pure water. The remaining block-shaped hydrogel is converted into aerogel by adopting a freeze-drying method until the aerogel is ready for use.
(4) Adding the obtained aerogel serving as an additive into the coating to obtain the anti-haze composite coating of the embodiment, wherein the addition amount of the graphene/Ag-carbon microsphere aerogel in the coating accounts for 5% of the total weight of the coating. When being used for indoor and outdoor decoration with this embodiment aerogel coating, its anti haze effect is comparatively close with embodiment 1.
Example 4
The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to the embodiment is shown in fig. 3 and 4, and includes the following steps:
(1) preparing carbon microspheres: the cellulose is used as raw material, and the carbon microsphere is prepared by a hydrothermal carbonization method.
Specifically, 0.7g of cellulose is weighed into a 20mL sample bottle, 10mL of deionized water is added, magnetic stirring is carried out for 25min at the rotating speed of 30r/min, the cellulose is uniformly dispersed in the solution, and then the solution is placed into a 25mL hydrothermal reaction kettle. Sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a muffle furnace, keeping the temperature constant at 210 ℃ for 6.5 hours, and naturally cooling the hydrothermal reaction kettle to room temperature in the muffle furnace. And (3) carrying out suction filtration on the lower-layer substances in the hydrothermal reaction kettle, washing with absolute ethyl alcohol and distilled water, and drying at 108 ℃ for 10.5 h. Putting the carbon microspheres into a crucible according to the impregnation ratio of KOH/C of 1.3, then putting the carbon microspheres into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 800W, and the activation time is 8 min; then adding dilute HCl to the obtained product to be neutral, and drying at 110 ℃, wherein the obtained product is the carbon microsphere with high specific surface area, and the scanning picture is shown in figure 1.
(2) Preparation of nano Ag-carbon microsphere
Taking the carbon microsphere suspension with the mass concentration of 0.4 percent by weight, pouring the carbon microsphere suspension into 15ml of distilled water, and then adding AgNO3Solution, mixing Ag in solution+Is 1.2mol/L, the mixed solution is shaken up and a magnetic rotor of 220rpm is usedStirring for 22 h; separating for 13min at the rotating speed of 2850rpm by adopting a centrifugal machine to remove redundant silver ions, then washing the obtained nano Ag-carbon microspheres (AgCS) by adopting distilled water and alcohol, and dispersing for 50min by adopting ultrasonic waves again to obtain uniform nano Ag-carbon microspheres, wherein the specific surface area of the carbon microspheres is 1800-1900 m2And g, the size of the nano silver ions in the obtained nano Ag-carbon microspheres is 50-90 nm.
(3) Preparation of graphene/Ag-carbon microsphere aerogel
Adding a graphene oxide suspension (the concentration of graphene oxide is 3.5mg/ml) into the nano Ag-carbon microsphere solution, uniformly mixing, adding cysteine accounting for 7% of the total amount of the nano Ag-carbon microsphere solution, and stirring to obtain a hydrogel mixture; and (3) placing the hydrogel mixture in hot oil at 78 ℃ for 8h, then washing to remove the 3D structure, and processing the blocky hydrogel by adopting a freeze-drying method to obtain the graphene/Ag-carbon microsphere aerogel.
(4) Adding the obtained aerogel serving as an additive into the coating to obtain the anti-haze composite coating of the embodiment, wherein the addition amount of the graphene/Ag-carbon microsphere aerogel in the coating accounts for 8% of the total weight of the coating. When the aerogel coating obtained in the embodiment is used for indoor and outdoor decoration, the anti-haze effect of the aerogel coating is slightly better than that of the aerogel coating obtained in the embodiment 1.
Claims (8)
1. A preparation method of a graphene/Ag-carbon microsphere aerogel coating is characterized in that the coating is an anti-haze coating, the method is prepared by adding graphene/Ag-carbon microsphere aerogel into the coating, and the preparation method comprises the following steps:
step one, preparation of nano Ag-carbon microspheres
Adding AgNO into carbon microsphere suspension with mass concentration of 0.3-0.5 wt%3The solution is mixed to obtain a mixed solution, and the obtained mixed solution is respectively subjected to magnetic stirring, centrifugal separation, washing and ultrasonic dispersion treatment to obtain uniform nano Ag-carbon microspheres;
step two, preparation of graphene/Ag-carbon microsphere aerogel
Adding the graphene oxide suspension into the nano Ag-carbon microsphere solution, uniformly mixing, adding cysteine, and stirring to obtain a hydrogel mixture; placing the hydrogel mixture in hot oil at the temperature of 75-85 ℃ for 8-10h, then washing to remove the 3D structure, and treating blocky hydrogel by adopting a freeze-drying method to obtain graphene/Ag-carbon microsphere aerogel;
step three, preparation of the coating
Adding the obtained aerogel serving as an additive into a coating to obtain the graphene/Ag-carbon microsphere aerogel haze-resistant coating, wherein the addition amount of the graphene/Ag-carbon microsphere aerogel in the obtained coating is 5-8% of the total weight of the coating;
the preparation method of the carbon microspheres in the first step comprises the following steps:
(1) uniformly dispersing cellulose in deionized water according to the amount of 5-8 g/100ml, then placing the mixture into a hydrothermal reaction kettle, keeping the temperature constant at 200-220 ℃ for 6-8 h, and naturally cooling to room temperature;
(2) performing suction filtration on substances on the lower layer in the hydrothermal reaction kettle, washing the substances with absolute ethyl alcohol and distilled water, and drying the substances at the temperature of 100-110 ℃ for 10-12 hours;
(3) putting the dried substance obtained in the step (2) and a KOH solution into a crucible according to the impregnation ratio of KOH/C = 1.3-1.5, then putting the crucible into a microwave oven for activation treatment, and introducing nitrogen, wherein the microwave power is 600-800W, and the activation time is 8-11 min;
(4) adding dilute HCl into the obtained activated product to be neutral, and then drying at 100-110 ℃ to obtain the activated product with the specific surface area of 1800-2200 m2The carbon microspheres are hollow structures.
2. The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to claim 1, which is characterized by comprising the following steps: the carbon microsphere-AgNO obtained in the step one3Ag in the mixed solution+The concentration of (b) is 1 to 1.5 mol/L.
3. The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to claim 2, which is characterized by comprising the following steps: the size of the nano silver ions in the nano Ag-carbon microspheres obtained in the first step is 50-200 nm.
4. The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to any one of claims 1 to 3, wherein the preparation method comprises the following steps: in the step one, carbon microsphere-AgNO is added3And stirring the mixed solution by a magnetic rotor at 180-220 rpm for 20-24 h, centrifuging at 2800-3000 rpm for 10-15 min to remove redundant silver ions, washing the obtained nano Ag-carbon microspheres by distilled water and alcohol, and dispersing by ultrasonic waves for 45-60 min again to obtain the uniform nano Ag-carbon microspheres.
5. The preparation method of the graphene/Ag-carbon microsphere aerogel coating according to any one of claims 1 to 3, wherein the preparation method comprises the following steps: in the second step, the concentration of graphene oxide contained in the graphene oxide suspension is 3-5 mg/ml, and the addition amount of cysteine is 5-10% of the total amount of the nano Ag-carbon microsphere solution.
6. The graphene/Ag-carbon microsphere aerogel haze-resistant coating prepared according to the method of any one of claims 1 to 5.
7. The application of the graphene/Ag-carbon microsphere aerogel coating as claimed in claim 6 in the field of indoor and outdoor decoration.
8. The application of the graphene/Ag-carbon microsphere aerogel coating according to claim 7, wherein the coating comprises the following components in percentage by weight: when the coating is used as an indoor and outdoor decoration coating, the coating is directly coated on the surface of a base material, or the coating is used as a functional surface coating and coated on the surfaces of other coatings.
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