CN115710838A - Conductive super-hydrophobic cellulose paper and preparation method thereof - Google Patents
Conductive super-hydrophobic cellulose paper and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of conductive super-hydrophobic cellulose paper, which comprises the following steps: s1, placing one side of blank cellulose paper coated with carbon slurry graphene in a drying box at 100 ℃, and drying for two hours; s2, taking out the cellulose paper obtained in the S1, and soaking the cellulose paper in a Co (NO 3) 2 solution for 4-10 min; s3, taking out the filter paper obtained in the S2, removing residual liquid on the surface of the cellulose paper, and then putting the cellulose paper into a sodium terephthalate solution for soaking for 5-20S; s4, taking out the cellulose paper obtained in the step S3, removing residual liquid on the surface of the cellulose paper, and soaking the cellulose paper in a low-surface-energy agent solution for 20-100 seconds; s5, taking out the cellulose paper obtained in the step S4, and drying the filter paper, wherein the method has the advantages that: the super-hydrophobic material has excellent super-hydrophobic performance, and the contact angle of the super-hydrophobic material can reach 165 +/-2 degrees; the conductive super-hydrophobic cellulose paper has conductivity, and can be applied to water bodies polluted by different oil stains to achieve the effect of oil-water separation.
Description
Technical Field
The invention relates to conductive super-hydrophobic cellulose paper and a preparation method thereof, in particular to conductive super-hydrophobic cellulose paper which can be used for oil-water separation and has photocatalytic degradation performance and a preparation method thereof.
Background
With the development of times of industrialization, enterprises generate more and more industrial wastewater and waste liquid, which have wide range, large quantity and difficult treatment and cause great pollution to the environment. At present, large-area water areas are increasingly polluted, the existing precautionary measures have no obvious effect, and the pollution range is expanded. Pollutants such as petroleum and byproducts thereof, metal salts and acid-base solutions, agricultural toxic residues, organic wastewater, domestic sewage, solid waste and the like are main pollutants polluting the environment, so that the research and development of a decontamination material which has simple and easily-controlled preparation process, high recycling rate and no pollution to the environment is urgent. Among them, cellulose paper materials have become one of the first materials to deal with such problems due to excellent properties of biodegradability, reproducibility, hygroscopicity, economy, etc.
Paper-based superhydrophobicity has been widely used in recent decades. There are many methods for preparing superhydrophobicity, such as templating, layer-by-layer assembly, spray coating, photolithography, plasma treatment, and wax printing. The super-hydrophobic materials prepared by the methods have a plurality of defects, such as the requirement of expensive materials and high-precision large-scale equipment; the material has poor durability and is not corrosion resistant; the production link is complex, the operation is inconvenient, and the production cost is increased; only for a specific substrate, etc. For example, chinese patent CN113789682A discloses a method for preparing super-hydrophobic filter paper for oil-water separation, which selects natural cotton fiber without environmental pollution as a basic raw material, but the preparation process is complex and the preparation flow is more complicated.
In addition, with the development of technology, the single-function paper-based super-hydrophobic material cannot meet the market demand more and more. Therefore, the Chinese patent CN111375320A discloses a preparation method for preparing a super-hydrophobic coating on the surface of a fiber membrane, and a composite cellulose membrane and a carbon nano tube are selected as basic raw materials to obtain a super-hydrophobic surface with a conductive effect. The catalyst has the function of oil-water separation, but does not have certain photocatalytic degradation capability, and is not beneficial to environmental protection.
In addition, related researches show that the conductive material with certain super-hydrophobic capacity has very important significance in the application field, but the conductive material is not paid enough attention by people. In order to meet the development requirement, it is necessary to design a material which has simple process, economical and practical oil-water separation and photocatalytic degradation performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing the conductive super-hydrophobic cellulose paper which can be used for oil-water separation and has photocatalytic degradation performance and the preparation method thereof.
The invention is realized by the following scheme: a conductive super-hydrophobic cellulose paper and a preparation method thereof are disclosed, the method comprises the following steps:
s1, coating graphene carbon slurry on one side of a cellulose membrane, and drying in a drying oven at 100 ℃ for 2 hours;
s2, taking out the conductive cellulose paper obtained in the S1, and soaking the conductive cellulose paper in Co (NO 3) 2 solutions with different concentrations for 5min;
s3, taking out the conductive cellulose paper obtained in the S2, removing residual liquid on the surface of the conductive cellulose paper, and then putting the conductive cellulose paper into a sodium terephthalate solution to be soaked for 5S;
s4, taking out the conductive cellulose paper obtained in the S3, removing residual liquid on the surface of the conductive cellulose paper, and then putting the conductive cellulose paper into a low-surface-energy agent solution to be soaked for 5min;
and S5, taking out the conductive cellulose paper obtained in the step S4, and drying until the surface of the conductive cellulose paper is simultaneously attached with cobalt hydroxide and cobalt oxide.
In the technical scheme, a soaking method is adopted, a micron-sized structure grows in situ on the surface of the conductive cellulose paper on the basis of the precipitation reaction of a heavy metal salt solution and an organic alkaline solution, and the surface energy of the conductive cellulose paper is reduced by soaking a low-surface-energy agent. In addition, the micro-nano structure deposited on the surface of the conductive cellulose paper also has certain photocatalytic degradation performance, and has stronger redox capability on organic dye under the illumination condition of 1000W/m < 2 >, so that the purpose of purifying polluted water can be achieved.
The conductive super-hydrophobic cellulose paper prepared by the invention has the performances of oil-water separation and photocatalytic degradation, meets the market demand, has the advantages of simple and convenient preparation process, low cost, small influence on the environment, mild reaction conditions and low requirement on reaction equipment, and can be produced in a large scale.
Specifically, in step S2, the concentration of the Co (NO 3) 2 solution is 0 to 0.7mol/L. The concentration is too low, and the generated precipitate is not uniformly distributed; the concentration is too high, and the generated precipitate is easy to agglomerate together in a complexing way and finally is locally enriched.
In the technical scheme, the proper concentration and proportion can ensure that the precipitate produced on the surface of the conductive cellulose paper has good uniformity and proper microstructure space, on one hand, the precipitate can be firmly combined with the conductive cellulose paper, on the second hand, enough support and proper space can be provided for a low-surface-energy agent, the hydrophobic property of the low-surface-energy agent is ensured to be reliable, and on the third hand, the cobalt hydroxide and the cobalt oxide on the surface of the dried filter paper can be distributed as uniformly as possible, so that the respective effects can be effectively exerted.
Preferably, in step S3, the low-surface-energy agent is any one of stearic acid (STA), polydimethylsiloxane (PDMS), perfluorooctyltriethoxysilane (POTS), fluorodecyl polyhedral oligomeric silsesquioxane (F-POSS), eicosane, octaisobutyl polyhedral oligomeric silsesquioxane (IB-POSS), and fluorooctyl polyhedral oligomeric silsesquioxane (FOO-POSS).
Further, in step S3, the concentration of the low-surfactant is 10g/L.
Preferably, in step S4, the drying process is: naturally drying for 9-12 h, or drying for 1-2 h at 50-90 ℃.
In the technical scheme, proper proportion of cobalt hydroxide and cobalt oxide can be obtained under two drying conditions, so that the photocatalytic degradation performance of the conductive super-hydrophobic cellulose paper is ensured.
Specifically, in step S4, the mass ratio of cobalt oxide on the conductive superhydrophobic cellulose paper is 60% to 80%.
The second aspect of the invention provides conductive super-hydrophobic cellulose paper with photocatalytic degradation performance for oil-water separation, which is prepared by the preparation method.
The invention has the beneficial effects that:
1. according to the invention, a coating method and a soaking method are adopted, and graphene carbon pulp is coated on one side of cellulose paper, so that the conductivity is obtained; then, a micron-sized structure is precipitated on the surface of the conductive cellulose paper by taking the precipitation reaction between a metal salt solution and an organic alkaline solution as a principle, and the surface energy of the filter paper is reduced by soaking a low-surface-energy agent, so that the preparation process is simple and convenient, the cost is low, the influence on the environment is small, the reaction condition is mild, the requirement on reaction equipment is low, and the large-scale production can be realized;
2. the raw materials adopted by the invention are green and environment-friendly, have wide sources and can be used for oil-water separation;
3. the preparation technology is simple and easy to control, expensive instruments are not needed, and different modified layers can be attached to the surface of the modified cellulose paper according to requirements to endow the modified cellulose paper with more performances;
4. the cellulose paper prepared by the method has excellent super-hydrophobic property, and the contact angle of the cellulose paper can reach 165 +/-2 degrees;
5. the conductive super-hydrophobic cellulose paper has conductivity, and can be applied to water bodies polluted by different oil stains to achieve the effect of oil-water separation;
6. the cellulose paper prepared by the invention has the performances of electric conduction super-hydrophobicity, photocatalytic degradation, oil-water separation and the like, meets the market demand, has simple and convenient preparation process, low cost, small influence on the environment, mild reaction conditions and low requirement on reaction equipment, and can be produced in a large scale.
Drawings
Fig. 1 is an electrical property stability test chart.
FIG. 2 is a graph of dark adsorption and photocatalytic degradation performance.
FIG. 3 is a graph showing the oil-water separation performance test.
Detailed Description
The invention will be further described with reference to fig. 1-3, without limiting the scope of the invention.
In the following description, for purposes of clarity, not all features of an actual implementation are described, well-known functions or constructions are not described in detail since they would obscure the invention with unnecessary detail, it being understood that in the development of any actual embodiment, numerous implementation details must be set forth in order to achieve the developer's specific goals, such as compliance with system-related and business-related constraints, changing from one implementation to another, and it being recognized that such development effort might be complex and time consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art.
In each example, the preparation method of the Co (NO 3) 2 solution was: taking Co (NO 3) 2 and deionized water, adding the deionized water into the Co (NO 3) 2 in batches, stirring and dissolving the mixture by using a glass rod until NO particles exist, and then pouring all the rest solution into the mixture to obtain the catalyst;
the preparation method of the sodium terephthalate solution comprises the following steps: taking terephthalic acid, sodium hydroxide and deionized water, pouring the deionized water into the terephthalic acid and the sodium hydroxide for mixing for multiple times, and cooling at room temperature to obtain the product;
the preparation method of the stearic acid solution comprises the following steps: mixing stearic acid and anhydrous ethanol, performing ultrasonic treatment for 20min, and stirring in a magnetic stirrer for 20 min.
Example 1 preparation of conductive superhydrophobic cellulose paper with photocatalytic degradation properties useful for oil-water separation
TABLE 1 parameters of each of the examples of the combination control group
The preparation process comprises the following steps: placing each solution and a plurality of pieces of conductive cellulose paper with proper size in a dust-free box, then sequentially immersing the solutions in a Co (NO 3) 2 solution, taking out the solutions to absorb residual liquid on the surface, then immersing the solutions in a sodium terephthalate solution for 5s, taking out the solutions to absorb residual liquid on the surface, then immersing the solutions in a stearic acid solution, and taking out the solutions for drying.
Example 2 Performance testing
1. Electrical stability Performance test
As one side of the conductive cellulose paper is coated with the graphene carbon paste, the conductive cellulose paper has conductive performance. The modified conductive superhydrophobic cellulose paper was subjected to a 70 minute electrical stability test and was connected to a power supply test, and the results are shown in fig. 1. The conductive superhydrophobic cellulose paper maintained high stability for 70 minutes of measurement.
2. Photocatalytic degradation Performance test
The method comprises the steps of taking methylene blue solution as a degradation indicator, putting modified conductive superhydrophobic cellulose paper into the prepared methylene blue solution, taking a point once in half an hour, and comparing degradation rates, wherein the conductive superhydrophobic cellulose film is found to have certain photocatalytic degradation performance. The results are shown in FIG. 2
3. Oil-water separation Performance test
Normal hexane-water, dimethyl carbonate-water, toluene-water and trichloromethane-water are taken as the four medium oil-water mixture for the oil-water separation. And the experimental results of 7 cycles of the test with n-hexane are shown in fig. 3.
As can be seen from the above description, the present invention has the following advantages: the conductive super-hydrophobic material has excellent conductive super-hydrophobic performance, photocatalytic degradation performance and oil-water separation performance, meets market requirements, is simple and convenient in preparation process, low in cost, mild in reaction condition, low in requirement on reaction equipment and capable of being produced in a large scale, and has little influence on the environment.
While the invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of conductive super-hydrophobic cellulose paper is characterized by comprising the following steps: the method comprises the following steps:
s1, coating carbon pulp graphene on one surface of cellulose paper, and drying for 2 hours in a drying oven at 100 ℃;
s2, soaking the cellulose paper obtained in the S1 in Co (NO 3) 2 solutions with different concentrations for 5min;
s3, taking out the cellulose paper obtained in the S2, removing residual liquid on the surface of the cellulose paper, and then putting the cellulose paper into a sodium terephthalate solution to be soaked for 5S;
s4, taking out the cellulose paper obtained in the S3, removing residual liquid on the surface of the cellulose paper, and soaking the cellulose paper in a low-surface-energy agent solution for 5min;
and S5, taking out the cellulose paper obtained in the S4, and drying at 50 ℃ for 2h.
2. The method for preparing an electrically conductive superhydrophobic cellulose paper of claim 1, wherein: in step S2, the concentration of the Co (NO 3) 2 solution is 0 to 0.7mol/L.
3. The method for preparing an electrically conductive superhydrophobic cellulose paper according to claim 1, characterized in that: in the step S3, the concentration of the sodium terephthalate solution is 0.134mol/L.
4. The method for preparing an electrically conductive superhydrophobic cellulose paper of claim 1, wherein: in the step S4, the low-surface-energy agent is any one of stearic acid (STA), polydimethylsiloxane (PDMS), perfluorooctyl triethoxysilane (PFOTS), fluorodecyl polyhedral oligomeric silsesquioxane (F-POSS), eicosane, octaisobutyl polyhedral oligomeric silsesquioxane (IB-POSS) and fluorooctyl polyhedral oligomeric silsesquioxane (FOO-POSS).
5. The method for preparing an electrically conductive superhydrophobic cellulose paper according to claim 1, characterized in that: in step S4, the concentration of the low-surface-energy agent is 10g/L.
6. The method for preparing an electrically conductive superhydrophobic cellulose paper according to claim 1, characterized in that: in step S4, the drying process is: drying for 1-2 h at 50-90 ℃.
7. An electrically conductive superhydrophobic cellulose paper, characterized by being produced by the production method according to any one of claims 1 to 6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116618275A (en) * | 2023-06-08 | 2023-08-22 | 南昌航空大学 | Composite foam copper liquid absorption core, preparation method and application thereof |
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| CN105369248A (en) * | 2015-11-16 | 2016-03-02 | 河南大学 | Preparation method for super-hydrophobic Co3O4 thin film of micro-nano composite structure |
| CN105735047A (en) * | 2016-02-01 | 2016-07-06 | 东南大学 | Preparation method of conductive and super-hydrophobic functional graphene paper |
| CN106009997A (en) * | 2016-06-24 | 2016-10-12 | 广德县中威新型材料有限公司 | Flexible waterproof coating |
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| US10876210B1 (en) * | 2016-05-05 | 2020-12-29 | Iowa State University Research Foundation, Inc. | Tunable nano-structured inkjet printed graphene via UV pulsed-laser irradiation for electrochemical sensing |
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| CN105369248A (en) * | 2015-11-16 | 2016-03-02 | 河南大学 | Preparation method for super-hydrophobic Co3O4 thin film of micro-nano composite structure |
| CN105735047A (en) * | 2016-02-01 | 2016-07-06 | 东南大学 | Preparation method of conductive and super-hydrophobic functional graphene paper |
| US10876210B1 (en) * | 2016-05-05 | 2020-12-29 | Iowa State University Research Foundation, Inc. | Tunable nano-structured inkjet printed graphene via UV pulsed-laser irradiation for electrochemical sensing |
| CN106009997A (en) * | 2016-06-24 | 2016-10-12 | 广德县中威新型材料有限公司 | Flexible waterproof coating |
| CN111254746A (en) * | 2020-01-20 | 2020-06-09 | 南昌航空大学 | Simple method for preparing super-hydrophobic filter paper by solution soaking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116618275A (en) * | 2023-06-08 | 2023-08-22 | 南昌航空大学 | Composite foam copper liquid absorption core, preparation method and application thereof |
| CN116618275B (en) * | 2023-06-08 | 2024-04-05 | 南昌航空大学 | Composite foam copper liquid absorption core, preparation method and application thereof |
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