Preparation and application of viscous composite material capable of being simply, conveniently and stably brushed

Abstract

The invention belongs to the technical field of environment and energy material synthesis, and particularly relates to preparation and application of a viscous composite material capable of being simply, conveniently and stably brushed. The preparation method comprises the following steps: firstly, preparing imidazole nano hollow spheres (PIL) with positive potential on the surfaces by a template method, and further grafting EY [M] liquid end long chains with negative potential through electrostatic acting force to form a new composite material (PIL-EY [M]). The coating can be easily brushed and firmly attached to various non-horizontal environment carriers, the problems that a solid material is unstable in an open environment, industrial application is difficult and the like are solved, meanwhile, functional design can be conducted on an internal solid material and an external liquid-state end according to different application requirements, for example, the liquid-state end with a catalysis-assisting effect can be excited by light, and the liquid-state end with a catalysis-assisting effect can be excited by light. An electron donor structure is formed to provide electrons for an imidazole reduction site, so that the yield of reducing CO2 into CO is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of environmental and energy material synthesis, and particularly relates to the preparation and application of a viscous composite material that can be easily and stably painted. Background Art

[0002] In the past few decades, various solid semiconductor catalysts have been developed, including nanotubes, nanosheets, amorphous nanoparticles, alloys, etc., aiming to improve the intrinsic catalytic activity during the reaction process. Nevertheless, the application of solid catalysts in long-term and open-environment reactions causes material loss, which greatly limits their practical applications. Generally, powder catalysts are embedded in specific carriers such as hydrogels, polymer fiber films, and flat plates to overcome the problem of mass loss of solid catalysts. However, the additional upfront operating costs, the bundling relationship between the specific carrier and the powder catalyst, and the limited application scenarios of large-volume carriers have not been well explored in the development of these powder catalytic systems for large-scale applications. From a practical perspective, the development of a liquid material that can be easily painted is expected to expand the application scenarios while achieving stabilization, especially in non-planar environments such as curved surfaces, inclined walls, and grids where powder catalytic systems are difficult to apply.

[0003] Recently, porous liquids, a type of liquid nanomaterial composed of an internal microporous framework and an external liquid terminal grafted together, have shown advantages in the catalytic field. The microporous framework serves as the main body of the catalytic reaction, and the liquid terminal is used to provide a stable and uniform flow state. Although the microporous nanoparticles are stably fixed by the liquid terminal, the porous liquid with good fluidity has a weak surface tension and is difficult to stably maintain on inclined surfaces with large slopes, grids, or strong wind environments at natural temperatures. Research has shown that the intermolecular interactions between the solvent itself or the solvent and solute in the liquid cause resistance during the flow of the liquid, which enhances the surface tension of the liquid and generates viscosity. Inspired by this, a liquid terminal with a large steric hindrance, such as polyetheramine M2070, has spatial restrictions around its side chains and functional groups, and is then grafted with a microporous nanosemiconductor through weak molecular forces such as electrostatic interactions to form a viscous nanoliquid material to immobilize the catalyst and cope with long-term applications in non-planar or open environments. However, the problem is that the liquid terminal with a large steric hindrance generally does not have catalytic ability, sacrificing catalytic activity while endowing fluidity. Therefore, viscous nanomaterials wrapped with a liquid terminal having a cocatalytic effect have become a research hotspot and difficulty. Summary of the Invention

[0004] In view of the technical problems that powder materials are difficult to fix and prone to loss, and are only suitable for large-scale applications in a planar environment, the present invention provides a viscous composite material that can be simply and stably painted. It consists of an internal nano-hollow framework and an external liquid end, and can be applied to various material fields. Due to the large steric effect and intermolecular interaction at the solid-liquid interface, the viscous composite material with a high surface tension can firmly adhere to the carrier, prevent the loss of the catalyst, and can be easily and stably coated in various non-planar environments such as curved surfaces, inclined walls, and meshes where it is difficult to load powder materials. The viscous composite material that can be simply and stably painted makes up for the difficult-to-apply environment of solid materials and shows potential commercial feasibility.

[0005] To achieve the above technical objectives, the present invention adopts the following technical solutions:

[0006] A preparation method of a viscous composite material that can be simply and stably painted is carried out according to the following steps:

[0007] Step 1: Synthesis of PIL:

[0008] First, add polystyrene microspheres to deionized water; then, add divinylbenzene and 1-vinylimidazole, and continuously stir to form a mixed system; then add a potassium persulfate solution to the mixed system, heat and stir, and obtain a precursor of PIL spheres; finally, add tetrahydrofuran, let it stand, and after centrifugation and drying, the obtained dried product is denoted as PIL.

[0009] Step 2: Synthesis of a viscous imidazole-based nanofluid composite material (PIL-EY[M]):

[0010] Add the PIL obtained in Step 1, eosin y, polyetheramine M2070, and absolute ethanol to deionized water, continuously stir the mixed solution, and the final product obtained after stirring is PIL-EY[M].

[0011] Preferably, in Step 1, the dosage relationship of polystyrene microspheres, deionized water, divinylbenzene, and 1-vinylimidazole is 0.05 g - 0.1 g: 37.5 mL: 1 mL: 2 mL; the diameter of the polystyrene microspheres is in the range of 100 nm - 400 nm.

[0012] Preferably, in Step 1, the time of continuous stirring is 1 h.

[0013] Preferably, in Step 1, the dosage relationship of divinylbenzene, potassium persulfate solution, and tetrahydrofuran is 1 mL: 6 mL: 40 - 60 mL, and the concentration of the potassium persulfate solution is 5 g / L.

[0014] Preferably, in Step 1, the temperature of heating and stirring is 75 °C, the stirring time is 12 hours; the standing time is 12 h.

[0015] Preferably, in step 1, the centrifugation time is 10 minutes and the rotation speed is 10,000 r / min.

[0016] Preferably, in step 1, the drying temperature is 70 - 75 °C and the drying time is 12 hours.

[0017] Preferably, in step 2, the dosage ratio of the PIL, eosin y, polyetheramine M2070, absolute ethanol and deionized water is 0.01 g: 0.15 g: 0.5 g: 10 mL: 10 mL.

[0018] Preferably, in step 2, the continuous stirring time is 12 hours and the stirring temperature is 70 - 75 °C.

[0019] The present invention designs a sticky composite material (PIL-EY[M]) that can be simply and stably coated. With PIL as the center, a long chain of organic molecules (EY[M]) with viscosity and fluidity is loaded on its outer surface, which consists of a positively charged microporous nanoimidazole-based hollow sphere inside and a negatively charged co-catalytic liquid end outside, forming a new composite material (PIL-EY[M]); due to the electrostatic interaction between internal molecules and the large steric hindrance effect of the liquid end, PIL-EY[M] has strong flow resistance, and can be simply coated and stably loaded in grid, inclined plane or even downward non-planar environments. By changing the internal solid material and the external liquid end, functional design can be carried out according to different application requirements. For example, the co-catalytic liquid end can be photoexcited to form an electron-donating structure, providing electrons for the imidazole reduction site, thereby increasing the yield of CO2 reduction to CO. These unique advantages have been verified by experiments and theories, and the practical advantages of PIL-EY[M] in large-scale catalytic reactions have been demonstrated.

[0020] Advantages of the present invention:

[0021] (1) A sticky composite material prepared by the present invention that can be simply and stably coated has adhesiveness, can firmly adhere to various carriers, such as non-planar environments like grids and inclined planes, and can effectively prevent losses caused by the application of materials in open environments.

[0022] (2) A sticky composite material prepared by the present invention that can be simply and stably coated has fluidity, can be easily coated on various carriers, such as can be easily and stably coated in various non-planar environments where it is difficult to load powder materials like curved surfaces, inclined walls, grids, etc.; simplifies the application steps of solid materials, makes up for the problem that solid materials are difficult to apply on some carriers, and effectively improves the use efficiency.

[0023] (3) A sticky composite material that can be easily and stably painted prepared by the present invention has uniformity, requires less usage of solid materials during the painting process, and can be evenly coated on a larger carrier area, saving material usage, and has good economic efficiency and market application prospects. Description of the Drawings

[0024] Figure 1 For the PIL sample 13 Solid-state NMR spectrum.

[0025] Figure 2 Scanning and transmission electron microscope images and element distribution of the PIL-EY[M] sample.

[0026] Figure 3 Low-temperature thermogravimetric diagrams of different samples; the samples are PIL-EY[M] and EY[M] respectively.

[0027] Figure 4 Painting property test of the PIL-EY[M] sample.

[0028] Figure 5 Images of the PIL-EY[M] sample loaded on different carriers; the carriers are grid, plastic, wood, metal, ceramic, and glass respectively.

[0029] Figure 6 Performance comparison diagrams of different samples in the CO2 reduction experiment; the samples are PIL-EY[M], PIL, EY, and EY[M] respectively. Detailed Embodiments

[0030] Now, various exemplary embodiments of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0031] It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0032] Without departing from the scope or spirit of the present invention, various modifications and variations can be made to the specific embodiments of the present invention's specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art.

[0033] CO2 reduction activity evaluation: In a 250 mL quartz reaction flask, the sample was evenly coated on a membrane support with a radius of 25 mm. After sealing, high-purity CO2 gas was continuously introduced into the reaction flask for 1 hour, and 1 mL of deionized water was injected as a proton donor. The light source used was a 360 nm ultraviolet lamp to simulate sunlight. Gas products were taken every 1 hour during the reaction. After 5 hours of reaction, the light source was turned off, and gas chromatography was used to measure the concentration of the product gas.

[0034] Example 1:

[0035] (1) Preparation of PIL: First, 0.05 g of polystyrene microspheres with a diameter of 200 nm were added to a round-bottom flask containing 37.5 mL of deionized water. Then, 1 mL of divinylbenzene and 2 mL of 1-vinylimidazole were added, and the mixture was continuously stirred for 1 hour to form a mixed system. Then, 6 mL of potassium persulfate solution (5 g / L) was added to the mixed system, and the temperature was raised and stirred at 75 °C for 24 hours to obtain a precursor of PIL spheres. Then, 40 mL of tetrahydrofuran was added to the PIL precursor and left to stand for 12 hours. After standing, it was centrifuged at 10000 r / min for 10 minutes, and the centrifuged product was collected and dried in an oven at 75 °C for 12 hours. The obtained dried product was denoted as PIL.

[0036] (2) Preparation of PIL-EY[M]: The PIL obtained in step one, eosin y powder, polyetheramine M2070, absolute ethanol, and deionized water were added to a beaker in a dosage ratio of 0.01 g: 0.15 g: 0.5 g: 10 mL: 10 mL to form a mixed solution. Subsequently, the mixed solution was stirred at 75 °C for 12 hours to obtain a viscous composite material, which was PIL-EY[M].

[0037] (3) Preparation of EY[M]: Eosin y powder, polyetheramine M2070, absolute ethanol, and deionized water were added to a beaker in a dosage ratio of 0.15 g: 0.5 g: 10 mL: 10 mL to form a mixed solution. Subsequently, the mixed solution was stirred at 75 °C for 12 hours to obtain the final sample, denoted as EY[M].

[0038] Figure 1 For PIL 1313C solid nuclear magnetic resonance spectrum; as shown in the figure, the peaks at 138 ppm and 128 ppm belong to the carbons on the imidazole ring, the peaks around 145 ppm and 113 ppm belong to the phenyl carbons, and the other peaks belong to the carbons on the carbon chain. The above results prove the successful preparation of PIL.

[0039] Figure 2 In (A) is the scanning electron microscope (SEM) of PIL-EY[M], and in (B) is the high-resolution transmission electron microscope (TEM) and its energy spectrum of the local area in (A). It can be seen from the SEM image that PIL-EY[M] appears as a viscous liquid, and the liquid end tightly wraps the internal PIL nanospheres. It can be seen from the TEM image that the PIL structure in PIL-EY[M] is well-preserved. The unique element Br in the liquid end is distributed on the surface of the sphere, which proves that the liquid end is wrapped outside the PIL sphere. The above results prove the successful preparation of PIL-EY[M].

[0040] Figure 3 is the low-temperature thermogravimetric graph of different samples; the inset is the physical map of EY[M] (left) and PIL-EY[M] (right); the results show that the melting temperature of PIL-EY[M] is -40 °C, so PIL-EY[M] can maintain good fluidity at room temperature.

[0041] Figure 4 is the viscosity test graph of PIL-EY[M]. As shown in the figure, when a force opposite to gravity is applied to PIL-EY[M] with a needle, resistance is shown inside PIL-EY[M] (A), proving its viscosity. At the same time, PIL-EY[M] can drip with the needle (B), proving its fluidity. Therefore, PIL-EY[M] can be easily brushed on the surface of the carrier, as shown in (C).

[0042] Figure 5 is the loading graph of PIL-EY[M] on different carriers. PIL-EY[M] can be coated on various material carriers such as grids, plastics, woods, metals, ceramics, and glasses with a brush, and placing it vertically downward will not cause PIL-EY[M] to separate from the surface of the carrier, proving the stability of the loading of PIL-EY[M].

[0043] Figure 6 is the CO2 reduction performance test graph of different samples; after five hours of reaction, carbon monoxide is the only product of all samples. The results show that the CO production rates of PIL, EY, and EY[M] are 21.24 μmol / m 2 / h, 87.82 μmol / m 2 / h, and 80.83 μmol / m 2 / h, respectively. In contrast, the production rate of PIL-EY[M] is 1228.68 μmol / m2 / h, which are 57.84, 13.99, and 15.20 times the yields of PIL, EY, and EY[M]CO, respectively.

[0044] Note: The above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; therefore, although the present specification has described the present invention in detail with reference to the above embodiments, those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced; and all technical solutions and their improvements that do not depart from the spirit and scope of the present invention shall be covered within the scope of the claims of the present invention.

Claims

1. A preparation method of a viscous composite material that can be easily and stably painted, characterized in that, It includes the following steps: Step 1: Synthesis of PIL: First, add polystyrene microspheres into deionized water; then, add divinylbenzene and 1-vinylimidazole, and continuously stir to form a mixed system; then add potassium persulfate solution into the mixed system, after heating and stirring, obtain the precursor of PIL spheres; finally, add tetrahydrofuran, after standing, centrifuge and dry, and the obtained dry product is denoted as PIL; Step 2: Synthesis of PIL-EY[M]: Add the PIL obtained in Step 1, eosin y, polyetheramine M2070 and absolute ethanol into deionized water, continuously stir the mixed solution, and the final sample obtained after stirring is PIL-EY[M].

2. The preparation method of a sticky composite material that can be simply and stably painted according to claim 1, characterized in that, In Step 1, the dosage relationship of polystyrene microspheres, deionized water, divinylbenzene and 1-vinylimidazole is 0.05 g - 0.1 g: 37.5 mL: 1 mL: 2 mL; the diameter of the polystyrene microspheres is in the range of 100 nm - 400 nm.

3. The preparation method of a sticky composite material that can be easily and stably painted according to claim 1, characterized in that, In Step 1, the continuous stirring time is 1 h.

4. The preparation method of a sticky composite material that can be easily and stably painted according to claim 1, characterized in that, In Step 1, the dosage relationship of divinylbenzene, potassium persulfate solution and tetrahydrofuran is 1 mL: 6 mL: 40 - 60 mL, and the concentration of the potassium persulfate solution is 5 g / L.

5. The preparation method of a sticky composite material that can be simply and stably painted according to claim 1, characterized in that, In Step 1, the temperature for heating and stirring is 75 °C, and the stirring time is 12 hours; the standing time is 12 h.

6. The preparation method of a sticky composite material that can be easily and stably painted according to claim 1, characterized in that, In Step 1, the centrifugation time is 10 minutes, and the rotation speed is 10000 r / min; the drying temperature is 70 - 75 °C, and the drying time is 12 hours.

7. The preparation method of a sticky composite material that can be simply and stably painted according to claim 1, characterized in that, In Step 2, the dosage ratio of PIL, eosin y, polyetheramine M2070, absolute ethanol and deionized water is 0.01 g: 0.15 g: 0.5 g: 10 mL: 10 mL.

8. The preparation method of a sticky composite material that can be easily and stably painted according to claim 1, wherein, In Step 2, the continuous stirring time is 12 hours, and the stirring temperature is 70 - 75 °C.

9. A sticky composite material that can be simply and stably painted, prepared by the method according to any one of claims 1-8, characterized in that The viscous composite material takes PIL as the center, and a long chain of organic molecules with viscosity and fluidity is loaded on its outer surface.

10. Use of the viscous composite material that can be simply and stably painted according to claim 10 in CO2 reduction.

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