A fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating and its preparation method and application

Abstract

The present invention belongs to the field of cultural relic protection technology, and specifically relates to a method for preparing an antibacterial hydrophobic coating for stone cultural relic protection. This method uses a simple wet chemical method and an electrochemical replacement method to synthesize a attapulgite / copper-iron Prussian blue analog / silver nanocomposite material. During the preparation process, the natural nanorod-shaped mineral attapulgite is used as a carrier, and Prussian blue analog nanoparticles are loaded on its surface by an in-situ precipitation method, effectively improving the antibacterial properties of the natural mineral material. Furthermore, the composite material is modified with nano-Ag to effectively enhance its antibacterial effect on bacteria and fungi, while also improving the photothermal properties of the Prussian blue analog, achieving the purpose of long-lasting antibacterial effects. Finally, the coating is treated with fluorinated silane for hydrophobicity to obtain an antibacterial, hydrophobic, self-cleaning coating for stone cultural relic protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of cultural relics protection, and in particular relates to a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating, and a preparation method and application thereof. Background Art

[0002] China has a long history and its traditional culture is even more extensive and profound. Looking back at the history of "five thousand years of Chinese history", countless cultural relics are like dazzling treasures, shining brightly in the long river of history. As historical evidence, cultural relics are irreplaceable. At the same time, they themselves have immeasurable historical value, cultural value, scientific value, artistic value, and educational value. However, problems such as damage, natural weathering, deliquescence, and mildew of cultural relics have always troubled countless scholars. Therefore, how to better preserve and pass on cultural relics has become the top priority of research topics for countless cultural relic protection scholars. There are few applications and research in this area in the existing technology. Therefore, in view of the various impacts of natural, human and other environments on cultural relics, it is urgent to study a protective coating that can be applied to the surface of cultural relics without causing damage to the cultural relics and at the same time achieve the purpose of "restoring the old as new".

[0003] Attapulgite is a hydrous magnesium-rich silicate clay mineral with a layered chain structure. It contains numerous pores, exhibits a unique fibrous morphology, and possesses a porous structure. It is a natural mineral with diverse applications and high added value. Its structure and composition are similar to those of stone cultural relics. Therefore, it is being considered to create a nanocomposite antimicrobial and hydrophobic protective coating with excellent hydrophobic and antibacterial properties for the preservation of stone cultural relics. This would be a novel approach. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing an antibacterial and hydrophobic coating for the protection of stone cultural relics, so as to solve problems such as cultural relic corrosion, bacterial contamination and mildew, and achieve good hydrophobicity and excellent antibacterial properties. This technology has the advantages of low cost, safety and environmental protection.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing a fluorinated silane / attapulgite / copper iron Prussian blue analog / silver antibacterial hydrophobic coating comprises the following steps:

[0007] Step 1: Weigh a certain amount of ferric chloride, copper chloride dihydrate, and attapulgite, disperse the two metal chlorides and attapulgite in a 1.0-5.0 mM citric acid aqueous solution, stir until the solution is uniformly dispersed, and ultrasonically disperse for 15-30 minutes to obtain solution A; weigh a certain amount of potassium ferrocyanide trihydrate, disperse it in a 1.0-5.0 mM citric acid aqueous solution, stir until the solution is uniformly dispersed, and ultrasonically disperse for 15-30 minutes to obtain solution B; transfer solution A to a constant temperature water bath, add solution B dropwise, react at a constant temperature for 2-10 minutes, move to room temperature, and continue stirring for 30 minutes; after the reaction is completed and naturally cooled, the obtained sample is centrifuged, and the solid precipitate is washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material;

[0008] Step 2: Weigh a certain amount of attapulgite / copper iron Prussian blue analog nanocomposite material and disperse it in deionized water, then add silver nitrate and stir for 2 hours. Centrifuge, wash, and dry the resulting composite material to obtain the attapulgite / copper iron Prussian blue analog / silver nanocomposite material;

[0009] Step 3: Mix the attapulgite / copper iron Prussian blue analogue / silver nanocomposite material with 1H,1H,2H,2H-perfluorodecyltriethoxysilane in an ethanol aqueous solution, then ultrasonically disperse for 15 to 30 minutes and stir at room temperature for 2 to 10 hours; finally, spray the mixed solution onto the sandstone cultural relic substrate through a spray gun to obtain a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating.

[0010] Furthermore, the mass ratio of ferric chloride, cupric chloride dihydrate and potassium ferrocyanide trihydrate added in the step 1 is 16:17:(30-72).

[0011] Furthermore, in the step 1, the amount of ferric chloride added is 8-32 g / L, and the amount of copper chloride dihydrate added is 8.5-34 g / L.

[0012] Furthermore, in the step 1, the amount of potassium ferrocyanide trihydrate added is 21-84 g / L.

[0013] Furthermore, in the step 2, the addition amount of the attapulgite / Prussian blue analog nanocomposite material is 5-10 g / L.

[0014] Furthermore, the amount of silver nitrate added in step 2 is 3.6-10 g / L.

[0015] Furthermore, in the step 3, the amount of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added is 10 mL / L, and the stirring time is 6 h.

[0016] A fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating prepared by any of the above preparation methods.

[0017] Furthermore, the modified Prussian blue analog nanoparticles are uniformly loaded on the surface of nanorod-shaped attapulgite, the length of the attapulgite is 200-500 nm, and the size of the Prussian blue analog nanoparticles is 5-50 nm.

[0018] An application of the above-mentioned fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating in the protection of leather cultural relics, paper cultural relics, bamboo and wooden articles, and murals.

[0019] Compared with the prior art, the present invention has the following technical effects:

[0020] The present invention uses natural nano-rod-shaped attapulgite mineral as a carrier and adopts a simple in-situ precipitation method and electrochemical replacement method to synthesize a attapulgite / copper-iron Prussian blue analogue / silver nanocomposite material, effectively solving the agglomeration problem of Prussian blue nanomaterials and improving the antibacterial performance and commercial value of low-cost natural clay minerals. The incorporation of nano-Ag further enhances the photothermal performance of the nanocomposite material and improves the antibacterial activity and photothermal performance of the nanocomposite coating. The addition of 1H,1H,2H,2H-perfluorodecyltriethoxysilane can reduce the surface energy of the coating, which complements the increased roughness of the attapulgite and greatly improves the hydrophobicity of the coating, thereby forming a nanocomposite antibacterial hydrophobic protective coating for stone cultural relics protection with good hydrophobicity and antibacterial properties.

[0021] (1) In the present invention, the excellent aspect ratio of attapulgite improves the dispersibility of the nanomaterial and the roughness of the coating, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane reduces the surface energy of the coating. The two complement each other and ultimately obtain a hydrophobic coating with a contact angle of 165°.

[0022] (2) Attapulgite can effectively solve the agglomeration problem of Prussian blue analogues. The dissolution effect of iron ions, copper ions and silver ions in Prussian blue analogues jointly improves the antibacterial activity of the nanocomposite material, forming a hydrophobic antibacterial coating with good hydrophobicity and excellent antibacterial properties. At the same time, the synergistic photothermal effect of silver nanoparticles and Prussian blue analogues further improves the antibacterial properties of the coating.

[0023] (3) The hydrophobic antibacterial coating prepared by the present invention has excellent performance, low price, safety, environmental protection and wide application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1From top to bottom are the XRD patterns of the attapulgite / copper iron Prussian blue analogue / silver (APT / CuFePBA / Ag) nanocomposite prepared in Example 1, the attapulgite / copper iron Prussian blue analogue (APT / CuFePBA) nanocomposite prepared in Comparative Example 1, the attapulgite / copper Prussian blue analogue (APT / CuPBA) nanocomposite, the attapulgite / Prussian blue (APT / PB) nanocomposite, and attapulgite (APT);

[0025] Figure 2 TEM image of the APT / CuFePBA nanocomposite prepared in Comparative Example 1;

[0026] Figure 3 TEM image of the APT / CuFePBA / Ag nanocomposite prepared in Example 1;

[0027] Figure 4 From top to bottom, the temperature changes of APT, APT / CuFePBA and APT / CuFePBA / Ag nanocomposite solutions with equal concentrations under xenon lamp irradiation are shown;

[0028] Figure 5 From left to right: water contact angle tests of untreated sandstone, sandstone treated with fluorinated silane / attapulgite (Fluor / APT), and sandstone treated with Fluor / APT / CuFePBA / Ag;

[0029] Figure 6 The effect of the amount of APT / CuFePBA / Ag nanocomposite added on the water contact angle of Fluor / APT / CuFePBA / Ag nanocomposite antibacterial hydrophobic coating;

[0030] Figure 7 This is a super-depth-of-field microscope photo of bacterial colony growth on the surface of untreated sandstone;

[0031] Figure 8 This is an ultra-depth-of-field microscope photo of bacterial colony growth on the sandstone surface sprayed with Fluor / APT coating;

[0032] Figure 9 This is an ultra-depth-of-field microscope photo of bacterial colony growth on a sandstone surface sprayed with a Fluor / APT / CuFePBA / Ag nanocomposite antibacterial hydrophobic coating; DETAILED DESCRIPTION

[0033] The specific contents of the present invention are further explained in detail below with reference to the embodiments.

[0034] Example 1

[0035] Step 1: First, 0.64g of ferric chloride, 0.68g of copper chloride dihydrate, and 1.69g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide was dispersed in citric acid aqueous solution (2mM) to obtain solution B, and the two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; in the middle, the two solutions were stirred until the solution was evenly dispersed, and ultrasonically dispersed for 30min to obtain solution B; solution A was transferred to a constant temperature water bath heating pot, and solution B was added dropwise, and the reaction was carried out at a constant temperature for 5min, and then moved to room temperature and continued to stir for 30min; finally, after the reaction was completed and naturally cooled, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material;

[0036] Step 2: Weigh 0.25 g of attapulgite / copper iron Prussian blue analogue and 0.17 g of silver nitrate respectively, disperse the attapulgite / copper iron Prussian blue analogue in deionized water and stir continuously, then add silver nitrate and stir for 2 hours. The resulting composite material is centrifuged, washed, and dried to obtain a attapulgite / copper iron Prussian blue analogue / silver nanocomposite material.

[0037] Step 3: Mix 0.2 g of attapulgite-silver-coated Prussian blue / copper Prussian blue analogue with 0.5 ml of 1H,1H,2H,2H-perfluorodecyltriethoxysilane in 50 ml of ethanol solution, then ultrasonically disperse for 30 minutes, stir at room temperature for 6 hours, and spray the mixed solution on the substrate with a spray gun to obtain a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating.

[0038] Example 2

[0039] Step 1: First, 0.64g of ferric chloride, 0.68g of copper chloride dihydrate, and 1.69g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide was dispersed in citric acid aqueous solution (2mM) to obtain solution B. The two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; Solution A was transferred to a constant temperature water bath, and Solution B was added dropwise. The reaction was continued at a constant temperature for 5min, and then moved to room temperature and stirred for 30min; Finally, after the reaction was completed and naturally cooled, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material;

[0040] Step 2: Weigh 0.25 g of attapulgite / copper iron Prussian blue analogue and 0.25 g of silver nitrate respectively, disperse the attapulgite / copper iron Prussian blue analogue in deionized water and stir continuously, then add silver nitrate and stir for 2 hours. Centrifuge the resulting composite material, wash, and dry to obtain a attapulgite / copper iron Prussian blue analogue / silver nanocomposite material.

[0041] Step 3: Mix 0.2 g of attapulgite / copper iron Prussian blue analogue / silver with 0.5 ml of 1H,1H,2H,2H-perfluorodecyltriethoxysilane in 50 ml of ethanol solution, then ultrasonically disperse for 30 minutes, stir at room temperature for 6 hours, and spray the mixed solution on the substrate with a spray gun to obtain a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating.

[0042] Example 3

[0043] Step 1: First, 0.64g of ferric chloride, 0.68g of copper chloride dihydrate, and 1.69g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide was dispersed in citric acid aqueous solution (2mM) to obtain solution B. The two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; Solution A was transferred to a constant temperature water bath, and Solution B was added dropwise. The reaction was continued at a constant temperature for 5min, and then moved to room temperature and stirred for 30min; Finally, after the reaction was completed and naturally cooled, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material;

[0044] Step 2: Weigh 0.25 g of attapulgite / copper iron Prussian blue analogue and 0.17 g of silver nitrate respectively, disperse the attapulgite / copper iron Prussian blue analogue in deionized water and stir continuously, then add silver nitrate and stir for 2 hours. Centrifuge the resulting composite material, wash, and dry to obtain a attapulgite / copper iron Prussian blue analogue / silver nanocomposite material.

[0045] Step 3: Mix 0.15 g of attapulgite / copper iron Prussian blue analogue / silver with 0.5 ml of 1H,1H,2H,2H-perfluorodecyltriethoxysilane in 50 ml of ethanol solution, then ultrasonically disperse for 30 minutes, stir at room temperature for 6 hours, and spray the mixed solution on the substrate with a spray gun to obtain a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating.

[0046] Example 4

[0047] Step 1: First, 0.64g of ferric chloride, 0.68g of copper chloride dihydrate, and 1.69g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide was dispersed in citric acid aqueous solution (2mM) to obtain solution B. The two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; Solution A was transferred to a constant temperature water bath, and Solution B was added dropwise. The reaction was continued at a constant temperature for 5min, and then moved to room temperature and stirred for 30min; Finally, after the reaction was completed and naturally cooled, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material;

[0048] Step 2: Weigh 0.25 g of attapulgite / copper iron Prussian blue analogue and 0.17 g of silver nitrate respectively, disperse the attapulgite / copper iron Prussian blue analogue in deionized water and stir continuously, then add silver nitrate and stir for 2 hours. The resulting composite material is centrifuged, washed, and dried to obtain a attapulgite / copper iron Prussian blue analogue / silver nanocomposite material.

[0049] Step 3: Mix 0.1 g of attapulgite / copper iron Prussian blue analogue / silver with 0.5 ml of 1H,1H,2H,2H-perfluorodecyltriethoxysilane in 50 ml of ethanol solution, then ultrasonically disperse for 30 minutes, stir at room temperature for 6 hours, and spray the mixed solution on the substrate with a spray gun to obtain a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating.

[0050] Comparative Example 1

[0051] Step 1: Mix 0.2 g of attapulgite with 0.5 ml of 1H,1H,2H,2H-perfluorodecyltriethoxysilane in 50 ml of ethanol solution, then ultrasonically disperse for 30 minutes, stir at room temperature for 6 hours, and spray the mixed solution on the substrate through a spray gun to obtain a fluorinated silane / attapulgite hydrophobic coating.

[0052] Comparative Example 2

[0053] Step 1: First, 0.64g of ferric chloride, 0.68g of copper chloride dihydrate, and 1.69g of potassium ferrocyanide trihydrate were weighed respectively, and the ferric chloride was dispersed in 0.4g of attapulgite citric acid aqueous solution to obtain solution A, and potassium ferrocyanide was dispersed in citric acid aqueous solution (2mM) to obtain solution B. The two solutions were stirred until they were evenly dispersed, and then ultrasonically dispersed for 30min; Solution A was transferred to a constant temperature water bath, and Solution B was added dropwise. The reaction was continued at a constant temperature for 5min, and then moved to room temperature and stirred for 30min; Finally, after the reaction was completed and naturally cooled, the obtained sample was centrifuged, and the precipitated solid was washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material;

[0054] Figures 1 to 9 These are the characterization results of Fluor / APT / CuFePBA / Ag nanocomposite antibacterial hydrophobic coating. Figure 1 From top to bottom are the XRD patterns of fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver (Fluor / APT / CuFePBA / Ag) nanocomposite prepared in Example 1, the attapulgite / copper iron Prussian blue analogue (APT / CuFePBA) nanocomposite prepared in Comparative Example 2, the attapulgite-copper Prussian blue analogue (CuPBA-APT) nanocomposite, the attapulgite-Prussian blue (PB-APT) nanocomposite and attapulgite (APT). All attapulgite-based composites clearly show the diffraction peak of attapulgite, which matches that of pure APT. In addition, obvious PB characteristic peaks (JCPDS 01-0239) appear in the XRD pattern of the PB-APT nanocomposite antibacterial agent. The diffraction peak of silver oxide also exists in the APT / CuFePBA / Ag spectrum, indicating that the APT / CuFePBA / Ag nanocomposite is successfully prepared.

[0055] Figure 2 This is a TEM photo of the APT / CuFePBA nanocomposite prepared in Comparative Example 2. Figure 3 TEM image of APT / CuFePBA / Ag prepared in Example 1. Figure 2 and Figure 3 It can be seen that the natural mineral clay attapulgite has a nanorod-like structure with a length of 400-500nm and a width of about 10nm, which has a large aspect ratio. It can be observed that there are a large number of nanoparticles on it, and they are relatively uniform. Combined with the XRD test results, it can be seen that they are PB and CuPBA nanoparticles. Figure 3 It can be observed that different Figure 2 The nanoparticles are presumably Ag2O nanoparticles, which further illustrates the successful preparation of Ag@PB / CuPBA-APT nanocomposites.

[0056] Figure 4 From top to bottom, the temperature changes of APT, APT / CuFePBA, and APT / CuFePBA / Ag solutions of the same concentration under xenon lamp irradiation (room temperature 25°C) are shown. After five minutes of xenon lamp irradiation, the temperature of deionized water did not change significantly, while that of the APT / CuFePBA aqueous solution increased by 7.2°C. At the same time, the temperature of the APT / CuFePBA / Ag aqueous solution increased by 11.9°C, indicating a good photothermal effect.

[0057] Figure 5From left to right, the water contact angle test results of untreated sandstone, sandstone sprayed with fluorinated silane / attapulgite (Fluor / APT) coating, and sandstone coated with Fluor / APT / CuFePBA / Ag nanocomposite antibacterial hydrophobic coating are shown. The hydrophobic properties of sandstone were greatly improved after spraying with Fluor / APT and Fluor / APT / CuFePBA / Ag coatings, with contact angles exceeding 165°. The increased roughness caused by the large aspect ratio of the APT nanocomposite is an important factor in the improved hydrophobic properties of the coating.

[0058] Figure 6 This is the effect of APT / CuFePBA / Ag addition on the water contact angle of Fluor / APT / CuFePBA / Ag nanocomposite antibacterial hydrophobic coating. With the increase of Ag@PB / CuPBA-APT addition in the solution, the water contact angle of the coating gradually increases, reaching 162.11° at 0.2g, which once again illustrates that the large aspect ratio of the APT nanocomposite increases the roughness of the coating surface, thereby improving the water contact angle and hydrophobic properties of the coating.

[0059] Figures 7-9 The super-depth-of-field microscope photos of the bacterial colony growth on the surfaces of untreated sandstone, sandstone sprayed with Fluor / APT coating, and sandstone sprayed with Fluor / APT / CuFePBA / Ag nano-composite antibacterial and hydrophobic coating, respectively. After 7 days of culture with the added mixed bacterial solution, it can be seen that the surface of the untreated sandstone is covered with hyphae; the hyphae on the surface of the sandstone sprayed with Fluor / APT coating is slightly reduced because the coating has good hydrophobic properties, making it difficult for bacteria and fungi to attach to the coating surface, but the coating does not have an antibacterial effect, so there are still more hyphae covering the surface; basically no hyphae can be observed on the surface of the sandstone sprayed with Fluor / APT / CuFePBA / Ag nano-composite antibacterial and hydrophobic coating. With the dual effects of hydrophobicity and antibacterial properties of the coating, it is extremely difficult for bacteria and fungi to grow on the coating, which effectively hinders the growth of bacteria and fungi and plays a good protective role for the sandstone.

[0060] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. It will be apparent to those skilled in the art that various modifications and variations may be made to the embodiments of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention shall be included within the scope of protection of the embodiments of the present invention.

Claims

1. A method for preparing a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating, characterized in that: The following steps are involved: Step 1: Weigh a certain amount of ferric chloride, copper chloride dihydrate, and attapulgite, disperse the two metal chlorides and attapulgite in a 1.0-5.0 mM citric acid aqueous solution, stir until the solution is uniformly dispersed, and ultrasonically disperse for 15-30 minutes to obtain solution A; weigh a certain amount of potassium ferrocyanide trihydrate, disperse it in a 1.0-5.0 mM citric acid aqueous solution, stir until the solution is uniformly dispersed, and ultrasonically disperse for 15-30 minutes to obtain solution B; transfer solution A to a constant temperature water bath, add solution B dropwise, react at a constant temperature for 2-10 minutes, move to room temperature, and continue stirring for 30 minutes; after the reaction is completed and naturally cooled, the obtained sample is centrifuged, and the solid precipitate is washed and dried to obtain a attapulgite / copper iron Prussian blue analog nanocomposite material; Step 2: Weigh a certain amount of attapulgite / copper iron Prussian blue analog nanocomposite material and disperse it in deionized water, then add silver nitrate and stir for 2 hours. Centrifuge, wash, and dry the resulting composite material to obtain the attapulgite / copper iron Prussian blue analog / silver nanocomposite material; Step 3: Mix the attapulgite / copper iron Prussian blue analogue / silver nanocomposite material with 1H,1H,2H,2H-perfluorodecyltriethoxysilane in an ethanol aqueous solution, then ultrasonically disperse for 15 to 30 minutes and stir at room temperature for 2 to 10 hours; finally, spray the mixed solution onto the sandstone cultural relic substrate through a spray gun to obtain a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating.

2. The method for preparing a fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 1, wherein: The mass ratio of ferric chloride, cupric chloride dihydrate and potassium ferrocyanide trihydrate added in the step 1 is 16:17:(30-72).

3. The method for preparing the fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 1, wherein: In the step 1, the amount of ferric chloride added is 8-32 g / L, and the amount of copper chloride dihydrate added is 8.5-34 g / L.

4. The method for preparing the fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 1, wherein: In the step 1, the amount of potassium ferrocyanide trihydrate added is 21-84 g / L.

5. The method for preparing the fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 1, wherein: In the step 2, the addition amount of the attapulgite / Prussian blue analog nanocomposite material is 5-10 g / L.

6. The method for preparing the fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 1, wherein: The amount of silver nitrate added in step 2 is 3.6-10 g / L.

7. The method for preparing the fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 1, wherein: In the step 3, the amount of 1H,1H,2H,2H-perfluorodecyltriethoxysilane added is 10 mL / L, and the stirring time is 6 h.

8. An antibacterial hydrophobic coating of fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver prepared by the preparation method according to any one of claims 1 to 7.

9. The fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 8, characterized in that The modified Prussian blue analogue nanoparticles are uniformly loaded on the surface of nanorod-shaped attapulgite. The length of the attapulgite is 200-500nm, and the size of the Prussian blue analogue nanoparticles is 5-50nm.

10. Use of the fluorinated silane / attapulgite / copper iron Prussian blue analogue / silver antibacterial hydrophobic coating according to claim 8 in the protection of leather cultural relics, paper cultural relics, bamboo and wooden articles, and murals.

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