Photocatalytic antibacterial detergent based on graphite carbon coated bimetallic and preparation method thereof

Abstract

The invention relates to the technical field of detergents, and discloses a graphite carbon coated bimetallic-based photocatalytic antibacterial detergent and a preparation method thereof, the graphite carbon coated bimetallic-based photocatalytic antibacterial detergent comprises the following components by weight: 0.1-1.0% of a NiO / PdO coated C nano composite material; 7%-25% of an anionic surfactant; 5%-10% of a nonionic surfactant; 0.5%-2% of a chelating agent; 0.1%-1.5% of an enzyme preparation; 0.3%-1% of a conditioning agent; and the balance of deionized water. The NiO / PdO-C nano composite material can efficiently generate reactive oxygen free radicals through the unique bimetallic heterojunction effect under the irradiation of visible light or sunlight, the strong oxidizing free radicals can thoroughly decompose chromophoric groups of stubborn organic pigments and destroy microbial cell structures, meanwhile, the graphite carbon layer tightly wraps the internal NiO / PdO active center, and therefore the catalytic activity of the NiO / PdO-C nano composite material is improved, and the service life of the NiO / PdO-C nano composite material is prolonged. And agglomeration and inactivation of nanoparticles can be prevented, and the service life of the product is prolonged.

Description

Technical Field

[0001] This invention relates to the field of detergent technology, specifically to a photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds and its preparation method. Background Technology

[0002] Laundry is a basic daily necessity, and traditional detergents mainly rely on a combination of chemical surfactants and biological enzymes to remove stains. However, with the upgrading of consumption and the increasing awareness of health and environmental protection, the limitations of this traditional technology are becoming increasingly apparent.

[0003] First, for stubborn organic pigment stains, such as juice, tea, and red wine, the chromophores have stable structures that traditional detergents struggle to break down effectively, resulting in limited stain removal. Consumers often have to resort to strong bleach for additional treatment, which is not only cumbersome but also carries risks of damaging fabric fibers, causing fading, and leaving chemical residues.

[0004] Secondly, in terms of hygiene and antibacterial properties, traditional detergents generally lack long-lasting and broad-spectrum antibacterial functions. Although they can remove some dirt, they are unable to effectively kill or inhibit pathogenic microorganisms hidden deep within the fibers, and cannot prevent cross-infection during the washing process. Especially in humid environments, residual bacteria can easily regenerate, posing a potential threat to the user's health.

[0005] Furthermore, in terms of cost, the active ingredients required by the traditional detergent industry heavily rely on high-cost chemical compounds, and existing technologies lack feasible solutions for the high-value application of waste agricultural and forestry biomass in the detergent field. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals and its preparation method. This detergent not only achieves efficient and gentle cleaning but also possesses independent photocatalytic antibacterial capabilities and can transform waste resources into high-value-added materials, thereby fundamentally improving the overall performance and environmental friendliness of the product.

[0007] To achieve this objective, the present invention adopts the following technical solution: On one hand, the present invention provides a photocatalytic antibacterial detergent based on graphite carbon-coated bimetal, comprising the following components by weight percentage: NiO / PdO@C nanocomposite material: 0.1%-1.0%; Anionic surfactants 7%-25%; Nonionic surfactants 5%-10%; Chelating agent 0.5%-2%; Enzyme preparations: 0.1%-1.5%; Regulator 0.3%-1%; Deionized water balance; Among them, the NiO / PdO@C nanocomposite material uses waste lignocellulosic biomass to prepare a carbon source solution, and adds nickel salt and palladium salt to the carbon source solution to form a precipitate containing metal precursors. The precipitate is then subjected to high-temperature heat treatment to obtain the nanocomposite material.

[0008] A preferred embodiment of a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals includes the following components: NiO / PdO@C nanocomposite material: 0.1%-0.3%; Anionic surfactants 10%-12%; Nonionic surfactants 5%-7%; Chelating agent 0.5%-0.8%; Enzyme preparations: 0.5%-0.9%; Regulator 0.7%-1%; Deionized water balance.

[0009] As a preferred embodiment of a photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds, the anionic surfactant is fatty alcohol polyoxyethylene ether sulfate, and the nonionic surfactant is an alkyl glycoside.

[0010] As a preferred embodiment of a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals, the chelating agent is ethylenediaminetetraacetic acid.

[0011] As a preferred embodiment of a photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds, the enzyme preparation is one or more of protease and lipase.

[0012] As a preferred embodiment of a photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds, the modifier is one or more of sodium citrate and phenoxyethanol.

[0013] On the other hand, the present invention provides a method for preparing the above-mentioned photocatalytic antibacterial detergent based on graphite carbon-coated bimetal, comprising the following steps: S1. Preparation of NiO / PdO@C nanocomposite materials; S2. Add 70% of the amount of deionized water to the main reactor and heat to 40-50℃. Then add the chelating agent and regulator and stir until completely dissolved. S3. Slowly add anionic and nonionic surfactants while stirring at low speed to ensure thorough mixing and formation of a surfactant mixture system; S4. Add the NiO / PdO@C nanocomposite powder to the remaining deionized water to form a high-concentration slurry. Use a high-shear homogenizer to efficiently homogenize the NiO / PdO@C slurry. S5. Slowly add the dispersed and stable NiO / PdO@C nano slurry to the surfactant mixing system in step S3 and stir until homogeneous. Then stop heating and cool to below 30°C. S6. Add enzyme preparation, preservative and fragrance in sequence, and stir gently. After mixing evenly, degas the mixture to obtain photocatalytic antibacterial detergent.

[0014] As a preferred embodiment of the preparation method of a photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds, step S1 specifically includes: S11. Preparation of carbon source solution: After pyrolysis and carbonization of waste lignocellulose biomass, it is ground into powder, dissolved in water by heating and centrifugation, and the brown supernatant is collected as carbon source solution. S12, Precursor Coprecipitation: Nickel salt and palladium salt are dissolved in the above carbon source solution, and a precipitant and an alkaline regulator are added to form a precipitate containing metal precursors; S13. High-temperature heat treatment: After cleaning and drying the above precipitate, heat treatment is carried out at a temperature of 600°C in an oxygen atmosphere to complete the oxidation and crystallization of NiO and PdO, and at the same time, a stable graphite carbon coating layer is formed on the surface to obtain NiO / PdO@C nanocomposite material.

[0015] Compared with the prior art, the present invention has the following beneficial effects: (1) The core functional additive NiO / PdO@C nanocomposite material used in this invention has a heterojunction structure formed by nickel palladium oxide, which can significantly promote the separation of photogenerated electrons and holes and improve the activity of the catalyst under light. Under visible light or sunlight, through its unique bimetallic heterojunction effect, it can efficiently generate active oxygen free radicals. These strong oxidizing free radicals can completely decompose the chromophores of stubborn organic pigments, achieving efficient stain removal without the need for additional treatment with bleach, fundamentally eliminating the problem of damage to fabric fibers and chemical residues. At the same time, the active free radicals generated in the photocatalytic process can not only decompose stains, but also penetrate the cell wall of microorganisms and effectively destroy their internal structure, thereby achieving broad-spectrum killing of a variety of common pathogens, providing higher hygiene and safety guarantees for the washing process and the wearing of clothes after washing.

[0016] (2) The core functional additive NiO / PdO@C nanocomposite material used in this invention has a stable and porous graphite carbon shell. The graphite carbon layer can tightly encapsulate the internal NiO / PdO active centers, so that the composite material has excellent barrier protection in the complex chemical environment of the detergent. This structure can significantly inhibit the leaching of active metal ions, prevent the aggregation and deactivation of nanoparticles, and increase the adsorption active sites, thereby ensuring the performance consistency of the detergent during storage and use, and extending the effective life of the product.

[0017] (3) This invention uses widely available and inexpensive waste lignocellulosic biomass as a precursor for graphite carbon coating, realizing the high-value utilization of waste resources and reducing preparation costs. Detailed Implementation

[0018] To better illustrate the objectives, technical solutions, and advantages of this invention, the following embodiments are provided. Obviously, the following embodiments are only a part of the embodiments of this invention, and not all of them; it should be understood that the embodiments of this invention are only used to illustrate the technical effects of this invention, and not to limit the scope of protection of this invention.

[0019] All raw materials used in the examples are commercially available; unless otherwise specified, the reagents, methods and equipment used in this invention are conventional reagents, methods and equipment in this technical field.

[0020] Example 1: This embodiment is based on a photocatalytic antibacterial detergent made from graphite carbon-coated bimetallic materials, which is obtained by reacting the following raw materials in weight percentage: NiO / PdO@C nanocomposite material 0.1%; 10% fatty alcohol polyoxyethylene ether sulfate; alkyl glycosides 5%; 0.5% ethylenediaminetetraacetic acid; Protease 0.3%; Lipase 0.2%; Sodium citrate 0.5%; Phenoxyethanol 0.2%; Deionized water balance.

[0021] When preparing a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals, the raw materials are added in the amounts described above, including the following steps: (1) Preparation of NiO / PdO@C nanocomposite materials; Carbon source solution preparation: After pyrolysis and carbonization of waste lignocellulose biomass such as coconut shell fiber, it is ground into powder, dissolved in water by heating and centrifugation, and the brown supernatant is collected as carbon source solution; Precursor coprecipitation: Nickel nitrate hexahydrate and palladium chloride are dissolved in the above carbon source solution, and dimethylglyoxime and NaOH are added to form a precipitate containing metal precursors; High-temperature heat treatment: After cleaning and drying the above precipitate, heat treatment is carried out at 600℃ in an oxygen atmosphere to complete the oxidation crystallization of NiO and PdO, and at the same time, a stable graphite carbon coating layer is formed on the surface to obtain NiO / PdO@C nanocomposite material.

[0022] (2) Add 70% of the amount of deionized water to the main reactor and heat it to 40-50°C. Then add ethylenediaminetetraacetic acid and sodium citrate and stir until completely dissolved. (3) Add fatty alcohol polyoxyethylene ether sulfate and alkyl glycoside slowly under low-speed stirring to ensure thorough mixing to form a surfactant mixture system; (4) Add NiO / PdO@C nanocomposite powder to the remaining deionized water to form a high-concentration slurry, and use a high-shear homogenizer to homogenize the NiO / PdO@C slurry efficiently; (5) Slowly add the dispersed and stable NiO / PdO@C nano slurry to the surfactant mixing system in step S3 and stir evenly. Then stop heating and cool to below 30°C. (6) Add protease, lipase, phenoxyethanol and fragrance in sequence, and stir gently. After mixing evenly, degas the mixture to obtain a photocatalytic antibacterial detergent.

[0023] Example 2: This embodiment is based on a photocatalytic antibacterial detergent made from graphite carbon-coated bimetallic materials, which is obtained by reacting the following raw materials in weight percentage: NiO / PdO@C nanocomposite material 0.3%; 10% fatty alcohol polyoxyethylene ether sulfate; alkyl glycosides 5%; 0.5% ethylenediaminetetraacetic acid; Protease 0.3%; Lipase 0.2%; Sodium citrate 0.5%; Phenoxyethanol 0.2%; Deionized water balance.

[0024] When preparing a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals, the raw materials are added in the amounts described above, including the following steps: (1) Preparation of NiO / PdO@C nanocomposite materials; Carbon source solution preparation: After pyrolysis and carbonization of waste lignocellulose biomass such as coconut shell fiber, it is ground into powder, dissolved in water by heating and centrifugation, and the brown supernatant is collected as carbon source solution; Precursor coprecipitation: Nickel nitrate hexahydrate and palladium chloride are dissolved in the above carbon source solution, and dimethylglyoxime and NaOH are added to form a precipitate containing metal precursors; High-temperature heat treatment: After cleaning and drying the above precipitate, heat treatment is carried out at 600℃ in an oxygen atmosphere to complete the oxidation crystallization of NiO and PdO, and at the same time, a stable graphite carbon coating layer is formed on the surface to obtain NiO / PdO@C nanocomposite material.

[0025] (2) Add 70% of the amount of deionized water to the main reactor and heat it to 40-50°C. Then add ethylenediaminetetraacetic acid and sodium citrate and stir until completely dissolved. (3) Add fatty alcohol polyoxyethylene ether sulfate and alkyl glycoside slowly under low-speed stirring to ensure thorough mixing to form a surfactant mixture system; (4) Add NiO / PdO@C nanocomposite powder to the remaining deionized water to form a high-concentration slurry, and use a high-shear homogenizer to homogenize the NiO / PdO@C slurry efficiently; (5) Slowly add the dispersed and stable NiO / PdO@C nano slurry to the surfactant mixing system in step S3 and stir evenly. Then stop heating and cool to below 30°C. (6) Add protease, lipase, phenoxyethanol and fragrance in sequence, and stir gently. After mixing evenly, degas the mixture to obtain a photocatalytic antibacterial detergent.

[0026] Example 3: This embodiment is based on a photocatalytic antibacterial detergent made from graphite carbon-coated bimetallic materials, which is obtained by reacting the following raw materials in weight percentage: NiO / PdO@C nanocomposite material 0.4%; 10% fatty alcohol polyoxyethylene ether sulfate; alkyl glycosides 5%; 0.5% ethylenediaminetetraacetic acid; Protease 0.3%; Lipase 0.2%; Sodium citrate 0.5%; Phenoxyethanol 0.2%; Deionized water balance.

[0027] When preparing a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals, the raw materials are added in the amounts described above, including the following steps: (1) Preparation of NiO / PdO@C nanocomposite materials; Carbon source solution preparation: After pyrolysis and carbonization of waste lignocellulose biomass such as coconut shell fiber, it is ground into powder, dissolved in water by heating and centrifugation, and the brown supernatant is collected as carbon source solution; Precursor coprecipitation: Nickel nitrate hexahydrate and palladium chloride are dissolved in the above carbon source solution, and dimethylglyoxime and NaOH are added to form a precipitate containing metal precursors; High-temperature heat treatment: After cleaning and drying the above precipitate, heat treatment is carried out at 600℃ in an oxygen atmosphere to complete the oxidation crystallization of NiO and PdO, and at the same time, a stable graphite carbon coating layer is formed on the surface to obtain NiO / PdO@C nanocomposite material.

[0028] (2) Add 70% of the amount of deionized water to the main reactor and heat it to 40-50°C. Then add ethylenediaminetetraacetic acid and sodium citrate and stir until completely dissolved. (3) Add fatty alcohol polyoxyethylene ether sulfate and alkyl glycoside slowly under low-speed stirring to ensure thorough mixing to form a surfactant mixture system; (4) Add NiO / PdO@C nanocomposite powder to the remaining deionized water to form a high-concentration slurry, and use a high-shear homogenizer to homogenize the NiO / PdO@C slurry efficiently; (5) Slowly add the dispersed and stable NiO / PdO@C nano slurry to the surfactant mixing system in step S3 and stir evenly. Then stop heating and cool to below 30°C. (6) Add protease, lipase, phenoxyethanol and fragrance in sequence, and stir gently. After mixing evenly, degas the mixture to obtain a photocatalytic antibacterial detergent.

[0029] Comparative Example 1: The detergent in this comparative example was obtained by reacting the following raw materials by weight percentage: 10% fatty alcohol polyoxyethylene ether sulfate; alkyl glycosides 5%; 0.5% ethylenediaminetetraacetic acid; Protease 0.3%; Lipase 0.2%; Sodium citrate 0.5%; Phenoxyethanol 0.2%; Deionized water balance.

[0030] When preparing detergent, add the raw materials according to the above-mentioned amounts, including the following steps: (1) Add deionized water to the main reactor and heat it to 40-50°C. Then add ethylenediaminetetraacetic acid and sodium citrate and stir until completely dissolved. (2) Add fatty alcohol polyoxyethylene ether sulfate and alkyl glycoside slowly under low speed stirring to ensure thorough mixing to form a surfactant mixture system. Then stop heating and cool to below 30°C. (3) Add protease, lipase, phenoxyethanol and fragrance in sequence, and stir gently. After mixing evenly, degas the mixture to obtain a detergent that does not contain NiO / PdO@C nanocomposite material.

[0031] Comparative Example 2: The detergent used in this comparative example was a standard detergent formulated in accordance with Appendix B of the national standard GB / T 13174-2021 "Determination of detergency and recycle performance of detergents for clothing".

[0032] The standard detergent composition is as follows: Alkylbenzene sulfonic acid (based on active ingredient) 8%, polyethoxylated fatty alcohol (average EO addition number of 9) 4%, ethoxylated alkyl sulfate sodium (2EO, based on active ingredient) 2%, triethanolamine 0.5%, trisodium citrate dihydrate 0.6%, preservative 0.1%, water balance.

[0033] Standard detergent laboratory preparation method: Add each ingredient to a certain amount of water in sequence, stirring to dissolve (heating if necessary), and adjust the pH of the solution to 8.5-9.0 with sodium hydroxide. Then, add water to bring the solution to 100%.

[0034] Comparative Example 3: This comparative example uses Libai brand bleach sold in the market, whose active ingredients include hydrogen peroxide, surfactants, and fragrances.

[0035] The effects of the examples and comparative examples were measured: I. Bleaching Power Test 1. Making soiled cloth 1.1 Cut 36 square pieces of standard white cotton fabric into 6cm*6cm square pieces along the warp and weft lines, put them into the washing machine, and wash using the normal program (total washing time 51min, including one 13min main wash, two rinses, and one 5min spin dry).

[0036] 1.2 After the washing machine finishes washing, take out the cloth and place it in a suitable container. Wash it with deionized water at about 60℃ for 30 minutes.

[0037] 1.3 After washing again, take out the cloth, spin dry, and iron it flat with an electric iron to obtain a blank soiled cloth for later use.

[0038] 1.4 The whiteness value of the blank soiled cloth shall be determined according to the method of GB / T 13174-2021 and recorded as F0.

[0039] 1.5 Immerse the prepared blank soiled cloth thoroughly in the red dye solution. If the cloth is not fully immersed, apply some pressure to the cloth. After 20 minutes, remove it and air dry at room temperature to obtain the dyed cloth. If the cloth is wrinkled, it can be ironed flat with an electric iron.

[0040] 1.6 The whiteness value of dye-stained fabric shall be determined according to the method of GB / T 13174-2021 and denoted as F1.

[0041] 2. Measurement Method 2.1 Prepare 0.2% test cleaning solutions from the detergent stock solutions of Examples 1-3 and Comparative Examples 1-3 respectively. Place them under a full-spectrum LED lamp and control the room temperature at 26°C. Take 4 pieces of dye-stained cloth and immerse them in the test cleaning solution for 13 minutes. The dye-stained cloth must be completely submerged.

[0042] 2.2 According to the stain removal and washing test in GB / T 13174-2021, the dye-stained cloth after soaking was rinsed, and after the last rinse and dehydration, the test piece was taken out and placed in an enamel dish to dry at room temperature, and the whiteness F2 was measured.

[0043] 3. Calculation of dye removal rate In the formula, i represents the i-th experimental group; F 0i -F 1i F represents the whiteness value of the soiled cloth sample in the i-th test group when stained with the experimental stain; 2i -F 1i The whiteness value of the soiled cloth sample after washing away the experimental stains in the i-th test group.

[0044] 4. Experimental Data Table 1: Whiteness values ​​of detergents from Examples 1-3 Table 2: Whiteness values ​​of detergents from Comparative Examples 1-3 5. Experimental Conclusions (1) By comparing the whiteness values ​​of Examples 1-3, it can be seen that when the amount of NiO / PdO@C nanocomposite material added is in the range of 0.3%, the bleaching power of the detergent is positively correlated with the amount added.

[0045] (2) By comparing the whiteness values ​​of Examples 1-3 and Comparative Example 3, it can be seen that the detergent with added NiO / PdO@C nanocomposite material has a bleaching power comparable to that of ordinary bleach on the market.

[0046] (3) By comparing the whiteness values ​​of Comparative Examples 1-2, it can be seen that the bleaching power of the detergent without the addition of NiO / PdO@C nanocomposite material is not up to standard and is comparable to that of ordinary detergent.

[0047] Experiments have confirmed that this invention achieves a fundamental improvement in bleaching power by adding NiO / PdO@C nanocomposite materials to detergents. This is mainly because the NiO / PdO@C nanocomposite materials have a heterojunction structure formed by nickel-palladium oxides, which can significantly promote the separation of photogenerated electrons and holes and improve the activity of the catalyst under light. Under visible light or sunlight irradiation, through its unique bimetallic heterojunction effect, it can efficiently generate active oxygen free radicals. These strong oxidizing free radicals can completely decompose the chromophores of stubborn organic pigments, achieving efficient stain removal without the need for additional treatment with bleach, fundamentally eliminating the problems of damage to fabric fibers and chemical residues.

[0048] Meanwhile, modern clothing dyes (especially reactive or disperse dyes used in textiles) are designed with high light and oxidation stability to ensure that clothing does not easily fade under sunlight exposure and traditional bleaching. In contrast, everyday stains (such as food coloring, coffee stains, and juice stains) have relatively unstable molecular structures and are more easily oxidized and decomposed by free radicals generated by photocatalysis. Therefore, the photocatalytic antibacterial detergent of this invention will not affect clothing dyes or fabric fibers.

[0049] II. Detergent cleaning power test 1. Select standard soiled cloths containing carbon black, protein, and sebum, and determine the whiteness value J0 of the standard soiled cloths according to the method in GB / T 13174-2021.

[0050] 2. Referring to GB / T 13174-2021, the detergent samples of Examples 1-3 and Comparative Examples 1-2 were cleaned and rinsed under a full-spectrum LED lamp. After the last rinse and dehydration, the test pieces were taken out and placed in an enamel dish to air dry at room temperature, and the whiteness value J1 was measured.

[0051] 3. Decontamination rate calculation 3.1 Calculation of the stain removal value of a certain type of soiled cloth: In the formula, i represents the i-th type of soiled cloth sample; Jwi represents the spectral reflectance of the i-th type of soiled cloth sample after washing; and Jsi represents the spectral reflectance of the i-th type of soiled cloth sample before washing.

[0052] 3.2 Calculation of the ratio of removal rate to standard detergent In the formula The stain removal rate of the sample; This represents the stain removal rate of standard detergents.

[0053] 4. Experimental Data Table 3: Decontamination rate ratio data of Examples 1-3 and Comparative Examples 1-2 5. Experimental Conclusions As can be seen from the stain removal ratio data of Examples 1-3, the detergent with added NiO / PdO@C nanocomposite material has significantly enhanced stain removal power for the three types of soiled cloths, especially for cloths soiled with protein and sebum.

[0054] III. Bactericidal and Antimicrobial Properties Tests 1. According to the industry standard QB / T2738-2023 Evaluation Method for Antibacterial and Bacteriostatic Effects of Daily Chemical Products, Staphylococcus aureus and Escherichia coli were selected, and the bactericidal effect was tested using Method 7.2 Test Method for Bactericidal Effect of Daily Chemical Products (Suspension Quantitative Method), and the antibacterial effect was tested using Method 7.4 Test Method for Antibacterial or Bacteriostatic Effect of Fabric Detergents (Simulation Method).

[0055] 2. Experimental Data Table 4: Bactericidal and antibacterial rate data for Examples 1-3 3. Experimental Conclusions According to the results of sterilization and antibacterial tests, the fabrics washed with the detergents in Examples 1-3 showed a sterilization rate of far exceeding 90% against Staphylococcus aureus and Escherichia coli. This is mainly because the active free radicals generated by the NiO / PdO@C nanocomposite material during the photocatalytic process can not only decompose stains, but also penetrate the cell walls of microorganisms and effectively destroy their internal structure, thereby achieving broad-spectrum killing of a variety of common pathogens.

[0056] IV. Stability and Long-Term Performance Testing 1. After placing Examples 1-3 at 50°C for 30 days, test them according to the above-described bleaching power and detergency test methods, and compare the test results.

[0057] 2. Experimental Data Table 5: Experimental data of Examples 1-3 after being placed at 50°C for 30 days 3. Experimental Conclusions According to the bactericidal and antibacterial test results, after 30 days of accelerated aging at 50°C, the detergents containing NiO / PdO@C nanocomposite materials in Examples 1-3 showed no significant reduction in appearance, detergency, and bactericidal / antibacterial rates, demonstrating a certain degree of stability. This is mainly because the NiO / PdO@C nanocomposite material has a stable and porous graphite carbon shell. The graphite carbon layer can tightly encapsulate the internal NiO / PdO active centers, giving the composite material excellent barrier protection in the complex chemical environment of the detergent solution. This structure can significantly inhibit the leaching of active metal ions, prevent the aggregation and deactivation of nanoparticles, and increase adsorption active sites, thereby ensuring the consistency of detergent performance during storage and use, and extending the effective life of the product.

[0058] Since NiO and PdO are in a stable oxide state and protected by a graphite carbon layer, the risk of allergies or toxicity caused by elemental metals or free ions is avoided. Furthermore, the nanoparticles are mainly bonded to the surface of clothing and other fibers through physical interactions such as van der Waals forces and electrostatic attraction. After rinsing, the nanoparticles will be carried away by the water flow, avoiding the risk of metal residue.

[0059] Meanwhile, this invention, based on graphite carbon-coated bimetallic photocatalytic antibacterial detergent, uses widely available and low-cost waste lignocellulosic biomass as a precursor for the graphite carbon coating layer, realizing the high-value utilization of waste resources. Although metal is used in the NiO / PdO@C nanocomposite material, the amount of metal used is extremely low, and the preparation cost is reduced compared to traditional detergents.

[0060] It should be stated that the above-described specific embodiments are merely preferred embodiments of the present invention and the technical principles employed. Those skilled in the art should understand that various modifications, equivalent substitutions, and variations can be made to the present invention. However, such variations, as long as they do not depart from the spirit of the present invention, should be within the scope of protection of the present invention. Furthermore, some terminology used in this specification and claims is not limiting, but merely for ease of description.

Claims

1. A photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds, characterized in that, By weight percentage, it includes the following components: NiO / PdO@C nanocomposite material: 0.1%-1.0%; Anionic surfactants 7%-25%; Nonionic surfactants 5%-10%; Chelating agent 0.5%-2%; Enzyme preparations: 0.1%-1.5%; Regulator 0.3%-1%; Deionized water balance; Among them, the NiO / PdO@C nanocomposite material uses waste lignocellulosic biomass to prepare a carbon source solution, and adds nickel salt and palladium salt to the carbon source solution to form a precipitate containing metal precursors. The precipitate is then subjected to high-temperature heat treatment to obtain the nanocomposite material.

2. The photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds according to claim 1, characterized in that, Includes the following components: NiO / PdO@C nanocomposite material: 0.1%-0.3%; Anionic surfactants 10%-12%; Nonionic surfactants 5%-7%; Chelating agent 0.5%-0.8%; Enzyme preparations: 0.5%-0.9%; Regulator 0.7%-1%; Deionized water balance.

3. The photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds according to claim 2, characterized in that, The anionic surfactant is fatty alcohol polyoxyethylene ether sulfate, and the nonionic surfactant is alkyl glycoside.

4. The photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds according to claim 2, characterized in that, The chelating agent is ethylenediaminetetraacetic acid.

5. The photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds according to claim 2, characterized in that, The enzyme preparation is one or more of protease and lipase.

6. The photocatalytic antibacterial detergent based on graphite carbon-coated bimetallic compounds according to claim 2, characterized in that, The regulator is one or more of sodium citrate and phenoxyethanol.

7. A method for preparing a photocatalytic antibacterial detergent based on graphite carbon-coated bimetals as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. Preparation of NiO / PdO@C nanocomposite materials; S2. Add 70% of the amount of deionized water to the main reactor and heat to 40-50℃. Then add the chelating agent and regulator and stir until completely dissolved. S3. Slowly add anionic and nonionic surfactants while stirring at low speed to ensure thorough mixing and formation of a surfactant mixture system; S4. Add the NiO / PdO@C nanocomposite powder to the remaining deionized water to form a high-concentration slurry. Use a high-shear homogenizer to efficiently homogenize the NiO / PdO@C slurry. S5. Slowly add the dispersed and stable NiO / PdO@C nano slurry to the surfactant mixing system in step S3 and stir until homogeneous. Then stop heating and cool to below 30°C. S6. Add enzyme preparation, preservative and fragrance in sequence, and stir gently. After mixing evenly, degas the mixture to obtain photocatalytic antibacterial detergent.

8. The preparation method of the photocatalytic antibacterial detergent based on graphite carbon-coated bimetal as described in claim 7, characterized in that, Step S1 specifically includes: S11. Preparation of carbon source solution: After pyrolysis and carbonization of waste lignocellulose biomass, it is ground into powder, dissolved in water by heating and centrifugation, and the brown supernatant is collected as carbon source solution. S12, Precursor Coprecipitation: Nickel salt and palladium salt are dissolved in the above carbon source solution, and a precipitant and an alkaline regulator are added to form a precipitate containing metal precursors; S13. High-temperature heat treatment: After cleaning and drying the above precipitate, heat treatment is carried out at a temperature of 600°C in an oxygen atmosphere to complete the oxidation and crystallization of NiO and PdO, and at the same time, a stable graphite carbon coating layer is formed on the surface to obtain NiO / PdO@C nanocomposite material.

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