Inorganic nano disinfectant and preparation method thereof

Abstract

The invention discloses an inorganic nano disinfectant and a preparation method thereof, and belongs to the technical field of nano materials and disinfection. The preparation method comprises the following steps: adding copper salt, zinc salt, silver salt and deionized water into a reaction kettle, and carrying out hydrothermal reaction to obtain a solution A; adding a surfactant and an alkaline pH regulator into the solution A, regulating the pH value of the solution, and carrying out heat preservation reaction to obtain a solution B; and adding an acidic pH regulator into the solution B to regulate the pH value of the solution, thereby obtaining the inorganic nano disinfectant. Microbial cell membranes and DNA / RNA are destroyed through metal ions, and the inactivation rates of H1N1 viruses, escherichia coli (ATCC 25922), staphylococcus aureus (ATCC 6538) and mites all reach 100%. Meanwhile, the pH is close to neutral, corrosion is avoided, and residual metal ions can be recycled through precipitation. According to the disinfectant prepared by the invention, low-concentration, broad-spectrum and long-acting disinfection of the disinfectant is realized by controllably synthesizing a nano-copper, zinc and silver composite system and combining pH regulation and surface modification technologies.

Description

Technical Field

[0001] The present invention relates to the field of nanomaterials and disinfection technology, and in particular to an inorganic nano disinfectant and a preparation method thereof. Background Art

[0002] Existing disinfectants, such as chlorine-containing preparations, alcohols, or quaternary ammonium salts, suffer from pungent odors, strong corrosiveness, and the tendency to develop drug resistance. These disinfectants face multiple technical bottlenecks in their application, primarily due to the inherent flaws of traditional chemical disinfectants, metal ion disinfectants, and nanomaterial disinfectants. These factors make it difficult to meet modern disinfection requirements for low-concentration, broad-spectrum, and long-lasting efficacy.

[0003] Traditional chemical disinfectants (such as sodium hypochlorite) are low-cost but have a strong pungent odor and are prone to corrosive effects on metal instruments. Alcohol disinfectants (such as 75% ethanol) have a short duration of action, inactivate less than 50% of hydrophilic viruses (such as norovirus), and at high concentrations can easily lead to the formation of a protective layer in microorganisms. Quaternary ammonium disinfectants (such as benzalkonium bromide) can induce microbial resistance with long-term use and are easily neutralized by anionic substances, resulting in a fungal kill rate of only 60-70%. Traditional metal ion disinfectants (such as silver ion) are highly stable, but the spectrum of action of a single metal ion is limited. Silver ion inactivates the H1N1 virus at a concentration of ≥100 ppm and for more than 30 minutes, while its contact kill rate against dust mites is only 45% over 24 hours. Copper ion is highly effective against bacteria (MIC ≤ 1 ppm) but is ineffective against viruses and fungi, and high concentrations (>50 ppm) can cause hemolysis. Furthermore, metal ions easily react and precipitate with environmental ions, posing a significant risk of toxicity when used at high concentrations. Nanometal materials can enhance their bactericidal properties due to their high surface area and high activity, but individual nanometals tend to aggregate and become inactivated. Chemical reduction methods require toxic reducing agents (such as sodium borohydride) and produce highly polluted wastewater (every ton of nanosilver produces 5 tons of boron-containing wastewater), while physical methods are expensive. Furthermore, existing nanodisinfectants suffer from unstable pH control, impacting dispersibility and safety.

[0004] Therefore, developing controllable synthesis of nano-metal composite systems and combining pH regulation and surface modification technology to optimize dispersibility and mechanism of action has become a key direction to break through the existing bottleneck. Summary of the Invention

[0005] The purpose of the present invention is to provide an inorganic nano disinfectant and a preparation method thereof, which realizes low-concentration, broad-spectrum, long-lasting disinfection of the disinfectant by controllably synthesizing a nano-copper, zinc, and silver composite system and combining pH regulation and surface modification technology.

[0006] To achieve the above object, the present invention provides a method for preparing an inorganic nano disinfectant, which specifically comprises the following steps:

[0007] (1) adding copper salt, zinc salt, silver salt and deionized water into a reaction kettle and performing a hydrothermal reaction to obtain solution A;

[0008] (2) adding a surfactant and an alkaline pH regulator to solution A to adjust the pH of the solution, and then heat-retaining the solution to obtain solution B;

[0009] (3) Adding an acidic pH regulator to solution B to adjust the pH value of the solution to obtain an inorganic nano disinfectant.

[0010] Preferably, in step (1), the copper salt is any one or more of copper sulfate and copper chloride, the zinc salt is any one or more of zinc acetate, zinc chloride, and zinc sulfate, and the silver salt is one or more of silver nitrate, silver sulfate, and silver acetate.

[0011] Preferably, in step (1), the ratio of copper salt, zinc salt, silver salt and deionized water is 0.2 mol: 0.02-0.04 mol: 0.003-0.006 mol: 1 L.

[0012] Preferably, in step (1), the temperature of the hydrothermal reaction is 70-90° C., and the time of the hydrothermal reaction is 90-120 min.

[0013] Preferably, in step (2), the surfactant is one or more of PVP, SDS, and PEG; the alkaline pH regulator is one or more of ammonia water, sodium hydroxide, sodium bicarbonate, potassium hydroxide, ammonium hydroxide, and calcium hydroxide, and the pH value of the solution is adjusted to 8-9.

[0014] Preferably, in step (2), the amount of surfactant added is related to the content of copper salt in solution A, and the ratio of surfactant to copper salt is 1-2g:100g.

[0015] Preferably, in step (2), the insulation reaction time is 30-60 minutes.

[0016] Preferably, in step (3), the acidic pH regulator is one or more of citric acid, dilute sulfuric acid, and dilute hydrochloric acid.

[0017] Preferably, in step (3), the pH value of the solution is adjusted to 6.5-7.

[0018] The present invention also provides an inorganic nano disinfectant prepared by the above preparation method.

[0019] The invention first hydrothermally reacts a mixed salt of copper, zinc, and silver ions to form metal oxides or composite nanoparticles. High temperature and high pressure promote the decomposition of the metal salts into ions, which then form nanoparticles through nucleation and growth. Copper is the primary component, supplemented by zinc and a trace amount of silver. The high copper content provides a broad-spectrum antibacterial foundation, while zinc enhances stability and silver strengthens the killing of viruses and drug-resistant bacteria.

[0020] The pH is then adjusted to 8-9 using an alkaline agent such as ammonia, prompting the metal ions to form hydroxide / oxide nanoparticles. Simultaneously, a surfactant coats the particle surface through physical adsorption or chemical bonding, preventing oxidation and agglomeration. The ratio of surfactant to copper salt ensures complete coverage of the particle surface, creating steric hindrance or electrostatic stabilization, extending the nanoparticle's dispersibility and sustained release.

[0021] Finally, a weak acid such as citric acid is added to adjust the pH to 6.5-7. This neutralizes the alkaline environment while allowing its carboxyl groups to form complexes with metal ions (such as silver citrate), enhancing particle stability and controlling the rate of ion release. A neutral pH reduces corrosion to instruments and the environment, and residual metal ions can be recovered through precipitation, reducing ecotoxicity.

[0022] Therefore, the present invention provides an inorganic nano disinfectant and a preparation method thereof, which has the following beneficial effects:

[0023] (1) Broad spectrum and high efficiency: The three metals synergistically cover different microbial targets, breaking through the resistance limitations of a single metal. Nanoparticles adsorb on the surface of microorganisms, and the released metal ions bind to the sulfhydryl (-SH) groups on the surface of membrane proteins, destroying the integrity of the microbial cell membrane. After penetrating the cells, the metal ions bind to nucleic acids and interfere with replication, or produce reactive oxygen species (ROS) that inactivate DNA / RNA. The inactivation rate for H1N1 virus, Escherichia coli (ATCC 25922), Staphylococcus aureus (ATCC 6538), and mites is 100%;

[0024] (2) Environmentally friendly: pH is close to neutral, non-corrosive, and residual metal ions can be recovered by precipitation;

[0025] (3) Long-term stability: Surfactants coat metal ion nanoparticles to prevent oxidation and aggregation, while controlling the slow release of metal ions, extending the antibacterial effect and inhibiting microbial regeneration. The high specific surface area of ​​nanoparticles enhances the contact efficiency with microorganisms.

[0026] (4) Low cost: Raw materials are readily available, the preparation process is simple, and it is suitable for industrial production.

[0027] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention is a flow chart for the preparation of the inorganic nano disinfectant. DETAILED DESCRIPTION

[0029] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. Any other changes, modifications, substitutions, combinations, simplifications made without violating the spirit and principles of the present invention should all be equivalent replacement modes and are included within the scope of protection of the present invention. In addition, it should be understood that after reading the contents of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims appended to this application and all belong to the scope of protection of the present invention.

[0030] References to "embodiments" herein mean that the specific features, structures, or characteristics described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the word "embodiment" in various places in the specification does not necessarily refer to the same embodiment, nor does it particularly limit its independence or relevance to other embodiments. In principle, in this application, as long as there are no technical contradictions or conflicts, the various technical features mentioned in the embodiments can be combined in any manner to form a corresponding implementable technical solution.

[0031] Unless otherwise defined, the technical terms used herein have the same meanings as those generally understood by those skilled in the art to which this application belongs; the use of relevant terms herein is only for describing specific embodiments and is not intended to limit this application.

[0032] Unless otherwise specified in the present invention, the reagents, instruments, and equipment used are those commonly used by those skilled in the art.

[0033] Example 1

[0034] This embodiment provides a method for preparing an inorganic nano disinfectant, which specifically includes the following steps:

[0035] (1) 50 g of copper sulfate, 4.4 g of zinc acetate, 0.51 g of silver nitrate, and 1 L of deionized water were added to a reactor and subjected to a hydrothermal reaction at 70°C for 120 min to obtain solution A.

[0036] (2) Add 0.5 g of PVP and ammonia water to solution A, adjust the pH value of the solution to 8, and keep the temperature to react for 60 minutes to obtain solution B.

[0037] (3) Add dilute sulfuric acid to solution B and adjust the pH value of the solution to 6.5 to obtain an inorganic nano disinfectant.

[0038] Example 2

[0039] This embodiment provides a method for preparing an inorganic nano disinfectant, which specifically includes the following steps:

[0040] (1) 34.1 g of copper chloride, 6.24 g of zinc chloride, 1.4 g of silver sulfate, and 1 L of deionized water were added to a reactor and subjected to a hydrothermal reaction at 80° C. for 105 min to obtain solution A.

[0041] (2) Add 0.5 g of SDS and sodium hydroxide to solution A, adjust the pH of the solution to 8.5, and keep the reaction warm for 45 minutes to obtain solution B.

[0042] (3) Add dilute hydrochloric acid to solution B to adjust the pH value of the solution to 6.8 to obtain an inorganic nano disinfectant.

[0043] Example 3

[0044] This embodiment provides a method for preparing an inorganic nano disinfectant, which specifically includes the following steps:

[0045] (1) 50 g of copper sulfate, 11.5 g of zinc sulfate, 1 g of silver acetate, and 1 L of deionized water were added to a reactor and subjected to a hydrothermal reaction at 90° C. for 90 min to obtain solution A.

[0046] (2) Add 1 g of PEG and sodium hydroxide to solution A, adjust the pH value of the solution to 9, and keep the reaction warm for 30 minutes to obtain solution B.

[0047] (3) Add citric acid to solution B and adjust the pH value of the solution to 7 to obtain an inorganic nano disinfectant.

[0048] Test Example 1

[0049] The antibacterial performance of the inorganic nano disinfectants prepared in Examples 1-3 was tested.

[0050] The antibacterial ability test was carried out with reference to the 2002 edition of the "Technical Specification for Disinfection" - 2.1.1.7.4 suspension quantitative sterilization test. The inorganic nano disinfectant stock solutions obtained in Examples 1-3 and each diluted 100 times were used for 20 minutes. The antibacterial rates of the inorganic nano disinfectant stock solutions obtained in Examples 1-3 and each diluted 100 times against Escherichia coli and Staphylococcus aureus are shown in Table 1.

[0051] Table 1

[0052]

[0053] Test Example 2

[0054] The inorganic nano disinfectants prepared in Examples 1-3 were tested for their mite killing performance.

[0055] The mite killing ability test was carried out in accordance with T / CIAA 017-2022 "Test Method and Evaluation 4.4 of Anti-mite and Mite Removal Performance of Household Cleaning Products". The mite killing rates of the inorganic nano disinfectants obtained in Examples 1-3 against mites are shown in Table 2.

[0056] Table 2

[0057]

[0058] As shown in Table 1, the prepared disinfectant solution exhibited 100% inhibition against both Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538), demonstrating its strong, immediate bactericidal properties. Even after 100-fold dilution, the inhibition rates remained as high as 99.45% to 99.97% for E. coli and 99.98% to 99.99% for Staphylococcus aureus, demonstrating its remarkable concentration-resistance and suitability for flexible formulation in practical applications.

[0059] From the data in Table 2, it can be seen that the prepared disinfectant has an inactivation rate of 100% on mites within 1 hour, indicating that it has a rapid and thorough killing effect on mites.

[0060] Therefore, the inorganic nano disinfectant prepared by the present invention has the advantages of broad-spectrum antibacterial, high-efficiency mite killing, environmental friendliness (neutral pH) and low cost, and is suitable for high-efficiency microbial inactivation in the fields of medical care, household, agriculture and public health.

[0061] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing an inorganic nano disinfectant, characterized in that: The specific steps include: (1) adding copper salt, zinc salt, silver salt and deionized water into a reaction kettle and performing a hydrothermal reaction to obtain solution A; (2) adding a surfactant and an alkaline pH regulator to solution A to adjust the pH of the solution, and then heat-retaining the solution to obtain solution B; (3) Adding an acidic pH regulator to solution B to adjust the pH value of the solution to obtain an inorganic nano disinfectant.

2. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (1), the copper salt is any one or more of copper sulfate and copper chloride, the zinc salt is any one or more of zinc acetate, zinc chloride and zinc sulfate, and the silver salt is one or more of silver nitrate, silver sulfate and silver acetate.

3. The method for preparing an inorganic nano disinfectant according to claim 1, wherein In step (1), the ratio of copper salt, zinc salt, silver salt and deionized water is 0.2 mol: 0.02-0.04 mol: 0.003-0.006 mol: 1 L.

4. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (1), the temperature of the hydrothermal reaction is 70-90° C., and the time of the hydrothermal reaction is 90-120 min.

5. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (2), the surfactant is one or more of PVP, SDS, and PEG; the alkaline pH regulator is one or more of ammonia water, sodium hydroxide, sodium bicarbonate, potassium hydroxide, ammonium hydroxide, and calcium hydroxide, and the pH value of the solution is adjusted to 8-9.

6. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (2), the amount of surfactant added is related to the content of copper salt in solution A, and the ratio of surfactant to copper salt is 1-2g:100g.

7. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (2), the heat preservation reaction time is 30-60 minutes.

8. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (3), the acidic pH regulator is one or more of citric acid, dilute sulfuric acid, and dilute hydrochloric acid.

9. The method for preparing an inorganic nano disinfectant according to claim 1, wherein: In step (3), the pH value of the solution is adjusted to 6.5-7.

10. An inorganic nano disinfectant, characterized in that: The inorganic nano disinfectant is prepared by the preparation method according to any one of claims 1 to 9.

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