CN114946880A - A kind of silver-loaded titanium dioxide, preparation method and application thereof, and a disinfection and deodorization spray comprising silver-loaded titanium dioxide - Google Patents

Abstract

The invention relates to the technical field of disinfectants. The invention provides silver-loaded titanium dioxide, a preparation method and application thereof, and a disinfection and odor removal spray containing the silver-loaded titanium dioxide. The silver-loaded titanium dioxide comprises the following components: silver nitrate aqueous solution, titanium dioxide and polyvinylpyrrolidone K30; the initial concentration of the silver nitrate aqueous solution is 0.02-0.08 mol/L; the mass ratio of the titanium dioxide to the silver nitrate aqueous solution is 0.8-2.0: 80-125; the mass ratio of the polyvinylpyrrolidone K30 to the silver nitrate aqueous solution is 0.5-1.5: 80 to 125. The sterilization capability of the silver-loaded titanium dioxide on pathogenic bacteria meets the relevant standard. The disinfection and peculiar smell removal spray prepared by the silver-loaded titanium dioxide not only has the sterilization capability, but also has the peculiar smell removal effect.

Description

A kind of silver-loaded titanium dioxide and its preparation method and application and a kind of disinfection and deodorization spray comprising silver-loaded titanium dioxide

technical field

The invention relates to the technical field of disinfectants, in particular to a silver-loaded titanium dioxide, a preparation method and application thereof, and a disinfection and deodorization spray comprising the silver-loaded titanium dioxide.

Background technique

With the continuous improvement of people's living standards, keeping pets has also become a habit of many families, but pets and pet sheds will breed microorganisms, and pet excrement will cause odor, which will bring a lot of discomfort to people's lives. How to quickly eliminate the microorganisms on pets and in the shed, and remove the odor brought by pets has become a trouble for pet families.

The active ingredients of the commonly used disinfectants in the prior art are chlorine-containing disinfectants, peroxide-based disinfectants, aldehyde-based disinfectants, alcohol-based disinfectants, iodine-containing disinfectants, phenol-based disinfectants, biguanide-based disinfectants and quaternary ammonium Salt-based disinfectants, etc. Chlorine-containing disinfectants have a strong pungent odor, are corrosive to metals and their properties are unstable, and are not suitable for disinfection of pets and their sites; peroxide-based disinfectants are extremely It is easily decomposed into oxygen and water, has no residual toxicity, and will not cause secondary pollution to the environment. However, when the concentration of hydrogen peroxide is too high, it is highly corrosive. Therefore, in actual use, only low-concentration peroxides are often used. Hydrogen, while low-concentration hydrogen peroxide has poor stability; alcohol-based disinfectants are greatly affected by organic matter, and their own odors can easily cause discomfort to pets; iodine-containing disinfectants are corrosive to divalent metals such as copper, aluminum, and steel However, there are often metal cages and other daily necessities in pet living sites, which are prone to corrosion, and iodine-based disinfectants are often accompanied by color. After disinfection, they need to be cleaned to remove the color, which has caused great inconvenience to the disinfection process; Type disinfectants and phenol type disinfectants are chemically stable, but they will pollute the environment; biguanide type disinfectants anionic surfactants can make them ineffective, and the presence of organic matter will weaken their bactericidal effect; quaternary ammonium salt type disinfectants are susceptible to water hardness and Influenced by organic matter, long-term use alone can easily lead to drug resistance.

Among the existing reagents for deodorization and deodorization, the most common ones are activated carbon physical deodorization, biological enzyme deodorization, chemical deodorization such as castor oil alkyd zinc, and plant extract deodorization, which can interact with disinfection ingredients. There are very few ingredients that do not interfere and can exert their respective functions. The principle of activated carbon physical deodorization is to remove odors through physical adsorption of porous substances, but they are insoluble in any solvent; biological enzymes deodorization uses microbial flora to metabolize Or its metabolites, it can effectively degrade common odor factors such as volatile fatty acids and hydrogen sulfide. It is safe for humans and animals, non-toxic, non-irritating, and biodegradable. However, it has a long deodorization and deodorization effect. effect has a greater impact.

To sum up, it can be seen that in the prior art, there is no reagent with both disinfection and deodorization effects, and no reagent is safer for disinfection and deodorization of pets.

Based on the deficiencies of the prior art, it is hereby invented.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a kind of silver-loaded titanium dioxide and its preparation method and application and a kind of disinfection and deodorization spray comprising the silver-loaded titanium dioxide.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a kind of silver-loaded titanium dioxide, comprising the following components:

Silver nitrate aqueous solution, titanium dioxide, polyvinylpyrrolidone K30;

The initial concentration of the silver nitrate aqueous solution is 0.02～0.08mol/L;

The mass ratio of the titanium dioxide to the silver nitrate aqueous solution is 0.8-2.0:80-125;

The mass ratio of the polyvinylpyrrolidone K30 to the silver nitrate aqueous solution is 0.5-1.5:80-125.

Preferably, the titanium dioxide is a mixed crystal form;

The particle size of the titanium dioxide is less than 50 nm.

The present invention also provides the preparation method of the described silver-loaded titanium dioxide, comprising the following steps:

(1) the silver nitrate aqueous solution is mixed with titanium dioxide, polyvinylpyrrolidone K30, ultrasonic, obtains suspension;

(2) subjecting the suspension to a photocatalytic reduction reaction to obtain a mixed solution containing silver-loaded titanium dioxide, and purifying the mixed solution to obtain silver-loaded titanium dioxide.

Preferably, the temperature of the ultrasonic wave in step (1) is 25-37°C;

The ultrasonic time is 10-30 min.

Preferably, the light of the photocatalytic reaction in step (2) is ultraviolet light;

The time of the photocatalytic reaction is 3-6 hours.

Preferably, the method for purification described in step (2) is centrifugation and/or suction filtration;

The rotating speed of the centrifugation is 8000～12000rpm;

The time of the centrifugation is 6～10min;

The pore size of the filter membrane during the suction filtration is 0.22-0.45 μm.

The present invention also provides a sterilizing and deodorizing spray comprising the silver-loaded titanium dioxide or the silver-loaded titanium dioxide prepared by the preparation method, including the following components by volume:

85-95 copies of silver-loaded titanium dioxide or silver-loaded titanium dioxide dilution;

5-15 parts of hydrogen peroxide solution;

The dilution ratio of the silver-loaded titanium dioxide diluent is 1 to 100 times;

The initial concentration of the hydrogen peroxide solution is 28-32 vt%.

Preferably, the disinfecting and deodorizing spray also includes a deodorant with a final concentration of 2-3 vt% and a flavoring agent with a final concentration of 0.5-1.5 vt%;

The deodorant is one or more of bamboo vinegar, fatty alcohol methacrylic acid, soybean ethyl sulfate morpholine, tea extract, and yucca extract;

The flavor enhancer is one or more of honeysuckle extract, mint extract, mugwort extract, and lily extract.

The invention also provides the application of the silver-loaded titanium dioxide or the silver-loaded titanium dioxide prepared by the preparation method in the preparation of a product that kills microorganisms on pet sheds or pets and has the ability to eliminate peculiar smell on pet sheds or pets.

The present invention also provides the use of the disinfecting and deodorizing spray in eliminating microorganisms in pet sheds or pets and eliminating peculiar odors on pet sheds or pets.

The invention provides a silver-loaded titanium dioxide, a preparation method and application thereof, and a disinfection and deodorization spray comprising the silver-loaded titanium dioxide.

The sterilization principle of the silver-loaded titanium dioxide of the present invention is as follows: the silver-loaded titanium dioxide is combined with the sulfhydryl group (-SH) on the bacterial protease, so that the protease loses its activity and leads to the death of the bacteria. When the bacteria die and crack, the nano-silver is in a free state again and is in contact with other bacteria again, so the nano-silver has a relatively long-lasting bactericidal effect. At the same time, the unique bactericidal mechanism of nano-silver has the advantages of wide bactericidal range and less irritation compared with other traditional bactericides such as hypochlorous acid and quaternary ammonium salts. It also kills odor-causing pathogens from the root, thereby reducing odor generation.

The silver-carrying titanium dioxide of the present invention is nano-level silver-carrying titanium dioxide, and the silver-carrying titanium dioxide of the present invention can uniformly distribute Ag on the surface of _TiO2 due to the uniformity of light distribution, which overcomes the instability of a single nanometer silver antibacterial agent and the high temperature Or the problem of easy discoloration in an oxidizing atmosphere.

The particle size of the selected titanium dioxide in the present invention is less than 50 nm, and it is a mixed crystal type nano-titanium dioxide, which has excellent photocatalytic performance. Under the irradiation of ultraviolet light, the existence of a small amount of rutile crystals in the mixed crystals produces electrons from the rutile phase to the The rapid transfer of lower energy levels to the trap sites of the anatase lattice results in stable charge separation and reduced electron/hole recombination rate, thereby enhancing the activity of mixed-crystal catalysts.

The pet disinfection and deodorization spray prepared by the invention has a simple preparation process, can be completed without complicated equipment, and has stable chemical properties.

The main disinfection and deodorization component of the present invention is nanometer silver-loaded titanium dioxide, and the nanometer silver-loaded titanium dioxide is diluted and then added with a small amount of hydrogen peroxide, and the disinfection effect is consistent with that of high-concentration nanometer silver-loaded titanium dioxide, especially the cost is reduced by 85-95%.

The deodorant of soybean ethyl sulfate ethyl sulfate morpholine and methacrylic acid fatty alcohol selected in the disinfectant and deodorant spray of the present invention is to convert the malodorous component and the deodorant component through oxidation, reduction, addition, and condensation reactions into non-odorous components. Odor substances, thoroughly decompose odor components, deodorize quickly and have good effect; tea extract and yucca extract contain chemical substances similar to catechol, hydroquinone and resorcinol, which can interact with odor molecules The chemical reaction of the group will weaken the chemical bonds in the odor molecules, and finally generate an odorless and non-toxic substance, which has a good decomposition and removal effect on ammonia, hydrogen sulfide and other odors.

The sterilizing effect of the disinfecting and deodorizing spray prepared according to the method of the invention meets the standard specified in GB27952 "General Rules for Disinfectants on the Surface of Ordinary Objects", the removal rate of formaldehyde can reach 95.05%, and the removal rate of ammonia gas can reach 95.05%. reached 91.07%.

Detailed ways

The invention provides a kind of silver-loaded titanium dioxide, comprising the following components:

Silver nitrate aqueous solution, titanium dioxide, polyvinylpyrrolidone K30;

The initial concentration of the silver nitrate aqueous solution is 0.02-0.08mol/L, preferably 0.05mol/L;

The mass ratio of the titanium dioxide to the silver nitrate aqueous solution is 0.8-2.0:80-125, preferably 1.4:102.5;

The mass ratio of the polyvinylpyrrolidone K30 to the silver nitrate aqueous solution is 0.5-1.5:80-125, preferably 1:102.5.

In the present invention, the titanium dioxide is of mixed crystal type; the particle size of the titanium dioxide is less than 50 nm.

The present invention also provides the preparation method of the described silver-loaded titanium dioxide, comprising the following steps:

(1) the silver nitrate aqueous solution is mixed with titanium dioxide, polyvinylpyrrolidone K30, ultrasonic, obtains suspension;

(2) subjecting the suspension to a photocatalytic reduction reaction to obtain a mixed solution containing silver-loaded titanium dioxide, and purifying the mixed solution to obtain silver-loaded titanium dioxide.

In the present invention, the ultrasonic temperature in step (1) is 25-37°C; the ultrasonic time is 10-30 minutes; the ultrasonic temperature is preferably 31°C; the ultrasonic time is preferably 20 minutes.

In the present invention, the light for the photocatalytic reaction in step (2) is ultraviolet light; the time for the photocatalytic reaction is 3-6 hours, preferably 4.5 hours.

In the present invention, the purification method in step (2) is centrifugation and/or suction filtration; the rotational speed of the centrifugation is 8000-12000rpm, preferably 10000rpm; the centrifugation time is 6-10min, preferably 8min; The pore size of the filter membrane during the suction filtration is 0.22-0.45 μm, preferably 0.335 μm.

The present invention also provides a sterilizing and deodorizing spray comprising the silver-loaded titanium dioxide or the silver-loaded titanium dioxide prepared by the preparation method, including the following components by volume:

Silver-loaded titanium dioxide or silver-loaded titanium dioxide dilution 85-95 parts, preferably 90 parts; hydrogen peroxide solution 5-15 parts, preferably 10 parts; the dilution ratio of the silver-loaded titanium dioxide dilution is 1-100 times, preferably is 50 times; the initial concentration of the hydrogen peroxide solution is 28-32 vt%, preferably 30 vt%.

In the present invention, the disinfecting and deodorizing spray also includes a deodorant with a final concentration of 2-3 vt% and a flavoring agent with a final concentration of 0.5-1.5 vt%; the final concentration of the deodorant is preferably 2.5vt%; the final concentration of the flavoring agent is 1vt%. The deodorant is one or more of bamboo vinegar, fatty alcohol methacrylic acid, soybean ethyl sulfate morpholine, tea extract, and yucca extract; in the present invention, the yucca extract The material was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.; the tea extract was purchased from Shaanxi Ruilin Panier Biotechnology Co., Ltd.; the mint extract was purchased from Ji'an Wansong Biotechnology Co., Ltd.; Lily extract was purchased from Miaoyue Tika Biomedical Technology (Shandong) Co., Ltd.

In the present invention, the preparation method of the sterilizing and deodorizing spray is as follows: (1) mixing silver-loaded titanium dioxide or silver-loaded titanium dioxide dilution with a hydrogen peroxide solution, and stirring for 10-20 min to obtain an intermediate solution; (2) mixing the The intermediate solution is mixed with deodorant and flavor enhancer, and stirred for 10-30 minutes. The stirring time of step (1) is preferably 15min; the stirring time of step (2) is preferably 20min.

The invention also provides the application of the silver-loaded titanium dioxide or the silver-loaded titanium dioxide prepared by the preparation method in the preparation of a product that kills microorganisms on pet sheds or pets and has the ability to eliminate peculiar smell on pet sheds or pets.

The present invention also provides the use of the disinfecting and deodorizing spray in eliminating microorganisms in pet sheds or pets and eliminating peculiar odors on pet sheds or pets.

The Chinese medicine compositions provided by the present invention are described in detail below in conjunction with the examples, but they should not be construed as limiting the protection scope of the present invention.

In the examples of the present invention, the Yucca extract was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.; the tea extract was purchased from Shaanxi Ruilin Panier Biotechnology Co., Ltd.; the mint extract was purchased from Ji'an Wansong Biotechnology Co., Ltd. Responsible company; honeysuckle extract, mugwort extract, and lily extract were purchased from Miaoyuetika Biomedical Technology (Shandong) Co., Ltd.

Example 1

Take 90g of 0.08mol/L silver nitrate aqueous solution, mix with 1g of mixed crystal titanium dioxide and 1g of polyvinylpyrrolidone K30, and sonicate for 20min at a temperature of 25°C. The obtained suspension is transferred to an ultraviolet photocatalytic reactor for catalysis. The reduction reaction was carried out for 3h, centrifuged at 8000rpm for 6min after the reaction, the filtrate was taken, and the filtrate was suction filtered. The pore size of the filter membrane of the suction filtration was 0.22 μm, and the clear light yellow solution obtained after the suction filtration was the silver-loaded solution. Titanium dioxide.

According to the "General Rules for Disinfectants on the Surface of Ordinary Objects" (GB27952-2020), the quantitative killing test method of the "Technical Specifications for Disinfection" (2002 Edition) is referenced in the sterilization indicators to determine the effect of silver-loaded titanium dioxide on Staphylococcus aureus and large intestine. Bacillus killing effect. The results are shown in Table 1.

The killing effect of table 1 silver-loaded titanium dioxide of the present invention on microorganisms

Table 1 shows that the killing effect of the silver-loaded titanium dioxide prepared by the present invention on Staphylococcus aureus and Escherichia coli meets the standard specified in the "General Rules for Common Surface Disinfectants".

Example 2

The silver-loaded titanium dioxide prepared in Example 1 was diluted 50 times to obtain a silver-loaded titanium dioxide dilution.

Mix 95 mL of silver-loaded titanium dioxide dilution with 5 mL of 30 vt% hydrogen peroxide solution, and stir for 20 minutes to obtain a disinfectant and deodorant spray. According to the "General Rules for Surface Disinfectants for Ordinary Objects" (GB27952-2020), the quantitative killing test method of the "Technical Specifications for Disinfection" (2002 Edition) is referenced in the sterilization indicators of microorganisms. and the killing effect of Escherichia coli. The results are shown in Table 2.

The disinfection and deodorization spray of table 2 embodiment 2 is to the killing effect of microorganism

Table 2 shows that the killing effect of the sterilizing and deodorizing spray prepared by the present invention on Staphylococcus aureus and Escherichia coli meets the standard specified in the "General Rules for Common Surface Disinfectants". The killing effect of the undiluted silver-loaded titanium dioxide in Example 1 is achieved.

Example 3

After adding the bamboo vinegar liquid with a final concentration of 2vt% to the disinfection and deodorization spray obtained in Example 2 and stirring for 20min, adding a honeysuckle extract with a final concentration of 1vt% and stirring to obtain the disinfection and deodorization spray of Example 3.

According to the "General Rules for Disinfectants on the Surface of Ordinary Objects" (GB27952-2020), the quantitative killing test method of the "Technical Specification for Disinfection" (2002 Edition), which is specified in the sterilization indicators, is used to detect the effect of the disinfection and deodorization spray in Example 3. Killing effect of Staphylococcus aureus and Escherichia coli. The results are shown in Table 3.

According to QB/T 2761-2006 Determination of Purification Effect of Indoor Air Purification Products and GB/T18204.2-2014 Public Places Hygiene Inspection Method Part 2: Chemical Pollutants 7.2 Phenolic Reagent Spectrophotometry, GB/T 18204.2-2014 Public Places Part 2 of Hygiene Inspection Methods: Chemical Pollutants 8.1 Indophenol Blue Spectrophotometric Detection of Formaldehyde and Ammonia Removal Ability of the Disinfection and Deodorant Spray Obtained in Example 3. Removal rate y(%)=[(C _A -C _B )/C _A ]×100%, C _A is the concentration of blank chamber, _CB is the concentration of test chamber), and the results are shown in Table 4.

The disinfection and deodorization spray that table 3 embodiment 3 obtains is to the killing effect of microorganism

Table 3 shows that the killing effect of the sterilizing and deodorizing spray obtained in Example 3 to Staphylococcus aureus and Escherichia coli meets the standard specified in the "General Rules for Common Surface Disinfectants", and is consistent with the effects of Examples 1 to 2 .

The sterilizing and deodorizing spray of table 4 embodiment 3 is to the removal effect of peculiar smell

Table 4 shows that the disinfection and deodorization spray obtained in Example 3 of the present invention can achieve a removal rate of 95.05% for formaldehyde, and a removal rate for ammonia gas of 91.07%.

Comparative Example 1

The silver-loaded titanium dioxide dilution obtained by diluting the silver-loaded titanium dioxide obtained in Example 1 by 50 times was used as a disinfectant and deodorant spray.

According to the method for killing microorganisms in Example 1, the killing effect of the disinfection and deodorizing spray of Comparative Example 1 on Staphylococcus aureus and Escherichia coli was detected. The results are shown in Table 5.

The killing effect of the disinfection and deodorization spray of table 5 comparative example 1 on microorganisms

Table 5 shows that the killing effect of the disinfecting and deodorizing spray of Comparative Example 1 on microorganisms does not meet the standard specified in the "General Rules for Disinfectants on Ordinary Object Surfaces". It shows that the sterilization effect of silver-loaded titanium dioxide diluted 50 times alone is not ideal.

As can be seen from the above embodiments, the present invention provides a silver-loaded titanium dioxide, a preparation method and application thereof, and a disinfection and deodorization spray comprising the silver-loaded titanium dioxide. The killing effect of the silver-loaded titanium dioxide on microorganisms of the present invention complies with relevant regulations. The sterilizing effect of the disinfecting and deodorizing spray prepared by using the silver-loaded titanium dioxide of the present invention also complies with relevant regulations, and the removal rate of formaldehyde can reach 95.05%, and the removal rate of ammonia gas can reach 91.07%. It is illustrated that the disinfection and deodorization spray prepared by the present invention not only has the effect of killing pathogenic bacteria, but also has the effect of removing odor.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. a silver-carrying titanium dioxide, is characterized in that, comprises following component: Silver nitrate aqueous solution, titanium dioxide, polyvinylpyrrolidone K30; The initial concentration of the silver nitrate aqueous solution is 0.02～0.08mol/L; The mass ratio of the titanium dioxide to the silver nitrate aqueous solution is 0.8-2.0:80-125; The mass of the polyvinylpyrrolidone K30 and the silver nitrate aqueous solution is 0.5-1.5:80-125. 2. The silver-loaded titanium dioxide according to claim 1, wherein the titanium dioxide is a mixed crystal form; The particle size of the titanium dioxide is less than 50 nm. 3. the preparation method of the described silver-carrying titanium dioxide of claim 1 or 2, is characterized in that, comprises the steps: (1) the silver nitrate aqueous solution is mixed with titanium dioxide, polyvinylpyrrolidone K30, ultrasonic, obtains suspension; (2) subjecting the suspension to a photocatalytic reduction reaction to obtain a mixed solution containing silver-loaded titanium dioxide, and purifying the mixed solution to obtain silver-loaded titanium dioxide. 4. The preparation method according to claim 3, wherein the temperature of the ultrasonic wave in step (1) is 25-37°C; The ultrasonic time is 10-30 min. 5. preparation method according to claim 4 is characterized in that, the light of the described photocatalytic reaction of step (2) is ultraviolet light; The time of the photocatalytic reaction is 3-6 hours. 6. The preparation method according to any one of claims 3 to 5, wherein the purification method in step (2) is centrifugation and/or suction filtration; The rotating speed of the centrifugation is 8000～12000rpm; The time of the centrifugation is 6～10min; The pore size of the filter membrane during the suction filtration is 0.22-0.45 μm. 7. A sterilizing and deodorizing spray comprising the silver-loaded titanium dioxide described in claim 1 or 2 or the silver-loaded titanium dioxide prepared by the preparation method described in any one of claims 3 to 6, characterized in that it comprises the following volume Serving Components: 85-95 copies of silver-loaded titanium dioxide or silver-loaded titanium dioxide dilution; 5-15 parts of hydrogen peroxide solution; The dilution ratio of the silver-loaded titanium dioxide diluent is 1 to 100 times; The initial concentration of the hydrogen peroxide solution is 28-32 vt%. 8 . The disinfecting and deodorizing spray according to claim 7 , wherein the disinfecting and deodorizing spray also includes a deodorant with a final concentration of 2 to 3 vt% and a deodorant with a final concentration of 0.5 to 1.5 vt% 8 . flavoring agent; The deodorant is one or more of bamboo vinegar, fatty alcohol methacrylic acid, soybean ethyl sulfate morpholine, tea extract, and yucca extract; The flavor enhancer is one or more of honeysuckle extract, mint extract, mugwort extract, and lily extract. 9. The silver-loaded titanium dioxide according to claim 1 or 2 or the silver-loaded titanium dioxide prepared by the preparation method according to any one of claims 3 to 6 is used to prepare and kill pet sheds or microorganisms on pets and has the ability to eliminate pet sheds. or applications in products with odors on pets. 10. Use of the disinfecting and deodorizing spray according to claim 7 or 8 in eliminating microorganisms on pet sheds or pets and eliminating peculiar smell on pet sheds or pets.