CN113907089A - Preparation method of compound air bactericide - Google Patents

Preparation method of compound air bactericide Download PDF

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CN113907089A
CN113907089A CN202111139546.1A CN202111139546A CN113907089A CN 113907089 A CN113907089 A CN 113907089A CN 202111139546 A CN202111139546 A CN 202111139546A CN 113907089 A CN113907089 A CN 113907089A
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dmf
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王丹亮
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Jiangsu Guoke Intelligent Equipment Co ltd
Jiangsu Gemusi Sports Science And Technology Research Institute Co ltd
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Jiangsu Guoke Intelligent Equipment Co ltd
Jiangsu Gemusi Sports Science And Technology Research Institute Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof

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Abstract

The invention provides a preparation method of a compound air bactericide, which comprises the following steps: (1) ZrCl4 and 2-amino-1, 4-phthalic acid are used for preparing a UiO-66 material, and the size of the generated UiO-66 is regulated and controlled by regulating the conditions such as the proportion of ZrCl4 and 2-amino-1, 4-phthalic acid, the reaction time and the like; (2) preparing a UiO-66/Ag composite material, fixing Ag particles on a frame pore channel and an outer wall of the UiO-66, controlling the using amount of AgNO3, and regulating and controlling the amount of Ag generated; (3) preparing a compound air bactericide material, dispersing UiO-66/Ag into a hypochlorous acid solution, and enhancing the bactericidal performance; the invention has stable property, no toxicity, no harm and good sterilization effect, and is a safe and effective compound air bactericide.

Description

Preparation method of compound air bactericide
Technical Field
The invention relates to an air bactericide, in particular to a preparation method of a compound air bactericide.
Background
Bacteria refer to one of the main groups of organisms, belonging to the bacterial domain. Is also the most abundant class of all organisms, and it is estimated that there are approximately 5 x 10^30 in total. The shape of the bacteria is quite diverse, mainly spherical, rod-like, and spiral. The bacteria have great influence on human activities, are pathogens of many diseases, can spread the diseases among normal human bodies through various modes, such as contact, alimentary canal, respiratory tract, insect bite and the like, have strong infectivity and have great harm to the society. Generally, the content of bacteria and viruses in indoor air is 5-10 times higher than that in outdoor air, and serious and even hundreds times higher. Bacteria and viruses in indoor air mainly originate from the following two aspects: firstly, the droplets can disperse microorganisms parasitizing the oral cavity and the throat of a person into the air in the form of droplets when the person breathes, speaks and sneezes deeply; and secondly, the average bacteria content of the scurf and the dust of the human body is calculated to reach 4 ten thousand, and the scurf and the dust can be suspended in the air to pollute the air along with the movement of the human body indoors, and particularly, when a patient is in the room, the corresponding pathogenic bacteria can be found in the air. Therefore, the air sterilization is an important means for controlling the spread of diseases and maintaining the health of human bodies.
The existing air sterilization technology has the defects of different types: ozone is used for air sterilization, ozone is toxic gas, and the excessive ozone can cause the respiratory system of a person to be obstructed, so that the ozone air sterilization device is required to be used in a sealing way, and the person can not stay in the environment with excessive ozone for too long time; plasma air sterilization is adopted, the system is complex and comprises a vacuum system, an exhaust filtering system, a plasma generating system and the like, the cost is high, and the plasma has great harm to human bodies and can be only used for sterilization in unmanned places; the negative ion air sterilization has an unobvious sterilization effect, the retention time of the negative ions in the air is short, the places with much dust are only retained for a few seconds, the negative ions are generated by high-voltage discharge, and a large amount of ozone is often generated during the high-voltage discharge, so that the human respiratory system is damaged; the photocatalyst air sterilization mainly utilizes ultraviolet light to irradiate the photocatalyst to generate the effect, and the ultraviolet light also has harm to human bodies. Therefore, there is a need for a novel air disinfectant which is harmless to human body and has broad-spectrum bactericidal effect.
Metal-organic framework Materials (MOFs) are coordination polymers which develop rapidly in the last decade, have three-dimensional pore structures, generally take metal ions as connecting points, and organic ligands support and form space 3D extension, are another important novel porous material besides zeolite and carbon nanotubes, and are widely applied to catalysis, energy storage and separation. The MOFs have rich designable structure types, permanent holes, ultra-high specific surface area and functionalized hole spaces, and are widely applied to the fields of gas storage and separation, catalysis, sensing, drug delivery and the like. It is the special property that the MOFs material not only can intercept and filter the pollution particles in the air, but also is expected to be used as a photocatalyst to degrade the air pollutants. In the MOF material, UiO-66 has higher high photocatalytic bactericidal activity.
Silver is a very powerful bacteria killing material, silver can kill bacteria without damaging beneficial bacteria and normal cells, because most pathogenic bacteria are unicellular microorganisms, and rely on protease to maintain metabolism and further propagate and influence normal cells, and an oxygen metabolism enzyme is also arranged in the protease, when silver meets the oxygen metabolism enzyme, the activity of the oxygen metabolism enzyme can rush away an electron of the silver, so that silver atoms are changed into positively charged silver ions, and the silver ions can attract the specific combination of thiol groups (-SH) with negative charges in the protease to effectively puncture cell walls and the appearance of cell membranes, further bacterial cells cannot breathe, metabolize and propagate because of protein denaturation until death, and the effect of sterilization is achieved. The survival time of the pathogenic bacteria is only dozens of minutes, the pathogenic bacteria can die naturally under the condition of incapable propagation, and the silver ions can return to the original electrons to be reduced into silver atoms. The bactericidal function of silver itself is not lost.
The UiO-66 is used for loading silver Ag, so that the large specific surface area of the MOF material can be utilized, the loading capacity of Ag is increased, the size of nano Ag can be reduced, and the sterilization effect of the nano Ag is further enhanced.
Hypochlorous acid is oxyacid containing chlorine element, has a chemical formula of HClO and a structural formula of H-O-Cl, wherein the valence of the chlorine element is + 1. It is only present in solution, and the dilute solution is colorless, a very weak acid, weaker than carbonic acid, and comparable to hydrogen sulfuric acid. Is widely used for disinfecting the surfaces of objects, polluted articles such as fabrics and the like, water, fruits, vegetables, eating and drinking utensils and the like. Besides the purposes, the disinfectant can also be used for disinfecting indoor air, surfaces of secondary water supply equipment facilities, hands, skin and mucous membranes.
Dispersing UiO-66/Ag in hypochlorous acid solution to wrap UiO-66/Ag with hypochlorous acid+The compound air bactericide has the advantages of stable property, no toxicity, no harm, good sterilization effect, safety and effectiveness.
Disclosure of Invention
The invention aims to provide a preparation method of a compound air bactericide.
The invention provides the following technical scheme:
a preparation method of a compound air bactericide is characterized by comprising the following steps:
1) preparation of UiO-66 Material
a. Preparing a DMF/HCl mixed solution: stirring DMF and HCl in different volume ratios by using a magnetic stirrer to obtain a DMF/HCl mixed solution;
b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a);
c. dissolving 2-amino-1, 4-phthalic acid in DMF;
d. mixing and stirring the products obtained in the step b) and the step c) together at normal temperature according to different molar ratios;
e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide);
f. solvent displacement of the product obtained in step e) with ethanol;
g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparation of UiO-66/Ag nano composite material
a. Dispersing UiO-66 powder in DMF;
b. mixing AgNO3Dispersed in DMF;
c. mixing AgNO3Adding the DMF solution into a DMF solution of UiO-66, stirring for 5min by using a magnetic stirrer, and standing for reaction;
d. centrifugally washing a DMF solution of UiO-66/Ag, removing supernatant, and drying for 48h by using a freeze dryer to obtain a UiO-66/Ag nano composite material;
3) preparation of compound air bactericide material
Electrolyzing sodium chloride and/or hydrochloric acid aqueous solution in an electrolytic tank with or without a diaphragm to generate hypochlorous acid aqueous solution with the pH value less than 7, adjusting the concentration of the hypochlorous acid aqueous solution, adding a dispersing agent and a protective agent into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding a certain proportion of UiO-66/Ag nano composite material, slowly stirring for 0.5-12 h until the aqueous solution is in a transparent colorless state, and adding a spraying matrix material into the aqueous solution.
Specifically, the method for adjusting the concentration of the hypochlorous acid aqueous solution comprises the steps of preparing hypochlorous acid by directly using a hypochlorous acid generator and adding the insoluble carbonate solid or the insoluble bicarbonate solid into the hypochlorous acid solution.
Specifically, the insoluble carbonate solid includes calcium carbonate, barium carbonate, zinc carbonate, manganese carbonate, iron carbonate, copper carbonate, and silver carbonate.
Specifically, the bicarbonate solid comprises sodium bicarbonate.
Specifically, the dispersant is an organic dispersant or an inorganic dispersant.
Specifically, the inorganic dispersant includes silicates and alkali metal phosphates.
Specifically, the organic dispersant comprises triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, Guel gum and fatty acid polyglycol ester.
Specifically, the spray matrix is one of hydroxypropyl methylcellulose, carbomer, sodium alginate and polyvinyl alcohol.
Specifically, the protective agent is sodium thiosulfate.
The invention has the beneficial effects that:
according to the invention, the size of UiO-66 is adjusted, and the loading capacity of Ag is controlled, so that the composite material of UiO-66/Ag is prepared; dispersing UiO-66/Ag in hypochlorous acid solution to wrap UiO-66/Ag with hypochlorous acid+The compound air bactericide has the advantages of stable property, no toxicity, no harm, good sterilization effect, safety and effectiveness.
Detailed Description
Example 1
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 1, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1, mixing and stirring together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 1, stirring for 5min by using a magnetic stirrer, and standing for reaction for 2 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing a sodium chloride aqueous solution in an electrolytic tank to generate a hypochlorous acid aqueous solution with the pH value of 6.2, adding calcium carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 50ppm, adding triethylhexylphosphoric acid and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 25% of UiO-66/Ag nano composite material, slowly stirring for 0.5h until the aqueous solution is in a transparent colorless state, and adding hydroxypropyl methylcellulose into the solution.
Example 2
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 2, stirring the DMF and the HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1.5, mixing and stirring together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 2, stirring for 5min by using a magnetic stirrer, and standing for reaction for 4 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing sodium chloride aqueous solution in an electrolytic tank to generate hypochlorous acid aqueous solution with pH of 6.4, adding barium carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 30ppm, adding sodium dodecyl sulfate and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 30% UiO-66/Ag nano composite material, slowly stirring for 1h until the aqueous solution is in a transparent colorless state, and adding carbomer.
Example 3
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 3, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 2, mixing and stirring the components together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 3, stirring for 5min by using a magnetic stirrer, and standing for reaction for 6 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing sodium chloride aqueous solution in an electrolytic tank to generate hypochlorous acid aqueous solution with pH of 6.3, adding zinc carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 60ppm, adding methyl amyl alcohol and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 15% UiO-66/Ag nano composite material, slowly stirring for 2h until the aqueous solution is in a transparent colorless state, and adding sodium alginate into the aqueous solution.
Example 4
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 4, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1, at normal temperatureMixing and stirring the components together; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 1, stirring for 5min by using a magnetic stirrer, and standing for reaction for 8 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing sodium chloride aqueous solution in an electrolytic tank to generate hypochlorous acid aqueous solution with pH of 6.5, adding manganese carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 70ppm, adding cellulose derivative and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 10% UiO-66/Ag nano composite material, slowly stirring for 4h until the aqueous solution is transparent and colorless, and adding polyvinyl alcohol.
Example 5
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 1, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1.5, mixing and stirring together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 2, stirring for 5min by using a magnetic stirrer, and standing for reaction for 10 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing a sodium chloride aqueous solution in an electrolytic tank to generate a hypochlorous acid aqueous solution with the pH value of 6.6, adding ferric carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 60ppm, adding polyacrylamide and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding a 5% UiO-66/Ag nano composite material, slowly stirring for 6h until the aqueous solution is in a transparent colorless state, and adding hydroxypropyl methylcellulose into the aqueous solution.
Example 6
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 2, stirring the DMF and the HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 2, mixing and stirring the components together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 3, stirring for 5min by using a magnetic stirrer, and standing for reaction for 12 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing a sodium chloride aqueous solution in an electrolytic bath to generate a hypochlorous acid aqueous solution with the pH value of 6.4, adding copper carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 40ppm, adding guar gum and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 30% UiO-66/Ag nano composite material, slowly stirring for 6h until the aqueous solution is in a transparent colorless state, and adding hydroxypropyl methylcellulose into the aqueous solution.
Example 7
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 1, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1, mixing and stirring together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 1, stirring for 5min by using a magnetic stirrer, and standing for reaction for 24 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing a sodium chloride aqueous solution in an electrolytic tank to generate a hypochlorous acid aqueous solution with the pH value of 6.7, adding silver carbonate to adjust the concentration of the hypochlorous acid aqueous solution to be 30ppm, adding fatty acid polyglycol ester and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 20% of UiO-66/Ag nano composite material, slowly stirring for 12h until the aqueous solution is in a transparent colorless state, and adding sodium alginate.
Example 8
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 1, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. dissolving 2-amino-1, 4-phthalic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1, mixing and stirring together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 1, stirring for 5min by using a magnetic stirrer, and standing for reaction for 2 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing sodium chloride aqueous solution in an electrolytic tank to generate hypochlorous acid aqueous solution with pH of 6.8, adding ferric carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 80ppm, adding sodium dodecyl sulfate and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 5% UiO-66/Ag nano composite material, slowly stirring for 5h until the aqueous solution is in a transparent colorless state, and adding polyacrylamide into the aqueous solution.
Example 9
A preparation method of a compound air bactericide comprises the following steps:
1) preparation of UiO-66 Material: a. preparing a DMF/HCl mixed solution: using a magnetic stirrer, the ratio of volume to volume is 1: 1, stirring DMF and HCl to obtain a DMF/HCl mixed solution; b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a); c. 2-amino-1, 4-benzeneDissolving dicarboxylic acid in DMF; d. the products obtained in step b) and step c) are mixed in a molar ratio of 1: 1.5, mixing and stirring together at normal temperature; e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide); f. solvent displacement of the product obtained in step e) with ethanol; g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparing a UiO-66/Ag composite material: a. dispersing UiO-66 powder in DMF; b. mixing AgNO3Dispersed in DMF; c. mixing AgNO3Is added to the DMF solution of UiO-66, wherein AgNO3And UiO-66 in a molar ratio of 1: 2, stirring for 5min by using a magnetic stirrer, and standing for reaction for 10 h; d. centrifugally washing the prepared UiO-66/Ag composite material, and drying for 48 hours by using a freeze dryer to obtain the composite material;
3) preparing a compound air bactericide material: electrolyzing sodium chloride aqueous solution in an electrolytic tank to generate hypochlorous acid aqueous solution with pH of 6.2, adding calcium carbonate to adjust the concentration of the hypochlorous acid aqueous solution to 40ppm, adding guar gum and sodium thiosulfate into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding 15% UiO-66/Ag nano composite material, slowly stirring for 8h until the aqueous solution is in a transparent colorless state, and adding polyvinyl alcohol into the aqueous solution.
[ TABLE 1 ]
Sterilizing rate (%) Pneumococcus Mycobacterium tuberculosis Clostridium tetani
Example 1 99.2 99.6 99.5
Example 2 99.4 99.4 99.7
Example 3 99.1 99.6 99.3
Example 4 98.7 99.5 99.5
Example 5 98.6 99.0 99.2
Example 6 98.9 99.4 99.6
Example 7 99.0 99.3 99.7
Example 8 99.4 99.2 99.8
Example 9 99.7 99.1 99.2
Comparison product 98.5 99.0 99.2
As shown in table 1 above, the sterilization rate of the compound air disinfectant provided by the present invention is higher than that of the mainstream products in the market.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a compound air bactericide is characterized by comprising the following steps:
1) preparation of UiO-66 Material
a. Preparing a DMF/HCl mixed solution: stirring DMF and HCl in different volume ratios by using a magnetic stirrer to obtain a DMF/HCl mixed solution;
b. reacting ZrCl4Dissolving in the mixed solution prepared in the step a);
c. dissolving 2-amino-1, 4-phthalic acid in DMF;
d. mixing and stirring the products obtained in the step b) and the step c) together at normal temperature according to different molar ratios;
e. centrifuging the product obtained in step d), and washing the product for multiple times by using DMF (dimethyl formamide);
f. solvent displacement of the product obtained in step e) with ethanol;
g. drying the product obtained in the step f) in an oven at 120 ℃ for later use;
2) preparation of UiO-66/Ag nano composite material
a. Dispersing UiO-66 powder in DMF;
b. mixing AgNO3Dispersed in DMF;
c. mixing AgNO3Adding the DMF solution into a DMF solution of UiO-66, stirring for 5min by using a magnetic stirrer, and standing for reaction;
d. centrifugally washing a DMF solution of UiO-66/Ag, removing supernatant, and drying for 48h by using a freeze dryer to obtain a UiO-66/Ag nano composite material;
3) preparation of compound air bactericide material
Electrolyzing sodium chloride and/or hydrochloric acid aqueous solution in an electrolytic tank with or without a diaphragm to generate hypochlorous acid aqueous solution with the pH value less than 7, adjusting the concentration of the hypochlorous acid aqueous solution, adding a dispersing agent and a protective agent into the hypochlorous acid aqueous solution, slowly pre-stirring for 5min, adding a certain proportion of UiO-66/Ag nano composite material, slowly stirring for 0.5-12 h until the aqueous solution is in a transparent colorless state, and adding a spraying matrix material into the aqueous solution.
2. The method for preparing a compound air bactericide as claimed in claim 1, wherein the method for adjusting the concentration of the hypochlorous acid aqueous solution comprises preparing hypochlorous acid directly using a hypochlorous acid generator and adding the sparingly soluble carbonate solid or the sparingly soluble bicarbonate solid to the hypochlorous acid solution.
3. The method for preparing a compound air disinfectant as claimed in claim 2, wherein the insoluble carbonate solid comprises calcium carbonate, barium carbonate, zinc carbonate, manganese carbonate, iron carbonate, copper carbonate, and silver carbonate.
4. The method of claim 2, wherein the bicarbonate solid comprises sodium bicarbonate.
5. The preparation method of the compound air bactericide as claimed in claim 1, wherein the dispersant is an organic dispersant or an inorganic dispersant.
6. The method for preparing a compound air bactericide as claimed in claim 5, wherein the inorganic dispersant comprises silicates and alkali metal phosphates.
7. The method for preparing a compound air disinfectant as recited in claim 5, wherein said organic dispersant comprises triethylhexylphosphoric acid, sodium dodecylsulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, and fatty acid polyglycol ester.
8. The method for preparing a compound air bactericide as claimed in claim 1, wherein the spray matrix is one of hypromellose, carbomer, sodium alginate and polyvinyl alcohol
9. The method for preparing a compound air bactericide as claimed in claim 1, wherein the protectant is sodium thiosulfate.
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