In-situ preparation method of hypochlorous acid

Abstract

The invention discloses an in-situ preparation method of hypochlorous acid, which comprises the following steps: adding piezoelectric material particles into a chloride ion solution, then applying mechanical force or ultrasound to the solution, and reacting to prepare a hypochlorous acid solution; and the piezoelectric material is a metal-loaded piezoelectric composite material. The method is simple to operate, does not need special instruments and complex processes, is high in applicability and controllability, can accurately control the generation of hypochlorous acid, is green and environment-friendly, is low in cost, and has a better application scene in the fields of environment disinfection, clinical infection treatment, personal portable disinfection devices and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of hypochlorous acid and specifically discloses an in-situ preparation method of hypochlorous acid. Background Art

[0002] The statements herein merely provide background information related to the present invention and do not necessarily constitute prior art.

[0003] Hypochlorous acid, with the chemical formula HClO, is an oxygen-containing acid of chlorine. The valence of chlorine is +1, which is the lowest valence oxygen-containing acid of chlorine. However, its oxidizing property is the strongest among the oxygen-containing acids of chlorine. Hypochlorous acid is often used as a bleaching agent, oxidant and disinfectant. Its sterilization speed is 80 times that of other chlorine-containing products. It can quickly kill bacteria, viruses and fungi, effectively eliminating the source of infection and cutting off the transmission route.

[0004] At present, there are three commonly used methods for preparing hypochlorous acid: (1) through the reaction of chlorine and water; (2) through the electrolysis of low-concentration hydrochloric acid or sodium chloride solution; (3) by mixing a low-concentration sodium hypochlorite solution with a hydrochloric acid solution and adjusting the pH of the mixed solution to a specified range. Among them, the chlorine gas reactant in the chlorine hydrolysis method is a toxic gas and is dangerous; the electrolysis method has an uncertain yield, an uncontrollable reaction process, and relatively complex instruments and equipment and consumes a lot of energy; the hypochlorite solution acidification method has high requirements for the pH of the system. In addition, hypochlorous acid only exists in solution and is extremely unstable and easily degraded and ineffective, which greatly limits its application. Summary of the invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide an in-situ preparation method of hypochlorous acid.

[0006] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0007] An in-situ preparation method of hypochlorous acid comprises the following steps:

[0008] Adding piezoelectric material particles into a chloride ion solution, and then applying mechanical force or ultrasound to the solution to react, thereby preparing a hypochlorous acid solution;

[0009] The piezoelectric material is selected from quartz crystal, tourmaline, zinc oxide, barium titanate or a piezoelectric composite material loaded with metal.

[0010] Under the stimulation of force, the piezoelectric material becomes polarized, generating electron-hole pairs. Chloride ions, as an electron-rich system, combine with the holes and are oxidized into hypochlorous acid.

[0011] In some embodiments, the chloride ion solution is a soluble hydrochloride solution or a hydrochloric acid solution.

[0012] Preferably, the soluble hydrochloride is selected from one or a combination of sodium chloride, potassium chloride, ammonium chloride, barium chloride, calcium chloride, magnesium chloride, aluminum chloride, manganese chloride, zinc chloride, iron chloride, ferrous chloride, or copper chloride.

[0013] Preferably, in the soluble hydrochloride solution, the concentration of chloride ions is 0.1 - 6 mol / L -1 ;

[0014] In the hydrochloric acid solution, the concentration of chloride ions is 0.1 - 6 mol / L -1 .

[0015] In some embodiments, the metal-loaded piezoelectric composite material is barium titanate loaded with metal, and the metal loaded on the barium titanate is selected from gold, silver, palladium, or platinum.

[0016] Preferably, the method for preparing the metal-loaded barium titanate is as follows: (1) Disperse barium titanate in absolute ethanol, add 3-(mercaptopropyl)trimethoxysilane, stir evenly and then perform ultrasonic treatment; after centrifugation, washing, and drying, mercapto-functionalized barium titanate is obtained;

[0017] (2) Disperse the mercapto-functionalized barium titanate in water, add a metal salt solution and an aqueous methanol solution, stir evenly, adjust the pH of the system to 9 - 10, and then perform ultrasonic treatment; after centrifugation, washing, and drying, a piezoelectric material with a surface-loaded metal is obtained.

[0018] Preferably, the piezoelectric material is barium titanate loaded with gold.

[0019] Preferably, the particle size of the metal-loaded barium titanate is 100 - 500 nm.

[0020] More preferably, the concentration of the piezoelectric material particles is 0.3 - 0.8 mg / ml.

[0021] In some embodiments, the mechanical force is stirring or oscillation.

[0022] Preferably, the stirring rate is 500 - 1000 rpm, and the stirring time is 10 - 20 min;

[0023] The oscillation frequency is 30 - 50 kHz, and the oscillation time is 3 - 8 min.

[0024] In some embodiments, the ultrasonic power is 0.8 - 1.2 W / cm 2 , and the ultrasonic time is 3 - 8 min.

[0025] The beneficial effects obtained by one or more of the above embodiments of the present invention are as follows:

[0026] The present invention discloses a method for in-situ generating hypochlorous acid using mechanical force / ultrasound. This method first proposes the preparation of hypochlorous acid by the action of mechanical force / ultrasound, opening up a new field for the preparation of hypochlorous acid. This method is simple to operate, does not require special instruments and complex processes, has strong applicability and controllability, and can precisely control the generation of hypochlorous acid. This method is green, environmentally friendly and low-cost, and its reactants are inexpensive hydrochloride salts or hydrochloric acid solutions, without the need to add additional chemicals. The technology of the present invention will have good application scenarios in the fields of environmental disinfection, clinical infection treatment, personal portable disinfection devices, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings forming a part of this invention are used to provide a further understanding of the invention. The schematic embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0028] Figure 1 Concentration comparison chart of hypochlorous acid generated by three solutions in Example 1;

[0029] Figure 2 Concentration comparison chart of hypochlorous acid generated by sodium chloride solutions with different concentrations in Example 2;

[0030] Figure 3 Conversion efficiency comparison chart of hypochlorous acid generated by sodium chloride solutions with different concentrations in Example 2. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0032] The present invention will be further described below in conjunction with embodiments.

[0033] Example 1

[0034] An in-situ preparation method of hypochlorous acid, comprising the following steps:

[0035] Preparation of BTAu particles: (1) Disperse 40 mg of barium titanate in 40 mL of absolute ethanol, add 400 μL of (3-mercaptopropyl) trimethoxysilane, stir evenly, and then ultrasonically vibrate for 30 min under the condition of an ultrasonic frequency of 40 kHz. Then, centrifuge for 10 min at a rotation speed of 5000 rmp to obtain a precipitate. Wash the obtained precipitate 3 times with absolute ethanol and dry it at 60 °C for 5 h to obtain mercapto-functionalized barium titanate.

[0036] (2) Disperse 10 mg of mercapto-barium titanate in 10 mL of deionized water, add 10 mL of 20 mmol / L HAuCl 4 solution and 10 mL of an aqueous methanol solution with a volume concentration of 20% (v / v). Adjust the pH value of the system to 9.7 with 0.5 mol / L K 2 CO 3 solution. Under the conditions of a temperature of 0 °C and an ultrasonic frequency of 40 kHz, ultrasonically treat for 60 min to obtain a mixture. Centrifuge the obtained mixture at a rotational speed of 10000 rmp for 10 min to obtain a precipitate. Wash the obtained precipitate with water 3 times and dry it at 80 °C for 7 h to obtain barium titanate loaded with gold on the surface, BTAu.

[0037] Preparation of hypochlorous acid: Prepare 3 portions of 10 ml of 0.1 mol / L sodium chloride solution. Among them, the first portion is not treated (US + 1M NaCl), and 5 mg of BTAu particles are added to the second portion (BTAu + 1M NaCl) and the third portion (BTAu + 1M NaCl + US) respectively. Then place the first portion and the third portion of the solution on an ultrasonic physiotherapy instrument (2W) for 5 min respectively, and the second portion is not treated.

[0038] After the action, centrifuge the second portion and the third portion of the solution respectively (12000 rpm, 10 min). Immediately add 0.5 ml of N,N-diethyl-1,4-phenylenediamine (DPD) solution (10 μmol / L) to the supernatant. After 15 min, measure the absorbance at 551 nm using a UV spectrophotometer; directly add 0.5 ml of N,N-diethyl-1,4-phenylenediamine (DPD) solution (10 μmol / L) to the first portion, and measure the absorbance at 551 nm using a UV spectrophotometer after 15 min, and then convert it to the hypochlorous acid concentration.

[0039] Figure 1 For the first, second, and third portions of the solution in Example 1, the concentrations of hypochlorous acid generated are 5.9 μmol / L, 4.9 μmol / L, and 23.98 μmol / L respectively. It can be seen that BTAu can catalyze the conversion of chloride ions to hypochlorous acid under ultrasonic stimulation.

[0040] Example 2

[0041] An in-situ preparation method of hypochlorous acid, comprising the following steps:

[0042] Preparation of BTAu particles: (1) Disperse 40 mg of barium titanate in 40 mL of absolute ethanol, add 400 μL of (3-mercaptopropyl)trimethoxysilane, stir evenly, and then ultrasonically oscillate for 30 min under the condition of an ultrasonic frequency of 40 kHz. After that, centrifuge for 10 min at a rotation speed of 5000 rmp to obtain a precipitate. Wash the obtained precipitate 3 times with absolute ethanol and dry it at 60 °C for 5 h to obtain mercapto-functionalized barium titanate.

[0043] (2) Disperse 10 mg of mercapto-functionalized barium titanate in 10 mL of deionized water, add 10 mL of 20 mmol / L HAuCl 4 solution and 10 mL of methanol aqueous solution with a volume concentration of 20% (v / v). Adjust the pH value of the system to 9.7 with 0.5 mol / L K 2 CO 3 solution. Ultrasonically treat for 60 min at a temperature of 0 °C and an ultrasonic frequency of 40 kHz to obtain a mixture. Centrifuge the obtained mixture for 10 min at a rotation speed of 10000 rmp to obtain a precipitate. Wash the obtained precipitate 3 times with water and dry it at 80 °C for 7 h to obtain barium titanate BTAu with gold loaded on the surface.

[0044] Preparation of hypochlorous acid: Prepare 10 ml of sodium chloride solutions with different concentrations (0, 0.15, 0.5, 1.0, 2.0 mol / L), add 5 mg of BTAu particles to each of them respectively, and place them on an ultrasonic physiotherapy instrument (2 W) for 5 min. After the action is completed, centrifuge (12000 rpm, 10 min), immediately add 0.5 ml of N,N-diethyl-1,4-phenylenediamine (DPD) solution (10 μmol / L) to the supernatant, and measure the absorbance at 551 nm using a UV-visible spectrophotometer after 15 min;

[0045] Figure 2 is the concentration of hypochlorous acid produced by sodium chloride solutions with different concentrations in Example 2. It can be seen that the concentration of hypochlorous acid formed by the conversion of chloride ions catalyzed by BTAu under ultrasonic stimulation increases with the increase of chloride ion concentration.

[0046] Figure 3 is the conversion efficiency of hypochlorous acid produced by sodium chloride solutions with different concentrations in Example 2. It can be seen that the conversion efficiency first increases and then decreases with the increase of chloride ion concentration, which provides data support for the effective utilization of chloride ions.

[0047] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An in-situ preparation method of hypochlorous acid, characterized in that: The steps include: Adding piezoelectric material particles into a chloride ion solution, and then applying mechanical force or ultrasound to the solution to react, thereby preparing a hypochlorous acid solution; The piezoelectric material is selected from quartz crystal, tourmaline, zinc oxide, barium titanate or a piezoelectric composite material loaded with metal.

2. The in-situ preparation method of hypochlorous acid according to claim 1, characterized in that: The chloride ion solution is a soluble hydrochloride solution or a hydrochloric acid solution.

3. The in-situ preparation method of hypochlorous acid according to claim 2, characterized in that: The soluble hydrochloride is selected from one or a combination of sodium chloride, potassium chloride, ammonium chloride, barium chloride, calcium chloride, magnesium chloride, aluminum chloride, manganese chloride, zinc chloride, ferric chloride, ferrous chloride or cupric chloride; Preferably, the concentration of chloride ions in the soluble hydrochloride solution is 0.1-6 mol L -1 ; In the hydrochloric acid solution, the concentration of chloride ions is 0.1-6 molL -1 .

4. The in-situ preparation method of hypochlorous acid according to claim 1, characterized in that: The metal-loaded piezoelectric composite material is metal-loaded barium titanate, and the loaded metal is selected from gold, silver, palladium or platinum.

5. The in-situ preparation method of hypochlorous acid according to claim 4, characterized in that: The preparation method of the metal-loaded barium titanate is: Dispersing barium titanate in anhydrous ethanol, adding 3-(mercaptopropyl)trimethoxysilane, stirring evenly and then ultrasonically treating; then centrifuging, washing and drying to obtain mercaptolated barium titanate; Disperse the barium titanate thiolate in water, add the metal salt solution and the methanol aqueous solution, stir evenly, adjust the pH of the system to 9-10, and then perform ultrasonic treatment; After centrifugation, washing and drying, a piezoelectric material with metal loaded on the surface is obtained.

6. The in-situ preparation method of hypochlorous acid according to claim 4, characterized in that: The piezoelectric material is gold-loaded barium titanate.

7. The in-situ preparation method of hypochlorous acid according to claim 4, characterized in that: The particle size of the metal-loaded barium titanate is 100-500 nm; Further preferably, the concentration of the piezoelectric material particles is 0.3-0.8 mg / ml.

8. The in-situ preparation method of hypochlorous acid according to claim 1, characterized in that: The mechanical force is stirring or shaking.

9. The in-situ preparation method of hypochlorous acid according to claim 1, characterized in that: The stirring rate is 500-1000 rpm, and the stirring time is 10-20 min; The frequency of oscillation is 30-50kHz, and the oscillation time is 3-8min.

10. The in-situ preparation method of hypochlorous acid according to claim 1, characterized in that: The power of ultrasound is 0.8-1.2W / cm 2 , the ultrasonic time is 3-8min.

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