TW201546020A - Ozone-decomposition material and method for fabricating the same - Google Patents

Abstract

Ozone-decomposition materials and a method for fabricating the same are provided. The Ozone-decomposition material is fabricated by a method having following steps. A manganese salt is dissolved into water obtaining a manganese-containing solution. Next, the pH value of the manganese-containing solution is adjusted to be between 7.5 and 11. A sodium silicate solution is added into the manganese-containing solution obtaining a first solution. The first solution is heated under a closed atmosphere to perform a silicate exfoliation, obtaining a second solution. The second solution is subjected to a drying procee, obtaining an intermediate. The intermediate is subjected to a calcination process, obtaining a manganese silicate porous material.

Description

Ozone decomposition material, and method of producing the same

The present invention relates to an ozone decomposing material and a method of producing the same.

The strong oxidizing power of ozone is widely used in the treatment of water and sewage, the sterilization of food factory facilities and equipment, and the sterilization of general households. It is also used for wafer surface cleaning in the semiconductor industry. However, the strong oxidizing power of ozone causes health injuries such as headache, vomiting, and pulmonary edema, so ozone that has not been reacted after use must be decomposed into harmless substances. However, existing ozone treatment equipment requires additional energy supply or dehumidification due to inability to resist moisture, resulting in inconvenience in use.

Based on the above, the industry needs a normal temperature ozone decomposing material with moisture resistance, which can reduce the harm of ozone to the human body under the condition of energy saving.

The present invention provides an ozonolysis material comprising a manganese citrate pore material. Since the manganese citrate pore material is prepared by the cerium oxide ablation reaction, the obtained manganese citrate pore material does not need to be supported on the carrier and has high specific surface area characteristics. Therefore, the ozone decomposing material of the present invention can effectively decompose ozone into oxygen even in a high humidity environment.

According to an embodiment of the invention, the invention discloses an ozone decomposing material comprising: a manganese citrate pore material. Wherein, the manganese citrate hole material The molar ratio of manganese to lanthanum is between 0.1 and 0.6. The ozone decomposing material has an ozone decomposition efficiency of more than 99% at a relative humidity of more than 95% RH. Here, the ozonolysis material of the present invention may comprise a product obtained by dissolving a manganese salt in water to obtain a manganese salt solution; adjusting the pH of the manganese salt solution to between 7.5 and 11; Adding an aqueous solution of sodium citrate to the manganese salt solution to obtain a first solution; heating the first solution in a closed environment, performing a cerium oxide ablation reaction to obtain a second solution; and performing a drying process on the second solution An intermediate product is obtained; and the intermediate product is subjected to a calcination process to obtain a manganese citrate pore material.

According to another embodiment of the present invention, the present invention also provides a method for preparing an ozone decomposing material, comprising: dissolving a manganese salt in water to obtain a manganese salt solution; adjusting a pH of the manganese salt solution to between 7.5 and 11; Adding a sodium citrate aqueous solution to the manganese salt solution to obtain a first solution; heating the first solution in a closed environment, performing a cerium oxide ablation reaction to obtain a second solution; and performing a second solution on the second solution The drying process provides an intermediate product; and the intermediate product is subjected to a calcination process to obtain a manganese citrate pore material.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

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20‧‧‧Manganese citrate pore material

21‧‧‧Spherical structure

22‧‧‧octahedral lattice manganese oxide layer

24‧‧‧tetrahedral lattice yttrium oxide layer

2C‧‧‧Area

Fig. 1 is a schematic view showing the manufacturing process of the ozone decomposing material of the present invention.

2A is a schematic view showing the formation of a manganese tantalate hole material by yttrium oxide ablation according to a preferred embodiment of the present invention.

Figure 2B is a schematic diagram of the spherical structure of the manganese citrate pore material.

Fig. 2C is an enlarged schematic view of the 2B area 2C.

The numbers and symbols corresponding to the different features are generally considered to be corresponding parts unless otherwise noted. The features illustrated are clearly labeled in the relevant embodiments and are not necessarily drawn to scale.

According to an embodiment of the present invention, there is provided an ozone decomposing material which is composed of a manganese manganate hole material. The ozone decomposing material has an ozone decomposition efficiency of more than 99% in an environment having a relative humidity of more than 95% RH. Wherein, the manganese tantalate pore material may have a molar ratio of manganese to lanthanum of 0.1 to 0.6.

In addition, according to another embodiment of the present invention, the present invention provides a method for producing an ozone decomposing material, comprising: dissolving a manganese salt in water to obtain a manganese salt solution; and adjusting the pH of the manganese salt solution to 7.5-11. In between (for example, 7.8-10); adding a sodium citrate aqueous solution to the manganese salt solution to obtain a first solution; heating the first solution in a closed environment to perform a cerium oxide ablation reaction to obtain a second solution And performing a drying process on the second solution to obtain an intermediate product; and, the intermediate product is subjected to a calcination process to obtain a manganese citrate pore material. Since the manganese citrate pore material is prepared by a cerium oxide ablation reaction, the manganese citrate pore material has high specific surface area characteristics and does not need to be further supported on other carriers. The manganese niobate hole material has a specific surface area of between 110 and 600 m ² /g.

Please refer to FIG. 1 , which is a flow chart for preparing an ozone decomposing material according to an embodiment of the present invention. First, a manganese salt is provided and dissolved in water to obtain a manganese salt solution (step 11). Wherein, the manganese salt solution may be manganese nitrate, manganese sulfate, manganese carbonate, manganese chloride, or a combination thereof, and the weight ratio of the manganese salt to water may be between 0.1 and 0.01. Next, the pH of the manganese salt solution is adjusted to between 7.5 and 11 (step 12). In the process of adjusting the pH, the pH of the above solution is adjusted with an alkaline solution. In an embodiment of the invention, the alkaline solution may be an aqueous solution of a commonly used inorganic basic salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate or aqueous ammonia. In some embodiments of the invention, the alkaline solution may be sodium carbonate to avoid excessive concentration of the manganese salt solution to cause aggregation due to the use of a strong base. If the pH of the manganese salt solution is less than 7.5, the manganese salt solution cannot be precipitated as manganese hydroxide. In addition, in some embodiments of the present invention, if the pH of the manganese salt solution is adjusted to be in the range of 7.8-10, the obtained manganese citrate hole material may have a specific surface area of between 110 and 600 m ² /g. The ozone decomposition efficiency of the manganese citrate pore material can be increased. Next, an aqueous solution of sodium citrate is added to the manganese salt solution to obtain a first solution (step 13). Wherein, the concentration of the sodium citrate aqueous solution may be between 0.01 and 0.1 M, and the molar ratio of manganese to cerium in the first solution is between 0.1 and 0.6. If the molar ratio of manganese to cerium is less than 0.1, the subsequently obtained manganese citrate pore material may have a low ozone decomposition efficiency due to a low proportion of manganese; if the molar ratio of manganese to cerium is greater than 0.6, then In the subsequently obtained manganese citrate pore material, the distribution of manganese will be less uniform, resulting in the formation of high crystallinity of manganese oxide, resulting in a decrease in surface area and activity of the resulting manganese citrate pore material, which is not conducive to catalysis. reaction. Next, the first solution is heated in a closed environment and subjected to a silicate exfoliation process to obtain a second solution (step 14). Wherein, heating the first solution in a closed environment ensures that the water in the solution does not dissipate during heating to facilitate the silicate exfoliation process during the formation of the manganese citrate. Wherein, the heating temperature in the step 14 may be between 80 and 150 ° C, and the reaction time may be between 1 and 72 hours. It should be noted that, referring to FIG. 2A-2B, the manganese citrate hole material 20 is composed of a plurality of hollow spherical structures 21. Referring to FIG. 2C, it is an enlarged view of the region 2C of FIG. 2B. In the process of forming the manganese citrate pore material 20 by silicate exfoliation, an octahedral lattice is formed first. The manganese oxide layer 22, and the tetrahedral lattice yttrium oxide 24, is gradually formed and deposited on the octahedral lattice manganese oxide layer 22. Due to the lattice mismatch, the subsequently obtained manganese citrate pore material is composed of a hollow spherical structure 21, which increases the specific surface area of the manganese citrate pore material. Next, the second solution is subjected to a drying process to obtain an intermediate product (step 15). Filtration may be carried out prior to the drying process, the water removed and the resulting filtrate dried. Wherein, the drying process temperature may be between 80-150 ° C, and the drying process may be between 1-24 hours. Finally, the intermediate product is subjected to a calcination process to obtain a manganese citrate hole material (step 16). Wherein, the temperature of the calcining process can be between 200-700 ° C, and the time of the calcining process can be between 3-24 hours.

Hereinafter, the ozonolysis material of the present invention and a preparation method thereof will be explained by the following examples to further clarify the technical features of the present invention.

Preparation of ozonolysis materials Example 1

First, 1.0 g of manganese nitrate (MnN ₂ O ₆ ) was added to 70.0 g of water to obtain an aqueous solution of manganese nitrate. Next, the manganese nitrate aqueous solution was titrated with 2.0 M sodium carbonate (Na ₂ CO ₃ ) water to adjust the pH to 10. Then, after stirring for 1 minute in a 40 ° C water bath, 13.64 g of sodium citrate solution (weight ratio of sodium citrate to water: 1:9) was added, and stirred at room temperature for 2.5 hours to obtain a monomanganate aqueous solution. , wherein the molar ratio of manganese to strontium is 1:2. Next, the aqueous manganese citrate solution was heated to 100 ° C in a closed atmosphere to carry out a cerium oxide ablation reaction for 24 hours. Next, the obtained product was filtered and the filtrate was collected and dried at 120 ° C for 2 hours. Next, calcination was carried out at 400 ° C for 3 hours to obtain a manganese niobate hole material (1). Finally, the manganese citrate pore material (1) was measured by a specific surface area (BET) analyzer, and the ratio of manganese to bismuth was measured by X-ray energy dispersive spectroscopy (EDS). The results are shown in Table 1.

Annex 1 is a transmission electron microscopy (TEM) spectrum of the manganese citrate pore material (1). Annex 2 is the scanning electron microscope (SEM) of the manganese citrate pore material (1), and the Annexes 3 and 4 are the manganese citrate pores by X-ray energy dispersive spectroscopy (EDS), respectively. Material (1) The distribution of manganese and strontium signals obtained by analysis. It can be seen from Annex 2-4 that manganese and lanthanide are uniformly dispersed in the citrate pore material (1).

Example 2

The experimental procedure was the same as in Example 1, except that the number of grams of sodium citrate solution (weight ratio of sodium citrate to water was 1:9) was changed so that the molar ratio of manganese to cerium of the obtained aqueous solution of manganese citrate was 1 : 3, to obtain a citrate hole material (2). The manganese citrate pore material (2) was measured by a specific surface area (BET) analyzer, and the ratio of manganese to bismuth was measured by X-ray energy dispersive spectroscopy (EDS). The results are shown in Table 1.

Example 3

The experimental procedure was the same as in Example 1, but the sodium citrate solution was changed (cartate The weight ratio of sodium to water is 1:9), so that the molar ratio of manganese to cerium in the obtained aqueous solution of manganese citrate is 1:4, and a cerium salt material (3) is obtained. The manganese citrate pore material (3) was measured by a specific surface area (BET) analyzer, and the ratio of manganese to bismuth was measured by X-ray energy dispersive spectroscopy (EDS). The results are shown in Table 1.

Example 4

The experimental procedure was the same as in Example 1, except that the number of grams of sodium citrate solution (weight ratio of sodium citrate to water was 1:9) was changed so that the molar ratio of manganese to cerium of the obtained aqueous solution of manganese citrate was 1 : 8, to obtain a citrate hole material (4). The manganese citrate pore material (4) was measured by a specific surface area (BET) analyzer, and the ratio of manganese to bismuth was measured by X-ray energy dispersive spectroscopy (EDS). The results are shown in Table 1.

Example 5

First, 1.0 g of manganese nitrate (MnN ₂ O ₆ ) was added to 70.0 g of water to obtain an aqueous solution of manganese nitrate. Next, the manganese nitrate aqueous solution was titrated with 2.0 M sodium carbonate (Na ₂ CO ₃ ) water to adjust the pH to 9.63. Then, after stirring for 1 minute in a 40 ° C water bath, 11.46 g of sodium citrate solution (weight ratio of sodium citrate to water: 1:9) was added, and stirred at room temperature for 2.5 hours to obtain a monomanganate aqueous solution. , wherein the molar ratio of manganese to strontium is 1:1.68. Next, the aqueous manganese citrate solution was heated to 100 ° C in a closed atmosphere to carry out a cerium oxide ablation reaction for 24 hours. Next, the obtained product was filtered and the filtrate was collected and dried at 120 ° C for 2 hours. Next, calcination was carried out at 400 ° C for 3 hours to obtain a manganese niobate hole material (5). Finally, the manganese citrate pore material (5) was measured by a specific surface area (BET) analyzer, and the results are shown in Table 2.

Example 6

The experimental procedure was the same as in Example 5 except that the aqueous manganese nitrate solution was adjusted to a pH of 8.9 to obtain a niobate hole material (6). The manganese citrate hole material (6) was measured by a specific surface area (BET) analyzer, and the results are shown in Table 2.

Example 7

The experimental procedure was the same as in Example 5 except that the aqueous manganese nitrate solution was adjusted to pH 8.06 to obtain a niobate hole material (7). The manganese niobate hole material (7) was measured by a specific surface area (BET) analyzer, and the results are shown in Table 2.

Example 8

The experimental procedure was the same as in Example 5 except that the aqueous manganese nitrate solution was adjusted to a pH of 7.83 to obtain a niobate hole material (8). The manganese niobate hole material (8) was measured by a specific surface area (BET) analyzer, and the results are shown in Table 2.

Ozone decomposition efficiency test

The citrate pore materials (1) and (4) obtained in Examples 1 and 4 were used as ozone decomposing materials, and were respectively filled in a catalyst chamber (tube diameter: 34 mm, filling height: 80 mm), and were respectively in relative The ozone catalytic efficiency test was carried out under the conditions of humidity of 60%, 80%, or >95%, and the results are shown in Table 3. The ozone catalytic efficiency test method was as follows: The ozone concentration (C0) before passing through the material was detected by a front-end Fourier transform infrared spectrometer (FTIR) with a steady gas flow of ozone gas (flow rate of 500 cc/min) at a concentration of 920 ppm. Then, the gas flow is passed through the catalyst chamber, and the ozone concentration (C1) is detected by a Fourier transform infrared spectrometer at a later stage, and the ozone catalytic efficiency is calculated as (1-C1/C0) x 100%.

According to the test results in Table 3, the decomposition efficiency of the tantalate pore material (1) or (4) to ozone is >99% under the conditions of relative humidity of 60%, 80%, or >95%.

As is apparent from the above experimental results, the present invention provides an ozonolysis material comprising a manganese citrate pore material. Since the manganese citrate pore material is prepared by the cerium oxide ablation reaction, the obtained manganese citrate pore material does not need to be supported on the carrier and has high specific surface area characteristics. Therefore, the ozone decomposing material of the present invention can effectively odor even in a high humidity environment. Oxygen is decomposed into oxygen.

The foregoing has been described in terms of the embodiments of the invention It will be apparent to those skilled in the art that the present invention can be understood and utilized in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; A person skilled in the art should be able to understand the corresponding description without departing from the spirit and scope of the invention, and various changes, substitutions and modifications can be made without departing from the spirit and scope of the invention.

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Claims (22)

An ozonolysis material comprising: a manganese citrate pore material, wherein a molar ratio of manganese to cerium is between 0.1 and 0.6, and an ozone decomposition efficiency of greater than 99% at a relative humidity greater than 95% RH. The ozonolysis material according to claim 1, wherein the manganese niobate hole material has a specific surface area of between 110 and 600 m ² /g. The ozonolysis material according to claim 1, wherein the manganese citrate pore material is a hollow spherical structure. The ozonolysis material according to claim 3, wherein the hollow spherical structure has an octahedral lattice manganese oxide layer, and a tetrahedral lattice yttria layer is formed in the octahedral lattice Above the manganese oxide layer. An ozonolysis material comprising the product obtained by dissolving a manganese salt in water to obtain a manganese salt solution; adjusting the pH of the manganese salt solution to between 7.5 and 11; adding an aqueous solution of sodium citrate to the manganese In the salt solution, a first solution is obtained; the first solution is heated in a closed environment, and a cerium oxide ablation reaction is performed to obtain a second solution; and the second solution is subjected to a drying process to obtain an intermediate product; The intermediate product is subjected to a calcination process to obtain a manganese citrate hole material. The ozonolysis material according to claim 5, wherein the pH of the manganese salt solution is adjusted to between 7.8 and 10. The ozonolysis material according to claim 5, wherein the manganese niobate hole material has a specific surface area of between 110 and 600 m ² /g. The ozonolysis material according to claim 5, wherein the molar ratio of manganese to cerium in the first solution is between 0.1 and 0.6. The ozonolysis material according to claim 5, wherein the manganese salt comprises manganese nitrate, manganese sulfate, manganese carbonate, manganese chloride, or a combination thereof. The ozonolysis material according to claim 5, wherein the temperature at which the first solution is heated in a closed environment is between 80 and 150 °C. The ozone decomposing material according to claim 5, wherein the drying process has a temperature between 80 and 150 °C. The ozone decomposing material according to claim 5, wherein the temperature of the calcining process is between 200 and 700 °C. The ozonolysis material according to claim 5, wherein the manganese niobate hole material has a hollow spherical structure. A method for producing an ozonolysis material, comprising: dissolving a manganese salt in water to obtain a manganese salt solution; adjusting a pH of the manganese salt solution to between 7.5 and 11; adding an aqueous solution of sodium citrate to the manganese salt solution Getting a first solution; Heating the first solution in a closed environment, performing a cerium oxide ablation reaction to obtain a second solution; performing a drying process on the second solution to obtain an intermediate product; and performing a calcination process on the intermediate product, A manganese citrate hole material is obtained. The method for producing an ozonolysis material according to claim 14, wherein the pH of the manganese salt solution is adjusted to between 7.8 and 10. The method for producing an ozone decomposing material according to claim 14, wherein the manganese niobate hole material has a specific surface area of between 110 and 600 m ² /g. The method for producing an ozone-decomposing material according to claim 14, wherein a molar ratio of manganese to cerium in the first solution is from 0.1 to 0.6. The method for producing an ozonolysis material according to claim 14, wherein the manganese salt comprises manganese nitrate, manganese sulfate, manganese carbonate, manganese chloride, or a combination thereof. The method for producing an ozone-decomposing material according to claim 14, wherein the temperature at which the first solution is heated in a closed environment is between 80 and 150 °C. The method for producing an ozone-decomposing material according to claim 14, wherein the drying process has a temperature of between 80 and 150 °C. The method for producing an ozonolysis material according to claim 14, wherein the temperature of the calcination process is between 200 and 700 °C. The system for preparing ozone decomposing materials as described in claim 14 In the method, a tetrahedral lattice yttria layer is formed on the octahedral lattice manganese oxide layer during the yttrium oxide ablation reaction.