Patent Application
20170156338
This application claims the priority benefit of Taiwan application serial no. 104140902, filed on Dec. 7, 2015. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.
Field of the Invention
The invention relates to a powder and an application thereof, and particularly to a composite powder, a hybrid material thereof, and a composite thin film thereof used for the visible light catalytic and anti-bacterial purposes.
Description of Related Art
A “photocatalyst” is a special catalyst. The photocatalyst may jump from valence band to conduction band by absorbing energy of light, and the place where an original electron exists appears an electric hole with positive electricity. That is a photogenerated electron or a photogenerated hole. Since such electron and hole has a stronger reduction and oxidation respectively, the reactant may proceed a chemical reaction to promote degradation, synthesis, and anti-bacteria of organic compounds. The above-mentioned process is called as a “photocatalytic reaction”.
Most of photocatalysts proceed a reaction under ultraviolet light nowadays. However, in the distribution of sunlight source, only about 5 percentage of whole solar energy is ultraviolet light. Thus, the efficiency of the usage of solar energy of such photocatalyst is very low, especially in a region without direct irradiation, a content of ultraviolet light thereof is lower. In addition, a content of ultraviolet light is very low in the light source in indoor environments. Also, ultraviolet light is harmful for human to induce skin diseases.
Currently, the industry is working on the study of the composite material having a photocatalytic characteristic with visible light irradiation and having an anti-bacterial ability without light irradiation simultaneously. The development of such material may make the photocatalyst toward to the inevitable trend of utility.
The invention provides a composite powder with a PN junction, a hybrid material thereof, and a composite thin film thereof used for the visible light catalytic and anti-bacterial purposes.
The invention also provides a composite powder used for degradation of a surrogate of chemical warfare agents so as to convert into a substance without toxicity.
The invention provides a composite powder used for the visible light catalytic and anti-bacterial purposes. The composite powder includes a plurality of N-type semiconductor particles and a plurality of P-type semiconductor nano-particles. The P-type semiconductor nano-particles cover surfaces of the N-type semiconductor particles respectively. A weight ratio of the N-type semiconductor particles and the P-type semiconductor nano-particles is in a range of 1:0.1 to 1:0.5. A PN junction is provided between each of the N-type semiconductor particles and the corresponding P-type semiconductor nano-particles.
According to an embodiment of the invention, a material of the N-type semiconductor particles comprises zinc oxide, and a material of the P-type semiconductor nano-particles comprises silver oxide.
According to an embodiment of the invention, a particle size of the N-type semiconductor particles is in a range of 0.1 μm to 5 μm, and a particle size of the P-type semiconductor nano-particles is in a range of 1 nm to 50 nm.
According to an embodiment of the invention, the P-type semiconductor nano-particles are uniformly distributed on the surfaces of the N-type semiconductor particles.
The invention provides a composite thin film used for the visible light catalytic and anti-bacterial purposes. The composite thin film includes the composite powder, wherein the composite thin film is formed on surfaces of a substrate from the composite powder by a sputtering process.
The invention provides a hybrid material used for the visible light catalytic and anti-bacterial purposes. The hybrid material comprises a polymer material and the composite powder. The composite powder is uniformly mixed with the polymer material.
According to an embodiment of the invention, the hybrid material covers a surface of a substrate or mixes within the substrate.
According to an embodiment of the invention, the polymer material comprises a thermoplastic resin material, a thermosetting resin material, or a combination thereof.
The invention also provides a composite powder used for the purpose of degradation of a surrogate of chemical warfare agents. The composite powder includes a plurality of support particles of alumina or zinc oxide and a plurality of silver oxide nano-particles. The silver oxide nano-particles cover surfaces of the support particles respectively. A weight ratio of the support particles and the silver oxide nano-particles covers a range from a low silver oxide ratio of 1:0.01 increasingly to pure silver oxide.
According to an embodiment of the invention, the surrogate includes 2-chloroethyl ethyl sulfide (2-CEES).
Based on the above description, in the composite material (including powders or thin films) of the invention, the N-type ZnO semiconductor particles in sub-micrometer size are covered by the P-type Ag2O semiconductor nano-particles in nanometer size to form the composite material with the PN junction. Thus, the ZnO/Ag2O composite material of the invention has an anti-bacterial ability without light irradiation, while the ZnO/Ag2O composite material of the invention has high photocatalytic ability and an advanced anti-bacterial ability under visible light irradiation. Therefore, the ZnO/Ag2O composite material of the invention may be applied in a variety of substrates to avoid vectors breeding. At the same time, the harmful organic substance in air may be continuously absorbed and degraded to achieve the effect of air purification.
In addition, the composite material of the invention may be mixed with the polymer material to form the hybrid material which has a photocatalytic characteristic and an anti-bacterial ability simultaneously. Besides, the invention also provides the Ag2O/Al2O3 and ZnO/Ag2O composite powders used for the purpose of degradation of a surrogate of chemical warfare agents, so that a threat of chemical war is reduced.
In order to make the aforementioned features and advantages of the disclosure more comprehensible, embodiments accompanied with figures are described in detail below.
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
Referring to
It should be noted that a PN junction is provided between each of the N-type semiconductor particles 102 and the corresponding P-type semiconductor nano-particles 104. In the composite powder 100 of the embodiment, the PN junction between the N-type semiconductor particles 102 and the corresponding P-type semiconductor nano-particles 104 may be formed a built-in electric field. When the composite powder 100 absorbs light energy of the embodiment, electrons and/or electric holes in the PN junction are separated by the built-in electric field, so that the visible light-excited electrons and/or electric holes have a stronger reduction capability and oxidation capability to conduct a photocatalytic reaction. The improved oxidation capability of this photocatalyst is expected to have the anti-bacterial ability. In another aspect, when the P-type semiconductor nano-particles 104 are silver oxide nano-particles of the embodiment, silver ions dissolved out therefrom may be used for the anti-bacterial purpose, so that the composite powder 100 has an anti-bacterial ability in a dark room (i.e. without light irradiation) of the embodiment. Therefore, the composite powder 100 of the embodiment not only has an anti-bacterial ability without light irradiation, but the composite powder 100 has high photocatalytic ability and an excellent anti-bacterial ability under visible light irradiation due to the collaborative capability of the PN junction.
In order to improve reliability of the invention, the following lists several examples and several comparative examples to illustrate the composite powder 100 of the invention further. Although the following experiments are described, the material used and the amount and ratio of each thereof, as well as handling details and handling procedures, etc., can be suitably modified without exceeding the scope of the invention.
Accordingly, restrictive interpretation should not be made to the invention based on the embodiments described below.
First, a manufacturing method and an experimental method of Example 1 (the composite powder with a plurality of zinc oxide particles and a plurality of silver oxide nano-particles which is called for short as ZnO/Ag2O composite powder hereinafter) is illustrated.
First, 73.593 mg silver nitrate is dissolved in 1000 ml deionized water to Balm silver nitrate aqueous solution which is uniformly stirred for 30 minutes. Next, 500 mg zinc oxide powder is added thereto and stirred for 30 minutes, so that silver ions are uniformly distributed on surfaces of zinc oxide. Then, 34.63 mg, 100 ml sodium hydroxide aqueous solution is dropwise added thereto, and then washed by deionized water and alcohol with high purity respectively for three times after reaction for 30 minutes. The temperature of the thermostatic water bath of the reduced pressure concentrator is set at 60° C. to remove excess alcohol and water.
Photocatalytic Experiment
The ZnO/Ag2O composite powder of Example 1 is used as a photocatalyst. Methylene Blue (MB) is selected as a dye. A 150 watt halogen light tube is selected as light source to provide visible light source.
First, 20 mg ZnO/Ag2O composite powder of Example 1 used as a catalyst is added into 100 ml prepared dye solution, and the decomposition experiment of visible light irradiation is conducted in 10 ppm dye solution. In the experiment, the catalyst is uniformly ultrasonic-vibrated and then is stirred in a dark room for 30 minutes in the dye solution. Then 5 ml dye solution is taken out. Next, the solution is placed and stirred on a magnet stirrer and irradiated with visible light. For the observation of changes in the dye concentration, 5 ml dye solution is taken out every 5-15 minutes until the dye is completely degraded or sustained for 30 minutes.
In the following, the manufacture and the experiment of the ZnO/Ag2O composite powders of Example 2 to Example 5 and the powders of Comparative Examples 1-2 are conducted in similar methods described above.
After that, results of the photocatalytic experiments of Examples 1-5 and Comparative Examples 1-2 are plotted to obtain a dye decomposition ratio along with time, wherein the horizontal axis is time (minute), and the vertical axis is the dye decomposition ratio (residue concentration/original concentration represented by C/Co).
As shown in
Following the results of the photocatalytic experiment, the ZnO/Ag2O composite powder of Example 2 having the best photocatalytic ability of the invention is used to conduct the anti-bacterial experiment of E. Coli.
Anti-Bacterial Experiment
First, the required Luria-Bertani broth (LB broth) and LB agar are prepared. The LB broth is the required nutrient solution mainly for bacterial growth while the LB agar is used as the last bacterial plating count to clearly observe the growing number of bacteria. The detailed experimental procedures are as follows. First, the LB in the liquid state is sterilized under high temperature and high pressure for 20 minutes. The sterilization process can remove the microorganism attached on the broth and the agar. The LB in the above-mentioned liquid state is to dissolve Tryptone and Yest extract into pure water. The LB agar is formed by adding agar in the liquid LB, sterilizing in the sterilizing compartment, and then pouring the LB agar into a dish in fixed-size to form the gel which is stored in the refrigerator cold room at 4° C.
When preparation of the strain liquid, E. Coli strain liquid which is continuously stirred and prepared the day before taken out is added into the LB broth in a ratio of 1:100 to amplify. The purpose thereof is to dilute and activate the E. Coli strain liquid. Then, 1 ml of the LB broth (without E. Coli) and 1 ml of the diluted E. Coli strain liquid are taken out respectively and dropped into different quartz tubes. A concentration of the strain liquid is measured by a biochemical analysis spectrometer. An optical density (OD; 1OD=6×107 CFU; CFU is Colony-Forming Units) of the diluted E. Coli strain liquid is measured by using 595 nm wavelength while the LB broth (without E. Coli) is used as a background value. After the measurement, 1 OD strain liquid is adjusted to a concentration of 8.2×108 CFU by the LB broth.
5 mg ZnO/Ag2O composite powder is uniformly mixed with the adjusted E. Coli strain liquid to form a mixed solution. Then, 1 ml mixed solution is taken out and placed in a 1.5 ml capacity plastic vial. The plastic vial with E. Coli strain liquid is placed under 20W LED light source (i.e. under visible light irradiation; the experimental results thereof as shown in
Example 6 is used the ZnO/Ag2O composite powder of Example 2 (i.e. a weight ratio of ZnO and Ag2O is 1:0.2) mixing uniformly with the adjusted 1 ml E. Coli strain liquid to form a mixed solution (which is called for short as ZnO/Ag2O mixed solution hereinafter). Next, under visible light irradiation, the ZnO/Ag2O mixed solution of Example 6 is used to conduct the above-mentioned anti-bacterial experiment.
Example 7 is used the ZnO/Ag2O mixed solution of Example 6 to conduct the above-mentioned anti-bacterial experiment in a dark room.
From
Composite thin Film Technology
In addition, the composite powder 100 of the embodiment maybe exist in a powder form and a thin film form. The following will illustrate the manufacturing method of the composite thin film.
In the embodiment, the composite powder 100 may be formed a composite thin film on a surface of a substrate by a sputtering process. For example, the forming procedures of the composite thin film are as follows. First, the composite powder 100 with a composition of Example 3 is placed in a graphite mold, and then is heated and pressed at 180° C. for 30 minutes under argon environment so as to form a 2-inch target. After that, the target is placed in a RF magnetron sputter to conduct physical vacuum sputtering thin film, so that the composite thin film 200 is sputtered on fabrics 300. As shown in
The anti-bacterial experiment for composite thin films is the same as Example 6 except that a diluted E. Coli strain liquid of 104 CFU by the LB broth is used to mix with the ZnO/Ag2O-coated nonwoven fabrics.
Example 8 is used the ZnO/Ag2O composite film, sputtered with a target of Example 3 on fabrics, to cut into the dimensions of 2 (length)×1.5 (width) cm2 and mix with the 1 ml diluted E. Coli strain liquid. After LED visible light irradiation for 1-3 hours, 0.1 ml strain liquid is taken out at each stage and uniformly coated on the LB agar dish. After the dish is placed in an incubator for 7 hours, the dish is taken out and the numbers of bacterial colonies are observed.
Example 9 is used the composite film of Example 8 to conduct the above-mentioned anti-bacterial experiment in a dark room.
From
Besides, the composite powder 100 may be used alone and used with other polymer materials together to increase the scope of the application. In specific, the invention provides a hybrid material including polymer materials and the composite powder 100 of the embodiment, wherein the composite powder 100 is uniformly mixed with the polymer materials. The polymer materials include thermoplastic resin materials, such as nylon, polyethylene, polypropylene, polyester, and the like, thermosetting resin materials, such as epoxy resin, polyurethane, and the like, or a combination thereof.
In an embodiment, the hybrid material of the embodiment may cover the surface of the substrate or mix within the substrate. The substrate may be, such as a filter, fabrics, non-fabrics, a plastic material, glass, tiles, a metallic material, a biomedical material, paint, or a variety of substrates which need to have a photocatalytic characteristic and an anti-bacterial ability simultaneously. The scope of the application of the hybrid material is not limited to the invention.
Organic/Inorganic Hybrid Composite Material Technology
A hybrid material of 40 wt % ZnO/Ag2O composite powder and 60 wt % nylon (Elvamide® Nylon 8061) is used as an example to illustrate. First, 860 mg nylon particles (Elvamide® Nylon 8061) are dissolved in 50 ml anhydrous ethanol, and then are heated to 80° C. by a heating plate and agitated by a magnet stirrer for 2 hours to prepare a nylon solution A. Next, the pre-weighed 80 mg ZnO/Ag2O composite powder is added into anhydrous ethanol respectively to prepare a solution B. The solution B is added into the nylon solution A according to the desired proportion, so that a total weight of the polymer and the inorganic powder is fixed in 200 mg, and then ultrasonic-vibrated for 3 hours to form a Nylon-ZnO/Ag2O coating solution. After that, the coating solution is poured in culture dishes, and the prepared nonwoven fabrics are immersed in the designate dishes respectively and ultrasonic-vibrated for 15 minutes. At this time, the nonwoven fabrics are covered by the Nylon-ZnO/Ag2O coating solution, and then taken out and placed in a fume hood. After drying the nonwoven fabrics for 12 hours, the nonwoven fabrics covering the Nylon-ZnO/Ag2O hybrid film are formed.
Example 10 is used the Nylon-ZnO/Ag2O hybrid film to cut into the dimensions of 2 (length)×1.5 (width) cm2 and mix with the 1 ml diluted E. Coli strain liquid as applied for Example 8. After LED visible light irradiation for 1-3 hours, 0.1 ml strain liquid is taken out at each stage and uniformly coated on the LB agar dish. After the dish is placed in an incubator for 7 hours, the dish is taken out and the numbers of bacterial colonies are observed.
Example 11 is used the hybrid film of Example 10 to conduct the above-mentioned anti-bacterial experiment in a dark room.
From
In addition, the embodiment also includes a composite powder used for the purpose of degradation of a surrogate of chemical warfare agents. The composite powder includes a plurality of support particles of alumina or zinc oxide and a plurality of silver oxide nano-particles. The silver oxide nano-particles uniformly and discontinuously cover surfaces of the support particles. In an embodiment, a weight ratio of the support particles and the silver oxide nano-particles covers a range from a low silver oxide ratio of 1:0.01 increasingly to pure silver oxide. The surrogate may be 2-chloroethyl ethyl sulfide, for example.
Toxic Chemical Elimination Experiment
Ag2O/Al2O3 Composite Powder
First, an isopropanol solution with a concentration of 0.35% and a volume of 50 ml 2-chloroethyl ethyl sulfide (C2H5SCH2CH2Cl, 2-CEES) is prepared. Next, the isopropanol solution with 2-CEES is added into 50 mg Ag2O/Al2O3 composite powder and quickly stirred, and then is separated into 3 batches to react for 15, 30, and 60 minutes respectively under the fluorescent room lamp. After the reaction, 1 ml isopropanol is added therein respectively to terminate the reaction. The terminated reaction solution is separated by a centrifugal machine, and the reactants are identified by a GC-MS (Perkin Elmer Clarus 600T, Turku, Finland) mass spectrometer.
In the following, experiments of the composite powders of Examples 12-13 and Comparative Examples 3-4 are conducted in similar methods described above.
As shown in
ZnO/Ag2O
In the following, toxic chemical elimination experiments of the composite powders of Examples 1-3 and Comparative Examples 1-2 are conducted in similar methods described above, except the dark test condition is also included.
As shown in
In summary, in the composite material (including powders or thin films) of the invention, the N-type ZnO semiconductor particles in sub-micrometer size are covered with the P-type Ag2O semiconductor nano-particles in nanometer size to form the composite material with the PN junction. Thus, the ZnO/Ag2O composite material of the invention has an anti-bacterial ability without light irradiation, while the ZnO/Ag2O composite material of the invention has a high photocatalytic ability and an advanced anti-bacterial ability under visible light irradiation. Therefore, the ZnO/Ag2O composite material of the invention may be applied in a variety of substrates to avoid vectors breeding. At the same time, the harmful organic substance in air may be continuously absorbed and degraded to achieve the effect of air purification.
In addition, the composite material of the invention may be mixed with the polymer material to form the hybrid material which has a photocatalytic characteristic and an anti-bacterial ability simultaneously. Besides, the invention also provides the Ag2O/Al2O3 and ZnO/Ag2O composite powders used for the purpose of degradation of a surrogate of chemical warfare agents, so that a threat of chemical war is reduced.
Although the invention has been described with reference to the above embodiments, it will be apparent to one of ordinary skill in the art that modifications to the described embodiments may be made without departing from the spirit of the invention. Accordingly, the scope of the invention is defined by the attached claims not by the above detailed descriptions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 104140902 | Dec 2015 | TW | national |
