JP5225337B2 - Composite materials that can expand the light absorption range of the original structural material - Google Patents

Description

  The present invention relates to a composite material capable of expanding the light absorption range of an original structural material. In green science and technology such as chemical processes, environmental processes, and solar cell applications, photo-induced physical or chemical reactions. To increase the operational reaction efficiency of the original structural material.

  In recent years, in addition to confronting the problem of shortage of storage due to drastic increase in the use of petroleum energy, the use of petroleum energy has led to a continuous increase in carbon dioxide emissions, and the greenhouse effect has been increasing. It becomes severe. Numerous scholars and experts have already invested in research on the problem of improving energy applications and removing carbon dioxide emissions in order to effectively solve the problem of shortage of petroleum energy and the continuous surge of carbon dioxide emissions. .

In energy development research, harvesting of sunlight and conversion of usable energy are important technologies that are clean and accepted by most people. Originally solar cells based on silicon (Si), cadmium (Cd), Group 3 and Group 4 (III-IV group) materials, as well as dye sensitization based on titanium dioxide (TiO ₂ ) As solar cells (dye-sensitized photovoltaics) have a huge price and manufacturing material advantage, they attract the attention and input of many R & D personnel. In addition, to reduce the carbon dioxide content in the atmosphere, photocatalytic reduction reaction is performed on carbon dioxide with semiconductors and photocatalysts such as titanium dioxide, silicon carbide (SiC), and gallium phosphorus (GaP) to formaldehyde (HCHO), methanol ( A method of obtaining a product such as CH ₃ OH) is utilized.

  In the two most advanced and popular green chemical technologies mentioned above, titanium dioxide is one of the preferred options for important structural materials, and the intrinsic band gap energy of titanium dioxide. Is 3.2 V, so that only the energy of light in the ultraviolet band (UV band) whose wavelength is smaller than 400 nm can be finally absorbed by titanium dioxide and converted into energy required for photochemical reaction. As a result, the wavelength range of light absorption and application of titanium dioxide is expanded to the visible light frequency band, and as a result, the operation efficiency of titanium dioxide becomes an important issue. The technology also produces relatively, but still lacks material modification methods and techniques that are flexible, light in weight, inexpensive, and do not require high temperature manufacturing processes.

  The inventor of the present application intends to improve and innovate in view of the respective disadvantages generated by the above-mentioned conventional method, and after earnestly researching through loneliness through hard work, finally the original structure of the present invention Successful research and completion of a composite material that can expand the light absorption range of the material.

  The main object of the present invention is to provide a composite material that contacts and fixes between homogeneous materials of different degrees of oxidation, and contacts an oxide containing one or more materials and its oxygen deficient oxide. The purpose is to achieve an increase in the light absorption frequency band range that effectively excites the light-driven reaction by fixing.

  A secondary object of the present invention is to provide a process for manufacturing a composite material that contacts and fixes homogeneous materials of different degrees of oxidation, and is composed of an oxide and an oxygen-deficient oxide. As such, there is no need for a high temperature calcinations process during the contact fixing operation process, and therefore it can be applied to plastics or other substrates not suitable for high temperature heating.

  An object of the present invention is to provide a composition method of a composite material that is flexible, light in weight, low in price, and does not require high temperature, and achieves a convenient and fast manufacturing process.

The foregoing invention object can be achieved, composite materials capable of expanding the light absorption range of the original structural material may include a single substrate, and one oxygen deficiency oxide film layer, and an oxide, the oxygen vacancies oxide film The layer and the oxide are composed of a material having the same composition material and different oxygen content, and the oxygen content of the oxygen deficient oxide is 50% or more of the oxygen content of the oxide, and the surface of the substrate oxygen vacancies oxide layer plated or deposited on, or the substrate itself is the i.e. oxygen deficiency oxide film layer, oxygen vacancies oxide of the oxygen-deficient oxide film layer was fixed in contact with the oxide later, to form a composite material, said the light sunlight or added to the composite material Ru is irradiated, can transmit the light energy in an oxygen-deficient oxide or oxygen deficiency oxide contact-fixing oxides in the By transferring, the electrons in the oxide (electro n) and holes are separated and the oxide undergoes a photocatalytic reaction .

It is the exploded view and synthetic | combination figure of the manufacturing process of the composite material which can expand the light absorption range of original structure material. It is the exploded view and synthetic | combination figure of the manufacturing process of the composite material which can expand the light absorption range of original structure material. It is the other exploded view and synthetic | combination figure of the manufacturing process of the composite material which can expand the light absorption range of original structure material. It is the other exploded view and synthetic | combination figure of the manufacturing process of the composite material which can expand the light absorption range of original structure material. It is a schematic diagram of implementation of the manufacturing process of the composite material which can expand the light absorption range of original structure material. It is the schematic diagram of other implementation of the composite material which can expand the light absorption range of original structure material. It is a spectrum measurement figure of the composite material which can expand the light absorption range of original structure material. A composite material that can expand the light absorption range of the original structural material is used for photocatalyst color removal reaction of methyl orange solution, and the ratio of methyl orange concentration to original concentration changes with the action time under irradiation of fluorescent lamp FIG.

[Example 1]
As shown with reference to FIG. 1 and FIG. 2, these are structural schematic diagrams of a composite material that can expand the light absorption range of the original structural material of the present invention. The substrate 1 includes a layer 2 and an oxide 3, and the substrate 1 is made of glass or plastic having a structural support strength, and oxygen deficient oxide particles can be plated or deposited on the surface of the substrate 1. An oxygen deficient oxide film layer 2 (shown with reference to FIGS. 1A and 1B) is formed on the substrate, or the substrate is made of titanium (Ti), tungsten (W), zinc (Zn), silicon (Si), Platinum (Pt), Silver (Ag), Cadmium (Cd), Iron (Fe), Tin (Sn), Indium (In), Antimony (Sb), Bismuth (Bi), Vanadium (V), Molybdenum (Mo), Metals such as lead (Pb) or strontium (Sr) and semiconductor materials themselves, their oxides Rui may be a composite with other materials, may be further substrate is also an oxygen-deficient oxide layer 2.
The oxygen-deficient oxide film layer 2 is composed by stacking oxygen-deficient oxide particles or inserting the oxygen-deficient oxide film layer 2, and the oxygen-deficient oxide film layer 2 contains titanium ( Ti), tungsten (W), zinc (Zn), silicon (Si), platinum (Pt), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium (In), antimony ( Sb), Bismuth (Bi), Vanadium (V), Molybdenum (Mo), Lead (Pb), Strontium (Sr) and other metals and semiconductor materials themselves, composed of oxides or composites with other materials .
The oxide 3 is composed of nano-oxide particles having photocatalytic activity after being irradiated with light, and is used to form a composite material after being fixed in contact with the oxygen-deficient oxide film layer 2.

  In addition, oxide particles can be deposited or plated on the substrate to form an oxide film layer, or the oxide film layer itself, that is, the substrate, and an oxygen-deficient oxide having the same composition as the oxide. After contacting and fixing the object, a composite material (not drawn in the drawing) is formed.

Among them, if the material of the substrate 1 is plastic, the oxygen-deficient oxide has the ability to reflect or absorb ultraviolet light, so that when the plastic material is regarded as the substrate 1, the service life of the plastic material substrate is extended. it can.
Among them, the oxygen-deficient oxide of the oxide 3 and the oxygen-deficient oxide film layer 2 are the same material, but have different degrees of oxidation, and the oxygen content of the oxygen-deficient oxide is insufficient. May form a fully oxidized compound state, and when the raw material is completely oxidized, the oxygen deficiency may be 50% or more of the required oxygen content.
Among them, the oxide particles of the oxygen-deficient oxide of the oxide 3 and the oxygen-deficient oxide film layer 2 can have a specific function, for example, a photocatalytic compound after being irradiated with the added light. .

As shown with reference to FIG. 3 to FIG. 4, these are schematic diagrams of implementations of composite materials that can expand the light absorption range of the original structural material of the present invention.
After the oxygen deficient oxide film layer 2 is plated or deposited on the surface of the substrate 1 and the oxygen deficient oxide 21 particles of the oxygen deficient oxide film layer 2 are in contact with and fixed to the oxide 3 particles, that is, The composite material 4 is formed, the light source 5 is absorbed, and the energy irradiated by, for example, sunlight or added light can be received by the particles of the oxygen deficient oxide 21, and the energy 6 is oxidized by the oxygen deficient oxidation. Can be transmitted into the particles of the oxide 21, or transferred into the particles of the oxide 3 that are in contact with and fixed to the oxygen-deficient oxide 21, and the energy in the particles of the oxide 3 is transmitted, thereby Electron 31 and hole 32 are separated, and the oxide 3 functions to perform photocatalytic reaction and light energy is also converted into other types of energy such as voice, light, heat, force, electricity or magnetism. Machine The drives.

  In addition, an oxide film layer can be plated or deposited on the surface of the substrate, or the substrate itself is an oxide film layer, and the oxide particles of the oxide film layer are in contact with and fixed to the oxygen-deficient oxide particles. Later, that is, a composite material (not drawn in the drawing) is formed.

In addition, among them, a crystal lattice (not drawn in the drawing) can be formed by itself, that is, a substrate having an oxygen-deficient oxide film layer through high-temperature treatment.
Among them, after the particles of the oxide 3 and the oxygen-deficient oxide 21 are contacted and fixed, the formed composite material 4 is heated to a temperature of 100 degrees Celsius or less for 1 hour or more to form the oxide 3 Water between the oxygen deficient oxide 21 can be removed.
Among them, the method of forming the composite material 4 by contacting and fixing the particles of the oxide 3 and the oxygen-deficient oxide 21 is the oxygen-deficient oxide film layer 2 on the surface of the substrate 1 or its own oxygen-deficiency. After the oxide film layer is immersed in an oxide colloid solution and the oxygen deficient oxide film layer is taken out, the solvent remaining on the oxygen deficient oxide film layer can be volatilized and removed.
Among them, the method of forming the composite material 4 by contacting and fixing the particles of the oxide 3 and the oxygen-deficient oxide 21 includes high temperature heating, electron beam heating, argon ion accelerated collision, laser peeling, or chemical vapor reaction. The oxide 3 particles float in the carrier gas or vacuum and can be adsorbed in contact with the oxygen-deficient oxide 21, and the oxide 3 particles floating in the carrier gas are also oxidized to the oxide 3 particles. Into the colloidal solution containing the carrier gas, allowing the carrier gas to float in the carrier gas as it leaves the colloidal solution.
Among them, after the particles of the oxide 3 and the oxygen-deficient oxide 21 are brought into contact with each other and fixed, extra materials such as organic substances, oxides, metals, and the like can be added for functional demand.
Among them, the oxide film layer or the oxygen-deficient oxide film layer that is itself a substrate can form a more stable crystal lattice through high-temperature treatment.

[Example 2]
In an embodiment of the present invention, titanium dioxide (TiO ₂ ) (oxide) and oxygen-deficient titanium dioxide (TiO _x, among which x is smaller than 2) substrate (oxygen-deficient oxide itself is the substrate) is contacted and fixed. The range of visible light can be expanded and applied to experiments for photocatalytic methyl orange removal reaction.

  The operation method is described as follows.

On a polystyrene substrate, oxygen deficient titanium dioxide (TiO ₂ ) is used as a target material, and a 60-nanometer TiO _x thin film is sputtered and coated, and among these, x is smaller than 2. The oxygen-deficient titanium dioxide thin film plating substrate is completed under the subsequent heat treatment greater than 100 ° C. yet. P-25 titanium dioxide having an average particle size of 21 nanometers dissolves in deionized water at a rate of 10 g / L to form a colloidal solution. The above-mentioned oxygen deficient titanium dioxide thin film plating substrate is placed in a P-25 titanium dioxide colloid solution, allowed to stand for 5 minutes, and then taken out. The above oxygen-deficient titanium dioxide substrate to which the P-25 colloidal solution is attached is heated in a general atmospheric environment at 90 ° C. for 10 minutes by a hot plate to volatilize and remove the solvent remaining on the substrate. The composite material substrate having a different structure is washed with a large amount of fresh water having a flow rate of more than 3 L / min for about 1 minute, and is naturally shaded in a general atmospheric environment to complete composite material plating substrates having different degrees of oxidation. As shown in FIG. 5, the main absorption peak boundary of the original P-25 titanium dioxide nanoparticles is about 380 nm. After being deposited on the TiO _x substrate, its main absorption peak is stretched to the visible light frequency band of 502 nm.

The above-mentioned composite plating substrates with different degrees of oxidation having a total area of about 8 cm ² are allowed to stand in a 50 cc methyl orange solution having a concentration of 4 uM. Observe that the concentration of methyl orange changes with time. As shown in FIG. 6, under visible light irradiation, the concentration of methyl orange in the solution decreases to 15% or less of the original concentration after 24 hours. The composite substrate of different structure of the present invention can absorb the light of the unusable visible light band of the original P-25 titanium dioxide nanoparticles, and performs the color removal reaction of the photocatalyst of the methyl orange solution.

  The composite material provided by the present invention capable of expanding the light absorption range of the original structural material further has the following advantages when compared with other conventional techniques.

1. When a specific material is used for a photo-induced chemical reaction and a light energy transfer reaction, an extension that induces an absorption range of an optical frequency band is realized.

2. The present invention does not require a high-temperature manufacturing process, so that a material such as plastic or glass can be used as the substrate, and the service life of the substrate can be extended.

  The foregoing detailed description is a specific description of the embodiments that can be implemented with respect to the present invention, but the embodiments are not used to limit the scope of the claims of the present invention. Any equivalent implementations or modifications completed without departing from the spirit of the present invention should be included in the claims of the present invention.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Oxygen deficient oxide film layer 3 Oxide 4 Composite material 5 Light source 6 Energy 21 Oxygen deficient oxide 31 Electron 32 Hole

Claims (15)

A composite material capable of expanding the light absorption range of an original structure material including one substrate, one oxygen-deficient oxide film layer, and an oxide,
The oxygen-deficient oxide film layer and the oxide are composed of the same composition material and different oxygen content materials,
The material of the substrate is glass or plastic having structural support strength,
The oxygen content of the oxygen deficient oxide is 50% or more of the oxygen content of the oxide,
Plating or depositing oxygen deficient oxide particles on the surface of the substrate to form an oxygen deficient oxide film layer on the substrate;
The oxygen deficient oxide film layer is composed of oxygen deficient oxide particles made of titanium (Ti) ,
The oxide is composed of nano-oxide particles made of titanium (Ti) ,
The oxide forms a composite material after fixing in contact with the oxygen deficient oxide of the oxygen deficient oxide,
When the composite material is irradiated with a light source, it can generate a phenomenon in which electrons and holes are separated,
A composite material that can expand the light absorption range of the original structural material.   The light absorption of the original structure material according to claim 1, wherein the oxygen-deficient oxide film layer is composed by stacking oxygen-deficient oxide particles or inserting an oxygen-deficient oxide film layer. Composite materials that can expand the range.   2. The composite capable of expanding the light absorption range of the original structural material according to claim 1, further comprising the oxygen deficient oxide film layer being capable of forming a more stable crystal lattice through a high temperature treatment. material.   The oxygen deficient oxide film layer is brought into contact with and fixed to the oxygen deficient oxide particles by immersing the oxygen deficient oxide film layer on the surface of the substrate in an oxide colloid solution, The light absorption range of the original structural material according to claim 1, further comprising volatilizing and removing the solvent remaining on the oxygen deficient oxide film layer after removing the layer. Composite material that can be expanded.   The method of contacting and fixing the oxide and oxygen-deficient oxide particles of the oxygen-deficient oxide film layer is performed by using high-temperature heating, electron beam heating, argon ion accelerated collision, laser peeling, or chemical vapor reaction. The range of light absorption of the original structural material according to claim 1, further comprising the oxide particles floating in a carrier gas or vacuum and adsorbing in contact with the oxygen-deficient oxide. Composite material. The oxide particles floating in the carrier gas further include injecting into the colloidal solution containing the oxide particles, and floating in the carrier gas as the carrier gas leaves the colloidal solution. A composite material capable of extending the light absorption range of the original structural material according to claim 5 .   After the oxide and the oxygen-deficient oxide film layer in the oxygen-deficient oxide film layer are contacted and fixed, the formed composite material is heated to a temperature of 100 degrees Celsius or less for 1 hour or more to thereby form the oxide and oxygen. The composite material capable of extending the light absorption range of the original structural material according to claim 1, further comprising removing moisture between the deficient oxide.   The method further includes adding another material such as an organic substance, an oxide, or a metal after the oxygen-deficient oxide film layer is in contact with and fixed between the oxygen-deficient oxide film layers. A composite material capable of expanding the light absorption range of the original structural material according to Item 1. A composite material capable of expanding the light absorption range of an original structure material including one substrate, one oxygen-deficient oxide film layer, and an oxide,
The oxygen-deficient oxide film layer and the oxide are composed of the same composition material and different oxygen content materials,
The oxygen content of the oxygen deficient oxide is 50% or more of the oxygen content of the oxide,
The oxygen deficient oxide film layer is composed of oxygen deficient oxide particles made of titanium (Ti) ,
The oxygen deficient oxide film layer itself is a substrate having structural strength,
The oxide is composed of nano-oxide particles made of titanium (Ti) ,
The oxide is fixed in contact with the oxygen deficient oxide of the oxygen deficient oxide film layer, and then forms a composite material,
When the composite material is irradiated with a light source, it can generate a phenomenon in which electrons and holes are separated,
A composite material that can expand the light absorption range of the original structural material. The light absorption of the original structure material according to claim 9 , wherein the oxygen deficient oxide film layer is composed by stacking oxygen deficient oxide particles or inserting an oxygen deficient oxide film layer. Composite materials that can expand the range. 10. The composite capable of expanding the light absorption range of the original structural material according to claim 9 , further comprising that the oxygen-deficient oxide film layer can form a more stable crystal lattice through high-temperature treatment. material. The method of contacting and fixing the oxide and oxygen-deficient oxide particles of the oxygen-deficient oxide film layer is performed by using high-temperature heating, electron beam heating, argon ion accelerated collision, laser peeling, or chemical vapor reaction. The light absorption range of the original structural material according to claim 9 , further comprising the oxide particles floating in a carrier gas or vacuum and adsorbing in contact with the oxygen-deficient oxide. Composite material. The oxide particles floating in the carrier gas further include injecting into the colloidal solution containing the oxide particles, and floating in the carrier gas as the carrier gas leaves the colloidal solution. A composite material capable of extending the light absorption range of the original structural material according to claim 12 . After the oxide and the oxygen-deficient oxide film layer in the oxygen-deficient oxide film layer are contacted and fixed, the formed composite material is heated to a temperature of 100 degrees Celsius or less for 1 hour or more to thereby form the oxide and oxygen. The composite material capable of extending the light absorption range of the original structural material according to claim 9 , further comprising removing moisture between the deficient oxide. After between oxygen deficiency oxide particles of the oxygen deficiency oxide film layer is in contact and fixed, extra other organics, the addition of a material such as oxide or metal, and further comprising, wherein Item 10. A composite material capable of expanding the light absorption range of the original structural material according to Item 9 .

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