TWI386308B - It is possible to enlarge the composite material in which the original constituent material absorbs the light range - Google Patents

Description

A composite material that can expand the range of light absorbed by the original constituent material

The composite material of the invention capable of expanding the absorption range of the original constituent materials is applied to green technologies such as chemical engineering, environmental engineering and solar cell applications, and needs to be applied to photo-induced physical or chemical reactions to increase the original composition. The operational efficiency of the material.

In recent years, due to the surge in the use of petroleum energy, the problem of insufficient storage is faced. Moreover, the use of petroleum energy has caused an increase in carbon dioxide emissions, which has made the greenhouse effect increasingly serious. In order to effectively solve the problem of oil shortage and carbon dioxide emissions, many scholars and experts have been investigating the improvement of energy applications and the elimination of carbon dioxide emissions.

In the study of energy development, the harvesting and conversion of sunlight into usable energy is an important technology that is clean and accepted by most people. In addition to the original solar cells based on bismuth (Si), cadmium (Cd), and III-IV group materials, titanium dioxide (TiO ₂ )-based dye-sensitized solar cells (dye-sensitized photovoltaic) ), such as U.S. Patents 4190950, 4127738, and 4105470, etc., attracting the attention and input of many research and development personnel due to their great price and manufacturing material advantages. In addition, in the reduction of the carbon dioxide content in the atmosphere, a photocatalytic reduction reaction of carbon dioxide with a semiconductor photocatalyst such as titanium dioxide, lanthanum carbide (SiC) or gallium phosphide (GaP) is carried out to obtain formaldehyde (HCHO) and methanol (CH ₃ OH). Product method.

Titanium dioxide is one of the most important constituent materials in the two most advanced green chemical technologies mentioned above, but since the band gap energy of titanium dioxide is 3.2V, only the ultraviolet band with a wavelength of less than 400nm ( UV band) The energy of light can be absorbed by titanium dioxide and converted into the required photochemical reaction energy. Therefore, it is an important issue to expand the range of wavelengths of light that can be absorbed and applied to the visible light band, thereby increasing the operating efficiency of titanium dioxide. Many materials of modification technology are also relatively produced, for example, US Pat. No. 6,306,343, 5,981,426, 5780380, 6592842 and 5853866, etc., but still lack a material modification method and technology for flexibility, light weight, low cost and no high temperature process.

In view of the shortcomings derived from the previous usage methods, the inventor of this case has improved and innovated, and after painstaking research, finally successfully developed a composite material that can expand the absorption range of the original constituent materials.

The main object of the present invention is to provide a composite material which is contact-fixed between homogenized materials with different degrees of oxidation. By contacting and fixing an oxide containing one or more materials and an oxygen-deficient oxide thereof, the absorption light for effectively exciting the light-driven reaction is achieved. The purpose of increasing the band range.

The secondary object of the present invention is to propose a process for contacting and fixing a composite material with different oxidation degrees of homogenous materials. When the oxide and the oxygen-deficient oxide are combined into a composite material, high-temperature calcination treatment is not required during the contact fixation operation ( Calcinations process), therefore suitable for use in plastic or other substrates that are not suitable for high temperature heating.

The object of the present invention is to provide a composite material composition method which is flexible, light in weight, inexpensive and does not require high temperature, and achieves the purpose of convenient and rapid process.

A composite material which can expand the absorption range of the original constituent material and a process thereof can be achieved by plating or depositing an oxygen-deficient oxide film layer on the surface of the substrate, or the substrate itself is an oxygen-deficient oxide a film layer, the oxygen-deficient oxide layer of the oxygen-deficient oxide film layer is contacted with the first oxide and fixed to form a composite material. After sunlight or external light is irradiated, the light energy can be received by the oxygen-deficient oxide to make the light Can be transferred into the oxygen-deficient oxide, or transferred to the oxide fixed in contact with the oxygen-deficient oxide, so that the electrons and holes in the oxide are separated to drive the oxide Photocatalytic reaction function.

Please refer to FIG. 1 ^to FIG. 2 , which is a schematic structural view of a composite material capable of expanding the absorption range of the original constituent material, comprising: a substrate 1 made of glass or plastic having structural support strength. Anodized oxide particles are plated or deposited on the surface of the substrate 1, and an oxygen-deficient oxide film layer 2 is formed on the substrate 1 (refer to FIG. 1A and FIG. 1B); or, the substrate It may also be titanium (Ti), tungsten (W), zinc (Zn), bismuth (Si), platinum (Pt), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium ( a metal or semiconductor material such as In), bismuth (Sb), bismuth (Bi), vanadium (V), molybdenum (Mo), lead (Pb) or strontium (Sr) itself, an oxide thereof, or a composite thereof with other materials The substrate is also an oxygen-deficient oxide film layer 2 (please refer to FIG. 2A and FIG. 2B); an oxygen-deficient oxide film layer 2 is deposited or embedded by particles of anoxic oxide. The oxygen-deficient oxide film layer 2 is composed of the oxygen-deficient oxide particles of the oxygen-deficient oxide film layer 2, which are titanium (Ti), tungsten (W), zinc (Zn), bismuth (Si), and platinum (Pt). ), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium (In), antimony (Sb), antimony (B) i) a metal or semiconductor material such as vanadium (V), molybdenum (Mo), lead (Pb) or strontium (Sr), an oxide thereof, or a composite thereof with other materials; an oxide 3, the oxidation The material 3 is composed of nano-oxide particles having photocatalytic activity after being irradiated with light, and is used for contact with an anoxic oxide film layer 2 to form a composite material.

In addition, the oxide particles may be deposited or plated on a substrate to form an oxide film layer, or the oxide film layer itself is a substrate, and the oxygen-deficient oxide having the same composition as the oxide may be used. After being fixed in contact with the oxide, a composite material (not shown in the drawings) is formed.

Wherein, if the material of the substrate 1 is plastic, the oxygen-deficient oxide has the ability of reflecting or absorbing ultraviolet light, and when the plastic material is used as the substrate 1, the service life of the plastic substrate can be prolonged; wherein the oxide 3 And the anoxic oxide layer of the anoxic oxide film layer 2 is a homogenous material, but has a different degree of oxidation, and the oxygen content of the anoxic oxide is insufficient to cause the material to form a fully oxidized state of the compound, and the degree of hypoxia can be It is 50% or more of the oxygen content required for the complete oxidation of the raw material; wherein the oxide particles of the oxide 3 and the oxygen oxide film layer 2 may have a specific function after being irradiated with external light, such as a photocatalyst. Compound.

Referring to FIG. 3 ^to FIG. 4 , a schematic diagram of a composite material capable of expanding the absorption range of the original constituent material is performed by plating or depositing an oxygen-deficient oxide film layer 2 on the surface of the substrate 1 . After the oxygen-deficient oxide 21 particles of the oxygen oxide film layer 2 are fixed in contact with the oxide 3 particles, a composite material 4 is formed, and the energy absorbed by the light source 5, such as sunlight or external light, can be absorbed by the oxygen-deficient oxide. The particles are received so that the energy 6 can be transferred into the particles of the anoxic oxide 21 or transferred to the oxide 3 particles fixed in contact with the anoxic oxide 21, and the energy transfer in the oxide 3 particles causes The electrons 31 and the holes of the oxide are separated to drive the oxide 3 to perform a photocatalytic reaction, and the light energy can be converted into other types such as sound, light, heat, force, electricity or magnetism. The function of energy.

In addition, an oxide film layer may be plated or deposited on the surface of the substrate, or the substrate itself is an oxide film layer, and after the oxide particles of the oxide film layer are in contact with an anoxic oxide particle, That is, a composite material is formed (not shown).

In addition, the substrate itself is an oxygen-deficient oxide film layer, which can be subjected to high temperature treatment to form further lattice stability (not shown); wherein the oxide 3 and the oxygen-deficient oxide 21 particles are interposed After the contact is fixed, the formed composite material 4 can be heated at a temperature below 100 degrees Celsius for more than one hour to remove moisture between the oxide 3 and the anoxic oxide 21; wherein the oxide 3 and the oxygen-deficient oxide 21 particles The method of forming the composite material 4 by contact between the two can be: immersing the oxygen-deficient oxide film layer 2 on the surface of the substrate 1 or the substrate anoxic oxide film layer in the oxide colloid solution, and taking out the After the oxygen-deficient oxide film layer, the residual solvent on the oxygen-deficient oxide film layer is volatilized and removed; wherein the contact between the oxide 3 and the anoxic oxide 21 particles is fixed to form the composite material 4, which may be: High temperature heating, electron beam heating, argon ion accelerated impact, laser stripping or chemical vapor phase reaction, so that the oxide 3 particles float in the carrier gas or vacuum, and the contact is adsorbed to the oxygen-deficient oxide 21; Yu Zai The oxide 3 particles of the body gas are injected into the colloidal solution containing the oxide 3 particles, and float in the carrier gas as the carrier gas leaves the colloidal solution; wherein, after the contact between the oxide 3 and the anoxic oxide 21 particles is fixed, Other organic materials, oxides or metals may be additionally added for further functional requirements; wherein the oxide layer or the oxygen-deficient oxide layer of the substrate itself may be subjected to high temperature treatment to form a more stable crystal. grid.

Example:

Embodiments of the present invention are titanium dioxide (TiO ₂ ) (oxide) and oxygen-deficient titanium dioxide (TiO _x , wherein x is less than 2) substrate (anoxic oxide itself is a substrate) in the visible range of visible light absorption expansion, and can be applied Experiment on photochromic methyl orange decolorization reaction.

The mode of operation is described as follows: on a polystyrene substrate, an oxygen-deficient titanium dioxide (TiO ₂ ) is used as a target, and a 60 nm TiO _x film is sputtered, wherein x is less than 2. The substrate is plated with an oxygen-deficient titanium dioxide film without subsequent heat treatment at more than 100 °C. P-25 titanium dioxide having an average particle size of 21 nm was dissolved in deionized water at a ratio of 10 g/L to form a colloidal solution. The anoxic titanium dioxide film-coated substrate was placed in a P-25 titania colloidal solution, and allowed to stand for 5 minutes, and then taken out. The anoxic titanium dioxide substrate to which the P25 colloidal solution was attached was heated by a hot plate at 90 ° C for 10 minutes in a general atmosphere, and the residual solvent on the substrate was volatilized and removed. The completed composite substrate of different structures is rinsed with a large amount of fresh water having a flow rate of more than 3 L/min for about 1 minute, and is naturally air-dried in a general atmosphere, and the composite substrate is plated with different oxidation degrees. The absorption spectrum is shown in Figure 5. The main absorption peak boundary of the original P-25 titanium dioxide nanoparticles is about 380 nm. After attaching it to the TiO _x substrate, its main absorption peak was extended to 502 nm in the visible light band.

The composite materials of different oxidation degrees with a total area of about 8 cm ² were plated, placed in a 50 cc methyl orange solution at a concentration of 4 uM, and allowed to stand under a 6 W removal ultraviolet ray lamp to observe the concentration of methyl orange in the solution. The change of time. As shown in Fig. 6, under visible light irradiation, the concentration of methyl orange in the solution was reduced to less than 15% of the original concentration after 24 hours. The composite structural substrate of the different structures of the present invention can absorb the light in the visible light band which cannot be used by the original P-25 titanium dioxide nanoparticle, and perform the photocatalytic decolorization reaction of the methyl orange solution.

The composite material provided by the invention can enlarge the absorption range of the original constituent material, and has the following advantages when compared with other conventional technologies:

1. Achieving the expansion of the absorption range of the excitation light band in a specific material for the photoinduced chemical reaction and the light energy transfer reaction.

2. The invention does not require a high temperature process, so a material such as plastic or glass can be used as the substrate, which can extend the service life of the substrate.

The detailed description of the preferred embodiments of the present invention is intended to be limited to the scope of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.

To sum up, this case is not only innovative in terms of technical thinking, but also able to enhance the above-mentioned multiple functions compared with conventional articles. It should fully comply with the statutory invention patent requirements of novelty and progressiveness, and apply in accordance with the law. I urge you to approve this article. Invention patent application, in order to invent invention, to the sense of virtue.

1. . . Substrate

2. . . Oxygen-deficient oxide film

3. . . Oxide

4. . . Composite material

5. . . light source

twenty one. . . Oxygen-deficient oxide

31. . . electronic

32. . . Hole

6. . . energy

FIG. 1A and FIG. 1B are process decomposition diagrams and composite diagrams of a composite material capable of expanding the absorption range of the original constituent material;

2A and 2B are another exploded view and a composite view of a process for expanding a composite material absorbing light range of the original constituent material;

Figure 3 is a schematic view showing a process for realizing a composite material capable of expanding the range of light absorbed by the original constituent material;

Figure 4 is a schematic view showing another embodiment of a composite material which can expand the range of light absorbed by the original constituent material;

Figure 5 is a spectrogram of a composite material that can expand the range of light absorbed by the original constituent material;

Fig. 6 is a photocatalytic color removal reaction for a methyl orange solution which can enlarge the composite material absorbing light range, and the ratio of methyl orange concentration to the original concentration ratio with the action time under the illumination of the fluorescent lamp.

twenty one. . . Oxygen-deficient oxide

3. . . Oxide

31. . . electronic

32. . . Hole

4. . . Composite material

5. . . light source

6. . . energy

Claims (21)

A composite material capable of expanding the range of light absorbed by the original constituent material, which is composed of a material having different oxygen content of the same constituent material, comprising: a monooxide which is contacted with an anoxic oxide to form a composite material. After the composite material is irradiated by the light source, electron hole separation occurs. A composite material according to claim 1, wherein the oxygen content of the oxygen-deficient oxide is 50% or more of the oxygen content of the oxide. A composite material according to the first aspect of the patent application, which can expand the absorption range of the original constituent material, wherein the constituent materials of the oxide are titanium (Ti), tungsten (W), zinc (Zn), and antimony (Si). , platinum (Pt), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium (In), antimony (Sb), antimony (Bi), vanadium (V), molybdenum (Mo) A metal or semiconductor material such as lead (Pb) or strontium (Sr) itself or a composite thereof with other materials. A composite material according to the first aspect of the invention, which can expand the absorption range of the original constituent material, wherein the constituent materials of the anoxic oxide are titanium (Ti), tungsten (W), zinc (Zn), and antimony ( Si), platinum (Pt), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium (In), antimony (Sb), antimony (Bi), vanadium (V), molybdenum ( A metal or semiconductor material such as Mo), lead (Pb) or strontium (Sr) itself or a composite thereof with other materials. The composite material capable of expanding the absorption range of the original constituent material comprises the following steps, comprising: a substrate, the material of which is a glass or plastic having structural support strength, which can be plated or deposited on the surface of the substrate. Oxygen oxide particles, on the substrate, forming an oxygen-deficient oxide film layer; an oxygen-deficient oxide film layer composed of particles of anoxic oxide; and an oxide, the oxide is Nye The rice oxide particles are formed by contact with an oxygen-deficient oxide layer of an anoxic oxide film to form a composite material. A composite material according to claim 5, which can expand the absorption range of the original constituent material, wherein the oxygen-deficient oxide particles of the oxygen-deficient oxide film layer are titanium (Ti), tungsten (W), Zinc (Zn), bismuth (Si), platinum (Pt), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium (In), antimony (Sb), antimony (Bi), A metal or semiconductor material such as vanadium (V), molybdenum (Mo), lead (Pb) or strontium (Sr) itself, an oxide thereof, or a composite thereof with other materials. A composite material according to claim 5, which is capable of expanding the absorption range of the original constituent material, wherein the oxygen-deficient oxide film layer is deposited by or embedded in an oxygen-deficient oxide film layer of an anoxic oxide particle. composition. A composite material according to claim 5, which can expand the absorption range of the original constituent material, wherein the oxygen-deficient oxide film layer further comprises a high temperature treatment to form a more stable crystal lattice. A composite material according to claim 5, which can expand the absorption range of the original constituent material, wherein the method of contacting and fixing the oxygen-deficient oxide particles of the oxygen-deficient oxide film layer further comprises vacating the surface of the substrate The oxygen oxide film layer is immersed in the oxide colloid solution, and after removing the oxygen-deficient oxide film layer, the residual solvent on the oxygen-deficient oxide film layer is volatilized and removed. A composite material according to claim 5, which can expand the absorption range of the original constituent material, wherein the method of contacting the oxide with the oxygen-deficient oxide particle of the oxygen-deficient oxide film layer further comprises: utilizing High temperature heating, electron beam heating, argon ion accelerated impact, laser stripping or chemical vapor phase reaction causes the oxide particles to float in a carrier gas or a vacuum while contacting the adsorbed oxygen-deficient oxide. The composite material according to claim 10, which can expand the absorption range of the original constituent material, wherein the oxide particles floating in the carrier gas further comprise: injecting into the colloidal solution containing the oxide particles, along with the carrier The gas leaves the colloidal solution and floats in the carrier gas. A composite material according to claim 5, which can enlarge the absorption range of the original constituent material, and the composite material formed by the contact between the oxide and the oxygen-deficient oxide film of the oxygen-deficient oxide film layer is further formed. It is heated at a temperature below 100 degrees Celsius for more than one hour to remove moisture between the oxide and the oxygen-deficient oxide. A composite material according to claim 5, which can enlarge the absorption range of the original constituent material, and the contact between the anoxic oxide particles of the anoxic oxide film layer is further fixed, and further includes adding other organic substances, oxides or Materials such as metal. A composite material capable of expanding the range of light absorbed by the original constituent material comprises the following steps: comprising: an oxygen-deficient oxide film layer composed of particles of anoxic oxide, which itself is a substrate having structural strength The monooxide, which is composed of nano-oxide particles, is used to form a composite material after being contacted with an oxygen-deficient oxide layer of an anoxic oxide film layer. A composite material according to claim 14, wherein the oxygen-deficient oxide particles of the oxygen-deficient oxide film layer are titanium (Ti), tungsten (W), Zinc (Zn), bismuth (Si), platinum (Pt), silver (Ag), cadmium (Cd), iron (Fe), tin (Sn), indium (In), antimony (Sb), antimony (Bi), A metal or semiconductor material such as vanadium (V), molybdenum (Mo), lead (Pb) or strontium (Sr) itself, an oxide thereof, or a composite thereof with other materials. A composite material according to claim 14, wherein the oxygen-deficient oxide film layer is deposited or embedded in an oxygen-deficient oxide film layer of particles of anoxic oxide. composition. A composite material according to claim 14, which can expand the absorption range of the original constituent material, wherein the oxygen-deficient oxide film layer further comprises a high temperature treatment to form a more stable crystal lattice. A composite material according to claim 14 which can expand the absorption range of the original constituent material, wherein the method for contacting the oxide with the oxygen-deficient oxide particles of the oxygen-deficient oxide film layer further comprises: utilizing High temperature heating, electron beam heating, argon ion accelerated impact, laser stripping or chemical vapor phase reaction causes the oxide particles to float in a carrier gas or a vacuum while contacting the adsorbed oxygen-deficient oxide. A composite material according to claim 18, which can expand the absorption range of the original constituent material, wherein the oxide particles floating in the carrier gas further comprise: injecting into the colloidal solution containing the oxide particles, along with the carrier The gas leaves the colloidal solution and floats in the carrier gas. A composite material according to claim 14 which can enlarge the absorption range of the original constituent material, and the composite material formed by the contact between the oxide and the oxygen-deficient oxide film of the oxygen-deficient oxide film layer is further formed. It is heated at a temperature below 100 degrees Celsius for more than one hour to remove moisture between the oxide and the oxygen-deficient oxide. A composite material according to claim 14 which can enlarge the absorption range of the original constituent material, and the contact between the oxygen-deficient oxide particles of the anoxic oxide film layer is further fixed, and further includes adding other organic substances, oxides or Materials such as metal.