KR102168260B1 - Photocatalytic composite activated carbon material introduced TiOF2 and manufacturing method thereof - Google Patents

Abstract

The present invention provides a photocatalytic composite activated carbon material into which titanium difluoride oxide is introduced and a method of manufacturing the same. The photocatalytic composite activated carbon material into which titanium difluorooxide is introduced can undergo a photocatalytic reaction even with a visible light source due to the introduction of a fluorine functional group, so that harmful substances such as formaldehyde and acetaldehyde can be drastically removed from room temperature and visible light. do. In addition, the manufacturing method of the present invention is not only a relatively simple process, but also the fact that titanium difluoride was introduced based on an activated carbon material, and a carbon material having a fluorine functional group introduced on the surface was prepared, thereby introducing titanium dioxide more effectively. Its characteristic is that titanium difluoride, which can react at room temperature and visible light, is introduced into the activated carbon material.

Description

The photocatalytic composite activated carbon material introduced TiOF2 and manufacturing method thereof

The present invention relates to a photocatalytic composite activated carbon material into which titanium difluorooxide (TiOF ₂ ) is introduced and a method for manufacturing the same, and more particularly, a carbon material into which a fluorine functional group is introduced on the surface is mixed with a titanium dioxide precursor solution, and energy is It relates to a photocatalytic composite activated carbon material in which titanium difluoride is introduced by treatment, and a method of manufacturing the same.

The present invention is to provide a new manufacturing method capable of introducing titanium difluoride oxide in a high content.

In addition, the present invention is to provide a new method for manufacturing a composite activated carbon material capable of remarkably removing harmful substances such as formaldehyde and acetaldehyde at room temperature and visible light.

With the development of the industry, the development of various building materials that satisfies functionality and convenience has been induced, and accordingly, the development and use of building materials composed of various chemical substances and composite materials has increased. However, these building materials emit various harmful substances such as formaldehyde (HCHO) and volatile organic compounds (VOCs), causing contamination of the indoor air. When exposed to the human body, residents may suffer from headache, vomiting, dizziness, and atopy. It is the cause of so-called sick house syndrome (Sick House Syndrome) that causes diseases.

As new buildings increase day by day, interest in indoor pollution is increasing, and materials such as zeolite, activated carbon, and activated carbon fiber are used to treat formaldehyde or acetaldehyde gas among harmful substances that cause sick house syndrome. Adsorption method is widely used. However, since it is difficult to completely remove only by physical adsorption by simple pores through these materials, various surface treatments for the above materials have been studied to improve this.

Surface treatment methods such as acid treatment, plasma treatment, and catalyst introduction are generally used. Among them, the oxidation method using a catalyst has the advantage of converting and removing harmful substances into substances harmless to the human body. However, there are many restrictions in that additional energy such as thermal energy or light energy is required to activate the catalyst. Therefore, there is an urgent need for a technology for producing a catalyst that operates in visible light without an additional energy source while the process is simple.

Korean Patent Publication No. 10-1419908

It is an object of the present invention to provide a photocatalytic composite activated carbon material into which titanium difluoride is introduced and a method for manufacturing the same.

The present invention is to provide a photocatalytic composite activated carbon material in which a relatively high content of titanium difluoride is easily introduced, and a method for manufacturing the same.

Another object of the present invention is to provide a photocatalytic composite activated carbon material into which titanium difluoride oxide is introduced and a method for manufacturing the same, thereby enabling toxic substances such as formaldehyde and acetaldehyde to be drastically removed at room temperature and visible light.

In order to achieve the above object, the present invention

It provides a photocatalytic composite activated carbon material in which titanium difluorooxide is introduced.

In addition, the present invention

Preparing a carbon material having a fluorine functional group introduced thereto;

Mixing the carbon material into which the fluorine functional group is introduced and a titanium dioxide precursor solution; And

Treating the mixture with energy to introduce titanium difluoride oxide into the carbon material; It provides a method of manufacturing a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced.

According to the present invention, a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced can be prepared by introducing titanium difluorooxide into the activated carbon material base.

The manufacturing method of the present invention is not only a relatively simple process, but the photocatalytic composite activated carbon material into which titanium difluorooxide is introduced can undergo a photocatalytic reaction even with a light source of visible light due to the introduction of a fluorine functional group, thus harmful to formaldehyde and acetaldehyde Substances can be drastically removed at room temperature and visible light.

1 shows SEM images of Examples 1 to 4 and Comparative Examples 1 and 2.
2 is an XRD analysis graph of Examples 1 to 4 and Comparative Examples 1 and 2

Hereinafter, the present invention will be described in detail.

Unless otherwise defined, terms used in this specification should be interpreted as generally understood by those of ordinary skill in the relevant field. The drawings and embodiments of the present specification are for a person skilled in the art to easily understand and implement the present invention, and contents that may obscure the gist of the invention in the drawings and examples may be omitted, and the present invention is limited to the drawings and examples. It does not become.

The singular form of the terms used in the present invention may be interpreted as including the plural form unless otherwise indicated.

In the present invention, the unit of% used unclearly without special mention means% by weight.

The present invention provides a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced to solve the above technical problem. This enables effective chemical adsorption and decomposition through photocatalyst as well as physical adsorption of harmful substances by simple pores, and unlike conventional activated carbon fibers into which titanium dioxide is introduced, formaldehyde reacts at room temperature and visible light by photocatalytic reaction. , It is possible to effectively remove harmful substances such as acetaldehyde at room temperature and visible light.

As an example of the activated carbon material, it may be selected from commonly known activated carbon, activated carbon fibers, and mixtures thereof. However, it is preferable that the activated carbon fiber is relatively easy to handle, but is not limited thereto.

The activated carbon material preferably has a specific surface area of 1000 m 2 /g or more in consideration of adsorption capacity and long-term use, but is not limited thereto.

The activated carbon material has 10 to 20% titanium and 5 to 15 fluorine functional groups on the surface in order to ensure effective resolution of harmful substances at room temperature and visible light, and to prevent a decrease in adsorption efficiency due to a decrease in adsorption point due to clogging of pores. % Is preferably introduced, but is not necessarily limited thereto.

In addition, the present invention provides a method of manufacturing a carbon material into which titanium difluoride oxide is introduced, the method comprising: preparing a carbon material into which a fluorine functional group is introduced into the surface; Mixing the carbon material into which the fluorine functional group is introduced and a titanium dioxide precursor solution; And treating the mixture with energy to introduce titanium difluorooxide into the carbon material. It is made including.

This manufacturing method is not only a relatively simple process, but also the fact that titanium difluoride was introduced based on the activated carbon material, and the carbon material with a fluorine functional group introduced on the surface was prepared to introduce titanium dioxide more effectively. It is characterized by the introduction of titanium difluoride, which can react at room temperature and visible light.

The carbon material in the above production method may be any known porous carbon material, and for example, it may be selected from commonly known activated carbon, activated carbon fibers, and mixtures thereof. However, it is preferable to use activated carbon fiber that is relatively easy to handle, but is not limited thereto.

The fluorine functional group may be introduced through a process including a surface treatment process using fluorine gas. This is a process for more effective introduction of titanium dioxide in a subsequent step. The fluorine gas can be introduced from various materials containing fluorine, and specifically, can be introduced through direct fluorination or fluorine plasma treatment. For example, in the process of introducing the fluorine functional group using the direct fluorination method, it is preferable to minimize side reactions by reacting with fluorine gas after injecting and evacuating an inert gas three times.

The surface treatment process using fluorine gas is preferably performed for 5 to 15 minutes at a temperature of 25 to 50° C. in order to prevent poor introduction of fluorine functional groups, structural deformation of pores due to overreaction, and decrease in adsorption efficiency accordingly. However, it is not necessarily limited thereto.

The surface treatment process using the fluorine gas is preferably performed in a range of 0.1 to 0.3 bar fluorine gas pressure relative to the inert gas in the reactor in an inert gas atmosphere for the same reason as described above, but is not limited thereto.

The carbon material into which the fluorine functional group is introduced may have a fluorine functional group content of 1 to 10 weight ratio. As described above, when the fluorine functional group is introduced in the carbon material in an appropriate amount, titanium dioxide can be more effectively introduced in the subsequent step, and the adsorption efficiency is reduced by blocking pores due to excessive introduction of titanium and fluorine functional groups. Because it can be prevented. However, it is not necessarily limited thereto.

The mixing ratio of the mixing step is 100 parts by weight of the titanium dioxide precursor solution in order to prevent the adsorption efficiency from deteriorating by preventing the titanium dioxide from being properly introduced to the surface of the carbon material, or by blocking the pores due to excessive introduction of titanium dioxide. The carbon material into which the fluorine functional group is introduced is preferably 1.5 to 3 parts by weight, but is not necessarily limited thereto.

The titanium dioxide precursor solution may be prepared by mixing an alcohol solvent and a titanium dioxide precursor.

The solvent mixed with the titanium dioxide precursor may be any solvent used in a conventional sol-gel reaction, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, benzyl alcohol, isoamyl alcohol, isobutyl alcohol, and It may be selected from the group consisting of mixtures thereof.

Titanium dioxide precursor may be used any compound containing titanium, for example, titanium ethoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium It can be selected from the group consisting of tetrabutoxide, titanium chloride, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium bromide, titanium sulfide, and mixtures thereof.

The mixing ratio of the alcohol solvent and the titanium dioxide precursor may be 8 to 43 parts by weight of the titanium dioxide precursor based on 100 parts by weight of the alcohol solvent. This is to prevent the introduction of agglomerated titanium dioxide into the carbon material while introducing titanium dioxide into the carbon material appropriately in the subsequent step, or introducing uneven particle size.

In the present invention, it may further include gelling the mixture after the mixing step. This makes it possible to more effectively introduce titanium dioxide and titanium difluoride oxide into the carbon material, and it is possible to expect a high surface area and a small pore size to have when the porous material is made in a thin form.

The step of gelling refers to a step in which the titanium precursor coating layer transitions from a sol state to a gel state under elevated temperature conditions to form a form of titanium dioxide and/or titanium difluoride oxide.

The gelling step is preferably performed for 12 to 24 hours at a temperature range of 25 to 30° C. in order to prevent hardening while proceeding the reaction, but is not limited thereto.

In the present invention, after the step of gelling the mixture, a step of additionally drying the gelled mixture may be further included. This is to more effectively proceed to the next step by removing the remaining solvent of the titanium dioxide precursor solution.

The energy treatment may include an energy treatment process using ultrasonic waves. The energy treatment process using ultrasonic waves is preferably carried out for 30 to 60 minutes in a frequency range of 10 to 50 kHz by adding the mixture to distilled water. This is to prevent occurrence of appropriate energy supply and side reactions, but is not necessarily limited thereto.

The present invention will be described in more detail through the following examples.

Hereinafter, analysis methods according to Examples and Comparative Examples of the present invention are as follows.

The dried activated carbon fiber (average diameter 10 μm, BET 1500 m 2 /g) was put into the reactor, and the inside of the reactor was maintained in an inactive state in order to introduce only fluorine functional groups through gas phase fluorine surface treatment. The process of evacuating the inside of the reactor under reduced pressure and injecting an inert gas of nitrogen was repeated three times. Thereafter, a fluorine gas pressure was injected into the reactor so that the pressure was 0.1 bar and reacted at room temperature for 10 minutes to introduce a fluorine functional group to the surface of the activated carbon fiber.

After introducing the fluorine functional group, a titanium dioxide precursor (titanium isopropoxide, TTIP, 97.0%, Aldrich, USA) was prepared so that an isopropyl alcohol solution of 0.5M. The gas phase fluorine surface-treated activated carbon fiber 3g and 200ml of the titanium dioxide precursor solution were mixed, stirred for about 12 hours, gelled and dried.

After the gelation, the dried activated carbon fiber was added to distilled water and subjected to ultrasonic treatment for 40 minutes to complete the conversion of titanium difluoride on the surface of the activated carbon fiber and introduced.

The prepared photocatalytic composite activated carbon fiber element content was measured using an X-ray photoelectron spectroscopy (XPS), Thermo Fisher Scientific's VG Multilab 2000 model, and the content is shown in Table 1.

In addition, the degree of introduction of titanium difluoride oxide was observed by magnifying 5000 times using a scanning electron microscope (SEM) (Hitachi's S-4800) and observed in FIG. 1.

In addition, XRD (X-ray diffraction) was measured using PANalytical's X'Pert PRO model, and it is described in FIG. 2. The sample was used after drying moisture in a vacuum drying oven, and the analysis was conducted by irradiating Cu KαX-rays at room temperature.

In addition, the evaluation results of the adsorption properties of acetaldehyde are shown in Table 2.

In the same manner as in Example 1, except that the concentration of the titanium dioxide precursor solution was 0.8 M in Example 1, titanium difluoride was introduced into the surface of the activated carbon fiber.

In Example 1, titanium difluoride was introduced on the surface of the activated carbon fiber in the same manner as in Example 1, except that the pressure of fluorine gas injected into the reactor was 0.2 bar.

In the same manner as in Example 1, except that the pressure of fluorine gas injected into the reactor in Example 1 was 0.2 bar, and the concentration of the titanium dioxide precursor solution was 0.8 M, the activated carbon fiber surface was Titanium difluorooxide was introduced.

<Comparative Example 1>

It is the activated carbon fiber of Example 1 without any treatment.

<Comparative Example 2>

Titanium dioxide was introduced to the surface of the activated carbon fiber in the same manner as in Example 1, except that the gas phase fluorine surface treatment process of Example 1 was omitted.

Property measurement result

Element content analysis

X-ray photoelectron spectroscopy (XPS) was measured using a Thermo Fisher Scientific VG Multilab 2000 model, and the sample was dried in a vacuum drying oven.

The contents of the titanium and fluorine functional groups introduced on the surfaces of the activated carbon fibers of Examples 1 to 4 and Comparative Example 2 of the present invention were measured and shown in Table 1.

Elemental analysis result Sample name Elemental content (at.%) C O Ti F Example 1 49.32 34.31 10.56 5.81 Example 2 48.41 35.14 11.01 5.44 Example 3 42.24 34.11 15.03 9.44 Example 4 41.01 35.80 15.05 9.14 Comparative Example 2 64.47 28.66 6.87 -

Analysis of surface morphology of activated carbon fiber

Scanning electron microscopy (SEM)

It was measured using Hitachi's S-4800 model. The sample was magnified by 5000 times to measure the surface change.

SEM analysis was performed to confirm the surface shape of Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention, and the images are shown in FIG. 1. As can be seen from FIG. 1, it can be seen that the surface of Comparative Example 1 is smooth, whereas in 2, very small titanium dioxide particles are introduced.

The surfaces of Examples 1 to 4 confirmed that titanium dioxide and titanium difluorooxide particles having a relatively large size were introduced. It can be seen that a larger amount of particles was introduced into the surface of the sample to which titanium dioxide was introduced after the pre-fluorination treatment than the sample to which titanium dioxide was introduced without the pre-fluorination process.

Crystal structure analysis of activated carbon fiber with titanium dioxide and titanium difluoride introduced

X-ray diffraction (XRD)

It was measured using PANalytical's X'Pert PRO model. The sample was used after drying moisture in a vacuum drying oven, and the analysis was conducted by irradiating Cu KαX-rays at room temperature.

XRD analysis was performed to confirm the crystal structures of titanium dioxide and titanium difluoride introduced on the surface of activated carbon fibers according to Examples 1 to 4 and Comparative Example 2 of the present invention. In the graph of FIG. 2, the X-axis represents the 2θ value and the Y-axis represents the intensity of the peak. As a result of introducing titanium dioxide into the activated carbon fiber without pre-fluorination treatment, as can be seen from FIG. 2, the amount of the introduced titanium dioxide was small and crystallinity was not large, so that a peak was hardly observed. On the other hand, when titanium dioxide was introduced after performing the pre-fluorination treatment, it was confirmed that the titanium difluorooxide peak appeared clearly.

Analysis of Acetaldehyde Adsorption Characteristics of Activated Carbon Fibers with Titanium Dioxide and Titanium Difluorooxide

Gas chromatography (GC, Agilent HP-6890) consisting of an injection device, a reaction device, and a measuring device was used for the acetaldehyde adsorption experiment. A quartz tube having an inner diameter of 10 mm, an outer diameter of 11 mm, and a height of 200 mm was used as the reactor, and 0.02 g of activated carbon fiber was added during the acetaldehyde adsorption test. Acetaldehyde gas (concentration 100 ppm) injected into the reactor was constantly injected at a flow rate of 100 sccm using a mass flow controller (MFC, Korea). Breakthrough started and the concentration of acetaldehyde discharged was measured at regular time intervals using a GC analyzer to calculate a breakthrough curve. At this time, the mounted column was DB-5MS, and the peak measurement temperature was set to 50 °C.

The acetaldehyde removal characteristics of the activated carbon fibers of Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention were analyzed using GC equipment, and the results are shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 100 minutes
Acetaldehyde reduction (%) 35.5 41.5 47 45.75 14 23.5

In the case of Comparative Example 1, only the adsorption effect by the pores of the activated carbon fiber is shown, and as can be seen from Table 2, the removal efficiency is the lowest. Comparative Example 2 is an activated carbon fiber into which titanium dioxide particles are introduced, and it can be confirmed that the acetaldehyde removal efficiency is increased compared to Comparative Example 1. In the case of Examples 1 to 4 in which titanium dioxide and titanium difluorooxide particles are introduced, It can be seen that it increased further.

Claims (18)

Carbon material surface-treated with fluorine gas; And a titanium dioxide precursor solution; a photocatalytic composite activated carbon material in which energy is treated to a mixture containing, and titanium difluorooxide (TiOF ₂ ) is introduced. The method of claim 1,
The activated carbon material is a photocatalytic composite activated carbon material incorporating titanium difluorocarbon, characterized in that any one selected from activated carbon, activated carbon fibers, and mixtures thereof. The method of claim 1,
A photocatalytic composite activated carbon material incorporating titanium difluoride, characterized in that the specific surface area of the activated carbon material is 1000 m 2 /g or more. The method of claim 1,
The activated carbon material is a photocatalytic composite activated carbon material incorporating titanium difluorooxide, characterized in that 10 to 20 At% of titanium and 5 to 15 At% of a fluorine functional group are introduced on the surface. Surface treatment of the carbon material using fluorine gas to prepare a carbon material into which a fluorine functional group is introduced;
Mixing the carbon material into which the fluorine functional group is introduced and a titanium dioxide precursor solution; And
The method of manufacturing a photocatalytic composite activated carbon material in which titanium difluorooxide is introduced, comprising: introducing titanium difluorooxide into a carbon material by treating energy in the mixture. The method of claim 5,
The carbon material is a method for producing a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced, characterized in that any one selected from activated carbon, activated carbon fibers, and mixtures thereof. delete The method of claim 5,
The surface treatment process using fluorine gas is a method for producing a photocatalytic composite activated carbon material in which titanium difluoride is introduced, characterized in that the surface treatment is performed for 5 to 15 minutes at a temperature of 25 to 50°C. The method of claim 5,
The surface treatment process using the fluorine gas is a method for producing a photocatalytic composite activated carbon material in which titanium difluorooxide is introduced, characterized in that the pressure of the fluorine gas relative to the inert gas in the reactor is in a range of 0.1 to 0.3 bar in an inert gas atmosphere. The method of claim 5,
The activated carbon material is a method of manufacturing a photocatalytic composite activated carbon material in which titanium difluorooxide is introduced, characterized in that 10 to 20 At% of titanium and 5 to 15 At% of a fluorine functional group are introduced on the surface. The method of claim 5,
The mixing ratio of the mixing step is a method for producing a photocatalytic composite activated carbon material containing titanium difluorooxide, characterized in that 1.5 to 3 parts by weight of the carbon material into which the fluorine functional group is introduced per 100 parts by weight of the titanium dioxide precursor solution . The method of claim 5,
The titanium dioxide precursor solution is a method of manufacturing a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced, characterized in that prepared by mixing an alcohol solvent and a titanium dioxide precursor. The method of claim 12,
The mixing ratio of the alcohol solvent and the titanium dioxide precursor is 8 to 43 parts by weight of the titanium dioxide precursor based on 100 parts by weight of the alcohol solvent. The method of claim 5,
After the step of mixing, the method for producing a photocatalytic composite activated carbon material into which titanium difluoride is introduced, further comprising gelling the mixture. The method of claim 14,
The step of gelling is a method for producing a photocatalytic composite activated carbon material in which titanium difluorooxide is introduced, characterized in that it takes place for 12 to 24 hours at a temperature range of 25 to 30°C. The method of claim 14,
After the step of gelling, the method of manufacturing a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced, further comprising the step of additionally drying the gelling mixture. The method of claim 5,
The energy treatment is a method of manufacturing a photocatalytic composite activated carbon material into which titanium difluorooxide is introduced, characterized in that it includes an energy treatment process using ultrasonic waves. The method of claim 17,
The energy treatment process using ultrasonic waves is a method of manufacturing a photocatalytic composite activated carbon material in which titanium difluorooxide is introduced, characterized in that the mixture is added to distilled water and is performed for 30 to 60 minutes in a frequency range of 10 to 50 kHz.

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