KR20210020693A - Photocatalyst Including conjugate polymer introduced absorption member and photocatalytic reaction using the same - Google Patents

Abstract

The present invention relates to use of an absorption member-like photocatalyst using a conjugated polymer for organic dye decomposition and organic synthesis. Particularly, a conjugated polymer capable of absorbing solar light and generating active oxygen species is synthesized, and a solution of the conjugated polymer is introduced to an absorption member, such as filter paper, to obtain a photocatalyst. Then, the photocatalyst can be used for decomposition of Rhodamin B, an organic dye, or for reduction of nitrophenol and oxidation of benzylamine. In addition, according to the present invention, since the conjugated polymer is incorporated to an absorption member, not a solid phase or solution phase, the photocatalyst can be operated with ease during the photocatalytic reaction, can be recycled, and can be recovered with ease after the reaction. Therefore, the conjugated polymer-containing sheet-like photocatalyst can be used for decomposition of pollutants, such as organic dyes, and for organic synthesis including oxidization or reduction of organic materials, and can be applied to inexpensive high-efficiency photocatalyst materials, since it can be recycled.

Description

Photocatalyst Including conjugate polymer introduced absorption member and photocatalytic reaction using the same {Photocatalyst Including conjugate polymer introduced absorption member and photocatalytic reaction using the same}

The present invention relates to an absorption member-type photocatalyst using a conjugated polymer and a photocatalytic reaction using the same, in particular, an absorption member type that can be applied to decomposition of organic dyes and oxidation/reduction reactions of organic compounds, and is easy to recover and reuse. It relates to a photocatalyst.

Conjugated polymers are structurally superimposed p-orbitals and alternately present saturated bonds and unsaturated bonds, so that when doped, electrical conductivity is generated and thus exhibits semiconductor properties. By applying these semiconductor properties, the oxidation-reduction potential difference or absorption by stimulation of external environments such as pH, temperature, light, and ions, or in the field of electronic materials such as organic light emitting devices, optical recording materials, organic thin film transistors, and organic solar cells. -It is actively applied in the field of chemical-bio sensor materials that can be detected by changes in emission spectrum.

Meanwhile, research on semiconductor photocatalytic materials based on conjugated polymers has recently been in the spotlight, and such conjugated polymers have the advantage of being able to control energy band gaps and electrical properties from the design of a chemical structure.

This semiconductor photocatalyst is a material that can convert solar energy into chemical energy, and can decompose environmental pollutants such as dyes and low molecular weight organic compounds, and is a self-cleaning material capable of decomposing bacteria and microorganisms. Do. In most cases, the decomposition reaction is due to the strong oxidizing power of reactive oxygen species (ROS) generated on the surface of the photocatalyst, but the overall mechanism is a series of reactive oxygen species as well as valence band holes, conduction band electrons, etc. The redox surface reaction occurs in a complex connection. The semiconductor photocatalyst absorbs light and excites electrons from the valence band to the conduction band, and the generated charge pair moves to the interface to cause electron transfer, and thus various kinds of oxidation/reduction reactions are involved. The photocatalytic reaction is key to the generation of charge pairs due to the absorption of bandgap energy of a semiconductor and electron transfer at the subsequent interface. The absorption of such bandgap energy can be controlled by diversifying the structural design of the conjugated polymer. In addition, the active oxygen species is a molecule that is reactive with a chemical containing an oxygen atom, the kind of superoxide (O ₂ ^-) and the like, hydrogen peroxide (H ₂ O _2), hydroxyl radicals (· OH).

On the other hand, active oxygen, which has a strong oxidizing ability, is considered to be a very important factor in the field of environment, and it can be decomposed by oxidizing dyes using reactive oxygen produced by dissolved oxygen dissolved in an organic solvent or a reaction system using water. In addition, it can be said to be an eco-friendly oxidizing agent such as organic synthesis through active oxygen species. Therefore, the fact that a photocatalyst capable of releasing reactive oxygen species can induce a catalytic reaction under the conditions of room temperature and pressure with only light is a great advantage as a practical environmental purification technology.

However, most of the photocatalytic materials studied so far are mainly used in a solution, dispersed in a solid, or coated or deposited on a glass slide. However, in the case of use in a solution, the use of the photocatalyst is limited because it can be used in a state in which it is dissolved in a solvent. In the case of colloids that disperse solids, additional processes such as filtration or centrifugation are involved. Because it exists in a colloidal state in the waste fluid, it acts as a disadvantage in terms of environment. In the case of using a glass slide, it is cumbersome to melt the catalyst material for coating or to dissolve it in a solvent, and since the catalyst material cannot penetrate the medium of the reaction system, instability acts as a disadvantage in terms of surface area.

Until now, the focus has been on the development of the material itself, such as photocatalytic performance and morphological studies of photocatalytic materials, and technology development such as a recovery process after photocatalytic reaction, a reuse method, and an immobilization method for ease of use of a photocatalyst is insufficient.

Accordingly, the present invention synthesizes a conjugated polymer having a photocatalytic function by generating active oxygen species upon irradiation with sunlight, and uses this to create an absorbing member-type photocatalyst introduced into an absorbing member to facilitate recovery and reuse after use. And also to present a photocatalytic reaction using the absorption member type photocatalyst.

(Prior Literature 0001) Korean Patent Publication No. 2012-0075321: Gold cluster titanium dioxide nanocomposite having photocatalytic activity, a method for preparing the same, and a method for decomposing organic dyes using the same (Prior Document 0002) Korean Patent Application Publication No. 2012-0051296: Method and apparatus for removing chromaticity of reactive anthraquinone dye wastewater using photocatalytic oxidation (Prior Document 0003) Korean Patent Publication No. 2012-0010300: Photocatalytic reaction device

An object of the present invention is to prepare an absorption member-type photocatalyst using a conjugated polymer, and to provide a photocatalytic reaction using the same. In more detail, the present invention proposes a photocatalyst that can be used for decomposition of dyes and oxidation/reduction reactions of organic compounds by generating active oxygen species under irradiation of sunlight, and the absorption member-type photocatalyst that can be recovered and reused by using the same Its purpose is to provide a manufacturing method.

The absorbent member-type photocatalyst in which the conjugated polymer having a photocatalytic function of the present invention is introduced into the absorbing member for achieving the above object includes: a conjugated polymer having a photocatalytic function having a structure represented by Formula 1 or Formula 2 below; And an absorption member into which the conjugated polymer having the photocatalytic function is introduced.

[Formula 1]

[Formula 2]

In addition, the absorbent member is preferably any one of non-woven fabric, woven fabric, pad, and filter paper.

In addition, the photocatalytic reaction using the absorption member type photocatalyst of the present invention is one of a decomposition reaction of an organic dye, an oxidation reaction of an organic compound, and a reduction reaction of an organic compound, and the organic dye is Rhodamine B (Rhodamine B) and methylene blue. It is any one of (methylene blue) and methylorange, and the oxidation reaction of the organic compound is preferably targeting any one of a benzaldehyde derivative, a benzylamine derivative, and a furoic acid. In addition, it is preferable that the reduction reaction of the organic compound targets 4-nitrophenol.

And the manufacturing method of the absorption member-type photocatalyst of the present invention, the first step (S100) of manufacturing a conjugated polymer; Dissolving the conjugated polymer prepared in the first step in an organic solvent to prepare a conjugated polymer solution 　 second step (S200); A third step (S300) of introducing the conjugated polymer solution prepared in the second step into an absorbent member; And a fourth step (S400) of heat-treating the absorbent member in which the conjugated polymer solution prepared in the third step is absorbed.

The absorption member-type photocatalyst using the conjugated polymer of the present invention can be used by absorbing the conjugated polymer in the absorbing member, unlike a solution photocatalyst used by dissolving in a solvent or a dispersed photocatalyst used by dispersing in a solvent. It has excellent wettability, and the catalytic efficiency is improved by increasing the reaction surface area and interaction with the reactant and the conjugated polymer. In addition, since the process of reabsorbing light again by scattering by immobilizing the conjugated polymer having a photocatalytic function on the absorbing member is repeated, the catalytic efficiency is higher than that of using the conjugated polymer in a single form. On the other hand, since a desired amount of the conjugated polymer can be absorbed into the absorbent member, the manufacturing process is simple and convenient, and the shape of the absorbent member can be freely modified as necessary, thereby providing a wide range of applications.

In addition, since the absorbing member-type photocatalyst using the conjugated polymer of the present invention uses a material such as non-woven fabric or woven fabric, which can be easily obtained commercially, the absorbing member-type photocatalyst using the conjugated polymer is used for the reaction and then recovered. It is easy to use, and since it can be dried and reused after washing, economical savings are very effective.

1 is a flow chart for a method of manufacturing an absorption member-type photocatalyst using a conjugated polymer according to the present invention,
Figure 2 is a graph showing the dye decomposition rate (%) according to reuse of the absorption member-type photocatalyst using the conjugated polymer of the present invention,
3 is a graph showing the conversion rate (%) according to reuse of the absorbing member type photocatalyst using the conjugated polymer of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and the following embodiments make the disclosure of the present invention complete, and the scope of the invention to those of ordinary skill in the art. It is provided to fully inform you. In addition, in the drawings for convenience of description, the size of the components may be exaggerated or reduced. In the drawings, for example, depending on manufacturing techniques and/or tolerances, variations of the illustrated shape can be expected. Accordingly, the present invention should not be construed as being limited to the specific shape of the region shown in the present specification, but should include, for example, a change in shape resulting from manufacturing.

Hereinafter, an absorption member-type photocatalyst using the conjugated polymer of the present invention and a photocatalytic reaction using the same will be described in detail.

In the present invention, the conjugated polymer is a polymer having a photocatalytic function by generating reactive oxygen species (ROS) under sunlight, and by introducing the conjugated polymer into the absorbing member, it is easy to recover and reuse. do.

In addition, the photocatalytic reaction using the absorption member type photocatalyst using the conjugated polymer of the present invention includes a decomposition reaction of an organic dye and an oxidation or reduction reaction of an organic compound. At this time, the organic dye is preferably any one of rhodamine B, methylene blue, and methyl orange, and the organic compound used in the oxidation reaction is a benzylamine derivative, benzaldehyde, or furoic acid. Any one of the derivatives is preferred, and the organic compound used in the reduction reaction is preferably any one of the 4-nitrophenol derivatives.

The conjugated polymer for preparing the absorbent member-type photocatalyst using the conjugated polymer of the present invention is preferably a compound composed of a repeating unit represented by the following formula (1) or (2).

[Formula 1]

In Formula 1, Z is C, CR ₁ R ₂ , N, S, O, NR ₃ , SO ₂ , and R ₁ , R ₂ , R ₃ are different from each other or the same, and each independently one or more halogens are substituted or It is an unsubstituted linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms.

[Formula 2]

In Formula 2, R ₄ , R ₅ are H, OR ₆ , R ₇ , R ₆ , R ₇ are different from each other or the same, and each independently has one or more halogen substituted or unsubstituted linear or branched carbon atoms It is an alkyl group or an alkoxy group of 1 to 12. Preferably, R ₄ , R ₅ is n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-ethylhexyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy And 2-ethylhexyloxy, or may be selected in combination. The values of X and Y represent the composition of each repeating unit in mole fraction, where X is a real number from 0 to 0.99, and Y is 1-X.

,

,

,

,

,

중 어느 하나이다.In addition, Ar in Formula 1 or Formula 2 below is

,

,

,

,

,

Is either.

In addition, the molecular weight of the conjugated polymer is not particularly limited, but it is preferable that the number average molecular weight is 3,000 to 100,000, and the range of the number average molecular weight may be appropriately adjusted according to the properties required for the application such as solubility.

The conjugated polymer represented by Formula 1 or 2 used in the present invention is prepared by a Suzuki Coupling reaction, but is not limited thereto and may be prepared through various synthesis routes.

A method of manufacturing an absorption member-type photocatalyst using the conjugated polymer of the present invention is as follows. That is, as shown in FIG. 1, the method of manufacturing an absorbing member-type photocatalyst of the present invention includes a first step (S100) of preparing a conjugated polymer; Dissolving the conjugated polymer prepared in the first step in an organic solvent to prepare a conjugated polymer solution 　 second step (S200); A third step (S300) of introducing the conjugated polymer solution prepared in the second step into an absorbent member; And a fourth step (S400) of heat-treating the absorbent member in which the conjugated polymer solution prepared in the third step is absorbed.

The organic solvent used in the second step is chloroform, tetrahydrofuran, methylene chloride, and the like, and the absorbent member used in the third step is conjugated to woven fabric, non-woven fabric, pad, filter paper, etc. Any absorbent member capable of absorbing a polymer is possible. In addition, in the fourth step, the heat treatment is preferably 80 to 120°C, which is higher than or equal to the boiling point of the organic solvent, and the heat treatment time is preferably 2 to 6 hours.

In addition, since the absorbent member must be sufficiently immersed in the reaction solution while entering the reaction vessel, it is preferable that it is 1cm x 1cm based on a 20 ml vial.

In addition, the photocatalytic reaction using the absorbing member-type photocatalyst of the present invention may proceed as follows. That is, the prepared absorption member-type photocatalyst is immersed in a 20 ml vial containing an organic dye solution or a reaction solution for oxidation/reduction reaction, and then light irradiated with a solar simulator while stirring. Here, the distance between the solar simulator and the vial is 5 to 10 cm, the intensity of the light source is in the range of 5 to 10 mA, and the reaction solution is recovered by time and the UV/Vis absorption spectrum or nuclear magnetic resonance (NMR) spectrum Check the product of the decomposition or oxidation/reduction reaction of the dye. In addition, it is also possible to confirm the reaction process by thin layer chromatography (TLC).

The absorption member type photocatalyst of the present invention has a feature that can be reused. That is, the conjugated polymer of the present invention is hydrophobic, and does not desorb from the absorbent member when washed with water, and remains in the absorbent member. Therefore, the absorbent member-type photocatalyst of the present invention used in the reaction solution can be reused by drying it after washing with water because the conjugated polymer, which is a photocatalyst, remains in the absorbing member even after use.

In addition, the photocatalytic mechanism of the conjugated polymer, which is a photocatalyst during the photocatalytic reaction, is as follows. Electrons present in the valence band of the conjugated polymer are excited by a light source having a wavelength of 300 to 700 nm, and the triplet oxygen present in the surroundings is converted into active oxygen species by holes and electrons generated in this process. Since the generated reactive oxygen species act as a strong oxidizing agent, they can decompose dyes such as rhodamine B, methylene blue, and methyl orange, as well as benzoic acid conversion by oxidation of benzaldehyde and oxidative coupling reaction of benzylamine. The resulting N-benzyl-1-phenylmethanediamine derivative can be converted to 4-aminophenol in the presence of sodium borohydride. It is also possible to convert furoic acid to furanone.

Hereinafter, the present invention will be described in detail as examples. However, these examples are intended to specifically illustrate the present invention, and the scope of the present invention is not limited to these examples.

[Preparation Example 1] Preparation of conjugated polymer (S100)

[Preparation Example 1-1] Preparation of fluorene-based conjugated polymer of Formula 1

9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester 0.558 g (1 mmol) and 1, to prepare the fluorene-based conjugated polymer of Formula 1 0.235.9 g (1 mmol) of 4-dibromobenzene and 0.059 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst were mixed with 10 mL of dehumidified toluene and 7 mL of 2 MK ₂ CO ₃ . It was dissolved in the mixed solution and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The solid obtained by filtration was washed sequentially in the order of methanol, acetone, and water, and dried. The obtained precipitate had a number average molecular weight of 10,000 or more, and a green conjugated polymer was prepared.

In the conjugated polymer (CP-1) prepared in Preparation Example 1-1, Z is CR ₁ R _2, where R ₁ and R ₂ are alkyl groups having 8 carbons, and Ar is benzene .

And CP-1 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.6~7.8 ppm(10H, aromatic), 3.3 ppm(4H, alkyl group), 2.2 ppm(4H, alkyl group), 2.17 ppm(4H, alkyl group), 1.34-0.94 ppm (22H, alkyl group)

[Preparation Example 1-2] Preparation of fluorene-based conjugated polymer of Formula 1

In order to prepare the fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 5, 8-dibromoquinoxaline 0.288 g (1 mmol) and tetrakis (triphenylphosphine) palladium catalyst 0.058 g (0.05 mmol) were dissolved in 5 ml of dehumidified toluene, and 2 MK ₂ CO ₃ 3 ml and water After adding 2 ml, 2-3 drops of Aliquat 336 were added and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a green conjugated polymer having a molecular weight of 30,000 or more.

In the conjugated polymer (CP-2) prepared in Preparation Example 1-2, Z is CR ₁ R _2, wherein R ₁ and R ₂ are an alkyl group having 8 carbons, and Ar is quinoxylin to be.

And CP-2 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300MHz, CDCl ₃ ) δ = 7.87-7.69 ppm (m, 10H, aromatic), 2.13 ppm (s, 4H, alkyl), 1.28-0.8 ppm (30H, alkyl).

[Production Example 1-3] Preparation of fluorene-based conjugated polymer of Formula 1

In order to prepare the fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 5, 8-dibromo-2,3-diphenylquinoxaline 0.44 g (1 mmol) and tetrakis (triphenylphosphine) palladium catalyst 0.058 g (0.05 mmol) were dissolved in 5 ml of moisture-removed toluene and 2 MK _{After adding 3 ml of 2} CO ₃ and 2 ml of water, 2-3 drops of Aliquat 336 were added and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a green conjugated polymer having a molecular weight of 30,000 or more.

In the conjugated polymer (CP-3) prepared in Preparation Example 1-3, Z is CR ₁ R _2, wherein R ₁ and R ₂ are an alkyl group having 8 carbons, and Ar is 2, It is 3-diphenylquinoxaline.

And CP-3 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ = 7.78 to 7.64 ppm (m, 18H, aromatic), 2.13 ppm (s, 4H, alkyl) 1.27 to 0.81 ppm (m, 26H, alkyl).

[Production Example 1-4] Preparation of fluorene-based conjugated polymer of Formula 1

9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester 0.558 g (1 mmol) and 4, to prepare the fluorene-based conjugated polymer of Formula 1 7-dibromobenzo[c][1,2,5]thiadiazole 0.294 g (1 mmol) and tetrakis(triphenylphosphine)palladium catalyst 0.059 g (0.05 mmol) in 10 mL of moisture removed Was dissolved in a mixed solution of toluene and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. . The precipitate obtained by filtration was washed sequentially in the order of methanol, acetone, and water, and then dried to prepare a yellow conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter referred to as CP-4) prepared in Preparation Example 1-4, Z is CR ₁ R _2, wherein R ₁ and R ₂ are an alkyl group having 8 carbons, and Ar is 2, It is 1,3-benzothiadiazole.

And CP-4 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=8.06 ppm (8H, aromatic), 3.32 ppm (4H, alkyl), 2.17 ppm (4H, alkyl), 1.3-0.94 (m, 26H, alkyl).

[Production Example 1-5] Preparation of fluorene-based conjugated polymer of Formula 1

In order to prepare the fluorene-based conjugated polymer of Formula 1, 0.65 g (1 mmol) of 2,7-dibromo-9,9-bis(6-bromohexyl)fluorene and 4,7-bis[5-( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]benzo-2,1,3-thiadiazole 0.552 g (1 mmol ) And 0.059 g (0.05 mmol) of a tetrakis(triphenylphosphine)palladium catalyst _{were dissolved in a mixed solution of 10 mL of toluene and 7 mL of 2 MK 2} CO ₃ from which moisture was removed, and at 90°C for 48 hours. Refluxed. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a red conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-5) prepared in Preparation Example 1-5, Z is CR ₁ R _2, wherein R ₁ and R ₂ are alkyl groups having 8 carbons, and Ar is biscy It is enylbenzothiadiazole.

And CP-5 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=8.14 to 8.16 ppm (12H, aromatic), 3.32 (2H, alkyl group), 2.03 (2H, alkyl group), 1.56 to 0.8 ppm (m, 30H, alkyl group).

[Preparation Example 1-6] Preparation of fluorene-based conjugated polymer of Formula 1

In order to prepare the fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 5, 7-dibromo-thieno[3,4- b ]pyrazine 0.294 g (1 mmol) and tetrakis (triphenylphosphine) palladium catalyst 0.058 g (0.05 mmol) dissolved in 5 ml of dehumidified toluene After 2 _{ml of MK 2} CO ₃ and 2 ml of water were added, 2-3 drops of Aliquat 336 were added and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in the order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more and a purple color.

In the conjugated polymer (CP-6) prepared in Preparation Example 1-6, Z is CR ₁ R _2, wherein R ₁ and R ₂ are an alkyl group having 8 carbons, and Ar is It is nopyrazine.

And CP-6 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=8.14~8.16 ppm(m, 8H, aromatic), 3.30-3.32(m, 2H, alkyl group), 2.13-2.2(s, 6H, alkyl group), 1.56~0.8 ppm (m, 26H, alkyl group).

[Production Example 1-7] Preparation of phenylene-based conjugated polymer of Formula 2

1,4-bis(octyoxy)-2,5-dibromobenzene 492 mg (1 mmol) and 1,4-benzenediboronic acid bis(pinacol) to prepare the phenylene-based conjugated polymer of Formula 2 Dissolve 0.165 g (0.5 mmol) of ester and 0.029 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst in a mixed solution of _{10 mL of toluene and 7 mL of 2 MK 2} CO _{3 from which moisture was removed,} It was refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (CP-7) prepared in Preparation Example 1-7, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is benzene.

And CP-7 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.2 to 8.1 ppm (6H, aromatic), 3.92 ppm (4H, alkyl group), 3.4 to 3.2 ppm (16H, alkyl group), 1.78 to 1.8 ppm (8H, alkyl group), 1.47 ppm (6H, alkyl group)

[Preparation Example 1-8] Preparation of phenylene-based conjugated polymer of Formula 2

To prepare the phenylene-based conjugated polymer of Formula 2, 1,4-bis(octyoxy)-2,5-dibromobenzene 492 mg (1 mmol), 1,4-benzenediboronic acid bis(pinacol) Esters 0.165 g (0.5 mmol), 5,8-dibromoquinoxaline 0.144 g (0.5 mmol) and tetrakis(triphenylphosphine)palladium catalyst 0.058 g (0.05 mmol) with 10 mL of dehumidified toluene It was dissolved in 7 mL of _{a mixed solution of 2 MK 2} CO ₃ and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (CP-8) prepared in Preparation Example 1-8, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is quinoxaline.

And CP-8 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.28 to 8.1 ppm (6H, aromatic), 3.92 ppm (4H, alkyl group), 3.8 to 3.4 ppm (16H, alkyl group), 1.76 to 1.82 ppm (8H, alkyl group), 1.23 ppm (6H, alkyl group)

[Production Example 1-9] Preparation of phenylene-based conjugated polymer of Formula 2

To prepare the phenylene-based conjugated polymer of Formula 2, 1,4-bis(octyoxy)-2,5-dibromobenzene 492mg (1 mmol), 1,4-benzenediboronic acid bis(pinacol) ester Moisture removal of 0.165 g (0.5 mmol), 0.22 g (0.5 mmol) of 5,8-dibromo-2,3-diphenylquinoxaline and 0.058 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst It was dissolved in a mixed solution of 10 mL of toluene and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (CP-9) prepared in Preparation Example 1-9, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is 2,3-diphenylquinoxaline.

And CP-9 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.28 to 8.1 ppm (10H, aromatic), 3.92 ppm (4H, alkyl group), 3.7 to 3.5 ppm (16H, alkyl group), 1.78 to 1.83 ppm (8H, alkyl group), 1.47 ppm (6H, alkyl group)

[Preparation Example 1-10] Preparation of phenylene-based conjugated polymer of Formula 2

1,4-bis(octyoxy)-2,5-dibromobenzene 492 mg (1 mmol) and 1,4-benzenediboronic acid bis(pinacol) to prepare the phenylene-based conjugated polymer of Formula 2 Ester 0.330 g (0.5 mmol), 4,7-dibromobenzo[c][1,2,5]thiadiazole 0.294 g (0.5 mmol) and tetrakis(triphenylphosphine)palladium catalyst 0.058 g ( 0.05 mmol) was dissolved in a mixed solution of 10 mL of toluene from which moisture was removed and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (CP-10) prepared in Preparation Example 1-10, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is 2,1,3-benzothiadiazole .

And CP-10 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.27~8.3 ppm(5H, aromatic), 3.94 ppm(4H, alkyl group), 3.23~3.42 ppm(16H, alkyl group), 1.76~1.82 ppm(8H, alkyl group), 1.38 ppm (6H, alkyl group)

[Production Example 1-11] Preparation of phenylene-based conjugated polymer of Formula 2

1,4-bis(octyoxy)-2,5-dibromobenzene 492 mg (1 mmol) and 1,4-benzenediboronic acid bis(pinacol) to prepare the phenylene-based conjugated polymer of Formula 2 Ester 0.165 g (0.5 mmol), 4,7-bis(5-bromothiophen-2-yl)benzo[c][1,2,5]thiadiazole 0.229 g (0.5 mmol) and tetrakis( Triphenylphosphine) palladium catalyst 0.058 g (0.05 mmol) _{was dissolved in a mixed solution of 10 mL of toluene and 7 mL of 2 MK 2} CO ₃ from which moisture was removed, and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter CP-11) prepared in Preparation Example 1-11, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is bisthienylbenzothiadiazole.

And CP-11 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.32 to 8.17 ppm (7H, aromatic), 3.92 ppm (4H, alkyl group), 3.2 to 3.48 ppm (16H, alkyl group), 1.78 to 1.8 ppm (8H, alkyl group), 1.47 ppm (6H, alkyl group)

[Production Example 1-12] Preparation of phenylene-based conjugated polymer of Formula 2

To prepare the phenylene-based conjugated polymer of Formula 2, 1,4-bis(octyoxy)-2,5-dibromobenzene 492 mg (1 mmol), 1,4-benzenediboronic acid bis(pinacol) Ester 0.330 g (1 mmol), 5,7-dibromo-thieno[3,4- b ]pyrazine 0.294 g (1 mmol) and tetrakis (triphenylphosphine) palladium catalyst 0.058 g (0.05 mmol) It was dissolved in a mixed solution of 10 mL of toluene from which moisture was removed and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially in order of methanol, acetone, and water, and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter CP-12) prepared in Preparation Example 1-12, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is thienopyrazine.

And CP-12 prepared as described above was confirmed its preparation as follows using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.76 to 8.5 ppm (5H, aromatic), 3.81 ppm (4H, alkyl group), 3.38 to 3.6 ppm (16H, alkyl group), 1.76 to 1.82 ppm (8H, alkyl group), 1.44 ppm (6H, alkyl group)

[Preparation Example 2] Preparation of absorbing member-type photocatalyst using conjugated polymer

A commercially available cellulose filter paper (WHATMAN ^TM ) was cut into a size of 1 cm X 1 cm and used as an absorbent member. And the conjugated polymers CP-1 to CP-12 prepared in Preparation Examples 1-1 to 1-12 were dissolved in THF at a concentration of 2 mg/ml to prepare a conjugated polymer solution (S200).

100 μL of the conjugated polymer solution prepared as described above was pulled out with a micropipette, dropped on the cut cellulose filter paper, absorbed, and dried (S300). ^{Subsequently, heat treatment is performed at a temperature of 80 o} C to completely dry the solvent (S400), so that a photocatalyst including conjugate polymer introduced absorption member (PCPAM), that is, PCPAM-1 using the conjugated polymer according to the present invention. To prepare PCPAM-12.

In the present invention, the absorption member-type photocatalyst prepared as described above can be applied to photocatalytic reactions such as decomposition reactions of organic dyes, oxidation reactions of organic compounds, or reduction reactions of organic compounds.

The photocatalytic reaction may include preparing an organic dye solution, an oxidation reaction solution of an organic compound, or a reduction reaction solution of an organic compound; Immersing an absorption member-type photocatalyst using a conjugated polymer in any one of the solutions; And irradiating light to any one of the solutions with a light source.

The organic dye is preferably any one of rhodamine B, methylene blue, and methyl orange, and the organic compound used in the oxidation reaction is a benzylamine derivative, benzaldehyde, or furoic acid. acid) derivatives, and the organic compound used in the reduction reaction is preferably any one of 4-nitrophenol derivatives.

The photocatalytic reaction method using the absorbing member type photocatalyst of the present invention is as follows. The prepared absorption member-type photocatalyst is immersed in a 20 ml vial containing an organic dye aqueous solution or a reaction solution for oxidation/reduction reaction, and then light irradiated with a solar simulator while stirring. The light irradiation may be any light source having a wavelength of 300 to 700 nm, such as an LED lamp, a xenon lamp, and a solar simulator, and in detail, it is preferable to use a solar simulator, but is not limited thereto.

During the photocatalytic reaction, the distance between the solar simulator and the vial is 5 to 10 cm, the intensity of the light source is in the range of 5 to 10 mA, and the reaction solution is recovered by time to obtain a UV/Vis absorption spectrum or nuclear magnetic resonance spectroscopy; NMR) spectrum confirms the product of the decomposition or oxidation/reduction reaction of the dye. In addition, it is also possible to confirm the reaction process by thin layer chromatography (TLC).

Hereinafter, the photocatalytic reaction of the absorbing member type photocatalyst of the present invention will be described in detail through examples using the absorbing member type photocatalyst of the present invention, that is, PCPAM-1 to PCPAM-12.

[Example 1] Dye decomposition reaction

Commercially available dyes, rhodamine B, methylene blue, and methyl orange (refer to Formulas 3 to 5 below) are dissolved in water to prepare a reaction solution at a concentration of 20 ppm. Add 10 mL each of the dye reaction solution prepared at the concentration of 20 ppm to a 20 mL vial, and add PCPAM-1 to PCPAM-12, the absorption member type photocatalysts of the present invention prepared as described above, to the reaction solution of the dye. Each was put to perform the dye decomposition reaction of Examples 1-1 to 1-12.

[Formula 3]

Rhodamine B

[Formula 4]

Methylene blue

[Formula 5]

Methyl orange

During the dye decomposition reaction of Examples 1-1 to 1-12, visible light (22 W/m ² , λ>450 nm) was irradiated for 4 hours, and the distance between the light source and the dye solution was 5 cm.

After light irradiation, the absorbance of the reaction solution was measured using a uv-vis absorption spectrometer, and the absorbance was converted to a concentration through a calibration curve, and the dye decomposition rate (%) was calculated according to [Equation 1] below. The maximum absorption wavelength of each dye is 544 nm for rhodamine B, 665 nm for methylene blue, and 500 nm for methyl orange.

[Equation 1]

[Comparative Example 1]

In Comparative Examples 1-1 to 1-12, 0.2 mg of the conjugated polymers CP-1 to CP-12 prepared in Preparation Examples 1-1 to 1-12 were directly added to the reaction solution of the dye without using an absorbing member. By dispersing, the dye decomposition rate (%) was measured. .

At this time, when measuring the dye decomposition rate (%) in Comparative Examples 1-1 to 1-12, other conditions are the same as in Example 1, and the measurement of the dye decomposition rate (%) performed in Example 1 and Comparative Example 1 The results are shown in Table 1.

Example Dye decomposition rate (%) Rhodamine B Methylene blue Methyl orange Example 1-1 95.4 90.2 45.8 Example 1-2 98.7 91.3 49.2 Example 1-3 99.2 94.2 52.3 Example 1-4 95.4 92.2 50.2 Example 1-5 89.9 94 51.2 Example 1-6 95 93.2 47.2 Example 1-7 94.3 94.2 49 Example 1-8 92 93.1 50.4 Example 1-9 94.5 91.2 47 Example 1-10 98.2 92 42.3 Example 1-11 91.2 94.2 46 Example 1-12 93 90 45.2 Comparative Example 1-1 1.2 1.5 0.05 Comparative Example 1-2 1.3 1.3 0.02 Comparative Example 1-3 2.1 2.3 0.06 Comparative Example 1-4 1.3 2.0 0.1 Comparative Example 1-5 0.9 2.1 0.09 Comparative Example 1-6 1.9 0.9 0.08 Comparative Example 1-7 1.2 0.8 0.1 Comparative Example 1-8 0.5 0.8 0.12 Comparative Example 1-9 One 0.6 0.3 Comparative Example 1-10 1.3 1.2 0.06 Comparative Example 1-11 1.6 1.1 0.08 Comparative Example 1-12 0.2 0.9 0.02

As shown in Table 1, as a result of measuring the dye decomposition rate (%) of Examples 1-1 to 1-12 using the absorption member-type photocatalysts PCPAM-1 to PCPAM-12 according to the present invention, rhodamine B In the case of and methylene blue, more than 90% were decomposed, and in the case of methyl orange, more than 40% were decomposed.

In contrast, 0.2 mg of the conjugated polymers CP-1 to CP-12 of Comparative Examples 1-1 to 1-12 were directly dispersed in the reaction solution of the dye without using an absorbing member, and then the dye decomposition rate (%) was determined. As a result of the measurement, it can be confirmed that the dye decomposition rate (%) does not exceed 3% in the case of rhodamine B and methylene blue. In particular, it can be seen that methyl orange is hardly decomposed.

[Example 2] Oxidation reaction of benzaldehyde derivatives

After dissolving 1 mmol of the following benzylaldehyde derivative in 5 mL of acetonitrile, a reaction solution was prepared. Add 10 mL each of the reaction solution prepared as above into a 20 mL vial, and add PCPAM-1 to PCPAM-12, the absorbing member-type photocatalysts of the present invention prepared as described above, into the reaction solution, and Examples 2-1 to The oxidation reaction of Examples 2-12 was carried out.

At this time, the chemical reaction formula for conversion from the reactant, the benzylaldehyde derivative, to the product, the benzoic acid derivative, may be represented by the following formula.

[Equation 2]

The conversion reaction was carried out by irradiating the reaction solutions of Examples 2-1 to 2-12 with visible light (22 W/m ² , λ>450 nm) for 4 hours, wherein the distance between the light source and the reaction solution was 5 It was made into cm.

After light irradiation, the solvent of the reaction solution was evaporated to remove it, and then analyzed by ^{nuclear magnetic resonance spectrum (1} H NMR, 300 MHz, Acetone-d _{6 ).}

In the nuclear magnetic resonance spectrum analysis, the conversion rate (%) was calculated from the area ratio of the aldehyde hydrogen spectrum of the benzaldehyde derivative (reactant) at 10 ppm and the hydrogen spectrum of the benzoic acid derivative (product) at 12 ppm. The conversion rate (%) can be calculated from Equation 3 below. .

[Equation 3]

In Equation 3, Xc is the area of the hydrogen spectrum of the benzoic acid derivative, and Xa is the area of the hydrogen spectrum of the benzaldehyde derivative.

[Comparative Example 2]

In Comparative Examples 2-1 to 2-12, 0.2 mg of the conjugated polymers CP-1 to CP-12 prepared in Preparation Examples 1-1 to 1-12 were added to the reaction solution of benzaldehyde without using an absorbing member. It was directly dispersed to measure the conversion rate (%). .

At this time, when measuring the conversion rate (%) in Comparative Examples 2-1 to 2-12, other conditions are the same as in Example 2, and the measurement results of the conversion rate (%) performed in Example 2 and Comparative Example 2 It is shown in Tables 2 and 3.

Example Conversion rate (%)

Example 2-1 98.8 99 99.4 98.3 Example 2-2 99.2 99.4 98.8 99.5 Example 2-3 99.4 99.8 95 99.4 Example 2-4 99.8 99.8 98.3 99.6 Example 2-5 98.7 99.3 99.3 95.6 Example 2-6 96.3 96.7 97 92 Example 2-7 80.2 89.2 84 78.9 Example 2-8 81.3 88.4 80.3 80.3 Example 2-9 84.2 89.9 82.2 83.4 Example 2-10 82.2 84.2 80.7 88.9 Example 2-11 78.9 82.3 81.2 89.7 Example 2-12 80.9 87.7 85.6 91.0 Comparative Example 2-1 0.5 0.3 0.6 1.1 Comparative Example 2-2 0.4 0.8 0.8 0.9 Comparative Example 2-3 1.2 0.6 0.3 0.7 Comparative Example 2-4 0.8 0.9 1.3 0.8 Comparative Example 2-5 0.2 0.2 0.2 0.6 Comparative Example 2-6 0.1 1.1 0.6 1.2 Comparative Example 2-7 0.08 0.7 0.5 0.3 Comparative Example 2-8 0.06 0.09 0.1 0.8 Comparative Example 2-9 0.9 0.06 0.03 0.4 Comparative Example 2-10 0.6 0.1 0.2 0.4 Comparative Example 2-11 0.03 0.3 0.6 0.09 Comparative Example 2-12 0.3 0.2 0.5 0.5

Example Conversion rate (%)

Example 2-1 78.6 75.3 43.2 40.3 Example 2-2 77.2 72.3 46.5 44.2 Example 2-3 78 78.2 48.3 49.3 Example 2-4 82 80.9 48.0 48.3 Example 2-5 88.3 81.2 50.2 46.3 Example 2-6 87.6 83.6 56.1 48.2 Example 2-7 79.6 78.8 48.9 51.5 Example 2-8 78.8 79.2 50.3 50.2 Example 2-9 82.3 75.6 52.2 58.3 Example 2-10 76.5 83.5 49.3 55.3 Example 2-11 78.3 86.4 47.6 52.3 Example 2-12 77.8 79.2 49.3 53.2 Comparative Example 2-1 0.03 0.06 0.01 0.06 Comparative Example 2-2 0.01 0.03 0.02 0.05 Comparative Example 2-3 0.02 0.1 0.01 0.04 Comparative Example 2-4 0.02 0.2 0.03 0.02 Comparative Example 2-5 0.06 0.06 0.03 0.1 Comparative Example 2-6 0.1 0.05 0.06 0.12 Comparative Example 2-7 0.16 0.19 0.01 0.03 Comparative Example 2-8 0.12 0.17 0.01 0.08 Comparative Example 2-9 0.11 0.09 0.09 0.07 Comparative Example 2-10 0.09 0.08 0.03 0.05 Comparative Example 2-11 0.13 0.03 0.04 0.15 Comparative Example 2-12 0.02 0.3 0.03 0.1

As shown in Tables 2 and 3, as a result of measuring the conversion ratio (%) of Examples 2-1 to 2-12 using PCPAM-1 to PCPAM-12, which are absorbing member-type photocatalysts of the present invention, all 40% It was determined that the abnormality was decomposed.

In contrast, 0.2 mg of the conjugated polymers CP-1 to CP-12 of Comparative Examples 2-1 to 2-12 were directly dispersed in the reaction solution of the dye without using an absorbing member, and the conversion rate (%) was measured. As a result, it can be confirmed that little conversion from the benzaldehyde derivative to the benzoic acid derivative occurred.

[Example 3] Oxidative coupling reaction of benzylamine derivatives

After dissolving 1 mmol of the benzylamine derivative as follows in 5 mL of acetonitrile, a reaction solution was prepared. Add 10 mL each of the reaction solution prepared as above into a 20 mL vial, and add PCPAM-1 to PCPAM-12, the absorbing member-type photocatalysts of the present invention prepared as described above, into the reaction solution, and Examples 3-1 to The coral coupling reaction of Example 3-12 was carried out.

At this time, the chemical reaction formula for conversion from the reactant, the benzylamine derivative, to the product, the dibenzylimine derivative, can be represented by Equation 4 below.

.

[Equation 4]

The conversion reaction was performed by irradiating the reaction solutions of Examples 3-1 to 3-12 with visible light (22 W/m ² , λ>450 nm) for 4 hours, at which time the distance between the light source and the reaction solution was 5 It was made into cm.

After light irradiation, the solvent of the reaction solution was evaporated to remove it, and then analyzed with a ^{nuclear magnetic resonance spectrum (1} H NMR, 300 MHz, CDCl _{3 ).}

In the nuclear magnetic resonance spectrum analysis, the conversion ratio is determined by the area ratio of the hydrogen spectrum of the benzyl position carbon of the benzylamine derivative (reactant) at 3.48 ppm and the hydrogen spectrum of the benzyl position carbon of the dibenzylimine derivative (product) at 4.8 ppm. Calculated. The conversion rate (%) can be calculated from Equation 5 below.

[Equation 5]

In [Equation 5], Xb is the area of the hydrogen spectrum of the benzyl site carbon of the product dibenzylimine derivative, and Xd is the area of the hydrogen spectrum of the benzyl site carbon of the benzylamine derivative, which is a reactant.

[Comparative Example 3]

In Comparative Examples 3-1 to 3-12, 0.2 mg of the conjugated polymers CP-1 to CP-12 prepared in Preparation Examples 1-1 to 1-12 were used as a reaction solution of a benzylamine derivative without using an absorbing member. It was directly dispersed in to measure the conversion rate (%).

At this time, when measuring the conversion rate (%) in Comparative Examples 3-1 to 3-12, other conditions are the same as in Example 3, and the measurement results of the conversion rate (%) performed in Example 3 and Comparative Example 3 are It is shown in Tables 4 and 5.

Example Conversion rate (%)

Example 3-1 98.7 95.3 99.7 88.4 Example 3-2 95.6 98.2 98.9 85.5 Example 3-3 99.3 97 99.3 89.8 Example 3-4 99.7 96.1 98 90.3 Example 3-5 99.8 95 97.3 91 Example 3-6 99.3 96.4 97 91.3 Example 3-7 98.2 98.9 90.3 92.2 Example 3-8 97.8 99.2 95.6 89.9 Example 3-9 95.6 97.2 97.3 89 Example 3-10 94 96 98 91.3 Example 3-11 93.2 94.6 98.3 92.3 Example 3-12 91 95.4 99.3 91 Comparative Example 3-1 0.6 0.9 1.2 1.2 Comparative Example 3-2 0.9 1.3 1.3 1.3 Comparative Example 3-3 0.2 1.2 One 1.2 Comparative Example 3-4 0.5 1.3 0.9 0.9 Comparative Example 3-5 1.2 One 0.8 0.9 Comparative Example 3-6 1.1 0.9 1.9 0.8 Comparative Example 3-7 0.9 0.8 0.2 One Comparative Example 3-8 0.6 0.6 0.5 0.7 Comparative Example 3-9 0.5 0.9 1.9 0.6 Comparative Example 3-10 0.8 0.7 1.8 1.2 Comparative Example 3-11 1.2 1.3 1.7 1.1 Comparative Example 3-12 One 1.6 0.5 1.3

Example Conversion rate (%)

Example 3-1 85.4 78.7 69.4 Example 3-2 79 75.5 67 Example 3-3 83 76.4 68.8 Example 3-4 85.4 74 65.3 Example 3-5 82 72.3 64.2 Example 3-6 86.1 73.9 66.1 Example 3-7 84.2 75 58.4 Example 3-8 83.6 79.2 57 Example 3-9 79.8 78.2 59.4 Example 3-10 78.5 76 56 Example 3-11 77.2 72.9 55.9 Example 3-12 75.9 77.2 58.4 Comparative Example 3-1 0.02 0.01 0.02 Comparative Example 3-2 0.01 0.3 0.03 Comparative Example 3-3 0.03 0.02 0.04 Comparative Example 3-4 0.12 0.05 0.04 Comparative Example 3-5 0.09 0.12 0.02 Comparative Example 3-6 0.06 0.11 0.01 Comparative Example 3-7 0.04 0.1 0.06 Comparative Example 3-8 0.03 0.09 0.09 Comparative Example 3-9 0.13 0.6 0.11 Comparative Example 3-10 0.15 0.05 0.1 Comparative Example 3-11 0.09 0.07 0.09 Comparative Example 3-12 0.11 0.06 0.05

As shown in Tables 4 and 5, as a result of measuring the conversion (%) of Examples 3-1 to 3-12 using PCPAM-1 to PCPAM-12, which are absorbing member-type photocatalysts of the present invention, 55.9 to 99.8 % Conversion (%).

In contrast, 0.2 mg of the conjugated polymers CP-1 to CP-12 of Comparative Examples 3-1 to 3-12 were directly dispersed in the reaction solution of the dye without using an absorbing member, and then the conversion rate (%) was measured. As a result, it can be seen that almost no conversion from the benzylamine derivative to the dibenzylimine derivative occurred.

[Example 4] Furoic acid oxidation reaction

After dissolving 1 mmol of furoic acid as follows in 5 mL of water, a reaction solution was prepared. Add 10 mL each of the reaction solution prepared as above into a 20 mL vial, and add PCPAM-1 to PCPAM-12, the absorbing member-type photocatalysts of the present invention prepared as described above, to the reaction solution, and Examples 4-1 to The oxidation reaction of Examples 4-12 was carried out.

At this time, the chemical reaction equation for conversion from the reactant furoic acid to the product furanone may be expressed as Equation 6 below.

[Equation 6]

The conversion reaction was performed by irradiating the reaction solutions of Examples 4-1 to 4-12 with visible light (22 W/m ² , λ>450 nm) for 4 hours, at which time the distance between the light source and the reaction solution was 5 It was made into cm.

After light irradiation, water of the reaction solution was evaporated to remove it, and then analyzed by ^{nuclear magnetic resonance spectrum (1} H NMR, 300 MHz, D _{2 O).}

In the nuclear magnetic resonance spectrum analysis, the conversion rate was calculated by the area ratio of the spectra of the furoic acid (reactant) hydrogen appearing at 7.67, 7.25, and 65.7 ppm and the furanone (product) hydrogen spectrum appearing at 7.42 and 6.25 ppm. The conversion rate (%) can be calculated from Equation 7 below.

[Equation 7]

[Comparative Example 4]

In Comparative Examples 4-1 to 4-12, 0.2 mg of the conjugated polymers CP-1 to CP-12 prepared in Preparation Examples 1-1 to 1-12 were directly added to the furoic acid reaction solution without using an absorbing member. Disperse to measure conversion (%).

At this time, when measuring the conversion rate (%) in Comparative Examples 4-1 to 4-12, other conditions are the same as in Example 4, and the measurement results of the conversion rate (%) performed in Example 4 and Comparative Example 4 are It is shown in Table 6.

Example Conversion rate (%) Comparative example Conversion rate (%) Example 4-1 95.4 Comparative Example 4-1 0.1 Example 4-2 94 Comparative Example 4-2 0.2 Example 4-3 98 Comparative Example 4-3 0.6 Example 4-4 94.3 Comparative Example 4-4 0.09 Example 4-5 92.1 Comparative Example 4-5 0.12 Example 4-6 94.3 Comparative Example 4-6 0.6 Example 4-7 92.1 Comparative Example 4-7 0.4 Example 4-8 91.0 Comparative Example 4-8 0.08 Example 4-9 89.9 Comparative Example 4-9 0.8 Example 4-10 88 Comparative Example 4-10 0.7 Example 4-11 89.4 Comparative Example 4-11 0.5 Example 4-12 88.5 Comparative Example 4-12 0.4

As shown in Table 6, as a result of measuring the conversion (%) of Examples 4-1 to 4-12 using the photocatalytic complexes PCPAM-1 to PCPAM-12 of the present invention, all of them were converted by 80% or more. Became.

In contrast, 0.2 mg of the conjugated polymers CP-1 to CP-12 of Comparative Examples 4-1 to 4-12 were directly dispersed in the reaction solution without using an absorbing member, and the conversion rate (%) was measured. , It can be seen that conversion of furoic acid to dafuranone hardly occurred.

[Example 5] Reduction reaction of 4-nitrophenol

After preparing a solution of 1,100 ppm of 4-nitrophenol as shown below, 11 mL each was added to a 20 mL vial, and sodium borohydride was added to prepare a reaction solution. Thereafter, the reaction solutions of Examples 5-1 to 5-12 were prepared by adding PCPAM-1 to PCPAM-12, which are absorbing member-type photocatalysts of the present invention, to the reaction solution.

At this time, the overall chemical reaction formula for conversion from the reactant 4-nitrophenol to the product 4-aminophenol can be expressed as Equation 8 below.

[Equation 8]

The conversion reaction was carried out by irradiating the reaction solutions of Examples 5-1 to 5-12 with visible light (22 W/m ² , λ>450 nm) for 4 hours, wherein the distance between the light source and the reaction solution was 5 It was made into cm.

After light irradiation, the reaction solution was measured for conversion (%) using a uv-vis absorption spectrometer. That is, when 4-nitrophenol (reactant) is converted to 4-aminophenol (product), the absorbance decreases at 400 nm, which is the maximum absorption wavelength of 4-nitrophenol. Conversion to 4-aminophenol (%) can be calculated.

[Equation 9]

[Comparative Example 5]

In Comparative Examples 5-1 to 5-12, 0.2 mg of the conjugated polymers CP-1 to CP-12 prepared in Preparation Examples 1-1 to 1-12 were reacted with 4-nitrophenol without using an absorbing member. It was directly dispersed in the solution to measure the conversion (%). .

At this time, when measuring the conversion rate (%) in Comparative Examples 5-1 to 5-12, other conditions are the same as in Example 5, and the measurement results of the conversion rate (%) performed in Example 5 and Comparative Example 5 It is shown in Table 7.

Example Conversion rate (%) Comparative example Conversion rate (%) Example 4-1 89.3 Comparative Example 4-1 0.4 Example 4-2 92.7 Comparative Example 4-2 0.2 Example 4-3 99 Comparative Example 4-3 0.09 Example 4-4 95.4 Comparative Example 4-4 0.12 Example 4-5 85.1 Comparative Example 4-5 0.6 Example 4-6 84.2 Comparative Example 4-6 0.5 Example 4-7 85.3 Comparative Example 4-7 0.7 Example 4-8 82 Comparative Example 4-8 0.4 Example 4-9 80.9 Comparative Example 4-9 0.08 Example 4-10 84.5 Comparative Example 4-10 0.6 Example 4-11 88.9 Comparative Example 4-11 0.7 Example 4-12 85.4 Comparative Example 4-12 0.8

As shown in Table 7, as a result of measuring the conversion (%) of Examples 5-1 to 5-12 using the photocatalytic complexes PCPAM-1 to PCPAM-12 of the present invention, all of them were converted by 80% or more. Became.

In contrast, 0.2 mg of the conjugated polymers CP-1 to CP-12 of Comparative Examples 5-1 to 5-12 were directly dispersed in the reaction solution without using an absorbing member, and the conversion rate (%) was measured. , It can be seen that almost no conversion of 4-nitrophenol to 4-aminophenol occurred.

[Example 6] Reuse experiment of absorption member type photocatalyst

[Example 6-1] Reuse experiment in dye decomposition reaction

In the case of dye decomposition, reuse experiment was conducted using PCPAM-3, which is an absorption member type photocatalyst of the present invention. Rhodamine B, methylene blue, and methyl orange used in the present invention were each dissolved in water to prepare reaction solutions of Examples 6-1-1 to 6-1-3 at a concentration of 20 ppm. Thereafter, 10 ml of the reaction solution and PCPAM-3, which is an absorption member type photocatalyst, were put together in a 20 ml vial and irradiated with visible light (22 W/m ² , λ>450 nm) for 4 hours to conduct a dye decomposition reaction. , At this time, the distance between the light source and the dye solution was 5 cm.

After irradiation with light for 4 hours, the PCPAM-3 was taken out, washed with water, dried, immersed in a new reaction solution, and irradiated with light under the same conditions for 4 hours to carry out dye decomposition reaction. The dye decomposition reaction was performed a total of 4 times, and after the reaction, the absorption spectrum of the reaction solution was measured.

Using the absorption spectrum of the reaction solution measured as above, the dye decomposition rate (%) was measured according to Equation 1. At this time, changes in the absorption spectrum of the reaction solution according to the number of reuses of PCPAM-3, an absorption member type photocatalyst, are shown in FIGS. 2A to 2C. That is, Figure 2 (a) to (c) shows the reaction solution according to the number of reuse of PCPAM-3, an absorption member type photocatalyst, using the reaction solutions of Examples 6-1-1 to 6-1-3. It shows the change in absorbance at the maximum absorption wavelength.

Referring to Figure 2 (a), in the case of the reaction solution of rhodamine B, in the case of PCPAM-3, which is an absorption member type photocatalyst of the present invention, the dye decomposition rate (%) was 72.3% even when reused 4 times. In addition, in the case of methylene blue and meting orange, even when the absorption member-type photocatalyst PCPAM-3 was reused 4 times, the dye decomposition rate (%) was measured to be 89.1% and 40.0%, respectively. That is, it can be seen that the absorption member-type photocatalyst of the present invention can be reused by still maintaining a high dye decomposition efficiency even when reused four times.

[Example 6-2] Reuse experiment in organic chemical reaction

The organic chemical reaction was reused using PCPAM-3, an absorption member type photocatalyst of the present invention. That is, benzaldehyde, benzylamine, furonic acid and 4-nitrophenol were each prepared at a concentration of 1 mmol to prepare reaction solutions of Examples 6-2-1 to 6-2-4. In preparing the reaction solution, acetonitrile was used as a solvent for the benzaldehyde and benzylamine, and water was used as the solvent for the furonic acid and 4-nitrophenol.

5 ml of the reaction solutions of Examples 6-2-1 to 6-2-4 prepared as described above were put into a 20 ml vial, and PCPAM-3, an absorbing member type photocatalyst, was immersed in each. Thereafter, the reaction was carried out by irradiating visible light (22 W/m ² , λ>450 nm) for 4 hours, and at this time, the distance between the light source and the dye solution was 5 cm.

After 4 hours of light irradiation, PCPAM-3, which is an absorption member type photocatalyst, was taken out, washed with each solvent, dried, immersed again in a new reaction solution, and irradiated again for 4 hours. The reaction was carried out a total of 4 times, and after the reaction, the solvent of the reaction solution was evaporated to remove it, followed by nuclear magnetic resonance spectroscopy.

The conversion rate (%) from the benzaldehyde, benzylamine, furonic acid and 4-nitrophenol to each product was calculated through Equations 3, 5, 7, 9, and each conversion reaction was calculated from the following Equations 10 to Same as Equation 13.

That is, the change in the conversion rate (%) of the reaction solution according to the number of reuses of the absorption member-type photocatalyst PCPAM-3 is shown in Figs. 3A to 3D and Table 8. That is, Figure 3 (a) to (d) is a conversion rate (%) to the number of reuse of the absorption member-type photocatalyst PCPAM-3 using the reaction solutions of Examples 6-2-1 to 6-2-4 Is shown.

Referring to Figure 3 (a) and Table 8, in the case of the benzaldehyde reaction solution, in the case of PCPAM-3, the absorption member type photocatalyst of the present invention, even when reused 4 times, the conversion rate (%) to benzoic acid is 86.4% or more. appear. In addition, looking at (b) to (d) of Figure 3 and Table 9, in the case of benzylamine, furonic acid, and 4-nitrophenol, respectively, the conversion rate (%) to dibenzylimine, furanone and 4-aminophenol is Even when the absorption member-type photocatalyst PCPAM-3 was reused 4 times, it was measured to be 84%, 86% and 92%, respectively. That is, it can be seen that the absorption member-type photocatalyst of the present invention can be reused by still exhibiting a high conversion rate (%) of organic compounds even when reused four times.

[Equation 10]

[Equation 11]

[Equation 12]

[Equation 13]

Example 6-2-1 Example 6-2-2 Example 6-2-3 Example 6-2-4 recycle
Count Conversion rate (%) 1 ^st 98 98 98 99 2 ^nd 92.3 89 97 98 3 ^rd 90.2 92 89 99 4 ^th 86.4 84 86 92

As described above, unlike a solution photocatalyst used by dissolving in a solvent or a dispersed photocatalyst used by dissolving in a solvent, the absorbing member type photocatalyst using the conjugated polymer of the present invention absorbs the conjugated polymer in the absorbing member. Because it is possible, since it has excellent wettability in the reaction system, the interaction between the reactant and the conjugated polymer and the reaction surface area increase, thereby improving the catalyst efficiency. In addition, since the process of reabsorbing light again by scattering is repeated by immobilizing a conjugated polymer having a photocatalytic function to the absorbing member, it is easy to recover and reuse after use. In addition, the manufacturing process is simple and convenient, and the shape of the absorbing member can be freely modified as necessary, so the application range is wide.

The present invention has been described with reference to the embodiments shown in the drawings, but these are merely exemplary, and those of ordinary skill in the art will appreciate that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical scope of the present invention should be determined by the technical spirit of the appended claims.

Claims (8)

As an absorbing member type photocatalyst in which a conjugated polymer having a photocatalytic function is introduced into the absorbing member,
A conjugated polymer having a photocatalytic function having the structure of Formula 1 or Formula 2 below; And
Absorbing member-type photocatalyst comprising; an absorbing member into which the conjugated polymer having the photocatalytic function is introduced.

[Formula 1]

In Formula 1, X is C, CR ₁ R ₂ , N, S, O, NR ₃ , SO ₂ , and R ₁ , R ₂ , R ₃ are different from each other or the same, and each independently one or more halogens are substituted or It is an unsubstituted linear or branched chain, and is an alkyl group or alkoxy group having 1 to 12 carbon atoms,

[Formula 2]

In Formula 2, R ₄ , R ₅ are H, OR ₆ , R ₇ , R ₆ , R ₇ are different from each other or the same, and each independently one or more halogens substituted or unsubstituted linear or branched chain 1 to It is a 12 alkyl group or an alkoxy group. Preferably, R ₄ , R ₅ is n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-ethylhexyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy And 2-ethylhexyloxy, or may be selected in combination. The values of X and Y represent the composition of each repeating unit in mole fraction, where X is a real number from 0 to 0.99, Y is 1-X,
In addition, Ar in Formula 1 or Formula 2 below is

,

,

,

,

,

Is either.
The method according to claim 1,
The absorbing member is an absorbent member type photocatalyst, characterized in that any one of non-woven fabric, woven fabric, pad, and filter paper.
Photocatalytic reaction using the absorption member type photocatalyst of claim 1 or 2
The method of claim 3,
The photocatalytic reaction is any one of a decomposition reaction of an organic dye, an oxidation reaction of an organic compound, and a reduction reaction of an organic compound.
The method of claim 4,
The organic dye is a photocatalytic reaction, characterized in that any one of rhodamine B (Rhodamine B), methylene blue (methylene blue), methyl orange (methylorange).
The method of claim 4,
The oxidation reaction of the organic compound is a photocatalytic reaction, characterized in that targeting any one of a benzaldehyde derivative, a benzylamine derivative and a furoic acid.
The method of claim 4,
A photocatalytic reaction, characterized in that the reduction reaction of the organic compound targets 4-nitrophenol.
A first step (S100) of preparing a conjugated polymer;
A second step (S200) of preparing a conjugated polymer solution by dissolving the conjugated polymer prepared in the first step in an organic solvent;
A third step (S300) of introducing the conjugated polymer solution prepared in the second step into an absorbent member; And
A fourth step (S400) of heat-treating the absorbing member into which the conjugated polymer solution prepared in the third step is absorbed. The method of manufacturing an absorbing member-type photocatalyst comprising:

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