KR20200031754A - a metal-complex mesoporous carbon membrane using silica nanoparticle and a method manufacturing the same - Google Patents

Abstract

The present invention relates to a mesoporous carbon porous membrane and a method for preparing the same. The method of the present invention comprises the steps of: (a) preparing silica nanoparticles having the diameter of 10 to 200 nm; (b) preparing a nanocomplex by stirring the silica nanoparticles, a carbon precursor and a solvent to apply a pressure thereto; (c) preparing a carbon complex by thermally treating the nanocomplex under an non-oxidizing atmosphere; (d) preparing a carbon porous membrane by treating the carbon complex with acid to remove the silica nanoparticles; (e) modifying a surface of the carbon porous membrane by treating the carbon porous membrane with diazonium salt having at least one functional group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group and a phosphoric acid group; and (f) preparing a metal-complex carbon porous membrane by treating the modified carbon porous membrane with a metal solution.

Description

A metal-complex mesoporous carbon membrane using silica nanoparticle and a method manufacturing the same}

The present invention relates to a mesoporous carbon porous membrane and a method for manufacturing the same, and more specifically, (a) preparing silica nanoparticles having a diameter of 10 to 200 nm; (b) preparing the nanocomposite by stirring the silica nanoparticles, carbon precursor and solvent and applying pressure; (c) preparing the carbon composite by heat-treating the nanocomposite under a non-oxidizing atmosphere; (d) removing the silica nanoparticles by acid-treating the carbon composite and preparing a carbon porous film; (e) treating the carbon porous membrane with a diazonium salt having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group and phosphoric acid group to modify the surface of the carbon porous film; And (f) a method for producing a mesoporous carbon porous membrane comprising the step of producing a metal complex-type carbon porous membrane by treating the modified carbon porous membrane with a metal solution and a mesoporous carbon porous membrane prepared therefrom.

Mesoporous materials are widely used in fields such as catalysts, supports, adsorbents, separators and sensors.

Since the mesoporous material has different characteristics depending on the size, distribution, shape, etc. of pores contained therein, various studies have been conducted to control the size, distribution, shape, etc. of the inner pores.

With regard to mesoporous materials, Korean Patent Registration No. 10-1852924, etc. discloses a hybrid porous structure including a porous region and a non-porous region forming a nanoporous structure.

However, the technology disclosed in the above document has low strength of the porous structure and poor surface characteristics of the structure, thereby inferior to harmful gas removal characteristics, fine dust removal characteristics, and antimicrobial properties, thereby satisfying the needs of consumers who require a high-functional carbon porous membrane. none.

Korean Registered Patent No. 10-1852924

The present invention is to solve the problems of the prior art, by forming a metal complex on the surface of the carbon porous film to provide a method for producing a mesoporous carbon porous film excellent in removing harmful gases, removing fine dust and antibacterial properties There is this.

In addition, an object of the present invention is to provide a mesoporous carbon porous membrane having a uniform internal pore size and excellent strength.

In order to achieve the above object, the present invention comprises the steps of (a) preparing silica nanoparticles having a diameter of 10 to 200 nm; (b) preparing the nanocomposite by stirring the silica nanoparticles, carbon precursor and solvent and applying pressure; (c) preparing the carbon composite by heat-treating the nanocomposite under a non-oxidizing atmosphere; (d) removing the silica nanoparticles by acid-treating the carbon composite and preparing a carbon porous film; (e) treating the carbon porous membrane with a diazonium salt having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group and phosphoric acid group to modify the surface of the carbon porous film; And (f) treating the modified carbon porous film with a metal solution to prepare a metal complex carbon porous film.

In one embodiment of the present invention, the step (a) comprises the steps of stirring the alcohol, ammonium hydroxide and water in a volume ratio of 10 to 100: 0.5 to 10: 1 for 10 to 60 minutes to prepare a first mixture; Preparing a second mixture by adding an alcohol and a silica precursor to the first mixture in a volume ratio of 1 to 10: 1 and stirring for 1 to 5 hours; And evaporating the solvent contained in the second mixture to prepare silica nanoparticles, wherein the volume ratio of the alcohol contained in the first mixture and the alcohol added to the second mixture is 5-50: 1. It is characterized by.

In one embodiment of the present invention, the step (b) comprises the steps of preparing the first mixture by stirring the silica nanoparticles and carbon precursor; Preparing a second mixture by adding a part of the solvent to the first mixture and then stirring; Preparing a third mixture by adding and stirring the remaining solvent to the second mixture; And manufacturing a nanocomposite by applying pressure to the third mixture.

In one embodiment of the present invention, step (e) is characterized in that 1 to 10 parts by weight of diazonium salt is used with respect to 100 parts by weight of the carbon porous film.

In one embodiment of the present invention, the step (f) is characterized in that the metal formed of the metal complex of the functional group and the metal solution formed on the surface of the carbon porous film.

In addition, the present invention provides a mesoporous carbon porous membrane prepared by the above manufacturing method.

The present invention can provide a method for producing a mesoporous carbon porous membrane having excellent gas removal characteristics, fine dust removal characteristics and antibacterial properties by forming a metal complex on the surface of the carbon porous membrane.

In addition, the present invention can provide a mesoporous carbon porous membrane that can be stably used for a long period of time in a mask, a filter, a catalyst, an adsorbent, a sensor, etc., because the size of the internal pores is uniform and has excellent strength.

1 shows the silica nanoparticles of the present invention.
Figure 2 shows the nanocomposite of the present invention.
3 shows the carbon composite of the present invention.
4 shows the carbon porous membrane after the acid treatment of the present invention.

Hereinafter, the present invention will be described in detail based on examples. The terms, examples, and the like used in the present invention are merely exemplified in order to explain the present invention in more detail and help a person of ordinary skill in the art understand, and the scope of the present invention should not be interpreted as being limited thereto.

Technical terms and scientific terms used in the present invention, unless otherwise defined, refer to meanings commonly understood by those skilled in the art to which this invention belongs.

The present invention (a) preparing a silica nanoparticle having a diameter of 10 ~ 200nm; (b) preparing the nanocomposite by stirring the silica nanoparticles, carbon precursor and solvent and applying pressure; (c) preparing the carbon composite by heat-treating the nanocomposite under a non-oxidizing atmosphere; (d) removing the silica nanoparticles by acid-treating the carbon composite and preparing a carbon porous film; (e) treating the carbon porous membrane with a diazonium salt having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group and phosphoric acid group to modify the surface of the carbon porous film; And (f) treating the modified carbon porous film with a metal solution to produce a metal complex carbon porous film.

The step (a) is a step of preparing silica nanoparticles, preparing a first mixture by stirring alcohol, ammonium hydroxide and water; Adding an alcohol and a silica precursor to the first mixture, followed by stirring to prepare a second mixture; And evaporating the solvent contained in the second mixture to prepare silica nanoparticles (FIG. 1).

As alcohol, methanol, ethanol, propanol, butanol and the like can be used without limitation, and ethanol is preferably used.

In order to promote the hydrolysis of the silica precursor, ammonium hydroxide, ammonia water, sodium hydroxide, potassium hydroxide, etc. may be used without limitation, and ammonium hydroxide is preferably used.

Silica precursors include alkoxysilanes such as tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS), sodium silicate, potassium silicate, silicon tetrachloride, etc., and can be used without limitation. It is preferred that ethoxysilanes are used.

Alcohol, ammonium hydroxide, water, and silica precursors are not mixed and stirred at the same time, because when mixed at the same time, the size of the prepared silica nanoparticles is not uniform, and the strength and adsorption properties of the carbon porous film are lowered.

First, the first mixture is prepared by stirring alcohol, ammonium hydroxide and water in a volume ratio of 10 to 100: 0.5 to 10: 1 for 10 to 60 minutes.

After adding the alcohol and silica precursor to the first mixture in a volume ratio of 1 to 10: 1, stirring for 1 to 5 hours to prepare a second mixture.

Silica nanoparticles are prepared by evaporating the solvent contained in the second mixture, and the volume ratio of the alcohol contained in the first mixture and the alcohol added to the second mixture is preferably 5-50: 1.

The diameter of the silica nanoparticles is 10 to 200 nm, preferably 30 to 150 nm. When the diameter is less than 10 nm, the pores of the produced carbon pore film are small, so that harmful gases and fine dust cannot be effectively adsorbed, and when it exceeds 200 nm, the strength, thermal properties and durability of the carbon pore film are deteriorated.

Since the silica nanoparticles produced through the step (a) have a uniform size, the carbon porous membrane produced through this has excellent strength and can stably adsorb harmful gases and fine dust.

The step (b) comprises the steps of preparing the first mixture by stirring the silica nanoparticles and the carbon precursor; Preparing a second mixture by adding a part of the solvent to the first mixture and then stirring; Preparing a third mixture by adding and stirring the remaining solvent to the second mixture; And preparing a nanocomposite by applying pressure to the third mixture (FIG. 2).

The prepared silica nanoparticles can be aggregated with each other to increase the size of the particles. To prevent such agglomeration, the silica nanoparticles may be surface treated with a surfactant, a stabilizer, and the like.

As the surfactant, cationic surfactants such as alkyl trimethylammonium halide; Neutral surfactants such as oleic acid and alkyl amines; Anionic surfactants such as sodium alkyl sulfate and sodium alkyl phosphate can be used without limitation.

The carbon precursor is a material that is carbonized in the heat treatment process, polyvinyl chloride, polyvinylpyrrolidone, polyvinyl alcohol, phenol resin, ketone resin, acrylic resin, monosaccharides, polysaccharides, etc. can be used without limitation, preferably poly It is recommended that vinyl chloride and polyvinyl alcohol are used at the same time.

The weight ratio of polyvinyl chloride and polyvinyl alcohol is preferably 60 to 80: 20 to 40, and when the content range is satisfied, the strength and adsorption properties of the carbon porous film are excellent.

As the solvent, alcohols such as water, methanol, ethanol, and ketones such as acetone and methyl ethyl ketone may be used without limitation, and preferably, a co-solvent of ethanol and methyl ethyl ketone is preferably used.

The weight ratio of ethanol and methyl ethyl ketone is preferably 20 to 40:60 to 80, and when the content range is satisfied, the strength and adsorption properties of the carbon porous membrane are excellent.

Silica nanoparticles, carbon precursors, and solvents are not mixed and stirred at the same time, because when mixed at the same time, the pore size of the prepared carbon pore film is not uniform, and the strength and adsorption properties of the carbon pore film are lowered.

First, the first mixture is prepared by stirring the silica nanoparticles and the carbon precursor in a weight ratio of 1: 1 to 6.

A portion of the solvent is added to the first mixture, followed by stirring to prepare a second mixture, and after adding the remaining solvent to the second mixture, stirred to prepare a third mixture, 80-500 ° C. to the third mixture. , After applying a pressure of 1 to 10 minutes at 50 ~ 150 atm, then a pressure of 10 to 2 hours at 160 ~ 500 atm to prepare a nanocomposite.

The weight ratio of the silica nanoparticles, carbon precursor, and solvent is preferably 1: 1 to 6: 1 to 6.

The solvent is not added at one time, but is divided and added several times.

It is preferable to add it in 2-6 times.

The carbon porous membrane prepared from the nanocomposite of step (b) has a uniform pore size and excellent strength, and can effectively adsorb harmful gases and fine dust.

The step (c) is a step of preparing a carbon composite by heat-treating the nanocomposite at 600 to 2,000 ° C. for 1 to 60 hours under a non-oxidizing atmosphere of argon or nitrogen (FIG. 3).

Through the step (c), the carbon precursor of the nanocomposite is carbonized to prepare a carbon composite.

The inflow rate of argon or nitrogen is preferably 1 to 10 L / min in terms of the adsorption properties of the produced carbon composite.

The step (d) is a step of preparing a carbon porous film by removing the silica nanoparticles by acid treatment of the carbon composite (FIG. 4).

The silica nanoparticles can be removed by a solvent such as a hydrofluoric acid solution or a sodium hydroxide solution.

For example, after the carbon composite is introduced into a 20-60% hydrofluoric acid solution, the silica nanoparticles can be removed by stirring at room temperature for 1-50 hours.

The step (e) is a step of modifying the surface of the carbon porous membrane by treating the carbon porous membrane with a diazonium salt having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group, and phosphoric acid group.

Through the surface modification, functional groups such as a carboxyl group, hydroxyl group, sulfonic acid group, and phosphoric acid group formed on the surface of the carbon porous film can be combined with a metal or various compounds, and adsorption properties and antibacterial properties can be improved.

The content of the diazonium salt is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the carbon porous membrane, and when the content of the diazonium salt is less than 1 part by weight, the introduction of a functional group is insignificant and the adsorption characteristics are lowered, and if it exceeds 10 parts by weight The porosity of the formed carbon pore membrane is rather small, so that it cannot effectively adsorb harmful gases and fine dust.

The diazonium salt may be prepared by reacting an aromatic primary amine having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group and phosphoric acid group with hydrochloric acid and sodium nitrite.

The diazonium salt is preferably a diazonium salt having a carboxyl group and a diazonium salt having a hydroxyl group at the same time.

The weight ratio of the diazonium salt having a carboxyl group and the diazonium salt having a hydroxyl group is preferably 60 to 80:20 to 40, and when the content range is satisfied, the strength and adsorption properties of the carbon porous film are excellent.

As an example, the first step of mixing and mixing 1,000 parts by weight of 0.2M HCl in a reaction vessel; A second step of mixing 4-aminobenzoic acid or 4-aminophenol with 10 to 1,000 parts by weight in the mixed solution of the first step; And a diazonium salt may be prepared through the third step of adding and adding 0.1 to 500 parts by weight of 0.02M sodium nitrite to the mixed solution of the second step.

When the carbon pore membrane is treated with a diazonium salt having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group, and phosphoric acid group, a diazonium salt is continuously bonded to the surface of the carbon pore film to form a graft polymer having excellent thermal stability. Can be.

When a graft polymer having excellent thermal stability is covalently bonded to the surface of the carbon porous membrane, the metal complex or compound is stably bonded because the graft polymer is thermally stable and does not decompose even under high temperature conditions such as a coating process and a filter manufacturing process. Adsorption characteristics and antibacterial properties can be expressed for a long time.

If a low-molecular compound is bound to the surface of the carbon porous membrane, the low-molecular compound is easily decomposed by heat, and the metal complex or compound is easily desorbed, and it is impossible to express adsorption characteristics, antibacterial properties, and the like.

To efficiently perform graft polymerization, a catalyst such as potassium sulfate or sodium nitrate may be used, and the catalyst is preferably used in an amount of 0.01 to 0.1 mol per 1 mol of the diazonium salt. When the content of the catalyst is less than 0.01 mol, the effect of the addition is negligible, and when it exceeds 0.1 mol, a large amount of a diazonium salt homopolymer is generated, and the adsorption characteristics are deteriorated.

The graft polymerization is preferably performed at 50 to 90 ° C for 10 minutes to 24 hours, and if the polymerization temperature is less than 50 ° C, polymerization occurs incompletely, and when it exceeds 90 ° C, the durability of the carbon porous film is reduced. In addition, if the polymerization time is less than 10 minutes, polymerization occurs incompletely, and if it exceeds 24 hours, a large amount of a diazonium salt homopolymer is generated, and the adsorption characteristics are deteriorated.

In addition, the present invention can further modify the surface by treating the modified carbon porous film with a copolymer of an acrylate group-containing silane coupling agent and an acrylic acid monomer.

The copolymer may be covalently bonded to the surface of the carbon porous film or may be combined with a graft polymer introduced by a diazonium salt, through which a number of carboxyl groups may be introduced to the surface of the carbon porous film.

A number of carboxyl groups included in the copolymer can be combined with a metal or various compounds, and adsorption properties, antibacterial properties, etc. can be improved.

When a copolymer having excellent thermal stability is covalently bonded to the surface of the carbon porous membrane, the metal complex or compound is stably bonded because the copolymer is thermally stable and does not decompose under high temperature conditions such as a coating process and a filter manufacturing process. Adsorption characteristics and antibacterial properties can be expressed for a long time.

The acrylate group-containing silane coupling agent is 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl tree And ethoxysilane, 3-acryloxypropyl trimethoxysilane, methacryloxymethyl triethoxysilane, and methacryloxymethyl trimethoxysilane.

The acrylic acid monomer is acrylic acid, methacrylic acid, methyl acrylic acid, ethyl acrylic acid, butyl acrylic acid, 2-ethyl hexyl acrylic acid, decyl acrylic acid, methyl methacrylic acid, ethyl methacrylic acid, butyl methacrylic acid, 2-ethyl hexyl methacrylic acid , Decyl methacrylic acid, and the like.

The weight ratio of the acrylate group-containing silane coupling agent and the acrylic acid monomer is preferably 10 to 30:70 to 90, and if the weight ratio is less than 10:90, the bonding strength with the carbon porous membrane decreases, and if it exceeds 30:70, adsorption The characteristics deteriorate.

The copolymer of the acrylate group-containing silane coupling agent and the acrylic acid monomer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the carbon porous membrane, and when the content of the copolymer is less than 1 part by weight, the introduction of a functional group is insignificant, resulting in adsorption characteristics. When it is lowered and exceeds 10 parts by weight, the porosity of the produced carbon porous film becomes rather small, and it is impossible to effectively adsorb harmful gases and fine dust.

The step (f) is a step of preparing a metal complex-type carbon porous film by treating the modified carbon porous film with a metal solution.

The functional group formed on the surface of the carbon porous film and the metal of the metal solution may form a metal complex.

That is, the functional group of the polymer graft polymerized on the surface of the carbon porous film and the carboxyl group of the copolymer can form a metal complex and a metal complex of the metal solution.

Functional groups such as a carboxyl group, a hydroxyl group, a sulfonic acid group, and a phosphoric acid group can form a stable complex with the metal, and the metal is not easily desorbed even under high temperature conditions.

As the metal, gold, silver, copper, cobalt, nickel, zinc, platinum, etc. can be used without limitation.

The metal formed on the surface of the carbon pore film can be combined with harmful gases, fine dust, viruses, and the like, so that adsorption properties, antibacterial properties, etc. can be improved.

A metal precursor may be used to form the metal complex, silver nitrate, silver sulfate, silver acetylacetonate, silver acetate, silver carbonate, silver chloride, copper nitrate, copper sulfate, copper acetylacetonate, copper acetate, copper carbonate, copper Chloride and the like can be used.

The content of the metal is preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the carbon porous film, and the effect of the addition is minimal when the content of the metal is less than 0.1 parts by weight, and a metal complex on the surface of the carbon porous film when it exceeds 5 parts by weight Cannot be uniformly distributed.

The present invention relates to a mesoporous carbon porous membrane produced by the above manufacturing method.

The size of the pores present in the carbon pore membrane is the same or similar to the size of the removed silica nanoparticles, and the diameter of the pores is preferably 10 to 200 nm and 30 to 150 nm.

When the diameter of the pores is less than 10 nm, the pores of the produced carbon pore film are small, so that harmful gases and fine dust cannot be effectively adsorbed, and when it exceeds 200 nm, the strength, mechanical properties, thermal properties and durability of the carbon pore films are deteriorated.

The carbon pore membrane has a uniform pore size and excellent strength, and can effectively adsorb harmful gases and fine dust, and has excellent mask removal characteristics, fine dust removal characteristics, and antibacterial properties. It can be used stably for a long period of time.

In addition, the metal formed on the surface of the carbon pore film can be combined with harmful gases, fine dust, etc., so that the adsorption properties, antibacterial properties, etc. of the carbon pore film can be improved.

Hereinafter, the present invention will be described in detail through examples and comparative examples. The following examples are only exemplified for the practice of the present invention, and the contents of the present invention are not limited by the following examples.

(Example 1)

A first mixture was prepared by stirring 790 ml of ethanol, 11.05 ml of ammonium hydroxide and 11.05 ml of water for 20 minutes.

After adding 79 ml of ethanol and 25 ml of tetraethoxysilane to the first mixture, the mixture was stirred for 2 hours to prepare a second mixture.

Silica nanoparticles having a particle diameter of 120 nm were prepared by evaporating the solvent contained in the second mixture.

The first mixture was prepared by stirring 2 g of the silica nanoparticles and 8 g of polyvinyl chloride for 1 minute.

2 g of methyl ethyl ketone was added to the first mixture, followed by stirring to prepare a second mixture.

A third mixture was prepared by adding 2 g of methyl ethyl ketone to the second mixture.

The third mixture was introduced into a press machine to apply a pressure of 1 minute at 100 atmospheres, and then a pressure of 30 minutes at 200 atmospheres to prepare a nanocomposite.

The nanocomposite was introduced into an electric furnace and heat treated at 1,000 ° C. for 5 hours in an argon atmosphere to prepare a carbon composite.

After adding the carbon composite to a 25% hydrofluoric acid solution, the mixture was stirred for 6 hours at room temperature to remove silica nanoparticles and dried to prepare a carbon porous membrane.

Meanwhile, 1 L of 0.2M HCl was added to a 2 L reaction vessel installed on an ice bath and stirred at 300 rpm.

After adding 27.428 g of 4-aminobenzoic acid, 250 mL of 0.02M NaNO ₂ was added using a peristaltic pump at a rate of 20 mL / min.

The mixture was stirred at 300 rpm for 2 hours to obtain a diazonium salt having a carboxyl group.

A constant temperature water tank maintained at 70 ° C was prepared on a hot plate, and a 500 mL flask was immersed in the constant temperature water tank, and 100 mL of the diazonium salt having the carboxyl group obtained above was added to the flask.

After impregnating by adding the dried carbon porous membrane to the flask, 0.03 mol of potassium sulfate was added to 1 mol of the diazonium salt having a carboxyl group, followed by stirring at 500 rpm for 1 hour to perform graft polymerization. At this time, the content of the diazonium salt was 5 parts by weight based on 100 parts by weight of the carbon porous membrane.

Thereafter, the carbon porous membrane was taken out, washed with distilled water, and dried at 70 ° C. for 3 hours using a vacuum oven.

To the flask, 250 mL of 0.2 mM silver nitrate solution was added, and the carbon pore membrane prepared above was added and stirred for 1 hour, and then the carbon pore membrane was taken out again, washed with distilled water and dried at 70 ° C. for 3 hours using a vacuum oven. At this time, the content of silver was 3 parts by weight compared to 100 parts by weight of the carbon porous membrane.

(Example 2)

A carbon porous membrane was prepared in the same manner as in Example 1, except that 2 g of silica nanoparticles and 1 g of polyvinyl chloride were stirred for 1 minute to prepare a first mixture.

(Example 3)

A carbon porous membrane was prepared in the same manner as in Example 1, except that 2 g of silica nanoparticles and 15 g of polyvinyl chloride were stirred for 1 minute to prepare a first mixture.

(Example 4)

A carbon porous film was prepared in the same manner as in Example 1, except that 2 g of silica nanoparticles, 6 g of polyvinyl chloride, and 2 g of polyvinyl alcohol were stirred for 1 minute to prepare a first mixture.

(Example 5)

Carbon was prepared in the same manner as in Example 1, except that 3 g of methyl ethyl ketone was added to the first mixture, followed by stirring to prepare a second mixture, and 1 g of ethanol was added to the second mixture to prepare a third mixture. A pore membrane was prepared.

(Example 6)

A copolymer was prepared by copolymerizing 20% by weight of 3-methacryloxypropyl trimethoxysilane and 80% by weight of methacrylic acid.

A carbon porous membrane was prepared in the same manner as in Example 1, except that the carbon porous membrane was treated with diazonium having a carboxyl group, followed by treatment with the copolymer, and then treated with a silver nitrate solution. At this time, a copolymer of 5 parts by weight compared to 100 parts by weight of the carbon porous membrane was used.

(Comparative Example 1)

A carbon porous membrane was prepared in the same manner as in Example 1, except that the diazonium salt was not treated.

The tensile strength and adsorption characteristics (deodorization rate) of the carbon porous membranes prepared from the above Examples and Comparative Examples were measured, and the results are shown in Table 1 below.

Tensile strength was measured according to ASTM D 638.

The adsorption characteristics were measured by using ammonia counting equipment to leave the carbon pore membrane in a closed tank, and in this state, NH ₄ OH solution was added to measure the concentration of ammonia in the tank using a gas detector tube.

The ammonia concentration in the tank was measured in the process of adsorption and decomposition of the ammonia solution to the sample left in the tank.

division Example Comparative example One 2 3 4 5 6 One The tensile strength
(kg / cm ² ) 4.2 3.6 3.8 5.2 5.1 4.7 2.9 Deodorization rate (%) 96.1 93.3 93.8 98.7 98.9 99.4 85.5

From the results of Table 1, it can be seen that the carbon porous films of Examples 1 to 6 are excellent in tensile strength and adsorption characteristics. In particular, Examples 4 to 6 have the best characteristics.

On the other hand, it can be seen that the carbon porous membrane of Comparative Example 1 is inferior to that of the Example.

Claims (6)

(a) preparing silica nanoparticles having a diameter of 10 to 200 nm;
(b) preparing the nanocomposite by stirring the silica nanoparticles, carbon precursor and solvent and applying pressure;
(c) preparing the carbon composite by heat-treating the nanocomposite under a non-oxidizing atmosphere;
(d) removing the silica nanoparticles by acid-treating the carbon composite and preparing a carbon porous film;
(e) treating the carbon porous membrane with a diazonium salt having at least one functional group selected from a carboxyl group, hydroxyl group, sulfonic acid group and phosphoric acid group to modify the surface of the carbon porous film; And
(f) A method for producing a mesoporous carbon porous membrane comprising the step of preparing a metal complex carbon porous membrane by treating the modified carbon porous membrane with a metal solution.
According to claim 1,
Step (a) is
Preparing a first mixture by stirring alcohol, ammonium hydroxide and water in a volume ratio of 10 to 100: 0.5 to 10: 1 for 10 to 60 minutes;
Preparing a second mixture by adding an alcohol and a silica precursor to the first mixture in a volume ratio of 1 to 10: 1 and stirring for 1 to 5 hours; And
And evaporating the solvent contained in the second mixture to prepare silica nanoparticles,
A method for producing a mesoporous carbon porous membrane, wherein the volume ratio of the alcohol contained in the first mixture and the alcohol added to the second mixture is 5-50: 1.
According to claim 2,
Step (b) is
Preparing a first mixture by stirring the silica nanoparticles and the carbon precursor;
Preparing a second mixture by adding a part of the solvent to the first mixture and then stirring;
Preparing a third mixture by adding and stirring the remaining solvent to the second mixture; And
Method of manufacturing a mesoporous carbon porous membrane comprising the step of preparing a nanocomposite by applying pressure to the third mixture.
According to claim 3,
Step (e) is
Method for producing a mesoporous carbon porous membrane, characterized in that 1 to 10 parts by weight of diazonium salt is used with respect to 100 parts by weight of the carbon porous membrane.
According to claim 4,
Step (f) is
A method for producing a mesoporous carbon porous membrane, wherein a metal complex of a functional group and a metal solution formed on the surface of the carbon porous membrane forms a metal complex.
A mesoporous carbon porous membrane produced by the method of any one of claims 1 to 5.

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