KR20210069198A - Porous gas permeable membranes and manufacturing method for the same - Google Patents

Abstract

The present invention relates to a porous gas permeable membrane manufacturing method including: a step of dissolving a metal precursor and a synthetic amino fatty acid represented by the following structural formula 1 in a solvent; a step of reducing the metal precursor to form metal nanoparticles; and a step of forming a self-assembly of the metal nanoparticles and the synthetic amino fatty acid and simultaneously allowing the self-assembly to float in the solvent to be positioned on the surface of the solvent. In structural formula 1, R1 is a C2 to C20 linear or branched alkyl group, a substituted or unsubstituted C2 to C20 aryl group, a substituted or unsubstituted C2 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 an alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C2 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

Description

Porous gas permeable membrane and manufacturing method thereof

The present application relates to a porous gas permeable membrane and a method for manufacturing the same.

Petroleum, a major resource in modern society, has regional and political problems, such as being highly ubiquitous in the region, and its supply fluctuates easily depending on the international situation. In addition, since greenhouse gases such as carbon dioxide generated in the process of burning petroleum cause global warming, development of alternative energy technologies capable of replacing petroleum resources is attracting attention.

Among these alternative energies, since water (H ₂ O) is emitted when hydrogen gas is burned, there is an advantage that can solve the problem of global warming caused by petroleum resources. However, hydrogen is very light and because of its simple structure, it can be formed with methane, carbon monoxide, water, carbon dioxide, etc. Therefore, in order to use hydrogen as an energy source, it is necessary to separate only hydrogen gas from among various mixed gases.

In order to separate very small and light hydrogen molecules, research on membranes is active. The membrane is for selectively separating specific particles using the pore size, electrical properties, and/or physical properties of the membrane, and only a desired material can be selectively obtained through the membrane. These membranes can be used for gas permeation membranes, water purification, etc., and thus are being studied a lot in modern society.

Ceramics, polymers, metals, and composite materials thereof have been suggested as materials that can be used for the membrane. However, the ceramic material is brittle and difficult to manufacture into a desired material, the polymer material does not have a constant pore size due to the internal volume (free volume), and in the case of a metal material, a problem of brittle fracture due to hydrogen, a complicated manufacturing process, and low hydrogen permeability per unit area.

Korean Patent Application Laid-Open No. 10-2010-0107960, which is the background technology of the present application, relates to a nanoporous membrane and a method for manufacturing the same. The above publication only manufactures a nanoporous membrane through heat treatment over two times, but does not recognize a silane layer for self-assembly of metal nanoparticles and pore size control.

An object of the present application is to provide a method for manufacturing a porous gas permeable membrane and a porous gas permeable membrane prepared by the method for solving the problems of the prior art.

However, the technical overlayer to be achieved by the embodiment of the present application is not limited to the technical problems as described above, and other technical problems may exist.

As a technical means for achieving the above technical problem, the first aspect of the present application comprises the steps of dissolving a metal precursor and a synthetic amino fatty acid represented by the following Structural Formula 1 in a solvent, wherein the metal precursor is reduced to form metal nanoparticles Providing a method for producing a porous gas permeable membrane, comprising: forming a self-assembly of the metal nanoparticles and the synthetic amino fatty acid, and simultaneously floating the self-assembly in the solvent to position the self-assembly on the surface of the solvent do.

[Structural Formula 1]

;

;

In Structural Formula 1, R ₁ is a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted It is a C ₂ to C ₂₀ heteroaryl group.

According to one embodiment of the present application, the self-assembly may be a network bond between the metal nanoparticles and the synthetic amino fatty acid, but is not limited thereto.

According to one embodiment of the present application, the synthetic amino fatty acid may include both a hydrophilic moiety and a hydrophobic moiety, but is not limited thereto.

According to one embodiment of the present application, the molar ratio of the metal precursor and the synthetic amino fatty acid may be 1:1 to 1:5, but is not limited thereto.

According to the exemplary embodiment of the present disclosure, the method may further include, but is not limited to, forming a silane layer for adjusting the pore size in the magnetic assembly.

According to the exemplary embodiment of the present application, the forming of the silane layer may include depositing a silane precursor represented by the following Structural Formula 2 or the following Structural Formula 3 on the metal nanoparticles, but is not limited thereto.

[Structural Formula 2]

SiR ₂ R ₃ R ₄ R ₅ ;

[Structural Formula 3]

R ₂ OSiR ₃ R ₄ R ₅ ;

In Structural Formulas 2 and 3, R ₂ to R ₅ are each independently a halogen element of F, Cl, Br, or I, hydrogen, a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, substituted or unsubstituted A substituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ an alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₂ to C ₂₀ heteroaryl group.

According to the exemplary embodiment of the present application, the step of reducing the metal precursor to form the metal nanoparticles may be performed at a temperature ranging from 20°C to 50°C, but is not limited thereto.

According to one embodiment of the present application, the metal precursor is Au, Pt, Ti, Ag, Ni, Zr, Ta, Zn, Nb, Cr, Co, Mn, Fe, Al, Mg, Si, W, Cu, and these It may include a metal selected from the group consisting of combinations of, but is not limited thereto.

According to one embodiment of the present application, the solvent may _{include a polar solvent selected from the group consisting of H 2} O, methanol, ethanol, ammonia, acetic anhydride, acetone, and combinations thereof, but is not limited thereto.

In addition, in the second aspect of the present application, in the porous gas permeable membrane formed by network bonding of metal nanoparticles and synthetic amino fatty acids, a silane compound is formed on the metal nanoparticles, and the porous gas permeates by the silane compound A porous gas permeable membrane is provided, wherein the pore size of the membrane is adjusted.

According to one embodiment of the present application, the thickness of the porous gas permeable membrane may be 100 nm to 2,000 nm, but is not limited thereto.

According to one embodiment of the present application, the silane compound may be combined with the metal nanoparticles and the synthetic amino fatty acid, but is not limited thereto.

According to one embodiment of the present application, the porous gas permeable membrane may include a multilayer structure of the network-bonded metal nanoparticles and the synthetic amino fatty acid, but is not limited thereto.

According to one embodiment of the present application, the metal nanoparticles are Au, Pt, Ti, Ag, Ni, Zr, Ta, Zn, Nb, Cr, Co, Mn, Fe, Al, Mg, Si, W, Cu, and It may include a metal selected from the group consisting of combinations thereof, but is not limited thereto.

According to one embodiment of the present application, the synthetic amino fatty acid may be represented by the following Structural Formula 1, but is not limited thereto.

[Structural Formula 1]

;

;

In Structural Formula 1, R ₁ is a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted It is a C ₂ to C ₂₀ heteroaryl group.

The above-described problem solving means are merely exemplary, and should not be construed as limiting the present application. In addition to the exemplary embodiments described above, additional embodiments may exist in the drawings and detailed description.

Since the conventional polymer-based separation membrane has a free volume inside the polymer, it can have large pores in a specific part, so the selectivity of the gas to be permeated is low, and a trade-off between the permeability and the selectivity can be obtained. have. In addition, in the case of a dense polymer membrane, it is difficult to separate gas molecules according to their size, since gas permeates using an adsorption and diffusion mechanism between the polymer and gas molecules.

However, since the porous gas permeable membrane according to the present application uses pores between metal nanoparticles, gas molecules can permeate according to the size of the pores, and the size of the pores can be controlled by silane, so that hydrogen, oxygen, and oxygen It is possible to easily separate gas molecules having similar sizes, such as carbon dioxide, oxygen, and nitrogen, and thus can have superior gas permeability and selectivity compared to conventional polymer-based separation membranes.

In addition, since the method for manufacturing the porous gas permeable membrane according to the present application uses a self-assembly process between metal nanoparticles and synthetic amino fatty acids, the porous gas permeable membrane can be manufactured at low cost.

In addition, since the method for manufacturing a porous gas permeable membrane according to the present application forms a silane layer to control the size of pores, mechanical properties can be improved compared to the conventional gas permeable membrane.

However, the effects obtainable herein are not limited to the above-described effects, and other effects may exist.

1 is a flowchart of a method for manufacturing a porous gas permeable membrane according to an embodiment of the present application.
2 is a schematic diagram of a method for manufacturing a porous gas permeable membrane according to an embodiment of the present application.
3 is a schematic diagram of a pore size control method of a porous gas permeable membrane according to an embodiment of the present application.
4 (a) and (b) are the manufacturing steps of the porous gas permeable membrane according to an embodiment of the present application.
5 is a photograph of a porous gas permeable membrane according to an embodiment of the present application.
Figure 6 (a) is a cross-sectional SEM image of the porous gas permeable membrane according to an embodiment of the present application, (b) is a top surface SEM image.
7 is a TEM image of a porous gas permeable membrane according to an embodiment of the present application.
8 is an AFM image and graph showing the relationship between the thickness of the porous gas permeable membrane and the reaction time according to an embodiment of the present application.
9 is an EDX graph of the porous gas permeable membrane according to an embodiment of the present application.
10 is a SEM image showing the relationship between the thickness of the porous gas permeable membrane and the reaction time according to an embodiment of the present application.
11 is a graph showing the relationship between the thickness of the porous gas permeable membrane and the concentration of the metal precursor according to an embodiment of the present application.
12 (a) is a TEM image of a porous gas permeable membrane monolayer according to an embodiment of the present application, and (b) is an EDX graph of the porous gas permeable membrane.
13 (a) is an SEM image of a multilayer porous gas permeable membrane according to an embodiment of the present application, and (b) is a TEM image.
14 (a) is a graph of the gas permeability of the nanoparticle membrane according to an embodiment of the present application, and (b) is a graph of the permeability of the nanoparticle membrane according to the size of organic molecules.
15 (a) is a graph showing the change in transmittance according to the deposition time of the silane layer of the porous gas permeable membrane according to an embodiment of the present application, and (b) is a graph showing the transmittance of gas molecules according to the size of the pores.

Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present application pertains can easily implement them.

However, the present application may be embodied in several different forms and is not limited to the embodiments described herein. And in order to clearly explain the present application in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a part is said to be "connected" to another part, it includes not only the case where it is "directly connected" but also the case where it is "electrically connected" with another element interposed therebetween. do.

Throughout this specification, when it is said that a member is positioned "on", "on", "on", "under", "under", or "under" another member, this means that a member is positioned on the other member. It includes not only the case where they are in contact, but also the case where another member exists between two members.

Throughout this specification, when a part "includes" a component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable manner. Also, throughout this specification, "step to" or "step to" does not mean "step for".

Throughout this specification, the term "combination of these" included in the mark of markush format means one or more mixtures or combinations selected from the group consisting of the constituents described in marks of markush form, and the constituents It is meant to include one or more selected from the group consisting of.

Throughout this specification, reference to “A and/or B” means “A or B, or A and B”.

Throughout this specification, the description of "substituted" indicates that a hydrogen atom in a compound is a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₆ to C ₃₀ aryl group, C ₇ to C ₃₀ arylalkyl group, C ₁ to C ₄ alkoxy group, C ₁ to C ₂₀ heteroalkyl group, C ₃ to C ₂₀ heteroarylalkyl group, C ₃ to It means substituted with a substituent selected from a _{C 30} cycloalkyl group, a C ₃ to C ₁₅ cycloalkenyl group, a C ₆ to C ₁₅ cycloalkynyl group, a C ₂ to C _{20 heterocycloalkyl group, and combinations thereof.}

Hereinafter, the porous gas permeable membrane of the present application and a method for manufacturing the same will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments and examples and drawings.

As a technical means for achieving the above technical problem, the first aspect of the present application comprises the steps of dissolving a metal precursor and a synthetic amino fatty acid represented by the following Structural Formula 1 in a solvent, wherein the metal precursor is reduced to form metal nanoparticles Providing a method for producing a porous gas permeable membrane, comprising: forming a self-assembly of the metal nanoparticles and the synthetic amino fatty acid, and simultaneously floating the self-assembly in the solvent to position the self-assembly on the surface of the solvent do.

[Structural Formula 1]

;

;

In Structural Formula 1, R ₁ is a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted It is a C ₂ to C ₂₀ heteroaryl group.

The porous gas permeable membrane according to the present application is also referred to as a gas permeable membrane, and refers to a device for selecting and separating specific gas molecules through pores or particles present in the membrane. For example, specific gas molecules may be removed by the electrical properties of the gas permeable membrane, and gas molecules may be separated using the pore size of the gas permeable membrane.

However, the conventional porous gas permeable membrane contains a ceramic, a metal organic framework (MOF), a metal, or a polymer, so there is a problem of reducing the gas permeability during the manufacturing process. For example, when the porous gas permeable membrane is formed of a metal material, it is difficult to control the pore size due to the metal reacts with gas molecules or the crystal structure of the metal itself. In addition, the polymer material has a characteristic that it is difficult to control the pore size due to the free volume present therein, and the ceramic material is brittle and thus difficult to manufacture into a desired shape.

The present application can provide a gas permeable membrane capable of controlling the size of pores by using metal nanoparticles and amino fatty acids in order to overcome the disadvantages of the conventional gas permeable membrane, and a method for manufacturing the same.

1 is a flowchart of a method for manufacturing a porous gas permeable membrane according to an embodiment of the present application, and FIG. 2 is a schematic diagram of a method for manufacturing a porous gas permeable membrane according to an embodiment of the present application.

First, a metal precursor and a synthetic amino fatty acid represented by the following Structural Formula 1 are dissolved in a solvent (S100).

According to one embodiment of the present application, the synthetic amino fatty acid may include both a hydrophilic moiety and a hydrophobic moiety, but is not limited thereto.

The amino fatty acid according to the present application is a type of amino acid, and refers to a material that includes a hydrophilic portion and a hydrophobic portion at the same time, meaning a so-called amphiphilic material. Such amino fatty acids may include natural amino acids such as tyrosine, tryptophan, and methionine, and synthetic amino acids such as aminooctanoic acid.

According to one embodiment of the present application, the metal precursor is Au, Pt, Ti, Ag, Ni, Zr, Ta, Zn, Nb, Cr, Co, Mn, Fe, Al, Mg, Si, W, Cu, and these It may include a metal selected from the group consisting of combinations of, but is not limited thereto.

As will be described later, the metal precursor may react with the synthetic amino fatty acid to form metal nanoparticles.

According to one embodiment of the present application, the solvent may _{include a polar solvent selected from the group consisting of H 2} O, methanol, ethanol, ammonia, acetic anhydride, acetone, and combinations thereof, but is not limited thereto.

Since the synthetic amino fatty acid is an amphiphilic substance, it is well soluble in polar as well as non-polar solvents. In this regard, when the synthetic amino fatty acid is dissolved in the solvent, the hydrophobic portion of the synthetic amino fatty acid and the area in contact with the solvent may be combined to be minimized, or may float to the surface of the solvent.

According to one embodiment of the present application, the molar ratio of the metal precursor and the synthetic amino fatty acid may be 1:1 to 1:5, but is not limited thereto.

For example, the molar ratio of the metal precursor and the synthetic amino fatty acid is from about 1:1 to about 1:5, from about 1:1 to about 1:4, from about 1:1 to about 1:3, from about 1:1 to about 1: 2, about 1: 2 to about 1: 5, about 1: 3 to about 1: 5, about 1: 4 to about 1: 5, about 1: 2 to about 1: 4, or about 1: 3 may be, but is not limited thereto. Preferably, the molar ratio of the metal precursor and the synthetic amino fatty acid is about 1:3.

When the molar ratio of the metal precursor and the synthetic amino fatty acid is less than 1: 3, the synthetic amino fatty acid may not sufficiently bind to the surface of the metal nanoparticles to be described later, so that the formation of the gas permeable membrane according to the present application may be delayed.

As the number of moles of the metal precursor and the amino fatty acid added to the solvent increases, the formation rate of the gas permeable film increases, which may be advantageous in forming a thick film in a short period of time.

Then, the metal precursor is reduced to form metal nanoparticles (S200).

According to one embodiment of the present application, the synthetic amino fatty acid may reduce the metal precursor, but is not limited thereto.

According to one embodiment of the present application, the synthetic amino fatty acid may be a stabilizer for maintaining the shape of the metal nanoparticles, but is not limited thereto.

Metal nanoparticles according to the present application means that the size of the particles corresponds to several nm. The metal nanoparticles may be prepared by adding a metal precursor to a solution containing a surfactant, heating and stirring, and reducing the metal precursor in the solution through a reducing agent.

In this regard, since the metal nanoparticles have a very small size and a large surface area, a reaction may occur easily and the time to exist in the form of nanoparticles may be short. In order to obtain metal nanoparticles, a reducing agent as well as a stabilizing agent for maintaining the shape of the metal nanoparticles are additionally required, and the synthetic amino fatty acid is used as a reducing agent and a stabilizer herein.

As described above, since the synthetic amino fatty acid is an amphiphilic material, it can be uniformly dissolved in a polar solvent and a non-polar solvent, thereby serving as a surfactant.

According to one embodiment of the present application, the self-assembly may be a network bond between the metal nanoparticles and the synthetic amino fatty acid, but is not limited thereto.

Self-assembly according to the present application refers to a phenomenon in which specific molecules form specific nanostructures by themselves without external interference. Accordingly, the self-assembly does not require a process such as stirring or heating, and the metal nanoparticles can be network-bonded by being connected to both ends of the synthetic amino fatty acid.

For example, when the metal nanoparticles are Au and the synthetic amino fatty acid is amino-octanoic acid, the self-assembly may be represented by the following Structural Formula 4, but is not limited thereto.

[Structural Formula 4]

Referring to Structural Formula 4, the NH group of the amino-octanoic acid is bonded to the surface of Au, and the O double bonded to C of COOH is hydrogen bonded to the OH group bonded to C of the COOH group of other synthetic amino acids. The particles and the synthetic amino fatty acids can self-assemble.

The self-assembly includes a hydrophobic group and a hydrophilic group of the synthetic amino fatty acid at the same time, but is network-bonded as described above. Accordingly, since the self-assembly floats to the surface of the solvent so as to reduce an area in which the hydrophobic group contacts the solvent, the self-assembly may be positioned on the surface of the solvent.

According to the exemplary embodiment of the present application, the step of reducing the metal precursor to form the metal nanoparticles may be performed at a temperature ranging from 20°C to 50°C, but is not limited thereto.

For example, the step of forming the metal nanoparticles is about 20 °C to about 50 °C, about 20 °C to about 45 °C, about 20 °C to about 40 °C, about 20 °C to about 35 °C, about 20 °C to about 30 °C, about 20 °C to about 25 °C, about 25 °C to about 50 °C, about 30 °C to about 50 °C, about 35 °C to about 50 °C, about 40 °C to about 50 °C, about 45 °C to about 50 °C , about 25 ℃ to about 45 ℃, about 30 ℃ to about 40 ℃, or may be about 35 ℃, but is not limited thereto.

Then, the self-assembly of the metal nanoparticles and the synthetic amino fatty acid is formed, and the self-assembly is floated in the solvent to be positioned on the surface of the solvent (S300).

In this regard, the step of forming the self-assembly ( S200 ) and the step of raising the self-assembly in the solvent ( S300 ) may be performed simultaneously.

According to one embodiment of the present application, the self-assembly may be synthesized on the surface of the solvent, but is not limited thereto.

In this regard, the self-assembly may be basically synthesized as a material having a single-layer structure. In this regard, the hydrophobic portion of the self-assembly that is not suspended on the surface of the solvent may be combined with the self-assembly located on the surface of the solvent to minimize the contact area with the solvent, so that the self-assembly may have a multi-layered structure. have.

According to the exemplary embodiment of the present application, the pores of the self-assembly may be 1.0 nm to 1.2 nm, but is not limited thereto. For example, the pores of the self-assembly are from about 1.0 nm to about 1.2 nm, from about 1.05 nm to about 1.2 nm, from about 1.1 nm to about 1.2 nm, from about 1.15 nm to about 1.2 nm, from about 1.0 nm to about 1.15 nm, about 1.0 nm to about 1.1 nm, about 1.0 nm to about 1.05 nm, about 1.05 nm to about 1.15 nm, or about 1.1 nm, but is not limited thereto.

As will be described later, the gas permeable membrane according to the present application is for selectively permeating gas by controlling the size of pores. In general, gas molecules to be separated using a gas permeable membrane are very small molecules such as helium, hydrogen, carbon dioxide, oxygen, nitrogen, and methane. Since the materials do not differ greatly in the size of the molecules while the difference in molecular weight exists, the materials may be selectively separated by controlling the size of the pores of the self-assembly.

According to the exemplary embodiment of the present disclosure, the method may further include, but is not limited to, forming a silane layer for adjusting the pore size in the magnetic assembly.

In this regard, the silane layer may be formed on the surface of the magnetic assembly, but is not limited thereto.

3 is a schematic diagram of a pore size control method of a porous gas permeable membrane according to an embodiment of the present application. In this regard, the porous gas-permeable membrane of FIG. 3 includes Au nanoparticles bound with synthetic amino fatty acids on the surface, and as will be described later, the size of the pores is controlled by the silane layer.

Referring to FIG. 3 , on the surface of the Au nanoparticles, COO, which is a part of the synthetic amino fatty acid, is bonded in the form of a line. In this regard, the Au nanoparticles may exist in a network bond by the synthetic amino fatty acid, but since the synthetic amino fatty acid is not for controlling the size of pores existing between the Au nanoparticles, the self-assembly It is difficult to separate molecules of similar size (eg, H ₂ and CO ₂ , O ₂ and N _-2, etc.) with high selectivity.

However, when the silane layer is formed on the metal nanoparticles, the size of pores existing between the metal nanoparticles may be reduced by the silane layer, so it is difficult to separate molecules of similar size with high selectivity. can be facilitated

In addition, by the silane layer, the mechanical properties of the self-assembly are improved, so that the degree of damage even when molecules having the same size as described above are received under a high pressure can be reduced.

According to the exemplary embodiment of the present application, the forming of the silane layer may include depositing a silane precursor represented by the following Structural Formula 2 or the following Structural Formula 3 on the metal nanoparticles, but is not limited thereto.

[Structural Formula 2]

SiR ₂ R ₃ R ₄ R ₅ ;

[Structural Formula 3]

R ₂ OSiR ₃ R ₄ R ₅ ;

In Structural Formulas 2 and 3, R ₂ to R ₅ are each independently a halogen element of F, Cl, Br, or I, hydrogen, a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, substituted or unsubstituted A substituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ an alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₂ to C ₂₀ heteroaryl group.

In this regard, the R ₂ or R ₂ O, and the R ₃ to R ₅ are present in combination with the Si.

For example, the silane precursor may be trichloro (3,3,3-trifluoropropyl) silane, or 4-butyltrichlorosilane However, it is not limited thereto.

For example, when the silane precursor is trichloro (3,3,3-trifluoropropyl) silane, it may react with water or a hydroxyl group when combined with the synthetic amino fatty acid or the metal nanoparticles. When the silane precursor reacts with the synthetic amino fatty acid present on the surface of the metal nanoparticles, HCl may be generated by reacting with the OH group of the COOH of the synthetic amino fatty acid. However, since the HCl is easily removed, Si of the silane precursor and C of the COOH may be bonded to the C through a single bonded O.

In addition, when the silane precursor reacts with water, Cl of the silane precursor may react with an H group of the water to form HCl. As described above, since HCl is easily removed, the silane precursor may be present by being bonded to each other through oxygen _{of water (H 2 O).}

In the case of the synthetic amino fatty acid present on the surface of the self-assembly, a COOH group or an NH ₂ group may be present on the surface. In this regard, a hydrogen atom of the COOH group or the NH ₂ group may be subjected to a _{condensation reaction with R 2 to R 5} of the silane precursor, thereby connecting the metal nanoparticles and the silane precursor.

In addition, in the second aspect of the present application, in the porous gas permeable membrane formed by network bonding of metal nanoparticles and synthetic amino fatty acids, a silane compound is formed on the metal nanoparticles, and the porous gas permeates by the silane compound A porous gas permeable membrane is provided, wherein the pore size of the membrane is adjusted.

With respect to the porous gas permeable membrane according to the second aspect of the present application, detailed descriptions of parts overlapping with the first aspect of the present application are omitted, but even if the description is omitted, the contents described in the first aspect of the present application The same can be applied to the side.

According to one embodiment of the present application, the porous gas permeable membrane may selectively separate gas by Knudsen diffusion or molecular sieving, but is not limited thereto.

Knudsen diffusion according to the present application means diffusion having a form in which gas molecules collide with a wall or a membrane when the average moving distance between gas molecules is large compared to the size of the pores. At this time, the colliding gas molecules are adsorbed to the wall or membrane for a very short period of time to selectively separate the gas. That is, when the gas molecules are light, they can pass through the membrane faster than heavy gas molecules.

In the case of the porous gas permeable membrane, the size of the pores is adjusted by the silane compound to become smaller than the size of the gas molecules. At this time, since gas molecules larger than the pores cannot pass through the permeable membrane, the gas that can pass through the porous gas permeable membrane is limited to those whose particle size is smaller than the pore size of the permeable membrane. This is called molecular sieving.

According to one embodiment of the present application, the thickness of the porous gas permeable membrane may be 100 nm to 2,000 nm, but is not limited thereto. For example, the thickness of the porous gas permeable membrane is about 100 nm to about 2,000 nm, about 100 nm to about 1800 nm, about 100 nm to about 1,600 nm, about 100 nm to about 1,400 nm, about 100 nm to about 1,200 nm , about 100 nm to about 1,000 nm, about 100 nm to about 800 nm, about 100 nm to about 600 nm, about 100 nm to about 400 nm, about 100 nm to about 200 nm, about 1,800 nm to about 2,000 nm, about 1600 nm to about 2,000 nm, about 1,400 nm to about 2,000 nm, about 1,200 nm to about 2,000 nm, about 1,000 nm to about 2,000 nm, about 800 nm to about 2,000 nm, about 600 nm to about 2,000 nm, about 400 nm to about 2,000 nm, about 200 nm to about 2,000 nm, about 200 nm to about 1800 nm, about 400 nm to about 1,600 nm, about 600 nm to about 1,400 nm, about 800 nm to about 1,200 nm, or about 1,000 nm However, it is not limited thereto.

According to one embodiment of the present application, the silane compound may be combined with the metal nanoparticles and the synthetic amino fatty acid, but is not limited thereto.

As described above, the silane compound may exist in combination with the metal nanoparticles via the synthetic amino fatty acid.

According to one embodiment of the present application, the porous gas permeable membrane may include a multilayer structure of the network-bonded metal nanoparticles and the synthetic amino fatty acid, but is not limited thereto.

As described above, the self-assembly of the metal nanoparticles and the synthetic amino fatty acid may have a basically single-layer structure, but as the time for self-assembly in the manufacturing step increases, the porous gas-permeable membrane may have a multi-layer structure. .

According to one embodiment of the present application, the metal nanoparticles are Au, Pt, Ti, Ag, Ni, Zr, Ta, Zn, Nb, Cr, Co, Mn, Fe, Al, Mg, Si, W, Cu, and It may include a metal selected from the group consisting of combinations thereof, but is not limited thereto.

According to one embodiment of the present application, the synthetic amino fatty acid may be represented by the following Structural Formula 1, but is not limited thereto.

[Structural Formula 1]

;

;

In Structural Formula 1, R ₁ is a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ An alkoxy group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted It is a C ₂ to C ₂₀ heteroaryl group.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

[Example 1]

0.01 mmol of chloroauric acid (III) (HAuCl ₄ , Alfa-Aesar) and _{0.03 mmol of 8-aminooctanoic acid (H 2} N(CH ₂ ) ₇ COOH) were each dissolved in 1 ml of ultrapure water. Then, 5 ml of ultrapure water was put into a petri dish having a diameter of 5 cm, and the aqueous chloroauric acid (III) solution and the aqueous 8-aminooctanoic acid solution were added, and then reacted at 35° C. for 1 hour to 24 hours without stirring. Then, after transferring the floating gold nano-particle multilayer separator on the surface of the mixed solution, it was transferred onto a PC substrate.

4 (a) and (b) are the manufacturing steps of the porous gas permeable membrane according to Example 1, and FIG. 5 is a photograph of the porous gas permeable membrane according to Example 1.

Referring to FIGS. 4 and 5 , it can be confirmed that the gold nanoparticle multilayer separator is formed to be very thin.

6 (a) is a cross-sectional SEM image of the porous gas permeable membrane according to Example 1, (b) is a top SEM image, FIG. 7 is a TEM image of the porous gas permeable membrane according to Example 1, and FIG. 8 are AFM images and graphs showing the relationship between the thickness and reaction time of the porous gas-permeable membrane according to Example 1, and FIG. 9 is an EDX graph of the porous gas-permeable membrane according to Example 1. FIG.

Referring to FIGS. 6 and 7 , it can be seen that the gold nanoparticle multilayer separator is porous.

Referring to FIG. 8 , it can be seen that as the reaction time increases, the thickness of the gold nanoparticle multilayer separator increases. Specifically, it can be seen that when the process of Example 1 is performed, a gold nanoparticle monolayer film is formed after 6 hours, and the thickness of the film is 6 nm.

Referring to FIG. 9 , it can be confirmed that C and O of 8-amino octanoic acid are present in the film of the gold nanoparticles. In this case, the Cu peak of FIG. 9 is only generated because the material of the TEM grid is Cu, and Cu is not included in the multi-layered separation film of gold nanoparticles.

[Example 2]

0.1 mmol of chloroauric acid (III) (HAuCl ₄ , Alfa-Aesar) and 0.3 mmol of 8-aminooctanoic acid (H ₂ N(CH ₂ ) ₇ COOH) were each dissolved in 1 ml of ultrapure water. Then, 5 ml of ultrapure water was put into a petri dish having a diameter of 5 cm, and the aqueous chloroauric acid (III) solution and the aqueous 8-aminooctanoic acid solution were added, and then reacted at 35° C. for 1 hour to 24 hours without stirring. Then, after transferring the floating gold nano-particle multilayer separator on the surface of the mixed solution, it was transferred onto a PC substrate.

10 is an SEM image showing the relationship between the thickness and reaction time of the porous gas-permeable membrane according to Example 2, and FIG. 11 is a relationship between the thickness of the porous gas-permeable membrane according to Examples 1 and 2 and the concentration of the metal precursor. is a graph for

Referring to FIG. 10 , it can be seen that when the concentration of chloroauric acid (III) is high (Example 2), the formation rate of the gold nanoparticle separation membrane is faster than when the concentration of chloroauric acid (III) is low (Example 1). can

11 is a detailed comparison of Examples 1 and 2, and it can be seen that as the concentration of chloroauric acid (III) increases, the thickness of the gold nanoparticle separation membrane rapidly increases.

[Example 3]

0.01 mmol of K ₂ PtCl ₄ and 0.03 mmol of 8-aminooctanoic acid (H ₂ N(CH ₂ ) ₇ COOH) were each dissolved in 1 ml of ultrapure water. Then, 5 ml of ultrapure water was put into a petri dish having a diameter of 5 cm, and the K ₂ PtCl ₄ aqueous solution and the 8-aminooctanoic acid aqueous solution were added, and then reacted at 35° C. for 1 hour to 24 hours without stirring. Then, after transferring the floating platinum nanoparticle multilayer separator on the surface of the mixed solution, it was transferred onto a PC board.

Fig. 12 (a) is a TEM image of a single layer of the porous gas permeable membrane according to Example 3, (b) is an EDX graph of the porous gas permeable membrane, and Fig. 13 (a) is a porous gas permeable membrane according to Example 3 It is an SEM image of the gas permeable membrane multilayer, and (b) is a TEM image.

12 and 13 , it can be confirmed that the platinum nanoparticle multilayer separator is also a porous material like the gold nanoparticle multilayer separator.

[Example 4]

The gold nanoparticle separation membrane of Example 1 was prepared. Then, the Petri dish containing the nanoparticle separation membrane and the Petri dish containing trichloro (3,3,3-trifluoropropyl) silane are placed in a vacuum desiccator, and reacted at a temperature of 0.1 MPa and 60° C. A size-controlled gold nanoparticle and a silane separator were prepared.

Next, the gas permeable membrane was placed in another vacuum desiccator to remove residual silane, thereby preparing a gas permeable membrane. In this case, the gas permeable layer may be expressed as B-Au-x, where x means a deposition time of silane.

[Comparative example]

A conventional PC porous gas permeable membrane was used.

[Experimental Example 1]

14 (a) is a graph of the gas permeability of the nanoparticle membrane according to Example 1 and the Comparative Example, (b) is a graph of the permeability of the nanoparticle membrane according to the size of the organic molecule, and FIG. 15(a) is a graph showing the change in transmittance according to the deposition time of the silane layer of the porous gas-permeable membrane according to Examples 1 and 4, and (b) is a graph showing the transmittance of gas molecules according to the size of the pores.

14 and 15 , it can be seen that the gas permeability of the gold nanoparticle separation membrane is lower than that of the conventional PC porous gas permeable membrane. However, the gold nanoparticle separation membrane can only separate gases having a particle size of 12 Å or more with high selectivity, but it is difficult to separate a gas having a particle size of 10 Å or less.

In order to overcome this point, in the gas permeable membrane, a silane layer is present on the gold nanoparticle separation membrane. Specifically, as the time for depositing the silane layer increases, hydrogen, carbon dioxide, and nitrogen may be efficiently separated.

In addition, unlike the gold nanoparticle separation membrane (F-Au, Examples 1 or 2), the gas permeable membranes (B-Au-8 and B-Au-10) control the deposition time of the silane layer, thereby reducing carbon dioxide and Molecules of similar size, such as oxygen, can be selectively separated.

The above description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present application.

Claims (15)

Dissolving a metal precursor and a synthetic amino fatty acid represented by the following Structural Formula 1 in a solvent;
reducing the metal precursor to form metal nanoparticles; and
forming a self-assembly of the metal nanoparticles and the synthetic amino fatty acid and flotation of the self-assembly in the solvent and positioning the self-assembly on the surface of the solvent;
containing,
Method for manufacturing porous gas permeable membrane:
[Structural Formula 1]

;
(In Structural Formula 1,
R ₁ is a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ alkoxy group, substituted Or an unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₂ to C _{20 It} is a heteroaryl group).
The method of claim 1,
The self-assembly is a method for manufacturing a porous gas permeable membrane, wherein the metal nanoparticles and the synthetic amino fatty acid are network-bonded.
The method of claim 1,
The synthetic amino fatty acid will include both a hydrophilic portion and a hydrophobic portion, the method for producing a porous gas permeable membrane.
The method of claim 1,
The molar ratio of the metal precursor and the synthetic amino fatty acid is 1:1 to 1:5, the method for producing a porous gas permeable membrane.
The method of claim 1,
Further comprising the step of forming a silane layer for adjusting the pore size in the interior of the self-assembly, the method of manufacturing a porous gas permeable membrane.
6. The method of claim 5,
The step of forming the silane layer will include depositing a silane precursor represented by the following Structural Formula 2 or the following Structural Formula 3 on the metal nanoparticles, a method for producing a porous gas permeable membrane:
[Structural Formula 2]
SiR ₂ R ₃ R ₄ R ₅ ;
[Structural Formula 3]
R ₂ OSiR ₃ R ₄ R ₅ ;
(In Structural Formulas 2 and 3,
R _{2 To} R ₅ are each independently F, Cl, Br, or I of a halogen atom, hydrogen, a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, substituted or unsubstituted C ₂ to C ₂₀ alkoxy group, substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, substituted or unsubstituted a _{cyclic C 2} to C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₂ to C ₂₀ heteroaryl group).
The method of claim 1,
The step of reducing the metal precursor to form the metal nanoparticles is a method for producing a porous gas permeable membrane that is performed at a temperature ranging from 20 ℃ to 50 ℃.
The method of claim 1,
The metal precursor is selected from the group consisting of Au, Pt, Ti, Ag, Ni, Zr, Ta, Zn, Nb, Cr, Co, Mn, Fe, Al, Mg, Si, W, Cu, and combinations thereof. A method for producing a porous gas permeable membrane comprising a metal.
The method of claim 1,
Wherein the solvent comprises a _{polar solvent selected from the group consisting of H 2} O, methanol, ethanol, ammonia, acetic anhydride, acetone, and combinations thereof.
A porous gas permeable membrane formed by network bonding of metal nanoparticles and synthetic amino fatty acids,
A silane compound is formed on the metal nanoparticles,
The pore size of the porous gas permeable membrane is adjusted by the silane compound,
porous gas permeable membrane.
11. The method of claim 10,
The thickness of the porous gas permeable membrane is 100 nm to 2,000 nm, the porous gas permeable membrane.
11. The method of claim 10,
The silane compound is bound to the metal nanoparticles and the synthetic amino fatty acid, the porous gas permeable membrane.
11. The method of claim 10,
The porous gas permeable membrane is a porous gas permeable membrane comprising a multilayer structure of the network-bonded metal nanoparticles and the synthetic amino fatty acid.
11. The method of claim 10,
The metal nanoparticles are from the group consisting of Au, Pt, Ti, Ag, Ni, Zr, Ta, Zn, Nb, Cr, Co, Mn, Fe, Al, Mg, Si, W, Cu, and combinations thereof. A porous gas permeable membrane comprising a selected metal.
11. The method of claim 10,
The synthetic amino fatty acid is represented by the following Structural Formula 1, a porous gas permeable membrane:
[Structural Formula 1]

;
(In Structural Formula 1,
R ₁ is a substituted or unsubstituted C ₂ to C ₂₀ linear or branched alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ aryl group, a substituted or unsubstituted C ₂ to C ₂₀ alkoxy group, substituted Or an unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkynyl group, a substituted or unsubstituted C ₂ to C ₂₀ cycloalkyl group, or a substituted or unsubstituted C ₂ to C _{20 It} is a heteroaryl group).

Images