KR102180500B1 - Processes for preparation Mesoporous copper oxide - Google Patents

Abstract

The present invention comprises the steps of preparing a mixed solution containing a copper precursor, a surfactant, nitric acid and an organic solvent, heating the mixed solution to form an intermediate phase, and sintering the intermediate phase at high temperature to form a mesoporous copper oxide. It provides a method for producing a mesoporous copper oxide containing.

Description

Mesoporous copper oxide production method {Processes for preparation Mesoporous copper oxide}

The present invention relates to a mesoporous copper oxide and a method for producing the same. More specifically, it relates to the preparation of mesoporous copper oxide having a high specific surface area by controlling the chemical process parameters of a mixed solution containing a copper precursor, a surfactant, an acid, and an organic solvent, and a method for preparing the same.

Conventionally, a method of producing nanoporous metal particles having a certain size by using a spray pyrolysis method has been developed to produce nanoporous particles, but there is a disadvantage that polymer particles used as materials are expensive. Porous materials are widely applied as catalysts or carriers due to their high internal surface area. These porous materials are classified into microporous of 2 nm or less, mesoporous of 2 to 50 nm, and macroporous of 50 nm or more according to the pore size. In the field of porous materials, control of the pore size can increase the selectivity for specific products in the catalytic reaction.

Control of the particle size or shape can also improve the mechanical safety of the catalyst support. Through the discovery of a synthetic mesoporous material with an ordered amorphous silica structure, a structure with improved properties has become possible.Mesoporous materials are generally silica or other metal oxides that exhibit rapid pore size distribution at the mesoscale (1.5-50 nm). It refers to a material having a composition.

In general, mesoporous materials with excellent properties for surface area improvement, sensing and catalyst are synthesized through hydrothermal reaction using organic molecules such as surfactants or amphoteric polymers as pore-forming materials, or organic acids or sugars are used as pore-conducting materials. After synthesis, the porous material is removed from the organic and inorganic composites through high-temperature sintering or an extraction process to obtain a powdery mesoporous material. Mesoporous silica, a representative mesoporous material, can be synthesized through a self-assembly process using a silicon precursor and a surfactant, but in the case of a transition metal oxide, the interaction between the precursor and the surfactant is weak and hydrolysis reaction. Due to difficulty in control, there was a limit to the application of a synthetic method such as mesoporous silica. Synthesis and synthesis of the mesoporous transition metal oxide template was possible using the mesoporous silica as a template, but there was a problem in that the manufacturing process was complicated in the existing template synthesis and removal.

Korean Registered Patent Publication No. 10-1558240 Korean Registered Patent Publication No. 10-1693227

The technical problem to be achieved by the present invention is to provide a copper oxide having a mesoporous structure having a high specific surface area characteristic and a manufacturing method thereof through a simpler synthesis method than the prior art.

The technical problem to be achieved by the present invention is not limited to the technical problems mentioned above, and other technical problems that are not mentioned can be clearly understood by those of ordinary skill in the technical field to which the present invention belongs from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention provides a step of preparing a mixed solution containing a copper precursor, a surfactant, nitric acid and an organic solvent, heating the mixed solution to form an intermediate phase, and forming the intermediate phase. It provides a method for producing a mesoporous copper oxide comprising the step of sintering at high temperature to form a mesoporous copper oxide.

In an embodiment of the present invention, the copper precursor may include copper nitrate, copper halide, copper acetate, copper phosphate, and copper alkoxide.

In an embodiment of the present invention, the surfactant may include an anion, a cation, a nonionic, a zwitterion, or a mixed ion.

In an embodiment of the present invention, the surfactant may be characterized in that polyethylene oxide (polyethylenoxide), polyethylene oxide (polyproylenoxide, PPO), triblock copolymer P123. .

In an embodiment of the present invention, the organic solvent is characterized in that it contains alcohol, toluene or benzene. For example, the organic solvent may include butanol, pentanol, hexanol and more carbon-containing alcohols, toluene, benzene, etc. as aliphatic, alicyclic, and aromatic hydrocarbons.

In an embodiment of the present invention, the mixed solution may be formed by a sol-gel method.

In an embodiment of the present invention, in the step of preparing the mixed solution, the molar concentration of the copper precursor may be 1X10 ^-3 M to 2X10 ^-1 M.

In an embodiment of the present invention, in the step of preparing the mixed solution, the molar concentration of nitric acid may be 3M to 10M.

In an embodiment of the present invention, in the step of forming the intermediate phase, a temperature for heating the mixed solution may be 120°C to 170°C.

In an embodiment of the present invention, the intermediate phase may be characterized in that C ₂ CuO ₄ H ₂ O.

In an embodiment of the present invention, between forming the intermediate phase and forming mesoporous copper oxide by sintering the intermediate phase at high temperature, washing the formed intermediate phase with alcohol to remove residues. It can be characterized.

In an embodiment of the present invention, the high temperature sintering temperature of the mesoporous copper oxide may be between 230°C and 270°C.

In an embodiment of the present invention, the pore size of the mesoporous copper oxide may be characterized in that an oxide having a high specific surface area of 130 m ² /g or more is obtained.

In an embodiment of the present invention, a mesoporous copper oxide prepared by the method for producing the mesoporous copper oxide of claim 1 is provided.

According to an exemplary embodiment of the present invention, the process method is not complicated, and there is an effective and efficient method of producing a mesoporous copper oxide in an efficient and economical method, and thereby forming a mesoporous copper oxide having a high specific surface area.

Specifically, when synthesizing a mixed solution containing a copper precursor, a surfactant, an acid, and an organic solvent, a high specific surface area mesoporous copper oxide (CuO) is prepared by controlling various process variables such as molar ratio, pH concentration, heat treatment time, and heat treatment temperature. To make.

By controlling the process parameters in this way, it is possible to minimize the hydrolysis and coagulation reaction of the copper precursor in the mixed solution to form a mesoporous structured copper oxide. This makes it possible to mass-produce mesoporous copper oxide having a high material diffusion rate and excellent sensitivity through a simple manufacturing process through a higher specific surface area than the existing process.

In addition, mesoporous copper oxide exhibiting such high-performance sensing and catalytic properties can be produced and utilized more efficiently, and it can be used in various ways such as sensors, catalysts, magnetic storage media membranes, low dielectric constant interiors, anti-radiative coatings and optical hosts. It can be used in industry.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flowchart of a manufacturing method according to an embodiment of the present invention.
2 is a graph showing specific surface area characteristics according to an amount of a copper precursor in an organic solvent and a heat treatment temperature.
3 is a sample comparison XRD graph of the resultant according to the change in the molar content of the copper precursor when 150 heat treatment is performed.
4 is an XRD graph of sample comparison of the resultant according to the change in the molar content of the copper precursor when subjected to 250 heat treatment.
5 is a sample comparison XRD graph of a result according to a change in the molar content of a copper precursor when 350 heat treatment is performed.
6 is a sample comparison XRD graph of the result according to the change in the molar content of the copper precursor when 450 heat treatment was performed.
7 is a qualitative comparison FT-IR spectrum of the result according to the change in the molar content of the copper precursor when 150 heat treatment is performed.
8 is a qualitative comparison FT-IR spectrum of the result according to the change in the molar content of the copper precursor when subjected to 250 heat treatment.
9 is a qualitative comparison FT-IR spectrum of a result according to a change in the molar content of a copper precursor when 350 heat treatment is performed.
10 is a qualitative comparison FT-IR spectrum of the result according to the change in the molar content of the copper precursor when 450 heat treatment was performed.
11 is a graph showing a low-angle XRD pattern according to an amount of a copper precursor in an organic solvent and a heat treatment temperature.
12 is a graph showing the BJH pore size according to the amount of copper precursor in the organic solvent and the heat treatment temperature.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, bonded)" with another part, it is not only "directly connected", but also "indirectly connected" with another member in the middle. "Including the case. In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

The terms used in the present specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a flowchart of a manufacturing method according to an embodiment of the present invention.

Referring to FIG. 1, in order to prepare the mesoporous copper oxide according to the present invention in the step (S100) of preparing the mixed solution of FIG. 1, a mixed solution containing a copper precursor, a surfactant, nitric acid, and an organic solvent is prepared. .

The copper precursor according to the present invention may include copper nitrate, copper halides, copper acetate, copper phosphate or copper alkoxide.

In addition, the organic solvent is characterized in that it contains alcohol, toluene or benzene. For example, the organic solvent may include butanol, pentanol, hexanol and more carbon-containing alcohols, toluene, benzene, etc. as aliphatic, alicyclic, and aromatic hydrocarbons.

Butanol is also called butyl alcohol. It is mainly used as an organic solvent, as an intermediate in chemical synthesis, and as a fuel. The chemical formula is C ₄ H ₉ OH, wherein one hydrogen of butane is substituted with a hydroxy group.

Further, the molar concentration of the copper precursor can be 1X10 ^-3 M to 2X10 ^-1 .

If the molar concentration of the copper precursor is less than 1X10-3M, the amount of the copper precursor that can participate in the sol-gel reaction inside the reverse micelle formed by the surfactant is insufficient, so that the nanobuilding block constituting the mesoporous structure is not effectively generated. There may be a problem.

If the molar concentration of the copper precursor is greater than 2X10 ^-1 M, the amount of the copper precursor in the organic solvent is excessive, causing the problem of nano-aggregation reaction of copper and the formation of a hydroxide complex outside the reverse micelle formed by the surfactant. It may be difficult to achieve the specific surface area property of.

In this case, the surfactant may include an anion, a cation, a nonionic, a zwitterion, or a mixed ion. For example, the surfactant may be polyethylene oxide (polyethylenoxide), polyethylene oxide (polyproylenoxide, PPO), triblock copolymer (triblock copolymer) P123.

Surfactant is one or more glucose, AB or BC polymer, where A is polyisoprene butylene, B is styrene, C is glucose, amine, carboxyl group complex (carboxyl) group-containing compound) and polyethylene glycol.

The mixed solution may be prepared by a generally known sol-gel process.

The sol-gel method is a method of preparing glass or inorganic oxide powder through a gel from a sol obtained by hydrolyzing an alkoxide, etc., and after dehydrating and deorganizing the sol, put it in a container and sintered it.

The advantage of the sol-gel method is that a chemical composition that cannot be obtained by a conventional method is obtained, a homogeneous solid is obtained in the order of atoms, and a high purity one is obtained. It is also a low-temperature process that can control the particle shape.

In this case, an organic and/or inorganic additive may be optionally added.

The organic and/or inorganic additives that may be optionally added include one or more of urea, decane octane, benzene, trimethyl benzene, or mesitylene, and substituted Benzene (substituted benzene), polyethylene glycol, thiourea, ethylene diamine, styrene, pyrene, naphthalene, azobenzene, aromatic dye molecules ( aromatic dye molecules), phenolic compound, formaldehyde, P-phenylene oxide (PPO), polyethylene oxide (PEO), D-fructose, glucose, sucrose ), cellulose, starch, citric acid, phenol, aromatic alcohols, aliphatic alcohols, carboxylic acid, tosylate, carboxyl ), acetylacetonate, lauric acids, toluene, cyclohexene, terpene, terpenoid hydrocabons, citrus,, d- It can be synthesized by adding limonene (d-limonene) or a mixture thereof.

The mixed solution according to the present invention exists in a non-liquid crystalline phase. It exists in an isotropic non-liquid crystal phase, not a liquid crystal phase, which is an anisotropic metaphase.

Specifically, it exists in the state of isotropic reverse micelles. In this case, in the inverse micelle phase, a hydrate formed from a metal precursor is surrounded by a surfactant, and an organic solvent surrounds the outside of the inverse micelle.

In order to make mesoporous copper oxide, a hydrate formed from a metal precursor forms a sol in the form of reverse micelles surrounded by a surfactant. The reverse micelle state acts as a chemical nanoreactor in the mixed solution to limit the hydrolysis and agglomeration reaction of the moisture-sensitive copper precursor inside the micelle, thereby preventing the agglomeration of the copper nanoparticles. Through this manufacturing method, a mesoporous copper oxide having a microporous structure having a certain size and excellent specific surface area can be prepared.

Compared to other transition metals, copper is more likely to transform into a hydrolytic composite. Therefore, by dispersing and synthesizing the copper precursor through the formation of reverse micelles in an organic solvent, it is possible to effectively suppress the agglomeration reaction of the copper oxide.

In addition, when the amount of the copper precursor in the organic solvent is excessive, the nano-aggregation reaction of copper and the formation of the hydroxide complex may cause problems outside the reverse micelle, so the molar concentration of the copper precursor should be set to 1X10 ^-3 M to 2X10 ^-1 M. I can.

In addition, in the step of preparing the mixed solution, the molar concentration of nitric acid may be 3M to 10M.

When the amount of the copper precursor in the organic solvent is 1X10 ^-3 M to 2X10 ^-1 M, the solution pH increases.Since the increase in pH activates the hydrolysis reaction of the copper particles, the molar concentration of nitric acid is increased from 3M to 3M. It can be processed by adjusting it to 10M. If the molar concentration of nitric acid is less than 3M, nano-aggregation reaction of copper may occur before the formation of reverse micelles due to activation of the hydrolysis reaction of the copper particles, making it difficult to form an effective mesoporous structure.If the molar concentration of nitric acid exceeds 10M, the interface Since the activator may be oxidized to prevent reverse micelle formation, the process while maintaining the molar concentration of nitric acid within the above range can be seen as an important procedure in the process of producing a high specific surface area mesoporous copper oxide.

Referring to FIG. 1, in the next step of forming an intermediate phase (S200), a mixed solution may be heated to form an intermediate phase in order to prepare the mesoporous copper oxide according to the present invention.

The heating time may be prepared between about 4 hours to about 12 hours, but the manufacturing process according to an embodiment of the present invention is not limited thereto.

At this time, the temperature for heating the mixed solution is characterized in that 120 ℃ to 170 ℃ can be prepared in the intermediate phase.

When the heating temperature is 120°C or less, a large amount of the organic solvent and surfactant contained in the mixed solution remain, and when the heating temperature is 170°C or more, it may be changed to a phase other than the intermediate phase according to an embodiment of the present invention.

Producing an intermediate phase at a heating temperature of 120° C. to 170° C. as described above has been demonstrated as an example of an intermediate phase capable of producing a high specific surface area mesoporous copper oxide (CuO) according to an embodiment of the present invention.

The intermediate phase formed within the above range was identified as C ₂ CuO ₄ H ₂ O. This intermediate phase is generated through a reaction between a surfactant that forms a reverse micelle and a metal precursor present inside the reverse micelle during heating. However, when the amount of the copper precursor is excessive, the nano-aggregation reaction of copper and the formation of the hydroxide complex occur outside the reverse micelle, and the Cu ₂ (NO ₃ )(OH) ₃ phase is generated through the reaction between the metal precursors.

Referring to FIG. 1, the final step is to prepare a mesoporous copper oxide by high-temperature sintering the intermediate phase formed in the step S200 of forming the intermediate phase in the step S300 of forming the mesoporous copper oxide of FIG. 1.

The high-temperature sintering time for producing the mesoporous copper oxide by sintering the intermediate phase at high temperature may be about 4 to 20 hours, but the manufacturing process according to an embodiment of the present invention is not limited thereto.

At this time, the high-temperature sintering temperature may be performed between 230°C and 270°C to form mesoporous copper oxide (CuO).

When the high-temperature sintering temperature is set to 230° C. to 270° C., a mesoporous copper oxide having excellent specific surface area characteristics can be prepared as shown in Table 1 to be described later.

Meanwhile, between the step of forming the intermediate phase (S200) and the step of forming a mesoporous copper oxide by sintering the intermediate phase at high temperature (S300), washing the formed intermediate phase with alcohol to remove residues. I can.

A small amount of residue in the mixed solution remains in the intermediate phase formed by heating at 120°C to 170°C for a predetermined period of time, and the intermediate phase of C ₂ CuO ₄ H ₂ O, which is dried powder after washing with alcohol to remove it, remains. Can be obtained. Thereafter, it can be seen that the mesoporous copper oxide (CuO) to be obtained in the present invention can be obtained as a result by sintering the intermediate phase formed as described above at high temperature as mentioned in the next step.

<Example 1>

Preparation Example 1: Synthesis of a sol containing copper oxide particles and formation of an intermediate phase

Copper nitrate precursor / surfactant (P123 (PEO ₂₀ PPO ₇₀ PEO ₂₀ ) / nitric acid (HNO ₃ ) / organic solvent (1-butanol) 0.002 mol, 2.04 * 10 ^-4 mol, 0.067 mol and 0.197 mol, respectively The sol as a solution was synthesized at room temperature for 1 hour, and the synthesized mixed solution was heated at 120°C to 170°C for 4 hours to 12 hours.

Preparation Example 2: Mesoporous copper oxide

The intermediate phase formed in Preparation Example 1 is filtered, washed, and dried. Then, high temperature sintering was performed to prepare a mesoporous copper oxide. At this time, high-temperature sintering was performed in an air atmosphere at a temperature of 230° C. to 270° C. for 4 to 20 hours.

<Experimental Example 1 Analysis Evaluation>

2 is a graph showing specific surface area characteristics according to an amount of a copper precursor in an organic solvent and a heat treatment temperature. Table 1 below is a table showing the measured values according to FIG. 2.

Heat treatment temperature
Surface Area (m ² /g) Metal Amount (Metal Concentration) 0.0005mol
(0.028M) 0.001 mol
(0.057M) 0.002 mol
(0.115M) 0.004 mol
(0.23M) 0.008 mol
(0.46M) 0.12 mol
(0.69M) 150℃ 42.13 41.33 48.98 21.26 13.35 9.12 250℃ 137.96 132.74 157.71 81.46 65.48 35.85 350℃ 52.98 53.84 59.78 29.42 32.79 22.87 450℃ 36.75 44.95 38.66 17.18 16.54 16.59

Table 1 is a table showing numerically the specific surface area characteristics of mesoporous copper oxide according to the amount of copper precursor in the organic solvent and the heat treatment temperature, and FIG. 2 is a table showing the specific surface area characteristics according to the amount of copper precursor in the organic solvent and the heat treatment temperature. This is the graph shown.

Referring to Table 1 and FIG. 2 on the basis of Preparation Example 1, when the total molar concentration of copper in the mixed solution according to an embodiment of the present invention is 0.115 M, it can be seen that the specific surface area characteristics of the mesoporous copper oxide are the best. I can.

Manufacturing process according to one embodiment of the present invention was described that can be produced in the step of preparing the mixed solution, the molar concentration of copper precursor to 1X10 ^-3 M to about 2X10 ^-1 M, in this Production Example 1 of the present invention; The molar concentration of the metal precursor was set to 0.115M.

When the concentration of the metal precursor is higher than 0.115M, a hydrolysis-aggregation reaction occurs, and it is difficult to stably obtain a mesoporous copper oxide having a high specific surface area, and the specific surface area characteristics can be confirmed in the tables and graphs.

In addition, when the molar concentration of the copper precursor is less than this amount based on 0.115M, the surface area characteristics are degraded, but the specific surface area characteristics that are maintained to some extent rather than when the concentration of the copper precursor is high can be confirmed. However, the best range is that the molar concentration of the copper precursor is 1X10 ^-3 M to 2X10 ^-1 M.At this time, when the amount of the copper precursor in the organic solvent decreases, the pH concentration increases. The molar concentration of the nitric acid is prepared by adjusting to 3M to 10M so that hydrolysis activation is suppressed.

In addition, in the case of the heat treatment temperature, a mesoporous copper oxide exhibiting high specific surface area characteristics can be prepared when the process is performed at 250° C., which is seen between 230° C. and 270° C. through Tables 1 and 2.

In addition, referring to FIG. 2, the specific surface area of mesoporous copper oxide (CuO), which is the result of the present invention, can be confirmed by numerical values and graphs. At this time, it can be seen that the specific surface area characteristics are excellent during the process between 230°C and 270°C, which is a range of the high-temperature sintering temperature suggested by the present invention. The high-temperature sintering temperature suggested in the present invention was found to be between 230°C and 270°C, and a graph showing the best specific surface area characteristics at (b)250°C, which is a process range.

In addition, when the heat treatment temperature is 230° C. or lower, such as the heat treatment temperature (a) 150° C. of FIG. 2, the specific surface area characteristics may be lowered by numerical values and graphs.

In addition, when the heat treatment temperature (c) 350°C and (d) 450°C of FIG. 2 is higher than 270°C, the specific surface area characteristics are significantly deteriorated. Therefore, the most preferable temperature range of the high-temperature sintering temperature according to an embodiment of the present invention was confirmed to be 230 ℃ to 270 ℃.

Through these process conditions, a high specific surface area mesoporous copper oxide having a pore size of 130 m ² /g or more can be obtained.

Mesoporous copper oxide with a high specific surface area of 130 m ² /g or more exhibits superior sensing and catalytic properties compared to non-porous copper oxide, so it is a gas sensor, catalyst, a membrane as a magnetic medium, a low dielectric constant interior, an anti-radiative coating, and an optical host. Besides, it can be used in various industrial fields.

<Experimental Example 2 Analysis Evaluation>

3 to 6 are XRD comparison graphs of mesoporous copper oxide according to the heat treatment temperature.

At this time, the conditions were the same as in Preparation Example 1, but the characteristics were analyzed by varying the amount of the copper precursor. That is, (a) to (f) of FIGS. 3 to 6 are different amounts of the copper precursor, and (a) is 0.0005 mol (0.028M), (b) is 0.001 mol (0.057M), (c) 0.002 mol (0.115M), (d) 0.004 mol (0.23M), (e) 0.008 mol (0.46M), (f) 0.012 mol (0.69M).

3 to 6, an intermediate phase (C ₂ CuO ₄ H ₂ O) was generated during heat treatment at 150° C. in FIGS. 3 (a) to (d), and 150 in FIGS. 3 (e) and (f) It can be seen that another intermediate phase (Cu ₂ (NO ₃ ) OH ₃ ) is generated during heat treatment at ℃.

And, referring to Figures 4 to 6, it can be seen that (a) to (f) are all phase converted to mesoporous copper oxide (CuO) during heat treatment at 250°C, 350°C and 450°C.

Therefore, when reducing the molar concentration of the copper precursor, Cu ₂ (NO ₃ )OH ₃ It can be seen that the C ₂ CuO ₄ H ₂ O intermediate phase appears.

<Experimental Example 3 Analysis and Evaluation>

7 to 10 are graphs comparing FT-IR spectra of mesoporous copper oxide according to the heat treatment temperature. Through this, qualitative analysis or structural determination of organic compounds can be analyzed.

At this time, the conditions were the same as in Preparation Example 1, but the characteristics were analyzed by varying the amount of the copper precursor. In other words, (a) to (f) of FIGS. 7 to 10 are different amounts of the copper precursor, and (a) is 0.0005 mol (0.028M), (b) is 0.001 mol (0.057M), (c) 0.002 mol (0.115M), (d) 0.004 mol (0.23M), (e) 0.008 mol (0.46M), (f) 0.012 mol (0.69M).

When the amount of the copper precursor is reduced as shown in FIGS. 7A to 7D, after heat treatment at 150°C, the band (1418cm-1) by Cu-OH decreases, and the band (1363.2) by C=O of the copper oxalate hydrate , 1319.2 cm-1) can be confirmed to increase, which proves that the intermediate phase, C ₂ CuO ₄ H ₂ O phase is generated.

In the case of heat treatment at 250° C. or higher as shown in FIGS. 8 to 10, it can be seen that the entire C ₂ CuO ₄ H ₂ O intermediate phase is decomposed and converted to mesoporous copper oxide (CuO).

<Experimental Example 4 Characteristic Evaluation>

11 is a graph showing a low-angle XRD pattern according to an amount of a copper precursor in an organic solvent and a heat treatment temperature.

Referring to FIG. 11 on the basis of Preparation Example 1, it can be confirmed through a graph that the mesoda spacing increases as the heat treatment temperature increases under a fixed condition of 0.002 mol (0.115 M) of the amount of copper precursor. have.

At this time, the heat treatment temperature proceeds from 150° C. to 450° C., and the peak is highest at 250° C., so the porous structure of the mesoporous copper oxide is proven to be the most pronounced.

The nano-sized mesoporous formation of the mesoporous copper oxide according to an embodiment of the present invention can be confirmed through an XRD graph.

<Experimental Example 5 Analysis and Evaluation>

12 is a graph showing the BJH pore size according to the amount of copper precursor in the organic solvent and the heat treatment temperature.

Referring to FIG. 12 on the basis of Preparation Example 1, it is possible to check the BJH pore size according to the heat treatment temperature under a fixed condition of 0.002 mol (0.115M) of the amount of the copper precursor.

The nano-sized porous size of the mesoporous copper oxide according to an embodiment of the present invention increases with the heat treatment temperature.

Therefore, in the present invention, in the case of copper oxide, a mesoporous structure having a high specific surface area can be formed by applying the process conditions in which the concentration of the copper precursor is reduced to suppress the formation of the hydroxide complex during synthesis by using the inverse micelle synthesis method. have.

According to an exemplary embodiment of the present invention, the process method is not complicated, and there is an effective and efficient method of producing a mesoporous copper oxide in an efficient and economical method, and thereby forming a mesoporous copper oxide having a high specific surface area.

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

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (14)

Preparing a mixed solution containing a copper precursor, a surfactant, nitric acid, and an organic solvent;
Heating the mixed solution to form an intermediate phase of C ₂ CuO ₄ H ₂ O; And
Including the step of sintering the intermediate phase at high temperature to form a mesoporous copper oxide,
In the step of preparing the mixed solution, the molar concentration of the copper precursor is 1X10 ^-3 M to 2X10 ^-1 M,
In the step of preparing the mixed solution, the molar concentration of nitric acid is characterized in that 3M to 10M,
In the step of forming the intermediate phase, the temperature for heating the mixed solution is characterized in that 120 ℃ to 170 ℃,
Method for producing a mesoporous copper oxide, characterized in that the high-temperature sintering temperature of the mesoporous copper oxide is between 230 ℃ and 270 ℃.
The method of claim 1,
The copper precursor is a method for producing a mesoporous copper oxide comprising copper nitrate, copper halide, copper acetate, copper phosphate, and copper alkoxide.
The method of claim 1,
The surfactant is a method for producing a mesoporous copper oxide containing an anion, a cation, a nonionic, a zwitterion or a mixed ion.
The method of claim 1,
The surfactant is polyethylene oxide (polyethylenoxide), polyethylene oxide (polyproylenoxide, PPO), triblock copolymer (triblock copolymer) P123, characterized in that the manufacturing method of mesoporous copper oxide.
The method of claim 1,
The organic solvent is a method for producing mesoporous copper oxide, characterized in that it contains alcohol, toluene or benzene.
The method of claim 1,
The mixed solution is a method for producing a mesoporous copper oxide formed by a sol-gel method.
delete delete delete delete The method of claim 1,
Between the step of forming the intermediate phase and the step of forming the mesoporous copper oxide by sintering the intermediate phase at a high temperature, washing the formed intermediate phase with alcohol to remove residues. Method of manufacturing.
delete The method of claim 1,
The method for producing a mesoporous copper oxide, characterized in that to obtain an oxide having a high specific surface area of 130 m ² /g or more with a pore size of the mesoporous copper oxide.
Mesoporous copper oxide prepared by the method for producing the mesoporous copper oxide of claim 1.

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