KR101950316B1 - Metal doped organic-inorganic nanoporous materials adsorbent of water and method for manufacturing of adsorbent of water using the same - Google Patents

Abstract

The present invention relates to a metal-doped organic / inorganic nanoporous material moisture adsorbent and a method for producing the same, and more particularly, to a metal-doped water- Organic nanoporous material moisture adsorbent having metal-doped inorganic nanoporous material formed thereon. The moisture adsorbent exhibits a property of having a maximum moisture adsorption amount of 400 mg / g or more in a driving pressure range of a device to which a moisture adsorbent such as a dehumidifier, a water adsorption type refrigerator, and a cooling and heating apparatus can be applied.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-doped organic / inorganic nanoporous material moisture adsorbent,

The present invention relates to a metal-doped organic or inorganic nanoporous material moisture adsorbent and a method for producing the same. More particularly, the present invention relates to a metal-doped organic or inorganic nano-porous body moisture sorbent prepared by simultaneously reacting a metal compound, an aluminum precursor, and fumaric acid, and a method for producing the same.

At present, efficient utilization of energy is becoming a big issue in the world, and researches on the application technology of various industrial waste heat generated in industrial sites are actively being actively carried out. The industrial waste heat is mostly in the range of 70 ° C to 90 ° C in various forms such as low and medium hot water and saturated water vapor, but is mostly discarded without being reused.

Adsorption - type refrigeration systems have attracted great interest as a way to effectively utilize these waste heat energy. From the early 1980s, adsorption systems such as water, alcohols, ammonia and natural refrigerants, silica gel, zeolite, and activated carbon were used in the absorption system. In Japan, in 1986, 17kW Adsorption type refrigerators have been commercialized. In Japan, Nishiyodo and Mayekawa are now commercializing 70 kW to 500 kW absorption chillers, while SorTech in Germany is selling 7.5 kW or 15 kW solar-powered cooling systems And develops and sells them.

The adsorption refrigeration system can use waste heat from each process as a driving source. It is an environmentally friendly system that is not related to ozone layer destruction by using water as a refrigerant. In the conventional commercialized adsorption refrigeration system, silica gel and water are used, but the silica gel has a tendency to start adsorption at a low water vapor partial pressure due to strong hydrophilic property. In addition, the adsorption rate at the operating pressure range (P / P ₀ = 0.1 to 0.3) on the adsorption refrigeration system is slow and the desorption is not easy and the amount of water adsorbed per unit adsorbent is 0.1 g-water / g-sorbent / g-sorbent: the number of adsorbed water per gram of adsorbent). The moisture adsorbent used for commercialized desiccant type dehumidifiers, adsorption heat pumps, dehumidification rotors, cooling and heating devices mainly includes porous silica and zeolite. In the case of the moisture adsorbent having such a constitution, the adsorption rate of water is low, It is necessary to research and develop a novel porous water adsorbent which can reach the limit of the adsorption amount and replace the limit. That is, in order to improve the performance of the device including the adsorption type refrigeration system, the desiccant type dehumidifier and the adsorption heat pump, and to reduce the maintenance cost, a new moisture adsorption composition having a higher water adsorption amount within the driving pressure range is developed This is a reality.

On the other hand, organic nanoporous materials have attracted attention as materials that can replace silica gel or zeolite, which is a porous structure. In general, metals easily form coordination compounds at room temperature with organic ligands having unpaired electron pairs. Such coordination compounds are polymerized in water or an organic solvent to form a three-dimensional skeleton structure. Such compounds are generally referred to as " Metal-Organic Frameworks (MOFs) ", and some compounds are sometimes referred to as " inorganic nano-structures " because they have nano- do. In addition, the organic nanoporous material can be applied to various fields by varying the structure depending on the number of coordination metal ions and the kind of the organic ligand compound, and it has been reported that the surface area of zeolite is 3 to 15 times larger than that of zeolite have. In addition, there is an advantage that zeolite composed of an inorganic metal exists in an unsaturated metal ion site which is not present, so that it is easy to impart reactivity and adsorption selectivity.

Korean Patent Publication No. 2011-0019804 (hereinafter referred to as prior art 1) relates to a method for producing an organic / inorganic hybrid nanoporous material and an adsorbent application of the organic / inorganic hybrid nanoporous material, (C1-C7) alkyl-1,3,5-benzenetricarboxylate as an organic ligand to produce a hybrid organic / inorganic hybrid material, that is, a metal organic framework (MOF) (C1-C7) alkyl-1,3,5-benzenetricarboxylate to increase the solubility and improve the crystallinity to synthesize a pure organic / inorganic hybrid nanoporous material and a method of synthesizing the organic / inorganic hybrid nano- Various gases and water as an adsorbent.

The above-mentioned prior art 1 provides a technique for synthesizing an organic / inorganic hybrid nanoporous material having improved crystallinity and its use as an adsorbent, but it is difficult to obtain the specifications required for the practical application of the adsorbent and the prepared organic / inorganic hybrid nano- There has been no disclosure about a technique for manufacturing an industrially applicable form.

Korea Patent Publication No. 2011-0019804

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a moisture adsorbent of the type capable of overcoming the limit of moisture adsorptivity of the moisture adsorbent. Specifically, a metal-doped moisture adsorbent, which is produced by simultaneously reacting a metal compound, an aluminum precursor, and fumaric acid, and has a maximum moisture adsorption amount of 400 mg / g or more at a driving pressure range of P / P ₀ = The present invention provides a method of manufacturing a semiconductor device.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a method for preparing a nanocomposite precursor, comprising: preparing an organic nanoporous material precursor by dissolving an aluminum precursor, fumaric acid, and a metal compound in water to produce an organic nanoporous material precursor; And a step of filtering and purifying the product, followed by drying. The present invention also provides a method for manufacturing a metal-doped organic / inorganic nanoporous material.

In an embodiment of the present invention, the aluminum precursor is selected from the group consisting of aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) Wherein the metal nanoporous material is a metal-doped organic nanoporous material.

In the present embodiment, the metal compound is lithium chloride (LiCl), zinc chloride (ZnCl _2), ferric chloride (Ⅱ) (FeCl _2), ferric chloride (Ⅲ) (FeCl _3), chloride, chromium (CrCl _3), cerium chloride (CeCl _3), cobalt nitrate _{(Co (NO 3) 2)} , nickel nitrate _{(Ni (NO 3) 2)} , copper nitrate _{(Cu (NO 3) 2)} , cobalt sulfate (CoSO _4), nickel sulfate ( NiSO ₄ ), CuSO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , Co (CH ₃ COO) ₂ , and Nickel acetic acid (Fe (CH ₃ COO) ₂ ), Ni (CH ₃ COO) ₂ ), copper acetate (Cu (CH ₃ COO) ₂ ) and iron acetate Or a method of manufacturing a nanoporous body.

In an embodiment of the present invention, the metal-doped organic / inorganic nanoporous material may be prepared by performing the reaction at a molar ratio of aluminum precursor to fumaric acid in a range of 10: 2.5 to 10:40.

In an embodiment of the present invention, the metal compound is carried out under a condition of 1 mol% to 2 mol% based on the total molar amount.

In the embodiment of the present invention, the crystallization reaction is performed at a temperature of 100 ° C to 200 ° C for 12 hours to 40 hours. The metal-doped organic / inorganic nanoporous material may be produced by the method.

According to an embodiment of the present invention, the drying may be performed at a temperature of 100 ° C to 200 ° C.

In an embodiment of the present invention, the average size of the metal-doped organic / inorganic nanoporous material is 100 nm to 20000 nm, and the average diameter of the pores is 0.3 nm to 1.5 nm. And may be a nano-porous body manufacturing method.

In an embodiment of the present invention, after the step of filtering and purifying the product and drying, the step of crushing the dried product and the step of vacuum drying to remove excess water present in the crushed product Or a metal-doped organic or inorganic nanoporous material.

According to another aspect of the present invention, there is provided a metal-doped organic or inorganic nanoporous material produced by the method.

According to another aspect of the present invention, there is provided a metal-doped organic / inorganic nanoporous material moisture adsorbent, which comprises the metal-doped organic / inorganic nanoporous material prepared by the above- do.

In the embodiment of the present invention, the metal-doped organic / inorganic nano-porous body moisture adsorbent has a maximum moisture adsorption amount (amount of water adsorbed per unit weight of the adsorbent) in the range of the driving pressure P / P ₀ = 0.1 to 0.3 And more preferably 400 mg / g or more. The metal-doped organic / inorganic nanoporous material may be a water-absorbing agent.

According to one embodiment of the present invention, the moisture adsorbing property of a single material can be improved by preparing a metal-doped organic or inorganic nano-porous body moisture adsorbent.

In particular, the hybrid moisture adsorbent according to an embodiment of the present invention exhibits an efficiency of a water adsorption amount of 400 mg / g or more in a range of P / P ₀ = 0.1 to 0.3, which is a driving pressure of an adsorption type air conditioner, a refrigerator, a dehumidifier, Can contribute to downsizing and high performance of an apparatus such as an adsorption type cooling and heating apparatus.

In one embodiment of the present invention, when the metal-doped organic / inorganic nanoporous material moisture adsorbent is doped with 1 mol% of iron (II) chloride (FeCl ₂ ) as a metal doping material, It can be confirmed that the maximum moisture adsorption amount reaches 450 mg / g or more.

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

FIG. 1 is a flowchart schematically showing a method of manufacturing a metal-doped organic / inorganic nanoporous material moisture adsorbent according to an embodiment of the present invention.
FIG. 2 is a moisture adsorption isotherm of a metal-doped organic / inorganic nano-porous body moisture sorbent according to an embodiment of the present invention. FIG.
FIG. 3 is a moisture adsorption isotherm of a metal-doped organic / inorganic nanoporous material moisture adsorbent according to the content of FeCl ₂ according to an embodiment of the present invention.
FIG. 4 is a moisture adsorption isotherm of a metal-doped organic / inorganic nano-porous body moisture sorbent according to an embodiment of the present invention.
5 is a moisture adsorption isotherm of a metal-doped organic / inorganic nano-porous body moisture sorbent according to an embodiment of the present invention.
FIG. 6 is a moisture adsorption isotherm of a metal-doped organic / inorganic nano-porous body moisture sorbent according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as " comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

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

Hereinafter, a method for producing a metal-doped organic / inorganic nanoporous material will be described.

FIG. 1 is a schematic view showing a method of manufacturing a metal-based organic / inorganic nanoporous material according to an embodiment of the present invention.

Referring to FIG. 1, a metal-doped organic / inorganic hybrid nanoporous material manufacturing method according to an embodiment of the present invention includes the steps of preparing an inorganic nanoporous material precursor by dissolving an aluminum precursor, fumaric acid, and a metal compound in water (S100 A step (S200) of producing a product by crystallization reaction of the organic / inorganic nanoporous material precursor, and a step (S300) of filtering and purifying the product and drying (S300) a metal-doped organic / inorganic nanoporous material . ≪ / RTI >

First, an aluminum precursor, fumaric acid, and a metal compound are dissolved in water to prepare an organic nanoporous precursor (S100).

In the embodiment of the present invention, the aluminum precursor is at least one selected from the group consisting of aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) But is not limited thereto.

Also, for example, fumaric acid, an organic ligand and one of unsaturated dicarboxylic acids, may be used as a reactant of the organic nanoporous precursor. This can be a more eco-friendly process by allowing reactions in water, and can be an organic or inorganic nanoporous reactant that is effective in forming a more robust organic nanoporous material.

Further, the metal compounds according to an embodiment of the present invention, lithium chloride (LiCl), zinc chloride (ZnCl _2), ferric chloride (Ⅱ) (FeCl _2), ferric chloride (Ⅲ) (FeCl _3), chloride, chromium (CrCl ₃₎ , cerium chloride (CeCl _3), cobalt nitrate _{(Co (NO 3) 2)} , nickel nitrate _{(Ni (NO 3) 2)} , copper nitrate _{(Cu (NO 3) 2)} , cobalt sulfate (CoSO _4), nickel sulfate (NiSO ₄ ), CuSO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , Co (CH ₃ COO) ₂ , Nickel acetic acid But is not limited to, at least one selected from the group consisting of Ni (CH ₃ COO) ₂ ), copper acetate (Cu (CH ₃ COO) ₂ ) and iron acetate (Fe (CH ₃ COO) ₂ ) . Also, the metal compound may be used as a reactant for preparing an organic nanoporous material precursor capable of further improving the moisture adsorption characteristics of the organic nanoporous material.

In an embodiment of the present invention, the molar ratio of the aluminum precursor to the fumaric acid may be in the range of 10: 2.5 to 10: 40. The molar ratio range is a desirable level for controlling the average size and pore size of the organic / inorganic nanoporous material so as to have the desired moisture adsorption characteristics.

In an embodiment of the present invention, the metal compound may be carried out at a molar ratio of 1 mol% to 2 mol% based on the mole of the aluminum precursor and the fumaric acid. When the content of the metal compound is less than 1 mol% based on the total molar amount, the metal compound is difficult to improve the properties of the organic nanoporous material. When the amount of the metal compound is more than 2 mol%, the nanoporous material is used In the case where the unreacted metal compound acts as an impurity to close the pores of the organic nanoporous material, the moisture adsorption characteristic may be deteriorated rather than the metallic compound, and the desorption of the adsorbed moisture is not easy and reuse may be disadvantageous Which is undesirable.

Next, the organic nanoporous material precursor is crystallized to produce a product (S200).

The organic or inorganic nanoporous material is a porous organic polymer compound formed by combining a center metal with an organic ligand, and is a crystalline compound containing both organic and inorganic materials in the skeleton and having a pore structure of a molecular size or nano size. The organic-inorganic nanoporous material of the present invention is formed by a crystallization reaction of aluminum precursor and fumaric acid which is an organic ligand, and can form a small pore compared to zeolite or silica, which is a conventional porous material for moisture adsorption, and can have a wide specific surface area. It is another object of the present invention to further improve the moisture adsorption property of a single material by doping a metal compound having hygroscopicity to the pores of the organic / inorganic nano-porous material having the property of adsorbing moisture in the porous material.

In the embodiment of the present invention, the crystallization reaction may be performed at a temperature of 100 ° C to 200 ° C for 12 to 40 hours. The crystallization reaction of the present invention may be a step of growing from fumaric acid coordinated to aluminum to an organic nanoporous material. If the reaction temperature is lower than 100 ° C, the reaction rate may be slower and the reaction time may be prolonged to lower the process efficiency. If the reaction temperature is higher than 200 ° C, it may be difficult to form an organic / inorganic nano- And the reaction rate is so high that impurities are easily mixed, which causes a problem of lowering the purity, which is not preferable.

Next, the product is filtered and purified and dried (S300).

In an embodiment of the present invention, the drying may be performed at a temperature of 100 ° C to 200 ° C. If the drying temperature is lower than 100 ° C, the evaporation of the solvent may be insufficient. If the drying temperature is higher than 200 ° C, it may be undesirable because it uses more energy than necessary.

In the exemplary embodiment of the present invention, the metal-doped organic / inorganic nanoporous material may have an average size of 100 nm to 20000 nm and an average diameter of pores of 0.3 nm to 1.5 nm. When the particle size is less than 100 nm, the surface energy is increased and the agglomeration characteristics of the particles are increased, so that the amount of adsorbed water It may be difficult to uniformly disperse them. In addition, when the particle size exceeds 20000 nm, the specific surface area may be lowered to improve the moisture adsorption property in the target driving pressure range.

In addition, for example, organic nanoporous materials have many nano-scale pores due to the regular combination of metal ions and organic ligands, and are capable of adsorbing gaseous molecules including moisture in nano-sized pores . Accordingly, as the specific surface area of the moisture adsorbent increases as the size of the pores formed in the organic nanoporous material decreases, the moisture adsorption amount and the moisture adsorption rate per unit weight of the adsorbent can be maximized. Therefore, the smaller the size of the pores provided in the organic nanoporous material particles, the more favorable characteristics are exhibited as a moisture adsorbent. However, when the pore size is less than 0.3 nm, the pore size may be excessively small, so that the permeability of water may be lowered and the water adsorption performance may be deteriorated, which may affect the doping of the metal compound, Is larger than 1.5 nm, the reduction of the specific surface area may be limited to realize the desired moisture adsorption performance.

The product is then filtered and purified and dried, followed by disruption of the dried product and vacuum drying to remove excess moisture present in the product.

For example, the moisture adsorbent of the organic nanoporous structure has a tendency to absorb more gas as the surface area is wider. Therefore, in order to maximize the moisture adsorption characteristic, it is preferable to carry out the step of pulverizing the product using a crusher for a predetermined time. Further, in the step of vacuum-drying the pulverized powder to prepare a metal-doped organic or inorganic nano-porous body, the excess moisture contained in the organic / inorganic nanoporous material is completely removed through a vacuum drier, It is a step.

Hereinafter, the metal-doped organic / inorganic nanoporous material produced by the metal-doped organic / inorganic nanoporous material manufacturing method will be described.

The metal-doped organic / inorganic nanoporous material of the present invention forms a pore structure by the crystallization reaction of an aluminum precursor and an organic ligand, and a metal is doped between the pores to form small pores compared to zeolite or silica, It can be a metal-doped organic or inorganic nano-porous body having not only a large specific surface area, but also improved water absorption characteristics. Particularly, the organic or inorganic nanoporous material uses fumaric acid, which is one of unsaturated dicarboxylic acids, as an organic ligand, which enables reaction in water to be produced in a more environmentally friendly manner, and a more rigid metal- Thereby forming a porous body.

Hereinafter, a metal-doped organic / inorganic nano-porous body moisture sorbent including a metal-doped organic / inorganic nano-porous body manufactured by a metal-doped organic / inorganic nanoporous material manufacturing method will be described.

In the embodiment of the present invention, the metal-doped organic / inorganic nanoporous material moisture adsorbent has a maximum moisture adsorption amount of 400 mg / g or more in the range of the driving pressure P / P ₀ = 0.1 to 0.3 , And the production examples and experimental examples to be described later will be described in detail.

Hereinafter, Preparation Examples and Experimental Examples of the present invention will be described. However, these production examples and experimental examples are intended to explain the constitution and effects of the present invention more specifically, and the scope of the present invention is not limited thereto.

[Production Example 1]

Metal Doped Organic and inorganic nanoporous material  Manufacture of moisture adsorbent

1.28 g of Al ₂ (SO ₄ ) ₃ .18H ₂ O, 0.45 g of fumaric acid, 0.24 g of urea and 1 mol% of FeCl ₂ were dissolved in 13 ml of water, mixed for 30 minutes and then charged into an autoclave reactor to obtain 32 Lt; / RTI > The reaction product was filtered and purified with water and ethanol, and then dried overnight in an oven at 100 ° C. The dried product was crushed and vacuum dried to prepare a metal-doped organic or inorganic nano-porous body moisture adsorbent.

[Production Example 2]

Except that FeCl ₂ was not used in Preparation Example 1, to prepare an organic nanoporous material moisture adsorbent.

[Production Example 3]

Except that FeCl ₃ was used instead of FeCl ₂ in Production Example 1, a metal-doped organic or inorganic nano-porous body moisture adsorbent was prepared.

[Production Example 4]

Except that 2 mol% of FeCl ₂ was used instead of 1 mol% of FeCl ₂ in Preparation Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 5]

Except that 3 mol% of FeCl ₂ instead of 1 mol% was used in Preparation Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 6]

Except that 5 mol% of FeCl ₂ instead of 1 mol% was used in Preparation Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 7]

Except that CeCl ₃ was used instead of FeCl ₂ in Production Example 1, a metal-doped organic or inorganic nano-porous body moisture adsorbent was prepared.

[Production Example 8]

Except that CrCl ₃ was used instead of FeCl ₂ in Preparation Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 9]

Except that Co (NO ₃ ) ₂ was used instead of FeCl ₂ in Production Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 10]

Except that Ni (NO ₃ ) ₂ was used instead of FeCl ₂ in Production Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 11]

Except that Cu (NO ₃ ) ₂ was used instead of FeCl ₂ in Production Example 1 to prepare a metal-doped organic or inorganic nano-porous body moisture adsorbent.

[Production Example 12]

Except that ZnCl ₂ was used instead of FeCl ₂ in Production Example 1 to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Production Example 13]

Except that LiCl was used instead of FeCl ₂ in Production Example 1, to prepare a metal-doped organic or inorganic nanoporous material moisture adsorbent.

[Experimental Example 1]

Of iron (Fe) Ionic  The resulting metal Doped Organic and inorganic nanoporous material  Moisture adsorption characteristics of moisture adsorbent

The water adsorption isotherms were analyzed at 25 ° C in order to investigate the water adsorption characteristics of iron (Fe) ions in metallic materials in metal-doped organic and inorganic nanoporous material adsorbents. The results are shown in FIG.

2, the organic nanoporous material of Production Example 2 in which the metal was not doped was found to have a maximum moisture adsorption amount of 425.7 mg / g in the range of the driving pressure P / P ₀ = 0.1 to 0.3, and iron (Fe ) Trivalent ion doped organic / inorganic nanoporous material of Production Example 3 was 431.5 mg / g, which was found to improve the water adsorption characteristic compared to Production Example 2. [ Further, it was confirmed that the maximum amount of moisture adsorption of the organic nanoporous material of Production Example 1 doped with iron (Fe) 2 ion was 457.7 mg / g. As a result, it was concluded that the metal nanoporous material doped with metal improves the water adsorption characteristics and further improves the water adsorption characteristics when iron (Fe) 2 ions are doped more than iron (Fe) 3 ions .

[Experimental Example 2]

FeCl ₂  The content of metal Doped Organic and inorganic nanoporous material  Moisture adsorption characteristics of moisture adsorbent

Water adsorption isotherms were analyzed at 25 ℃ in order to investigate the water adsorption characteristics of metal-doped organic and inorganic nanoporous water adsorbents according to the content of metal compounds. The results are shown in FIG.

Referring to FIG. 3, the metal-doped organic / inorganic nanoporous material of Production Example 1 doped with 1 mol% of FeCl ₂ had a maximum moisture adsorption amount of 457.7 mg / g at a driving pressure P / P _{0 of} 0.1 to 0.3 And it was confirmed that the moisture adsorption characteristics were slightly decreased as the molar content was increased. It can be judged that when the metal compound enters the excess amount than the proper amount, the metal compound acts as an impurity and closes the pores of the organic nanoporous material, the moisture adsorption characteristics may be lowered.

[Experimental Example 3]

Metal according to the kind of trivalent metal compound Doped Organic and inorganic nanoporous material  Moisture adsorption characteristics of moisture adsorbent

Water adsorption isotherms were analyzed at 25 ℃ in order to investigate the water adsorption characteristics of the metal-doped organic and inorganic nanoporous water adsorbents according to the type of the trivalent metal compound. The results are shown in FIG.

4, Production Example 3 doped with FeCl ₃ , Production Example 7 doped with CeCl ₃ , and Metal-doped organic nanoporous material of Production Example 8 doped with CrCl ₃ had a driving pressure P / P ₀ = It was confirmed that the maximum moisture adsorption amounts in the range of 0.1 to 0.3 were 431.5 mg / g, 446.6 mg / g and 425.3 mg / g, respectively. These results suggest that the dewatered nanoporous material may be doped with a trivalent metal compound to improve the water adsorption characteristics.

[Experimental Example 4]

The metal according to the kind of the divalent metal compound Doped Organic and inorganic nanoporous material  Moisture adsorption characteristics of moisture adsorbent

Water adsorption isotherms were analyzed at 25 ° C in order to investigate the water adsorption characteristics of the metal-doped organic and inorganic nanoporous material adsorbents according to the kind of the divalent metal compound. The results are shown in FIG.

Referring to FIG. 5, it can be seen that Example 9 which is doped with Co (NO ₃ ) ₂ , Production Example 10 doped with Ni (NO ₃ ) ₂ , Production Example 11 doped with Cu (NO ₃ ) ₂ and ZnCl ₂ the metal of Preparation 12 doped inorganic nanoporous body is a drive pressure P / P ₀ = 0.1 to 0.3 respectively, 426.8 mg / g the amount of the maximum water absorption in the range of, 439.5 mg / g, 435.9 mg / g and 437.3 mg / g. These results suggest that the dewatered metal compound doped with organic nanoporous materials improves the water adsorption characteristics.

[Experimental Example 5]

Metal according to the type of monovalent metal compound Doped Organic and inorganic nanoporous material  Moisture adsorption characteristics of moisture adsorbent

In order to investigate the water adsorption characteristics according to the type of monovalent metal compound in the metal-doped organic or inorganic nanoporous material adsorbent, moisture adsorption isotherms were analyzed at 25 ° C. and the results are shown in FIG.

Referring to FIG. 6, it was confirmed that the metal-doped organic-inorganic nanoporous material of Production Example 13 doped with LiCl had a maximum moisture adsorption amount of 453.4 mg / g in the range of the driving pressure P / P ₀ = 0.1 to 0.3. These results indicate that the adsorption characteristics of water can be improved by doping a monovalent metal compound with an organic nanoporous material.

Thus, referring to the Production Examples and Experimental Examples of the present invention, the metal-doped organic or inorganic nano-porous body has a maximum moisture adsorption capacity in the range of driving pressure P / P ₀ = 0.1 to 0.3 And the results showed that the moisture adsorption characteristics of the metal-doped organic / inorganic nanoporous material were improved. In particular, the organic or inorganic nano-porous body doped with 1 mol% FeCl ₂ metal compound has a maximum moisture adsorption amount of 457.7 mg / g in the range of the driving pressure P / P ₀ = 0.1 to 0.3, . Also, it was confirmed that the amount of adsorption of water decreased as the amount of metal compound was increased than that of water adsorbent.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (12)

Aluminum precursor, fumaric acid and a metal compound in water to prepare an organic nanoporous precursor;
Preparing a product by subjecting the organic / inorganic nanoporous material precursor to a crystallization reaction; And
Filtering and purifying the product, and drying the product;
Wherein the molar ratio of aluminum precursor to fumaric acid is in the range of 10: 2.5 to 10: 40,
The metal compound is lithium chloride (LiCl), zinc chloride (ZnCl _2), ferric chloride (Ⅱ) (FeCl _2), ferric chloride (Ⅲ) (FeCl _3), chloride, chromium (CrCl _3), cerium chloride (CeCl _3), nitric acid cobalt _{(Co (NO 3) 2)} , nickel nitrate _{(Ni (NO 3) 2)} , copper nitrate _{(Cu (NO 3) 2)} , cobalt sulfate (CoSO _4), nickel sulfate (NiSO _4), copper sulfate (CuSO ₄ ), iron sulfate (ⅱ) (FeSO _4), ferrous sulfate _{(ⅲ) (Fe 2 (SO} 4) 3), cobalt acetate _{(Co (CH 3 COO) 2} ), nickel acetate _{(Ni (CH 3 COO) 2} ) , Copper acetate (Cu (CH ₃ COO) ₂ ) and iron acetate (Fe (CH ₃ COO) ₂ )
Wherein the metal compound is performed at a molar ratio of 1 mol% to 2 mol% based on the total molar amount of the metal compound.
The method according to claim 1,
Wherein the aluminum precursor comprises at least one selected from aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) (Method for manufacturing metal - doped organic / inorganic nanoporous material).
delete delete delete The method according to claim 1,
Wherein the crystallization is performed at a temperature of 100 ° C to 200 ° C for 12 hours to 40 hours.
The method according to claim 1,
Wherein the drying is performed at a temperature of 100 ° C to 200 ° C.
The method according to claim 1,
Wherein the metal-doped organic / inorganic nanoporous material has an average size of 100 nm to 20000 nm and an average diameter of pores of 0.3 nm to 1.5 nm.
The method according to claim 1,
After filtering and purifying the product and drying,
Crushing the dried product; And
And vacuum-drying the organic nanoporous material to remove excess water present in the crushed product.
A metal-doped organic or inorganic nano-porous body produced by the manufacturing method of claim 1.
A metal-doped organic or inorganic nano-porous body moisture sorbent, comprising a metal-doped organic or inorganic nano-porous body produced by the method of claim 1.
12. The method of claim 11,
The metal-doped organic / inorganic nano-porous body moisture adsorbent has a maximum water adsorption amount (amount of water adsorbed per unit weight of the adsorbent) of 400 mg / g or more in the range of the driving pressure P / P ₀ = 0.1 to 0.3 A metal-doped organic or inorganic nano-porous body moisture sorbent.

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