KR101937811B1 - Organic-inorganic Hybrid Porous Adsorbent And Method For Preparing The Same - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid porous adsorbent and a process for producing the organic-inorganic hybrid porous adsorbent, wherein the organic or inorganic hybrid adsorbent can be prepared by a relatively simple method of controlling the addition amount of the organic acid, By having surface area and pore volume, it is possible to realize gas storage and gas adsorption ability with excellent efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic-inorganic hybrid porous adsorbent and a method for producing the same,

The present invention relates to an organic-inorganic hybrid porous adsorbent containing a non-aromatic organic acid and a method for producing the same.

Porous organic-inorganic hybrid materials are used in a wide range of terms, commonly referred to as porous coordination polymers, and also referred to as metal-organic frameworks (MOF). The porous hybrid inorganic-organic materials have recently begun to develop due to the combination of molecular coordination and material science. The hybrid materials have high surface area and molecular size or nano-sized pores, and can be used as an adsorbent, gas storage, sensor, Has been actively studied since it can be used not only for functional thin films, catalysts and catalyst supports, but also for trapping guest molecules smaller than pore size or separating molecules according to the size of molecules using pores.

The metal-organic framework is a kind of coordination polymer compound composed of a metal salt and an organic ligand, and forms various coordination structures ranging from a linear primary structure to a secondary and complex three-dimensional structure . Such metal-organic skeletons have been extensively studied because of their potential applications in various fields such as molecular adsorption and separation processes, photoelectronics, etc., when they have permanent porosity.

Metal-organic skeletons are attracting attention not only for their various chemical properties and skeletal structure, but also for their properties such as gas storage, separation of organic molecules and gases, ion exchange, catalysis, and structure of metal nanoparticles.

Particularly in recent years, the use of hydrogen and / or methane as an energy carrier of the future in automobiles and electronic products has become important, but its application is limited due to difficulties in storing sufficient amounts of hydrogen and / or methane. Gas adsorption for storing a sufficient amount of hydrogen and / or methane can be increased by using a metal-organic skeleton having a large surface area and a large pore volume. The metal-organic skeleton with such a large surface area and large pore volume can be produced by using a long organic linker (linker), but the metal-organic skeleton formed by the long organic linkage is well collapsed when the guest is removed and the single- It is difficult to fully explain the structure of the metal-organic skeleton that is desolvated by the diffraction analysis.

Although the metal-organic skeleton is a useful methane storage material, it still has difficulties in achieving DOE levels for Adsorbed Natural Gas (ANG). In order to reach the above-mentioned DOE level, a method of making defects in the metal-organic skeleton pores is considered. In one of the methods, a mixture of Cu ²⁺ and TPTC (terphenyltetracarboxylate), which is a typical reaction mixture of NOTT- With the addition of isophthalic acid (IPA), the isophthalic acid is arranged in the copper ion cluster instead of the TPTC. This substitution produces relatively large pores, but the BET surface area of NOTT-101 is not increased.

On the other hand, HKUST-1 is one of the most studied metal-organic skeletons and has high methane and carbon dioxide capture capacity. When such HKUST-1 is fragmented by IPA, the BET surface area is increased, but the absorption amount of methane is decreased due to the reduction of the density of the coordinative unsaturated metal site (CUS).

Therefore, it is urgently required to develop a porous adsorbent having a large BET surface area and a large pore volume so as to satisfy the ability to store a sufficient amount of hydrogen gas, methane gas, and the like.

Korean Patent Publication No. 10-2010-0089340.

It is an object of the present invention to provide an organic-inorganic hybrid porous adsorbent having improved BET surface area and total pore volume and having excellent gas storage and gas adsorption ability and a method for producing the same.

In order to solve the above problems,

A structure in which an organic ligand is coordinated to a metal ion cluster,

Wherein some of said organic ligands are alternatively bound to non-aromatic organic acids,

BET surface area of at least 1,800 m ² / g,

The metal ion may be at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, At least one ion selected from the group consisting of Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi / RTI >

The organic ligand may be a carboxyl group (-COOH), a carboxylic anion group (-COO-), an amine group (-NH ₂ ), an imino group (-NH ₂ ), a nitro group (-NO ₂ ), a hydroxy group , A halogen group (-X), and a sulfonic acid group (-SO ₃ H). The present invention also provides an organic / inorganic hybrid porous adsorbent.

Also, the present invention provides a method for producing a liquid crystal display, comprising: preparing a first mixed liquid in which a metal precursor, an organic compound capable of acting as a ligand, and a solvent are mixed; Adding an aromatic acid-free organic acid to the prepared first mixed liquid to prepare a second mixed liquid; And heating and drying the second mixed liquid to produce an organic hybrid porous adsorbent,

The metal of the metal precursor is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, , One selected from the group consisting of Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Ti, Si, Ge, Pb, As, Sb and Bi ≪ / RTI >

The organic compound capable of acting as the ligand is at least one selected from the group consisting of benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Heptanedioic acid, and cyclohexyldicarboxylic acid, and at least one member selected from the group consisting of heptanedioic acid,

Wherein the produced organic / inorganic hybrid porous adsorbent has a BET surface area of 1,800 m ² / g or more.

The adsorbent according to the present invention can be prepared by a relatively simple method of controlling the addition amount of the non-aromatic organic acid, and the adsorbent prepared by controlling the addition amount of the organic acid has an improved specific surface area and pore volume, Adsorption capability can be realized.

1 shows NMR results of a porous adsorbent according to Example 3 (FIG. 1A), Comparative Example 3 (FIG. 1B) and Comparative Example 5 (FIG.
2 is a graph showing N ₂ adsorption isotherm curves of the porous adsorbent according to Examples 1 to 5 (FIGS. 2A to E) and Comparative Example 1 (FIG. 2F) under the condition of 77K.
Fig. 3 shows the BET surface area measurement results of Examples 1 to 5 (Figs. 3A to 3E), Comparative Example 1 (I of Fig. 3) and Comparative Examples 3 to 5 (Figs.
4 is a graph showing the volume of methane adsorbed on the surface of the porous adsorbent according to Examples 1 and 2 and Comparative Example 1 and the total volume of methane.
5 is a graph showing the adsorption amount (methane total volume) of methane when the adsorption of methane was performed for 8 times using the porous adsorbent according to Example 2 (Fig. 5A) and Example 3 (Fig. 5B) to be.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.

It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by terms. Terms are used only for the purpose of distinguishing one component from another.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention. Therefore, various equivalents And variations.

Hereinafter, the porous adsorbent according to the present invention will be described in detail.

In the present invention, 'porous adsorbent' may have the same meaning as 'organic hybrid porous adsorbent'.

In the case of NOTT-101 prepared by adding isophthalic acid to a mixture of Cu ^{2 +} and TPTC with a gas adsorbent utilizing a conventional metal-organic skeleton, the BET surface area is not increased, and HKUST-1 , The BET surface area is increased when the IPA is used to form a detect site, but the absorption amount of methane is decreased due to the decrease of the density of the coordinative unsaturated metal site (CUS).

DISCLOSURE OF THE INVENTION The present invention has been conceived to solve the problems described above, and it is an object of the present invention to provide a hybrid organic porous adsorbent according to the present invention, in which a part of an organic ligand is alternatively combined with a nonaromatic organic acid to form a discontinuity in a crystal, Has an improved porosity and specific surface area due to the formation of a detect site, thereby exhibiting excellent methane uptake and gas storage performance.

The organic-inorganic hybrid porous adsorbent according to the present invention is characterized in that,

Wherein the organic ligand is substituted with a nonaromatic organic acid and has a BET surface area of 1,800 m ² / g or more, and the metal ion is at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Wherein the organic ligand comprises at least one ion selected from the group consisting of Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, (-NH ₂ ), a nitro group (-NO ₂ ), a hydroxy group (-OH), a halogen group (-X (O) ) And a sulfonic acid group (-SO ₃ H).

In the present invention, a structure in which an organic ligand is coordinated to a metal metal ion cluster may mean a metal-organic skeleton. The metal material, which is a constituent of the metal-organic skeleton material, can be any metal, and can be any metal, and can be any of metals such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, , As, Sb, and Bi are typical metal materials. Particularly, transition metals which are well-coordinated compounds are suitable, and among the transition metals, they may include chromium, vanadium, iron, nickel, cobalt, copper, titanium and manganese. Specifically, copper may be used as the metallic material herein.

An organic ligand, which is another member of the metal-organic framework material, may be an organic material. These organic substances are also referred to as linkers, and any organic substance having a functional group capable of coordinating can be used. The functional group capable of coordinating is a carboxyl group (-COOH), a carboxylic acid anion group (-COO-), an amino group (-NH ₂ ), An imino group (-NH), an amide group (-CONH ₂ ), a nitro group (-NO ₂ ), a hydroxy group (-OH), a halogen group (-X), a sulfonic acid group (-SO ₃ H) (-SO ₃ ^- ), a methanedithioic acid group (-CS ₂ H), a methanedithioic acid ion group (-CS ₂ ^- ), a pyridine group, or a pyrazine group. In order to induce a more stable metal-organic skeleton material, it may be an organic material having two or more sites that can be coordinated, for example, bidentate or tridentate. Examples of the organic substance include a neutral organic substance such as bipyridine and pyrazine, and an anionic organic substance such as a carbonic acid anion which may be exemplified by terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, glutarate, As well as cationic materials. Representative examples of organic materials that can be used include benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Heptanedioic acid, or cyclohexyldicarboxylic acid, and their anions, pyrazines, bipyridines, and the like. In addition, one or more organic substances may be mixed and used. Specifically, benzene dicarboxylic acid may be used as an organic substance in the present invention.

The fact that some of the organic ligands are alternatively bound to the non-aromatic organic acid may mean a structure in which a non-aromatic organic acid is partially substituted with an organic ligand coordinated to a metal ion cluster. The organic-inorganic hybrid porous adsorbent according to the present invention has improved porosity and specific surface area due to the formation of defect sites, which are vacant spaces generated due to the discontinuous bonding of a part of organic ligands to non-aromatic organic acids, Good methane uptake and gas storage performance.

The organic-inorganic hybrid porous adsorbent according to the present invention has a BET surface area of 1,800 m ² / g or more. Specifically, BET specific surface area of the porous adsorbent is 1,800m ² / g to ^{3,000m 2 / g, 1,850m 2 /} g to ^{2,800m 2 / g, 1,900m 2 /} g to 2,750m ² / g, 2,000m ² / g to ^{2,750m 2 / g, 2,050m 2 /} g to ^{2,700m 2 / g, 2,100m 2 /} g to ^{2,650m 2 / g, 2,150m 2 /} g to ^{2,650m 2 / g, 2,170m 2 /} g to ^{2,600m 2 / g, 2,200m 2 /} g to ^{2,600m 2 / g, 2,250m 2 /} g to ^{2,550m 2 / g, 2,300m 2 /} g to ^{2,550m 2 / g, 2,350m 2 /} g to 2,500m ² / g, it may be an 1,850m ² / g to 2,450m ² / g or 2,370m ² / g to 2,450m ² / g. The porous adsorbent of the present invention satisfies the improved gas storage performance by having the BET surface area in the above range, and in particular, has an excellent methane storage capacity.

As an example, when the N ₂ adsorption isotherms were measured up to 1 bar at 77 K using a BET-specific surface area analyzer for the porous adsorbent, from the measured N ₂ adsorption isotherm curves, Brunauer-Emmett-Teller When the internal surface area is calculated using the model (BET), the BET surface area can satisfy the BET surface area of 1,850 m ² / g to 2,450 m ² / g or 2,350 m ² / g to 2,500 m ² / g.

The organic / inorganic hybrid porous adsorbent may have a total pore volume of 0.79 cc / g or more. Specifically, the total pore volume is from 0.79 cc / g to 3 cc / g, from 0.795 cc / g to 2.5 cc / g, from 0.8 cc to 2.2 cc / g, from 0.801 to 2.1 cc / g, / g, from 0.815 to 1.85 cc / g, from 0.82 to 1.8 cc / g, from 0.915 to 1.75 cc / g, from 0.92 to 1.75 cc / g, from 0.93 to 1.7 cc / g, G, 1.65 cc / g, 1.95 cc / g to 1.65 cc / g, 1 cc / g to 1.6 cc / g, 1.05 cc / g to 1.6 cc / g, 1.1 cc / g to 1.55 cc / cc / g to 1.5 cc / g. The porous adsorbent of the present invention satisfies the improved gas storage performance by having the total pore volume within the above range, and particularly has an excellent methane storage capacity.

As an example, when the N ₂ adsorption isotherms were measured up to 1 bar at 77 K using a BET-specific surface area analyzer for the porous adsorbent, from the measured N ₂ adsorption isotherm curves, Brunauer-Emmett-Teller When the total pore volume (total pore volume) is predicted from the data of P / P ₀ = 0.995 after calculating the internal surface area using the model (BET), the total pore volume is 0.79 cc / g to 3 cc / g or 1.1 cc / g to 1.55 cc / g.

In the organic-inorganic hybrid porous adsorbent according to the present invention, a part of the organic ligand is substituted with a nonaromatic organic acid, and the ratio of the substitution of the nonaromatic organic acid in 100 mole% of the entire organic ligands coordinated to the metal ion cluster is 0.3 to 5 mol%. Specifically, the proportion of the non-aromatic organic acid substituted in 100 mole% of the total of the organic ligands coordinated to the metal ion cluster is 0.5 mol% to 4 mol%, 0.6 mol% to 3.5 mol%, 0.7 mol% to 3 mol%, 0.8 From 1.1 mol% to 1.68 mol%, from 1.2 mol% to 1.65 mol%, from 1.3 mol% to 1.63 mol%, 1.35 mol%, from mol% to 2.5 mol%, from 0.9 mol% to 2 mol% , 1.5 to 1.6 mol%, 1.52 to 1.58 mol%, or 1.53 to 1.57 mol%, based on the total weight of the composition. By replacing the non-aromatic organic acid in the above-mentioned mol% range in 100 mol% of the total of the organic ligands coordinated to the metal ion clusters, the organic-inorganic hybrid porous adsorbent according to the present invention has the defect of void space generated due to the discontinuity in the crystal It has an improved porosity and specific surface area due to proper formation of sites, thereby exhibiting excellent methane absorption and gas storage performance.

The organic-inorganic hybrid porous adsorbent according to the present invention may have a methane total volume of 250 cc / g (STP) or higher when measuring the adsorption capacity of methane (CH ₄ ). Specifically, the total volume of the methane may be measured under STP (standard temperature and pressure) conditions. Specifically, it is 250 cc / g to 450 cc / g, 260 cc to 430 cc / g, 265 cc / G, 280cc / g to 410cc / g, 290cc / g to 390cc / g, and 290.5cc / g to 420cc / g, 270cc / g to 420cc / g, 275cc / 295 cc / g to 370 cc / g, 293 to 290 cc / g to 370 cc / g, 294 to 290 cc / g to 370 cc / 350 cc / g, 296 cc / g to 345 cc / g, 300 cc / g to 350 cc / g, or 310 cc / g to 335 cc / g. The porous adsorbent according to the present invention has an excellent BET surface area and a total pore volume, thereby satisfying the excellent total volume of methane in the above range. This indicates that the porous adsorbent according to the present invention can be effectively used for various gas adsorbents, gas storage, sensors, membranes, functional thin films, catalysts, and catalyst carriers.

As one example, the total volume of methane was measured by measuring the volume (adsorption amount) of methane adsorbed on the porous adsorbent surface using a high pressure adsorption volume meter (Belsorp-HP, Microtrac BEL Corp.) Lt; / RTI >

[Formula 1]

N _excess means the volume of methane adsorbed on the surface of the porous adsorbent through the high pressure adsorption volume meter and V _p is the N ₂ adsorption isotherms at 77K using a BET- , P _bulk means the density of methane measured at 298 K and 1 bar. That is, the total methane volume (n _total ) may be the total amount of methane stored at 298 K and 1 bar converted on the basis of the density of methane (p _bulk ).

Hereinafter, a method for producing the organic / inorganic hybrid porous adsorbent will be described in detail.

The method for producing an organic / inorganic hybrid porous adsorbent according to the present invention comprises:

Preparing a first mixed solution obtained by mixing a metal precursor, an organic compound capable of acting as a ligand, and a solvent; Adding an aromatic acid-free organic acid to the prepared first mixed liquid to prepare a second mixed liquid; And heating and drying the second mixed liquid to produce an organic hybrid porous adsorbent,

The metal of the metal precursor is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, , One selected from the group consisting of Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Ti, Si, Ge, Pb, As, Sb and Bi ≪ / RTI >

The organic compound capable of acting as the ligand is at least one selected from the group consisting of benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Heptanedioic acid, and cyclohexyldicarboxylic acid, and at least one member selected from the group consisting of heptanedioic acid,

The organic or inorganic hybrid adsorbent prepared through the above step has a BET surface area of 1,800 m ² / g or more.

The metal material of the metal precursor may be any metal and may be any of metals such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, As typical examples of the metals are Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, It is a metal substance. Particularly, transition metals which are well-coordinated compounds are suitable, and among the transition metals, they may include chromium, vanadium, iron, nickel, cobalt, copper, titanium and manganese. Specifically, copper may be used as the metallic material herein.

The organic compound capable of acting as the ligand may be an organic substance. These organic substances are also referred to as linkers, and any organic substance having a functional group capable of coordinating can be used. The functional group capable of coordinating is a carboxyl group (-COOH), a carboxylic acid anion group (-COO-), an amino group (-NH ₂ ), An imino group (-NH), an amide group (-CONH ₂ ), a nitro group (-NO ₂ ), a hydroxy group (-OH), a halogen group (-X), a sulfonic acid group (-SO ₃ H) (-SO ₃ ^- ), a methanedithioic acid group (-CS ₂ H), a methanedithioic acid ion group (-CS ₂ ^- ), a pyridine group, or a pyrazine group. In order to induce a more stable metal-organic skeleton material, it may be an organic material having two or more sites that can be coordinated, for example, bidentate or tridentate. Examples of the organic substance include a neutral organic substance such as bipyridine and pyrazine, and an anionic organic substance such as a carbonic acid anion which may be exemplified by terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, glutarate, As well as cationic materials. Representative examples of organic materials that can be used include benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Heptanedioic acid, or cyclohexyldicarboxylic acid, and their anions, pyrazines, bipyridines, and the like. In addition, one or more organic substances may be mixed and used. Specifically, benzene dicarboxylic acid can be used as the organic compound which can act as a ligand in the present invention.

In the step of preparing the first mixed solution, the solvent may be any solvent that can dissolve both the metal material and the organic compound. Examples of the solvent include alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone (H ₂ O), dimethylformamide (DMF), and the like can be used, and two or more kinds of solvents can be used in combination. Among them, water, dimethyl form Amide or ethanol may be used as the solvent. Specifically, the solvent may be a mixture of water, dimethylformamide and ethanol in a weight ratio of 1: 1: 1.

Specifically, the first mixed solution may be prepared by mixing a mixture obtained by dissolving a metal precursor in water and a mixture obtained by dissolving an organic compound capable of acting as a ligand in dimethylformamide, both of the two mixtures being mixed with ethanol. At this time, water, dimethylformamide and ethanol may be mixed in a weight ratio of 1: 1: 1.

As one example, an organic ligand formed from an organic compound capable of acting as a ligand is coordinate-bonded to a metal ion cluster formed from a metal precursor according to the present invention, and in the step of preparing the second mixed solution, The organic acid may be added so that 0.3 to 5 mol% of the organic ligand is substituted for the ligand bound to the metal ion cluster. Specifically, in the step of preparing the second mixed solution, the aromatic acid-free organic acid may be used in an amount of 0.5 mol% to 4 mol%, 0.6 mol% to 3.5 mol%, or 0.5 mol% to 100 mol% 0.7 mol% to 3 mol%, 0.8 mol% to 2.5 mol%, 0.9 mol% to 2 mol%, 1 mol% to 1.7 mol%, 1.1 mol% to 1.68 mol%, 1.2 mol% to 1.65 mol%, 1.3 mol %, 1.63 mol% to 1.62 mol%, 1.35 mol% to 1.6 mol%, 1.45 mol% to 1.6 mol%, 1.5 mol% to 1.6 mol%, 1.52 mol% to 1.58 mol% or 1.53 mol% And 1.57 mol% of the polyisocyanate compound are substituted.

In the production of the second mixed solution, the organic acid not containing an aromatic group is added so that the mole% of the organic ligands coordinated to the metal ion clusters in the above range is individually bonded, so that the organic / inorganic hybrid porous adsorbent produced has discontinuity in the crystal The vacancy space, which is an empty space to be generated, is suitably formed, thereby having improved porosity and specific surface area, and further exhibits excellent methane absorption capacity and gas storage performance.

As an example, the aromatic acid-free organic acid may be added in an amount of 0.3 to 5 parts by weight based on 100 parts by weight of the first mixed solution. Specifically, the addition amount of the aromatic acid-free organic acid is 0.3 to 5 parts by weight, 0.35 to 4.8 parts by weight, 0.4 to 4.5 parts by weight, 0.45 to 4.2 parts by weight, 0.5 to 4 parts by weight based on 100 parts by weight of the first mixed solution, 0.5 to 3.9 parts by weight, 0.55 to 3.8 parts by weight, 0.55 to 3.5 parts by weight, 0.8 to 2.5 parts by weight, 1.5 to 3 parts by weight, 1.6 to 3.5 parts by weight, 0.9 to 3.6 parts by weight or 1.5 to 2.3 parts by weight. When the organic acid not containing an aromatic is added in the above-mentioned weight parts, the BET surface area and the total pore volume of the produced organic-inorganic hybrid porous adsorbent are effectively improved.

As an example, when the first mixed solution is 15 ml, the aromatic acid-free organic acid may be used in a range of 0.05 to 0.66 ml, 0.08 to 0.6 ml, 0.15 to 0.55 ml, 0.25 to 0.55 ml, 0.25 to 0.45 ml, ≪ / RTI >

In the step of heating the second mixed solution, the heating temperature may be 50 to 230 캜. Specifically, the heating temperature may be 60 ° C. to 220 ° C., 65 ° C. to 90 ° C., 70 ° C. to 80 ° C., 110 ° C. to 170 ° C., 130 ° C. to 160 ° C., 150 ° C., 200 ° C. to 230 ° C., 1 < / RTI > The method for preparing an organic / inorganic hybrid porous adsorbent according to the present invention can control the BET surface area and the pore volume by controlling the content of the organic acid not containing an aromatic substance so that the BET surface area and the total pore volume Thereby improving the fairness of the image forming apparatus.

The aromatic organic acids may be selected from the group consisting of acetic acid, formic acid, trifluoroacetic acid (TFA), oxalic acid, oxalacetic acid, fumaric acid, malic acid malic acid, succinic acid, butyric acid, palmitic acid, alanine, valine, isoleucine, leucine, methionine, lysine, But not limited to, lysine, arginine, histidine, aspartic acid, serine, threonine, glutamine acid, asparagine, glutamine, cysteine, ), Glycine (Glycine) and proline. Specifically, acetic acid may be used as an organic acid which does not contain aromatics in the present invention. The present invention can improve the BET surface area and pore size of an organic / inorganic hybrid porous adsorbent prepared by containing an aromatic acid-free organic acid as described above.

Best Mode for Carrying Out the Invention Hereinafter, the present invention will be described in more detail with reference to examples and drawings based on the above description. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Example  One

(74 mg, 0.352 mmol) of Cu (NO ₃ ) ₂揃 2.5H ₂ O (124 mg, 0.533 mmol) and 1,3,5-benzenetricarboxylate were dissolved in 5 ml of H ₂ O and 5 ml of DMF, And ultrasonicated. The two ultrasonically treated solutions and 5 ml of anhydrous ethanol were transferred to a 20 ml vial and mixed. 0.1 ml of acetic acid was added to the mixture, the vial was covered, and the mixture was kept at 75 占 폚 for 24 hours. The synthesized blue crystalline powder was washed several times with DMF. The solvent was then exchanged with anhydrous ethanol and the solvent molecules in the pores of the crystals of the blue crystalline powder were removed using a supercritical CO ₂ drier (Samdri®-PVT-3D, passive critical drier) to remove the organic or inorganic hybrid adsorbent . At this time, 0.05 g of the sample was used for the supercritical CO ₂ drying treatment, and it took 40 minutes or longer to exchange the anhydrous ethanol with the supercritical CO ₂ .

Example  2 to 5

Porous adsorbents were prepared in the same manner as in Example 1 except that the addition amounts of acetic acid were changed to 0.2 ml, 0.3 ml, 0.4 ml and 0.5 ml, respectively, in Examples 2, 3, 4 and 5.

Comparative Example  One

A porous adsorbent was prepared in the same manner as in Example 1 except that acetic acid was not added.

Comparative Example  2

A porous adsorbent was prepared in the same manner as in Example 1, except that 80 mg of isophthalic acid (IPA) was used instead of acetic acid.

Comparative Example  3 to 5

Comparative Examples 3, 4 and 5 were prepared in the same manner as in Example 1 except that the addition amounts of acetic acid were changed to 0.7 ml, 1.4 ml and 2.1 ml, respectively.

1 shows NMR results showing that the porous adsorbent according to Example 3 (FIG. 1A), Comparative Example 3 (FIG. 1B) and Comparative Example 5 (FIG. 1C) contains acetic acid. Here, D is the result of acetic acid (AcOH) NMR, and E is the result of Comparative Example 1 produced by a general HKUST-1 production method without addition of acetic acid.

Experimental Example  1: BET Specific surface area  And pore volume evaluation

In order to evaluate the BET specific surface area and pore volume of the porous adsorbents according to Examples 1 to 5 and Comparative Examples 1 to 5, 77K N ₂ adsorption isotherms were measured with a BET-specific surface area analyzer (Autosorb-iQ, Quantachrome Instruments ) Was measured to 1 bar. At this time, prior to measuring the BET specific surface area and pore volume, degassing of the porous adsorbent was carried out at 150 ° C and for 12 hours under dynamic vacuum using a degassing system in the analyzer. The internal surface area was calculated from the measured N ₂ adsorption isotherm curves using the Brunauer-Emmett-Teller model (BET) and the total pore volume (total pore volume) was estimated from the data of P / P ₀ = 0.995, 2, 3 and Table 1 below.

2 shows the results of adsorption isotherms of 77 K N ₂ of porous adsorbents according to Examples 1 to 5 (FIG. 2 A to E) and Comparative Example 1 (FIG. 2 F), and FIG. 3 shows the results of Examples 1 to 5 3 A to E), Comparative Example 1 (I in Fig. 3) and Comparative Examples 3 to 5 (F to H in Fig. 3).

division Amount of acetic acid [ml] BET surface area [m ² / g] Total pore volume [cc / g] Example 1 0.1 1,870 0.802 Example 2 0.2 1,946 0.82 Example 3 0.3 2,396 1.196 Example 4 0.4 2,197 0.958 Example 5 0.5 2,073 0.925 Comparative Example 1 0 1,787 0.77 Comparative Example 2 80 mg (IPA) 1.610 0.71 Comparative Example 3 0.7 1.441 0.574 Comparative Example 4 1.4 1,240 0.488 Comparative Example 5 2.1 1,244 0.487

According to Table 1, the BET surface area and the total pore volume of the porous adsorbent are controlled according to the amount of acetic acid added. When the amount of acetic acid is 0.3 ml, the BET surface area and the total pore volume are the best.

Experimental Example  2: Methane ( CH ₄ ) Adsorption amount evaluation

To evaluate the amount of adsorbed methane of the porous adsorbent according to Examples 2, 3 and Comparative Example 1, a high pressure adsorption volume meter (Belsorp-HP, MicrotracBEL Corp.) was used at 298K and 0 bar to 100 bar conditions (Adsorption amount) of methane adsorbed on the porous adsorbent was calculated using the following equation (1). At this time, prior to measurement of methane adsorption amount, degassing of the porous adsorbent was carried out at 150 ° C for 12 hours under dynamic vacuum using a degassing system in the measuring instrument.

[Formula 1]

Where n _excess is the volume of methane adsorbed on the surface of the porous adsorbent via the high pressure adsorption volume meter, V _p is the total pore volume measured previously and p _bulk is the density of methane measured at 298 K and 1 bar conditions . That is, the total methane volume (n _total ) refers to the total amount of methane stored at 298 K and 1 bar, based on the density of methane (p _bulk ).

The results are shown in FIG. 4 and the following Table 2, where A, B and C are the volumes of methane adsorbed on the surface of the porous adsorbent according to Examples 1 and 2 and Comparative Example 1, respectively, and D, E And F are the total volume of methane adsorbed on the porous adsorbent according to Examples 1 and 2 and Comparative Example 1, respectively.

division BET surface area
[m ² / g] Total pore volume
[cc / g] The total volume of methane (35 bar) The total volume of methane (65 bar) The total volume of methane (65 bar) after eight adsorption / desorption Example 2 1,946 0.82 250.1cc / g 295cc / g 294.8cc / g Example 3 2,396 1.196 263.53 cc / g 320cc / g 317.5cc / g Comparative Example 1 1,787 0.77 239.7cc / g 282.3cc / g - Comparative Example 2 1.610 0.71 235.2 cc / g 286.7cc / g -

According to the results of FIG. 4 and Table 1, the volume adsorption amount of methane adsorbed on the surface of the porous adsorbent (A, B and C in FIG. 3) showed the highest amount of adsorbed methane in the porous adsorbent according to Example 2 at 65 bar (D, E and F in FIG. 3), the porous adsorbent according to Example 3 exhibited a total methane bulk of 263.53 cc / g at a pressure of 35 bar and the highest methane adsorption amount .

On the other hand, the porous adsorbent of Comparative Example 1 showed a total methane volume of 239.7 cc / g, the porous adsorbent of Comparative Example 2 had a total methane volume of 235.2 cc / g, Of methane was increased by about 10% as compared with Comparative Examples 1 and 2.

Also, at 65 bar pressure, the porous adsorbent according to Example 3 showed the highest methane total adsorption volume with 320 cc / g methane total volume, while the porous adsorbent according to Comparative Example 1 had a total methane bulk of 282.3 cc / g , The porous adsorbent according to Comparative Example 2 showed a total volume of methane of 286.7 cc / g, indicating that the storage capacity of the porous adsorbent according to Example 3 was increased by about 13% as compared with Comparative Examples 1 and 2 there was. This is due to the effect of total pore volume, which is one of the parameters for converting the volume (adsorption amount) of methane adsorbed on the surface of the porous adsorbent to the total volume (adsorption amount) of methane.

As shown in Table 1, the total pore volume of the porous adsorbent according to Example 3 is 1.196 cc / g, which is larger than the total pore volume of the porous adsorbent according to Comparative Example 1 by 0.426 cc / g. Thus, it was confirmed that the total adsorption amount of methane can be greatly increased when the total pore volume of the porous adsorbent is increased.

FIG. 5 is a graph showing the adsorption amount of methane when the adsorption of methane was performed for 8 times using the porous adsorbent according to Example 2 and Example 3 at 298 K and 5 bar to 65 bar. In FIG. 5, A means the porous adsorbent according to Example 2, and B means the porous adsorbent according to Example 3. According to Fig. 5, the total volume of methane in the porous adsorbents according to Examples 2 and 3 increased to about 234.6 ± 5 cc / g, while the pressure increased from 5 bar to 65 bar.

The total volume increase of the methane was maintained during the 8-time methane adsorption / desorption experiment. After the methane adsorption / desorption experiment was performed 8 times, the total volume of methane of the porous adsorbent according to Example 2 was 294.8 cc / g at 65 bar And the total volume of methane of the porous adsorbent according to Example 3 was still 317.5 cc / g at 65 bar (see Table 2).

These results show that the porous adsorbent according to the present invention has a large BET surface area and a total pore volume so that the gas adsorption and gas storage capacity are significantly improved and that even when the porous adsorbent is reused many times, Amount) can be kept excellent.

Claims (8)

A structure in which an organic ligand is coordinated to a metal ion cluster,
Wherein the organic ligand is derived from an aromatic containing organic acid and an aromatic free organic acid,
BET surface area of at least 1,800 m ² / g,
The metal ion may be at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, At least one ion selected from the group consisting of Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi / RTI >
An organic acid which does not contain an aromatic-containing organic acid, or aromatic group, a carboxyl group (-COOH), a carboxylic acid anion group (-COO-), an amine group (-NH _2), and an imino group (-NH), a nitro group (-NO ₂ ), A hydroxyl group (-OH), a halogen group (-X), and a sulfonic acid group (-SO ₃ H)
Wherein an aromatic acid-free organic acid is bound in an amount of 0.3 mol% to 5 mol% in 100 mol% of the total of the organic ligands coordinated to the metal ion clusters.
delete The method according to claim 1,
Wherein the organic or inorganic hybrid porous adsorbent has a total pore volume of 0.79 cc / g or more.
The method according to claim 1,
The organic / inorganic hybrid porous adsorbent is characterized in that the total volume of methane is at least 250 cc / g (STP) when measuring the adsorption capacity of methane (CH ₄ ).
Preparing a first mixed solution obtained by mixing a metal precursor, an aromatic containing organic acid, and a solvent;
Adding an aromatic acid-free organic acid to the prepared first mixed liquid to prepare a second mixed liquid; And
And heating and drying the second mixed liquid to prepare an organic hybrid porous adsorbent,
The metal of the metal precursor is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, , One selected from the group consisting of Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Ti, Si, Ge, Pb, As, Sb and Bi ≪ / RTI >
The aromatic containing organic acid or aromatic organic acid not containing an aromatic may be at least one selected from the group consisting of benzene dicarboxylic acid, naphthalene dicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridine dicarboxylic acid, bipyridyl dicarboxylic acid, formic acid, oxalic acid, malonic acid, , Hexane dioic acid, heptane dioic acid, and cyclohexyl dicarboxylic acid,
The prepared organic / inorganic hybrid porous adsorbent has a BET surface area of 1,800 m ² / g or more,
A metal ion cluster formed from the metal precursor is coordinated with an organic ligand capable of acting as a ligand,
Wherein the organic ligand is derived from an aromatic containing organic acid and an aromatic free organic acid,
Wherein the aromatic acid-free organic acid is added in an amount of from 0.3 mol% to 5 mol% in 100 mol% of the entire organic ligands coordinated to the metal ion cluster in the step of preparing the second mixed solution. A method for producing a porous adsorbent.
delete 6. The method of claim 5,
Wherein the heating temperature in the step of heating the second mixed solution is 50 ° C to 230 ° C.
6. The method of claim 5,
Organic acids that do not contain aromatics,
Acetic acid, formic acid, trifluoroacetic acid (TFA), oxalic acid, oxalacetic acid, fumaric acid, malic acid, succinic acid, Butyric acid, palmitic acid, alanine, valine, isoleucine, leucine, methionine, lysine, arginine, (Eg, histidine, aspartic acid, serine, threonine, glutamine acid, asparagine, glutamine, cysteine, glycine and proline Proline). ≪ / RTI >

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