KR100982641B1 - Adsorbent including crystalline porous organic-inorganic hybrid materials - Google Patents

Adsorbent including crystalline porous organic-inorganic hybrid materials Download PDF

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KR100982641B1
KR100982641B1 KR1020080124810A KR20080124810A KR100982641B1 KR 100982641 B1 KR100982641 B1 KR 100982641B1 KR 1020080124810 A KR1020080124810 A KR 1020080124810A KR 20080124810 A KR20080124810 A KR 20080124810A KR 100982641 B1 KR100982641 B1 KR 100982641B1
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inorganic hybrid
adsorbent
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porous organic
acid
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황영규
장종산
서유경
장인태
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한국화학연구원
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form

Abstract

The present invention relates to an adsorbent containing a crystalline porous organic-inorganic hybrid, specifically, preparing a reactant mixture by mixing a metal precursor of an inorganic acid including chloride, an organic compound that can act as a ligand, and a solvent (step 1 ); Heating the reactant mixture to 80 ° C. or more by irradiating with electric heating or microwave to form an organic-inorganic hybrid (step 2); and converting the porous organic-inorganic hybrid obtained in step 2 into an inorganic salt, an acidity regulator or a solvent. It relates to an adsorbent containing a crystalline porous organic-inorganic hybrid prepared by the production method comprising the step of purifying by treatment (step 3). The adsorbent according to the present invention contains a nanoporous organic-inorganic hybrid having a uniform particle size distribution having high crystallinity. When the present invention is used as a moisture adsorbent, the adsorbent is easily desorbed at a low temperature of 100 ° C. or lower, and thus, a humidifier or It can be usefully used as a dehumidifying agent. In addition, when the present invention is used as an adsorbent for removing volatile organic compounds (VOC) and the like, it is possible to effectively remove specific harmful substances, which can be useful for preventing sick house syndrome and removing various harmful substances.
Organic-inorganic hybrids, hydrothermal synthesis, nanoparticles, pore materials, adsorbents, microwave synthesis, volatile organic mixtures (VOC)

Description

Adsorbent including crystalline porous organic-inorganic hybrid materials

The present invention relates to an adsorbent containing a crystalline porous organic-inorganic hybrid containing no fluorine.

Porous organic-inorganic hybrids are termed broadly and generally referred to as porous coordination polymers [Angew. Chem. Intl. Ed., 43, 2334. 2004] also known as metal-organic frameworks [Chem. Soc. Rev., 32, 276, 2003]. The porous organic-inorganic hybrids have recently been newly developed by incorporating molecular coordination bonds and materials science, and the hybrids have high surface area and molecular or nano-sized pores, so that adsorbents, gas storage, sensors, membranes, In addition to being used in functional thin films, catalysts and catalyst carriers, they have been actively studied recently because they can be used to trap guest molecules smaller than the pore size or to separate the molecules according to the size of the molecules using pores.

In particular, the crystalline organic-inorganic hybrid nanoporous body may be defined as a porous organic-inorganic polymer compound formed by combining a central metal ion with an organic ligand, and includes both organic and inorganic substances in a skeletal structure and has a molecular or nano-sized pore structure. It means a crystalline compound having a.

In preparing the porous organic-inorganic hybrid as described above, in order to control the crystallinity, a hydrothermal synthesis method including a step of adding a complex acid such as nitric acid and hydrofluoric acid was mainly used. Representative porous organic-inorganic hybrid prepared by the hydrothermal synthesis as the formula Cr 3 O (H 2 O) 2 F [C 6 H 3- (CO 2 ) 3 ] 2 · nH 2 O (n ~ 14.5) MIL -100 (Cr), Fe 3 O (H 2 O) 2 F [C 6 H 3- (CO 2 ) 3 ] 2 nH 2 O (n-14.5), and Cr 3 F (H 2 O) 2 O MIL-101 (Cr), [C 6 H 4 (CO 2 ) 2 ] 3 nH 2 O (n-25), has been reported [Science 23, 2040, 2005; Chemical Communication 2820, 2007, Accounts of Chemical Research, 38, 217, 2005]. However, when the hydrofluoric acid is used as in the conventional process, the material that can be used in the synthesis reactor is very limited in the scale-up process, which is a practical application step of the porous organic-inorganic hybrid, and the waste disposal cost is also relatively high.

Recently, Korean patent application 2007-0063881 discloses a method for producing an organic-inorganic hybrid from a synthetic solution containing nitric acid without using hydrofluoric acid in the synthesis of existing organic-inorganic hybrid pores. However, due to the relatively low crystallinity of the prepared organic-inorganic hybrid, very small crystal size (less than 100nm), it takes a long time to filter, the crystal shape is not uniform, there is a relatively low surface area.

On the other hand, the adsorbent for easily adsorbing and desorbing moisture has various uses. For example, the dehumidifier may utilize an adsorbent having a desorption characteristic when the moisture is adsorbed at a low temperature and then heated to a high temperature. In addition, if the adsorbent is used in the air conditioner, it adsorbs the outdoor moisture at low temperature during heating and then enters the room and desorbs at the high temperature indoor to take the role of a humidifier. It can be detached from the high temperature outdoor and sent to the outside, so you can get a pleasant indoor atmosphere. Air conditioners and humidity controllers applying this concept have been proposed in US Patent No. 6978635, 6959875, 6675601 and the like. However, no specific reference is made to the adsorbents used in these devices and only mentions the use of silica gels, zeolites, ion exchange resins or the use of adsorbents. In addition, in the case of such an adsorbent, not only the adsorption amount is low but also the desorption requires a high temperature of 100 deg.

Recently, Korean Patent 806586 has reported an application example for a porous organic-inorganic hybrid capable of adsorption and desorption of moisture at low temperature. However, the surface area has to be crystallized to more than 1,000 m 2 , the pore volume of more than 1.0 ml / g had a disadvantage that the manufacturing process cost must be very high.

Therefore, in order to easily use as an adsorbent, it is very necessary to develop an adsorbent that can be detached even at low temperatures, the difference in the amount of adsorption and desorption is large, and the manufacturing process is economical. However, when the amount of adsorption increased, desorption was difficult. When the amount of adsorption was small, there was always a problem in which the difference between the amount of adsorption and the amount of desorption was small.

In addition, activated carbon, hydrophobic, and zeolite have been mainly used as adsorbents to remove organic compounds present in indoor spaces. Activated carbon has a very large specific surface area due to the development of micropores and strong adsorption power to nonpolar molecules, which is excellent in exhaust gas removal, odor removal, and decolorization, while zeolite is a hydrophilic adsorbent having a pore diameter of about 3 to 10 Å. Carbon dioxide and moisture adsorption characteristics are strong. However, most of them have only hydrophobic properties, which makes it difficult to effectively adsorb and remove volatile organic compounds containing water.

Accordingly, the present inventors have developed an adsorbent containing a crystalline porous organic-inorganic hybrid having a uniform particle size distribution without using hydrofluoric acid or nitric acid, and the adsorbent is easily absorbed and desorbed even at low temperatures, and volatile organic materials are commercially available. It confirmed the adsorption effect better than the adsorbents completed the present invention.

An object of the present invention is to provide an adsorbent containing a crystalline porous organic-inorganic hybrid that does not contain fluorine.

In order to achieve the above object, the present invention provides an adsorbent containing a crystalline porous organic-inorganic hybrid that does not contain fluorine.

It is a nanoporous hybrid having a uniform particle size distribution having high crystallinity even though hydrofluoric acid or nitric acid is not used in hydrothermal synthesis using the crystalline porous organic-inorganic hybrid contained in the present invention. In particular, when the adsorbent of the present invention is used as a moisture adsorbent, desorption occurs easily at a low temperature of 100 ° C. or lower, and can be usefully used as a humidifier or a dehumidifying agent. In addition, when the adsorbent of the present invention is used as an adsorbent for removing a small amount of volatile organic compounds (VOC), etc. present in the indoor space, it is possible to effectively remove specific harmful substances, which is useful for preventing sick house syndrome and removing various harmful substances. Can be.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of preparing a reactant mixture by mixing a metal precursor of an inorganic acid containing chloride, an organic compound that can act as a ligand and a solvent (step 1);

Heating the reactant mixture to 80 ° C. or more by electric heating or microwave irradiation (step 2); And

It provides an adsorbent containing a crystalline porous organic-inorganic hybrid prepared by the manufacturing method comprising the step (step 3) of purifying by treating the porous organic-inorganic hybrid obtained in step 2 with an inorganic salt, acidity regulator or solvent. .

Hereinafter, a step-by-step detailed description of the organic-inorganic hybrid production method contained in the adsorbent of the present invention.

In the method of preparing the crystalline porous organic-inorganic hybrid, step 1 is a step of preparing a reactant mixture by mixing a metal precursor of an inorganic acid including chloride, an organic compound that can act as a ligand, and a solvent.

Step 1 is a step of preparing a composition by mixing the raw material of the crystalline porous organic-inorganic hybrid, a composition for preparing an organic-inorganic hybrid having a uniform particle size distribution of nano size using inorganic acids of chloride, without using hydrofluoric acid or nitric acid Mixing step.

In order to control the crystal growth rate of the organic-inorganic hybrid nanoporous body, it was conventionally a method for producing a complex acid including hydrofluoric acid, such as nitric acid, hydrochloric acid, hydrofluoric acid [Science 23, 2040, 2005; Accounts of Chemical Research, 38, 217, 2005]. However, there was a limitation in using a reactor other than taperon in the process using hydrofluoric acid. The crystal growth rate of organic-inorganic hybrid nanoporous bodies has been known to be slow in nucleation, while the crystal growth rate is relatively fast. Therefore, in the reaction product containing hydrofluoric acid, due to the strong binding property between the metal ion and the fluorine ion, the rate of nucleation was relatively low, and thus the nanoporous body having small crystal size could not be obtained. In addition, a porous organic-inorganic hybrid prepared using only nitric acid without using hydrofluoric acid has a relatively inferior crystallinity.

However, in the method for preparing a porous organic-inorganic hybrid according to the present invention, it is possible to prepare a porous organic-inorganic hybrid nanoporous body having a particle size of a relatively uniform particle size distribution than a conventional organic-inorganic hybrid by using an inorganic acid of chloride.

At this time, the metal in the metal precursor of the porous organic-inorganic hybrid may be any metal, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh , Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As , Sb, Bi and the like are representative metal materials. In particular, transition metals which make coordination compounds well are preferred. Among the transition metals, chromium, vanadium, iron, aluminum, nickel, cobalt, copper, titanium, manganese, and the like are more preferable, and chromium or iron is most preferred. In addition to transition metals, metals such as lanthanum may be used as well as typical elements for making coordination compounds. Among the typical elements, aluminum and silicon are suitable, and among lanthanum metals, cerium and lanthanum are suitable. As the metal source, any compound of the metal may be used as well as the metal itself.

An organic compound capable of acting as a ligand, which is another member of the organic-inorganic hybrid, is also called a linker and can be any organic compound having a coordinating functional group, and the coordinating functional group is a carboxylic acid group, a carboxylic acid. Anionic group, amino group (-NH 2 ), imino group (

Figure 112008084775463-pat00001
), Amide group (-CONH 2), a sulfonic acid group (-SO 3 H), a sulfonic acid anion group (-SO 3 -), methane dithiol Osan group (-CS 2 H), methane dithiol Osan anion group (-CS 2 - ), Pyridine group or pyrazine group and the like can be exemplified. In order to induce a more stable organic-inorganic hybrid, an organic compound having two or more coordinating sites, for example, bidentate or tridentate, is preferable. Organic compounds include neutral organic compounds such as bipyridine and pyrazine, and terephthalates, naphthalenedicarboxylates, benzenetricarboxylates, glutarates, succinates and the like. Cationic materials as well as anionic organic compounds are possible. In the case of the carbonic acid anion, for example, in addition to having an aromatic ring such as terephthalate, any of anions having a linear carbonic acid such as formate and an anion having a non-aromatic ring such as cyclohexyldicarbonate can be used. Organic compounds having coordinating sites, as well as organic compounds having potentially coordinating sites and converted to coordinating under reaction conditions may be used. That is, even if an organic acid such as terephthalic acid is used, it can be combined with a metal component with terephthalate after the reaction. Representative examples of organic compounds that can be used include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexane Organic acids selected from diioic acid, heptanedioic acid, or cyclohexyldicarboxylic acid and their anions, pyrazine, bipyridine and the like. It is also possible to mix and use one or more organic compounds.

In step 1, a solvent capable of dissolving both the metal component and the organic compound is required, and alcohols such as water, methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, hexane, heptane and octane Any materials such as hydrocarbons can be used, and two or more solvents can be mixed and used, of which water is most preferable.

In the method of preparing the crystalline porous organic-inorganic hybrid, step 2 is a step of heating the reactant mixture to 80 ℃ or more by irradiation with electric heating or microwave.

Step 2 is a step in which a metal precursor is combined with an organic compound to form an organic-inorganic hybrid by applying heat to the reactant mixture.

At this time, the heating temperature is not practically limited, but 80 ° C. or more is appropriate and a temperature of 80 ° C. or more and 250 ° C. or less is preferable. If the heating temperature is less than 80 ℃, the formation rate of the organic-inorganic hybrid is not effective, and if the heating temperature exceeds 250 ℃, it is easy to obtain an organic-inorganic hybrid without pores, the reaction rate is too fast and impurities are mixed Not only is there an easy problem, but the internal pressure of the reactor is high, which makes the construction of the reactor uneconomical. The reactor pressure is practically unlimited but it is easy to synthesize at the autogeneous pressure of the reactants at the reaction temperature. In addition, inert gases such as nitrogen and helium may be added to carry out the reaction at high pressure.

The heating is also possible by the hydrothermal synthesis method of the electric heating method, the hydrothermal synthesis by a batch or continuous method by microwave irradiation and the electrochemical manufacturing method proposed in the US patent application US2008-0214806. In addition, the organic-inorganic hybrid membrane or thin film may be prepared by immersing the substrate in the reactant mixture in step 1 and heating by irradiating microwaves. The method of irradiating the microwave can be irradiated locally with high energy, it is possible to produce an organic-inorganic hybrid of particles smaller than the electric heating method.

In addition, in the method for producing the crystalline porous organic-inorganic hybrid, step 3 is a step of purifying the porous organic-inorganic hybrid obtained in step 2 by treatment with an inorganic salt, acidity regulator or solvent.

In step 3, instead of using a solvent to remove the metal or organic ligand present in the pores of the conventional porous organic-inorganic hybrid, an inorganic salt, an acidity regulator is used to remove the organic or inorganic impurities chelated in the pores It can be additionally carried out by increasing the surface area of the organic-inorganic hybrid.

At this time, the inorganic salts used are monovalent or divalent cations selected from the group consisting of NH 4 + , alkali metals and alkaline earth metals, halogen anions, carbonate ions (CO 3 2- ), nitrate ions and sulfate ions. and is one selected from the group consisting of or to use a divalent anion, preferably 2 is a Ca 2+ or Mg 2+ and the monovalent anion as cation F -, I - would be made of, or 1 - or Br One or more selected from the group consisting of cations and divalent anions, or NH 4 F, KF, KI and KBr can be used.

The pH adjusting agent may realize an economical purification process by shortening the purification process time of the porous organic-inorganic hybrid. At this time, the pH adjusting agent may be a basic compound, preferably ammonia or potassium chloride (KOH) may be used.

Through step 3, the adsorption amount of the porous organic-inorganic hybrid was confirmed to increase by about 100 ~ 500 ml / g.

In the adsorbent according to the present invention, the porous organic-inorganic hybrid is an adsorbent containing a crystalline porous organic-inorganic hybrid, characterized in that having a MIL-100 (MIL: Material of Institut Lavoisier), MIL-101 or HKUST-1 structure To provide.

Further, the porous organic-inorganic hybrid is M 3 O (H 2 O) 2 Cl 1-x OH x [C 6 H 3- (CO 2 ) 3 ] 2 nH 2 O (n ~ 14.5), (0 <x <1, M = Cr, Fe, Al, Cu, Mn and V) or M 3 Cl 1-x OH x (H 2 O) 2 O [C 6 H 4 (CO 2 ) 2 ] 3 nH 2 O ( n-25) (0 <x <1, M = Cr, Fe, Al, Cu, Mn and V) may have a chemical formula, and in the formula, -OH may be partially substituted. More preferably, it may be chromium terephthalate, iron terephthalate, aluminum terephthalate, copper terephthalate, vanadium terephthalate or manganese terephthalate.

In this case, the porous organic-inorganic hybrid may be in the form of nanoparticles, powder, thin film, honeycomb pellets, rotor or membrane. Furthermore, when the porous organic-inorganic hybrid is a nanoparticle size powder, it has a large surface area and can maximize the adsorption efficiency when used as an adsorbent.

In addition, the present invention provides a water absorbent comprising the crystalline porous organic-inorganic hybrid.

The moisture adsorbent according to the present invention includes a porous organic-inorganic hybrid having a uniform crystal shape and a high specific surface area without using hydrofluoric acid or nitric acid, and thus can adsorb 0.1 to 1 g of adsorbent per 1 g of adsorbent. Desorption is easy at or below 10 deg. C, preferably at 10 to 100 deg. Furthermore, compared to the organic-inorganic hybrid containing the hydrofluoric acid, the moisture adsorbent according to the present invention has been confirmed that the initial moisture absorption rate of 1.5 times or more and the water absorption amount of 3 times or more have been increased, thereby making it excellent in humidification and dehumidification at low temperatures. It was.

On the other hand, the present invention provides a vapor or particulate particulate adsorbent of volatile organic compounds (VOCs) comprising the porous organic-inorganic hybrid.

The volatile organic compound is a vapor or particulate matter such as formaldehyde, acetaldehyde, tar, nitrosoamines, polycyclic aromatic hydrocarbons, etc., which cause sick house syndrome, in addition to volatile organic compounds such as toluene, benzene and methyl ethyl ketone. Can be effectively removed.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the following Examples are merely to illustrate the invention, the present invention is not limited by the Examples.

<Example 1> Adsorbent containing porous organic-inorganic hybrid consisting of [Cr-BDCA]

Step 1. Preparation of reactant mixture

CrCl 3 · 9H 2 O, and 1,4-benzenedicarboxylic acid (BDCA) were added to the Teflon reactor and distilled water was added to mix the final molar ratio of the reactants to Cr: BDCA: H 2 O = 1: 1: 272. It was.

Step 2. Formation of Organic-Inorganic Hybrids

 The Teflon reactor containing the reactant mixture was placed in an electric oven, reacted at 210 ° C. for 16 hours, cooled to room temperature, centrifuged, washed with distilled water, dried, and chromium terephthalate (Cr-BDCA) as a porous organic-inorganic hybrid. Was formed.

It was confirmed that the XRD pattern of the chromium terephthalate crystal obtained in Example 1 is consistent with the literature value [Science 23, 2040, 2005]. In addition, nitrogen adsorption and desorption resulted in a adsorption amount of 1200 ml / g at a relative pressure of 0.5 and a high surface area of 3800 m 2 / g.

As a result, it was found that a porous organic-inorganic hybrid was obtained very effectively by an environmentally friendly process that does not use hydrofluoric acid (HF). In addition, as a result of ICP analysis, the obtained porous organic-inorganic hybrid chromium terephthalate does not contain fluorine and its structure is the same as that of MIL-101, but does not contain fluorine in the structure: Cr 3 (Cl 0.8 OH 0.2 ) ( H 2 O) 2 O [C 6 H 4 (CO 2 ) 2 ] 3 It was confirmed that the material can be represented by nH 2 O (n ~ 25).

Example 2 Adsorbent Containing a Porous Hybrid Made of [Fe-BDCA]

Step 1. Preparation of reactant mixture

To the Teflon reactor was added 40.8 mmol of metal tetrachloride ((FeCl 3 ), and 26.8 mmol of 1,3,5-benzenetricarboxylic acid (BTCA), followed by distilled water, and the final molar ratio of the reactants was FeCl 3: BTCA: H 2 O. = 1: 0.66: 54 The reaction was stirred at 500 rpm for 20 minutes at room temperature to give a uniform reaction.

Step 2. Formation of Organic-Inorganic Hybrids

The Teflon reactor containing the pretreated reactant was maintained at a reaction temperature of 160 ° C. for 8 hours to perform a crystallization reaction, and then cooled to room temperature (distilled water) and dried to form a porous organic-inorganic hybrid (Fe-BTCA).

It was confirmed that the shape of the X-ray diffraction spectrum was the same as that of the MIL-100 (Fe) structure which is the crystal structure of [Chemical Communication 2820, 2007] in the literature (Fig. 1 (a)). The porous organic-inorganic hybrid iron terephthalate obtained from ICP analysis does not contain fluorine and its structure is the same as that of MIL-100, but does not contain fluorine in the structure, and the formula Fe 3 O (H 2 O) 2 Cl [C 6 H 3 -(CO 2 ) 3 ] 2 · nH 2 O (n ~ 14.5) was identified as a substance. As a result of the nitrogen adsorption and desorption experiment, it was confirmed that the surface area of Example 2 was 1500 m 2 / g, and the adsorption amount was 450 ml / g at P / P 0 = 0.5 (FIG. 2 (a)). As a result of electron microscopic analysis, the particle size was found to be very small (200 ~ 500 nm or less) (Fig. 3 (a)).

Example 3 Adsorbents Containing Porous Organic-Inorganic Hybrids After Purification

1 g of the porous organic-inorganic hybrid prepared in step 2 is placed in 50 ml of 1 M NH 4 F, and stirred at a temperature of 70 ° C. to remove impurities present in the pores of the pores, thereby improving the organic-inorganic hybrid having a specific surface area. Prepared.

From the X-ray diffraction spectrum (Fig. 1 (b)) it can be seen that after the ammonium fluoride treatment is maintained without damage to the crystallinity. In addition, the specific surface area of the porous organic-inorganic hybrid after the ammonium fluoride treatment was measured to be 1820 m 2 / g, and the surface area increased by 280 m 2 / g by the ammonium fluoride treatment, and the adsorption amount was P / Po = 0.5 At 550 ml / g, it was confirmed that the amount of adsorption increased by 100 ml / g by the ammonium fluoride treatment (Fig. 2b).

<Example 4> Adsorbent containing a porous organic-inorganic hybrid consisting of [Fe-BDCA] prepared using electromagnetic waves

In the second step of Example 2, it was prepared in the same manner as in Example 2 except that the heating was performed by microwave heating method of electromagnetic waves instead of the electric heating method. In the microwave heating, the Teflon reactor containing the mixed solution prepared in Step 1 of Example 2 was mounted in a microwave reactor (CEM Co., Model Mars-5) and irradiated with microwave (2.54 Hz) to raise the temperature to 180 ° C., and then to 180 ° C. After maintaining at 30 ° C. for a crystallization reaction, the mixture was cooled to room temperature, centrifuged, washed (distilled water) and dried to prepare a porous organic-inorganic hybrid (Fe-BTCA).

As a result of XRD analysis, the crystal structure of the prepared organic-inorganic hybrid was different, but the diffraction pattern was obtained at the same position as in Example 2. As a result of the surface area measurement, it was confirmed that 200 m 2 / g higher than the electric heating method. As a result of analysis by electron microscope, the size of the organic-inorganic hybrid particles was found to be relatively uniform as 1 μm (FIG. 3B).

Example 5 Adsorbent Containing Porous Organic-Inorganic Hybrids Composed of [Cr-BDCA] Prepared Using Electromagnetic Waves

In Step 2 of Example 1, a porous organic-inorganic hybrid was prepared in the same manner as in Example 1 except that the heating method by microwave irradiation is used instead of the electric heating method. However, by using a microwave reactor of 2.5GHz frequency, the organic-inorganic hybrid was prepared by maintaining the reaction time for 40 minutes at 210 ℃. X-ray diffraction spectrum analysis showed that the material of the same structure as in Example 1.

<Example 6> Adsorbent containing porous organic-inorganic hybrid consisting of [V-BDCA]

Example 2 was prepared in the same manner as in Example 2, except that VCl 3 was used instead of FeCl 3 in Step 1.

In Example 6, the material having the same structure as in Example 1 was obtained from the X-ray diffraction spectrum, and it was found from the electron micrograph that an organic-inorganic hybrid having a uniform particle size characteristic of about 100 nm was obtained.

Example 7 Moisture Adsorbent Prepared Using Electromagnetic Waves and Containing a Porous Organic-Inorganic Hybrid Made of [Cu-BDCA]

CuCl 2 is used instead of FeCl 3 in Step 1 of Example 2, and the final molar ratio after adding H 2 O and ethanol mixed solution as a solvent is Cu: BTCA: Ethanol: 14.4: 14.4 = 1: 0.56: 14.4: 14.4 The reactant mixture was prepared to be. At this time, the reactant mixture prepared in step 1 was irradiated with ultrasonic waves at room temperature and pretreated for 5 minutes to make the reactants as uniform as possible and to facilitate nucleation. The Teflon reactor containing the pretreated reactant was mounted in a microwave reactor (CEM, Model Mars-5) and heated to 140 ° C. over 2 minutes by irradiation of microwave at 2.45 GHz. Thereafter, the mixture was held at 140 ° C. for 30 minutes to react, and then cooled to room temperature, and then the powder was filtered using a paper filter. It was confirmed that the shape of the X-ray diffraction spectrum was the same as that of the HKUST-1 structure, which is the crystal structure of Science 283 (1999) 114 8 in the literature.

<Comparative Example 1> [Cr-BDCA] porous organic-inorganic hybrid prepared using hydrofluoric acid

In step 1 of Example 1, a porous organic-inorganic hybrid was prepared using hydrofluoric acid. At this time, the final molar ratio of the reaction mixture was set to Cr: HF: BDCA: H 2 O = 1: 1: 1: 272. As a result of surface area analysis of Comparative Example 1, it was confirmed that the adsorption amount was 1044 ml / g and the specific surface area was 3439 m 2 / g at P / Po = 0.5.

<Comparative Example 2> [Fe-BDCA] porous organic-inorganic hybrid prepared without chloride

An organic-inorganic hybrid was formed in the same manner as in Example 2, except that Fe was used instead of FeCl 3 in Step 1 of Example 2, followed by purification in the same manner as in Example 3.

Comparative Example 2 confirmed that the material of the same structure as in Example 2 from the X-ray diffraction form, but the amorphous organic-inorganic hybrids were observed on the electron micrograph, which is Fe when forming the organic-inorganic hybrids in Example 2 The particle formation rate due to the bonding of -Cl is reduced and the specific surface area is 1820 m 2 / g, whereas in Comparative Example 2, there is no factor that can reduce the particle formation rate. A sieve was prepared, which reduced the surface area of Comparative Example 2 to 1300 m 2 / g.

Experimental Example 1 Measurement of Water Adsorption

0.1 g of each of the adsorbents ([Fe-BTCA] porous organic-inorganic hybrid) obtained in Examples 3, 4 and Comparative Example 2 was vacuum-dried at 150 ° C. for 30 minutes, and the adsorption experiment of moisture was carried out by gravimetric method. 4 is shown.

As shown in FIG. 4, the moisture adsorption amount per weight of the adsorbent even at 60% relative humidity was determined to be 0.28 g / g and 0.31 g / g in Example 4 within the initial 5 minutes. This shows 47% and 63% improvement over 0.19 g / g adsorption amount of Comparative Example 2, respectively. In particular, it was confirmed that the water adsorption rate (initial water adsorption rate) in the entire area from the initial adsorption to 5 minutes is very fast.

As described above, the adsorbent of the present invention is larger than the adsorption amount of the conventional porous organic-inorganic hybrid prepared using hydrofluoric acid, the method of irradiating electromagnetic waves rather than the electric heating method to increase the amount of adsorption by reducing the particles of the organic-inorganic hybrid Confirmed.

Furthermore, when the porous organic-inorganic hybrid according to the present invention is used as a low temperature moisture adsorbent, it exhibits easy desorption property at 100 ° C. or lower, and it is possible to achieve very excellent performance in humidification, dehumidification, etc. by using such a property. Able to know.

Experimental Example 2 Measurement of Adsorption Amount of Volatile Organic Compound

5 shows the results of the experiment of isothermal adsorption of benzene as a volatile organic compound at 32 ° C. using the adsorbent according to the present invention.

As shown in FIG. 5, 19.5 mmol of benzene was adsorbed with respect to 1 g of Example 1 (the adsorbent containing the [Cr-BDCA] porous organic-inorganic hybrid). In terms of mass, the adsorbent according to the present invention adsorbed 1.48 g of benzene. In comparison, 8.7 mmol of benzene was adsorbed to 1 g of commercial activated carbon from Darco (surface area 1600 m 2 / g), and 0.68 g of benzene was found to be converted to mass. From this, it was confirmed that the adsorption amount of benzene is 2.24 times higher than that of activated carbon in the case of Cr-BDCA.

From the results of the above examples and comparative examples, a porous organic-inorganic hybrid having the same crystallinity can be produced by the method for producing a crystalline porous organic-inorganic hybrid containing no hydrofluoric acid or nitric acid, compared to the conventional process using hydrofluoric acid. In addition, the surface area was increased by more than 18% when treated with inorganic salts such as ammonium salt and potassium fluoride. In particular, when the porous organic-inorganic hybrid according to the present invention is used as a low temperature moisture adsorbent, it shows easy desorption property at 100 ° C. or lower, and it can be seen that very excellent performance can be achieved by using such a property in humidification and dehumidification. Can be. In addition, it was confirmed that vapor and particulate specific harmful substances such as volatile organic compounds can be effectively removed.

Figure 1 shows the results of X-ray diffraction analysis before and after purification of the porous organic-inorganic hybrid chromium terephthalate prepared according to the purification method of Example 3 of the present invention, (a) is the result before purification (Example 2) And (b) is the result after purification;

2 is a nitrogen adsorption isotherm result in iron carboxylate which is a porous organic-inorganic hybrid obtained by Examples 2 and 3 of the present invention;

3 is an electron micrograph of iron benzene tricarboxylate as a porous organic-inorganic hybrid obtained by Example 4 and Comparative Example 2 of the present invention;

4 is a result of water adsorption characteristics of the porous organic-inorganic hybrid including iron obtained by Examples 3 and 4 and Comparative Example 2 of the present invention; And

 Figure 5 is a result showing the adsorption isotherm for benzene of the porous organic-inorganic hybrid obtained by Example 1 and Experimental Example 2 of the present invention.

Claims (16)

  1. Preparing a reactant mixture by mixing a metal precursor of an inorganic acid including chloride, an organic compound which may act as a ligand, and a solvent (step 1),
    Here, the organic compound capable of acting as the ligand is a carboxylic acid group, an anionic group of carboxylic acid, an amino group (-NH 2 ), an imino group (
    Figure 112010052232188-pat00008
    ), Amide group (-CONH 2), a sulfonic acid group (-SO 3 H), a sulfonic acid anion group (-SO 3 -), methane dithiol Osan group (-CS 2 H), methane dithiol Osan anion group (-CS 2 - ), A compound having at least one functional group selected from the group consisting of a pyridine group and a pyrazine group, or a mixture thereof;
    Heating the reactant mixture with electric heating or microwave to 80 ° C. to 250 ° C. to form an organic-inorganic hybrid (step 2); And
    Adsorbent containing a crystalline porous organic-inorganic hybrid prepared by a manufacturing method comprising the step (step 3) of purifying by treating the porous organic-inorganic hybrid obtained in step 2 with an inorganic salt, acidity regulator or solvent.
  2.      According to claim 1, wherein the metal precursor of step 1 is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd , Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi Adsorbent containing a crystalline porous organic-inorganic hybrid, characterized in that at least one metal selected from the group or a compound thereof.
  3. The crystalline porous organic-inorganic hybrid according to claim 1, wherein the metal precursor of step 1 is at least one metal selected from the group consisting of Cr, Fe, Al, Cu, Mn and V or a compound thereof. Adsorbent.
  4. delete
  5. The compound having an anionic group of carboxylic acid is benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalene tricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid Adsorbent containing a crystalline porous organic-inorganic hybrid, characterized in that derived from a compound selected from the group consisting of glutaric acid, hexanedioic acid, heptanedioic acid and cyclohexyl dicarboxylic acid.
  6. delete
  7. According to claim 1, The inorganic salt used in step 3 is a monovalent or divalent cation selected from the group consisting of ammonium ion (NH + 4 ), alkali metal and alkaline earth metal, halogen anion, carbonate ion (CO 3 2- ), a monovalent or divalent anion selected from the group consisting of nitrate ions and sulfate ions, characterized in that the impurities in the porous organic-inorganic hybrids are purified by treating the porous organic-inorganic hybrids using the inorganic salt. Adsorbent containing a crystalline porous organic-inorganic hybrid to be.
  8. The method of claim 1, wherein the porous organic-inorganic hybrid is any one selected from the group consisting of chromium terephthalate, iron terephthalate, aluminum terephthalate, copper terephthalate, vanadium terephthalate, and manganese terephthalate, or a mixture thereof. Adsorbent containing a crystalline porous organic-inorganic hybrid to be.
  9. The method of claim 1, wherein the porous organic-inorganic hybrid is M 3 O (H 2 O) 2 Cl 1-x OH x [C 6 H 3- (CO 2 ) 3 ] 2 nH 2 O (n ~ 14.5), (0 <x <1, M = Cr, Fe, Al, Cu, Mn and V) Adsorbent containing a crystalline porous organic-inorganic hybrid, characterized in that.
  10. The method of claim 1, wherein the porous organic-inorganic hybrid is M 3 Cl 1-x OH x (H 2 O) 2 O [C 6 H 4 (CO 2 ) 2 ] 3 nH 2 O (n ~ 25) (0 <x <1, M = Cr, Fe, Al, Cu, Mn and V) Adsorbent containing a crystalline porous organic-inorganic hybrid, characterized in that.
  11. The adsorbent of claim 1, wherein the porous organic / inorganic hybrid is in the form of nanoparticles, powders, thin films, honeycomb pellets, rotors, or membranes.
  12. A water absorbent, wherein the water absorbent is adsorbed using the adsorbent of claim 1.
  13. The water absorbent according to claim 12, wherein the adsorbent is capable of adsorbing 0.1 to 1 g of adsorbent per 1 g of adsorbent at 10 to 100 ° C.
  14. The water absorbent of claim 12, wherein the adsorbent is easily desorbed at 10 to 100 ° C.
  15. Adsorbent, characterized in that used for the adsorption of volatile organic compounds (VOCs) in the vapor or particulate form using the adsorbent of claim 1.
  16. The adsorbent of claim 1 is used for adsorption of one or more vapor or particulate matter selected from the group consisting of formaldehyde, acetaldehyde, tar, nitrosoamines and polycyclic aromatic hydrocarbons, which cause sick house syndrome. Adsorbent, characterized in that.
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KR20190061338A (en) 2017-11-27 2019-06-05 연세대학교 산학협력단 Organic-inorganic hybrid particles, porous materials for storing mathane comprising the same and method of preparing the same
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KR20190123944A (en) 2018-04-25 2019-11-04 연세대학교 산학협력단 A carbon monoxide adsorbents with carbon monoxide selectivity and manufacturing method of the same
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KR101333182B1 (en) 2011-11-25 2013-11-27 부산대학교 산학협력단 Porous composite for removing volatile organic compounds and ozone catalytic oxidation reactor using the composite
KR20190061338A (en) 2017-11-27 2019-06-05 연세대학교 산학협력단 Organic-inorganic hybrid particles, porous materials for storing mathane comprising the same and method of preparing the same
KR20190061326A (en) 2017-11-27 2019-06-05 연세대학교 산학협력단 a separation adsorbent with olefins sorption selectivity and manufacturing method of the same
KR20190123944A (en) 2018-04-25 2019-11-04 연세대학교 산학협력단 A carbon monoxide adsorbents with carbon monoxide selectivity and manufacturing method of the same
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