CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national phase application under 35 U.S.C. § 371 of International Application No. PCT/KR2016/005276 filed May 18, 2016, which claims the benefit of priority of Republic of Korea Patent Application No. 10-2015-0069157 filed May 18, 2015. The contents of each of the above-referenced applications are incorporated into the present application by reference.

TECHNICAL FIELD

The present disclosure relates to a water and/or alcohol adsorbent including organic-inorganic hybrid nanoporous materials, and use thereof.

BACKGROUND ART

In general, organic-inorganic hybrid nanoporous materials are also called as “porous coordination polymers” [Angew. Chem. Intl. Ed., 43, 2334. 2004], or “metal-organic frameworks” [Chem. Soc. Rev., 32, 276, 2003]. The organic-inorganic hybrid nanoporous materials have been newly developed through integration of molecular coordination bond and material science. The organic-inorganic hybrid nanoporous materials have a large surface area and molecular-sized or nano-sized pores, and thus can be used not only for an adsorbent, a gas storage material, a sensor, a membrane, a functional thin film, a drug delivery material, a catalyst, a catalyst carrier, etc., but also for encapsulating guest molecules smaller than their pore size or separating molecules according to the sizes of the molecules by using their pores. Thus, the organic-inorganic hybrid nanoporous materials have been actively studied.

In particular, the organic-inorganic hybrid nanoporous material can be defined as a porous organic-inorganic polymer compound formed by bonding a central metal ion to an organic ligand, and the organic-inorganic hybrid nanoporous material refers to a crystalline compound with molecular-sized or nano-sized pores, including both organic material and inorganic material in its framework structure. In the organic-inorganic hybrid nanoporous material, a polar metal ion and a carboxylate oxygen anion are both included in its crystalline framework, and a non-polar ligand aromatic compound group coexists therein, and therefore, hydrophilicity and hydrophobicity are exhibited at the same time.

Meanwhile, an adsorbent that can easily adsorb and desorb water has various applications. For example, the adsorbent can be utilized in a water adsorption heat pump which is used for heating and cooling of industrial, medium-large sized buildings, and houses by heat energy generated or absorbed upon water adsorption/desorption of the adsorbent installed in a closed system. When solar heat, industrial waste heat, geothermal heat, etc. of 100° C. or lower is used for regeneration of the water adsorbent during operation of the water adsorption heat pump, CO2generation can be greatly reduced and energy efficiency can be increased, and therefore, it is expected to gain interest as a future environment-friendly energy-saving technology. Further, a dehumidifier may utilize the adsorbent having a property of adsorbing water at low temperature and desorbing water when it is heated to high temperature. In addition, in case where the adsorbent is used in coolers/heaters, during heating operation, the adsorbent can act as a humidifier by adsorbing the outdoor moisture of low temperature to introduce the moisture to the inside, and desorbing it in the indoor where the temperature is high, and during cooling operation, the adsorbent can achieve a comfortable indoor atmosphere by adsorbing the indoor moisture of low temperature, taking it to the outside and desorbing it in the outdoor where the temperature is high. These cooling-heating systems or adsorption heat pumps have been paid much attention as an environment-friendly technology in terms of energy efficiency. The US-Department of Energy estimated that these cooling-heating systems could reduce annual energy consumption by 117.2 million MWh and carbon dioxide emissions by 6 million tons [Desiccant Cooling: State of Art Assessment. October 1992, Ahmed Pasaran et al. NREL]. As these cooling-heating systems are simply operated and inexpensive to manufacture, they have the potential to capture a significant portion of the total $32 billion worldwide air-conditioning market.

Commercially, an adsorbent such as silica gel or zeolite (silico-alumino-phosphate) SAPO-34 is used in the water adsorption cooler and heating pump, but the adsorbent is required to have a high water adsorption amount at a temperature of 20˜40° C. and a low relative humidity and a high water desorption amount at 100° C. or lower in order to increase energy efficiency. To this end, there is a need to develop a new type of a porous water adsorbent. Air-conditioners and humidity controllers applying ideas of the cooling-heating systems have been suggested in U.S. Pat. Nos. 6,978,635, 6,959,875, 6,675,601, etc. However, these patents do not describe the adsorbent used in such devices in detail, but only mention that silica gel, zeolite, ion exchange resin are used, or that an adsorbent is used. In addition, such adsorbents not only have a low adsorption amount, but also cause the operation costs to rise by requiring a high temperature of 100° C. or higher for desorption.

Until now, activated carbon and hydrophobic zeolite have been mainly used as adsorbents that can remove organic compounds present in an indoor space. Further, inorganic porous materials such as zeolite, metal phosphate, mesoporous, clay, etc. have been mainly reported as water adsorption materials (Microporous and Mesoporous Materials 114 (2008) 1-6). Since activated carbon has a very large specific surface area due to a number of nanopores and has a strong adsorption strength to non-polar molecules, it has an excellent effect in removing exhaust gas and removing smell and color, whereas zeolite is a hydrophilic adsorbent having a pore diameter of about 3 to 10 Å and thus has a strong adsorption property to carbon monoxide, carbon dioxide, and water.

On the other hand, Korean Patent No. 806,586 has suggested organic-inorganic hybrid nanoporous materials capable of adsorbing and desorbing water even at low temperature. However, the organic-inorganic hybrid nanoporous materials have to be crystallized such that they have a surface area of 1,000 m2/g or greater and a pore volume of 1.0 ml/g or greater. Accordingly, there is a disadvantage that an additional purification process is required, leading to very high manufacturing costs. There is also a disadvantage that the adsorbent exhibits sufficient adsorption capacity at a high relative humidity, but exhibits low adsorption capacity at a low relative humidity.

Meanwhile, J. Am. Chem. Soc. 2009, 131, 2776-2777 reported application of ISE-1{[Ni3(μ3-btc)2)(μ4-btre)2(μ-H2O)2].˜22H2O}(benzene-1,3,5-tricarboxylate (btc), 1,2-bis(1,2,4-triazol-4-yl)ethane (btre)) as an organic-inorganic hybrid nanoporous material to the adsorbent for the heat pump. However, there is a disadvantage that this organic-inorganic hybrid nanoporous material is very expensive, toxic due to the presence of nickel, and a complex ligand is used in the preparation process. There is also a disadvantage that a difference between water adsorption and desorption amounts is relatively small, and thus it is difficult to apply the organic-inorganic hybrid nanoporous material to the adsorbent for the heat pump using a low-temperature heat source of 95° C. or lower.

Further, US Patent Publication No. 2012/0251438 discloses an organic-inorganic hybrid nanoporous material applicable to gas separation or storage and also applicable to removal of gas-phase water from water-containing natural gas, in which a central metal ion is an aluminum ion, a magnesium ion, an iron ion, a zinc ion, or a copper ion, and a ligand is furan dicarboxylic acid anion or thiophene dicarboxylic acid anion. However, this patent does not disclose information about chemical formula and pore structure of the synthesized hybrid nanoporous material. As disclosed in the patent, a water adsorption isotherm of the hybrid nanoporous material named Al-2,5-Thiophene dicarboxylic acid MOF, which is synthesized from aluminum and thiophene dicarboxylic acid, shows that the water adsorption amount increased linearly with a low slope at a relative humidity from 15% to 55%, and the water adsorption amount at a relative humidity of 35% is only 12% by weight or less. Therefore, the organic-inorganic hybrid nanoporous material is not suitable as the adsorbent for the water adsorption heat pump.

International Patent Application No. WO 2004/113227 discloses an adsorbent including zeolite, and a humidity controlling device and a heat pump including the same. A method of increasing efficiency of a water adsorbent-applied system such as a dehumidifier, a dryer, a heat pump, etc. includes a method of optimizing the system or a method of optimizing operation conditions. However, these methods are not fundamental solutions to improvement of the system efficiency, and there is a demand for a water adsorbent having a high adsorption amount at a low relative humidity, of which desorption/regeneration is possible at a low temperature.

DISCLOSURE OF INVENTION

Technical Problem

An object of the present invention is to provide a water and/or alcohol adsorbent having a high adsorption amount at a low relative humidity or partial pressure, of which desorption/regeneration is possible at a low temperature, and use thereof.

Solution to Problem

An aspect of the present invention provides an adsorption heat transfer device using water or alcohol as a working fluid, the adsorption heat transfer device including, as a water adsorbent or an alcohol adsorbent, organic-inorganic hybrid nanoporous materials having 0.5 to 3 mol of a hydrophilic hydroxyl group (OH) or a hydroxide anion (OH−) group as a ligand per 1 mol of a central metal ion in a nanopore.

Another aspect of the present invention provides an adsorption water controlling device including, as a water adsorbent, organic-inorganic hybrid nanoporous materials having 0.5 to 3 mol of a hydrophilic hydroxyl group (OH) or a hydroxide anion (OH−) group as a ligand per 1 mol of a central metal ion in a nanopore.

Still another aspect of the present invention provides an organic light emitting device or a secondary battery device including, as a getter, organic-inorganic hybrid nanoporous materials having 0.5 to 3 mol of a hydrophilic hydroxyl group (OH) or a hydroxide anion (OH−) group as a ligand per 1 mol of a central metal ion.

Still another aspect of the present invention provides a water or alcohol adsorbent including organic-inorganic hybrid nanoporous materials having 0.5 to 3 mol of a hydrophilic hydroxyl group (OH) or a hydroxide anion (OH−) group as a ligand per 1 mol of a central metal ion in a nanopore.

Still another aspect of the present invention provides an organic-inorganic hybrid nanoporous material having a structure of an orthorhombic space group or a tetragonal space group, the organic-inorganic hybrid nanoporous material including 0.5 to 3 mol of a hydrophilic hydroxyl group (OH) or a hydroxide anion (OH−) group as a ligand per 1 mol of a central metal ion in a nanopore.

Still another aspect of the present invention provides an organic-inorganic hybrid nanoporous material represented by any one of the following Chemical Formulae 1 to 8:
[Al(OH)[(O2C)—C4OH2—(CO2)]·n(solvent)  [Chemical Formula 1]
[Al(OH)[(O2C)—C4OH2—(CO2)]  [Chemical Formula 2]
[Al(OH)[(O2C)—C5NH3—(CO2)]·n(solvent)  [Chemical Formula 3]
[Al(OH)[(O2C)—C5NH3—(CO2)]  [Chemical Formula 4]
[Al(OH))[(O2C)—C4SH2—(CO2)]·n(solvent)  [Chemical Formula 5]
[Al(OH)[(O2C)—C4SH2—(CO2)]  [Chemical Formula 6]
Al2(OH)4[(O2C)—C3N2H2—(CO2)]·n(solvent)  [Chemical Formula 7]
Al2(OH)4[(O2C)—C3N2H2—(CO2)]  [Chemical Formula 8]

in Chemical Formula 1, the solvent is H2O, and n is a real number of 0.1 to 10,

in Chemical Formula 3, the solvent is H2O, an organic solvent such as DMF, or a combination thereof, and n is a real number of 0.1 to 10,

in Chemical Formula 5, the solvent is H2O, an organic solvent such as DMF, or a combination thereof, and n is a real number of 0.1 to 10, and

in Chemical Formula 7, the solvent is H2O, and n is a real number of 0.1 to 10.

Advantageous Effects of Invention

According to the present invention, provided is a water and/or alcohol adsorbent having a high adsorption amount at low relative humidity or partial pressure, of which desorption/regeneration is possible at a low temperature, the water and/or alcohol adsorbent including organic-inorganic hybrid nanoporous materials having 0.5 to 3 mol of a hydrophilic hydroxyl group (OH) or a hydroxide anion (OH−) group per 1 mol of a central metal ion in a nanopore. The adsorbent may be usefully applied to an adsorption refrigerator, a dehumidifier, a solar cooling system, a heat pump, a dryer, an organic light emitting device, or a secondary battery device.

