KR101176878B1 - Metal-organic framework with stepwise and hysteretic gas sorption properties and its use for gas storage material and method for manufacturing the same - Google Patents

Abstract

The present invention relates to an infiltrating 3D framework that adsorbs gas even at low pressure, and more particularly, is a 3D metal-organic framework or solvate thereof represented by the formula (1). In the metal-organic framework of the present invention, gas adsorption and desorption is stepwise and hysteresis, and shows a good gas adsorption amount at various pressures as well as low pressure. The metal-organic framework of the present invention can be usefully used in the fields of adsorption and separation, ion exchange, catalyst, sensor, crystallographic design, and the like as a gas reservoir.

Metal-organic framework, hysteresis, staged, low pressure gas adsorption

Description

Metal-organic framework with step-and-hysteresis gas adsorption and desorption properties, and a method for producing a gas-storage and metal-organic framework comprising the same {metal-organic framework with stepwise and hysteretic gas sorption properties and its use for gas storage material and method for manufacturing the same}

The present invention relates to a 3D metal-organic framework that adsorbs gas even at low pressure, and more particularly, is an infiltrating 3D metal-organic framework or a solvate thereof represented by [Formula 1], having a hysteresis and low pressure. It relates to 3D metal-organic frameworks and solvates thereof that can adsorb gases at various pressures, including ranges, and exhibit staged and hysteresis gas adsorption and desorption properties.

Metal-organic frameworks (MOFs) are a type of coordination polymer compound composed of metal salts and organic ligands, ranging from linear primary, plate-like secondary, and complex three-dimensional structures. Form various coordination structures. When such metal-organic frameworks have permanent porosity, they have been widely studied because they have potential applications in various fields such as molecular adsorption and separation processes, optoelectronics and the like.

The purpose of building MOFs is to obtain materials with characteristic and multifunctional properties. In particular, selective adsorption and separation of organic molecules [(a) Chen, B. Liang, C. Yang, J. Contreras, DS Clancy, YL Lobkovsky, EB Yaghi, OM Dai, S. Angew . Chem. Int. Ed. 2006, 45, 1390-1393. (b) Choi, HJ Suh, MP J. Am. Chem. Soc. 2004, 126, 15844-15851], formation of metal nanoparticles [(a) Cheon, YE; Suh, MP Chem . Eur . J. 2008, 14, 3961. (b) Schröder, F .; Esken, D .; Cokoja, M .; van den Berg, MWE; Lebedev, OI; Van Tendeloo, G .; Walaszek, B .; Buntkowsky, G .; Limbach, H.-H .; Chaudret, B .; Fischer, RA J. Am. Chem. Soc. 2008, 130, 6119], storage of gases [Lee, YG; Moon, HR; Cheon, YE; Suh, MP Angew . Chem . 2008, 120 , 7855-7859; Angew . Chem ., Int . Ed . 2008, 47 , 7741-7745] and isolated [Cheon, YE; Suh, MP Chem . Eur . J .2008, 14, 3961-3967], ion-exchange [Min, KS; Suh, MP J. Am . Chem . Soc . 2000, 122, 6834-6840 and sensor technology [Chen, B .; Wang, L .; Zapata, F .; Qian, G .; Lobkovsky, EB J. Am . Chem . Soc . 2008, 130 , 6718-6719], and the potential to apply. However, in the prior art, since the gas was not adsorbed at low pressure, there was a limit in using the gas for storage and separation, ion exchange, and sensors.

Therefore, the development of flexible, dynamic, permanently porous MOFs capable of adsorbing gases at low pressures, which possess single crystals and can change their structure in response to external stimuli is important for the development of specific designs and sensors. .

Accordingly, the present invention changes the structure in response to an external stimulus and adsorbs gas even at low pressure, so that the porous porous 3D metal-organic skeleton can be used for gas separation device, gas storage device, ion exchange device and sensor more effectively. To provide a sieve.

The present invention relates to a metal-organic framework or solvate thereof which is an interpenetrated 3D framework represented by the following [Formula 1].

{[M ₂ (L1) ₂ (L2)] X (Sol1)? Y (Sol2)} _n

Wherein M is a metal selected from the group consisting of Zn, Cu, Cd and Mn; L 1 is a ligand selected from the group consisting of BPnDC, OBA and CPMA; L2 is a ligand selected from the group consisting of bpy, bpe, bpea and bpt; Sol1 and Sol2 are each selected from DEF, MeOH, DMF, DMA, and MeCN; X and Y are each an integer from 0-20; n is an integer of at least 0; The framework (or solvate) has a double interpenetrating structure.

The metal-organic framework of the present invention forms an interpenetrating 3D framework, showing three stages of adsorption isotherms with hysteresis for nitrogen and oxygen gases and two steps with hysteresis for hydrogen and carbon dioxide, depending on the pressure. Adsorption isotherm is shown. This step adsorption behavior and hysteresis during desorption make it more difficult to discharge than when the skeleton is used as a gas reservoir, and consequently extends the period in which physical properties such as gas storage capacity and gas separation capacity can be maintained. Can be seen. In addition, gas adsorption of nitrogen, oxygen, hydrogen and carbon dioxide is possible at low pressures. Such a metal-organic framework of the present invention can be usefully used in the fields of adsorption and separation, ion exchange, catalyst, sensor, crystallographic design, etc. as a gas reservoir.

DETAILED DESCRIPTION OF THE INVENTION The present invention is a dual interpenetrating 3D skeleton having excellent gas absorption capacity at various pressures, including low pressures, having a permanent porosity and a good surface area, and relates to metal-organo-metal-organic for gas devices and sensors. In addition, the metal-organic framework of the present invention, whose structure changes in response to external stimuli, has functions such as switching, sensing, and information storage, and as a result, certain devices (gas separation device, gas storage device, and ion) Exchangers, etc.) and sensors.

On the other hand, the inventor of the present invention has prepared a [M ₂ (LIG1) ₂ (LIG2)] framework using DMF and EtOH solvent (LIG1 = BPnDC, bis (4-carboxyphenyl) methane, N, N- LIG2 = pyrazine, 4-4'-bipyridine, 4-diazabicyclo [2,2,2] octane, etc., such as bis (4-carboxyphenyl) amine). However, this framework is a non-invasive structure that is not interpenetrating, and two metal ions are bound together by four different carboxy ligands in the form of an outer ring to form a secondary or three-dimensional structure. Are combined to form a structure that extends or connects in the vertical direction.

On the other hand, in the metal-organic framework of the present invention, two metal ions combine with two carboxy ligands and a pyridine ligand to form a two-dimensional planar structure, and then two carboxy ligands connect the two-dimensional planar structure. It is bound as a role and expanded to a three-dimensional structure. The structure may be similar to the above non-invasive framework, but the structure of the four carboxy ligands does not form two ring ions in the outer ring type in the bonding method. Can be said to be completely different. In addition, it is a completely different compound in that two basic frameworks that are independent of each other in addition to each other in addition to the difference in the binding method and the structure of the framework are completely different. As a result, the properties of the framework are also very different. Do.

As such, in general, even if two frameworks have the same chemical formula, this only means that the composition of atoms or molecules in the two frameworks is the same, and does not mean that the structures and physical properties are the same. For example, even though the metal-organic framework has the same chemical formula, there may be a 'non-penetrating' metal-organic framework and a 'double interpenetrating' metal-organic framework having different X-ray crystal structures. These two skeletons differ greatly in their macroscopic or microscopic structure, including the crystal structures identified by X-rays, and the physical properties such as surface area, pore size and distribution, and gas adsorption capacity are greatly different.

The difference in the structural properties is mainly due to the difference in reaction conditions and process order for preparing the skeleton, and in particular, the product of the interpenetrating framework can be confirmed when prepared according to the present invention. However, the present invention should not be construed as being included in the scope of rights as long as it is a metal-organic skeleton having a composition of a chemical formula within the scope of the present invention and exhibiting 'interpenetrating' structure, without being limited to such a preparation method, and specific reaction conditions Obviously, the process conditions, solvent conditions and the like cannot be interpreted.

Hereinafter, the present invention will be described in detail. Metal-organic frameworks often decay when the object molecules that occupy their space are removed, are easily destroyed under vacuum at high or even low temperatures due to heat instability, often dissolved in solvents and dissociated into building units On the other hand, the metal-organic frameworks according to the invention have this instability resolved and have a substantially permanent porosity. Therefore, in the present invention, the expression "permanent porous framework" and the like refers to a framework in which such instability is resolved to obtain a substantially permanent porosity, and has a permanent porosity under any extreme conditions or a condition such as heat. It does not mean absolute stability that is not destroyed at all. Whether the metal-organic framework is substantially permanently porous or otherwise easily decomposed due to temperature, pressure, or solvent conditions can be easily determined through simple experiments. As it is widely used in the field, it will be easily understood by those skilled in the art.

The present invention increases the adsorption amount of nitrogen, carbon dioxide and methane gas as well as hydrogen by producing a long organic linker (linker) and having a double interpenetrating metal-organic framework having a large surface area and large pore volume.

In the present invention, the term 'penetration' or 'interpenetrated' structure is used in the meaning and widely understood in the art, and refers to a structure in which one linear unit is physically bonded to another unit without chemical bonding. do.

One aspect of the present invention relates to a 3D metal-organic framework or a solvate thereof represented by the following [Formula 1].

[Formula 1]

{[M ₂ (L1) ₂ (L2)] X (Sol1)? Y (Sol2)} _n

Wherein M is a metal selected from the group consisting of Zn, Cu, Cd and Mn; L 1 is a ligand selected from the group consisting of BPnDC, OBA and CPMA; L2 is a ligand selected from the group consisting of bpy, bpe, bpea and bpt; Sol1 and Sol2 are each selected from DEF, MeOH, DMF, DMA, and MeCN; X and Y are each an integer from 0-20; n is an integer of 0 or more and the framework or solvate has a double interpenetrating 3D structure.

According to an embodiment of the present invention, the metal-organic skeleton of [Formula 1] has a Langmuir surface area of 100-3500 m ² / g, preferably 200-2800 m ² / g; The BET surface area is 100-2000 m ² / g, preferably 200-1800 m ² / g; Pore volume is 0.05-4.5 cm ² / g, preferably 0.08-3.0 cm ² / g; The pore diameter is 3-20 mm 3, preferably 5-18 mm 3.

In addition, the metal-organic framework of [Formula 1] can adsorb gas even at low pressure, and adsorb gas at 77-310 K and 0.0001-110 bar.

The metal-organic framework of [Formula 1] may adsorb oxygen and nitrogen gas in three stages, and hydrogen and carbon dioxide may adsorb in two stages.

Oxygen gas is 9-27 wt%, preferably 11-25 wt% at ① 0.00035-0.003 bar at 75-90 K, ② 20-35 wt% at preferably 0.005-0.08 bar, preferably 21-28 wt% % And ③ are adsorbed at 33-59% by weight, preferably 37-54% by weight, at 0.1-1.0 bar. The nitrogen gas is 4-12% by weight at 1 .00505-0.003 bar, preferably 6-10% by weight, 77-90 K, 11-30% by weight at 0.005-0.3 bar, preferably 13-28% by weight. % And ③ adsorbed at 28-35% by weight, preferably 29-34% by weight, at 0.7-1.2 bar. The hydrogen gas is 0.5-2.5% by weight, preferably 0.5-2.0% by weight at 10-25 bar, at 75-80 K, 2-7.5% by weight, preferably 4.5-7% at 70-100 bar. % Is adsorbed. Carbon dioxide is 8-15% by weight at 0.05-0.25 bar, preferably 9-14% by weight at 180-280 K, 1-50% by weight at 0.5-10 bar, preferably 2-45% by weight. 8-13% by weight at 785 bar, preferably 9-11% by weight at 285-300K, 22-36% by weight at 35-45 bar, preferably 25-33% by weight. Is adsorbed.

In the present invention, there is a case where a certain range of physical properties such as surface area and pore volume are described as a representation of a preferred embodiment, and such physical properties must have a limited range in the present invention, and thus the interpenetrated 3D of the present invention Forming a framework can be usefully used in the fields of adsorption and separation, ion exchange, catalysts, sensors, crystallographic design, and the like as gas reservoirs as the desired embodiments of the present invention are intended.

Although the physical properties in the above ranges could not be achieved at all in the metal-organic framework of the same structure in the past, the physical properties could be prepared by following the specific process described in the Examples of the present invention, but the present invention is It cannot be interpreted as being limited by the manufacturing method, and it can be said that it can be said that it contains all the compounds which have the said structure and satisfy | fill the said physical property.

In the present invention, BPnDC is benzophenone 4,4'-dicarboxylic acid, OBA is 4,4'-oxybisbenzoic acid, and CPMA is bis (4-carboxyphenyl) -N-methylamine ), bpy is 4,4'-bipyridine, bpe is trans-1,2-bis (4-pyridyl) ethylene, bpea is 1,2-bis (4-pyridyl) ethane, bpt is 3,5- Bis (pyridin-4-yl) -1,2,4-triazole, DEF means diethylformamide.

According to one embodiment of the present invention, the metal-organic skeleton of [Formula 1] relates to a metal-organic skeleton represented by the following [Formula 2].

[M ₂ (BPnDC) ₂ (bpy)] n

The metal-organic skeleton of [Formula 2] has a Langmuir surface area of 200-2000 m ² / g, BET surface area of 200-1500 m ² / g, pore volume of 0.1-1.5 cm ² / g, pore diameter of 4 It is preferable that it is -15 Hz.

In addition, the metal-organic framework of [Formula 2] may adsorb gas at 77-310 K and 0.0003-110 bar.

The metal-organic skeleton of [Formula 2] is 10-23% by weight, preferably 12-22% by weight, when the oxygen gas is ① 0.0004-0.0025 bar at 75-90 K, ② 20 when 0.01-0.06 bar Adsorb 35-55% by weight, preferably 37-53% by weight at -30% by weight, preferably 21-28% by weight and ③ 0.15-0.8 bar.

In addition, the metal-organic skeleton of [Formula 2] is 6-9% by weight, preferably 6-8% by weight, and ② 0.01-0.1 bar when nitrogen gas is ① 0.0009-0.003 bar at 77-90 K. Adsorb 29-34% by weight, preferably 30-33% by weight at -25% by weight, preferably 16-23% by weight and ③ 0.8-1.0 bar.

In addition, the metal-organic framework of [Formula 2] is 0.7-2.0% by weight, preferably 0.9-1.5% by weight and ② 80-95 bar when hydrogen gas is ① 13-22 bar at 75-80 K. -7% by weight, preferably 5-7% by weight adsorption.

In addition, the metal-organic framework of [Formula 2] is 9-15% by weight, preferably 10-14% by weight, and 0.5-10 bar at 1,05-0.25 bar of carbon dioxide at 180-280 K. Adsorbs 50% by weight, preferably 4-45% by weight, 8-12% by weight at 785 bar, preferably 9-11% by weight at 285-300K, 25- at 35-45 bar. 36% by weight, preferably 26-33% by weight adsorption.

As shown above, it shows three-stage adsorption isotherms with notable hysteresis for nitrogen and oxygen gas, and two-stage adsorption isotherms for hydrogen and carbon dioxide.

The metal-organic skeleton of [Formula 2] is preferably prepared by heating the solvate of [Formula 3] under a vacuum of 40-80 ° C. for 1-3 hours to desolvate it.

{[M ₂ (BPnDC) ₂ (bpy)]? 6MeOH} n

The metal-organic skeleton of [Formula 3] has a Langmuir surface area of 300-2000 m ² / g, BET surface area of 300-1400 m ² / g, pore volume of 0.1-1.4 cm ² / g, pore diameter of 4 It is preferable that it is -13 Hz.

[Formula 4] is prepared by dissolving H ₂ BPnDC and bpy ligand in DEF and M (NO ₃ ) _{2 ~} 6H ₂ O dissolved in MeOH mixed with each other and heated to 60-100 ℃ for 20-28 hours, The metal-organic framework of [Formula 3] is preferably prepared by a guest molecule modification of exchanging DEF and MeOH with MeOH of [Formula 4], which is caused by a desolvent.

{[M ₂ (BPnDC) ₂ (bpy)]? 2DEF? 2MeOH} n

The metal-organic framework of [Formula 4] has a Langmuir surface area of 300-2000 m ² / g, BET surface area of 200-1400 m ² / g, pore volume of 0.2-1.4 cm ² / g, pore diameter of 4 It is preferable that it is -14 Hz.

As can be seen in the examples of the present invention, the structure of the framework is reversibly changed by the fact that the framework of the invention is soft and by removal or reintroduction of guest molecules.

Another aspect of the present invention is a gas device using a gas reservoir containing the metal-organic skeleton of the formula [1] includes a gas device such as a gas storage device, gas separation device, gas sensor device and ion exchange device do.

The gas is particularly preferably selected from nitrogen, carbon dioxide, methane, hydrogen, oxygen and mixtures thereof. In particular, as confirmed in the following experimental example, the selective gas adsorption and desorption characteristics of the carbon dioxide to methane gas of [Formula 2] can be usefully applied to the gas separation system.

The following Examples are intended to specifically explain the contents of the present invention, whereby the scope of the present invention is never limited and can be interpreted.

In particular, if a compound belonging to the present invention is not described in the following Preparation Examples, Examples, and Experimental Examples, based on the disclosure of the present invention, those skilled in the art to which the present invention pertains are based on common knowledge in the art. It can be said that it can be easily manufactured and obtained.

Example

In the examples below, all chemicals and solvents used in the synthesis were used as reagent grade without further purification. Infrared spectroscopy was recorded with a Perkin Elmer Spectrum One FT-IR spectrophotometer, and elemental analysis was performed with a Perkin-Elmer 2400 Series II CHN analyzer. In addition, thermogravimetric analysis (TGA) was performed under N ₂ at a scanning rate of 5 ° C./min using TA Instruments' TGA Q50 and DSC Q10, respectively, and high resolution powder X-ray diffraction (PXRD) data were obtained. Measurement was performed on beamline 11A1 PXS using a synchrotron radiation source ( l = 1.22152 Hz, scan speed = 0.01 ^o / sec, step size = 0.01 ^o in 2θ).

Example  One: {[ Zn ₂ ( BPnDC ) ₂ (bpy)]? 2 DEF ?2 MeOH } n (1)

BPnDC (0.054 g, 2.0 x 10 -4 mol) and bpy (0.016 g, 1.1 x 10 -4 mol) was dissolved in a DEF (6 mL), Zn ( NO 3) 2? 6H 2 O (0.080 g, 2.7 x 10 ^-4 mol) was dissolved in MeOH (3 mL). The solutions were mixed with each other, tightly capped with a silicone stopper and an aluminum seal, placed in a glass serum bottle and heated at 80 ° C. for 24 hours. Upon cooling to room temperature, colorless rod-like crystals formed which were filtered off and simply washed off with methanol.

Yield: 0.08 g (67%). FT-IR (Nujol mull) for (1): ν _OH , 3608, 3468; ν _{C═O ( DEF )} , 1670; ν _{C═O ( BPnDC )} , 1658; ν _{C═C ( aromatic )} , 1607; ν _{OC = O ( carboxylate )} , 1558 cm ⁻¹ . Elemental Analysis for Zn ₂ C ₅₂ H ₅₄ O ₁₄ N ₄ (calculated): C, 57.31; H, 4.99; N, 5.14. Found: C, 56.63; H, 4.52; N, 5.10.

Example  2: {[ Zn ₂ ( BPnDC ) ₂ (bpy)]? 6 MeOH } n (2)

The crystal of (1) was immersed in methanol for 10 hours and the solvent was discarded. The crystals were further immersed for 12 hours to replenish fresh methanol and replace all DEF guest molecules with MeOH.

FT-IR (Nujol mull) for (2): ν _OH , 3369; ν _{C═O (BPnDC)} , 1659; ν _{C = C (aromatic)} , 1607; ν _{OC = O (carboxylate)} , 1557 cm ^-1 _. Elemental Analysis for Zn ₂ C ₄₄ H ₄₄ O ₁₆ N ₂ (calculated): C, 52.55; H, 4.61; N, 2.79. Found: C, 52.93; H, 4.76; N, 2.79.

Example  3: [ Zn ₂ ( BPnDC ) ₂ (bpy)] n (3)

(2) Heated in vacuum at 60 ° C. Schlenk tube for 1.5 h.

FT-IR (Nujol mull): ν _{C═O ( BPnDC )} , 1667; ν _{C═C ( aromatic )} , 1609; ν _{OC = O ( carboxylate )} , 1588 cm ⁻¹ . Elemental Analysis for Zn ₂ C ₄₀ H ₂₄ O ₁₀ N ₂ (calculated): C, 58.35; H, 2.94; N, 3.40. Found: C, 57.70; H, 2.71; N, 3.39.

Experimental Example  1. Gas adsorption and desorption according to pressure

1-1: low pressure gas Adsorption and desorption  Research

Gas adsorption-desorption experiments were performed with an automated micropore gas analyzer Autosorb-1 or Autosorb-3B (Quantachrome Instruments). The synthesized crystal of (2) was introduced directly into the gas-adsorption and desorption apparatus, and the degassing process was performed by heating the sample at 60 ° C. under vacuum for 1.5 hours. At this time, all the gases used were 99.999% pure.

Nitrogen and oxygen gas adsorption and desorption isotherms were measured at 77 K and 87 K, and hydrogen isotherms were measured at 77 K. Carbon dioxide and methane gas adsorption and desorption isotherms were measured at 195 K at each equilibrium pressure by a stationary volumetric method.

After each gas adsorption and desorption measurement, the sample weight was again measured accurately. Surface area and total pore volume were also determined from N ₂ adsorption isotherms at 77 K. Multi-point BET (Brunauer-Emmett-Teller) and Lange for the evaluation of specific surface area data is Muir each P / P ₀ = 0.040-0.16 and P / P ₀ = 0.029 to 0.31 was obtained in the range.

1-2: high pressure gas Adsorption and desorption  Measure

High pressure gas adsorption and desorption isotherms for (3) were measured by gravimetric method using a Rubotherm MSB (magnetic suspension balance) instrument. All gases used were 99.999% pure. Hydrogen adsorption and desorption isotherms were measured at 77 K and 298 K, while carbon dioxide and methane adsorption and desorption isotherms were measured at 298 K.

Solid (2) was heated in a 60 ° C. Schlenk tube under vacuum for 2 hours, and the dried solid was accurately measured and introduced into a gas adsorption and desorption instrument, and activated at 60 ° C. under vacuum. He isotherms (up to 90 bar) were measured at 298 K to obtain the volume of the skeletal framework prior to gas adsorption and desorption measurements. The data were corrected for buoyancy by measuring excess adsorption and desorption isotherms and multiplying the density of the gas corresponding to each pressure and temperature by the volume of the skeleton skeleton (3). In converting the weight data (% by weight) into volume data (g / L), the crystallographic density of desolvated (2) ( d = 1.106 g / cm ³ ) was applied.

Experimental Example  2. X-ray crystallography

(One) And the diffraction data of (2) are Quantum 210 CCDs with synchrotron radiation (λ = 0.79998 for (1) and λ = 82655 for (2)) at Pohang Accelerator Laboratory (PAL) Polymer Crystallography II 6C1. Collected at 100 K with a diffractometer. The crystals were covered with Paraton oil to prevent loss of guest molecules, and the crystals rotated through a total of 360 ^° . Raw data was processed and scaled using the program HKL2000. Crystal structures were analyzed in detail by full-matrix least-squares analysis using the SHELXL - 97 computer program. Positions without hydrogen atoms were purified with anisotropic substitutions. Hydrogen atoms were geographically located using the riding model. (One) And the density of the disordered guest molecules in (2) was flattened using PLATON's SQUEEZE option.

Experimental Example  3. X-ray structure and properties of solids (1), (2) and (3)

Of a colorless crystal of (1) at 80 ℃ for 24 hours of _{Zn (NO 3) 2? 6H} 2 O, H 2 BPnDC (benzophenone4,4'-dicarboxylicacid) and 4,4'-bipyridine (bpy) on DEF / MeOH It synthesize | combined from the solvent heat reaction. In Fig. 1, the single crystal X-ray structure of (1) shows a double interpenetrating 3D coordination network. The differences in the metal ions or types of pillars connecting the Zn ₂ cluster units have a significant impact on the framework structure. In (1), there are two other Zn atoms (Zn ₁ and Zn ₂ ) in the asymmetric unit. Zn ₁ has three different BPnDC ^{2 -} is coordinated with three oxygen atoms and one nitrogen atom of the ligand bpy from looks three-dimensional structure of the tetrahedron. Zn ₂ coordinates five oxygen atoms in one nitrogen atom and four other BPnDC ^2- ligands in bpy to form an octahedral conformation. The Zn-O _BPnDC ^2- bond distance averaged 2.073 (1) Å and the Zn-N _bpy bond distance averaged 2.048 (2) Å. They are free BPnDC ² on two types of crystallography ^- a ligand (BPnDC-1 and BPnDC-2). BPnDC-1 and BPnDC-2 behave like tetradentate ligands. The two carboxylate groups in BPnDC-1 adopt a bimodal ligand model (Figs. 2 (a) and (b)) in which two Zn ^II ions chelate. In BPnDC-2, one carboxylate group coordinates with two Zn ^II ions (Figure 2 (b)) while the other carboxylate group coordinates with one Zn ^II ion (Figure 2 (c)). . BPnDC ^2- is the 휜 linker and the dihedral angles between the two phenyl rings are 57.90 (14) and 52.21 (19) ^o at BPnDC-1 and BPnDC-2, respectively. Although bpy is expected to be a linear linker, it is remarkably subtracted with a 24.47 (20) ^o dihedral between two pyridyl rings. In general, 2D layers are formed from M ₂ units of dinuclei and dicarboxylate linkers, and 3D MOFs can be constructed by diamine columns connecting 2D layers.

However, the Zn ₂ units of the nucleus with a Zn ^II -Zn ^II distance of (1) to 3.147 (1) for the shape of the malformed 2D square grid {Zn ₂ (BPnDC) (bpy)} on the ab plane Connected by BPnDC-1 and bpy (FIG. 3 (a)). Interestingly, along the c axis, BPnDC-2 acts as a column and connects adjacent layers to help obtain a 3D framework (Figure 3 (b)). The two 3D frameworks interpenetrate each other to produce 3D curved channels (Figs. 3 (c) and (d)). The solvent acceptable volume expected by PLATON is 37.5%. The pores in the guest molecule could not be purified by the severe disorders common in microporous MOFs. Therefore, the presence and number of guest molecules (2DEF and 2MeOH) in (1) were determined based on IR, elemental analysis and TGA data. The final structural model was refined without guest molecules by using PLATON's SQUEEZE option. Thermogravimetric analysis (TGA) on skeletal body (1) measured under N ₂ atmosphere shows that solvent guest molecules are lost as soon as crystal (1) is removed from the mother liquor. The TGA of (1) shows a 13.2% weight loss, corresponding to a reduction of one DEF and one MeOH guest molecule per formula unit (calculated 12.2%) at 25-90 ° C., and one DEF and at 90-220 ° C. Followed by an additional weight loss of 12.4% corresponding to one MeOH guest molecule (calculated 12.2%). TGA data as well as powder X-ray diffraction (PXRD) measured at various temperatures suggest that (1) is heat stable up to 300 ° C. (FIGS. 4 and 5).

When single crystal (1) is dissolved in methanol for 24 hours, (1) is not completely dissolved, while maintaining transparency as well as monocrystalline, the DEF guest molecule in (1) is exchanged with methanol, which is {[Zn ₂ ( BPnDC) ₂ (bpy)]-6MeOH} _n (2).

If crystal {[Zn ₂ (BPnDC) ₂ (bpy)]? DEF? MeOH} _n ( 1 ) is immersed in crystal 1 for 24 hours in MeOH showing complete insolubility, the guest molecule is substituted monocrystal {[Zn ₂ (BPnDC) ₂ (bpy)]? MeOH} _n ( 1 m ) is produced. The X-ray crystal parameters as well as the 1 m framework structure are very similar to Crystal 1 (see figure). When crystal 1 is heated at 60 ° C. for 1.5 hours, a desolvent solid [Zn ₂ (BPnDC) ₂ (bpy)] _n ( SNU- 9 ) is formed, and a decrease in transparency and single crystal is observed. Comparing the synchrotron PXRD patterns of crystals 1 , 1m and SNU- 9 , it can be seen that the framework structure is not changed by substitution of the guest molecule, but the structure is greatly changed when the guest molecule is removed. However, by exposure to MeOH vapor it was confirmed that the recovery to the PXRD pattern of SNU- 9 . These phenomena show that the framework of the present invention is soft and that the structure of the framework is reversibly changed by removal or reintroduction of guest molecules.

The state of the X-ray data of (2) is as good as (1). Cell parameters including the cell volume of (2) are mostly the same as (1). The overall skeletal connectivity in (2) remains the same as in (1). In Fig. 6, the powder X-ray diffraction (PXRD) patterns of (1) and (2) are compared. It also shows that the framework structures of (1) and (2) are identical. The TGA for framework (2) measured under N ₂ atmosphere was determined by ca. Heating at 60 ° C. showed a 16.5% weight loss, consistent with the loss of 6MeOH molecules (calculated 18.1%). The measured PXRD pattern in (1) is almost identical to the imaginary pattern obtained from the X-ray single crystal data, which shows that a large number of samples are the same as the single crystal, but the electron density corresponding to the disordered guest molecule is determined using PLATON's SQUEEZE option. Slightly different from the imaginary pattern you ignored.

(2) results in desolvated solid [Zn ₂ (BPnDC) ₂ (bpy)] _n (3) when heated in a Schlenk tube at 60 ° C. under vacuum for 1.5 hours. Crystal (3) lost transparency and crystallinity, and thus its X-ray crystal structure could not be measured. However, it can be seen that the structure is modified by the removal of the guest molecule (Fig. 6). The TGA for (3) was shown to be heat stable up to 300 ° C. (FIG. 7).

Experimental Example  4. Gas adsorption and desorption characteristics of (3)

N ₂ adsorption-desorption isotherm of (3) is shown in Figure 8 (a). Interestingly, the adsorption isotherm shows three distinct steps in the low pressure range of P / P ₀ <0.03. At low comparative pressures ( P / P ₀ = 0.00096-0.0010), the pore volume measured by Dubinin-Radushkevich was 0.106 cm ³ / g, Langmuir and Brunauer- Both surface areas of Brunauer-Emmett-Teller (BET) are 268 m ² / g. In the range P / P ₀ = 0.001-0.019, the adsorption isotherm shows a steep rise and then flattens as shown in Type I (small diagram in FIG. 8 (a)) isotherm. At P / P ₀ values higher than 0.019, the curves show different steep rises and finally saturation levels (262 cm ³ / g at 0.91 atm). The pore volume predicted at the third absorption ( P / P ₀ = 0.029-0.31) is 0.367 cm ³ / g depending on the pore volume of (2) calculated in the crystal structure (0.353 cm ³ / g). In the last step, the Langmuir and BET surface areas are 1040 and 820 m ² / g, respectively.

(2) (1910 m ² g ⁻ ) using a Materials Studio program (version 4.1, Accelrys) with a lattice spacing of 0.25 mm 3 and a pore radius of 1.82 mm ₂ appropriate for N ₂ derived from N ₂ adsorption ^Note that it is much lower than expected from the X-ray crystal structure of ¹ ). The scheme of pore size distribution based on the Harvath-Kawazoe (HK) model has a pore diameter of 7.5 and 11.3 mm 3 in (3). At 87 K, the clear third stage bent shape is shifted at higher pressures, but each stage shows almost the same amount from the adsorbed N ₂ . The N ₂ isotherm reveals a pronounced hysteresis curve between the adsorption and desorption isotherms at both irreversible temperatures at reduced pressure. N ₂ adsorption are even if the pressure of the N ₂ that shows a limiting effect on the porosity decrease P / P ₀ = 10 ^-3 is desorbed ⁽³ / g desorption amount 70 cm) only partially. It is a state previously reported as light source gas in porous MOFs.

The O _{2 adsorption and desorption} isotherms at 77 K and 87 K look similar to the N ₂ adsorption and desorption isotherms (FIG. 8 (b)). At both temperatures the O ₂ adsorption isotherm represents a clear third step with the indicated hysteresis. In the first and second stages, the adsorption isotherm shows a slight rise. (3) is 17.2% by weight of O ₂ (5.37 mmol / g at STP, 120 cm ³ / g) is adsorbed at 77 K and 0.00045 atm in the second stage, 24.0% by weight at 7.5 K and 0.014 atm (7.51 mmol / g at STP) Absorb up to 168 cm ³ / g). After reaching the point at 0.014 atm, the O ₂ adsorption rises abruptly and the total amount of adsorbed O ₂ is 51.4 wt% (16.1 mmol / g in STP, 360 cm ³ / g) at 0.20 atm. At 87 K, the three clear steps are moved to higher pressure and (3) adsorbs 39.2% by weight (12.3 mmol / g in STP, 275 cm ³ / g) at 0.61 atm. At both temperatures the O ₂ isotherm cannot be changed to reduced pressure. The adsorption density (volume measurement capacity) of N ₂ at 77 K and 0.91 atm is 362 g / L and the density of O ₂ at 77 K and 0.20 atm is 569 g / L. For the densities of N ₂ and O ₂ liquids (804 and 1142 g / L, respectively), this value indicates that the gas is highly compressed in the pores of (3) even at very low pressures.

In FIG. 8 (b), the H ₂ gas adsorption isotherm is a solid (3) It showed little adsorption of H ₂ gas at 77 K and 1 atm (0.24 wt% in STP, 27 cm ³ / g). However, when the H ₂ pressure rises to 90 bar, (3) shows 3.63 wt% excess adsorption (FIG. 9). The total H ₂ absorption capacity reaches 6.23% by weight at 77 K and 90 bar when the skeletal density is measured for He gas at room temperature and the crystalline density of the sample is taken into account. Interestingly, the high pressure H ₂ adsorption isotherm shows two stages with hysteresis. In the first stage (3) adsorbs 1.32% by weight of H ₂ at 15 bar and in the second stage H ₂ adsorption isotherm saturated at 90 bar with a storage capacity of 3.63% by weight and ca. Steep rises at 20 bar. The desorption isotherm does not retrace the adsorption isotherm at 20-2 bar, which exhibits hysteresis in the adsorption and desorption isotherms, and shows a sudden decrease at 10 bar. At 77 K and 90 bar the hydrogen volumetric capacity is 40.2 g / L. The hydrogen volumetric capacity is close to the DOE target of 45 g / L by 2010.

CO ₂ of (3) at 195 K and 273 K And adsorption-desorption isotherms for the CH ₄ gas are measured in FIG. 10 (a). The adsorption and desorption isotherm for CO ₂ gas at 195 K shows a two-stage adsorption bent shape with desorption steep slopes with large hysteresis and two sudden jumps. At 195 K, the adsorption isotherm seems to increase steeply at low pressures up to 0.026 atm and rise abruptly at 0.16 atm until it reaches a plateau. (3) is 11.8% by weight of CO ₂ at 0.16 atm (2.69 mmol / g in STP, 60.1 cm ³ / g), 43.0% by weight at 1 atm in the second stage (9.78 mmol / g in STP, 219 cm ³ / Absorb and adsorb to g). Interestingly, the desorption isotherm shows a sudden steep slope at 0.039 atm without going back to the adsorption isotherm. Hysteresis between adsorption and desorption isotherms was reproducible in several cycles. CO ₂ gas adsorption and desorption isotherms at 273 K have a solid (3) It showed little adsorption of CO ₂ (5.49 wt% in STP, 28 cm ³ / g) gas at 273 K. The CH ₄ gas isotherm at 195 K has (3) No absorption of CH ₄ (2.13 wt.%, 30 cm ³ / g in STP).

The thing which dried 3a, (3) containing the gas which dried the solid 3 can be represented by 3b. In this case, 3a and 3b is the same as the formula (3), but the structure is different. CO _{2 in} 3a The large difference between and CH ₄ adsorption capacity can be applied to the separation of these gases. At high pressure and 298 K, (3) again shows two stage CO ₂ adsorption with large hysteresis (FIG. 10 (b)). The second adsorption jump is ca. Starting at 8 bar and reaching an excess capacity of 29.9% by weight at 40 bar, the adsorption bent shape shows a sharp decrease at 3.5 bar. The CH ₄ gas isotherm at high pressure and 298 K has (3) 2.64 weight percent (29.2 g / L and 40.9 v / v) at 35 bar and 3.40 weight percent (37.6 g / L and 52.6 v (STP) at 65 bar). / v) can store up to. This is much lower than the CO ₂ storage capacity. The stepped and hysteretic gas adsorption and desorption isotherms at 3a are due to the guest-induced structural transition to the adsorption or desorption gas. Conventional methods can be applied to the test isotherms of H ₂ and CO ₂ to account for the two-stage isotherms in the dual structure transition between two phases 3a and 3b. FIG. 11 shows that the two clear steps are well suited by Langmuir isotherms, and that the slope of Langmuir suitable at P = 0 shows the Henry's constant for adsorption measuring adsorption affinity. H ₂ And the adsorption affinity of CO ₂ is greater than 3a. Higher in 3b . The adsorption of N ₂ at 77 K shows the same structure as 3a based on the similarity of the pore volume, with the solid pore volume 3b being rather small and the fully open framework. At empty and very low pressure, 3a is essentially stable. As the pressure increases, the high affinity of 3a leads to a 3a → 3b transition and a higher gas pressure causes the larger pore volume of the open structure to become a smooth transition and the 3b → 3a transition must be maintained.

This phase transition with gas pressure can be demonstrated by structural analysis at specific temperatures and pressures. The synchrotron x-ray powder pattern analysis of 1,2,3 confirmed that the structural modification by the exchange and removal of the guest and the metal-organic framework of the present invention had very flexible properties. Table 1 below is gas adsorption data of (3).

gas Temperature
(K) pressure
(bar) Surface area
(m ² g ^-1 ) ^{a, b} Pore volume
(cm ³ g ^-1 ) Gas (mmol)
/ Host (g) gas
(weight%) Adsorbed gas
/ Host ^c volume (gL ^-1 ) N ₂ 77 0.9 1040 ^a , 820 ^b 0.367 11.7 32.7 362 N ₂ 87 0.9 10.7 30.9 333 O ₂ 77 0.2 16.4 51.4 569 O ₂ 87 0.6 12.3 39.2 434 H ₂ 77 1.0 1.21 0.24 2.65 H ₂ 77 90 18.0 3.63 ^d , 6.23 ^e 40.2 ^d , 68.9 ^e CO ₂ 195 1.0 9.78 43.0 476 CO ₂ 273 1.0 1.25 5.49 60.7 CO ₂ 298 40 6.79 29.9 331 CH ₄ 195 1.0 1.34 2.13 23.6 CH ₄ 298 65 2.12 3.40 37.6

[a] Langmuir surface area; [b] BET surface area; [c] the mass (g) of the adsorbed gas x the density of the sample (density: 1106 gL ^-1 ), assuming that the cell volume of (2) is maintained in the desolvated solid (3); [d] excess adsorption capacity; [e] Total adsorption capacity at 77 K and 70 bar

Table 2 below is gas adsorption data according to the pressure of (3).

gas Temperature (K) Pressure (bar) Gas (% by weight) N ₂ 77 0.000997 7.67 0.0194 18.5 0.9 32.7 87 0.00208 7.84 0.0992 19.2 0.9 30.9 O ₂ 77 0.00045 17.2 0.014 24.0 0.2 51.4 87 0.00217 11.0 0.0501 21.6 0.61 39.2 H ₂ 77 15 1.32 90 6.23 CO ₂ 195 0.16 11.8 1.0 43.0 273 1.0 5.49 298 8.11 10.3 40 29.9

Example 4: [Cd ₂ (BPnDC) ₂ (bpy)] n

H ₂ BPnDC (0.054 g, 2.0 x 10 ^-4 mol) and bpy (0.016 g, 1.1 x 10 ^-4 mol) were dissolved in DEF (6 mL) and Cd (NO ₃ ) ₂ -4H ₂ O (90 g , 2.9 x 10 ^-4 mol) were dissolved in MeOH (3 mL), mixed with each other, tightly capped with a silicone stopper and aluminum seal, and placed in a glass serum bottle and heated at 80 ° C. for 24 hours. It was then cooled to room temperature and filtered to quickly wash the colorless rod-shaped crystals with methanol. The resulting crystals were immersed in methanol for 1 day (the methanol was replaced after 10 hours) to produce guest modified crystals which were then heated in a Schlenk tube to 60 ° C. under vacuum for 1.5 hours [ Cd ₂ (BPnDC) ₂ (bpy)] n was prepared.

As a result, the [Cd ₂ (BPnDC) ₂ (bpy)] n metal-organic framework has a Langmuir surface area of 1500-3400 m ² g ⁻¹ , a BET surface area of 150-2000 m ² g ⁻¹ , and a pore volume. Is 0.06-4.0 cm ³ g ^-1 and pore diameter is 3-20 mm ³ . And oxygen gas is adsorbed at 15-19 wt% at 75-90 K at 0.00035-0.003 bar, 20-29 wt% at 0.005-0.07 bar and 35-53 wt% at 0.1-1.0 bar; The nitrogen gas is adsorbed at 5-7 wt% at 0.0006-0.0009 bar at 77-90 K, 13-20 wt% at 0.006-0.01 bar and 29-35 wt% at 0.7-1.2 bar; Hydrogen gas is adsorbed 0.5-2.5% by weight at 10-25 bar at 75-80 K, 4.0-7.0% by weight at 70-100 bar, 8-15 at carbon dioxide 0.05-0.25 bar at 180-280 K 2% to 40% by weight at 0.5-9 bar, 8-12% at 7-9 bar at 285-300K, 23-29% at 36-40 bar.

Comparative Example 1: [Cu ₂ (BPnDC) ₂ (bpy)] n

H ₂ BPnDC (0.056 g, 2.0 x 10 ^-4 mol) and bpy (0.018 g, 1.2 x 10 ^-4 mol) were dissolved in DMF (6 mL) and Cu (NO ₃ ) ₂ -2.5H ₂ O (0.061 g, 3.3 × 10 ⁻⁴ mol), dissolved in EtOH (3 mL), mixed with each other, tightly covered with a silicone stopper and an aluminum stopper, and placed in a glass serum bottle and heated at 80 ° C. for 24 hours. After cooling to room temperature, blue diamond crystals were formed which were filtered off and quickly washed with DMF. The resulting crystals were heated in a Schlenk tube at 100 ° C. for 2 hours to prepare [Cu ₂ (BPnDC) ₂ (bpy)] n.

As a result, the [Cu ₂ (BPnDC) ₂ (bpy)] n metal-organic framework has a Langmuir surface area of 2000-4500 m ² g ⁻¹ , BET surface area of 1500-3500 m ² g ^−1, and dubinin Radschkevic pore volume is 0.3-3.0 cm ³ g ^-1 and pore size is 8-30 mm ³ . In addition, the hydrogen gas is at least 4% by weight at 77K and 70 bar, and the carbon dioxide is at least 100% by weight at 195K and 1 atm. As described above, Comparative Example 1 does not adsorb gas in stages as in the present invention.

In addition, X-ray measurement confirmed that the metal and the carboxy ligand was made by the outer ring method.

1 is an X-ray structure of (1). (a) 3D skeletal structure of 1 (blue). Yellow represents another interpenetrating 3D framework. (b) Line drawing of the double interpenetrating structure of (1). Briefly, depicting two Zn ^II ions, BPnDC ^{2 -} carboxylate carbon atoms and nitrogen atoms of bpy as lines.

2 is a coordination model of the carboxylate group in (1).

Fig. 3 shows (a) a malformed 2D square lattice {Zn ₂ (BPnDC) (bpy)}. (B) A layer structure of 3D columnar shapes of 1 along the a axis. H atoms are omitted for clarity. Color composition: Zn, yellow; BPnDC-1, blue; BPnDC-2, green; bpy, pink. (c) 3D skeleton of 1 (dark blue). Yellow represents another infiltrated 3D framework. (d) shows 3D curved channel of 1. Surfaces accessible to the channel appear green.

4 shows TGA / DSC results for 1. FIG.

5 shows the XRPD pattern of 1 (from R.T to 330 ° C.) measured at various temperatures

6 is a synchrotron ( λ = 1.22152 Hz) PXRD pattern measured at room temperature. (a) PXRD pattern simulated from single crystal X-ray data of 1 in synthesized state, (b) Crystal 1 , (c) solid ( 1m ) with guest molecule substituted by MeOH, (d) 1m single crystal X-ray PXRD pattern simulated by data, (e) SNU- 9 obtained by drying 1 m in vacuum at 60 ° C. for 1.5 hours, (f) solid formed after exposing sample (e) to MeOH vapor for 6 hours.

7 shows TGA / DSC results for 1, 2 and 3. FIG.

FIG. 8 shows excess (black) and total (blue) H ₂ adsorption isotherms from 77 K to 90 bar. Filled form: adsorption. Open shape: detachable.

FIG. 9 shows excess (black) and total (blue) H ₂ adsorption isotherms from 77 K to 90 bar. Filled form: adsorption. Open shape: detachable.

10 is (a) CO ₂ and CH _{4 adsorption and desorption} isotherms for (3) at 195 K and 273 K, 1 atm. (b) Excess (black) and total (blue) adsorption isotherms of CO ₂ and CH ₄ for (3) at 298 K and high pressure. Filled form: adsorption. Open shape: detachable.

11 shows (a) suitable Langmuirs in the range 0-16 bar and 20-90 bar, respectively, in dotted lines of red and blue as well as H ₂ adsorption isotherms at 77 K. FIG. (b) CO ₂ adsorption isotherms at 195 K and 1 atm. The dotted blue line is suitable for the lower part ( P <0.15 atm) and the red dotted line is suitable for the upper part ( P > 0.4 atm).

Claims (19)

As the metal-organic skeleton represented by the following [Formula 1]: [Formula 1] {[M ₂ (L1) ₂ (L2)] X (Sol1)? Y (Sol2)} _n The metal-organic framework is a combination of the two metals, two carboxy ligands and a pyridine ligand to form a two-dimensional planar structure, and then the carboxy ligands are bonded to form a three-dimensional structure, in [Formula 1] M is Zn; L1 is BPnDC; L2 is bpy; Sol1 is any one selected from the group consisting of DEF, MeOH, and mixtures thereof; And wherein Sol2 is MeOH. delete delete According to claim 1, wherein the metal-organic framework of the formula [1] is 100-3500 m ² / g Langmuir surface area, 100-2000 m ² / g BET surface area, 0.05-4.5 cm ² / g of pores Metal-organic framework with a volume, pore diameter of 3-20 mm 3. According to claim 1, wherein the metal-organic skeleton of [Formula 1] (i) 9-27% by weight at 0.00035-0.003 bar, ② 20-35% by weight at 0.005-0.08 bar, ③ 33-59% by weight at 0.1-1.0 bar at 75-90 K for oxygen gas. Shows a three-step adsorption history of sequentially adsorbing; (ii) For nitrogen gas, 4-12% by weight at 77-90 K ① 11-12% by weight 0.005-0.33 bar ② 11-30% by weight 0.005-0.3 bar ③ ③ 28-35% by weight 0.7-1.2 bar Metal-organic framework showing a three-step adsorption history to sequentially adsorb. According to claim 1, wherein the metal-organic skeleton of [Formula 1] (i) the hydrogen gas shows a two-stage adsorption history that sequentially adsorbs 0.5-2.5% by weight at 10-25 bar and 4-7.5% by weight at 70-100 bar at 75-80 K; (ii) For carbon dioxide, 8-15% by weight at 0.05-0.25 bar ① 8-15% by weight at 180-280K ② 1-50% by weight 0.5-10 bar, 8 at 7-9bar ① 285-300K -13 wt%, ② the two-stage adsorption history to sequentially adsorb 22-36 wt% at 35-45 bar metal-organic framework. The method of claim 1, wherein the metal-organic framework of [Formula 1] (i) reacting by mixing L1 / DEF solution, L2 / DEF solution, M / MeOH solution with each other or (ii) (L1 and L2 Mixture of) / DEF solution and M / MeOH solution, which is prepared by a method comprising the step of reacting with each other. The metal-organic framework of claim 1, wherein the metal-organic framework is represented by the following [Formula 4]. [Formula 4] {[M ₂ (BPnDC) ₂ (bpy)]? 2DEF? 2MeOH} n According to claim 8, wherein the metal-organic framework of [Formula 4] is 300-2000 m ² / g Langmuir surface area, 200-1400 m ² / g BET surface area, 0.2-1.4 cm ² / g of pores Metal-organic framework with a volume, pore diameter of 4-14 mm 3. The metal-organic framework of claim 1, wherein the metal-organic framework of [Formula 1] is represented by [Formula 3]. (3) {[M ₂ (BPnDC) ₂ (bpy)]? 6MeOH} n The method according to claim 10, wherein the metal-organic framework of [Formula 3] is 300-2000 m ² / g Langmuir surface area, 300-1400 m ² / g BET surface area, 0.1-1.4 cm ² / g of pores A metal-organic framework with a volume, pore diameter of 4-13 mm 3. The metal-organic skeleton of [Chemical Formula 2] according to claim 10, wherein the metal-organic skeleton of [Formula 2] is prepared by desolventing the metal-organic skeleton of [Formula 3]. [Formula 2] [M ₂ (BPnDC) ₂ (bpy)] n The method of claim 12, wherein the [formula 2] of the metal-organic framework material is 200-2000 m ² / g of the Langmuir surface area, BET specific surface area of 200-1500 m ^{2 / g, 0.1-1.5 cm 2 /} g of the pore Metal-organic framework with a volume, pore diameter of 4-15 mm 3. The metal-organic skeleton of claim 12, wherein the metal-organic skeleton of [Formula 2] is prepared by heating the solvate of [Formula 3] under a vacuum of 40-80 ° C. for 1-3 hours. A gas device comprising the metal-organic framework according to any one of claims 7 to 14, wherein the metal device is any one selected from a gas separation device, a gas storage device, an ion exchange device, and a gas sensor device. A device comprising an organic framework. 16. The device of claim 15, wherein the gas device comprises a metal-organic framework that adsorbs a gas selected from the group consisting of oxygen, nitrogen, hydrogen and carbon dioxide at 77-310 K and 0.0001-110 bar. H ₂ BPnDC and bpy dissolved in DEF, M (NO ₃ ) _{2 ~} 6H ₂ O dissolved in MeOH and mixed with each other and then prepared by heating to 60-100 ℃ for 20-28 hours to prepare a metal-organic skeleton : [Formula 4] {[M ₂ (BPnDC) ₂ (bpy)]? 2DEF? 2MeOH} n M is a metal selected from the group consisting of Zn, Cu, Cd and Mn. 18. The method of claim 17, wherein the metal-organic skeleton of [Formula 4] is immersed in methanol to produce the metal-organic skeleton of [Formula 3]. (3) {[M ₂ (BPnDC) ₂ (bpy)]? 6MeOH} n The method of claim 18, wherein the metal-organic skeleton of [Formula 3] is prepared by heating for 1 to 3 hours under a vacuum of 40-80 ° C. [Formula 2] [M ₂ (BPnDC) ₂ (bpy)] n

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