JP5196413B2 - Adsorption material - Google Patents

Description

  The present invention relates to an adsorbing material.

Gas adsorbing materials are used in various fields such as vacuum holding, removal of trace gases from rare gases, and removal of gases from fluorescent lamps.
A rare gas used in the semiconductor manufacturing industry is desired to be purified to a high purity by removing nitrogen, hydrocarbon, carbon monoxide, carbon dioxide, oxygen, hydrogen, water vapor and the like in the rare gas. In particular, it is difficult to remove nitrogen, which is a stable molecule.

  For example, there is a method in which a rare gas is brought into contact with a getter material of a ternary alloy composed of zirconium, vanadium, and tungsten in order to remove nitrogen or hydrocarbons in the rare gas (see, for example, Patent Document 1).

  This method is to remove impurities such as nitrogen from a rare gas by bringing the alloy into contact with the rare gas at a temperature of 100 to 600 ° C.

  As the non-evaporable getter alloy having high gas adsorption efficiency with respect to nitrogen, there is an alloy containing one element of zirconium, iron, manganese, yttrium, lanthanum, and a rare earth element (for example, see Patent Document 2).

This alloy can act at room temperature against adsorption of hydrogen, hydrocarbons, nitrogen and the like by subjecting the alloy to an activation treatment at a temperature of 300 to 500 ° C. for 10 to 20 minutes.
As a nitrogen adsorption alloy at a low temperature, a Ba-Li alloy has been proposed (for example, see Patent Document 3).
This Ba-Li alloy is incorporated in a device for maintaining a vacuum in a heat insulating jacket in combination with a desiccant, and is reactive to gases such as nitrogen even at room temperature.

A gas adsorbent made of a metal complex has been proposed (see, for example, Patent Document 4).
This is a gas adsorbent composed of a metal complex containing a dicarboxylic acid, a specific divalent metal, and an organic ligand capable of bidentate coordination to the metal.

A gas adsorbent made of a metal complex has been proposed (see, for example, Patent Document 5).
This is because the adsorption / desorption isotherm shows a hysteresis loop, and the total number of coordination bonds, covalent bonds, ionic bonds, and hydrogen bonds is 1, and the total number of hydrogen bonds is 0.2 or more. It is a gas adsorbent.
JP-A-6-135707 Special table 2003-535218 gazette Japanese National Patent Publication No. 9-512088 JP 2001-348361 A JP 2004-74026 A

  However, in the above-described conventional configuration described in Patent Document 1, it is necessary to continue heating at 300 to 500 ° C., and since the heating is performed at a high temperature, the energy cost is large and the environment is bad, and the gas at a low temperature is used. Cannot be used if adsorption is desired.

  The conventional configuration described in Patent Document 2 requires pretreatment at 300 to 500 ° C., and gas removal when pretreatment at high temperature is difficult, for example, removing gas in a plastic bag at room temperature It is difficult.

  The conventional configuration described in Patent Document 3 does not require heat treatment for activation and can adsorb nitrogen at room temperature. However, it reacts with moisture, nitrogen, etc. in the air during handling, and is necessary. The problem remains in the handleability for ensuring activity at the time. In addition, further increase in capacity for nitrogen adsorption is desired, and Ba is a deleterious substance-designated substance, and therefore, it is desired to have no problem for the environment and human body when used industrially.

  In the above-described conventional configuration described in Patent Document 4, the adsorption amount per unit weight is larger than that of the alloy material, but gas adsorption is manifested by bringing it into contact with a gas under a pressurized condition. Desorption occurs under reduced pressure. Although it can be applied in applications where the occlusion behavior is required, such as adsorption under high pressure and desorption under reduced pressure, it is inappropriate for applications for completely removing gas.

  In the conventional configuration described in Patent Document 5, the amount of adsorption per unit weight is larger than that of the alloy material as in Patent Document 4, but gas adsorption is manifested by contacting with gas under pressurized conditions. Desorption occurs under normal pressure and reduced pressure.

The present invention solves the above-described conventional problems, and an object of the present invention is to provide an adsorptive compound having a high gas adsorption activity even at room temperature and normal pressure or at room temperature and reduced pressure, and particularly high adsorption performance for nitrogen.
Furthermore, it aims at providing what does not have a problem with respect to an environment or a human body.

  The present invention has been made in view of the above problems, and provides an adsorptive integrated metal complex having an open metal site. Adsorption occurs as a result of molecular coordination of the open metal site to the open metal site due to the open metal site expressing intermolecular interactions with the gas molecules.

  The open metal site may be composed of metal ions that are saturated with coordination or unsaturated, but the open metal site has four coordination sites and has at least one empty coordination site. Those having 3 or less sites composed of metal ions in a coordinated state have stronger intermolecular interactions with gas molecules.

  Since the adsorptive integrated metal complex of the present invention has an open metal site, it has a molecular weight of 45 or less and causes a strong interaction with molecules that are gases under the conditions of 293 K and 130 Pa, so that nitrogen, oxygen, hydrogen, It has a very high activity against gases such as carbon dioxide, carbon monoxide and moisture, especially nitrogen.

The adsorptive integrated metal complex of the present invention has an open metal site.
One aspect of an open metal site is when the metal ion is coordination unsaturated and has at least one vacant site in its coordination state. In this case, the adsorbed molecule can interact with the empty site.

Another embodiment of the open metal site is a case where even if the metal ion is coordination-saturated, it exhibits adsorption activity due to twisting and distortion between the ligands.
An example of a method for synthesizing an integrated metal complex having at least one vacant site will be described. A structure in which one easily detachable functional group is arranged in advance in a metal center, or 1 detachable functional group is 1 The structure having a single metal center is appropriately heat-treated to remove an easily detachable functional group for synthesis.
Similarly, when synthesizing an integrated metal complex having two free sites, the number of easily detachable functional groups may be set to two.

Further, the molecule to be adsorbed may be a liquid or a gas, but the purpose of the present invention is to adsorb the gas molecule.
Further, the adsorptive integrated metal complex may have a porous structure or a non-porous structure. In order to adsorb a larger amount of gas, a porous structure is desirable.

  In a preferred aspect of the present invention, an open metal site is composed of metal ions having four coordination sites, at least one vacant coordination site, and not more than three sites in a coordinated state. It is that.

  An open metal site having more than 4 saturated coordination sites is likely to have an adsorption inhibiting action due to steric hindrance, and therefore has 4 coordination sites.

  In a preferred embodiment of the present invention, in the adsorptive integrated metal complex, the metal ion contains a copper ion.

  It was confirmed that copper ions have high gas adsorption activity and show high adsorptivity to nitrogen, carbon monoxide, hydrogen, and oxygen, which are particularly difficult to adsorb. In particular, a copper monovalent ion is preferable.

One preferred embodiment of the present invention is characterized in that, in the adsorptive integrated metal complex, an empty coordination site is generated by heating.
A site that becomes an empty coordination site by heating is prepared by previously coordinating some compound that is desorbed by heating, such as a solvent during synthesis, and this configuration can block gas adsorption activity. For example, before heating, handling in the atmosphere is possible, and arbitrary processing and molding are easy.

  The heating temperature at this time can be determined by thermal analysis (TG) of the adsorptive integrated metal complex. The temperature at which the content rate of the desorbing compound matches the weight reduction rate due to heating is defined as the heating temperature.

  As a compound that is desorbed by heating, a substance having a weak binding force with respect to a metal ion, that is, a ligand having a weak basicity, a solvent during synthesis of an integrated metal complex, or the like can be used.

  When heating, normal pressure or reduced pressure may be used, but reduced pressure may be preferable depending on the type of compound desorbed by heating. The atmosphere gas is not particularly specified, but an inert atmosphere is desirable.

  The heating temperature is preferably 200 ° C. or lower in consideration of handling properties. Examples of the compound that is eliminated by heating include acetonitrile, low molecular weight alcohols such as methanol and ethanol, carbon monoxide, and ethylene.

  Further, when a compound having a low boiling point such as acetone is coordinated, desorption occurs at a temperature lower than 200 ° C., and gas adsorption activity is exhibited. Compared with a conventional alloy material, the heating temperature is low, which is advantageous in terms of energy.

  One preferred embodiment of the present invention is characterized in that, in the adsorptive integrated metal complex, the vacant coordination site has a molecular weight of 45 or less and can adsorb molecules that are gases under the conditions of 293 K and 130 Pa. .

  Examples of molecules that have a molecular weight of 45 or less and are gaseous under the conditions of 293 K and 130 Pa include hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, and ethylene. The adsorptive integrated metal complex in the present invention realizes adsorption of these gases and exhibits strong activity particularly with respect to nitrogen which is difficult to adsorb.

  One manufacturing method of the adsorptive integrated metal complex is a process of self-integrating a metal ion compound and at least two bridging ligand compounds L1 and L2.

  In this configuration, the metal ion compound is necessary for forming the integrated metal complex structure and the open metal site, the bridging ligand compound L1 is used for forming the integrated metal complex structure, and L2 is the open metal site. It is necessary as a coordination compound.

  The synthesis is performed by mixing a metal ion compound and at least two bridging ligand compounds L1 and L2 in a suitable solvent and self-assembling them. If necessary, a ligand may be further added.

The metal ion compound can be used as long as it is a salt composed of a metal ion and an inorganic ion, and a salt composed of a metal ion, an inorganic ion, and a low molecular weight ligand. For example, CuBr or Cu (NO ₃ ) ₂ , [Cu (CH ₃ CN) ₄ ] PF ₆ , [Cu (CH ₃ CN) ₄ ] BF ₄ , and the like.

The bridging ligand compound L1 is a bidentate or more multidentate ligand, and has an oxygen atom or a nitrogen atom serving as a bonding site with a metal ion at the terminal.
L1 needs to be a multidentate ligand of at least bidentate in order to act to form an integrated metal complex structure, and an oxygen atom or nitrogen atom that serves as a binding site with a metal ion at the terminal It becomes possible to form a porous and stable integrated metal complex structure.

The following two types of L2 can be applied.
First, it is a compound that coordinates to a metal ion that is an open metal site, and later desorbs at 200 ° C. or less under reduced pressure, and is a substance that has a weak binding force to the metal ion, that is, a weak basic coordination. Ligands, solvents for synthesizing integrated metal complexes, and the like can also act as L2. For example, acetonitrile, low molecular weight alcohols such as methanol and ethanol, carbon monoxide, and ethylene.

次の分子がＬ２として作用する。

The other has a function of forming a coordinated metal ion as an open metal site by combination with L1. Depending on the combination with L1, for example, for the following L1,

The next molecule acts as L2.

  Another production method of the adsorptive integrated metal complex of the present invention is a process in which a metal ion compound and a bridging ligand compound having an open metal site are self-assembled.

  In this configuration, the metal ion compound is necessary only for the formation of the integrated metal complex structure, and is not used for the formation of the open metal site. The metal ions of the open metal site are prepared in advance in a state of being incorporated into the bridging ligand compound, and the adsorptivity is obtained by self-assembling the metal ion compound and the bridging ligand compound having an open metal site. An integrated metal complex is synthesized.

In the synthesis, a metal ion compound and a bridging ligand compound having an open metal site are brought into contact with each other in a suitable solvent, and these are self-assembled.
Moreover, the bridge | crosslinking ligand compound which has an open metal site is a metal complex mainly coordinated unsaturated.

のようなものである。Ｅ，Ｆ，Ｇは隣接する原子などと環構造を構成しており、Ｊは環構造へ結合している配位可能な官能基である。
飽和配位サイトが５個で、空きサイトが１つのオープンメタルサイトを有する架橋配位子化合物は、

となり、Ａ、Ｂ、Ｃ、Ｄも隣接する原子などと環構造を構成している。 For example, a bridged ligand compound having four saturated coordination sites and one open metal site as a free site is

It ’s like that. E, F, and G form a ring structure with adjacent atoms and the like, and J is a coordinating functional group bonded to the ring structure.
A bridging ligand compound having five saturated coordination sites and one open metal site as a free site is

Thus, A, B, C, and D also form a ring structure with adjacent atoms.

などである。ここでαは、水素やアルカリ金属元素など、任意に選択できる。 Here, M can be used as long as it is a metal ion, and ions of the first transition metal and the second transition metal are desirable. Copper ions are particularly suitable, and copper monovalent ions are more preferred. A to G are applicable as long as they are elements capable of coordinating to metal ions, such as oxygen, nitrogen, phosphorus, and sulfur. J is a functional group having a site capable of coordinating with a metal ion,

Etc. Here, α can be arbitrarily selected from hydrogen and alkali metal elements.

また、配位飽和な金属錯体配位子あっても、配位子間のねじれ、ゆがみにより、オープンメタルサイトが吸着活性を示すものは利用可能である。 Examples of the bridging ligand compound having an open metal site include the following substances.

Moreover, even if it is a coordination saturated metal complex ligand, what has an open metal site which shows adsorption activity by the twist and distortion between ligands can be utilized.

  One preferable aspect of the present invention is to form an adsorptive integrated metal complex using a copper complex as a metal ion compound.

In this configuration, the open metal site containing copper ions formed from a copper complex has high adsorption activity and is particularly adsorbable to nitrogen, carbon monoxide, hydrogen, and oxygen, which are considered difficult to adsorb. Is very useful for showing. In particular, a copper monovalent complex can be preferably used, and [Cu (CH ₃ CN) ₄ ] PF ₆ , [Cu (CH ₃ CN) ₄ ] BF _{4 and the} like can be preferably used.

  By the said manufacturing method, it is possible to generate | occur | produce an open metal site reliably and easily in an adsorptive integrated metal complex.

  The present invention further relates to an adsorptive integrated metal complex in which an open metal site is composed of coordination-saturated metal ions having twisted and distorted coordination states and space tolerance that allows adsorbed molecules to interact with each other. Is to provide.

  An example of a method for synthesizing the adsorptive integrated metal complex is a method in which a metal ion compound having an adsorptive activity and a ligand are mixed and stirred in an appropriate solvent, or dissolved in an appropriate solvent and contacted. is there.

Here, the number of ligands may be one, or two or more.
In addition, in the case of a combination of a metal ion compound as a starting material and a ligand, and when there are multiple ligands, the combination of ligands twists and distorts the coordination state of the open metal site. It is important to let

The present invention further provides an adsorptive metal complex having an open metal site.
The open metal site of this adsorptive metal complex is twisted and distorted by the coordination state of the metal ions that are coordinatively saturated, and the adsorbed molecule has a space tolerance that allows interaction with the metal ion. Even if it exists, it is a metal ion which is coordination-unsaturated and may have at least one vacant site in the coordination state. In addition, as for an open metal site, it is desirable that a metal ion is a copper ion, especially a copper monovalent ion.

As the open metal site-adsorptive metal complex composed of coordination unsaturated metal ions, for example, a metal complex such as [Cu (CH ₃ CN) ₄ ] PF ₆ is used, under appropriate conditions (heating and under reduced pressure). Can be produced by removing one ligand.

  Furthermore, the present invention provides an adsorptive integrated metal complex including at least a part of the decomposition product of the starting material and the decomposed product of the adsorptive integrated metal complex.

The decomposition product here refers to a thermal decomposition product generated mainly by heating to produce a free coordination site, but includes intermediate products generated during synthesis, unreacted starting materials, etc., and intended adsorption. This includes all side reaction products other than the active metal complex. Here, the part of the decomposition product may be a part of the amount or a part of the components.
With this configuration, the history of the starting material and heating of the adsorptive integrated metal complex can be confirmed.

  The present invention also provides an adsorptive metal complex containing at least a part of the decomposition product of the starting material and the decomposition product of the adsorbent metal complex.

The decomposition product here refers to a thermal decomposition product generated mainly by heating to produce an empty coordination site, including intermediates generated during synthesis, unreacted starting materials, etc. Includes all incomplete polymers. Here, part of the decomposed product has the same meaning as described above.
With this configuration, it is possible to confirm the history of the starting material and heating of the adsorptive metal complex.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

(Embodiment 1)
The adsorptive integrated metal complex according to Embodiment 1 of the present invention is obtained by self-integrating a metal ion compound and at least two bridging ligand compounds L1 and L2.
Results of structural analysis by powder X-ray diffraction (XRPD) and evaluation results of nitrogen adsorption / desorption curves for adsorptive integrated metal complexes synthesized with metal ion compounds and examples of two bridging ligand compounds L1 and L2 It shows in Examples 1-3. The nitrogen adsorption / desorption curve was measured using AUTOSORB-1-c (manufactured by Kantachrome) under the condition of 25 ° C.

を、Ｌ２として

を用い、溶媒には水を用いた。これらを混合後、１７０℃で保持、室温まで冷却後に得られた結晶を構造解析した結果、多孔構造の集積型金属錯体であることがわかった。 Example 1
Cu (NO ₃ ) ₂ as the metal ion compound and the bridging ligand compound L1

As L2

And water was used as the solvent. As a result of structural analysis of the crystal obtained after mixing and holding at 170 ° C. and cooling to room temperature, it was found to be an integrated metal complex having a porous structure.

FIG. 1 shows a unit structure of the adsorptive integrated metal complex in Example 1.
FIG. 2 shows the crystal structure of the porous body of the adsorptive integrated metal complex in Example 1.
As a result of structural analysis, it was found that the open metal site in this integrated metal complex is a coordination-unsaturated copper monovalent ion. In Example 1, the coordination saturation of the copper monovalent ions was tetracoordinate, of which 3 coordination was used for bonding, and it was confirmed that 1 coordination was an empty coordination site. .
FIG. 3 shows a nitrogen adsorption / desorption curve in the adsorptive integrated metal complex of Example 1.
FIG. 3 shows that the integrated metal complex in Example 1 can adsorb nitrogen from the low pressure region. Further, the adsorption / desorption curve shows hysteresis, and it can be confirmed that the open metal site strongly interacts with the nitrogen molecule.

Ｌ２として、４，４−ビピリジン：

を用いた。 (Example 2)
FeCl ₂ .4H ₂ O as the metal ion compound, naphthalene-2,6-dicarboxylate as the bridging ligand compound L 1:

As L2, 4,4-bipyridine:

Was used.

An ethanol solution of naphthalene-2,6-dicarboxylate and 4,4-bipyridine dissolved in water is used as a ligand solution, and an aqueous FeCl ₂ .4H ₂ O solution is used as an aqueous metal ion solution. The ligand solution is gently poured into the quartz tube containing the metal ion aqueous solution (between the metal ion aqueous solution and the ligand solution, there is a buffer solution with ethanol: water = 1: 2).
As a result of structural analysis of the brown crystals deposited between these two layers, it was found to be an integrated metal complex having a porous structure.

FIG. 4 shows a unit structure of the adsorptive integrated metal complex in Example 2.
FIG. 5 shows the crystal structure of the porous body of the adsorptive integrated metal complex in Example 2. In addition, we submit clear figure with reference sheet 1 with article presentation.
As a result of structural analysis, it was found that the open metal site in this integrated metal complex was a coordinated unsaturated iron divalent ion. The coordination saturation of iron divalent ions is 6 coordination, of which 5 coordination is used for bonding, and it has been confirmed that 1 coordination is an empty coordination site.

Similarly to Example 1, the adsorption / desorption curve in Example 2 showed hysteresis, and it was confirmed that open metal sites interacted strongly with nitrogen molecules.
However, nitrogen adsorption in the low pressure region was inferior to Example 1. The reason is that the open metal site was divalent iron.

(Example 3)
[Cu (CH ₃ CN) ₄ ] BF ₄ was used as the metal ion compound, 4,4-bipyridine was used as the bridging ligand compound L1, and acetonitrile was used as L2. Acetonitrile also acts as a solvent.

4,4-bipyridine dissolved in acetonitrile is added to [Cu (CH ₃ CN) ₄ ] BF ₄ dissolved in acetonitrile and stirred. As a result of structural analysis of the yellow powder produced by precipitation, it was found to be an integrated metal complex.

  In FIG. 6, the crystal structure of the porous body of the adsorptive integrated metal complex in Example 3 is shown. In addition, we submit clear figure as reference figure 2 with article presentation. FIG. 7 shows the thermal analysis (TG) result of this powder (thermogravimetric change rate of the porous body of the adsorptive integrated metal complex). In this integrated metal complex, the compound to be eliminated was acetonitrile, and the heating temperature corresponding to the expected elimination was determined to be 110 ° C., and heating was performed at 110 ° C. under reduced pressure.

  As a result of structural analysis after heating, it was confirmed that an integrated metal complex having a porous structure was formed. Moreover, it turned out that an open metal site is a coordinative unsaturated copper monovalent ion. Coordination saturation of copper monovalent ions is tetracoordinate, of which 3 coordination is used for bonding, and it was confirmed that 1 coordination is an empty coordination site.

  FIG. 8 shows a nitrogen adsorption isotherm of the porous body of the adsorptive integrated metal complex in Example 3. FIG. 8 shows that the integrated metal complex in Example 3 can adsorb nitrogen from the low pressure region. Further, the adsorption amount is larger than that of Example 1. This is considered to be because, as in Example 1, it has copper monovalent as an open metal and is further heated under an appropriate reduced pressure.

  The porous integrated metal complex of Example 3 includes a small amount of unreacted starting materials, and side reaction products other than the adsorptive integrated metal complex, such as thermal decomposition products and intermediates generated during synthesis. This was confirmed by thermal extraction / mass spectrometry (temperature range: room temperature to 500 ° C.) and infrared absorption analysis.

(Embodiment 2)
The adsorptive integrated metal complex according to Embodiment 2 of the present invention is obtained by self-integrating at least a metal ion compound and a bridging ligand compound having an open metal site.
An example of an adsorptive integrated metal complex synthesized from a metal ion compound and a bridging ligand compound having an open metal site is shown in Example 4. The evaluation method was in accordance with the first embodiment.

さらにもう１種の架橋配位子化合物、ピラジン−２，３−ジカルボキシレートナトリウム塩

を使用した。
テトラヒドロフランと水との混合溶液（混合比１：１）に溶解したＬ１とピラジン−２，３−ジカルボキシレートナトリウム塩を入れた石英管に、静かにＣｕ（ＣｌＯ_４）_２・６Ｈ_２Ｏの水溶液をそそぎ入れる。
これら二層間に析出した青色平板状の結晶を構造解析した結果、多孔構造の集積型金属錯体であることがわかった。 Example 4
As a metal ion compound Cu (ClO ₄ ) ₂ · 6H ₂ O, as a bridging ligand compound having an open metal site,

Yet another bridging ligand compound, pyrazine-2,3-dicarboxylate sodium salt

It was used.
In a quartz tube containing L1 and pyrazine-2,3-dicarboxylate sodium salt dissolved in a mixed solution of tetrahydrofuran and water (mixing ratio 1: 1), gently put Cu (ClO ₄ ) ₂ · 6H ₂ O. Pour the aqueous solution.
As a result of structural analysis of the blue tabular crystals deposited between these two layers, it was found to be an integrated metal complex having a porous structure.

FIG. 9 shows a crystal structure of the porous body of the adsorptive integrated metal complex in Example 4. In addition, we submit clear figure by reference sheet 3 with article presentation.
As a result of structural analysis, it was found that the open metal site in this integrated metal complex is a coordinatively unsaturated copper divalent ion. Coordination saturation of copper divalent ions was 6-coordinate, of which 4-coordination was used for bonding, and it was confirmed that 2 coordination was an empty coordination site.

The adsorption / desorption curve in Example 4 showed hysteresis similarly to Example 1, and it was confirmed that the open metal site strongly interacted with nitrogen molecules.
However, nitrogen adsorption in the low pressure region was inferior to Example 1. This is because the open metal site was copper bivalent.

(Embodiment 3)
The adsorptive metal complex in Embodiment 3 of the present invention has at least an open metal site. Example 5 shows an adsorptive metal complex in which an open metal site is a coordination unsaturated metal ion generated by heating at 200 ° C. or lower under reduced pressure.

(Example 5)
{Cu (CH ₃ CN) ₄ } PF ₆ is used as a starting material, heated at 180 ° C. under reduced pressure for 4 hours, and 1 of 4 CH ₃ CN groups coordinated to copper ions. By removing one, a non-porous adsorptive metal complex having an open metal site was synthesized.
As a result of structural analysis, it was found that the open metal site in this metal complex is a coordination unsaturated copper monovalent ion. Coordination saturation of copper monovalent ions is tetracoordinate, of which 3 coordination is used for bonding, and it was confirmed that 1 coordination is an empty coordination site.

FIG. 10 shows a nitrogen adsorption / desorption curve in the adsorptive metal complex of Example 5.
In FIG. 10, it can be confirmed that nitrogen can be adsorbed from the low pressure region, and since the adsorption curve and desorption curve show hysteresis, the adsorptive metal of Example 5 characterized by having an open metal site It was found that the complex exhibited an adsorption activity for gas molecules due to the formation of coordination-unsaturated open metal sites in the complex.
Moreover, in Example 5, since it was a metal complex with a non-porous structure, the amount of adsorption was relatively small. For the purpose of adsorption, a porous structure having a large specific surface area and capable of effectively contacting an adsorption active site with a gas is desirable.
Next, a comparative example for the adsorptive integrated metal complex of the present invention is shown.

(Comparative Example 1)
The integrated metal complex of Comparative Example 1 has an open metal site synthesized by adding Cu (ClO ₄ ) ₂ · 6H ₂ O to Na ₂ -pyrazine-2,3-dicboxylate and 4,4′-bipyridine, No integrated metal complex was used.
No hysteresis was confirmed in the nitrogen adsorption / desorption curve of the adsorptive integrated metal complex of Comparative Example 1 (FIG. 11). That is, it was suggested that the metal complex of Comparative Example 1 has no intermolecular interaction with nitrogen and only physical adsorption under pressure occurs.

  The adsorptive integrated metal complex having an open metal site of the present invention, or the adsorptive metal complex has a high gas adsorbing activity and particularly a high adsorption performance to nitrogen. It can be used in various fields such as removal of trace gases from rare gases and gas separation.

The figure which shows the unit structure of the adsorptive integrated type metal complex in Example 1 of this invention The figure which shows the crystal structure of the porous body of the adsorptive integrated type metal complex in Example 1 of this invention The characteristic view which shows the nitrogen adsorption desorption curve in the adsorptive integrated metal complex of Example 1 of this invention The figure which shows the unit structure of the adsorptive integrated metal complex in Example 2 of this invention The figure which shows the crystal structure of the porous body of the adsorptive integrated type metal complex in Example 2 of this invention The figure which shows the crystal structure of the porous body of the adsorptive integrated-type metal complex in Example 3 of this invention The characteristic view which shows the thermogravimetric change rate of the porous body of the adsorptive integrated metal complex in Example 3 of this invention The characteristic view which shows the nitrogen adsorption isotherm of the porous body of the adsorptive integrated metal complex in Example 3 of this invention The figure which shows the crystal structure of the porous body of the adsorptive integrated-type metal complex in Example 4 of this invention The characteristic figure which shows the nitrogen adsorption / desorption curve in the adsorptive integrated-type metal complex of Example 5 of this invention Characteristic chart showing nitrogen adsorption / desorption curve in the adsorptive integrated metal complex of Comparative Example 1

Claims (1)

An adsorbing material capable of adsorbing molecules that are gases under conditions of 293K and 130Pa,
The adsorbing material is an adsorptive integrated metal complex or an adsorbing metal complex,
The adsorptive integrated metal complex is a metal complex having an open metal site composed of coordination unsaturated metal ions, and self-assembles the metal ion compound and at least two bridging ligand compounds L1 and L2. Or a second type obtained by self-assembling a metal ion compound and a bridging ligand compound having an open metal site,
The first type is
(1) Cu (NO ₃ ) ₂ as a metal ion compound ,
As the bridging ligand compound L1, a compound of the following chemical formula 1,

A metal complex obtained by self-integrating a compound of the following chemical formula 2 as the bridging ligand compound L2,

(2) FeCl ₂ .4H ₂ O as a metal ion compound ,
Naphthalene-2,6-dicarboxylate as the bridging ligand compound L1,
A metal complex obtained by self-assembling 4,4-bipyridine as the bridging ligand compound L2,
(3) [Cu (CH ₃ CN) ₄ ] BF ₄ as a metal ion compound ;
It is any one of metal complexes formed by self-integrating 4,4-bipyridine as the bridging ligand compound L1 and acetonitrile as the bridging ligand compound L2.
The second type is
Cu (ClO ₄ ) ₂ · 6H ₂ O as a metal ion compound ,
As a bridging ligand compound having an open metal site, a compound of the following chemical formula 3,

Furthermore, it is a metal complex formed by self-integrating pyrazine-2,3-dicarboxylate sodium salt as a bridging ligand compound,
The adsorptive metal complex is a metal complex having a coordination unsaturated metal ion generated by heating at 200 ° C. or lower, and [Cu (CH ₃ CN) ₄ ] PF ₆ is heated at 200 ° C. or lower under reduced pressure. An adsorbing material, which is a metal complex .

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