WO2015152001A1 - Complexe métallique et son procédé de fabrication - Google Patents

Complexe métallique et son procédé de fabrication Download PDF

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WO2015152001A1
WO2015152001A1 PCT/JP2015/059400 JP2015059400W WO2015152001A1 WO 2015152001 A1 WO2015152001 A1 WO 2015152001A1 JP 2015059400 W JP2015059400 W JP 2015059400W WO 2015152001 A1 WO2015152001 A1 WO 2015152001A1
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metal complex
aluminum
raw material
material mixture
terephthalic acid
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PCT/JP2015/059400
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English (en)
Japanese (ja)
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前浜　誠司
小林　渉
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東ソー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids

Definitions

  • the present invention relates to a metal complex. More specifically, the present invention relates to a porous metal complex that is inexpensive and practical and is expected to be applied to uses such as an adsorbent and a catalyst.
  • a porous metal complex (Metal Organic Framework: MOF) composed of metal ion clusters and organic ligands has a higher specific surface area and pore volume than zeolite and activated carbon. Therefore, as an alternative material such as zeolite, porous metal complexes are expected to be applied to gas adsorption, separation, and storage, as well as to catalyst use, and further to drug delivery and other uses.
  • MOF Metal Organic Framework
  • Terephthalic acid is one of the most important divalent organic ligands because it forms porous metal complexes with many kinds of metal ions and is an industrially inexpensive raw material.
  • a porous metal complex containing terephthalic acid as an organic ligand MIL-53 (Cr), MIL-53 (Al), MIL-53 (V), MIL-68 (Al), MIL-88B (Cr), Specific examples include MIL-88B (Fe), MIL-101 (Cr), and MIL-101 (Fe).
  • Non-Patent Document 1 discloses MIL-101 (Cr) composed of a coordinate bond between a chromium (Cr) ion cluster and terephthalic acid.
  • MIL-101 (Cr) has a BET specific surface area of 3000 m 2 / g or more, a pore having a pore diameter of 29 mm, and a pore having a pore diameter of 34 mm, and has a heat resistance of about 300 ° C.
  • Non-Patent Document 2 discloses MIL-101 (Fe) composed of a coordinate bond between an iron (Fe) ion cluster and terephthalic acid.
  • MIL-101 (Fe) had a BET specific surface area of 3200 m 2 / g and a pore volume of 1.4 cm 3 / g.
  • MIL-53 (Al) was reported in Non-Patent Document 3 and MIL-68 (Al) was reported in Non-Patent Document 4 as porous metal complexes composed of coordination bonds between aluminum ion clusters and terephthalic acid. Yes.
  • Non-Patent Document 5 discloses NH 2 -MIL-101 composed of an aluminum (Al) ion cluster and 2-aminoterephthalic acid as a porous metal complex having an analogous compound of terephthalic acid as an organic ligand. (Al) is disclosed.
  • MIL-101 (Cr) was a porous metal complex containing toxic chromium ions. Therefore, MIL-101 (Cr) cannot be used for environmental use or biological use. Furthermore, MIL-101 (Cr) has a thermal decomposition temperature of 300 ° C. and is not only easily deteriorated by heat treatment but also has limited applications. Furthermore, the synthesis of MIL-101 (Cr) requires the use of high temperature of 200 ° C. or higher and highly toxic hydrogen fluoride (HF). Therefore, there is a problem in that the synthesis requires special equipment and management, and the cost is increased.
  • HF highly toxic hydrogen fluoride
  • MIL-101 (Fe) has a thermal decomposition temperature of about 180 ° C., and is not only easily deteriorated by heat treatment as compared with MIL-101 (Cr), but also applicable applications are further limited.
  • the space group to which the crystal structure of MIL-53 (Al) belongs is Pnam, and the space group to which the crystal structure of MIL-68 (Al) belongs is Cmcm.
  • MIL-53 (Al) and MIL-68 (Al) have relatively high heat resistance, but their specific surface area was as low as about 1500 m 2 / g due to such a crystal structure. Therefore, higher specific surface area and pore volume are required for applications such as adsorbents.
  • NH 2 -MIL-101 (Al) has a structure similar to MIL-101 (Cr), the specific surface area and pore volume are relatively high. However, its thermal decomposition temperature is as low as about 250 ° C. For this reason, NH 2 -MIL-101 (Al) has a limited use in comparison with MIL-101 (Cr). Furthermore, 2-aminoterephthalic acid is an expensive compound, and NH 2 -MIL-101 (Al) containing 2- aminoterephthalic acid is also expensive.
  • the porous metal complex having terephthalic acid as an organic ligand has only a high specific surface area but low heat resistance, or high heat resistance but low specific surface area.
  • an object of the present invention is to provide a porous metal complex having terephthalic acid as a ligand and having high heat resistance and high specific surface area. Furthermore, it is another object to provide a simple method for producing such a porous metal complex.
  • the present inventors examined a porous metal complex having terephthalic acid as an organic ligand and having both high heat resistance and high specific surface area. As a result, we focused on aluminum ion clusters from among a number of metal ion clusters, and found that porous metal complexes consisting of terephthalic acid and having a specific crystal structure have both high heat resistance and high specific surface area. It was. Further, the inventors have found that such a porous metal complex can be obtained for the first time by paying attention to the water content in the raw material and controlling it, and have completed the present invention.
  • the gist of the present invention is as follows.
  • [1] A metal complex having a structure in which terephthalic acid is coordinated to an aluminum ion cluster and having a space group of Fd-3m.
  • [2] The metal complex according to [1], wherein the BET specific surface area is 1500 m 2 / g or more.
  • [3] The metal complex according to [1] or [2], wherein the thermal decomposition temperature is 400 ° C. or higher.
  • a production method comprising a reaction step of reacting a raw material mixture containing an aluminum source, terephthalic acid and an aprotic solvent, wherein the molar ratio of water to aluminum in the raw material mixture is 1.0 or less.
  • the method for producing a metal complex according to any one of [1] to [3].
  • [5] The method according to [4], wherein the raw material mixture has an aluminum concentration of 0.01 mol / L or more.
  • [6] The production method according to [4] or [5], wherein a molar ratio of terephthalic acid to aluminum in the raw material mixture is 0.20 or more.
  • the aprotic solvent consists of the group of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, and N-methyl-2-pyrrolidone.
  • a porous metal complex having terephthalic acid as a ligand and having high heat resistance and high specific surface area can be provided. Furthermore, since the metal complex of the present invention does not contain a toxic metal, a metal complex that can be applied to uses such as drug delivery can be provided.
  • the metal complex of the present invention can be used as a nitrogen adsorbent and a catalyst, and can be expected to be used as an adsorbent and a catalyst other than this.
  • the production method of the present invention can provide a simple production method of such a porous metal complex. Furthermore, since the metal complex is obtained from an inexpensive raw material such as an aluminum source and terephthalic acid by the production method of the present invention, it can be provided as an inexpensive metal complex and a production method thereof.
  • the present invention is a metal complex, more specifically a porous metal complex.
  • the porous metal complex is a crystalline organometallic complex having a skeleton structure composed of metal ion clusters and organic ligands.
  • the structure of the metal complex of the present invention is shown in FIG.
  • the metal complex of the present invention has a structure in which terephthalic acid is coordinated to an aluminum (Al) ion cluster as a metal ion cluster. More specifically, the metal complex of the present invention has a tetrahedral structure in which a terephthalate anion is coordinated to each aluminum ion (Al 3+ ) of an aluminum ion cluster (FIG. 1 (a)) composed of A1 3 —O. (FIG. 1B).
  • the skeleton structure of the metal complex of the present invention has a three-dimensional structure similar to that of MTN zeolite, in which the unit skeletons are continuously bonded (FIG. 1 (c)). Note that the unit skeleton exists at a position corresponding to each vertex of the MTN framework.
  • the space group of the metal complex of the present invention is Fd-3m. That is, the symmetry of the crystal structure of the metal complex of the present invention belongs to the space group Fd-3m.
  • the metal complex of the present invention has a skeletal structure composed of aluminum ion clusters and terephthalic acid, and has a high heat resistance and a high specific surface area by having a crystal structure belonging to the space group. Furthermore, the pore volume tends to increase.
  • XRD powder X-ray diffraction
  • the space group and crystal structure of the metal complex of the present invention can be identified by comparing with the XRD pattern of MIL-101 (Cr).
  • MIL-101 (Cr) is a porous metal complex having a chromium ion cluster as a metal ion cluster and coordinated with terephthalic acid, and its space group is Fd-3m.
  • the crystal structure and space group of the metal complex of the present invention can be identified by having the same crystal structure and space group as MIL-101 (Cr).
  • the metal complex of the present invention Compared to a conventional porous metal complex containing terephthalic acid as an organic ligand, the metal complex of the present invention has higher heat resistance. Therefore, the thermal decomposition temperature of the metal complex of this invention is 400 degreeC or more, Furthermore, it is 450 degreeC or more. Even when the metal complex of the present invention is at 400 ° C. or higher, thermal decomposition of the organic ligand and thermal dissociation of the bond between aluminum and oxygen in the aluminum ion cluster hardly occur. By having such high heat resistance, the metal complex of the present invention can be used for applications such as catalysts and adsorbents that are used at high temperatures. The higher the thermal decomposition temperature, the wider the range of applications that can be used.
  • the thermal decomposition temperature of the metal complex of the present invention is preferably 490 ° C. or higher, more preferably 495 ° C. or higher, and even more preferably 500 ° C. or higher.
  • Examples of the thermal decomposition temperature of the metal complex of the present invention include 400 ° C. to 600 ° C., 400 ° C. to 500 ° C., 490 ° C. to 500 ° C., and 495 ° C. to 500 ° C. be able to.
  • the thermal decomposition temperature of the metal complex can be determined by thermogravimetric analysis (TG analysis).
  • the metal complex of the present invention has a high specific surface area.
  • the specific surface area of the metal complex of this invention is 1500 m ⁇ 2 > / g or more as a BET specific surface area, Furthermore, 2500 m ⁇ 2 > / g or more, Furthermore, it is 3000 m ⁇ 2 > / g or more. Since the use which can be applied increases as the specific surface area increases, the BET specific surface area of the metal complex of the present invention is preferably 3200 m 2 / g or more.
  • the BET specific surface area of the metal complex of the present invention is 4500 m 2 / g or less, and further 4000 m 2 / g or less.
  • As preferable range of the BET specific surface area for example, 3000 m 2 / g or more 4500 m 2 / g or less, further 3030m 2 / g or more 4500 m 2 / g or less, or even 3200 m 2 / g or more 4500 m 2 / g or less, or even it is 3000 m 2 / g or more 4000 m 2 / g or less, or even 3030m 2 / g or more 4000 m 2 / g or less, or even can be given 3200 m 2 / g or more 4000 m 2 / g or less.
  • More specific BET specific surface area of the metal complexes of the present invention 3030m 2 / g or more 3260m 2 / g or less, further may include the following 3200 m 2 / g or more 3260m 2 / g.
  • the BET specific surface area can be measured by a nitrogen adsorption method. For example, after vacuum-degassing the dried metal complex, nitrogen gas is introduced at 77 K, and the equilibrium pressure and adsorption amount are measured to obtain an adsorption isotherm. What is necessary is just to obtain
  • the metal complex of the present invention has a pore volume of 0.9 cm 3 / g or more, further 1.0 cm 3 / g or more, and further 1.5 cm 3 / g or more. As the pore volume increases, the adsorption amount of the adsorbed substance tends to increase.
  • the catalyst in applications such as adsorbent or drug delivery system, for example, a pore volume of 4.0 cm 3 / g or less, as long as more 3.0 cm 3 / g or less.
  • the pore volume is 0.9 cm 3 / g or more 4.0 cm 3 / g or less, further 1.0 cm 3 / g or more 4.0 cm 3 / g or less
  • 1.56 cm 3 / g or more and 4.0 cm 3 / g or less further 1.75 cm 3 / g or more and 4.0 cm 3 / g or less, or further 1.56 cm 3 / g or more and 3.0 cm.
  • the metal complex of the present invention has the same structure as MIL-101 (Cr). Therefore, the metal complex of the present invention has two types of pores having a pore diameter of 29 mm and a pore diameter of 34 mm.
  • the metal complex of the present invention is a production method having a reaction step of reacting a raw material mixture containing an aluminum source, terephthalic acid and an aprotic solvent, wherein the molar ratio of water to aluminum in the raw material mixture is 1.0 or less. It can be obtained by a manufacturing method characterized in that it exists.
  • the production method of the present invention has a reaction step of reacting a raw material mixture containing an aluminum source, terephthalic acid and an aprotic solvent.
  • the metal complex of the present invention can be obtained by reacting an aluminum source and terephthalic acid in an aprotic solvent and crystallizing them.
  • the molar ratio (mol / mol) of water to aluminum in the raw material mixture in the reaction step (hereinafter referred to as “H 2 O / Al”) is 1.0 or less, further 0.5 or less, and further 0.2. It is as follows.
  • H 2 O / Al exceeds 1.0, the metal complex of the present invention cannot be obtained.
  • the resulting metal complex is a metal complex having a space group other than Fd-3m, such as MIL-53 (Al) or MIL-68 (Al), or these It becomes a metal complex containing.
  • H 2 O / Al is may be at 1.0 or less, H 2 O / Al is 0.1 or less, or even 0.05 or less.
  • the water (H 2 O) in the raw material mixture includes aluminum source, terephthalic acid, and crystal water derived from any of aprotic solvents, adsorbed water and other water.
  • the aluminum source is a compound containing aluminum, and H 2 O / Al in the raw material mixture may be 1.0 or less.
  • an aluminum source aluminum chloride, aluminum chloride hexahydrate, aluminum fluoride, aluminum bromide, aluminum iodide, aluminum sulfate, aluminum sulfate 16 hydrate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum hydroxide, At least one selected from the group consisting of aluminum ethoxide and aluminum isopropoxide, and also aluminum chloride, aluminum fluoride, aluminum bromide, aluminum iodide, aluminum sulfate, aluminum nitrate, aluminum hydroxide, aluminum ethoxide, and The at least 1 sort (s) chosen from the group of aluminum isopropoxide can be mentioned.
  • the aluminum source is preferably an aluminum halide anhydride, more preferably anhydrous aluminum chloride.
  • the aluminum source may be a solid or an aluminum source solution dissolved in an aprotic solvent.
  • the aluminum concentration of the raw material mixture can be 0.01 mol / L or more, and further 0.03 mol / L or more.
  • the aluminum concentration may be 2.0 mol / L or less, and further 1.0 mol / L or less.
  • the terephthalic acid only needs to have a low water content such as adsorbed water, and any terephthalic acid may be used as long as H 2 O / Al in the raw material mixture is 1.0 or less.
  • Terephthalic acid is an aromatic compound comprising a benzene ring having a carboxylic acid group at the 1-position and 4-position, and is an aromatic compound having no substituent other than the carboxylic acid group. Therefore, terephthalic acid having a substituent other than a carboxylic acid group such as aminoterephthalic acid and methylterephthalic acid is not included.
  • the purity of terephthalic acid is preferably 90% by weight or higher, preferably 95% by weight or higher, more preferably 98% by weight or higher.
  • the terephthalic acid may be a solid or a terephthalic acid solution dissolved in an aprotic solvent.
  • the terephthalic acid concentration in the raw material mixture is 0.2 or more, more preferably 0.4 or more, as the molar ratio (mol / mol) of terephthalic acid to aluminum in the raw material mixture (hereinafter referred to as “TA / Al”). Can be mentioned.
  • TA / Al is 0.2 or more, the yield of the metal complex of the present invention tends to increase. If TA / Al is 1.2 or less, and further 1.0 or less, the metal complex of the present invention can be obtained in a sufficient yield.
  • Examples of TA / Al include 0.2 or more and 1.2 or less, further 0.4 or more and 1.2 or less, and further 0.4 or more and 1.0 or less.
  • the aprotic solvent is a polar or nonpolar solvent that does not have a proton donating property, and any H 2 O / Al in the raw material mixture may be 1.0 or less.
  • Specific aprotic solvents include at least the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, and N-methyl-2-pyrrolidone. One type can be mentioned.
  • the aprotic solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-diethylformamide, Is preferably N, N-dimethylformamide.
  • the reaction in the reaction step is performed by, for example, mixing an aluminum source, terephthalic acid, and an aprotic solvent to obtain a raw material mixture, and then crystallizing the raw material mixture as a predetermined reaction temperature, either an aluminum source or terephthalic acid.
  • a predetermined reaction temperature either an aluminum source or terephthalic acid.
  • the other raw material of terephthalic acid or aluminum source is mixed with this to form a raw material mixture, and the raw material mixture is crystallized.
  • an aluminum source, terephthalic acid, or a mixture thereof is mixed with the aprotic solvent to form a raw material mixture, and the raw material mixture is crystallized.
  • the reaction step the raw material mixture is heated to crystallize it to obtain the metal complex of the present invention.
  • the reaction temperature in the reaction step can be lower than 200 ° C., further 170 ° C. or lower, further 160 ° C. or lower, or 130 ° C. or lower.
  • the reaction temperature is 90 ° C. or higher, further 100 ° C. or higher, and further 110 ° C. or higher, crystallization of the raw material mixture is easily promoted.
  • the reaction temperature is preferably 90 ° C. or higher and 150 ° C. or lower.
  • the reaction temperature is, for example, 90 ° C.
  • the reaction temperature may be changed during the reaction.
  • the temperature during the reaction may be higher than the reaction start temperature, and conversely, it may be lower than the reaction start temperature.
  • reaction time 0.5 hour or more and 36 hours or less, Furthermore, 1 hour or more and 24 hours or less can be mentioned.
  • the reaction step can be performed at 1 atm or more and 2 atm or less. Since a general reaction apparatus can be used, the reaction step is preferably performed in an open system, for example, in the atmosphere. On the other hand, the reaction step may be performed at a higher pressure using a closed reactor such as an autoclave.
  • the reaction may be performed with the raw material mixture standing, but the raw material mixture may be reacted with stirring, or after stirring, the reaction may be stopped and the reaction may be performed while standing.
  • the metal complex of the present invention can be easily obtained by reacting the raw material mixture with stirring within one hour after the reaction starts at the reaction temperature, for example, terephthalic acid and the aluminum source.
  • a washing step or a firing step may be included after the reaction step.
  • washing process impurities attached to the metal complex can be removed.
  • the washing method is arbitrary, washing with the same kind of solvent as the aprotic solvent contained in the raw material mixture, alcohol or the like can be mentioned.
  • the firing step unreacted terephthalic acid and the solvent adsorbed on the metal complex are removed.
  • the firing method is arbitrary, and examples thereof include various gas atmospheres and heat treatments under reduced pressure.
  • Examples of the heat treatment conditions include a method of heat treatment at 100 to 500 ° C. for 1 to 100 hours in any atmosphere under dry air, dry nitrogen stream or reduced pressure.
  • the crystal structure of the sample was measured by XRD measurement.
  • the crystal structure and space group were identified by comparing the XRD pattern of the obtained sample with the XRD pattern of the target sample.
  • the measurement apparatus and measurement conditions for XRD measurement are as follows. Apparatus: M03XHF, manufactured by Mac Science Co., Ltd.
  • X-ray source: Cu-K ⁇ ray Measurement range: 2 ⁇ 3 to 43 ° Step width: 0.02 ° / sec
  • MIL-101 (Cr) synthesized by the following method was used as a target sample.
  • BET specific surface area and pore volume The BET specific surface area and pore volume of the sample were measured by the BET multipoint method.
  • the measurement apparatus and measurement conditions for the BET specific surface area and pore volume are as follows. Apparatus: BELSORP 28SA, manufactured by Nippon Bell Co., Ltd. Analysis software: BELMaster version 5.3.3.0 Pretreatment: 200 ° C., 6.5 hours, deaeration treatment
  • Adsorption gas Nitrogen Adsorption / desorption temperature: ⁇ 196 ° C. (boiling point of nitrogen) Equilibrium relative pressure used for calculation of specific surface area: 0.05 ⁇ p / p 0 ⁇ 0.15.
  • the thermal decomposition temperature of the sample was measured by TG.
  • the measurement apparatus and measurement conditions for TG measurement are as follows. Apparatus: TG / DTA6300, manufactured by SEIKO, Inc. Temperature range: 20-600 ° C Temperature increase rate: 10 ° C / min Gas atmosphere: Dry air The temperature corresponding to the intersection of the tangent at the inflection point of the weight loss curve obtained by TG measurement and the extended line with the base line was defined as the thermal decomposition temperature.
  • MIL-101 (Cr) was synthesized as a target sample.
  • MIL-101 (Cr) was synthesized by a method according to the synthesis method of MIL-101 (Cr) in Non-Patent Document 1.
  • the XRD pattern of the target sample is shown in FIG. 4 and the XRD pattern of MIL-101 (Cr) in the space group Fd-3m described in Fig. 4, and Fig. Of Reference (Chem. Commun., Pp. 4192-4194 (2008)).
  • a pattern similar to the XRD pattern of MIL-101 (Cr) by the calculation described in S3 was shown. This confirmed that the target sample was MIL-101 (Cr) in the space group Fd-3m.
  • Example 1 ⁇ Synthesis> In a 200 mL eggplant flask, 0.67 g (5.0 mmol) of anhydrous aluminum chloride, 0.50 g (3.0 mmol) of terephthalic acid, and N, N-dimethylformamide (hereinafter referred to as “DMF”) having a water content of 10 ppm by weight or less. .) 120 mL was mixed to obtain a raw material mixture. H 2 O / Al of the raw material mixture was below the detection limit (0.02), TA / Al was 0.6, and aluminum concentration was 0.042 mol / L.
  • DMF N, N-dimethylformamide
  • the raw material mixture was heated to 110 ° C. in 20 minutes with stirring, and maintained at 110 ° C. for 3 hours while continuing the stirring. Then, stirring was stopped and the white metal complex was obtained by leaving still at 110 degreeC for 12 hours.
  • the metal complex was collected by filtration, washed with 20 mL of DMF, and then rinsed with 20 mL of ethanol. The washed metal complex was dried at 100 ° C. for 3 hours under a nitrogen stream to obtain 0.66 g of a crude product. 0.50 g of the crude product was dispersed in 25 mL of ethanol and washed at 80 ° C. for 12 hours. After washing, filtering, and heating at 100 ° C. for 6 hours under a flow of dry nitrogen, a metal complex of this example was obtained.
  • the XRD pattern of the metal complex of this example was the same as the XRD pattern of the target sample. From this, it was confirmed that the metal complex of this example was the space group Fd-3m and had the same crystal structure as MIL-101 (Cr).
  • the XRD pattern of the metal complex of this example is shown in FIG. 2, and the main XRD peaks are shown in Table 2.
  • the metal complex of this example had a specific surface area of 3030 m 2 / g and a pore volume of 1.56 cm 3 / g. This confirmed that the metal complex had a high specific surface area and pore volume.
  • the nitrogen adsorption isotherm of the metal complex and the target sample (MIL-101 (Cr)) is shown in FIG.
  • the metal complex was confirmed to exhibit an adsorption isotherm similar to MIL-101 (Cr). This suggests that the metal complex has a pore structure similar to MIL-101 (Cr), that is, has two types of pores with a pore diameter of 29 mm and a pore diameter of 34 mm. Moreover, it was confirmed that the metal complex of the present invention can be applied as a nitrogen adsorbent.
  • FIG. 4 shows the thermal decomposition behavior of the metal complex of this example and the target sample.
  • the thermal decomposition temperature of the metal complex of this example was 500 ° C.
  • the thermal decomposition temperature of MIL-101 (Cr) was 310 ° C.
  • MIL-101 (Cr) has the same organic ligand, crystal structure and space group
  • the metal complex of this example has a significantly higher thermal decomposition temperature than MIL-101 (Cr). It was confirmed to have The results are shown in Table 3.
  • Example 2 ⁇ Synthesis> In a 200 mL eggplant flask, 0.67 g (5.0 mmol) of anhydrous aluminum chloride, 0.50 g (3.0 mmol) of terephthalic acid, and 60 mL of DMF having a water content of 250 ppm by weight were mixed to obtain a raw material mixture.
  • the raw material mixture had H 2 O / Al of 0.16, TA / Al of 0.6, and an aluminum concentration of 0.083 mol / L.
  • the raw material mixture was heated to 130 ° C. in 20 minutes with stirring, and maintained at 130 ° C. for 3 hours while stirring was continued. Thereafter, stirring was stopped, and the mixture was allowed to stand at 130 ° C. for 12 hours to obtain a white solid metal complex.
  • the metal complex was collected by filtration, washed with 20 mL of DMF, and then rinsed with 20 mL of ethanol. The washed metal complex was dried at 100 ° C. for 3 hours under a nitrogen stream to obtain 0.87 g of a crude product.
  • Example 3 ⁇ Synthesis> A 200 mL eggplant flask was mixed with 0.67 g (5.0 mmol) of anhydrous aluminum chloride, 0.50 g (3.0 mmol) of terephthalic acid and 60 mL of N, N-dimethylformamide having a water content of 125 ppm by weight to obtain a raw material mixture. .
  • the raw material mixture had an H 2 O / Al ratio of 0.08, a TA / Al ratio of 0.6, and an aluminum concentration of 0.083 mol / L.
  • the raw material mixture was heated to 110 ° C. in 20 minutes with stirring, and kept at 110 ° C. for 1 hour while continuing stirring. Then, it heated at 160 degreeC and made it react for 2 hours, making a raw material mixture recirculate
  • the metal complex was collected by filtration, washed with 20 mL of DMF, and then rinsed with 20 mL of ethanol. The washed metal complex was dried at 100 ° C. for 3 hours under a nitrogen stream to obtain 0.75 g of a crude product.
  • the 0.50 g of the crude product was dispersed in 25 mL of ethanol and washed at 80 ° C. for 12 hours. After washing, filtering, and heating at 100 ° C. for 6 hours under a flow of dry nitrogen, a metal complex of this example was obtained.
  • Comparative Example 1 A metal complex of this comparative example was obtained in the same manner as in Example 2 except that DMF having a water content of 1000 ppm by weight was used as DMF.
  • the H 2 O / Al of the raw material mixture was 1.05
  • TA / Al was 0.6
  • the aluminum concentration was 0.083 mol / L.
  • the obtained crude product was 0.72 g of a white solid.
  • the metal complex of this comparative example was evaluated in the same manner as in Example 1.
  • the metal complex of this comparative example was MIL-53 (Al) and its space group was Pnam.
  • the BET specific surface area was 1100 m 2 /, and the pore volume was 0.62 cm 3 / g.
  • the XRD pattern is shown in FIG.
  • Comparative Example 2 A metal complex of this comparative example was obtained in the same manner as in Example 2 except that 1.21 g (5.0 mmol) of aluminum chloride hexahydrate was used as the aluminum source.
  • the raw material mixture contains water (H 2 O) derived from the hydrate of the aluminum source, the H 2 O / Al is 6.0 or more.
  • TA / Al of the raw material mixture was 0.6, and the aluminum concentration was 0.083 mol / L.
  • the obtained crude product was 0.68 g of a white solid.
  • Comparative Example 3 A metal complex of this comparative example was obtained by the same method as in Comparative Example 2 except that DMF was 120 mL and the reaction temperature was 120 ° C.
  • the raw material mixture contains water (H 2 O) derived from the hydrate of the aluminum source
  • the H 2 O / Al is 6.0 or more.
  • TA / Al of the raw material mixture was 0.6, and the aluminum concentration was 0.042 mol / L.
  • the obtained crude product was 0.80 g of a white solid.
  • the metal complex of this comparative example was evaluated in the same manner as in Example 1.
  • the metal complex of this comparative example was MIL-68 (Al) and the space group was Cmcm.
  • the BET specific surface area was 1420 m ⁇ 2 > /, and the pore volume was 0.87 cm ⁇ 3 > / g.
  • the XRD pattern is shown in FIG.
  • Comparative Example 1 is the same as Example 2 except for H 2 O / Al.
  • the metal complex of the present invention can be obtained by paying attention to the amount of water in the raw material mixture and controlling it.
  • the metal complex of the present invention has high heat resistance and a high specific surface area, and further has a high pore volume. Therefore, the metal complex of the present invention can be applied to gas adsorption, separation, or storage of hydrogen, carbon dioxide, nitrogen, hydrocarbons such as methane and propane, and mixed gas thereof. Furthermore, the metal complex of the present invention can be applied as a catalyst as it is, or can be applied as a catalyst after immobilizing a noble metal such as platinum or palladium on the surface.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention se rapporte à un complexe de métal poreux comportant de l'acide téréphtalique en tant que ligand, le complexe métallique poreux présentant à la fois une grande résistance thermique et une grande surface spécifique. Le complexe métallique est caractérisé en ce que le complexe métallique a une structure dans laquelle l'acide téréphtalique est coordonné en amas d'ions aluminium, et le groupe d'espace est Fd-3m. Un tel complexe métallique peut être obtenu à l'aide d'un procédé de fabrication qui comporte une étape de réaction dans laquelle un mélange de matières de départ comprenant un source d'aluminium, de l'acide téréphtalique et un solvant aprotique est mis à réagir. Le procédé de fabrication est caractérisé en ce que le rapport molaire de l'eau à l'aluminium dans le mélange de matières de départ est de 1,0 ou moins.
PCT/JP2015/059400 2014-04-03 2015-03-26 Complexe métallique et son procédé de fabrication WO2015152001A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110841717A (zh) * 2019-11-21 2020-02-28 合肥工业大学 负载纳米级银单质的介孔铬基金属有机框架化合物中空微球壳及其制备方法
CN111250167A (zh) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 一种Fe基双金属有机骨架电催化剂及其制备和应用
CN111408413A (zh) * 2020-03-30 2020-07-14 浙江工商大学 一种改性氮化碳/Fe基MOF复合材料及其制备方法和应用
CN114409917A (zh) * 2022-01-26 2022-04-29 华中师范大学 一种具有催化臭氧分解能力的抗湿性铁基金属有机框架材料及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016185534A (ja) * 2015-03-27 2016-10-27 新日鐵住金株式会社 ガス吸着材ならびにガス分離装置及びガス貯蔵装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009506991A (ja) * 2005-08-22 2009-02-19 ビーエーエスエフ ソシエタス・ヨーロピア 主族金属イオンを含有する金属有機骨格材料の製造方法
US20100076220A1 (en) * 2007-04-24 2010-03-25 Basf Se Novel metal organic frameworks based on aluminum, iron and chromium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009506991A (ja) * 2005-08-22 2009-02-19 ビーエーエスエフ ソシエタス・ヨーロピア 主族金属イオンを含有する金属有機骨格材料の製造方法
US20100076220A1 (en) * 2007-04-24 2010-03-25 Basf Se Novel metal organic frameworks based on aluminum, iron and chromium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111250167A (zh) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 一种Fe基双金属有机骨架电催化剂及其制备和应用
CN110841717A (zh) * 2019-11-21 2020-02-28 合肥工业大学 负载纳米级银单质的介孔铬基金属有机框架化合物中空微球壳及其制备方法
CN110841717B (zh) * 2019-11-21 2022-05-06 合肥工业大学 负载纳米级银单质的介孔铬基金属有机框架化合物中空微球壳及其制备方法
CN111408413A (zh) * 2020-03-30 2020-07-14 浙江工商大学 一种改性氮化碳/Fe基MOF复合材料及其制备方法和应用
CN111408413B (zh) * 2020-03-30 2022-09-20 浙江工商大学 一种改性氮化碳/Fe基MOF复合材料及其制备方法和应用
CN114409917A (zh) * 2022-01-26 2022-04-29 华中师范大学 一种具有催化臭氧分解能力的抗湿性铁基金属有机框架材料及其制备方法和应用

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