MOF material for shaping, shaped body, gas adsorbent, gas adsorption device, and method for producing MOF material for shaping

Abstract

This MOF material for shaping composed of a metal-organic framework (MOF) is localized on the surfaces of crystal particles forming the MOF and contains silicon (Si).

Description

MOF material for shaping, shaped body, gas adsorbent, gas adsorption device, and method for producing MOF material for shaping

[0001] The present disclosure relates to a MOF material for shaping, a shaped body, a gas adsorbent, a gas adsorption device, and a method for producing a MOF material for shaping.

[0002] Metal-organic frameworks (MOFs) are complex crystals formed by the coordination of metal ions and organic ligands. They have a highly regular, porous coordination network structure formed by the metal ions and organic ligands, and contain numerous nanospaces within. By utilizing these nanospaces, MOFs can be used as materials for occluding and separating various substances such as gases, or as catalytic materials. Because MOFs are generally synthesized as powders, when used as gas occlusion / separation materials or catalytic materials, as described above, the powdered MOFs must be molded (shaped). Conventional methods for shaping powdered MOFs include molding methods using binders such as binders or polymers (see, for example, Patent Documents 1 and 2).

[0003] Patent No. 4980918 Patent No. 6272696

[0004] However, when MOFs are shaped by binding MOF particles using a binder or the like as described above, the pores of the porous MOF are blocked, reducing the specific surface area of ​​the MOF, which may result in a loss of its ability to occlude and separate gases using nanospaces. Even if the functionality of the MOF is not impaired, the addition of a binder has created a problem in that the amount of adsorption per unit weight decreases. Therefore, there has been a demand for a technology for shaping MOFs without using a binder or other binding agent, or by reducing the amount of binder or other binding agent used, while suppressing the deterioration of MOF performance.

[0005] The present disclosure can be realized in the following forms. (1) According to one embodiment of the present disclosure, a MOF material for shaping is provided, which is composed of a metal-organic framework (MOF). This MOF material for shaping contains silicon (Si) localized on the surface of the crystalline particles constituting the MOF. With this form of MOF material for shaping, silicon-mediated bonding occurs on the surface of the MOF, eliminating the need for a binder or other binding agent to shaping the MOF, or making it possible to reduce the amount of binder or other binding agent used. (2) In the above-described form of MOF material for shaping, the atomic fraction ratio of the complex metal contained in the MOF to silicon (Si) (complex metal contained in the MOF:Si) may be 0.98:0.02 to 0.9:0.10. This configuration can prevent a decrease in performance, such as the gas adsorption capacity of the MOF, due to an excessive amount of Si added, while facilitating the shaping of the MOF. (3) According to another aspect of the present disclosure, a shaped object is provided that is made of the MOF material for shaping described in (1). This form of shaped object allows silicon-mediated bonding on the surface of the MOF, eliminating the need for a binder or other binding agent to shape the MOF, or making it possible to reduce the amount of binder or other binding agent used. (4) The shaped object of the above form may have an average particle size of 1 mm or more. This configuration enhances the effects of shaping MOFs, such as easier handling of the MOF material, reduced pressure loss in equipment containing the MOF material, and reduced problems associated with vacuum pumping for gas separation when applying the MOF material to a gas adsorption device. (5) When the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping in the above-described form is measured at a measurement temperature of 0°C and compared with the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more, the carbon dioxide adsorption amount may be 1.5 times or more greater than that of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon. This configuration ensures the carbon dioxide adsorption performance of the MOF material for shaping.(6) When the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping in the above-described form is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, the carbon dioxide adsorption amount may be 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon. This configuration ensures the carbon dioxide adsorption performance of the MOF material for shaping. (7) When the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping in the above-described form is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, the carbon dioxide adsorption amount may be 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon. This configuration ensures the carbon dioxide adsorption performance of the shaped body. (8) When the carbon dioxide adsorption / desorption isotherm of the shaped body is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, the carbon dioxide adsorption amount may be 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon. This configuration ensures the carbon dioxide adsorption performance of the shaped body. (9) When the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping is measured at a measurement temperature of 0°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 45 cm. ３ (STP) / g or more. This configuration ensures the carbon dioxide adsorption performance of the MOF material for shaping. (10) In the MOF material for shaping of the above form, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 25 cm ３ (STP) / g or more. This configuration ensures the carbon dioxide adsorption performance of the MOF material for shaping. (11) In the shaped body of the above form, when the carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 40 cm ３(STP) / g or more. With this configuration, the carbon dioxide adsorption performance of the shaped object can be ensured. (12) In the shaped object of the above form, when the carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 20 cm ３ (STP) / g) or more. This configuration ensures carbon dioxide adsorption performance in the shaped body. (13) According to yet another aspect of the present disclosure, there is provided a gas adsorbent for adsorbing and releasing gas. The gas adsorbent is composed of the shaped body according to any one of (3), (4), (7), (8), (11), and (12). According to this aspect of the gas adsorbent, silicon-mediated bonding occurs on the surface of the MOF, eliminating the need for a binder or other binding agent when shaping the MOF to produce the gas adsorbent, or enabling the amount of binder or other binding agent to be reduced. (14) According to yet another aspect of the present disclosure, there is provided a gas adsorption device including the gas adsorbent according to (13). This gas adsorption device can suppress problems associated with evacuation for gas separation. (15) According to yet another aspect of the present disclosure, there is provided a method for producing a shaped MOF material. This method for producing a shaped MOF material involves adding a silane derivative having a functional group capable of forming a chemical bond with a functional group on the surface of a metal-organic framework (MOF). According to this method for producing a shaped MOF material, the silane derivative forms a chemical bond with the functional group on the surface of the MOF, bonding the MOF and the silane derivative, facilitating shaping of the MOF. As a result, a binder or other binding agent is not required to shape the MOF, or the amount of binder or other binding agent used can be reduced. The present disclosure can be realized in various forms other than those described above, such as a gas adsorbent formed of a shaped body, a gas adsorption device including a gas adsorbent, or a method for producing a shaped body.

[0006] 1 is an explanatory diagram showing the structure of UiO-66-COOH into which a carboxy group has been introduced. 2 is an explanatory diagram showing an example of a silane derivative. 3 is an explanatory diagram schematically showing the configuration of the MOF material for shaping according to the present embodiment. 4 is an explanatory diagram showing the prepared MOF material for shaping and a shaped body. 5 is a TEM image of Zr element mapping performed on sample S2. 6 is a TEM image of Si element mapping performed on sample S2. 7 is a TEM image of Zr element mapping performed on sample S11. 8 is a TEM image of Si element mapping performed on sample S11. 9 is an explanatory diagram showing the results of determining the atomic fractions of samples S1 to S3 and S11. 10 is an explanatory diagram showing a graph plotting the calculation results of the atomic fractions. 11 is an explanatory diagram showing the results of measuring a carbon dioxide adsorption / desorption isotherm at 25°C. 12 is an explanatory diagram showing the results of measuring a BET specific surface area and the amount of carbon dioxide adsorption at 0°C. 13 is an explanatory diagram showing the results of measuring a carbon dioxide adsorption / desorption isotherm at 0°C. 14 is an explanatory diagram showing the results of measuring a BET specific surface area and the amount of carbon dioxide adsorption at 25°C. An explanatory diagram showing the results of measuring a carbon dioxide adsorption / desorption isotherm at 25° C. An explanatory diagram showing the results of measuring a carbon dioxide adsorption / desorption isotherm at 25° C. An explanatory diagram showing the results of measuring a carbon dioxide adsorption / desorption isotherm at 25° C.

[0007] A. Structure of the MOF Material for Shaping: The MOF material for shaping of this embodiment is composed of a metal-organic framework (MOF) and contains silicon (Si) localized on the surface of the crystalline particles constituting the MOF. MOFs are porous metal complexes obtained by utilizing the self-organization of metal ions and organic ligands. They are crystalline materials that form a highly regular array structure, and have countless nanospaces within the array structure, thereby achieving a high surface area. The MOF material for shaping of this embodiment "contains silicon (Si) localized on the surface of the crystalline particles constituting the MOF," and the metal ions and organic ligands constituting the MOF do not substantially contain silicon (Si). The MOF material for shaping of this embodiment contains silicon (Si) localized on the surface of the crystalline particles constituting the MOF, making it possible to shaping without using a binder or other binding agent, or by reducing the amount of binder or other binding agent used, while suppressing the deterioration of MOF performance due to the use of a binder or other binding agent. As will be described later, the MOF material for shaping according to this embodiment can be produced by preparing an MOF formed using a material that is substantially free of silicon (Si), and then adding a silane derivative, which is a compound containing silicon (Si), to the MOF.

[0008] The MOFs constituting the MOF material for shaping of the present embodiment may be appropriately selected depending on the application of the shaped body formed from the MOF material for shaping (for example, gas storage, separation, or catalytic application, or the type of target gas, etc.), and are not particularly limited. Metal ions as complex metals constituting the MOFs include, for example, zirconium ions (Zr ４＋ ), zinc ions (Zn ２＋ ), copper ions (Cu ２＋ ), aluminum ions (Al ３＋ ), iron ions (Fe ３＋ ), cobalt ions (Co ３＋ ), nickel ions (Ni ２＋ ), magnesium ions (Mg ２＋ ), chromium ions (Cr ３＋ ), manganese ions (Mn ２＋) can be at least one selected from the group consisting of: organic ligands constituting the MOF; for example, at least one selected from carboxylic acids such as dicarboxylic acids including aromatic dicarboxylic acids such as terephthalic acid; amines; imidazoles; and derivatives thereof. By combining a complex metal with an organic ligand, it becomes possible to adjust various performances such as the chemical stability of the resulting MOF, the pore size and pore surface properties, the type and amount of gas adsorbed, or catalytic activity, magnetism, and polarity. For example, when using a MOF material for shaping by utilizing its ability to adsorb gases such as carbon dioxide, it is desirable for it to have properties that suppress the adsorption of other gases such as nitrogen and water vapor. In addition, the MOF constituting the MOF material for shaping of this embodiment may be a MOF having a relatively rigid framework structure and exhibiting a specific pore size, or a so-called soft MOF having a relatively flexible framework structure in which the framework expands and contracts upon adsorption and desorption of gases.

[0009] The MOF material for shaping according to this embodiment can be produced by adding a silane derivative to a MOF. The silane derivative added to the MOF has a functional group (hereinafter also referred to as a "silane derivative functional group") capable of forming a chemical bond with a functional group on the surface of the MOF (hereinafter also referred to as a "MOF functional group"). The "chemical bond" formed by the silane derivative and the MOF functional group can include both a chemical bond formed between the silane derivative and the MOF functional group, and a chemical bond formed between silane derivatives. Such a "chemical bond" can include a siloxane bond (-Si-O-Si-) and a bond represented by (-O-Si-). Examples of the "MOF functional group" involved in such a chemical bond include a carboxyl group (-COOH) and a hydroxyl group (-OH). When the organic ligand contained in the MOF originally has the above-mentioned "MOF side functional group," it is possible for such functional group to form a chemical bond with the silane derivative, but it is preferable to use a MOF in which a "MOF side functional group" has also been introduced into the organic ligand. The MOF material for shaping can be produced, for example, by stirring and mixing the MOF, silane derivative, and organic solvent such as ethanol under appropriate conditions, such as room temperature, followed by removing the solvent by suction filtration or the like, and then vacuum drying. After the drying step, a MOF material for shaping is obtained that can be easily converted into a powder.

[0010] Figure 1 shows an example of a MOF in which a "MOF-side functional group" is introduced into an organic ligand, UiO-66 (Zr ６ O ４ (OH) ４ (BDC) ６ 1 is an explanatory diagram showing the structure of UiO-66-COOH, in which a carboxy group (—COOH) has been introduced into a silane derivative (BDC = 1,4-benzenedicarboxylic acid). By actively introducing a “MOF-side functional group” into a MOF in this way, it is possible to increase the efficiency with which the “silane derivative-side functional group” of the silane derivative added to the MOF forms a chemical bond with the MOF-side functional group.

[0011] As described above, the silane derivative added to the MOF to produce the MOF material for shaping according to the present embodiment may have a "silane derivative side functional group" capable of forming a chemical bond with the "MOF side functional group." For example, the "silane derivative side functional group" may be a methoxy group (—OCH ３ ) and ethoxy group (-OC ２ H ５ A silane coupling agent containing a hydrolyzable group such as an alkoxy group, represented by the formula (I), can be used. The silane derivative may be a compound other than a silane coupling agent, as long as it has a "silane derivative-side functional group" capable of forming a chemical bond with the MOF-side functional group. An example of a suitably usable silane derivative is a methoxy-type alkylsilane.

[0012] Furthermore, the silane derivative may have two or more "silane derivative-side functional groups." In such cases, one silane derivative molecule can bond to multiple "MOF-side functional groups." When the silane derivative has two silane derivative-side functional groups, for example, when the silane derivative has a linear structure composed of alkyl groups or the like, it is desirable to have silane derivative-side functional groups at both ends of the linear structure. Examples of such silane derivatives include bistrimethoxy-type silane derivatives at both ends. The number of carbon atoms (the number of methylene groups) in the alkyl group portion of the silane derivative can be, for example, 2 to 10.

[0013] FIG. 2 is an explanatory diagram showing examples of such silane derivatives. In FIG. 2, silane derivatives with different linear alkyl groups are exemplified, including 1,2-bis(trimethoxysilyl)ethane (e.g., KBM-3026 manufactured by Shin-Etsu Chemical Co., Ltd.) with two methylene groups, 1,6-bis(trimethoxysilyl)hexane (e.g., KBM-3066 manufactured by Shin-Etsu Chemical Co., Ltd.) with six methylene groups, and 1,8-bis(trimethoxysilyl)octane (e.g., KBM-3086 manufactured by Shin-Etsu Chemical Co., Ltd.) with eight methylene groups. When preparing the MOF material for shaping according to this embodiment, a single type of silane derivative may be used, or multiple types of silane derivatives mixed in any desired ratio may be used.

[0014] When manufacturing the MOF material for shaping according to this embodiment, the amount of silane derivative added to the MOF is preferably small, as long as the effect of silicon (Si) being contained locally on the surface of the crystalline particles constituting the MOF can be obtained. For example, the amount is preferably 2.5 wt% or less of the total of the MOF and the silane derivative, and can be about 1.0 wt%. By reducing the amount of silane derivative added in this way, it is possible to prevent the pores of the MOF from being blocked by the silane derivative, thereby reducing the performance of the MOF (e.g., gas adsorption ability).

[0015] In the MOF material for shaping according to this embodiment, the atomic fraction ratio of the complex metal contained in the MOF constituting this MOF material to silicon (Si) (complex metal contained in the MOF:Si) can be 0.98:0.02 to 0.9:0.10. Such atomic fractions can be determined using an EDS-equipped transmission electron microscope (TEM-EDS) or an EDS-equipped scanning transmission electron microscope (STEM / EDS). Combining EDS with the above-described electron microscope enables elemental mapping, and quantitative mapping (wt%) can be performed to determine the atomic fraction. If the measured value of the ratio of Si (atomic fraction of Si) when the sum of the complex metal and silicon (Si) in the elemental composition ratio is 1 is 0.02 or more, it can be said that a sufficiently distinguishable amount of Si is present in the MOF material for shaping, and the effect of the present application, that is, the localization of Si on the surface of the crystalline particles constituting the MOF, which facilitates shaping, can be more fully achieved. Furthermore, if the measured atomic fraction of Si is 0.10 or less, it is possible to prevent the pores of the MOF from being blocked due to an excessive amount of Si being added, which would result in a decrease in the performance of the MOF, such as the gas adsorption capacity. From the viewpoint of preventing an excessive amount of Si being added, the atomic fraction of Si is more preferably 0.09 or less, and even more preferably 0.08 or less.

[0016] B. Regarding the Shaped Body: The MOF material for shaping, obtained, for example, in powder form by the aforementioned production method, may be molded (shaped) into a shaped body for use. Various methods, such as injection molding, extrusion molding, blow molding, compression molding, powder molding, calendar molding, and thermoforming, can be used to mold the MOF material for shaping. Various shapes, such as spherical, cylindrical, and rectangular, can be used for the shaped body. The shaped body molded from the MOF material for shaping of this embodiment can be used, for example, as a gas adsorbent in a gas adsorption device. Molding the MOF material into a shaped body as described above facilitates handling of the MOF material. Furthermore, converting the MOF material into a shaped body can reduce pressure loss in a device equipped with the MOF material. Furthermore, in a gas adsorption device (gas separation device) using pressure swing adsorption (PSA), for example, using a shaped gas adsorbent can reduce problems associated with evacuation for gas separation. If the gas adsorbent is in powder form, problems may arise such as the gas adsorbent being sucked in and lost when the vacuum is drawn (dissipation by gas flow), or the vacuum pump malfunctioning due to the sucking of the powder.

[0017] The shaped body may have an average particle size of, for example, 1 mm or more. This can enhance the effects already described by molding the MOF material into a shaped body. From the viewpoint of obtaining the effects of the shaping described above, the average particle size of the shaped body is more preferably 2 mm or more, and even more preferably 3 mm or more. Furthermore, from the viewpoint of ensuring gas diffusibility in a device equipped with the shaped body, the average particle size of the shaped body may be, for example, 10 mm or less, more preferably 8 mm or less, and even more preferably 6 mm or less. Various methods can be used to measure the average particle size of the shaped body as long as they can be measured with sufficient accuracy, and can be measured using, for example, a vernier caliper, a digital microscope, an image dimension measuring device, etc.

[0018] When forming a shaped body by molding the MOF material for shaping of this embodiment, a binder may be added during molding, or a binder may not be added. The presence or absence of a binder and the amount of binder added may be appropriately determined depending on the molding method for shaping and the performance required of the resulting shaped body. For example, when forming a shaped body by compression molding, a relatively strong compressive force is applied during molding, which makes it easier to reduce the amount of binder added during molding and facilitates binderless molding. Furthermore, when forming a shaped body by extrusion molding, for example, the compressive force applied during molding is relatively small, so it is also preferable to add a binder. When molding a powdered MOF using the binding force of a binder, a binder in an amount exceeding 10 wt% is generally required. However, when molding the MOF material for shaping of this embodiment, even if a binder is added, the amount of binder added can be 10 wt% or less, and even a smaller amount can be added to achieve sufficient shaping. The amount of binder added to the MOF material for shaping in this embodiment can be, for example, 2 to 5 wt %.

[0019] When a binder is used to mold the MOF material for molding according to this embodiment, various binders conventionally known as binders for molding powdered materials can be used. From the viewpoint of ensuring heat resistance, it is desirable to use inorganic binders such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and polyethylene oxide (PEO). Among resins that can be used as binders, PVP is desirable because it has higher heat resistance and is therefore more stable even under relatively high temperature conditions, such as those used in MOF activation treatments. Furthermore, as described above, among resins that can be used as binders, PVP exhibits a higher moisture absorption rate, thereby mitigating the effects of moisture on MOFs. Furthermore, PVP's relatively good adhesiveness and dispersibility make it easier to enhance the bonding between MOFs and silane derivatives.

[0020] The shaped body obtained by molding the MOF material for shaping according to this embodiment can be applied to various devices by utilizing the properties of the MOF related to gas adsorption / separation and catalytic activity. For example, a gas adsorption device can be formed using a gas adsorbent formed using the shaped body according to this embodiment. Examples of gas adsorption devices include a pressure swing adsorption (PSA) device in which the gas pressure in an adsorption tower equipped with a gas adsorbent is varied between predetermined high and low pressure states, and gas is separated by utilizing the difference between the amount of gas adsorbed at high pressure during gas adsorption and the amount of gas adsorbed at low pressure during gas desorption. Alternatively, a temperature swing adsorption (TSA) device can be formed by varying the temperature of the adsorption tower between predetermined high and low temperatures, and gas is separated by utilizing the difference between the amount of gas adsorbed at low temperature during gas adsorption and the amount of gas adsorbed at high temperature during gas desorption. Alternatively, a device using pressure and thermal swing adsorption (PTSA) that combines the above-mentioned pressure fluctuations and temperature fluctuations may be used. The PSA method is preferred from the viewpoint of being able to switch between the adsorption process and the desorption process in a relatively short time.

[0021] The MOF material for shaping according to the present embodiment is prepared by adding a silane derivative having a silane derivative-side functional group capable of forming a chemical bond with the MOF-side functional group to the MOF, resulting in silicon (Si) localized on the surface of the crystalline particles that make up the MOF. This eliminates the need for a binder or other binding agent for shaping the MOF, or allows for a reduction in the amount of binder or other binding agent used.

[0022] FIG. 3 is an explanatory diagram showing the structure of the MOF material for shaping according to the present embodiment, which is prepared by adding a silane derivative to a MOF, i.e., a state in which the MOF is bonded to the silane derivative to form the MOF material for shaping. When preparing the MOF material for shaping by adding a silane derivative to a MOF, the hydrolyzable group (e.g., a methoxy group (-OCH ３)) is hydrolyzed to produce silanol (Si-OH) and alcohol, and then a condensation reaction proceeds between the silanol produced by the hydrolysis and the functional groups on the MOF, forming a chemical bond and bonding the MOF and the silane derivative. Furthermore, in some silane derivatives, a condensation reaction proceeds between the silanols of the silane derivatives, bonding the silane derivatives together. As a result, it is believed that a MOF material for shaping, such as that shown in Figure 3, can be obtained. Furthermore, it is believed that some crystalline particles of the MOF are bonded together via the silane derivative.

[0023] In this way, the MOF-side functional groups present on the surface of the MOF are bonded together via the silane derivative, thereby fixing the shape and making the MOF easier to shape as a MOF material for shaping. Furthermore, silane derivatives with relatively large molecules, such as the silane derivative having a long chain linked to a methylene group shown in Figure 2, generally have difficulty entering the pores of the MOF, and bonding between the MOF-side functional groups and the silane derivative-side functional groups proceeds almost exclusively on the MOF surface. Furthermore, of the silane derivatives added to the MOF during the preparation of the MOF material for shaping, excess silane derivatives not used to bond with the MOF surface are thought to be removed together with the solvent when removing the solvent from the MOF during the production process of the MOF material for shaping. As a result, the silane derivative (and silicon derived from the silane derivative) is localized on the surface of the MOF. This prevents the silane derivative from blocking the internal pores of the MOF, thereby suppressing the deterioration of MOF performance due to the blocking of the MOF pores. In particular, in the MOF material for shaping of this embodiment, the amount of silane derivative added can be made small compared to the amount of a typical binder added, thereby enhancing the effect of suppressing pore blockage due to the addition of the silane derivative.

[0024] Furthermore, the MOF material for shaping according to this embodiment and the shaped body formed from such a MOF material for shaping can increase the gas adsorption capacity compared to the MOF constituting the MOF material for shaping. This is thought to be because, as shown in Figure 3, the bonding between the MOF and the silane derivative on the surface of the MOF creates new sites where gas (shown as carbon dioxide in Figure 3) can be adsorbed between the surface of the MOF and the silane derivative, i.e., a new gas adsorption mechanism is created.

[0025] Furthermore, with the MOF material for shaping according to this embodiment and the shaped body formed from such a MOF material for shaping, the silane derivative forms a chemical bond with the MOF-side functional group, forming a siloxane bond (-Si-O-Si-), which is a type of chemical bond with very high bond energy. This increases the chemical stability of the MOF material, thereby improving the heat resistance and weather resistance of the MOF material for shaping. Therefore, even when relatively high-temperature treatments are performed, such as activation treatments of MOFs at temperatures exceeding 100°C under vacuum, or when the use conditions are relatively high, the stability of the MOF material can be easily ensured.

[0026] As described above, the MOF material for shaping and the shaped body of this embodiment can increase the gas adsorption capacity compared to the MOF that constitutes the MOF material for shaping. When measuring the carbon dioxide adsorption / desorption isotherm at a measurement temperature of 0°C and comparing the carbon dioxide adsorption capacity at an absolute pressure of 0.4 or higher, the MOF material for shaping of this embodiment desirably exhibits a carbon dioxide adsorption capacity that is 1.5 times or more the carbon dioxide adsorption capacity of an MOF having a composition common to the MOF material for shaping of this embodiment except for the absence of silicon. Furthermore, when measuring the carbon dioxide adsorption / desorption isotherm at a measurement temperature of 25°C and comparing the carbon dioxide adsorption capacity at an absolute pressure of 0.4 or higher, the MOF material for shaping of this embodiment desirably exhibits a carbon dioxide adsorption capacity that is 1.5 times or more the carbon dioxide adsorption capacity of an MOF having a composition common to the MOF material for shaping of this embodiment except for the absence of silicon.

[0027] Furthermore, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, the shaped object made of the MOF material for shaping of this embodiment desirably exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition that is common to the MOF material for shaping of this embodiment except for not containing silicon. Furthermore, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, the shaped object made of the MOF material for shaping of this embodiment desirably exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition that is common to the MOF material for shaping of this embodiment except for not containing silicon.

[0028] Here, in the MOF material or shaped body of the present embodiment described above, "MOF having a composition common to the MOF material for shaping of the present embodiment except for not containing silicon" can be the MOF used as the target to which a silane derivative is added when preparing the MOF material for shaping. To identify a MOF corresponding to "a MOF having a composition common to the MOF material for shaping of the present embodiment except for not containing silicon" for a specific MOF material or shaped body, the crystal structure of the MOF constituting the target MOF material for shaping or shaped body can be analyzed by X-ray diffraction (XRD) and compared with known information on the crystal structure, such as the Cambridge Crystal Structure Database (CSD) provided by the Cambridge Crystallographic Data Centre (CCDC). Hereinafter, "MOF having a composition common to the MOF material for shaping of the present embodiment except for not containing silicon" will also be referred to as "raw material MOF." When a MOF-side functional group is introduced into the starting MOF, the starting MOF can be identified by combining quantitative analysis techniques such as nuclear magnetic resonance analysis (NMR) and infrared spectroscopy (IR) with the above-mentioned XRD analysis. To identify the starting MOF, including the state of introduction of the MOF-side functional group, the change in the BET specific surface area of ​​the MOF caused by the introduction of the MOF-side functional group (for example, the BET specific surface area of ​​the aforementioned UiO-66 is 1500 m) can be determined. ２ / g, whereas the BET specific surface area of ​​UiO-66-COOH in Figure 1, which has a carboxyl group introduced therein, is 700 m ２ / g), the magnitude of the OH vibration peak in IR analysis, or the difference in the amount of thermal decomposition or the oxidative decomposition temperature in simultaneous thermogravimetry and differential thermal analysis (TG-DTA analysis), may also be used.

[0029] Furthermore, when the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping of this embodiment was measured at a measurement temperature of 0°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 was 45 cm ３ (STP) / g or more. In addition, when the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping of this embodiment is measured at a measurement temperature of 25°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is preferably 25 cm ３ (STP) / g or more.

[0030] Furthermore, when the carbon dioxide adsorption / desorption isotherm of the shaped object made of the MOF material for shaping of this embodiment was measured at a measurement temperature of 0°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 was 40 cm ３ (STP) / g or more. In addition, when the carbon dioxide adsorption / desorption isotherm of the shaped object made of the MOF material for shaping of this embodiment is measured at a measurement temperature of 25°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is preferably 20 cm ３ (STP) / g or more. The carbon dioxide adsorption amount at an absolute pressure of 0.4 when measuring the carbon dioxide adsorption / desorption isotherm of the above-mentioned MOF material for shaping or shaped body refers to the carbon dioxide adsorption amount shown by the lower adsorption curve in the carbon dioxide adsorption / desorption isotherm.

[0031] The properties related to the carbon dioxide adsorption capacity of the MOF material for shaping or the shaped body described above can be adjusted as appropriate, for example, by the combination of the complex metal and organic ligand that constitute the MOF, the type of silane derivative added to the MOF, etc. For example, when UiO-66-COOH, which is a Zr-based MOF UiO-66 with a carboxyl group (—COOH) introduced as a MOF functional group, is used as the MOF, and 1,6-bis(trimethoxysilyl)hexane (e.g., KBM-3066 manufactured by Shin-Etsu Chemical Co., Ltd.) with six methylene groups is used as the silane derivative, it becomes possible to easily satisfy the above-mentioned numerical value related to the carbon dioxide adsorption capacity.

[0032] <Preparation of MOF Materials for Shaping and Shaped Objects> Figure 4 is an explanatory diagram showing MOF materials for shaping and shaped objects prepared for performance evaluation. Samples S1 to S3 are powdered MOF materials for shaping. Samples S4 to S10 are shaped objects molded from the MOF materials for shaping. Sample S11 is the MOF (raw material MOF) used as the material for preparing Samples S1 to S10. When preparing Samples S1 to S10, a silane derivative having a functional group capable of forming a chemical bond with the MOF-side functional group of the raw material MOF was added to the raw material MOF to prepare the MOF material for shaping. The starting MOF for preparing the MOF materials for shaping according to Samples S1 to S10, i.e., the MOF for Sample S11, was UiO-66-COOH (manufactured by Atomis Corporation), which was prepared by introducing a carboxyl group (—COOH) into the previously described UiO-66. The silane derivative added to the starting MOF was 1,6-bis(trimethoxysilyl)hexane (KBM-3066 manufactured by Shin-Etsu Chemical Co., Ltd.). The preparation of each sample will be described below in order.

[0033] [Samples S1 to S3] MOF materials for shaping, Samples S1 to S3, were prepared by mixing MOF (UiO-66-COOH), a silane derivative (KBM-3066), and an organic solvent (ethanol) at room temperature for 24 hours, removing the solvent by suction filtration, and then vacuum drying at 130°C for 5 hours. The amount of silane derivative added during preparation of each sample (the ratio of the silane derivative to the total of the MOF and the silane derivative) was 2.5 wt% for Sample S1, 5 wt% for Sample S2, and 10 wt% for Sample S3.

[0034] [Samples S4, S9, S10] The MOF material for shaping of sample S2 was compression molded to produce the shaped bodies of samples S4, S9, and S10. Specifically, the MOF material for shaping of sample S2 was uniaxially pressed to form a cylindrical shape with a diameter of 3 mm and a height of 3 mm (corresponding to an average particle size of 3 mm). The compression pressure (press load) was 1 MPa for samples S4 and S9, and 5 MPa for sample S10. Sample S4 was not tapped, while samples S9 and S10 were tapped. Here, "tapping" refers to the process of filling the MOF material for shaping while tapping (vibrating up and down) to firmly fill the material.

[0035] [Samples S5-S8] The shaped body of Sample S5 was produced by extrusion molding the MOF material for excipient of Sample S2. The shaped bodies of Samples S6-S8 were also produced by extrusion molding the MOF material for excipient of Sample S1. Specifically, the MOF material for excipient of Sample S1 or S2 was mixed with polyvinylpyrrolidone (K-85, manufactured by Nippon Shokubai Co., Ltd.) as a binder, and then purified water was added and kneaded. The mixture was then extruded into a cylindrical shape with a diameter of 3 mm and a height of 3 mm (corresponding to an average particle size of 3 mm). The amount of binder added (the ratio of the binder to the total of the MOF material for excipient and the binder) was 5 wt% for Samples S5 and S6, 10 wt% for Sample S7, and 20 wt% for Sample S8.

[0036] <Measurement Method> (Calculation of Specific Surface Area) The specific surface area of ​​the sample was evaluated using the BET multipoint method. The BET specific surface area is expressed as an area relative to weight, and the unit is "m ２ / g".

[0037] (Calculation of Gas Adsorption Amount) The gas adsorption amount (amount of carbon dioxide adsorption) was measured by a volumetric method (in accordance with JIS Z8831-2 and JIS Z8831-3) using a gas adsorption amount measuring device, and the gas adsorption amount was calculated by creating an adsorption / desorption isotherm.

[0038] (Calculation of atomic fractions of complex metal and Si in MOF) The atomic fractions were determined by quantitative element mapping (wt%) using a transmission electron microscope equipped with EDS (TEM-EDS).

[0039] <Confirmation of localization of Si on MOF particle surface> Figures 5A and 5B are TEM images obtained by elemental mapping of sample S2, and Figures 6A and 6B are TEM images obtained by elemental mapping of sample S11. Figures 5A and 6A are analytical images of elemental mapping of zirconium (Zr), and Figures 5B and 6B are analytical images of elemental mapping of silicon (Si).

[0040] As shown in Figures 5A and 6A, the results of elemental mapping of Zr confirmed the presence of Zr throughout the crystalline particles of the MOF in both sample S2, which corresponds to the MOF material for shaping according to the embodiment, and sample S11, which is the raw MOF constituting the MOF material for shaping. In contrast, as shown in Figures 5B and 6B, the results of elemental mapping of Si confirmed that in sample S2, Si was present locally on the surface of the crystalline particles of the MOF, and in sample S11, a signal considered to be background was present in areas where no crystalline particles were present on the entire screen, confirming the absence of Si. Note that Figures 5A and 5B show the results of sample S2, but in samples S1, S3 to S10, which correspond to the MOF material for shaping according to the embodiment and the shaped body, the presence of Si was also observed localized on the surface of the crystalline particles of the MOF (data not shown).

[0041] <Atomic Fraction> FIG. 7 is an explanatory diagram showing the results of determining the atomic fractions for samples S1 to S3 and sample S11. FIG. 8 is an explanatory diagram showing a graph plotting the calculation results of the atomic fractions shown in FIG. 7. As mentioned above, samples S1 to S3 differ in the amount of silane derivative added to the raw material MOF during the preparation of each sample. In FIG. 8, the horizontal axis shows the amount of silane derivative added, and the vertical axis shows the atomic fraction of Si. FIGS. 7 and 8 show the results of measuring the atomic fraction twice for each sample.

[0042] As shown in Figure 8, up to about 0.5 wt% of the silane derivative, there was a positive correlation between the amount of silane derivative and the Si atomic fraction. As the amount of silane derivative added increased, the Si atomic fraction also increased. However, even when the amount of silane derivative added exceeded 0.5 wt%, the increase in the Si atomic fraction was suppressed. This is thought to be because excess silane derivative that was not used to bond with the MOF-side functional groups on the MOF surface was removed along with the solvent when the solvent was removed from the MOF during the production process of the MOF material for shaping. Furthermore, from the results shown in Figure 8, it can be seen that if the Si atomic fraction is 0.02 or more, it can be said that a sufficiently distinguishable amount of Si is present in the MOF material for shaping. In the MOF material for shaping, by adding 2.5 wt% or more of the silane derivative, it is easy to achieve a Si atomic fraction of 0.02 or more. As a result, it is thought that the effect of facilitating shaping due to the localization of Si on the surface of the crystalline particles that make up the MOF can be more fully obtained.

[0043] <Carbon Dioxide Adsorption Amount> FIG. 9 is an explanatory diagram showing the results of measuring the carbon dioxide adsorption / desorption isotherms for samples S1 to S3 and S11 at a measurement temperature of 25°C. In FIG. 9, the horizontal axis represents absolute pressure, and the vertical axis represents the amount of carbon dioxide adsorption. As shown in FIG. 9, the carbon dioxide adsorption / desorption isotherms for samples S1 to S3 are all shifted upward relative to the carbon dioxide adsorption / desorption isotherm for sample S11, confirming that the amount of carbon dioxide adsorption increased by adding the silane derivative to the MOF. Furthermore, it was confirmed that, within the range of 2.5 wt% to 10 wt% of the silane derivative, the smaller the amount of silane derivative added, the greater the degree of increase in the amount of carbon dioxide adsorption. Specifically, for example, by setting the amount of silane derivative to 5 wt% or less, the amount of carbon dioxide adsorption at an absolute pressure of 0.4 when measuring the carbon dioxide adsorption / desorption isotherm at a measurement temperature of 25°C was increased by 25 cm ３ (STP) / g or more.

[0044] Fig. 10 is an explanatory diagram showing the results of measuring the BET specific surface area and the carbon dioxide adsorption amount at 0°C for samples S2, S4, S5, and S11. Fig. 11 is an explanatory diagram showing the results of measuring the carbon dioxide adsorption / desorption isotherms at a measurement temperature of 0°C for samples S2, S4, S5, and S11. Fig. 12 is an explanatory diagram showing the results of measuring the BET specific surface area and the carbon dioxide adsorption amount at 25°C for samples S2, S4, S5, and S11. Fig. 13 is an explanatory diagram showing the results of measuring the carbon dioxide adsorption / desorption isotherms at a measurement temperature of 25°C for samples S2, S4, S5, and S11.

[0045] 10 and 12 show the results of two measurements of the BET specific surface area for samples S5 and S11. Also, in FIGS. 10 and 12, the maximum carbon dioxide adsorption amount is shown as the carbon dioxide adsorption amount, that is, the adsorption amount at an absolute pressure of 1.00 in the carbon dioxide adsorption / desorption isotherms shown in FIGS. 11 and 13. Furthermore, in FIGS. 10 and 12, for samples S2, S4, and S5, the increase ratio compared to the carbon dioxide adsorption amount of sample S11 is shown in parentheses along with the carbon dioxide adsorption amount. Hereinafter, the ratio of the carbon dioxide adsorption amount of the MOF material for shaping or the shaped body to the carbon dioxide adsorption amount of the MOF (raw material MOF) having a composition common to the MOF material for shaping except that it does not contain silicon at a specific measurement temperature and absolute pressure is also referred to as the "increase ratio."

[0046] As shown in Figures 9 to 13, samples S1 to S3, which are MOF materials for shaping in which a silane derivative is added to MOF, sample S4 obtained by compression molding sample S2, and sample S5 obtained by extrusion molding sample S2, were measured at both 0 ° C. and 25 ° C. It was confirmed that the carbon dioxide adsorption amount was significantly increased compared to the MOF before the addition of the silane derivative. As shown in Figure 10, under the conditions of an absolute pressure of 1.00 at which the carbon dioxide adsorption amount is maximized and a measurement temperature of 0 ° C., the increase in the carbon dioxide adsorption amount compared to sample S11 was 2.3 times for sample S2, 2.15 times for sample S4, and 2.4 times for sample S5. Also, as shown in Figure 12, under the conditions of an absolute pressure of 1.00 at which the carbon dioxide adsorption amount is maximized and a measurement temperature of 25 ° C., the increase in the carbon dioxide adsorption amount compared to sample S11 was 3.1 times for sample S2, 2.65 times for sample S4, and 3.1 times for sample S5.

[0047] When the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping described above is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, the carbon dioxide adsorption amount can be 1.5 times or more the carbon dioxide adsorption amount of the MOF (raw material MOF) having a common composition with the MOF material for shaping described above except that it does not contain silicon. Furthermore, when the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping described above (for example, samples S1 to S3 shown in FIG. 9) is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or higher is compared, it was confirmed that the carbon dioxide adsorption amount can be 1.5 times or more the carbon dioxide adsorption amount of the raw material MOF (for example, sample S110 shown in FIG. 9).

[0048] Furthermore, when the carbon dioxide adsorption and desorption isotherms of the shaped bodies molded from the MOF material for shaping (for example, samples S4 and S5 shown in FIG. 11) were measured at a measurement temperature of 0 ° C. and compared to the carbon dioxide adsorption amounts at absolute pressures of 0.4 or higher, it was confirmed that the carbon dioxide adsorption amount was 1.5 times or more the carbon dioxide adsorption amount of the MOF (raw material MOF, for example, sample S11 shown in FIG. 11) having a composition common to the MOF material for shaping except that it does not contain silicon. Furthermore, when the carbon dioxide adsorption and desorption isotherms of the shaped bodies molded from the MOF material for shaping (for example, samples S4 and S5 shown in FIG. 13) were measured at a measurement temperature of 25 ° C. and compared to the carbon dioxide adsorption amounts at absolute pressures of 0.4 or higher, it was confirmed that the carbon dioxide adsorption amount was 1.5 times or more the carbon dioxide adsorption amount of the raw material MOF (for example, sample S11 shown in FIG. 13).

[0049] As shown in Figures 9, 11, and 13, and Figures 14 and 15, which will be described later, the carbon dioxide adsorption and desorption isotherms of the MOF (sample S11), the MOF material for shaping in which a silane derivative is added to the MOF (samples S1 to S3), and the shaped body molded from the MOF material for shaping (samples S4 to S10) are so-called type I adsorption and desorption isotherms, as is commonly seen in adsorption and desorption isotherms of adsorbents, etc., with micropores having a pore diameter of 2 nm or less. Therefore, when the absolute pressure is relatively low (for example, less than 0.3 absolute pressure), the amount of carbon dioxide adsorption increases rapidly with an increase in absolute pressure, and when the absolute pressure is relatively high (for example, 0.3 absolute pressure or higher), the degree of increase in the amount of carbon dioxide adsorption with an increase in absolute pressure is suppressed. Furthermore, not only when the absolute pressure is relatively low, but also when the absolute pressure is relatively high, regardless of the measurement temperature, the slope of the carbon dioxide adsorption / desorption isotherm of the MOF material for shaping (samples S1 to S3) and the shaped body (samples S4 to S10) in which a silane derivative is added to the MOF is larger than the slope of the carbon dioxide adsorption / desorption isotherm of the MOF (raw material MOF, sample S11) which has a common composition with the MOF material for shaping except that it does not contain silicon. Therefore, when the carbon dioxide adsorption amount of the MOF material for shaping or the shaped body at an absolute pressure of 0.4 shows a specific increase ratio relative to the carbon dioxide adsorption amount of the raw material MOF at an absolute pressure of 0.4, it can be said that the increase ratio shows a specific value or more under conditions of an absolute pressure of 0.4 or higher.

[0050] In the MOF material for excipient described above, the carbon dioxide adsorption amount at an absolute pressure of 0.4 in the carbon dioxide adsorption / desorption isotherm measured at 0°C was 45 cm ３ In addition, in such a MOF material for shaping, the carbon dioxide adsorption amount at an absolute pressure of 0.4 measured at 25°C is 25 cm ３ (STP) / g) or more (for example, samples S1 and S2 shown in FIG. 9).

[0051] In addition, in the case of a shaped body molded from a MOF material for shaping, the carbon dioxide adsorption amount at an absolute pressure of 0.4 in the carbon dioxide adsorption / desorption isotherm measured at 0°C was 40 cm ３It was confirmed that the carbon dioxide adsorption rate at an absolute pressure of 0.4 in the carbon dioxide adsorption / desorption isotherm measured at 25°C was 20 cm3 or more (for example, samples S4 and S5 shown in Figure 11). ３ (STP) / g or more (for example, samples S4 and S5 shown in FIG. 13, samples S6 to S8 shown in FIG. 14, and samples S4 and S9 shown in FIG. 15).

[0052] <Extrusion Conditions> Figure 14 is an explanatory diagram showing the results of carbon dioxide adsorption / desorption isotherms measured at a temperature of 25°C for Sample S1, a MOF material for shaping, and S6 to S8, shaped bodies extruded from the MOF material for shaping. It was confirmed that Samples S1, S6 to S8 all had increased carbon dioxide adsorption compared to the raw MOF (see, for example, Sample S11 in Figures 9 and 13). Samples S6 to S8, which are extrusion-molded bodies, were molded with the addition of a binder (PVP). As shown in Figure 14, it was confirmed that the amount of carbon dioxide adsorption was suppressed as the amount of binder added increased. However, Sample S6, which had the lowest amount of binder added (5 wt%), showed a carbon dioxide adsorption amount similar to that of Sample S1, a MOF material for shaping that did not contain a binder. This is thought to be because, as explained using Figure 3, adding a silane derivative to the MOF bonds the MOF and the silane derivative, forming new sites between the MOF surface and the silane derivative where gas can be adsorbed. In other words, due to the occurrence of a new gas adsorption mechanism, even when a small amount of binder was added, the effect of suppressing the amount of carbon dioxide adsorption due to the addition of the binder was canceled, and the amount of carbon dioxide adsorption was thought to have remained almost unchanged. Furthermore, extrusion molding applies less pressure during molding than compression molding, and the degree to which the MOF particles are pressed down is relatively small, so gas can easily flow into the interior of the shaped body, and it is thought that the amount of carbon dioxide adsorption can be easily secured.

[0053] <Compression Molding Conditions> Figure 15 is an explanatory diagram showing the results of measuring carbon dioxide adsorption / desorption isotherms at a measurement temperature of 25°C for samples S4, S9, and S10, which are shaped bodies obtained by compression molding the MOF material for molding. It was confirmed that the amount of carbon dioxide adsorbed was increased in all of samples S4, S9, and S10 compared to the raw MOF (see, for example, sample S11 in Figures 9 and 13). As shown in Figure 15, the amount of carbon dioxide adsorbed in the shaped body was reduced as the press load during compression molding increased (samples S9 and S10). Furthermore, the amount of carbon dioxide adsorbed in the shaped body was also reduced by using a tap (filling while tapping during compression molding) (samples S4 and S9).

[0054] The present disclosure is not limited to the above-described embodiments, and can be realized in various configurations without departing from the spirit thereof. For example, the technical features in the embodiments corresponding to the technical features in each aspect described in the Summary of the Invention section can be appropriately replaced or combined to solve some or all of the above-described problems or achieve some or all of the above-described effects. Furthermore, if a technical feature is not described as essential in this specification, it can be appropriately deleted.

[0055] The present disclosure can also be realized in the following forms. [Application Example 1] A shaped MOF material composed of a metal-organic framework (MOF), characterized in that the MOF material contains silicon (Si) localized on the surfaces of crystal particles constituting the MOF. [Application Example 2] The shaped MOF material according to Application Example 1, characterized in that the atomic fraction ratio of the complex metal contained in the MOF to silicon (Si) (complex metal contained in the MOF:Si) is 0.98:0.02 to 0.9:0.10. [Application Example 3] A shaped object composed of the shaped MOF material according to Application Example 1 or 2. [Application Example 4] The shaped object according to Application Example 3, characterized in that the average particle size is 1 mm or more. [Application Example 5] The MOF material for shaping according to Application Example 1 or 2, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the MOF material for shaping exhibits an amount of carbon dioxide adsorption that is 1.5 times or more the amount of carbon dioxide adsorption of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon. [Application Example 6] The MOF material for shaping according to any one of Application Examples 1, 2, and 5, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the MOF material for shaping exhibits an amount of carbon dioxide adsorption that is 1.5 times or more the amount of carbon dioxide adsorption of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon. [Application Example 7] The shaped body according to Application Example 3 or 4, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the shaped body exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition that is common to the MOF material for shaping except that it does not contain silicon.[Application Example 8] The shaped body according to any one of Application Examples 3, 4, and 7, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the shaped body exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to the MOF material for shaping but not containing silicon. [Application Example 9] The MOF material for shaping according to any one of Application Examples 1, 2, 5, and 6, wherein, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 45 cm. ３ (STP) / g or more. [Application Example 10] The MOF material for shaping according to any one of Applications 1, 2, 5, 6, and 9, wherein, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 25 cm ３ (STP) / g or more. [Application Example 11] The shaped object according to any one of Applications 3, 4, 7, and 8, wherein when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 40 cm ３ (STP) / g or more. [Application Example 12] The shaped object according to any one of Application Examples 3, 4, 7, 8, and 11, wherein when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C, the carbon dioxide adsorption amount at an absolute pressure of 0.4 is 20 cm ３(STP) / g or more. [Application Example 13] A gas adsorbent for adsorbing and releasing gas, characterized in that it is constituted by the shaped body according to any one of Application Examples 3, 4, 7, 8, 11, and 12. [Application Example 14] A gas adsorption device comprising the gas adsorbent according to Application Example 13. [Application Example 15] A method for producing a shaped MOF material, comprising adding to a metal-organic framework (MOF) a silane derivative having a functional group capable of forming a chemical bond with a functional group on the surface of the MOF.

Claims

1. A MOF material for excipients, which is composed of a metal-organic framework (MOF), and which contains silicon (Si) localized on the surface of crystal particles constituting the MOF.

2. The MOF material for shaping according to claim 1, characterized in that the atomic fraction ratio of the complex metal contained in the MOF to silicon (Si) (complex metal contained in the MOF:Si) is 0.98:0.02 to 0.9:0.

10.

3. A shaped body, characterized in that it is made of the MOF material for shaping described in claim 1 or 2.

4. The shaped body according to claim 3, characterized in that the average particle size is 1 mm or more.

5. The MOF material for excipient use according to claim 1 or 2, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the MOF material for excipient use exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to the MOF material for excipient use except that it does not contain silicon.

6. An MOF material for shaping according to any one of claims 1, 2 and 5, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C and a carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the carbon dioxide adsorption amount is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to said MOF material for shaping except that it does not contain silicon.

7. The shaped body according to claim 3, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the shaped body exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to said MOF material for shaping except that it does not contain silicon.

8. The shaped body according to claim 3, characterized in that, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C and the carbon dioxide adsorption amount at an absolute pressure of 0.4 or more is compared, the shaped body exhibits a carbon dioxide adsorption amount that is 1.5 times or more the carbon dioxide adsorption amount of an MOF having a composition common to the MOF material for shaping except that it does not contain silicon.

9. The MOF material for molding according to claim 1 or 2, wherein the carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C, and the amount of carbon dioxide adsorbed at an absolute pressure of 0.4 is 45 cm ３ (STP) / g or more.

10. The MOF material for molding according to claim 1 or 2, wherein, when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C, the amount of carbon dioxide adsorbed at an absolute pressure of 0.4 is 25 cm ３ (STP) / g or more.

11. The shaped body according to claim 3, wherein when a carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 0°C, the amount of carbon dioxide adsorbed at an absolute pressure of 0.4 is 40 cm ３ (STP) / g or more.

12. The shaped body according to claim 3, wherein the amount of carbon dioxide adsorption at an absolute pressure of 0.4 is 20 cm when the carbon dioxide adsorption / desorption isotherm is measured at a measurement temperature of 25°C. ３ (STP) / g or more.

13. A gas adsorbent for adsorbing and releasing gas, characterized in that it is composed of a shaped body according to any one of claims 3, 4, 7, 8, 11 and 12.

14. A gas adsorption device comprising the gas adsorbent according to claim 13.

15. A method for producing an MOF material for shaping, comprising adding to a metal-organic framework (MOF) a silane derivative having a functional group capable of forming a chemical bond with a functional group on the surface of the MOF.

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