Activated amino containing metal-organic constructs (MOFs) - how to use

Abstract

This invention provides organometallic frame (MOF) compositions, methods for preparing the same, and methods for using the same. [Solution] The MOF composition is characterized in that at least a portion of the linker molecule is an amino group-containing organic linker. Furthermore, the MOF has a crystal size greater than 1 μm and, after treatment with acid washing, provides an MOF in which at least 55% of the amino groups are activated amino groups in the form of -NH2. The MOF composition is useful for adsorbing various pollutants from various gas streams. A specific example is the adsorption of NO2 from an air stream.

Description

Technical Field

[0001] Description of Federally Sponsored Research or Development This invention was made with government support under contract number W911SR18C0031 awarded by the U.S. Army Combat Capabilities Development Command Chemical Biological Center (CCDC CBC). The government has certain rights in this invention. Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 003,260, filed March 30, 2020

[0003] Technical Field The present invention relates to metal - organic framework (MOF: METAL ORGAN IC FRAMEWORK) compositions having linker molecules with amino groups. The present invention further relates to methods (processes) for preparing and activating the amino groups of the MOF compositions, and to methods for using the MOF compositions

[0004]

Background Art

[0005] Applicants have found that regulators are used to synthesize MOF compositions with larger crystal sizes In addition, their resulting activity for gas adsorption is compared to nanocrystalline MOF compositions. They found that this decreases when at least one of the linker molecules has an amino portion. This is especially true in the case of: The applicant shall use the as-synthesized MOF composition (at least 1 μm The process involves washing the crystals (which have an average crystal size) with an acid such as hydrochloric acid, nitric acid, or sulfuric acid. This problem was solved by finding the process. When the washed MOF is dried, nano It was found to have adsorption properties similar to those of a MOF composition with crystal size. [Overview of the project]

[0006] One embodiment of the present invention is a metal in which Zr, V, Al, Fe, Cr, Ti, Hf, Cu, Zn, Ni, Ce, and A metal ion atom selected from these mixtures and at least one organic compound containing an amino group At least one organic ligand containing a ligand or amino group and at least one not containing an amino group Corner metal element including a linker molecule selected from combinations with another organic ligand The MOF includes the position, has an average crystal size of 1 μm or more, and at least 55% of the amino groups are -NH2 A metal-organic frame (MOF) composition characterized by an activated amino group of the form of ru.

[0007] In another embodiment, at least one organic ligand containing an amino group is 2-aminobenzene- l,4-dicarboxylic acid (NH2-BDC), 5-aminoisophthalic acid, 3-aminobenzoic acid, 4-aminobenzoic acid Selected from ferrous acid and mixtures thereof.

[0008] In yet another embodiment, at least one organic ligand that does not contain an amino group is tereph Taric acid (BDC), isophthalic acid, benzoic acid, trimesic acid, acrylic acid, and these Selected from a mixture.

[0009] In certain embodiments, the corner metal unit comprises a zirconium atom, and the linker is It contains a ligand that is 2-aminobenzene-l,4-dicarboxylic acid (NH2-BDC).

[0010] In another embodiment, the MOF is at least 1000m 2 It has a BET surface area of ​​ / g.

[0011] In yet another embodiment, the MOF has an average crystal size of about 1 μm to about 100 μm.

[0012] In another embodiment, the MOF has pores of about 5 to about 30 Å.

[0013] In a further embodiment, at least one corner metal unit of the MOF is at least one It has a free coordination site.

[0014] In another embodiment, the MOF can adsorb at least one contaminant from the gas stream. ru.

[0015] In yet another embodiment, the contaminants that the MOF can adsorb are cyanogen chloride, hydrogen cyanide, Hydrogen sulfide, phosgene, sulfur dioxide, boron tribromide, boron trichloride, bromine, bromine chloride, trifu Bromine fluoride, carbonyl fluoride, chlorine, chlorine pentafluoride, chlorine trifluoride, chlorosulfonic acid, Dichlorosilane, ethylphosphone dichloride, fluorine, hydrogen bromide, hydrogen chloride, hydrogen cyanide, Hydrogen fluoride, hydrogen iodide, hydrogen sulfide, phosphorus trichloride, silicon tetrafluoride, sulfur dioxide, trioxide Sulfur, sulfuric acid, sulfuryl chloride, titanium tetrachloride, tungsten hexafluoride, bromine pentafluoride From hydrogen selenide, nitric acid, nitrogen dioxide, nitrogen tetroxide, nitrogen trioxide, and mixtures thereof A group can be selected from the following:

[0016] Another embodiment is a method for preparing a metal-organic frame (MOF) composition, which includes the following: include. a. The metal is selected from Zr, V, Al, Fe, Cr, Ti, Hf, Cu, Zn, Ni, Ce, and mixtures thereof. A metal compound and at least one organic ligand containing an amino group, or a ligand containing an amino group A combination of at least one organic ligand and at least one organic ligand that does not contain an amino group. A ligand selected from the combination, along with dimethylformamide, water, ethanol, and isopropanol. A solvent selected from these, and mixtures thereof, as well as an organic acid, preferably formic acid, Monochemicals such as acetic acid, benzoic acid, dichloroacetic acid, trifluoroacetic acid, and mixtures thereof. Selected from benzoic acid, or a mixture of one or more inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid. To form a reaction mixture with a regulator, b. Reacting a reaction mixture at a certain temperature and time to form an MOF. c. Isolating MOFs and providing MOF powders. d. Wash the MOF with an inorganic acid selected from hydrochloric acid, nitric acid, sulfuric acid, and mixtures thereof. When mixed with one or more organic acids, at least 55% of the amino groups are activated in the -NH2 form. A MOF characterized by having an amino group and an average crystal size greater than 1 μm. To provide.

[0017] In another embodiment, the acid-washed MOF is heated to a temperature of about 60°C to about 150°C or from about 60°C to Dry at a temperature of approximately 200°C.

[0018] Further embodiments involve a gas stream containing at least one contaminant being transmitted through a metal-organic structure (MOF). ) Contact with the composition, thereby removing at least one contaminant in the gas stream A method for purifying a gas stream, which includes removing a portion of the MOF, wherein the MOF is preferably made of metal. The elements are selected from Zr, V, Al, Fe, Cr, Ti, Hf, Cu, Zn, Ni, Ce, and mixtures thereof. A metal ion atom and at least one organic ligand containing an amino group or a small amount containing an amino group A combination of at least one organic ligand and at least one organic ligand that does not contain an amino group. MOFs include corner metal units with linker molecules selected from the combination, and are less Both have an average crystal size of approximately 1 μm, and at least 55% of the amino groups are activated in the form of -NH2. This method is characterized by the presence of a modified amino group.

[0019] In another embodiment, the gas flow is an air flow, and the pollutants are cyanogen chloride, hydrogen cyanide, Hydrogen sulfide, phosgene, sulfur dioxide, boron tribromide, boron trichloride, bromine, bromine chloride, trifu Bromine fluoride, carbonyl fluoride, chlorine, chlorine pentafluoride, chlorine trifluoride, chlorosulfonic acid, Dichlorosilane, ethylphosphone dichloride, fluorine, hydrogen bromide, hydrogen chloride, hydrogen cyanide, Hydrogen fluoride, hydrogen iodide, hydrogen sulfide, phosphorus trichloride, silicon tetrafluoride, sulfur dioxide, trioxide Sulfur, sulfuric acid, sulfuryl chloride, titanium tetrachloride, tungsten hexafluoride, bromine pentafluoride From hydrogen selenide, nitric acid, nitrogen dioxide, nitrogen tetroxide, nitrogen trioxide, and mixtures thereof Selected.

[0020] In a further embodiment, the MOF is at least 50% or less of the contaminant. Remove 90%, or at least 99%, of both.

[0021] These and other purposes and embodiments will become apparent after the detailed description of the present invention. Ro. [Brief explanation of the drawing]

[0022] [Figure 1A] Microscopic image of a commercially available Zr(NH2-BDC) aggregate of tiny nano-sized particles (2.00 μm scale).

[0023] [Figure 1B] Micrograph of Zr(NH2-BDC)-NH2 from Example 1-1, having a crystal size of 1-5 μm (10 μm scale).

[0024] [Figure 2A] These are the 1H-NMR spectra of various Zr(NH2-BDC) degradation preparations. The inset shows the crystallographic structure of Zr(NH2-BDC) with the formamide group still present.

[0025] [Figure 2B] The solid-state 15N-NMR spectrum of the Zr(NH2-BDC) formulation before degradation is shown.

[0026] [Figure 3] This paper demonstrates how to decompose Zr(NH2-BDC) MOF and determine the degree of formamide group presence.

[0027] [Figure 4] This paper demonstrates the acid washing of a MOF containing a formamide group, converting the formamide group to a free amine. [Modes for carrying out the invention]

[0028] In accordance with the disclosure herein, amino group-containing metal-organic structure (MOF) compositions are less than Synthesized with an average crystal size of at least about 1 μm, the amino groups are activated to provide free amino groups in the form of -NH2 of more than 55% and the MOF has a BET surface area of at least 1000 m 2 / g. Prior to the invention as disclosed herein, it was difficult to synthesize MOFs having crystals of at least about 1 μm (micron) containing linker molecules with free amino groups . The micron-sized MOFs as disclosed herein are advantageous in applications such as air filtration, toxic gas capture, and respirators . When referring to amino groups, the term "activated" as used herein means that the amino group is an unsubstituted group of the formula -NH2 and the nitrogen atom is bonded to the organic ligand of the MOF .

[0029]

[0030] In one aspect of the invention, the MOF is a coordination product of a metal ion and at least a bidentate organic ligand . The MOF contains corner metal units including metal ion atoms and linkers or ligand molecules, forming a structure with a high surface area and pores of uniform size . The metal ions are Li + , Na + , K + , Rb + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zri 4+ , Hf 4 + 5+ 4+ , V 3+ , V 4+ , V 3+ , Nb 3+ , Ta 3+, Cr 3+ , Cr 2+ Mo 3+ , W 3+ , Mn 3+ Fe 3+ Fe 2+ , Ru 3+ , Ru 2 + Os 3+ Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ ,Cu + Ag + , Au + , Zn 2+ , Al 3+ ,Ga 3+ In 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ , Cd 2+ , Mn 2+ , Tb 3+ , Gd 3+ , Ce 3+ , La 3+ , Cr 4+ and mixtures thereof, but not limited to these. It is not the case that... The preferred set or subset of the above metals includes Zr, V, Al, Fe, Cr, Ti This includes, but is not limited to, Hf, Cu, Zn, Ni, and Ce.

[0031] Organic ligands that react with metal ions to form linkers between corner metal units are amino At least one organic ligand containing a group, or at least one organic coordination containing an amino group It is selected from a combination of at least one organic ligand that does not contain an amino group. An example of an organic ligand containing a mino group is 2-aminobenzene-l,4-dicarboxylic acid (NH2-BDC). , 5-aminoisophthalic acid, 3-aminobenzoic acid, 4-aminobenzoic acid and mixtures thereof Examples include, but are not limited to, organic ligands that do not contain an amino group. For example, terephthalic acid (BDC), isophthalic acid, benzoic acid, trimesic acid, acrylic acid, and mixtures thereof are examples, but are not limited to these. Ligands are A At least one organic ligand containing an amino group and at least one organic coordination that does not contain an amino group When combined with a child, the amino-containing ligand:non-amino-containing ligand in the MOF product The molar ratios are 1:99 to 99:1, or 10:90 to 90:10, or 20:80 to 80:20, or 30:70. It changes from ~70:30, or 40:60 to 60:40 or 50:50.

[0032] In one embodiment, the metal of the corner metal unit is Zr, and the organic ligand is 2-aminobenzene. - Contains l,4-dicarboxylic acid (NH2-BDC). In one embodiment, the MOF is Zr(NH2-BDC), and Ui It is also known as O-66-NH2.

[0033] The MOF of the present invention is characterized by the following properties. One property is that at least 1,00 0, or at least 1,100, or at least 1,200, or at least 1,300 m 2 / g, or at least 1,400 m 2It has a Brunauer-Emmett-Teller (BET) surface area of ​​ / g. Another characteristic is that MOFs have at least 1 μm along at least one dimension, or less Both should have an average crystal size of 5 μm, or at least 50 μm. More details The crystal size is at least about 1 μm to about 100 μm, or about 1 μm to about 10 μm, The size is approximately 1 μm to 5 μm, or approximately 10 μm to 50 μm. This refers to the size of the individual crystals, and does not refer to the size of the crystals that have formed aggregates. Average size, For example, given 1 μm, the crystal has a specific average size in at least one dimension. It has a size, but the size in the other two dimensions can be smaller or larger. It is understood that the crystal does not need to have a cubic shape, but can be an octahedron, with its vertices cut by planes. It can have any shape, such as an octahedron, cuboctahedron, or needle-shaped body.

[0034] MOFs generally have the characteristic of having an open pore system. The MOF of the present invention is about 5 to about 3 It has an average pore diameter of 0 Å, or approximately 5 to 20 Å, or approximately 5 to 10 Å.

[0035] The MOF of this invention has a concentration of approximately 0.2 cc / g to approximately 0.8 cc / g, or approximately 0.3 to approximately 0.8 cc / g, or approximately 0.4 to approximately 0. Fine particles of 8cc / g, or 0.5 to approximately 0.8cc / g, or approximately 0.4 to approximately 0.7cc / g, or approximately 0.4 to approximately 0.6cc / g The pore volume is controlled.

[0036] Metal ions that form corner metal units either have all of their coordination sites occupied, or It may have at least one free or open coordination site. Specific implementation In its morphology, at least one corner metal unit has at least one free coordination site do.

[0037] The MOF of the present invention has numerous applications. One particular application is in which small amounts are found in gaseous flows. At the very least, by adsorbing one or more pollutants, the gas stream is purified. This is the case. Gas flows that can be purified include air flows, industrial gas flows, off-gas flows, and This includes, but is not limited to, polluted gas flows.

[0038] Pollutants that can be adsorbed by MOFs include cyanogen chloride, hydrogen cyanide, hydrogen sulfide, and phosgene. Sulfur dioxide, boron tribromide, boron trichloride, bromine, bromine chloride, bromine trifluoride, fluoride Rubonyl, chlorine, chlorine pentafluoride, chlorine trifluoride, chlorosulfonic acid, dichlorosilane, 2 Ethylphosphone chloride, fluorine, hydrogen bromide, hydrogen chloride, hydrogen cyanide, hydrogen fluoride, iodide Hydrogen, hydrogen sulfide, phosphorus trichloride, silicon tetrafluoride, sulfur dioxide, sulfur trioxide, sulfuric acid, sulfuric acid Rufuryl, titanium tetrachloride, tungsten hexafluoride, bromine pentafluoride, hydrogen selenide, nitrate This includes acids, nitrogen dioxide, nitrogen tetroxide, nitrogen trioxide, and mixtures thereof, but these Not limited.

[0039] Especially in applications involving the adsorption of pollutants, MOFs with small crystal sizes or nanocrystalline forms are preferable. Furthermore, MOFs having a larger crystal size of approximately 1 μm or more are preferred. The inventors of the present invention have found that amino The modifiers used to synthesize larger-than-nanosize crystals of MOFs containing the amino group are amino We discovered that the group can be converted to an amide group. This amide group is used when amino functionality is required. It does not react. The inventors have found that the as-synthesized MOF can be treated with an acid such as HC1 (see description below) When processed, the amide is essentially cleaved and the amino group is regenerated, i.e., activated. It was also discovered that the MOFs processed as disclosed herein have at least one amino group 55%, or at least 60%, or at least 65%, or at least 70%, or At least 75%, or at least 80%, or at least 85%, or at least 90% Or at least 95% activated. Such an increase in amino activation is compared to untreated MO This leads to an increase in the adsorption capacity of the MOF to F or other amino functionalities. Thus, the present invention The MOF has large crystals and exhibits adsorption equivalent to or substantially the same as MOFs with nano-sized crystals. It has the advantage of having capacity or other amino functionalities. This is a nano-sized MOF. Although unsuitable for this application, it has virtually the same adsorption capacity as nano-sized MOFs or other applications. This represents a significant advance in the synthesis of MOFs with mino functionality.

[0040] As used above and throughout this specification and the claims, “substantially” This is at least 70%, or at least 80%, or at least 90%, or at least 95%. It means that.

[0041] Another aspect of the present invention is a method for preparing an MOF having an activated amino group. The first step in the synthesis is to prepare a solution of the desired metal ion with at least one ligand. The process involves introducing metals as metal salts. These salts include nitrates, halides, and sulfuric acids. Salts, carbonates, oxyhalides, oxynitrates, oxysulfates, oxycarbonates, etc. It is possible to have mixtures of these. Specific examples of salts that can be used include silicon chloride. Zirconium, zirconium bromide, oxynitrate, zirconium, zirconium oxychloride, Vanadium chloride, copper sulfate, iron chloride, zinc nitrate, or zinc carbonate, and mixtures thereof These are some examples, but are not limited to them.

[0042] As described above, the ligand used was at least one organic ligand containing an amino group. However, at least one organic ligand containing an amino group and at least one ligand not containing an amino group It may also be combined with an organic ligand. An example of an organic ligand containing an amino group is 2- Aminobenzene-l,4-dicarboxylic acid (NH2-BDC), 5-aminoisophthalic acid, 3-aminobenzoic acid Examples include, but are not limited to, acids, 4-aminobenzoic acid, and mixtures thereof. There are none. Examples of organic ligands that do not contain an amino group include terephthalic acid (BDC) and isofta. Examples include acrylic acid, benzoic acid, trimesic acid, acrylic acid, and mixtures thereof. It is not limited to these. In synthesis, a mixture of amino and non-amino ligands. When using them, they are in a molar ratio such that they become the desired molar ratio in the MOF as described above. It is added as follows. The molar ratio of the metal salt to the ligand is also adjusted so that a specific molar ratio in the MOF is achieved. To be organized.

[0043] The metal salt and at least one ligand are mixed in a solvent or a mixed solvent. Examples of usable solvents include amides, alcohols, water, and mixtures thereof. However, it is not limited to these. Specific mixtures include dimethylformamide and water. Examples include ethanol and isopropanol.

[0044] The adjusting agent is added to the reaction mixture either before, during, or after the addition of other reagents. Preferably, the regulator contains at least one monocarboxylic acid. Specific examples of stimulants include formic acid, acetic acid, benzoic acid, dichloroacetic acid, trifluoroacetic acid, and Examples of mixtures include, but are not limited to, these. Optionally, the modifier is, A mixture of one or more monocarboxylic acids and one or more inorganic acids, such as hydrochloric acid, nitric acid, and sulfuric acid. This is possible. Those skilled in the art can change the order of addition of reagents to optimize solubility and reaction conditions. They will realize that they are capable of doing so.

[0045] Once the reaction mixture is formed, that is, once all the components are solubilized, the reaction mixture is desired The reaction takes place at a temperature and time that forms the MOF. The reaction temperature ranges from approximately 50°C to approximately 200°C. Alternatively, the temperature can vary from about 75°C to about 125°C. The reaction mixture can be reacted for about 1 hour to about 78 hours, or When you choose from 8 hours to approximately 48 hours, approximately 22 hours to approximately 48 hours, or approximately 12 hours to approximately 24 hours. The reaction is carried out at the desired temperature. Once the MOF is formed, it is processed by methods such as filtration or centrifugation. It is isolated.

[0046] When an amino-containing MOF is prepared using a regulator in the reaction mixture, the result is amino At least one hydrogen atom of the group is substituted at another site, thereby achieving the desired activity of the amino group. Products that interfere with the properties can be obtained. The substitution site is a regulator such as a monocarboxylate salt. It can be a residue of the amino group. For example, when formic acid is used as a modifier, the formic acid group can be a residue of the amino group. It can act as a substitution group, generating a formamide group in place of the desired unsubstituted amino group. Furthermore, when DMF is used as the solvent, some of the solvent reacts with some of the amino groups, and formaldehyde It can form an amide group.

[0047] According to one aspect of the present invention, this problem is solved by washing the MOF with an inorganic acid, as shown in Figure 4. The solution is to cleave the substituent from the amino group and restore the amino group to its unsubstituted, activated form. In one embodiment, the MOF powder isolated from the metal-ligand reaction mixture is then salted. Acids, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and mixtures thereof, at least one non-toxic acid This provides an MOF having activated amino groups, which has been washed with an acid wash containing an acid. In the selection, the acid washing may be a mixture of one or more inorganic acids and one or more organic acids. Preferred inorganic Acids include hydrochloric acid, nitric acid, and sulfuric acid. Preferred organic acids include formic acid. Before being used in its intended application, the MOF is wet and acid-treated, and then subjected to temperatures of approximately 40°C to 250°C. They are dried at temperatures ranging from approximately 75°C to 150°C. The drying time for wet MOFs can vary substantially. However, typically it takes about 2 hours to 336 hours, or about 8 hours to 168 hours, or about 8 hours to 48 hours. This is between approximately 48 and 168 hours.

[0048] When MOFs are used as adsorbents, M is treated with acid washing as disclosed herein. OF adsorbs more pollutants than as-synthesized MOF. For example, acid-treated MOF. This is at least 10%, at least 20%, and at least 3% compared to the as-synthesized MOF. 0% or more, at least 40% or more, at least 50% or more, at least 60% or more, at least 7 It is possible to adsorb 0% or more, at least 80% or more, or at least 90% or more. Acid-treated MOFs are prepared in amounts of 2, 3, 5, 10, 15, 20, 30, 50, or 100 times the amount of as-synthesized MOF. It can adsorb pollutants.

[0049] As described above, the MOFs of the present invention can (reversibly) adsorb various molecules. They are characterized in that they can detect at least one contaminant in the gas stream. It is used to purify the gas stream by at least partially adsorbing the dye. This can be done. Gas flows that require purification include air flows, industrial gas flows, off-gas flows, and polluted gas flows. These include, but are not limited to, these. They are present in these flows and can be removed by the MOF of the present invention. Possible pollutants include cyanogen chloride, hydrogen cyanide, hydrogen sulfide, phosgene, sulfur dioxide, Boron tribromide, boron trichloride, bromine, bromine chloride, bromine trifluoride, carbonyl fluoride, chlorine Chlorine pentafluoride, chlorine trifluoride, chlorosulfonic acid, dichlorosilane, ethyl phosphate dichloride Fluorine, hydrogen bromide, hydrogen chloride, hydrogen cyanide, hydrogen fluoride, hydrogen iodide, hydrogen sulfide Phosphorus trichloride, silicon tetrafluoride, sulfur dioxide, sulfur trioxide, sulfuric acid, sulfuryl chloride, tetrasalt Titanium dioxide, tungsten hexafluoride, bromine pentafluoride, hydrogen selenide, nitric acid, nitrogen dioxide This includes, but is not limited to, nitrogen tetroxide, nitrogen trioxide, and mixtures thereof. The amount of contaminants that can be removed by the MOF is at least 50%, or at least 60% of the contaminants. , or at least 70%, or at least 80%, or at least 90%, or less Both are 95%, or at least 99%. In one embodiment, the gas flow is an air flow, and contamination The substance is NO2, and the MOF removes at least 80% of the NO2 in the airflow. In another embodiment... This involves a container having inlet and outlet ports, filled with MOF material, through which a gas flow occurs. This effectively removes pollutants from the flow. To achieve the desired removal amount... The gas flow is at a speed of approximately 10 L / min to approximately 500 L / min, or approximately 30 L / min to approximately 200 L / min, It flows through the MOF at a speed of approximately 50 L / min to 120 L / min.

[0050] The MOF composition of the present invention can be used in powder form, but can also be used in pellet, sphere, or disc form. In some cases, it is advantageous to form them into various shapes such as monoliths, amorphous particles, and extruded materials. Methods for forming these types of shapes are well known in the art. MOF materials It can be formed into various shapes, either by itself or by including a binder. When selecting a binder, consider the surface area and adsorption capacity after the desired shape has been formed. It is important to select a binder that will not negatively affect the quantity. Materials that can be used include cellulose, silica, carbon, alumina, and these Examples include, but are not limited to, mixtures.

[0051] The formation process typically involves mixing the MOF composition with a solvent or a binder + solvent. This includes preparing a thick paste-like material. Once the paste-like material is formed, it is The material is extruded through a die with a hole of approximately 1-2 mm, producing extruded materials of various lengths, for example, 6-10 mm. It can be formed by pressurizing the paste or powder itself under high pressure to form pellets or Tablets can be formed. Other means of forming the shape include pressure forming, metal forming, These include pelletizing, granulation, extrusion, rolling, and marmarizing.

[0052] Another aspect of the present invention includes depositing a catalyst metal onto a molded MOF body or MOF powder. The catalyst metals are zinc, copper, nickel, chromium, molybdenum, tungsten, niobium, and chromium. Nium, vanadium, silver, platinum, palladium, rhodium, iridium, and mixtures thereof Compounds can be selected. Deposition of catalyst metals onto molded MOF supports is usually performed using the desired metal. Take a solution containing the compound, impregnate the molded MOF body with it, then dry it, and perform any calcination. This is carried out by conventional means, including processes such as reprocessing and / or reduction.

[0053] In yet another aspect of the present invention, the MOF material is a monolith, a spherical support, a ceramic foam Glass fibers, woven fabrics, nonwoven fabrics, membranes, pellets, extruded products, amorphous particles, and mixtures thereof. It can be deposited on objects and other items, but is not limited to these. Products include monoliths, spherical supports, ceramic foams, pellets, extruded materials, or amorphous particles. If so, prepare a slurry of the MOF composition and use methods such as dipping and spray drying. The material is deposited onto the object, then dried and optionally fired. In the case of a film, the MOF is applied directly onto the film. It is possible to form a composition. The MOF composition of the present invention can be electrospinned, directly grown, And by techniques such as stratified deposition, deposits can be made on fabrics (woven and nonwoven) or polymers. It can be distributed.

[0054] The MOF-containing articles described in the previous paragraph purify air or other gas streams containing contaminants. It can be used as is for that purpose. Air or other gas streams can be used on articles, such as monoliths. It can flow through foam, membranes, and cloth, thereby allowing the MOF to be used as detailed above. At least a portion of the contaminants are adsorbed onto the material in the percentage amounts detailed above. The MOF material is Furthermore, they can be placed in various types of rigid containers. For example, extruded products, tablets, or spheres. The body can be placed in a bed through which air or other gas currents are flowed. The bed is an entrance It can be placed in various types of housings, such as filter canisters that have an outlet. Yes, it is possible. Cloth (both woven and nonwoven) can also be formed into filters such as pleated filters. This filter can, but is not limited to, the flow to be processed. It can be housed in a rigid container such as a cartridge through which the liquid flows. The pleated filter is Furthermore, it is supported by frames of various shapes and sizes, and the gas flow can flow through them. Yes, it's possible. Frames can be made from various materials such as metal, wood, and plastic. However, it is not limited to these. Glass fibers are formed into glass wool, and rigid fiber It can be housed in a filter frame.

[0055] In the following embodiments, unless otherwise specified, all N2 gas adsorption and desorption measurements were performed at 77K. This was performed using the icromeritics Tristar II 3020 system (Micromeritics, Norcross, GA). The surface area for N2 was calculated using the Brunauer-Emmet Teller (BET) model, which is 0.005. <P / Po<0 The calculation was performed within the range of 0.05. The amount of N2 adsorbed was measured at P / Po = 0.9. Here, P / Po is relative to atmospheric pressure. This is the measured pressure.

[0056] In the following embodiments, all nitrogen dioxide adsorption and desorption measurements were performed by applying absolute pressure and for 3 seconds. By using the equilibration interval, Micromeritics 3Flex Surface Characterization Analyzer The study was conducted at 25°C in Micromeritics, Norcross GA. Examples Example 1

[0057] A series of experiments were conducted to synthesize a series of Zr(NH2-BDC)MOFs. The parameters are shown in Table 1. The general procedure is to first dissolve NH2-BDC in DMF at room temperature. This included causing the NH2-BDC to dissolve, then adding the acid regulator to the reaction mixture and heating to 90°C. Once the target temperature was reached, Zr0(N03)2 was administered as a single dose or at a predetermined flow rate. Added. Once the addition was complete, the final reaction mixture was reacted for the desired time. The obtained MOF The powder was isolated by filtration, washed with DMF and acetone, and dried at 100°C for 12 hours. Table 1 Parameters for MOF synthesis [Table 1]

[0058] The sample from the above example was treated at 100°C for 12 hours under vacuum, and its BET surface area, nitrogen adsorption amount, and The pore volume was investigated. These results are shown in Table 2. Table 2. Characterization of synthesized MOFs [Table 2]

[0059] For comparison, a control sample of UiO-66-BDC-NH2MOF was obtained from Strem Chemicals, Inc., Newburypor. Purchased from t, MA, catalog no. 40-1109, which contains particle sizes of 0.1 to 0.5 microns and 0.3 It is stated to have a pore volume of 1 to 0.41 cc / g.

[0060] Figure 1A shows a 2-micron control sample containing much smaller particles, presumably nanoparticles. This is a micrograph on a scale. Figure 1B shows raw material from Example 1-1 with a crystal size of 1-5 μm. This is a 10-micron scale micrograph of the finished product. A larger scale is needed to observe the particle structure of the control sample. A certain magnification is required, and even at higher magnifications, the particles of the control sample do not form properly and clump together. You will see that it appears to be.

[0061] The control samples and the nanoparticle aggregates of Examples 1-7 were synthesized using a modifier and were in the 1-5 μm range. Compared to the MOF of the present invention which provides single crystals or more, in the filtration of air pollutants It is not very suitable for this use. Furthermore, the surface area of ​​the control MOF is 800-1075 m². 2 / g range In this specification, MOFs synthesized according to the present invention using modifiers and acid washings are described as follows: Materials with improved surface area, improved crystal size, and improved amino functionality. It brings about. Example 2 Large quantities of MOFs were prepared using the procedure of Example 1-1. Samples of the obtained MOFs were subjected to different acid The mixture is treated with the solution, and the formamide substituent is hydrolyzed according to the reaction shown in Figure 4. The amino group on the MOF was activated by exposing the amino group and releasing formic acid. This involves taking the MOF, washing it with acid, and then drying it. Sample B-0 of this specification is... For each, 200g of Zr(NH2-BDC)MOF was used to determine the degree of amide hydrolysis and maintain porosity. To determine durability, the material was washed with 2L of acid of various concentrations. 200g of MOF was then mixed with 2L of acidic solution. The mixture was stirred at different temperatures for 12 hours. After acid washing, the MOF was washed with acetone, and the remaining acid, water, and Alternatively, hydrolyzed formic acid was removed from the amide. After washing with acetone, the MOF was heated at 100°C for 12 hours. After drying, the BET surface area, N2 adsorption amount, and NO2 adsorption amount were measured (Table 3). Sample A is an example. The sample in 1-1 was not acid-washed, while the control sample was a commercially available material that was not acid-washed. This is a sample. Table 3. Characterization of acid-washed MOFs [Table 3]

[0062] Table 3 shows the results of these experiments using washing with different acids and different concentrations of acid. Table 3 Sample A shows the characterization of the MOF of Example 1-1 that was not acid-washed. The ratio of formic acid was found to be 2.55:1 (this is because formic acid is directly bonded to the metal structure). (Containing a group and a formic acid group bonded to an organic ligand). When this is compared to sample B, the acid washing Furthermore, despite only a slight decrease in MOF surface area, formic acid against MOF linker The ratio decreased significantly to 0.08:1. This decrease in the ratio of formic acid to NH2-BDC is due to the acid washing process. This indicates that the formamide group was hydrolyzed at the TEPP stage, and the amino group was regenerated.

[0063] Table 3 shows how different acids and acid concentrations affect the hydrolysis of amide groups and the surface area of ​​MOFs. It also shows whether it has an effect. For all three acids (HC1, HNO3, and H2SO4), moles When the concentration is reduced from 1M to 0.05M, the amount of hydrolysis that occurs decreases. The ratio of formic acid to NH2-BDC decreased from 2.55:1 to 1.10:1. When the acid concentration is reduced, M The surface area of ​​OF is not significantly affected. For all three acids, from room temperature (rt) to 60°C. Raising the temperature increases the amount of amide that is hydrolyzed, but the surface area is smaller compared to room temperature treatment. The decrease is even greater. In the case of nitric acid, the decrease in surface area is greater at high acid concentrations (1M to 0.25M). Similarly, when the amide group is treated with a 1M sulfuric acid solution while hydrolyzing it, the reduction in surface area is significant. It will get worse.

[0064] The degree of hydrolysis of the amide is, 1 The following measurements were taken using an H-NMR spectrophotometer. Each MOF sample, which was washed and dried to activate the amino groups as shown in Figure 3, is a sample of the MOF. According to the reaction scheme, NaOD / EEO is used to decompose the MOF and completely cleave the formamide group. The mixture was treated with a solution and contained activated NH2-BDC (a linker cleaved from the MOF structure) and cleaved formic acid. The mixture was left behind. 1 The H-NMR spectrum was measured to detect the formamine remaining after acid washing. This was used to calculate the amount of the do group. Refer to Figure 3. 1 The H-NMR spectrum is NH2-BDC The Hc (δd, 7.55 ppm) on the linker and the Hd (δs, 8.3 ppm) on the cleaved formic acid were compared and used. It can be seen that the higher the proportion of formic acid that is cleaved, the higher the proportion of MOF before decomposition. This indicates that it had a lumamide group, and the lower the proportion of cleaved formic acid, the lower the MOF before decomposition. It had a low proportion of formamide groups, that is, form was removed by the acid washing step. This indicates that the amide group was hydrolyzed, activating the amino group.

[0065] Figure 2A shows that spectrum A corresponds to sample B, spectrum B is the control sample, and spectrum C is Examples 1-7 (Table 1) that were not acid-washed, Spectrum D corresponds to Sample A in Table 3, and four fractions The sample that was solved 1 The 1H-NMR spectrum is shown. The illustration in Figure 2A shows the MOF structure before acid washing. And which protons on the MOF structure 1 This indicates whether it corresponds to the H-NMR peak. At 8.3 ppm... The peaks are coupled to MOF ligands and MOF corner metal units, as shown in the inset in Figure 2A. This represents the sum of signals from Hd protons on the carbon atoms of the formamide group. This peak is MO Spectrum corresponding to sample A, which was not acid washed, using formic acid as a modifier in F synthesis. It can be seen that the highest level is at D. Also, commercially available control sample (spectrum B) and HC1 A significant formamide peak is also observed in the sample using (spectrum C). In spectrum A, corresponding to sample B washed with 1.0 M HC1, there is no peak for formamide. It has become small enough to be seen.

[0066] These results are shown in Figure 2B, where the peaks indicate the presence of amide and amine groups. Solid of the same sample 15 It matches the N-NMR spectrum. For reference, the E spectrum is a free ligand. This shows the chemical shift of the free amine peak. 15 This is NH2-BDC. Spectrum F represents the formation of sample B. The substance, spectrum G is the product from Examples 1-7 (Table 1), and spectrum H is sample A. The spectrum shows that formylamide is present in all Zr(NH2-BDC) preparations that have not been acid-washed. This indicates that it is present. Sample A (spectrum H), which has not undergone acid washing, is essentially It showed a prominent amide peak, and almost no amine peak, but after acid washing... Sample B (spectrum F) showed virtually no amide peak and instead exhibited a strong amine peak.

[0067] The increase in free amino groups, corresponding to the removal of the formamide group, is measured by the NO2 single-component isotherm. Increase the amount of NO2 adsorbed that is measured (Table 3). Specifically, untreated MOF (sample in Table 3) In A), the NO2 adsorption capacity measured at 50 Torr and 25°C was only 0.58 mmol / g, but it was washed with HC1. Then, at 50 Torr and 25°C, the NO2 volume increased to 8.3 mmol / g (Sample B; Table 3). Nitric acid (Sun Similar results were obtained with pull (H) and sulfuric acid (sample N).

[0068] Furthermore, the control MOF reduced the number of amide groups available for reactivity by 45%. This shows the degree (Figure 2A (spectrum B) and Table 3). In contrast, the acid-treated MOF is undesirable. 255% incorporation of amide groups (formamide groups attached to ligands and corner metal units) (Including those attached to the site) 3-8% incorporated (Figure 2A (spectrum A) and Table 3) It shows a decrease in and therefore releases most of the amino groups due to reactivity with polluted air. This is possible. Increased crystal size, increased highly reactive free amines, and high surface area and These improved properties make it more desirable than commercially available materials, especially for air filtration. You will be able to obtain MOF with specific characteristics.

Claims

1. The metal is selected from Zr, V, Al, Fe, Cr, Ti, Hf, Cu, Zn, Ni, Ce, and mixtures thereof. A metal ion atom and at least one organic ligand containing an amino group, or an amino group A combination of at least one organic ligand containing an amino group and at least one organic ligand that does not contain an amino group MOFs include corner metal units with linker molecules selected from combinations, and are less It has an average crystal size of at least 1 μm in at least one dimension, and at least 55% of the amino groups ga-NH 2 It is characterized by being an activated amino group of the form, Metal-organic framework (MOF) compositions.

2. A method for purifying a gas stream containing at least one pollutant, The gas flow is brought into contact with a composition containing the metal-organic frame (MOF) composition described in claim 1. This removes at least a portion of at least one contaminant in the gas stream. A method that includes this.

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