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公开(公告)号：US12037349B2
公开(公告)日：2024-07-16
申请号：US17310633
申请日：2020-03-30
CPC分类号： C07F3/06 , C01B37/00 , C01B39/00 , C07F3/003 , C07F3/02 , C07F15/045 , C07F15/065 , C07F19/005
摘要： Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. MOFs may comprise a plurality of metal centers, and a multidentate organic ligand coordinated via at least two binding sites to the plurality of metal centers to define an at least partially crystalline network structure having a plurality of internal pores, and in which the multidentate organic ligand comprises first and second binding sites bridged together with a third binding site comprising a diimine moiety. The multidentate organic ligand may comprise a reaction product of a vicinal dicarbonyl compound and an amine-substituted salicylic acid to define the first, second and third binding sites. Particular MOFs may comprise 5,59′-(((1E,2E)-ethane-1,2-diylidene)bis-(azaneylylidene))bis(2-hydroxybenzoic acid) as a multidentate organic ligand.
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2.发明公开公开(公告)号：US20240286112A1
公开(公告)日：2024-08-29
申请号：US18572045
申请日：2022-06-23
IPC分类号： B01J20/22
CPC分类号： B01J20/226
摘要： Provided herein are post-synthesis methods of thermally stabilizing a metal-organic framework having defects that decomposes after about 12 hours at a first temperature. The methods include contacting the metal-organic framework with a stabilizing solution to provide a treated metal-organic framework. The treated metal-organic framework is thermally stable after 12 hours at a second temperature at least about 50° C. greater than the first temperature. Also, the treated metal-organic framework has a PXRD pattern that is substantially the same as the PXRD pattern of the untreated metal-organic framework. Provided herein are also post-synthesis methods to improve CO2 adsorption of metal-organic frameworks. Provided herein are also modified EMM-71 metal-organic frameworks.
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公开(公告)号：US11891407B2
公开(公告)日：2024-02-06
申请号：US17400742
申请日：2021-08-12
发明人： Carter W. Abney , Joseph M. Falkowski , Mary S. Abdulkarim , Anna C. Ivashko , Julie J. Seo , Aaron W. Peters , Matthew T. Kapelewski , Gerardo J. Majano Sanchez , Wesley Sattler , Simon C. Weston
CPC分类号： C07F3/02 , B01D53/04 , B01J20/226 , C01B37/00 , B01D2253/204 , B01D2257/504
摘要： Provided herein are methods of novel methods of synthesizing a metal-organic framework system by vapor-phase appending of a plurality of ligands appended to a metal-organic framework. Also, provided are methods of recycling metal-organic framework systems by detaching the ligand and re-appending the same ligand or appending a different ligand to the metal-organic framework to provide a recycled or repurposed metal-organic framework system.
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公开(公告)号：US20240261759A1
公开(公告)日：2024-08-08
申请号：US18561646
申请日：2022-05-31
CPC分类号： B01J20/226 , B01J20/28064 , B01J20/28066 , B01J20/28071 , B01J20/28073 , B01J20/3078 , B01J2531/48
摘要： Provided are methods of making a MOF UiO-66 comprising reacting zirconium oxychloride with terephthalic acid or derivative thereof and acetic acid in a solvent to provide a reaction solution; diluting the reaction solution with water, heating the diluted reaction solution and reducing the reaction temperature of the reaction mixture to provide the MOF UiO-66 having a micropore volume greater than or equal to 0.45 cc/g and a crystal size of between about 20 nm and about 1000 nm. Also provided are methods of making a MOF UiO-66 where a zirconium hydroxide acetate and zirconium hydroxide are reacted with a carboxylic acid or derivative thereof and acetic acid in a solvent to produce the metal-organic framework MOF UiO-66 having a micropore volume at least 0.35 cc/gram.
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公开(公告)号：US12036539B2
公开(公告)日：2024-07-16
申请号：US17621281
申请日：2020-05-28
CPC分类号： B01J31/1691 , B01J35/617 , B01J35/618 , B01J35/633 , B01J35/635 , B01J35/643 , B01J35/647 , B01J37/04 , B01J37/30 , C07C5/03 , C07F3/06 , B01J2231/645 , B01J2531/0205 , B01J2531/0211 , B01J2531/0238 , B01J2531/26 , B01J2531/72 , B01J2531/845 , B01J2531/847 , C07C2531/22
摘要： Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers. MOFs having ambient condition stability may comprise a plurality of metal clusters comprising one or more M4O clusters (M is a metal), and a plurality of 4-pyrazolecarboxylate ligands coordinated to the plurality of metal clusters to define an at least partially crystalline network structure having a plurality of internal pores. The MOFs may have a Pa3 symmetry, which upon activation may convert into Fm3m symmetry. Methods for synthesizing the MOFs may comprise combining a metal source, such as a preformed metal cluster, with 4-pyrazolecarboxylic acid, and reacting the preformed metal cluster with the 4-pyrazolecarboxylic acid to form a MOF having an at least partially crystalline network structure with a plurality of internal pores defined therein and comprising a plurality of metal clusters coordinated to a multidentate organic ligand comprising 4-pyrazolecarboxylate.
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公开(公告)号：US20240300983A1
公开(公告)日：2024-09-12
申请号：US18572039
申请日：2022-06-23
CPC分类号： C07F7/003 , B01J20/226 , B01J20/3078 , B01J20/3085 , B01J31/1691 , B01J37/031 , B01J37/04 , B01J37/08 , B01J2531/48 , B01J2531/49
摘要： Provided herein are methods of making a metal-organic framework comprising: combining a pre-ligand with a metal source to provide a plurality of solid reactants; adding a solvent to the plurality of solid reactants to form a reaction mixture, wherein at least 50 wt % of the reaction mixture are the plurality of solid reactants; heating the reaction mixture wherein the pre-ligand is converted to a ligand in the reaction mixture and the ligand reacts with the metal component; and cooling the reaction mixture to produce the metal-organic framework. The present methodologies are performed without dimethylformamide in the reaction mixture. The present methods may further comprise the step of adding a crystallization aid such as zinc oxide to the reaction mixture.
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公开(公告)号：US20240278208A1
公开(公告)日：2024-08-22
申请号：US18572034
申请日：2022-06-23
CPC分类号： B01J20/226 , B01J20/0225 , B01J20/0237 , B01J20/0244 , B01J20/0251 , B01J20/0288 , B01J20/0296 , B01J20/28066 , B01J20/28071 , B01J20/28073 , B01J20/28076 , B01J20/3085
摘要： Provided are metal-organic frameworks made by the process of comprising the steps of reacting a first metal source that can generate a tetravalent metal cation in solution, a linear dicarboxylic acid, a second metal source that can generate a divalent cation in solution, and one or more monocarboxylic acid modulators in a solvent to provide a reaction solution. The reaction solution is heated to provide a metal-organic framework having between about 0 wt. % to 10 wt. % of divalent cation, surface area between about 1100 m2/g and 2700 m2/g, a porosity of between about 0.45 cc/g and 1.1 cc/g, and a relative intensity equal to or greater than 0.35 and a peak width ratio of less than 3.0.
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公开(公告)号：US20240254148A1
公开(公告)日：2024-08-01
申请号：US18413176
申请日：2024-01-16
CPC分类号： C07F7/00 , B01J20/226 , C07B2200/13
摘要： Provided herein are methods of making metal-organic frameworks comprising combining a first pre-ligand and at least one of a second pre-ligand or a first ligand with a metal source comprising a metal component to provide a plurality of reactants where at least 50 wt % of the reaction mixture is the plurality of reactants after solvent has been added to the plurality of reactants. Also provided herein are methods of making metal-organic frameworks comprising combining a pre-ligand with a metal source selected from metal acetates, metal hydroxyacetates, metal carbonates, metal hydroxycarbonates, and mixtures thereof.
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