CN111234259A - Method for efficiently preparing ferrous metal organic framework material - Google Patents
Method for efficiently preparing ferrous metal organic framework material Download PDFInfo
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- CN111234259A CN111234259A CN202010335455.4A CN202010335455A CN111234259A CN 111234259 A CN111234259 A CN 111234259A CN 202010335455 A CN202010335455 A CN 202010335455A CN 111234259 A CN111234259 A CN 111234259A
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Abstract
The invention discloses a method for efficiently preparing ferrous Metal Organic Frameworks (MOFs), which is prepared from [ Fe (Cp) (CO)2]2And various nitrogen-containing aromatic carboxylic acid ligands, and obtaining the ferrous MOFs material through self-assembly under the hydrothermal condition. The invention uses [ Fe (Cp) (CO)2]2When the method replaces the common ferric salt to prepare the ferrous MOFs, the hydrolysis of ferric ions can be effectively prevented, and the convenient and efficient preparation of the ferrous MOFs material is realized. The invention provides a brand new method for preparing the ferrous MOFs material, solves the problem of difficult preparation, has the advantages of simple and efficient preparation, and has extremely wide application prospect in the field of preparation of ferrous functional materials.
Description
Technical Field
The invention relates to the technical field of preparation of ferrous Metal Organic Frameworks (MOFs) materials, in particular to a method for efficiently preparing ferrous MOFs materials.
Background
MOFs materials have attracted great interest to researchers because not only do they have a wide variety of interesting topologies, but they can be used as potential functional materials in the fields of gas separation, storage, and magnetism. During the last decades, much effort has been devoted to obtaining magnetic MOFs, mainly prepared by modifying organic ligands and metal ions. Considering that the nature of metals has a large influence on the magnetic behaviour, 3d transition metals may be the best candidates for introducing important magnetic properties in magnetic molecular materials. To date, a large number of 3d transition metals (e.g., Mn, Co, Ni, and Cu) MOFs have been synthesized, and their magnetic properties have also been extensively studied.
In comparison, iron-based MOFs are relatively rare because they are relatively difficult to prepare, most likely because fe (ii) ions are very easily oxidized to fe (iii) ions, which are subsequently hydrolyzed under hydrothermal conditions to form iron sesquioxide. A kind of preventionThe method for hydrolyzing the iron ions comprises the following steps: adopts hydrofluoric acid as mineralizer to eliminate OH-Ionic effects, for example, synthesis of the well-known MIL-53, MIL-62 and MIL-68 sequences. Another method of preventing hydrolysis of iron ions is: using non-aqueous solvents, e.g.N,N' -dimethylformamide or a mixed solvent of pyridine and ethanol, such as synthetic MOF-235 and MOF-236. Despite these successes, there remains a need to develop more efficient and rapid methods for synthesizing ferrous-based MOFs.
Disclosure of Invention
The invention aims to overcome the defects of the existing preparation method and develop a method for preparing the ferrous MOFs material more efficiently and quickly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for efficiently preparing ferrous MOFs materials is characterized by comprising the following steps: (1) adding iron-containing metal salt and nitrogen-containing aromatic carboxylic acid ligand into a polytetrafluoroethylene reaction kettle according to a certain proportion, and adding a proper amount of solvent or mixed solvent to fully dissolve the iron-containing metal salt and the nitrogen-containing aromatic carboxylic acid ligand. (2) Then the hydrothermal reaction kettle is at 100-180 DEG CoAnd C, fully reacting for 2-5 days, cooling to room temperature, cleaning the prepared crystal material with a solvent, and drying to obtain the ferrous MOFs material.
The method for efficiently preparing the ferrous MOFs material comprises the following steps of [ Fe (Cp) (CO) ]2]2、Fe(Cp)2、Fe(CO)5And Fe2(CO)9And the like.
In the method for efficiently preparing the ferrous MOFs material, the nitrogen-containing aromatic carboxylic acid ligand comprises but is not limited to nicotinic acid, isonicotinic acid, 3, 5-pyridinedicarboxylic acid, 5-pyridylisophthalic acid, 5, 6-benzimidazoledicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 3, 4-pyridinedicarboxylic acid and the like.
The method for efficiently preparing the ferrous MOFs material comprises the following steps of,N,N' -dimethylformamide, dioxane, or the like,N,N' -dimethylacetamide,N,N' -DiethylmethylAny one or more of amide, benzene, toluene and acetonitrile is mixed according to any proportion.
Preferably, the reaction temperature and the reaction time are 100-180-oAnd C, the reaction time is 2-5 days.
The invention has the advantages that: with [ Fe (Cp) (CO)2]2When the method replaces the common ferric salt to prepare the ferrous MOFs, the hydrolysis of ferric ions can be effectively prevented, and the convenient and efficient preparation of the ferrous MOFs material is realized. The invention provides a brand new method for preparing the ferrous MOFs material, solves the problem of difficult preparation, has the advantages of simple preparation and high efficiency, and has obvious industrialization prospect and high industrialization value in the field of functional material preparation.
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FIG. 1 shows a preparation route of six examples of ferrous-based MOFs materials.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
nicotinic acid (0.50 mmol) and [ Fe (Cp) (CO)2]2(0.125 mmol) was placed in a 20 mL Teflon hydrothermal pot, then 7.0 mL CH was added3CN/H2O (v/v = 4: 3) solvent. The mixture is heated to 160 ℃ within 4 hours and kept at this temperature for 2 days, finally slowly cooled to room temperature within 2 days, washed 3 times with acetonitrile to obtain [ Fe ]2(Nic)4(μ-H2O)]·CH3Yellow crystals of CN (1) in about 61% yield based on [ Fe (Cp) (CO)2]2. Compound 1 has a three-dimensional dia structure in which the iron ion exhibits positive divalent.
Example 2:
mixing 5-pyridylisophthalic acid (0.50 mmol) with [ Fe (Cp) (CO)2]2(0.125 mmol) was placed in a 20 mL Teflon hydrothermal pot, then 7.0 mL CH was added3CN/H2O (v/v = 4: 3) solvent. The mixture was heated to 160 ℃ in 4 hours and held at this temperature for 2 days, and finally slowly cooled to 2 daysWashing with acetonitrile at room temperature for 3 times to obtain [ Fe (PIP) (H)2O)]·H2Yellow crystals of O (2) in a yield of about 50%, based on [ Fe (Cp) (CO)2]2. The compound 2 has a two-dimensional kgd layered structure which can be further expanded into a three-dimensional supramolecular structure through a hydrogen bond, wherein iron ions show positive bivalence.
Example 3:
mixing 5, 6-benzimidazole dicarboxylic acid (0.50 mmol) and [ Fe (Cp) (CO)2]2(0.125 mmol) was placed in a 20 mL Teflon hydrothermal pot, then 7.0 mL CH was added3CN/H2O (v/v = 4: 3) solvent. The mixture was heated to 160 ℃ in 4 hours and held at this temperature for 2 days, finally slowly cooled to room temperature in 2 days, washed 3 times with acetonitrile to give [ Fe (Hbidc)) (H2O)](3) In about 50% yield based on [ Fe (Cp) (CO)2]2. The compound 3 has a two-dimensional kgd layered structure which can be further expanded into a three-dimensional supramolecular structure through a hydrogen bond, wherein iron ions show positive divalent.
Example 4:
mixing 5, 6-benzimidazole dicarboxylic acid (0.50 mmol) and [ Fe (Cp) (CO)2]2(0.125 mmol) was placed in a 20 mL Teflon hydrothermal pot, then 7.0 mL toluene/H was added2O (v/v = 4: 3) solvent. The mixture was heated to 160 ℃ over 4 hours and held at this temperature for 2 days, finally slowly cooled to room temperature over 2 days, washed 3 times with toluene to give [ Fe (Hbidc) ]](4) In about 72% yield based on [ Fe (Cp) (CO)2]2. The compound 4 has a two-dimensional layered structure which can be further expanded into a three-dimensional supramolecular structure by hydrogen bonding, in which iron ions exhibit positive divalent.
Example 5:
mixing 3, 4-pyridinedicarboxylic acid (0.50 mmol) and [ Fe (Cp) (CO)2]2(0.125 mmol) was placed in a 20 mL Teflon hydrothermal pot, then 7.0 mL CH was added3CN/H2O (v/v = 4: 3) solvent. The mixture was heated to 160 ℃ in 4 hours and held at this temperature for 2 days, and finally slowly over 2 daysSlowly cooling to room temperature, washing with acetonitrile for 3 times, and manually separating to obtain [ Fe (Py-3,4-BDC) (H)2O)2]·H2Orange crystals of O (5) and [ Fe (Py-3,4-BDC) (H)2O)2](6) In 32% and 45% respectively based on [ Fe (Cp) (CO)2]2. The compounds 5 and 6 have two-dimensional kgd and sql layered structures, respectively, and can be further expanded into three-dimensional supramolecular structures through hydrogen bonds, wherein iron ions both show positive divalent property.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that any modification and improvement made within the scope of the principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for efficiently preparing ferrous Metal Organic Frameworks (MOFs) materials is characterized by comprising the following steps: adding iron-containing metal salt and nitrogen-containing aromatic carboxylic acid ligand into a polytetrafluoroethylene reaction kettle according to a certain proportion, and adding a proper amount of solvent or mixed solvent to fully dissolve the iron-containing metal salt and the nitrogen-containing aromatic carboxylic acid ligand.
2. Then the hydrothermal reaction kettle is at 100-180 DEG CoAnd C, fully reacting for 2-5 days, cooling to room temperature, washing the prepared crystal material with a solvent, and drying to obtain the ferrous MOFs crystal material.
3. The method of claim 1, wherein the method comprises the following steps: the iron-containing metal salt is [ Fe (Cp) (CO)2]2、Fe(Cp)2、Fe(CO)5And Fe2(CO)9And the like.
4. The method of claim 1, wherein the method comprises the following steps: the ligand of the nitrogenous aromatic carboxylic acid is nicotinic acid, isonicotinic acid, 3, 5-pyridinedicarboxylic acid, 5-pyridylisophthalic acid, 5, 6-benzimidazole dicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 3, 4-pyridinedicarboxylic acid and the like.
5. The method of claim 1, wherein the method comprises the following steps: the solvent is water,N,N' -dimethylformamide, dioxane, or the like,N,N' -dimethylacetamide,N,N' -one or more of diethylformamide, benzene, toluene and acetonitrile in any proportion.
6. The method of claim 2, wherein the method comprises the following steps: the reaction temperature is 100-180-oAnd C, the reaction time is 2-5 days.
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| CN112745493A (en) * | 2020-12-29 | 2021-05-04 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104001532A (en) * | 2014-05-12 | 2014-08-27 | 昆明理工大学 | Preparation method for supported metal cluster catalyst |
| CN107596391A (en) * | 2017-11-09 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of metal organic frame base nanometer diagnosis and treatment probe and products thereof and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104001532A (en) * | 2014-05-12 | 2014-08-27 | 昆明理工大学 | Preparation method for supported metal cluster catalyst |
| CN107596391A (en) * | 2017-11-09 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of metal organic frame base nanometer diagnosis and treatment probe and products thereof and application |
Non-Patent Citations (1)
| Title |
|---|
| QIPENG LI ET AL: ""An alternative strategy to construct Fe(II)-based MOFs with multifarious structures and magnetic behaviors"", 《CRYSTENGCOMM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745493A (en) * | 2020-12-29 | 2021-05-04 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester resin and preparation method thereof |
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