CN107739444B - Metal-organic framework materials based on amino-functionalized YbIII hexanuclear molecular building blocks and their preparation methods and applications - Google Patents
Metal-organic framework materials based on amino-functionalized YbIII hexanuclear molecular building blocks and their preparation methods and applications Download PDFInfo
- Publication number
- CN107739444B CN107739444B CN201711128860.3A CN201711128860A CN107739444B CN 107739444 B CN107739444 B CN 107739444B CN 201711128860 A CN201711128860 A CN 201711128860A CN 107739444 B CN107739444 B CN 107739444B
- Authority
- CN
- China
- Prior art keywords
- amino
- organic framework
- hexanuclear
- metal
- functionalized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 238000007306 functionalization reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- HEVMDQBCAHEHDY-UHFFFAOYSA-N (Dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=CC=C1 HEVMDQBCAHEHDY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 2
- -1 Yb(NO 3 ) 3 Chemical compound 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000010523 cascade reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种基于氨基功能化YbIII六核分子结构单元的金属有机框架材料及其制备方法和应用。采用的技术方案：将Yb(NO3)3，邻氟苯甲酸，2‑氨基对苯二甲酸，N,N‑二甲基甲酰胺，硝酸和水加入容器内，于常温下搅拌30分钟；将容器密封后放入烘箱中，于温度378K下保持3天；缓慢冷却到室温，得到卡其色八面体晶体；用N,N‑二甲基甲酰胺洗涤、过滤、干燥，得目标产物。本发明所制备的基于氨基功能化YbIII六核分子结构单元的金属有机框架材料，制备方法简单，并且对deacetalization‑Knoevenagel缩合反应展示出良好的催化性能。
The invention relates to a metal-organic framework material based on amino-functionalized Yb III hexanuclear molecular structural unit, a preparation method and application thereof. The technical scheme adopted: adding Yb(NO 3 ) 3 , o-fluorobenzoic acid, 2-aminoterephthalic acid, N,N-dimethylformamide, nitric acid and water into the container, and stirring at normal temperature for 30 minutes; After sealing the container, put it into an oven and keep it at a temperature of 378K for 3 days; slowly cool to room temperature to obtain khaki octahedral crystals; wash with N,N-dimethylformamide, filter and dry to obtain the target product. The metal-organic framework material based on the amino-functionalized Yb III hexanuclear molecular structural unit prepared by the invention has a simple preparation method and exhibits good catalytic performance for the deacetalization-Knoevenagel condensation reaction.
Description
Technical Field
The invention relates to a metal organic framework material, in particular to Yb based on amino functionalizationIIIThe metal organic framework material of the hexanuclear molecular structural unit and the application thereof in catalyzing deacetalization-Knoevenagel condensation reaction.
Background
Metal-organic framework Materials (MOFs) are currently a hot research area in coordination chemistry and in material science. The structure of the MOFs is designable, post-synthesis modification can be performed, the pore size is adjustable, and the types of active functional groups can be controlled, so that the MOFs play an important role in the field of catalytic research. Multinuclear metal clusters have become the leading area of greatest interest today. In recent years, discrete four-nucleus, five-nucleus, six-nucleus, seven-nucleus, eight-nucleus, nine-nucleus, ten-nucleus, twelve-nucleus, fifteen-nucleus, etc. have been synthesized one after another. The professor of Longrashigan at Xiamen university utilizes threonine ligand to synthesize four chiral sixty-nucleus rare earth cluster compounds, which are the rare earth cluster compounds with the highest nucleus number found at present. In recent years, with the rapid development of research on multi-core rare earth cluster compounds, functional rare earth cluster metal organic framework materials are synthesized by taking rare earth clusters as molecular structural units, and due to unique structures, abundant holes and functional sites, chemists and materials scientists pay attention to the materials and the materials organic framework materials become a research hotspot.
The tandem reaction is an economical, efficient and environmentally friendly chemical process that has attracted the interest of a large number of chemical researchers. The tandem reaction often refers to a series of reactions in which two or more steps occur continuously and a final product is obtained directly without separating intermediate products, thereby effectively reducing the use of chemicals and the emission of pollutants. Therefore, in the field of organic catalysis, the development of the tandem reaction is bound to become a new development direction.
Disclosure of Invention
The invention aims to construct a novel Yb based on amino functionalization by using 2-amino terephthalic acid as an organic ligand and utilizing a solvothermal method through adjusting synthesis conditionsIIIThe metal-organic framework of the structural unit of the hexanuclear molecule of (A) and its use as a Lewis acid and a Lewis acid
The alkali bifunctional catalyst has the catalytic performance on deacetalization-Knoevenagel condensation reaction.
The technical scheme adopted by the invention is as follows: amino-based functionalized YbIIIThe metal organic framework material with six nuclear molecular structural units has the molecular formula of [ (CH)3)2NH2][Yb6(μ3-OH)8(BDC-NH2)6(H2O)]·(solv)XThe crystal belongs to a cubic crystal system, the space group is Fm-3m and is composed of [ Yb6(μ3-OH)8(O2C-)12]As a node, from the ligand BDC-NH2The three-dimensional structure formed by bridging comprises a polyhedral cage with octahedron and tetrahedron.
Amino-based functionalized YbIIIThe preparation method of the metal organic framework material with the hexanuclear molecular structural unit comprises the following synthetic steps:
1) reacting 2-amino terephthalic acid (H)2BDC-NH2)、Yb(NO3)3Adding o-fluorobenzoic acid and N, N-Dimethylformamide (DMF) into a container, stirring at normal temperature to dissolve, adding a small amount of nitric acid and water, and stirringHomogenizing;
preferably, 2-amino terephthalic acid (H) in a molar ratio2BDC-NH2):Yb(NO3)3＝1:0.8-1.5；
Preferably, N, N-dimethylformamide to HNO in a volume ratio3＝10-15:1。
2) Sealing the container, putting the container into an oven, heating the container under 373-383K, and keeping the container for 3 days; the heating rate is 10 K.min-1；
3) Slowly cooling to room temperature, standing for at least 1 day to obtain crystals; preferably, the cooling rate of the slow cooling to room temperature is 10 K.min-1(ii) a Washing with N, N-dimethylformamide, filtering and drying to obtain the target product.
Amino-based functionalized Yb of the inventionIIIThe metal organic framework material with six-core molecular structural unit contains rich unsaturated Yb (III) center and amino group in the structure, and can be used as Lewis acid and
the alkali bifunctional catalyst is used for catalyzing deacetalization-Knoevenagel condensation reaction. The method comprises the following steps: taking benzaldehyde dimethyl acetal, malononitrile, dimethyl sulfoxide and a catalyst into a reaction tube, and introducing N into the reaction tube under the condition of stirring2Reacting for 24 hours at the temperature of 50 ℃; the catalyst is the above Yb based on amino functionalizationIIIThe metal-organic framework material of the hexanuclear molecular structural unit. The reaction formula is as follows:
the invention has the beneficial effects that: the amino-based functionalized Yb prepared by the inventionIIIThe Yb (III) ions in the metal organic framework material with the six-core molecular structural unit are all nine-coordinated, so that the structure contains rich unsaturated Yb (III) centers which can be used as Lewis acid sites, and ligands contain-NH2Can be used as
A base site. Thus, the complexes of the invention can be made as Lewis acids and
the alkali bifunctional catalyst shows good catalytic performance for deacetalization-Knoevenagel condensation reaction. And because of the amino-functionalized Yb prepared according to the inventionIIIThe hexanuclear molecular structure unit metal organic framework material has simple synthesis method and application prospect.
Drawings
FIG. 1 shows a 12-linked Yb-hexanuclear cluster building block in the structure of a metal-organic framework material according to the invention.
FIG. 2a is a schematic view of an octahedral cage in the structure of the metal-organic framework material of the present invention.
FIG. 2b is a schematic representation of tetrahedral cages in the metal organic framework material structure of the present invention.
FIG. 3 is a schematic diagram of the cage framework structure in the metal-organic framework material structure of the present invention.
FIG. 4 is a NMR chart of the reaction of example 2 with time.
FIG. 5 shows the catalytic activity of the metal organic framework material of the present invention for four cycles of catalytic reactions.
FIG. 6 is an XRD pattern of four cycles of catalytic reactions performed on the metal-organic framework material of the present invention.
Detailed Description
Example 1 amino-based functionalization of YbIIIMetal organic framework material with six-core molecular structural unit
H is to be2BDC-NH2(9.0mg,0.048mmol)，Yb(NO3)3·6H2O (19.3mg,0.0413mmol) and O-fluorobenzoic acid (48.7mg) were charged into a 5 mL-volume high-temperature resistant screw-top glass bottle, 2.2mL of DMF was added, and the mixture was dissolved under stirring at room temperature, followed by addition of H2O (0.5mL) and 3.57M HNO3(0.2mL) and stirring for 20 minutes until the metal salt is completely dissolved and is uniformly mixed with the organic ligand, sealing the glass bottle and then putting the glass bottle into an oven, wherein the heating rate is 10 K.min-1Heating to 378K, heating at the temperature for 3 days at 10 K.min-1The temperature reduction rate of (1) is slowly cooled to room temperature, octahedral crystals with karite color are generated, and the target product, namely the amino-functionalized Yb is obtained by washing with DMF, filtering and dryingIIIThe yield of the metal organic framework material with the structural unit of the hexanuclear molecule is 63 percent.
The invention synthesized based on amino-functionalized YbIIIThe structure of the metal organic framework material with the six-core molecular structural unit is shown in figures 1-3, the crystal structure belongs to a cubic crystal system, and the space group is Fm-3 m. The molecular formula is [ (CH)3)2NH2][Yb6(μ3-OH)8(BDC-NH2)6(H2O)]·(solv)XThe compound is composed of [ Yb ]6(μ3-OH)8(O2C-)12]As a node, as shown in FIG. 1, from the ligand BDC-NH2Three-dimensional structure formed by bridging. Cation [ (CH)3)2NH2]+As a counter ion, in the pores of the MOF. Each 2-aminoterephthalic acid ligand is bound to four Yb3+Ion coordination, six Yb3+Ions with six oxygens from the carboxyl group of 2-amino terephthalic acid and six mu3-OH coordination. Along the b-axis, the framework comprises polyhedral cages, both octahedral and tetrahedral, as shown in fig. 2a and 2 b.
Example 2 amino-based functionalization of YbIIICatalysis function of metal organic framework material with six-nuclear molecular structural unit on deacetalization-Knoevenagel condensation reaction
The method comprises the following steps: amino-functionalized Yb prepared as in example 1IIIThe metal organic framework material with the six-core molecular structural unit is used as a catalyst for catalyzing deacetalization-Knoevenagel condensation reaction.
1) Activating treatment of the catalyst: taking a certain amount of amino-based functionalized YbIIIAnd (3) vacuumizing and drying the metal organic framework material with the six-core molecular structural unit for 24 hours under the heating condition of 298K.
The method comprises the following steps: taking 100mg of activated amino-based functionChemical YbIIIAdding 2.0mmol of benzaldehyde dimethyl acetal, 2.1mmol of malononitrile and 2mL of dimethyl sulfoxide into a 10mL reaction tube, and introducing N under the condition of stirring2The temperature is 50 ℃, and the reaction time is 24 h. The experimental results were detected by hydrogen nuclear magnetic resonance spectroscopy.
During the reaction, the amino-based functionalized YbIIIThe experimental results of the catalytic performance of metal organic framework materials with six nuclear molecular structural units on deacetalization-Knoevenagel condensation reaction are shown in FIG. 4, the yield of the reaction gradually increases with the reaction, and the conversion rate of the reaction reaches a maximum of 97% when the reaction is carried out for 24 hours.
2) Recyclable and reusable catalyst in Deacetalization-Knoevenagel condensation reaction
And (3) recovering the catalyst: after the reaction is finished, filtering, separating the catalyst from the reaction mixture, washing with methanol, soaking in methanol for 4 hours, filtering and drying.
Specific operation of the cycling experiment: the recovered catalyst is used for catalyzing deacetalization-Knoevenagel condensation reaction, and the reaction is carried out for 24 hours at 50 ℃.
The results of the experiment are shown in fig. 5 and 6, and the activity of the catalyst is not reduced when the cycle experiment is carried out to the 4 th round. Illustrating the amino-based functionalization of YbIIIThe metal organic framework material with the six-core molecular structural unit can be recycled as a catalyst for catalyzing deacetalization-Knoevenagel condensation reaction.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711128860.3A CN107739444B (en) | 2017-11-15 | 2017-11-15 | Metal-organic framework materials based on amino-functionalized YbIII hexanuclear molecular building blocks and their preparation methods and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711128860.3A CN107739444B (en) | 2017-11-15 | 2017-11-15 | Metal-organic framework materials based on amino-functionalized YbIII hexanuclear molecular building blocks and their preparation methods and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107739444A CN107739444A (en) | 2018-02-27 |
| CN107739444B true CN107739444B (en) | 2020-05-12 |
Family
ID=61234714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711128860.3A Active CN107739444B (en) | 2017-11-15 | 2017-11-15 | Metal-organic framework materials based on amino-functionalized YbIII hexanuclear molecular building blocks and their preparation methods and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107739444B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722488B (en) * | 2018-05-04 | 2021-02-12 | 江苏师范大学 | Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof |
| CN109054043B (en) * | 2018-09-19 | 2021-10-01 | 辽宁大学 | Y(III)-based hexanuclear rare earth cluster metal-organic framework material and its preparation method and application |
| CN110092734B (en) * | 2019-05-22 | 2021-12-31 | 华侨大学 | Tandem synthesis method of 2- (phenylmethylene) malononitrile or derivatives thereof |
| CN111001442B (en) * | 2019-12-19 | 2023-01-17 | 辽宁大学 | A kind of metal-organic framework MIL-101 (Cr) loaded chitosan material and its preparation method and application |
| CN118206764B (en) * | 2022-12-16 | 2024-12-03 | 中国科学院精密测量科学与技术创新研究院 | A multi-component metal-organic framework material and its application in the preparation of Hyper-CEST signal enhancement reagents |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397797A (en) * | 2016-08-29 | 2017-02-15 | 山东师范大学 | Gold-MOFs-polymer composite membrane, and production method and application thereof |
| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3143033B1 (en) * | 2014-05-16 | 2019-04-10 | The Texas A&M University System | Chromium metal organic frameworks and synthesis of metal organic frameworks |
-
2017
- 2017-11-15 CN CN201711128860.3A patent/CN107739444B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397797A (en) * | 2016-08-29 | 2017-02-15 | 山东师范大学 | Gold-MOFs-polymer composite membrane, and production method and application thereof |
| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107739444A (en) | 2018-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107739444B (en) | Metal-organic framework materials based on amino-functionalized YbIII hexanuclear molecular building blocks and their preparation methods and applications | |
| CN108273555B (en) | A porous crystalline core-shell hybrid material based on UiO-66@SNW-1 and its preparation method and application | |
| CN112280052B (en) | Hierarchical pore ZIF-8 material and preparation method and application thereof | |
| CN105348071B (en) | Preparation method and application of a class of discrete metal-organic nanotubes based on tetraphenylethylene derivatives | |
| Sani et al. | A study of contemporary progress relating to COF materials for CO 2 capture and fixation reactions | |
| CN104324756A (en) | Preparation method and applications of mesoporous metal organic complex base composite material | |
| CN104324760B (en) | A kind of preparation method and application of feature coordination polymer | |
| CN110075921A (en) | A kind of Ni (II) base crystalline-state catalyst and its preparation method and application | |
| CN105693506A (en) | Synthesis method of porous titanium crystal metal organic framework material | |
| CN115536860A (en) | A kind of bio-MOF material for electrocatalysis and photocatalysis and its preparation method and application | |
| CN115254189B (en) | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof | |
| CN107903399A (en) | A kind of MOF material preparation methods for being catalyzed amidation process | |
| CN110116024A (en) | A kind of inhomogeneous three dimensional bivalent state Cu-MOF catalyst and preparation method and application | |
| CN109369689A (en) | A kind of copper metal organic framework (Cu-MOF) catalytic material, preparation method and application | |
| CN105772080B (en) | Tripolite loading palladium catalyst, preparation method and applications | |
| KR101091875B1 (en) | A purification method of porous metal-organic framework materials | |
| CN111001442B (en) | A kind of metal-organic framework MIL-101 (Cr) loaded chitosan material and its preparation method and application | |
| CN103709204B (en) | A kind of cobalt complex, preparation method and its usage | |
| CN113817174A (en) | Preparation method and application of in-situ hydrazide three-dimensional MOFs material | |
| CN106732785B (en) | Application of a rare earth-based porous metal-organic framework compound in siliconitrile reaction | |
| CN104072525B (en) | A kind of 5-Isonicotinamide pyridyl different metatitanic acid Porous Cu title complex and its preparation method and application | |
| CN103073420B (en) | A kind of method that contains -SO3H metal-organic framework compound catalytic esterification | |
| CN110743582A (en) | Preparation and application of palladium catalyst supported by marine biological waste oyster shell | |
| CN113896897B (en) | A kind of metal organic framework material for photocatalytic aerobic reaction and preparation method thereof | |
| CN110124738B (en) | Fe-Zn bimetal crystalline catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201130 Address after: 241100 8 / F, building 5, Wuhu navigation Innovation Park, Wanbi Town, Wuhu County, Wuhu City, Anhui Province Patentee after: Wuhu Digital Information Industrial Park Co., Ltd Address before: 110000, Liaoning, Shenyang, Shenbei New Area moral South Avenue No. 58 Patentee before: LIAONING University |