CN111036305A - Polyion liquid loaded metal organic framework and preparation method and application thereof - Google Patents
Polyion liquid loaded metal organic framework and preparation method and application thereof Download PDFInfo
- Publication number
- CN111036305A CN111036305A CN201911402009.4A CN201911402009A CN111036305A CN 111036305 A CN111036305 A CN 111036305A CN 201911402009 A CN201911402009 A CN 201911402009A CN 111036305 A CN111036305 A CN 111036305A
- Authority
- CN
- China
- Prior art keywords
- mil
- organic framework
- pil
- dvb
- preparation
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a polyion liquid loaded metal-organic framework and a preparation method and application thereof. The technical scheme is as follows: adding metal organic framework MIL-101, ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide and p-divinylbenzene into N, N-dimethylformamide, uniformly mixing at normal temperature, adding azobisisobutyronitrile, and reacting the obtained mixture at 80 ℃ for 24 hours; and after natural cooling, sequentially washing, filtering and drying by using N, N-dimethylformamide and acetone to obtain the target product, namely the polyion liquid loaded metal organic framework PIL-DVB @ MIL-101. The composite catalyst material prepared by the invention can efficiently catalyze the carbon dioxide cycloaddition reaction.
Description
Technical Field
The invention relates to preparation and application of a polyion liquid-loaded metal organic framework, in particular to preparation of a composite material capable of combining the advantages of polyion liquid and the metal organic framework and application of the composite material in cycloaddition of carbon dioxide and epoxide.
Background
MOFs have been developed vigorously in the field of material research due to their diversity in structure and properties. Large specific surface area, ordered structure, diverse pore sizes, diverse pore surface functional groups and surface potentials, and often containing unsaturated metal sites are the most prominent advantages of MOF materials. As such MOFs have been applied to a wide variety of fields such as gas storage, catalysts and catalyst supports, pharmaco, electrochemistry, sensing, and the like. Ionic liquids are generally composed of asymmetric, bulky organic cations and inorganic anions. It has unique advantages such as: low vapor pressure, wide liquid path, good thermal stability, good chemical stability and the like. Therefore, the ionic liquid is widely used in the fields of organic synthesis, catalysis, extraction, absorption and electrochemistry.
Recently, composite materials of MOFs have been the focus of research by a large number of researchers. The incorporation of polyionic liquids into MOFs is a new method for the synthesis of PIL/MOF composites. By incorporating polyionic liquids into the highly ordered channels of MOFs, the desirability of integrating multiple functional components into a composite material is achieved. Therefore, the physical and chemical properties and the gas affinity of the MOF are changed, so that the effect of the two in synergistic catalysis is achieved, and the MOF is used for catalyzing the carbon dioxide cycloaddition reaction.
Disclosure of Invention
The invention aims to use MIL-101 as a framework, polymerize ionic liquid in pore channels thereof at a certain temperature, and synthesize a polyion liquid-loaded metal organic framework by utilizing a post-synthesis method.
The technical scheme adopted by the invention is as follows: a preparation method of a polyion liquid-loaded metal-organic framework is PIL-DVB @ MIL-101, and comprises the following steps: adding metal organic framework MIL-101, ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide and p-divinylbenzene into N, N-dimethylformamide, uniformly mixing at normal temperature, adding azobisisobutyronitrile, and reacting the obtained mixture for 24 hours at 80 ℃; and after natural cooling, sequentially washing, filtering and drying by using N, N-dimethylformamide and acetone to obtain the target product, namely the polyion liquid loaded metal organic framework PIL-DVB @ MIL-101.
Preferably, the preparation method of the metal-organic framework MIL-101 comprises the following steps: mixing chromium salt, terephthalic acid (H)2BDC) and H2And O, uniformly mixing, reacting for 18 hours at 200 ℃, washing reactants by using N, N-dimethylformamide and ethanol in sequence, filtering and drying to obtain the metal organic framework MIL-101.
More preferably, the chromium salt is chromium nitrate.
More preferably, the reaction is washed with N, N-dimethylformamide and ethanol, filtered, and dried: firstly, boiling a reactant by using N, N-dimethylformamide for 3 hours, filtering and drying; decocting the obtained product with ethanol for 3 hr, filtering, and drying.
Preferably, the preparation method of the ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide comprises the following steps: placing 1-vinyl imidazole and 2-bromoethanol in acetone, reacting for 24 hours at 70 ℃, cooling to room temperature, washing with diethyl ether, filtering and drying to obtain the ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide.
More preferably, the reaction is carried out under anhydrous and oxygen-free conditions, and the acetone is first degassed before use.
The polyion liquid-supported metal organic framework PIL-DVB @ MIL-101 prepared by the method is used as a catalyst for catalyzing carbon dioxide cycloaddition reaction. The method comprises the following steps: adding the PIL-DVB @ MIL-101 prepared by the method and epoxide into a stainless steel high-pressure reaction kettle, and introducing CO2Heating at 80 deg.C under 1MPa, and stirring.
Preferably, the epoxide is propylene oxide.
Preferably, 1.5mg of PIL-DVB @ MIL-101 is added per 1mmol of epoxide.
The invention has the beneficial effects that: the prepared metal organic framework loaded with polyion liquid can be used as a catalyst to catalyze the carbon dioxide cycloaddition reaction. The preparation method of the polyion liquid loaded metal organic framework is simple, the catalytic effect is obvious, and the application prospect is wide.
Drawings
FIG. 1 is a nuclear magnetic diagram of 1-vinyl-3-carboxyethylimidazole bromide according to the present invention.
FIG. 2 is a comparative XRD plot of the inventive composites PIL-DVB @ MIL-101, MIL-101.
FIG. 3 is a graph of the IR contrast of inventive composites PIL-DVB @ MIL-101, and polymer.
FIG. 4 is a graph comparing the adsorption curves of the inventive composites PIL-DVB @ MIL-101, MIL-101.
FIG. 5 is a scanning electron micrograph of MIL-101(a) and composite PIL-DVB @ MIL-101(b) of the present invention.
FIG. 6 is a thermogravimetric comparison of the composite materials PIL-DVB @ MIL-101, PIL-DVB of the present invention.
FIG. 7 is an XPS plot of the Br 3d orbital in the composite PIL-DVB @ MIL-101 of the present invention.
FIG. 8 shows the use of the composite material PIL-DVB @ MIL-101 of the invention for catalyzing CO2Cyclic XRD pattern of cycloaddition reaction with propylene oxide.
Detailed Description
Example 1 polyionic liquid-loaded Metal organic framework PIL-DVB @ MIL-101
The preparation method comprises
1. Preparation of Metal organic framework MIL-101
2mmol of Cr (NO)3)3·9H2O, 2mmol of H2BDC, 12mL of deionized water was added to the autoclave and held at 200 ℃ for 18 hours to give a green product. Heating the green product with N, N-Dimethylformamide (DMF) at 60 deg.C for 3h, filtering, drying at 150 deg.C, heating the obtained product with ethanol at 60 deg.C for 3h, filtering, and drying at 150 deg.C to obtain green powder metal organic framework MIL-101 with yield of 78%.
2. Synthesis of ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide
Acetone pretreatment: acetone was placed in a round bottom flask and sealed, and nitrogen was continuously introduced for degassing.
53mmol of 1-vinylimidazole and 67mmol of 2-bromoethanol were added to 20mL of acetone, and the mixture was heated to 70 ℃ under anhydrous and oxygen-free conditions and reacted for 24 hours. And after cooling to room temperature, fully washing the solid product with diethyl ether, filtering and drying to obtain the ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide. The synthetic route is as follows:
3. preparation of PIL-DVB @ MIL-101
200mg of metal-organic framework MIL-101, 100mg of ionic liquid 1-vinyl-3-hydroxyethylimidazolium bromide and 170mg of p-divinylbenzene were added to 5mL of DMF, stirred at room temperature for 10 hours, then 25mg of azobisisobutyronitrile was added, and the resulting mixture was reacted at 80 ℃ for 24 hours. And after natural cooling, washing the filtered product with DMF and excessive acetone in sequence, filtering, and drying at 50 ℃ to obtain the target product, namely the polyion liquid loaded metal organic framework PIL-DVB @ MIL-101.
(II) detection
1. FIG. 1 is a nuclear magnetic diagram of 1-vinyl-3-carboxyethylimidazole bromide. As can be seen from FIG. 1, the synthesized ionic liquid is pure and free of impurities.
2. FIG. 2 is a comparative XRD plot of composite PIL-DVB @ MIL-101, MIL-101. As can be seen from figure 2, the synthesized composite material PIL-DVB @ MIL-101 does not damage the original structure of the MIL-101, has good crystallinity and high matching degree with the XRD pattern of the raw material.
3. FIG. 3 is a graph of IR contrast of composite PIL-DVB @ MIL-101, and polymer, with the characteristic peaks of the catalyst visible from the Fourier transform infrared (FT-IR) spectrum of FIG. 3. 1500cm-1And 880cm-1The nearby peaks correspond to the characteristic bands of the imidazole ring.
4. FIG. 4 is a graph comparing the adsorption curves of composite materials PIL-DVB @ MIL-101, MIL-101. FIG. 4 shows that the BET specific surface area of the composite PIL-DVB @ MIL-101 can still be obtainedUp to 900m2And about/g.
5. FIG. 5 is a scanning electron micrograph of MIL-101(a) and composite PIL-DVB @ MIL-101 (b). The SEM of fig. 5 shows that MIL-101 itself is octahedral and that the catalyst surface loaded with the ionic liquid has no change, indicating that the ionic liquid is indeed polymerized in the channels of MIL-101 rather than being coated on the surface of MIL-101.
Fig. 3, 4 and 5 all show the successful loading of polyionic liquids in the MIL-101 pores.
6. FIG. 6 is a thermogravimetric comparison of composite materials PIL-DVB @ MIL-101, PIL-DVB. From FIG. 6, it can be seen that the composite material PIL-DVB @ MIL-101 has relatively stable properties, can maintain a good structure at 300 ℃ below zero, and is a catalyst material with excellent properties.
7. FIG. 7 is an XPS plot of the Br 3d orbital in composite PIL-DVB @ MIL-101. Figure 7 demonstrates the presence of ionic liquid in the MIL-101 pore channels.
Example 2 polyionic liquid-loaded metal organic framework PIL-DVB @ MIL-101 catalyzed carbon dioxide cycloaddition reaction
The carbon dioxide catalyzes the propylene oxide cycloaddition reaction, and the reaction formula is as follows:
the method comprises the following steps: 20mmol of propylene oxide and 30mg of PIL-DVB @ MIL-101 are put into a stainless steel high-pressure reaction kettle, stirred and reacted for 3 hours at 80 ℃ and 1MPa, and the product propylene carbonate is obtained through gas phase detection. The calculated yield was 96%.
Comparative example 1: 20mmol of propylene oxide is taken to be put in a stainless steel high-pressure reaction kettle, stirred and reacted for 3 hours at 80 ℃ and 1MPa, and the product propylene carbonate is obtained by gas phase detection, and the calculated yield is 1.87%.
Comparative example 2: 20mmol of propylene oxide and 30mg of MIL-101 are put into a stainless steel high-pressure reaction kettle, stirred and reacted for 3 hours at 80 ℃ and 1MPa, and the product propylene carbonate is obtained by gas phase detection, and the calculated yield is 60%.
Number of cycles
After the catalytic reaction, the catalyst PIL-DVB @ MIL-101 is washed and recovered, and a circulation experiment is carried out, as shown in figure 8, the catalyst structure is still kept good after four cycles of circulation, which proves that the composite material is a good catalyst.
Claims (10)
1. A preparation method of a polyion liquid-loaded metal organic framework is characterized in that the polyion liquid-loaded metal organic framework is PIL-DVB @ MIL-101, and the preparation method comprises the following steps: adding metal organic framework MIL-101, ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide and p-divinylbenzene into N, N-dimethylformamide, uniformly mixing at normal temperature, adding azobisisobutyronitrile, and reacting the obtained mixture for 24 hours at 80 ℃; and after natural cooling, sequentially washing, filtering and drying by using N, N-dimethylformamide and acetone to obtain the target product, namely the polyion liquid loaded metal organic framework PIL-DVB @ MIL-101.
2. The method of claim 1, wherein the metal-organic framework MIL-101 is prepared by a method comprising the steps of: mixing chromium salt, terephthalic acid and H2And O, uniformly mixing, reacting for 18 hours at 200 ℃, washing reactants by using N, N-dimethylformamide and ethanol in sequence, filtering and drying to obtain the metal organic framework MIL-101.
3. The method of claim 2, wherein the chromium salt is chromium nitrate.
4. The preparation method according to claim 2, wherein the reaction mixture is washed with N, N-dimethylformamide and ethanol, filtered, and dried: firstly, boiling a reactant by using N, N-dimethylformamide for 3 hours, filtering and drying; decocting the obtained product with ethanol for 3 hr, filtering, and drying.
5. The preparation method according to claim 1, wherein the preparation method of the ionic liquid 1-vinyl-3-hydroxyethyl imidazolium bromide comprises the following steps: placing 1-vinyl imidazole and 2-bromoethanol in acetone, reacting for 24 hours at 70 ℃, cooling to room temperature, washing with diethyl ether, filtering and drying to obtain the ionic liquid 1-vinyl-3-hydroxyethyl imidazole bromide.
6. The method of claim 5, wherein the reaction is carried out under anhydrous and oxygen-free conditions, and the acetone is first degassed before use.
7. Use of the polyionic liquid-loaded metal-organic framework PIL-DVB @ MIL-101 prepared according to the process of claim 1 as a catalyst for catalyzing a carbon dioxide cycloaddition reaction.
8. Use according to claim 7, characterized in that the method is as follows: charging a stainless steel autoclave with PIL-DVB @ MIL-101 and an epoxide prepared according to the method of claim 1, and introducing CO2Heating at 80 deg.C under 1MPa, and stirring.
9. Use according to claim 8, wherein the epoxide is propylene oxide.
10. The use according to claim 8, wherein 1.5mg PIL-DVB @ MIL-101 is added per 1mmol of epoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911402009.4A CN111036305B (en) | 2019-12-31 | 2019-12-31 | Polyion liquid loaded metal organic framework and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911402009.4A CN111036305B (en) | 2019-12-31 | 2019-12-31 | Polyion liquid loaded metal organic framework and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111036305A true CN111036305A (en) | 2020-04-21 |
| CN111036305B CN111036305B (en) | 2023-01-17 |
Family
ID=70242555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911402009.4A Active CN111036305B (en) | 2019-12-31 | 2019-12-31 | Polyion liquid loaded metal organic framework and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111036305B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113828359A (en) * | 2021-09-17 | 2021-12-24 | 福州大学 | Zr-based MOFs composite material for preparing immobilized organic strong base by bottle-in-bottle shipbuilding method and application thereof |
| CN114713288A (en) * | 2022-04-24 | 2022-07-08 | 南京工业大学 | Photoresponse metal organic polyhedral catalyst, preparation method and application thereof |
| CN115007212A (en) * | 2022-05-13 | 2022-09-06 | 浙江大学 | Integrated metal-organic framework-based CO 2 Photo-thermal catalyst and preparation method and application thereof |
| CN115025817A (en) * | 2022-06-17 | 2022-09-09 | 河南大学 | MIL-101(Cr) -supported hydroxyimidazole ionic liquid and method for catalytically synthesizing cyclic carbonate by using same |
| CN115197435A (en) * | 2021-04-09 | 2022-10-18 | 天津师范大学 | Polyion liquid @ metal organic framework composite material and removal method thereof 99 Application of Tc nuclide |
| CN115318341A (en) * | 2022-08-30 | 2022-11-11 | 广西大学 | Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof |
| CN116328842A (en) * | 2022-12-29 | 2023-06-27 | 石家庄铁道大学 | Preparation method of core-shell type activated persulfate electrocatalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663614A (en) * | 2019-01-08 | 2019-04-23 | 太原理工大学 | Carboxyl-functional imidazole ion liquid/MIL-101 composite catalyst and preparation method thereof |
| CN109939738A (en) * | 2019-03-22 | 2019-06-28 | 武汉理工大学 | A kind of copper ion induction micropore-mesopore functional form MOF catalyst and its preparation method and application technology |
| CN110496608A (en) * | 2019-08-13 | 2019-11-26 | 辽宁大学 | A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application |
-
2019
- 2019-12-31 CN CN201911402009.4A patent/CN111036305B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663614A (en) * | 2019-01-08 | 2019-04-23 | 太原理工大学 | Carboxyl-functional imidazole ion liquid/MIL-101 composite catalyst and preparation method thereof |
| CN109939738A (en) * | 2019-03-22 | 2019-06-28 | 武汉理工大学 | A kind of copper ion induction micropore-mesopore functional form MOF catalyst and its preparation method and application technology |
| CN110496608A (en) * | 2019-08-13 | 2019-11-26 | 辽宁大学 | A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 李军等: "MIL-101固载化羧基咪唑离子液体在温和条件下催化CO_2环加成反应", 《天然气化工(C1化学与化工)》 * |
| 杨万园: "MOFs-聚离子液体杂化材料的制备及其催化CO2合成环状碳酸酯的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 杨美等: "离子液体催化二氧化碳合成环状碳酸酯的研究进展", 《化工进展》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197435A (en) * | 2021-04-09 | 2022-10-18 | 天津师范大学 | Polyion liquid @ metal organic framework composite material and removal method thereof 99 Application of Tc nuclide |
| CN113828359A (en) * | 2021-09-17 | 2021-12-24 | 福州大学 | Zr-based MOFs composite material for preparing immobilized organic strong base by bottle-in-bottle shipbuilding method and application thereof |
| CN113828359B (en) * | 2021-09-17 | 2023-07-07 | 福州大学 | Zr-based MOFs composite material with organic alkali immobilized by 'shipbuilding in bottle' method and application thereof |
| CN114713288A (en) * | 2022-04-24 | 2022-07-08 | 南京工业大学 | Photoresponse metal organic polyhedral catalyst, preparation method and application thereof |
| CN114713288B (en) * | 2022-04-24 | 2023-04-28 | 南京工业大学 | Photo-responsive metal-organic polyhedral catalyst, preparation method and application thereof |
| CN115007212A (en) * | 2022-05-13 | 2022-09-06 | 浙江大学 | Integrated metal-organic framework-based CO 2 Photo-thermal catalyst and preparation method and application thereof |
| CN115007212B (en) * | 2022-05-13 | 2023-08-11 | 浙江大学 | Integrated metal organic framework based CO 2 Photo-thermal catalyst and preparation method and application thereof |
| CN115025817A (en) * | 2022-06-17 | 2022-09-09 | 河南大学 | MIL-101(Cr) -supported hydroxyimidazole ionic liquid and method for catalytically synthesizing cyclic carbonate by using same |
| CN115025817B (en) * | 2022-06-17 | 2024-01-19 | 河南大学 | MIL-101 (Cr) loaded hydroxy imidazole ionic liquid and method for synthesizing cyclic carbonate by using same |
| CN115318341A (en) * | 2022-08-30 | 2022-11-11 | 广西大学 | Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof |
| CN115318341B (en) * | 2022-08-30 | 2023-12-15 | 广西大学 | Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof |
| CN116328842A (en) * | 2022-12-29 | 2023-06-27 | 石家庄铁道大学 | Preparation method of core-shell type activated persulfate electrocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111036305B (en) | 2023-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111036305B (en) | Polyion liquid loaded metal organic framework and preparation method and application thereof | |
| Kuruppathparambil et al. | A solid solution zeolitic imidazolate framework as a room temperature efficient catalyst for the chemical fixation of CO 2 | |
| Leng et al. | A tannin-derived zirconium-containing porous hybrid for efficient Meerwein–Ponndorf–Verley reduction under mild conditions | |
| CN111229320B (en) | Metal organic framework composite material grafted with ionic liquid and preparation method and application thereof | |
| CN107376997B (en) | Preparation and application of catalyst for preparing benzaldehyde by oxidizing benzyl alcohol | |
| Wang et al. | Conversion of glucose into 5-hydroxymethylfurfural catalyzed by chromium (III) Schiff base complexes and acidic ionic liquids immobilized on mesoporous silica | |
| CN113087918B (en) | Zirconium-based metal organic framework material and preparation method and application thereof | |
| Liu et al. | The mega-merger strategy: M@ COF core-shell hybrid materials for facilitating CO2 capture and conversion to monocyclic and polycyclic carbonates | |
| Wang et al. | Catalytic transfer hydrogenation of biomass-derived 5-hydroxymethylfurfural into 2, 5-dihydroxymethylfuran over Co/UiO-66-NH 2 | |
| CN111889141A (en) | Ionic liquid functionalized bipyridine porous polymer catalyst for catalyzing cycloaddition reaction of carbon dioxide and epoxide | |
| Jiang et al. | Imidazolium-based poly (ionic liquid) s@ MIL-101 for CO 2 adsorption and subsequent catalytic cycloaddition without additional cocatalyst and solvent | |
| Zhang et al. | Polymeric organophosphate-hafnium unconventional MOFs nanohybrids enable high-efficiency upgrading of biomass feedstocks via cascade catalytic transfer hydrogenation-dehydration | |
| Huang et al. | Boehmite-supported CuO as a catalyst for catalytic transfer hydrogenation of 5-hydroxymethylfurfural to 2, 5-bis (hydroxymethyl) furan | |
| CN111495419B (en) | Metal-supported hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof | |
| Gu et al. | Crown ether-based covalent organic frameworks for CO 2 fixation | |
| CN113828359A (en) | Zr-based MOFs composite material for preparing immobilized organic strong base by bottle-in-bottle shipbuilding method and application thereof | |
| CN111001442B (en) | Metal organic framework MIL-101 (Cr) loaded chitosan material and preparation method and application thereof | |
| Cai et al. | Two Ln-MOFs containing abundant Lewis acid sites as the efficient and heterogeneous catalyst to activate epoxides for cycloaddition of CO2 | |
| CN105601942B (en) | One kind being based on InIIIMetal organic framework and its preparation method and application | |
| CN115318341B (en) | Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof | |
| Wang et al. | Bifunctional heterogeneous catalysts derived from the coordination of adenosine monophosphate to Sn (iv) for effective conversion of sucrose to 5-hydroxymethylfurfural | |
| CN111732736A (en) | Ni (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof | |
| CN111135831A (en) | Preparation method of catalyst for preparing 2-methyltetrahydrofuran by gas-phase hydrogenation of 2-methylfuran | |
| CN115155553A (en) | Preparation method of amorphous aluminosilicate solid acid catalyst and application of amorphous aluminosilicate solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation | |
| CN110201717B (en) | Preparation method and application of copper-based metal organic polyhedral composite material |
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 |