CN112979971A - Triazole-based biological MOF material, and preparation method and application thereof - Google Patents
Triazole-based biological MOF material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN112979971A CN112979971A CN201911287582.5A CN201911287582A CN112979971A CN 112979971 A CN112979971 A CN 112979971A CN 201911287582 A CN201911287582 A CN 201911287582A CN 112979971 A CN112979971 A CN 112979971A
- Authority
- CN
- China
- Prior art keywords
- mof
- bio
- triazole
- preparation
- biological
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a triazole-based biological metal organic framework material (triazole-Bio-MOF-11), and a preparation method and application thereof. The triazole-Bio-MOF-11 material is characterized in that N is obtained by reacting Bio-MOF-113-Bio-MOF-11 intermediate, then by Cu (I) catalyzed azido-alkynyl Husigen cycloaddition. The adenine biological metal organic framework Bio-MOF-11 is obtained by reacting cobalt acetate tetrahydrate with adenine. The preparation method disclosed by the invention is characterized in that a Triazol-Bio-MOF-11 material is prepared by utilizing a Husige cycloaddition reaction and performing one-pot two-step functionalization at room temperature, and the prepared triazole-based biological MOF material has higher stability and is an ideal separation, catalysis and biological material.
Description
Technical Field
The invention relates to a triazole-based biological MOF material (triazole-Bio-MOF-11), a preparation method and application thereof, and belongs to the field of material chemical separation.
Background
Metal-organic frameworks (MOFs) are a class of highly ordered Metal-organic frameworks formed by coordination of Metal ions (clusters) with organic ligandsOrdered porous organic-inorganic hybrid materials. In recent years, biological MOF materials formed with biologically active substances (e.g., amino acids, adenine, peptides, proteins, endonucleases, etc.) as organic ligands have received attention. Particularly, Bio-MOF-11 is the most widely studied. The Bio-MOF-11 is formed by coordination of Zn or Co ions and adenine and has great application potential in the fields of adsorption separation, drug delivery, catalysis and the like (Rojas S.J.Mater.chem.B,2017,5, 2560). For example, adenine ligands in Bio-MOF-11 can be conjugated to CO due to multiple Lewis base sites (amino and pyrimidine nitrogens)2The interaction is a star adsorbent in recent years. Triazoles are nitrogen-rich heterocyclic compounds. Compared with tetrazole with extremely high nitrogen content, the tetrazole derivative has excellent safety and stability coefficients. Nitrogen atoms of triazoles with CO2And gases such as alkane have strong interaction, which can promote gas capture and separation (Liao P. nat Comm,2015,6: 8697). Triazole is also an important catalyst active component and can catalyze various types of organic reactions (Li P Z, JACS,2016: jacs.5b13335). In addition, the triazole has bactericidal, bacteriostatic and pharmaceutical activities. If the triazole ligand is introduced into Bio-MOF-11, the synergistic effect of the triazole ligand and the inherent adenine ligand provides a new opportunity for the application in the fields of adsorption, catalysis, biomedicine and the like.
Disclosure of Invention
The invention aims to provide a triazole-based biological MOF material (triazole-Bio-MOF-11), and a preparation method and application thereof
Bio-MOF-11 (Co) -based2(ad)2(CO2CH3)2·2DMF·0.5H2O) preparation method of triazole-based biological MOF material (triazole-Bio-MOF-11), comprising the following steps:
(1) activated Bio-MOF-11, nitrite and trimethylsilyl azide (TMSM)3) Or sodium azide reaction to obtain an intermediate product N3-Bio-MOF-11；
(2) Intermediate product N obtained in step (1)3And carrying out azide-alkynyl Husigen cycloaddition reaction on the-Bio-MOF-11 and azidobenzene or propargylamine under the catalytic action of a Cu (I) compound to obtain the triazole-based biological MOF material (triazole-Bio-MOF-11). The triazole-Bio-MOThe structural formula of F-11 is Co2(ad-triazole)2(CO2CH3)2·2DMF·0.5H2O is-NH of adenine ligand in skeleton of Bio-MOF-11 material2Partial conversion of the group to-triazole.
Preferably, the Bio-MOF-11 is subjected to an activation treatment before a one-pot two-step functionalization reaction (preparation of the triazole-based biological MOF material). The activation treatment was performed by soaking in methanol for solvent exchange. The Bio-MOF-11 activation treatment comprises the following steps: and soaking the Bio-MOF-11 in methanol for 48-72h, centrifuging, and drying the product at 80-150 ℃ for 24-72h under a vacuum condition to obtain the activated Bio-MOF-11.
Preferably, the Bio-MOF-11 activation treatment is performed by changing the methanol solution every 12 h.
Preferably, the adenine biological metal organic framework Bio-MOF-11 is obtained by the reaction of cobalt acetate tetrahydrate and adenine, and the preparation method comprises the following steps: uniformly mixing cobalt acetate tetrahydrate with adenine and a Dimethylformamide (DMF) solvent, carrying out a solvothermal reaction at 100-150 ℃ under a sealed condition for 12-120 h, centrifuging, washing and drying to obtain an activated product Bio-MOF-11.
Preferably, in the preparation method of Bio-MOF-11, the molar ratio of the cobalt acetate tetrahydrate, the adenine and the DMF solvent is 1: 1-5: 200-2000.
Preferably, in the preparation method of Bio-MOF-11, the solvent used for washing is Dimethylformamide (DMF).
Preferably, in the preparation method of Bio-MOF-11, the drying conditions are as follows: drying for 6-24h at 50-80 ℃.
Preferably, in the preparation method of the triazole-based biological MOF material, the nitrite ester is tert-butyl nitrite (tBuONO) or isoamyl nitrite.
Preferably, in the preparation method of the triazole-based biological MOF material, the Cu (I) compound is copper tetrakis-cyanide hexafluorophosphate (Cu)I(CH3CN)4PF6) Cuprous bromide or iodide.
Preferably, in the preparation method of the triazole-based biological MOF material, the azidobenzene is phenylacetylene.
Preferably, in the preparation method of the triazole-based biological MOF material, the activated Bio-MOF-11, nitrite and trimethylsilyl azide (TMSM)3) Or the molar ratio of the sodium azide to the sodium azide is 1: 3.5-24: 3-20;
the molar ratio of the activated Bio-MOF-11, azidobenzene or propargylamine to the Cu (I) compound is 1: 5-80: 1-2.
Preferably, in the preparation method of the triazole-based biological MOF material, the solvent used in the reaction process is Tetrahydrofuran (THF), and the molar ratio of the activated Bio-MOF-11, Tetrahydrofuran (THF), nitrite and trimethylsilyl azide (TMSM3) or sodium azide is as follows: 1: 900-3000: 3.5-24: 3-20.
Preferably, in the step (1), the reaction temperature of the Bio-MOF-11 powder, Tetrahydrofuran (THF), nitrite and trimethylsilyl azide (TMSM3) or sodium azide is 20-40 ℃, and the reaction time is 0.5-120 h;
preferably, in the step (2), the reaction temperature of the azide-alkynyl Husigen cycloaddition reaction catalyzed by Cu (I) is 20-40 ℃, and the reaction time is 0.1-36 h.
Preferably, the Bio-MOF-11 (Co) base2(ad)2(CO2CH3)2·2DMF·0.5H2O) preparation method of triazole-based biological MOF material (triazole-Bio-MOF-11), which comprises the following steps:
(1) activated Bio-MOF-11 powder, Tetrahydrofuran (THF), nitrite and trimethylsilyl azide (TMSM)3) Or mixing sodium azide and stirring for reaction at 20-40 ℃ for 0.5-120 to obtain an intermediate product N3-Bio-MOF-11；
(2) To the above system was added phenylacetylene and THF-dissolved copper tetraethyl hexafluorophosphate (Cu)I(CH3CN)4PF6) Stirring and reacting for 0.1-36 h at 20-40 ℃, carrying out Cu (I) -catalyzed azide-alkynyl Husigen cycloaddition reaction to obtain a product, centrifuging, washing and drying the product after the reaction is finishedAnd (5) drying.
Preferably, in step (2), the washing is with THF and CH, respectively2Cl2And (6) washing.
Preferably, in the step (2), the drying temperature is 30-80 ℃, and the vacuum drying is preferably carried out at 50-60 ℃ for 12-48 h.
The present invention relates to the protection of triazole-based biological MOF materials prepared by the methods described above.
The invention also relates to the use of the triazole-based biological MOF materials described above as adsorbents, catalysts and biopharmaceutical formulations, the adsorbent being H2、CO2、CH4And adsorbents for each hydrocarbon molecule.
The triazole-based biological MOF material is prepared by a Husige cycloaddition reaction through one-pot two-step functionalization at 20-40 ℃, has high stability, is an ideal separation, catalysis and biological material, and is simple in preparation method process, mild in condition, high in yield and capable of accurately regulating and controlling the number of triazole groups. The preparation method provided by the invention has universality for other biological MOF materials.
Compared with the prior art, the invention has the advantages that:
(1) the preparation process is environment-friendly and simple, and is a green chemical synthesis method;
(2) the experimental design is ingenious. The preparation method comprises the steps of simply and effectively utilizing the reaction of metal ions and organic ligands to prepare the Bio-based MOF through solvothermal reaction, and obtaining the functionalized modified material triazole-Bio-MOF-11 powder through one-pot two-step functionalization reaction at the temperature of 20-40 ℃. ,
drawings
The invention is illustrated in figure 10:
FIG. 1 is an X-ray diffraction pattern of Bio-MOF-11 powder in example 1 before and after chloroform activation.
FIG. 2 is an SEM photograph of the Bio-MOF-11 powder material in example 1.
FIG. 3 is the thermogravimetric plot of the Bio-MOF-11 powder material of example 1 before and after activation.
FIG. 4 shows Bi in example 2O-MOF-11 powder material, N3-the X-ray diffraction pattern of the Bio-MOF-11-2 intermediate, the triazole-Bio-MOF-11-2 material.
FIG. 5 shows Bio-MOF-11 powder material, N in example 23Fourier transform infrared spectroscopy of the Bio-MOF-11-2 intermediate, the triazole-Bio-MOF-11-2 material.
FIG. 6 shows N in example 23Of the-Bio-MOF-11-2 material1H NMR spectrum.
FIG. 7 shows the preparation of the Triazol-Bio-MOF-11-2 material of example 21H NMR spectrum.
FIG. 8 shows the CO content of the triazine-Bio-MOF-11-2 material of example 2 at 25 ℃, 35 ℃ and 45 ℃2Single component adsorption curve.
FIG. 9 shows CH of the Triazol-Bio-MOF-11-2 material of example 2 at 25 ℃, 35 ℃ and 45 ℃4Single component adsorption curve.
FIG. 10 is an X-ray diffraction pattern of the material Triazol-Bio-MOF-11-1, Triazol-Bio-MOF-11-2, and Triazol-Bio-MOF-11-3 in examples 1 to 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1 Synthesis of functionalized post-modification Material Triazole-Bio-MOF-11-1
Cobalt acetate tetrahydrate and adenine (Aladdin, not less than 99.5%) are respectively dissolved in DMF solvent to prepare 0.1M solution. 15ml of 0.1M cobalt acetate tetrahydrate solution and 45ml of 0.1M adenine solution were mixed, stirred at room temperature for 4 hours, and poured into a polytetrafluoroethylene-lined reaction vessel. The lined reactor was sealed in a stainless steel autoclave, placed in an oven and heated to 130 ℃, and then kept at a constant temperature for reaction for 72 hours.
After the reaction is finished, naturally cooling to room temperature, opening the lining reaction kettle, pouring out supernatant, transferring purple precipitate at the bottom of the reaction kettle to a centrifuge tube, shaking up, performing centrifugal treatment, washing for 3 times by using DMF, and drying in an oven at 60 ℃ overnight to obtain a product Bio-MOF-11-as. And soaking the dried Bio-MOF-11 powder for 48h by using a certain amount of fresh methanol solution, and then drying for 24h in a vacuum oven at 100 ℃ to obtain activated Bio-MOF-11 powder.
0.89g (0.27 mmol-NH) was weighed2) The freshly dried Bio-MOF-11 powder was placed in a 10mL sample vial, 3mL of Tetrahydrofuran (THF), 0.22mL of tert-butyl nitrite (tBuONO) (1.84mmol, 7eq) and 0.2mL of azidotrimethylsilane (TMSM3) (1.51mmol, 6eq) were added in succession and the reaction was stirred at room temperature for 24h to give the intermediate product N3-Bio-MOF-11; 0.96mL of phenylacetylene (8.8mmol, 36eq) and 48mg of copper tetrakishexafluorophosphate (Cu) dissolved in 1mL of THF were then added to the systemI(CH3CN)4PF6) (0.27mmol, 1 eq.) and subjected to Cu (I) -catalyzed azide-alkynyl Husigen cycloaddition reaction, the reaction was stirred at room temperature for 24h.
After the reaction is finished, transferring the product into a centrifuge tube, shaking up and then carrying out centrifugal treatment, and sequentially using THF and CH2Cl2After 3 times of washing, the mixture was dried overnight in a vacuum oven at room temperature to obtain the product, triazole-Bio-MOF-11-1.
Example 2 Synthesis of functionalized post-modification Material Triazole-Bio-MOF-11-2
The same procedure was used to prepare activated Bio-MOF-11 powder analogously to example 1.
0.89g (0.27 mmol-NH) was weighed2) The freshly dried Bio-MOF-11 powder was placed in a 10mL sample vial, 3mL of Tetrahydrofuran (THF), 0.67mL of tert-butyl nitrite (tBuONO) (5.51mmol, 21eq) and 0.63mL of azidotrimethylsilane (TMSM3) (4.53mmol, 18eq) were added in succession and the reaction was stirred at room temperature for 24h to give intermediate N3-Bio-MOF-11; 0.96mL of phenylacetylene (8.8mmol, 36eq) and 48mg of copper tetrakishexafluorophosphate (Cu) dissolved in 1mL of THF were then added to the systemI(CH3CN)4PF6) (0.26mmol, 1eq) to undergo Cu (I) -catalyzed azide-alkynyl Husige cycloaddition,the reaction was stirred at room temperature for 24h.
After the reaction is finished, transferring the product into a centrifuge tube, shaking up and then carrying out centrifugal treatment, and sequentially using THF and CH2Cl2After 3 times of washing, the mixture was dried overnight in a vacuum oven at room temperature to obtain the product, triazole-Bio-MOF-11-2.
Selecting CO of the material Triazol-Bio-MOF-11-2 at 25 deg.C, 35 deg.C, and 45 deg.C2、CH4Single component adsorption curve.
Example 3 Synthesis of functionalized post-modification Material Triazole-Bio-MOF-11-3
The same procedure was used to prepare activated Bio-MOF-11 powder analogously to example 1.
0.89g (0.27 mmol-NH) was weighed2) The freshly dried Bio-MOF-11 powder was placed in a 10mL sample vial, 3mL of Tetrahydrofuran (THF), 1.48mL of tert-butyl nitrite (tBuONO) (12.48mmol, 48eq) and 1.30mL of azidotrimethylsilane (TMSM3) (9.88mmol, 38eq) were added in succession and the reaction was stirred at room temperature for 24h to give intermediate N3-Bio-MOF-11; 1.92mL of phenylacetylene (17.6mmol, 74eq) and 96mg of copper tetrakishexafluorophosphate (Cu) dissolved in 1.5mL of THF were then added to the systemI(CH3CN)4PF6) (0.52mmol, 2eq), Cu (I) -catalyzed azido-alkynyl Husigen cycloaddition takes place and the reaction is stirred at room temperature for 24h.
After the reaction is finished, transferring the product into a centrifuge tube, shaking up and then carrying out centrifugal treatment, and sequentially using THF and CH2Cl2After 3 times of washing, the mixture was dried overnight in a vacuum oven at room temperature to obtain the product, triazole-Bio-MOF-11-3.
Characterization was performed using X-ray diffractometry (XRD), Scanning Electron Microscopy (SEM), fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TG), Nuclear Magnetic Resonance (NMR). The shape structure and stability of the prepared triazole-Bio-MOF-11 material are as follows:
FIG. 1 shows the X-ray diffraction patterns of the dried Bio-MOF-11 powder and after chloroform solvent exchange activation in example 1, and the patterns show that the synthesized material is actually Bio-MOF-11, and the crystal form of the powder material is not changed after chloroform solvent exchange.
FIG. 2 is an SEM photograph of the Bio-MOF-11 powder material in example 1. SEM test results show that the experimentally synthesized Bio-MOF-11 powder has a regular octahedral shape and the particle size is about 80 μm.
FIG. 3 is the thermogravimetric plot of the Bio-MOF-11 powder material of example 1 before and after activation. The thermogravimetric curve shows that the first step weight loss of the material is from 40 ℃ to 150 ℃ due to the release of methanol molecules adsorbed within the pore size of the material. The second weight loss started at 310 ℃ due to the decomposition of adenine ligands of the material and the collapse of the backbone structure. The thermogravimetric curve after activation shows that the ligands and solvent molecules adsorbed in the pore channels of the Bio-MOF-11 powder material can be effectively removed through methanol soaking solvent exchange and vacuum drying.
FIG. 4 shows the Bio-MOF-11 powder material, N, of example 23The X-ray diffraction pattern of the-Bio-MOF-11-2 intermediate and the material of the triazole-Bio-MOF-11-2 shows that the crystal form of the material is not changed in the process of one-pot two-step functionalization reaction.
FIG. 5 shows Bio-MOF-11 powder material, N in example 23Fourier transform infrared spectroscopy of the Bio-MOF-11-2 intermediate, the triazole-Bio-MOF-11-2 material. N is a radical of3Spectrum of the intermediate Bio-MOF-11-2 at 2123cm-1Has an absorption band of-N3The characteristic peak of asymmetric stretching vibration shows that the experiment succeeds in separating-NH in the Bio-MOF-11 material2Conversion of radicals to-N3Group, triazole-Bio-MOF-11-2 at 2123cm-1The absorption band of (B) disappeared, indicating that most of-N3The group participates in azide-alkynyl Husigen cycloaddition reaction to generate triazole-Bio-MOF-11-2.
FIG. 6 and FIG. 7 show N in example 23Of the materials Bio-MOF-11-2 and triazole-Bio-MOF-11-21H NMR spectrum, which shows that the experiment succeeds in obtaining-NH in Bio-MOF-11 material2Conversion of radicals to-N3And finally to a triazole group.
FIGS. 8 and 9 show the three-zole-Bio-MOF-11-2 material of example 2 at 25 deg.C, 35 deg.C and 45 deg.C, respectivelyCO2、CH4The single component adsorption curve shows that the material has CO pair under the condition of 298K and 20bar2And CH4The amounts of adsorption of (A) were 1.52mmol/g and 0.69mmol/g, respectively.
FIG. 10 shows X-ray diffraction patterns of the three-azole-Bio-MOF-11-1, three-azole-Bio-MOF-11-2, and three-azole-Bio-MOF-11-3 materials of examples 1-3, which indicate that the three-azole-Bio-MOF-11 powder materials prepared in the present invention have the same crystal form.
Claims (10)
1. A preparation method of a triazole-based biological MOF material based on Bio-MOF-11 is characterized by comprising the following steps:
(1) reacting the activated Bio-MOF-11, nitrite and trimethylsilyl azide or sodium azide to obtain an intermediate product;
(2) and (2) reacting the intermediate product obtained in the step (1) with azidobenzene or propargylamine under the catalytic action of a Cu (I) compound to obtain the triazole-based biological MOF material.
2. The method for preparing the Bio-MOF-11-based triazole-based biological MOF material according to claim 1, wherein in the step (1), the activated Bio-MOF-11 is obtained by activating the Bio-MOF-11, and the step of activating the Bio-MOF-11 is: the Bio-MOF-11 is soaked in methanol for 48 to 72 hours and dried under vacuum at 80 to 150 ℃ for 24 to 72 hours.
3. The Bio-MOF-11 based method for preparing triazole-based MOF material according to claim 2, wherein the Bio-MOF-11 is prepared by: uniformly mixing cobalt acetate tetrahydrate with adenine and dimethylformamide, reacting for 12-120 h at 100-150 ℃ under a sealed condition, centrifuging, washing and drying.
4. The Bio-MOF-11 based method for the preparation of triazole based MOF material according to claim 3, wherein the molar ratio of cobalt acetate tetrahydrate, adenine and dimethylformamide is: 1:1 to 5:200 to 2000.
5. The method of preparing a Bio-MOF-11 based triazole-based MOF material according to claim 1, wherein the nitrite is tert-butyl nitrite or isoamyl nitrite; the Cu (I) compound is copper hexachlorophosphate, cuprous bromide or cuprous iodide; the azidobenzene is phenylacetylene.
6. The method for preparing the Bio-MOF-11 based triazole-based Bio-MOF material according to claim 1, wherein the activated Bio-MOF-11, nitrite and trimethylsilyl azide (TMSM)3) Or the molar ratio of the sodium azide to the sodium azide is 1: 3.5-24: 3-20;
the molar ratio of the activated Bio-MOF-11, azidobenzene or propargylamine to the Cu (I) compound is 1: 5-80: 1-2.
7. The preparation method of the Bio-MOF-11-based triazole biological MOF material, according to claim 1, wherein a solvent used in a reaction process is tetrahydrofuran, and the molar ratio of the activated Bio-MOF-11, the tetrahydrofuran, the nitrite and the trimethylsilyl azide or the propargylamine is 1: 900-3000: 3.5-24: 3-20.
8. The preparation method of the Bio-MOF-11-based triazole biological MOF material, according to claim 1, wherein in the step (1), the reaction temperature is 20-40 ℃, and the reaction time is 0.5-120 h; in the step (2), the reaction temperature is 20-40 ℃, and the reaction time is 0.1-36 h.
9. A triazole-based biological MOF material prepared by the method of any one of claims 1 to 8.
10. Use of the triazole-based biofmof material described in claim 9 as adsorbents, catalysts and biopharmaceutical formulations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911287582.5A CN112979971B (en) | 2019-12-14 | 2019-12-14 | Triazole-based biological MOF material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911287582.5A CN112979971B (en) | 2019-12-14 | 2019-12-14 | Triazole-based biological MOF material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112979971A true CN112979971A (en) | 2021-06-18 |
| CN112979971B CN112979971B (en) | 2022-04-08 |
Family
ID=76342674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911287582.5A Active CN112979971B (en) | 2019-12-14 | 2019-12-14 | Triazole-based biological MOF material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112979971B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2578593A1 (en) * | 2011-10-04 | 2013-04-10 | Fundació Privada Institut Català de Nanotecnologia | Method for the preparation of metal organic frameworks |
| CN106518794A (en) * | 2016-10-13 | 2017-03-22 | 北京大学 | Metallic organic framework material with carboxyl group, and preparation method and application thereof |
| CN108384025A (en) * | 2018-04-08 | 2018-08-10 | 东华大学 | A kind of biological MOF and preparation method thereof based on adenine |
| CN109316978A (en) * | 2018-10-25 | 2019-02-12 | 上海科技大学 | A kind of MOFs material and its preparation method and application |
| CN109369547A (en) * | 2018-11-27 | 2019-02-22 | 杭州师范大学 | A kind of novel aggregation-induced emission richness nitrogen yl carboxylic acid ligand and preparation method thereof |
| CN109908965A (en) * | 2019-03-21 | 2019-06-21 | 长治学院 | CuBr2@Zr-MOF catalyst and the preparation method and application thereof |
-
2019
- 2019-12-14 CN CN201911287582.5A patent/CN112979971B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2578593A1 (en) * | 2011-10-04 | 2013-04-10 | Fundació Privada Institut Català de Nanotecnologia | Method for the preparation of metal organic frameworks |
| CN106518794A (en) * | 2016-10-13 | 2017-03-22 | 北京大学 | Metallic organic framework material with carboxyl group, and preparation method and application thereof |
| CN108384025A (en) * | 2018-04-08 | 2018-08-10 | 东华大学 | A kind of biological MOF and preparation method thereof based on adenine |
| CN109316978A (en) * | 2018-10-25 | 2019-02-12 | 上海科技大学 | A kind of MOFs material and its preparation method and application |
| CN109369547A (en) * | 2018-11-27 | 2019-02-22 | 杭州师范大学 | A kind of novel aggregation-induced emission richness nitrogen yl carboxylic acid ligand and preparation method thereof |
| CN109908965A (en) * | 2019-03-21 | 2019-06-21 | 长治学院 | CuBr2@Zr-MOF catalyst and the preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| GUI BO ET AL.: ""Postsynthetic Modification of Metal-Organic Frameworks through Click Chemistry"", 《CHINESE JOURNAL OF CHEMISTRY》 * |
| MARIE SAVONNET ET AL.: ""Generic Postfunctionalization Route from Amino-Derived Metal-Organic Frameworks"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| PEI-ZHOU LI ET AL.: ""Click chemistry as a versatile reaction for construction and modification of metal-organic frameworks"", 《COORDINATION CHEMISTRY REVIEWS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112979971B (en) | 2022-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6045683B2 (en) | EMM-19: Novel zeolite imidazolate framework material, method for producing the same, and use thereof | |
| CN106883419B (en) | Rapid synthesis method and application of cobalt-based metal-organic framework material | |
| KR102373799B1 (en) | Multi-functional metal-organic composite having active sites for adsorbing or reacting with two or more kinds of substances and use thereof | |
| Tayebee et al. | Phosphotungstic acid grafted zeolite imidazolate framework as an effective heterogeneous nanocatalyst for the one‐pot solvent‐free synthesis of 3, 4‐dihydropyrimidinones | |
| CN110003483B (en) | Preparation method of zeolite imidazole framework structure material | |
| CN109908965A (en) | CuBr2@Zr-MOF catalyst and the preparation method and application thereof | |
| Kassymova et al. | Post-synthetically modified MOF for the A 3-coupling reaction of aldehyde, amine, and alkyne | |
| CN107597190A (en) | A kind of preparation method and applications of zeolite molecular sieve grain surface assembling metal organic framework film | |
| CN109912809B (en) | Non-noble metal-metal organic framework composite material, preparation method and application thereof | |
| CN108117526B (en) | Alkynyl functionalized covalent organic framework material and synthesis method and application thereof | |
| CN106693906A (en) | Method for preparing APTES modified MIL-101(Cr) material | |
| Di Giuseppe et al. | Chitin-and chitosan-anchored methyltrioxorhenium: An innovative approach for selective heterogeneous catalytic epoxidations of olefins | |
| Zhiani et al. | Ruthenium–birhodanine complex supported over fibrousphosphosilicate for photocatalytic CO2 reduction to formate | |
| Zhang et al. | Selective hydroboration of alkynes via multisite synergistic catalysis by PCN-222 (Cu) | |
| Cui et al. | Engineering noble-metal-free metal–organic framework composite catalyst for efficient CO2 conversion under ambient conditions | |
| Kim et al. | Functional tolerance in an isoreticular series of highly porous metal–organic frameworks | |
| El Eter et al. | Well-defined azazirconacyclopropane complexes supported on silica structurally determined by 2D NMR comparative elucidation | |
| Maity et al. | A post-synthetically modified metal–organic framework for copper catalyzed denitrative C–N coupling of nitroarenes under heterogeneous conditions | |
| Nguyen et al. | Structural design of core-shell zeolitic imidazolate frameworks as an efficient catalyst for CO2 cycloaddition to epoxides | |
| CN112979984B (en) | Ionic MOFs material, preparation method thereof and application thereof in preparation of cyclic carbonate | |
| CN111349246A (en) | Metal organic framework for nitrogen adsorption and/or storage and application thereof | |
| CN112979971B (en) | Triazole-based biological MOF material, and preparation method and application thereof | |
| Pharande et al. | An expedient heterogeneous catalyst for one-pot tandem synthesis of 1-aryl-1, 2, 3-triazoles through Huisgen 1, 3-cycloaddition | |
| CN108285465A (en) | Metal-organic framework material, preparation method, modification metal-organic framework material and preparation method thereof | |
| CN115894955B (en) | Zirconium-based metal organic framework material, synthesis 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 |