CN110898855A - Synthetic method for rod-shaped MOF-74(Mn) assembled by sheets - Google Patents
Synthetic method for rod-shaped MOF-74(Mn) assembled by sheets Download PDFInfo
- Publication number
- CN110898855A CN110898855A CN201911179183.7A CN201911179183A CN110898855A CN 110898855 A CN110898855 A CN 110898855A CN 201911179183 A CN201911179183 A CN 201911179183A CN 110898855 A CN110898855 A CN 110898855A
- Authority
- CN
- China
- Prior art keywords
- assembled
- rod
- mof
- sheets
- reaction
- 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.)
- Pending
Links
- 239000013118 MOF-74-type framework Substances 0.000 title claims abstract 8
- 238000010189 synthetic method Methods 0.000 title description 2
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000013239 manganese-based metal-organic framework Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000000376 reactant Substances 0.000 abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A synthesis method of rod-shaped MOF-74(Mn) assembled by sheets comprises the steps of dissolving 2, 5-dihydroxy terephthalic acid and 50% manganese nitrate solution in mixed solution of N, N-dimethylformamide, absolute ethyl alcohol and deionized water to obtain mixed solution, transferring the mixed solution into a reaction kettle, and heating for a period of time; after the reaction is finished, the rod-shaped manganese-based MOF assembled by sheets is obtained by centrifugal washing and drying. The synthesis method is simple and feasible, the tablets are obtained by a hydrothermal synthesis method and assembled into the rod-shaped manganese-based MOFs, and the MOFs size and shape can be controlled by adjusting the reactant proportion, the reaction solvent, the reaction temperature and the reaction time. The sheet of the invention is assembled into a rod-shaped MOF-74(Mn) material, belongs to a metal-organic framework material, can be used as a new catalytic material, and has a better application prospect.
Description
Technical Field
The invention relates to synthesis of a novel micron material, in particular to a synthesis method of rod-shaped MOF-74(Mn) assembled by sheets.
Background
Metal-organic frameworks (MOFs) materials are a new class of organic-inorganic hybrid materials formed by self-assembly of inorganic metal ions and organic ligands. Compared with the traditional inorganic porous material, the material has higher specific surface area, porosity and regular pore channels, and the structure and the property of the material are easy to regulate and control. Most of the currently synthesized MOFs are massive crystals, and the morphology, size and regulation of the MOFs are lack of research, so that the performance of the MOFs is further improved by controlling the morphology and size of the MOFs. Compared with metal oxides and noble metals, no study has been reported on the current synthesis method of rod-shaped MOF-74(Mn) assembled from sheets by adjusting reaction conditions during the synthesis of Mn-based MOFs.
Disclosure of Invention
The invention aims to provide a synthesis method for assembling rod-shaped MOF-74(Mn) from sheets, and realizes the control of MOFs size and morphology by adjusting reactant proportion, reaction solvent, reaction temperature and reaction time.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method of synthesis of MOF-74(Mn) in rod form assembled from sheets comprising the steps of:
s1: dissolving 2, 5-dihydroxyterephthalic acid and a 50% manganese nitrate solution in a mixed solution of N, N-dimethylformamide, absolute ethyl alcohol and deionized water to obtain a mixed solution, transferring the mixed solution into a reaction kettle, and heating for a period of time;
s2: after the reaction is finished, the rod-shaped manganese-based MOF assembled by sheets is obtained by centrifugal washing and drying.
In a more preferable embodiment, the molar ratio of the 2, 5-dihydroxyterephthalic acid to the 0.5mmol 50% manganese nitrate solution is 0.5 to 2: 1.
as a further preferable technical scheme, the volume ratio of the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 9: 5: 1.
in a more preferred embodiment, in step S1, the reaction kettle is a 25mL polytetrafluoroethylene reaction kettle.
In a further preferable technical scheme, in the step S1, the heating temperature is 150-200 ℃, and the reaction time is 2 hours.
The invention also provides the tablet assembled rod-shaped Mn-based MOF prepared by the synthesis method.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a synthesis method for assembling rod-shaped MOF-74(Mn) from sheets, which is simple and feasible, and the rod-shaped manganese-based MOF assembled from the sheets is obtained by a hydrothermal synthesis method;
the MOFs size and shape can be controlled by adjusting the reactant proportion, the reaction solvent, the reaction temperature and the reaction time;
the sheet of the invention is assembled into a rod-shaped MOF-74(Mn) material, belongs to a metal-organic framework material, can be used as a new catalytic material, and has a better application prospect.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) and X-ray powder diffraction (XRD) of a sheet-assembled, rod-like Mn-based MOF prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a sheet-assembled, rod-like Mn-based MOF prepared in example 2 of the present invention;
FIG. 3 is a scanning electron micrograph of a sheet-assembled, rod-like Mn-based MOF prepared in example 3 of the present invention.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method of synthesizing MOF-74(Mn) in rod form assembled from sheets, comprising:
dissolving 1mmol of 2, 5-dihydroxy terephthalic acid and 0.5mmol of 50% manganese nitrate solution in N, N-dimethylformamide, absolute ethyl alcohol and deionized water in a volume ratio of 9: 5: 1, the above mixed solution was transferred to a 25mL teflon reaction vessel, heated to 150 ℃ and reacted for 2 hours. And after the reaction is finished, centrifugally washing and drying to obtain the sheet-assembled rod-like manganese-based MOF. FIG. 1 shows the scanning electron micrographs (a, b) and XRD (c) of the product obtained under the experimental conditions described above. The XRD pattern indicated that the resulting product was Mn-based MOF (MOF-74), and the scanning electron micrograph indicated that the resulting product was a rod-like Mn-based MOF assembled from sheets, and the thickness of the sheets was relatively uniform.
Example 2
In this example, a rod-shaped Mn based MOF was prepared by adjusting the amount of 2, 5-dihydroxyterephthalic acid to 0.25mmol, 0.5mmol, 0.75mmol, and 1.0mmol based on example 1. FIG. 2(a-d) is a scanning electron micrograph showing the products obtained when the amount of 2, 5-dihydroxyterephthalic acid was 0.25mmol, 0.5mmol, 0.75mmol and 1.0mmol, in that order; by scanning electron micrographs of the product obtained by changing the amount of the reactant (2, 5-dihydroxyterephthalic acid) as described above, it can be seen that the uniform sheet-assembled rod-shaped Mn-based MOFs with different sizes and morphologies can be obtained when the amount of the reactant (2, 5-dihydroxyterephthalic acid) in the present invention is in the range of 0.25mmol to 1.0 mmol.
Example 3
In this example, the reaction temperature was adjusted to 200 ℃ in addition to example 1, and FIG. 3(a) is a scanning electron micrograph of a product having a reaction temperature of 150 ℃ and FIG. 3(b) is a scanning electron micrograph of a product having a reaction temperature of 200 ℃. Scanning electron micrographs of products obtained by different reaction temperatures show that the uniform sheet assembled rod-shaped Mn-based MOF with different sizes and appearances can be obtained by adjusting the reaction temperature of the invention within the range of 150-200 ℃.
Claims (6)
1. A method of synthesizing MOF-74(Mn) in rod form assembled from sheets, comprising the steps of:
s1: dissolving 2, 5-dihydroxyterephthalic acid and a 50% manganese nitrate solution in a mixed solution of N, N-dimethylformamide, absolute ethyl alcohol and deionized water to obtain a mixed solution, transferring the mixed solution into a reaction kettle, and heating for a period of time;
s2: after the reaction is finished, the rod-shaped manganese-based MOF assembled by sheets is obtained by centrifugal washing and drying.
2. The synthesis method of MOF-74(Mn) rods assembled from sheets according to claim 1, wherein the molar ratio of the 2, 5-dihydroxyterephthalic acid to the 0.5mmol 50% manganese nitrate solution is 0.5-2: 1.
3. a synthesis method of MOF-74(Mn) in rod form assembled from sheets according to claim 1, wherein the volume ratio of N, N-dimethylformamide, absolute ethanol and deionized water is 9: 5: 1.
4. the method for synthesizing MOF-74(Mn) in rod form assembled from sheets according to claim 1, wherein in step S1, the reaction kettle is a 25mL teflon reaction kettle.
5. The synthesis method of MOF-74(Mn) rods assembled from sheets according to claim 1, wherein in step S1, the heating temperature is 150-200 ℃ and the reaction time is 2 h.
6. A sheet-assembled, rod-like Mn-based MOF prepared by the synthesis method of any preceding claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911179183.7A CN110898855A (en) | 2019-11-27 | 2019-11-27 | Synthetic method for rod-shaped MOF-74(Mn) assembled by sheets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911179183.7A CN110898855A (en) | 2019-11-27 | 2019-11-27 | Synthetic method for rod-shaped MOF-74(Mn) assembled by sheets |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110898855A true CN110898855A (en) | 2020-03-24 |
Family
ID=69819971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911179183.7A Pending CN110898855A (en) | 2019-11-27 | 2019-11-27 | Synthetic method for rod-shaped MOF-74(Mn) assembled by sheets |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110898855A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121763A (en) * | 2020-09-21 | 2020-12-25 | 广东石油化工学院 | Carbon-based Mn-MOF-500 adsorption material and preparation method thereof |
| CN112844323A (en) * | 2021-01-11 | 2021-05-28 | 潍坊学院 | M-MOF-74/silicon oxide composite material and preparation method and application thereof |
| CN114950568A (en) * | 2022-06-29 | 2022-08-30 | 中国科学院上海硅酸盐研究所 | Mn-MOF material and application thereof in degrading ozone in mobile phase system |
| CN118652444A (en) * | 2024-08-15 | 2024-09-17 | 山东海化集团有限公司 | Preparation method for accurately regulating and controlling morphology of UiO-67 material and application of prepared material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269984A1 (en) * | 2010-04-30 | 2011-11-03 | The Board Of Regents Of The University Of Texas System | Acetylene storage using metal-organic frameworks of the formula M2(2,5-dihydroxyterephthalate) |
| CN106345527A (en) * | 2016-09-30 | 2017-01-25 | 上海理工大学 | Mn base metal organic skeletal catalyst, and preparation method and application thereof in air pollution prevention |
| CN108786920A (en) * | 2018-04-19 | 2018-11-13 | 上海理工大学 | A kind of Mn bases catalyst and Mn bases organic backbone and SBA-15 composite materials |
| CN110090621A (en) * | 2019-05-16 | 2019-08-06 | 南京林业大学 | Derivative porous carbon materials of a kind of metal organic framework and the preparation method and application thereof |
-
2019
- 2019-11-27 CN CN201911179183.7A patent/CN110898855A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269984A1 (en) * | 2010-04-30 | 2011-11-03 | The Board Of Regents Of The University Of Texas System | Acetylene storage using metal-organic frameworks of the formula M2(2,5-dihydroxyterephthalate) |
| CN106345527A (en) * | 2016-09-30 | 2017-01-25 | 上海理工大学 | Mn base metal organic skeletal catalyst, and preparation method and application thereof in air pollution prevention |
| CN108786920A (en) * | 2018-04-19 | 2018-11-13 | 上海理工大学 | A kind of Mn bases catalyst and Mn bases organic backbone and SBA-15 composite materials |
| CN110090621A (en) * | 2019-05-16 | 2019-08-06 | 南京林业大学 | Derivative porous carbon materials of a kind of metal organic framework and the preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| DOUFENG WU ET AL.: ""Defect engineering of Mn-based MOFs with rod-shaped building units by organic linker fragmentation"", 《INORGANICA CHIMICA ACTA》 * |
| 李志华等: ""双金属功能化的MOF-74合成及气体吸附性能"", 《无机化学学报》 * |
| 王慧琴: ""金属有机骨架材料MOF-74的制备及低温SCR脱硝性能研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121763A (en) * | 2020-09-21 | 2020-12-25 | 广东石油化工学院 | Carbon-based Mn-MOF-500 adsorption material and preparation method thereof |
| CN112121763B (en) * | 2020-09-21 | 2023-08-04 | 广东石油化工学院 | Carbon-based Mn-MOF-500 adsorption material and preparation method thereof |
| CN112844323A (en) * | 2021-01-11 | 2021-05-28 | 潍坊学院 | M-MOF-74/silicon oxide composite material and preparation method and application thereof |
| CN114950568A (en) * | 2022-06-29 | 2022-08-30 | 中国科学院上海硅酸盐研究所 | Mn-MOF material and application thereof in degrading ozone in mobile phase system |
| CN118652444A (en) * | 2024-08-15 | 2024-09-17 | 山东海化集团有限公司 | Preparation method for accurately regulating and controlling morphology of UiO-67 material and application of prepared material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110898855A (en) | Synthetic method for rod-shaped MOF-74(Mn) assembled by sheets | |
| CN108806998B (en) | Synthesis of ZIF-8-based ternary composite ZnO/ZnCo by solvothermal method2O4Method for producing NiO and use thereof | |
| CN109433238B (en) | Iron-nitrogen doped oxygen reduction carbon catalyst with ordered hierarchical pores and preparation method thereof | |
| WO2019109831A1 (en) | Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen | |
| CN110813334B (en) | Preparation method and application of foam nickel loaded iron-nickel based composite material | |
| CN109467493B (en) | Preparation method of metal organic framework material modified nano metal particles | |
| CN103551153B (en) | A kind of copper-based catalysts for carbon dioxide methanation and preparation method thereof | |
| CN106957439B (en) | Method for preparing Co-MOF material based on cobalt-containing bimetallic oxide without solvent | |
| CN110760074B (en) | Preparation method of hierarchical porous metal organic framework material in ionic liquid system | |
| CN110270333A (en) | A kind of bimetallic organic frame nano flower and its derivative and preparation method and application | |
| CN109319826B (en) | In with core-shell structure2O3Synthesis method of dodecahedron | |
| CN108031483B (en) | Carbon-coated nitrogen-doped TiO2Synthesizing method of butterfly-shaped nano material | |
| CN112569959A (en) | Preparation method of manganese-modified carbon nanotube-loaded cobalt oxide, product and application thereof | |
| CN112442186A (en) | Metal organic framework Mn-MOF single crystal material and nanosheet as well as preparation and application thereof | |
| CN110665484A (en) | Preparation method of self-supporting mesoporous metal organic framework material with cooperative growth | |
| CN113649045A (en) | Modified titanium nitride nanotube with Ni-MOF as precursor and preparation method and application thereof | |
| CN106699550B (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN106082298B (en) | Preparation method of cerium-bismuth composite oxide nanorod material | |
| CN109167067B (en) | Flower-shaped electro-catalytic material and preparation method and application thereof | |
| CN111250167A (en) | Fe-based bimetallic organic framework electrocatalyst and preparation and application thereof | |
| CN112844392A (en) | Method for constructing indium oxide micron rod epitaxial growth copper oxide nanosheet photocatalyst | |
| CN108479761B (en) | Method for preparing spherical perovskite catalyst by taking casein as biological template | |
| CN107321374B (en) | Nickel boride modified graphite phase carbon nitride catalyst and preparation method thereof | |
| CN101659407A (en) | Thermal continuous synthesis method of lithium iron phosphate supercritical solvent | |
| CN111203254B (en) | Co-N high-activity species modified vanadium sulfide hydrogen-producing electrocatalyst 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200324 |