CN105541926B - One kind mixes Fe metal organic frame crystal and preparation method thereof - Google Patents
One kind mixes Fe metal organic frame crystal and preparation method thereof Download PDFInfo
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- CN105541926B CN105541926B CN201511024656.8A CN201511024656A CN105541926B CN 105541926 B CN105541926 B CN 105541926B CN 201511024656 A CN201511024656 A CN 201511024656A CN 105541926 B CN105541926 B CN 105541926B
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- 239000013078 crystal Substances 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 17
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 11
- 239000011565 manganese chloride Substances 0.000 claims description 11
- 229910001510 metal chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 1
- 230000005415 magnetization Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 6
- 239000012917 MOF crystal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005621 ferroelectricity Effects 0.000 description 3
- 239000007775 ferroic material Substances 0.000 description 3
- 230000005307 ferromagnetism Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000005690 magnetoelectric effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910015136 FeMn Inorganic materials 0.000 description 1
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005308 ferrimagnetism Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
-
- 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)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Compounds Of Iron (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention belongs to multiferroic functional crystal material research field, and in particular to one kind mixes Fe metal organic frame crystal and preparation method thereof, and the molecular formula of the crystal is [(CH3)2NH3]M(HCOO)3, wherein M is Fe0.1Mn0.9、Fe0.2Mn0.8Or Fe0.3Mn0.7.It is of the present invention to mix Fe metal organic frames [(CH3)2NH2]M(HCOO)3The maximum doping quantity of crystal, wherein Fe is 30%, and with not mixing Fe metal organic frames crystal phase ratio (intensity of magnetization 0.46emu/g), its intensity of magnetization has more apparent raising, and the intensity of magnetization can reach 0.74emu/g~1.1emu/g.
Description
Technical field
The invention belongs to multiferroic functional crystal material research field, and in particular to one kind mixes Fe metal organic frame crystal
And preparation method thereof.
Background technology
Multi-ferroic material is a kind of magneto-electric functional material to grow up in recent years, it refers at a certain temperature while deposits
In two kinds or a kind of compound of two or more ferroelectricitys, ferromagnetism and ferroelasticity ordered state.Wherein, most there is research significance
It is to integrate ferroelectricity and ferromagnetism, and there are magnetoelectric effect between both, thus in information storage, spin electricity
Sub- device, Magnetic Sensor, capacitance-inductance integration device and microwave technology etc. have very big development potentiality.But
The single-phase multi-ferroic material that is found is simultaneously few, they ferromagnetism and ferroelectricity could can only at the same time occur at low temperature mostly,
And magnetoelectric effect, therefore, it is necessary to explore new multi-ferroic material according to the present situation of current multiferroic research.
Metal organic frame (Metal-Organic Frameworks, abbreviation MOFs) is that had by metal ion with multi-functional
The polymer that machine ligand is self-assembly of, they are stable nano-porous materials, there is machinery and heat endurance well.With showing
There is porous material to compare, MOFs has high-specific surface area, pore size reconfigurable, is easy to functionalization, special light, electricity spy
The remarkable advantages such as property, so that the storage of adsorbing separation, gas in gas, organic catalysis, photoelectromagnetic material, chemical sensor etc.
Field has shown good application prospect.
The content of the invention
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide one kind mixes Fe metal organic frames crystal and its preparation
Method.
For achieving the above object, the technical solution adopted by the present invention is：
One kind mixes Fe metal organic frame crystal, its molecular formula is [(CH3)2NH3]M(HCOO)3, it is characterised in that it is described
M is Fe0.1Mn0.9、Fe0.2Mn0.8Or Fe0.3Mn0.7。
The above-mentioned preparation method for mixing Fe metal organic frame crystal, it is characterised in that include the following steps：By metal chlorination
Thing is added in n,N-Dimethylformamide (DMF) aqueous solution, is sufficiently stirred so that metal chloride is completely dissolved；Then will
Mixed solution is placed in autoclave, is carried out pyroreaction, after reaction, is taken supernatant liquor, obtain after crystallized and filtered
Crystal.
In such scheme, the metal chloride is frerrous chloride and manganese chloride, and the frerrous chloride and manganese chloride rub
You are than being 1:9~3:7.
In such scheme, on the basis of 1mmol metal chlorides, the dosage of the DMF aqueous solutions is 12ml~15ml；Institute
State in DMF aqueous solutions, the volume ratio of DMF and water is 1:1.
In such scheme, the temperature of the pyroreaction is 140 DEG C~160 DEG C, and the reaction time is 3~7 days.
In such scheme, the temperature of the crystallization is 25 DEG C~30 DEG C, and the time is 3~7 days.
Beneficial effects of the present invention are as follows：(1) it is of the present invention to mix Fe metal organic frames [(CH3)2NH2]M(HCOO)3
The maximum doping quantity of monocrystal, wherein Fe is 30%, with not mixing Fe metal organic frames crystal phase ratio (intensity of magnetization 0.46emu/
G), its intensity of magnetization has more apparent raising, and the intensity of magnetization can reach 0.74emu/g~1.1emu/g；(2) gold of the present invention
Belong to organic frame [(CH3)2NH2]M(HCOO)3In monocrystal, with the increase of the volume of Fe, crystal is just more difficult to grow, and brilliant
Body size is also smaller, uses the method for the invention that the maximum doping quantity of Fe can be prepared as 30% metal organic frame list
Crystal, crystallite dimension is sufficiently large, and convenient processing orientation carries out the test of every property, is [(CH3)2NH3]M(HCOO)3Crystal material
The preparation of material and the research of its intrinsic physics provide the reliable means of sample preparation.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
In following embodiments, the DMF solution, frerrous chloride (FeCl2), manganese chloride (MnCl2) tried for Chinese medicines group chemistry
The high-purity N of agent Co., Ltd production, dinethylformamide (DMF), Iron dichloride tetrahydrate, four chloride hydrate manganese.
Embodiment 1
One kind mixes Fe metal organic frames [(CH3)2NH3]M(HCOO)3Crystal, wherein M are Fe0.1Mn0.9, pass through such as lower section
Method is prepared：By the FeCl of 0.5mmol2, 4.5mmol MnCl2It is added in 30ml DMF solutions and 30ml deionized waters,
Agitating solution, is completely dissolved solid particle；Mixed liquor is then transferred to the autoclave of 100ml polytetrafluoroethyllining linings
In, 140 DEG C are heated in an oven keeps the temperature 3 days；Supernatant liquor is transferred in glass beaker after the completion of reaction, is tied at room temperature
Cubic crystal is obtained after 3 days brilliant, cubic crystal is filtered from mother liquor, then is cleaned with ethanol.
(the Fe0.1Mn0.9)-MOF crystal that the present embodiment is prepared carries out Magnetic Test, the results are shown in Table 1, gained crystal
With not mixing the increase of Fe crystal phases specific magnetization, magnetic transition temperature slightly reduces；Corresponding Jie of 100kHz under room temperature (300K)
Electric constant slightly reduces.
Embodiment 2
One kind mixes Fe metal organic frames [(CH3)2NH3]M(HCOO)3Crystal, wherein M are Fe0.2Mn0.8, pass through such as lower section
Method is prepared：By the FeCl of 1mmol2, 4mmol MnCl2It is added in 30ml DMF solutions and 30ml deionized waters, stirs
Solution, is completely dissolved solid particle；Then mixed liquor is transferred in the autoclave of 100ml polytetrafluoroethyllining linings,
140 DEG C are heated in an oven keeps the temperature 3 days；Supernatant liquor is transferred in glass beaker after the completion of reaction, crystallizes 5 at room temperature
Cubic crystal is obtained after it, cubic crystal is filtered from mother liquor, then is cleaned with ethanol.
By (Fe made from the present embodiment0.2Mn0.8)-MOF crystal carry out Magnetic Test, the results are shown in Table 1, illustrate crystal with
The increase intensity of magnetization of the molar ratio of Fe also increased, and magnetic transition temperature change is smaller；300kHz pairs under room temperature (300K)
The dielectric constant answered further reduces.
Embodiment 3
One kind mixes Fe metal organic frames [(CH3)2NH3]M(HCOO)3Crystal, wherein M are Fe0.3Mn0.7, pass through such as lower section
Method is prepared：By the FeCl of 1.5mmol2, 3.5mmol MnCl2It is added in 30ml DMF solutions and 30ml deionized waters,
Agitating solution, is completely dissolved solid particle；Mixed liquor is then transferred to the autoclave of 100ml polytetrafluoroethyllining linings
In, 150 DEG C are heated in an oven keeps the temperature 3 days；Supernatant liquor is transferred in glass beaker after the completion of reaction, is tied at room temperature
Cubic crystal is obtained after 7 days brilliant, cubic crystal is filtered from mother liquor, then is cleaned with ethanol.
Experiment proves：If continuing to increase the doping concentration of Fe, pure (FeMn)-MOF crystal can not be obtained, therefore recognize
For (Fe0.3Mn0.7)-MOF be available maximum Fe adulterate MOF crystal.By (Fe made from the present embodiment0.3Mn0.7)-
MOF crystal carries out Magnetic Test, and analysis finds (Fe0.3Mn0.7) mutation of a series of properties occurs in-MOF, especially magnetism is ground
Study carefully proof, three transition temperatures occurs in crystal, corresponds to Mn (8.3K), the coupling (40.3K) of Mn-Fe and the coupling of Fe-Fe respectively
Close (118.3K), with the increase of Fe contents, the local ferrimagnetism of appearance causes the magnetism of material to significantly improve, such as the institute of table 1
Show, the intensity of magnetization increases to 1.1emu/g ((Fe from 0.46emu/g (Mn-MOF)0.3Mn0.7)-MOF)。
Comparative example
One kind does not mix Fe metal organic frames [(CH3)2NH3]M(HCOO)3Crystal, wherein M are Mn, are made by the following method
It is standby to obtain：By 5mmol MnCl2It is added in 30ml DMF solutions and 30ml deionized waters, agitating solution, makes MnCl2It is completely molten
Solution；Then mixed liquor is transferred in the autoclave of 100ml polytetrafluoroethyllining linings, is heated to 140 DEG C of guarantors in an oven
Temperature 3 days；Supernatant liquor is transferred in glass beaker after the completion of reaction, cubic crystal is obtained after crystallizing 3 days at room temperature, will be vertical
Square crystal is filtered from mother liquor, then is cleaned with ethanol.
[(the CH that comparative example is prepared3)2NH3]Mn(HCOO)3Crystal carries out magnetic and measurement, the results are shown in Table
1。
Table 1 the result shows that：It is of the present invention to mix Fe metal organic frames [(CH3)2NH2]M(HCOO)3Monocrystal, wherein
The maximum doping quantity of Fe is 30%, and with not mixing Fe metal organic frames crystal phase ratio (intensity of magnetization 0.46emu/g), it magnetizes strong
Degree has more apparent raising, and the intensity of magnetization can reach 0.74emu/g~1.1emu/g.
The test result for 3 crystal of [(CH3) 2NH3] M (HCOO) that 1 embodiment 1~3 of table and comparative example are prepared
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (3)
1. a kind of preparation method for mixing Fe metal organic frame crystal, it is characterised in that include the following steps：By metal chloride
It is added in n,N-Dimethylformamide aqueous solution, is completely dissolved metal chloride after being sufficiently stirred；Then by mixed solution
It is placed in autoclave, carries out pyroreaction, after reaction, take supernatant liquor, obtain mixing Fe metals after crystallized and filtered
Organic frame crystal；The metal chloride is frerrous chloride and manganese chloride, and the molar ratio of the frerrous chloride and manganese chloride is
1:9~3:7；The temperature of the pyroreaction is 140 DEG C ~ 160 DEG C, and the reaction time is 3 ~ 7 days；The temperature of the crystallization for 25 DEG C ~
30 DEG C, the time is 3 ~ 7 days.
2. preparation method according to claim 1, it is characterised in that on the basis of 1mmol metal chlorides, the N,
The dosage of dinethylformamide aqueous solution is 12ml ~ 15ml；In the n,N-Dimethylformamide aqueous solution, N, N- diformazans
The volume ratio of base formamide and water is 1:1.
3. any preparation method of claim 1 ~ 2 prepares the preparation method that gained mixes Fe metal organic frame crystal, its point
Minor is [(CH3)2NH3]M(HCOO)3, the M is Fe0.1Mn0.9、Fe0.2Mn0.8Or Fe0.3Mn0.7。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725434A (en) * | 2015-03-09 | 2015-06-24 | 陈谦 | Magnesium-doped metal-organic frame DMMg0.5Co0.5F single-crystal material and preparation method thereof |
| CN104788505A (en) * | 2015-03-09 | 2015-07-22 | 浙江理工大学 | Metal-organic framework single crystal epitaxially grown DMCoF/DMMnF heterojunction material and preparation method thereof |
| CN104788507A (en) * | 2015-03-09 | 2015-07-22 | 浙江理工大学 | Magnesium doped metal-organic framework DMMg0.5Mn0.5F single crystal material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725434A (en) * | 2015-03-09 | 2015-06-24 | 陈谦 | Magnesium-doped metal-organic frame DMMg0.5Co0.5F single-crystal material and preparation method thereof |
| CN104788505A (en) * | 2015-03-09 | 2015-07-22 | 浙江理工大学 | Metal-organic framework single crystal epitaxially grown DMCoF/DMMnF heterojunction material and preparation method thereof |
| CN104788507A (en) * | 2015-03-09 | 2015-07-22 | 浙江理工大学 | Magnesium doped metal-organic framework DMMg0.5Mn0.5F single crystal material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Multiferroic Behavior Associated with an Order-Disorder Hydrogen Bonding Transition in Metal-Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture;Prashant Jain et al.;《J.Am.Chem.Soc.》;20090902;第131卷(第38期);第13625-13627页，参见第13625页右栏第2段 * |
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