CN107955043A - A kind of manganese-based low-temperature magnetic refrigeration metal-organic framework material and preparation method thereof - Google Patents
A kind of manganese-based low-temperature magnetic refrigeration metal-organic framework material and preparation method thereof Download PDFInfo
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- CN107955043A CN107955043A CN201711283808.5A CN201711283808A CN107955043A CN 107955043 A CN107955043 A CN 107955043A CN 201711283808 A CN201711283808 A CN 201711283808A CN 107955043 A CN107955043 A CN 107955043A
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 19
- 239000011572 manganese Substances 0.000 title claims description 16
- 229910052748 manganese Inorganic materials 0.000 title claims description 14
- 239000000463 material Substances 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000005057 refrigeration Methods 0.000 title description 5
- 239000012621 metal-organic framework Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000002178 crystalline material Substances 0.000 claims description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- 239000010953 base metal Substances 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 239000003507 refrigerant Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 8
- 230000003993 interaction Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical compound O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-UHFFFAOYSA-L 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/24—1,3 - Benzenedicarboxylic acid
-
- 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
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/017—Compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to the crystal MnLi with high magnetothermal effect as molecule base refrigerant2(C8O4H4)2(H2O)2And its preparation and use.The compound molecular weight is：433.08, belong to monoclinic system, space group C2/c, cell parameter is Alpha=90 °, beta=111.528 °, gamma=90 °, Z=4, unit cell volume isPrepared using hydro-thermal method.Compound MnLi2(C8O4H4)2(H2O)2The hot entropy Δ S of its magnetic under conditions of 2.0K, Δ H=8Tm30.4J Kg are reached‑1K‑1。
Description
Technical field
The applicable domain of inorganic chemistry of the present invention, falls within materials science field, it is related to a kind of magnetic cooling effect crystal
Preparation method, also relates to application of the crystalline material in high-tech area.
Background technology
For the medium of paramagnetic, magnetic field is adiabatically reduced, the temperature of material can be reduced, this phenomenon is referred to as magnetic
Fuel factor (magnetocaloric effect, be abbreviated as MCE), mainly becomes (Δ S by magnetic entropy under isothermym) weigh
Its size.Magnetic refrigeration based on magnetothermal effect becomes substitution conventional vapor circularly cooling technology because of its efficient, free of contamination feature
Effective alternative.The magnetic refrigeration application of early stage in liquefaction helium (3He in device), but because its raw material is rare and price
Costliness, so scientists are directed to finding and are readily synthesized and cheap new magnetic refrigerants in recent years.Therefore, molecule base
Magnetic refrigerants have come into everybody sight and have received strong concern.Good magnetothermal effect value is obtained at low temperature,
Need big ground state spin angular momentaum, weak Spin Interaction, and negligible magnetic anisotropy.Consider
The above requirement, trivalent gadolinium ion (Gd3+) become preferable selection, several gadolinium base magnetic systems with good magnetic refrigeration performance
Cryogen has been synthesized.Although we obtain some gadolinium base refrigerants with high magnetothermal effect value, gadolinium is as dilute
Earth elements are rare and price is high, therefore its daily use is greatly limited.Items with five unpaired electrons are same
Divalent manganesetion (the Mn of property2+) cost is low and easy acquisition, it is the material of extraordinary replacement trivalent gadolinium ion.But Mn2+
And Mn2+Between magnetic interaction compare Gd3+Between high two orders of magnitude, and Mn2+And Mn2+Between magnetic interaction very
Hardly possible is controlled, so the research with high magnetothermal effect manganese base magnetic refrigerants is a very big challenge.It is desirable that by drawing
Enter nonmagnetic metal ion, increase adjacent Mn2+Distance, reduce its magnetic interaction, obtain with good magnetothermal effect
Manganese base magnetic refrigerating material.Research in relation to this respect at present there is no literature reported on.Therefore we are diamagnetic by introducing in this patent
The Li of property+Ion increases the distance between manganese ion to weaken its interaction, so as to carry high molecular magnetic as magnetic spacer
Fuel factor, we use easy hydrothermal method, are prepared for the manganese base magnetic refrigerants of superior performance.
The content of the invention
It is an object of the invention to prepare a kind of manganese base magnetic refrigerating crystal of good magnetothermal effect with convenient method.
The chemical formula of crystalline material provided herein is MnLi2(C8O4H4)2(H2O)2, molecular weight 433.08, belongs to
Monoclinic system, space group C2/c, cell parameter are
Alpha=90 °, beta=111.528 °, gamma=90 °,Z=4.
Preferably, the crystalline material is monocrystal material.
In affiliated crystal structure, contain half of manganese ion in crystallography asymmetric cell, a lithium ion and one
M-phthalic acid ligand and a water of coordination molecule.Manganese atom takes hexa-coordinate mode and the different M-phthalic acid roots in four, periphery
The O atom of offer forms distorted octahedron, and lithium atom and three oxygen atoms provided by carboxylate radical and a hydrone provide
Oxygen atom ligand, form tetrahedral coordination, its coordination environment is as shown in Figure 1.MnO6Two adjacent LiO of octahedra periphery4Four
Face body is connected in a manner of common vertex and altogether side respectively, the one-dimensional infinite chain formed by manganese and lithium polyhedron is produced, such as Fig. 2 institutes
Show.The one-dimensional infinite chain is built into the organic framework compounds of three-dimensional by the interconnection of ligand, as shown in Figure 3.The chemical combination
The distance between the adjacent manganese of thing and manganese reachCarboxylic acid chain compared to other one-dimensional manganese bases is much bigger.Chemical combination
Thing thermogravimetric test curve is with good stability as shown in figure 4, show that compound is decomposed after 449 DEG C.
According to the another aspect of the application, there is provided the preparation method of the crystalline material, it is characterised in that manganese will be contained
Element, elemental lithium, the mixture of M-phthalic acid root and water, crystallization is no less than 3 days at a temperature of not less than 120 DEG C, gained
Solid product is the crystalline material；
Manganese element in the mixture, elemental lithium, the molar ratio of M-phthalic acid root and water are：Mn:Li:C8O4H4:H2O
=1:2:2:2.
Preferably, manganese element described in mixture comes from four acetate hydrate manganese.
Preferably, elemental lithium described in mixture comes from lithium hydroxide.
Preferably, M-phthalic acid root described in mixture comes from M-phthalic acid.
Preferably, the crystallization temperature is 120~130 DEG C, and crystallization time is 3~4 days.
According to the another aspect of the application, there is provided a kind of method for preparing the crystalline material, it is characterised in that pass through water
Hot method synthesis, after four acetate hydrate manganese, M-phthalic acid, lithium hydroxide, glacial acetic acid and isopropanol are mixed evenly, Yu Te
Determine crystallization under crystallization temperature to obtain.
Shown by Magnetic Test, since farther out, its magnetic interaction is very for the distance between adjacent manganese ion in compound
It is weak, therefore there is outstanding magnetic cooling performance, compound hot entropy of its magnetic under conditions of 2.0K, Δ H=8T has reached 30.4J
Kg-1K-1.In energy shortage and environmental pollution getting worse instantly, the molecule base magnetic refrigerants be readily synthesized, it is cheap and
Environment will not be polluted, there is very big application value.
Brief description of the drawings
Fig. 1 is crystal coordination context diagram.
Fig. 2 is the one-dimensional chain figure that manganese and lithium are formed.
Fig. 3 is the tomograph of crystal.
Fig. 4 is the thermogravimetric curve collection of illustrative plates of crystal.
Fig. 5 is that single crystal data the XRD diffraction theories collection of illustrative plates being fitted and the XRD diffracting spectrums that experiment measures contrast.
Fig. 6 is the hot entropy variation with temperature curve map of magnetic of the crystal under different magnetic field intensity.
Embodiment
Scheme is as follows：
Example 1：By four acetate hydrate manganese (0.12 gram), M-phthalic acid (0.165g) and lithium hydroxide (0.024g) are at the same time
Add in the polytetrafluoroethyllining lining hydro-thermal can container of volume 20ml, add 6ml aqueous isopropanols, 8 drip glacial acetic acid solutions, then
Stirring ten minutes, is placed in chamber type electric resistance furnace, 120 DEG C, isothermal reaction 4320min is warming up to from 30 DEG C by 240min, then
Room temperature is down to through 4320min.Obtain a large amount of bar-shaped clear crystals.
Example 2：Four acetate hydrate manganese (0.24 gram), M-phthalic acid (0.33 gram) is same with lithium hydroxide (0.048 gram)
When add in the polytetrafluoroethyllining lining hydro-thermal can container of volume 20ml, add 12ml aqueous isopropanols, 16 drop glacial acetic acid solutions,
It is subsequently agitated for ten minutes, is placed in chamber type electric resistance furnace, 120 DEG C, isothermal reaction 4320min is warming up to from 30 DEG C by 240min,
After room temperature is down to through 4320min.Obtain a large amount of bar-shaped clear crystals.It is determined through X-ray single crystal diffraction and powder diffraction
Chemical composition is consistent with compound.
Implement the structural characterization of sample
The X-ray single crystal diffraction of sample carries out on MercuryCCD type single crystal diffractometers, Mo targets, K α radiation source (λ=
0.07107nm), test temperature 293K.And structure elucidation is carried out to it by Shelxtl97.The X-ray powder diffraction of sample
Material phase analysis (XRD) carries out on the MiniFlexII type X-ray diffractometers of Rigaku companies, Cu targets, K α radiation source (λ=
0.154184nm).The XRD diffraction theories collection of illustrative plates being fitted by single crystal data and the XRD diffracting spectrums ratio that test obtains in fact
It is more as shown in Figure 5, it can be seen that the XRD diffracting spectrums being fitted by single crystal data and the XRD diffraction patterns that test obtains in fact
Compose highly consistent.
Implement the magnetothermal effect test of sample
The magnetothermal effect test of sample in PhysicalPropertyMeasurementsystem, PPMS (PPMS-9T,
QuantumDesign on), test scope 0-8T (0.1T/ steps), test data is by calculating as shown in Figure 6, the results showed that, sample
Product have very big magnetic cooling effect, and the magnetothermal effect of its powder reaches 30.4J Kg-1K-1, Δ H=8T.
It is not for limiting claim, any this area skill although the application is disclosed as above with preferred embodiment
Art personnel can make some possible variations and modification on the premise of the application design is not departed from, therefore the application
Protection domain should be subject to the scope that the application claim is defined.
Claims (8)
- A kind of 1. manganese Base Metal organic frame compound, it is characterised in that：Its chemical formula is MnLi2(C8O4H4)2(H2O)2, molecule Measure as 433.08, belong to monoclinic system, space group C2/c, cell parameter is Alpha=90 °, beta=111.528 °, gamma=90 °,Z=4.
- 2. crystalline material according to claim 1, it is characterised in that the crystalline material is monocrystal material.
- 3. prepare the method for crystalline material described in claim 1, it is characterised in that manganese element, elemental lithium, isophthalic diformazan will be contained The mixture of acid group and hydrone, crystallization is no less than 3 days at a temperature of not less than 120 DEG C, and obtained solid product is described Crystalline material.
- 4. prepare the method for crystalline material described in claim 3, it is characterised in that manganese element described in mixture is from four hydrations Manganese acetate, elemental lithium and sulfate radical come from lithium hydroxide, and M-phthalic acid root carrys out M-phthalic acid.
- 5. according to the method described in claim 3, it is characterized in that, 120~130 DEG C of the crystallization temperature, crystallization time for 3~ 4 days.
- 6. prepare the method for crystalline material described in claim 1, it is characterised in that prepared using easy hydro-thermal method, Jiang Sishui After the raw materials such as conjunction manganese acetate, M-phthalic acid, lithium hydroxide, glacial acetic acid, isopropanol stir evenly, it is placed in band polytetrafluoroethylene (PTFE) In the synthesis reactor of lining, after 120~130 DEG C of crystallization 3~5 days, room temperature was cooled down to through 2~3 days, obtained solid product is institute State crystalline material.
- 7. according to the method described in claim 6, it is characterized in that, manganese element, elemental lithium, M-phthalic acid in the mixture The molar ratio of root and water is：Mn:Li:C8O4H4:H2O=1:2:2:2.
- 8. a kind of magnetic refrigerating material, it is characterised in that and/or will according to right containing the crystalline material described in claim 1 and 2 The crystalline material for asking any one of 3 to 7 the methods to be prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711283808.5A CN107955043A (en) | 2017-12-07 | 2017-12-07 | A kind of manganese-based low-temperature magnetic refrigeration metal-organic framework material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711283808.5A CN107955043A (en) | 2017-12-07 | 2017-12-07 | A kind of manganese-based low-temperature magnetic refrigeration metal-organic framework material and preparation method thereof |
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| CN107955043A true CN107955043A (en) | 2018-04-24 |
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| CN201711283808.5A Pending CN107955043A (en) | 2017-12-07 | 2017-12-07 | A kind of manganese-based low-temperature magnetic refrigeration metal-organic framework material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113855A (en) * | 2013-01-23 | 2013-05-22 | 中国科学院福建物质结构研究所 | Low-temperature magnetic refrigeration metal-organic framework material as well as preparation method and use thereof |
| CN103554190A (en) * | 2013-10-31 | 2014-02-05 | 天津理工大学 | 3d dissimilar metal methanoic acid compound with high magnetocaloric effect |
-
2017
- 2017-12-07 CN CN201711283808.5A patent/CN107955043A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113855A (en) * | 2013-01-23 | 2013-05-22 | 中国科学院福建物质结构研究所 | Low-temperature magnetic refrigeration metal-organic framework material as well as preparation method and use thereof |
| CN103554190A (en) * | 2013-10-31 | 2014-02-05 | 天津理工大学 | 3d dissimilar metal methanoic acid compound with high magnetocaloric effect |
Non-Patent Citations (1)
| Title |
|---|
| XUE LI-PING等，: "A New Acentric Heterometallic Inorganic-organic Hybrid Framework [ZnK2(m-BDC)2(H2O)2]n: Fluorescent, NLO and Ferroelectric Properties", 《结构化学（JIEGOU HUAXUE ）CHINESE J. STRUCT. CHEM.》 * |
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