CN102977155A - Preparation method of 3d-3d metal complex with large magnetocaloric effect - Google Patents
Preparation method of 3d-3d metal complex with large magnetocaloric effect Download PDFInfo
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- CN102977155A CN102977155A CN201210530209XA CN201210530209A CN102977155A CN 102977155 A CN102977155 A CN 102977155A CN 201210530209X A CN201210530209X A CN 201210530209XA CN 201210530209 A CN201210530209 A CN 201210530209A CN 102977155 A CN102977155 A CN 102977155A
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Abstract
The invention discloses a preparation method of a 3d-3d metal complex with a large magnetocaloric effect. The 3d-3d metal complex is a dissimilar metal formate compound, has a chemical formula of C7H12NCrMnO12, belongs to a trigonal system and has a space group of P-31c. The 3d-3d metal complex is prepared by taking CrCl3.H2O and MnCl2.4H2O as 3d metal salts, and formic acid and N,N-dimethylformamide (DMF) with a volume ratio of 1:1 as a mixed solvent by adopting a solvothermal synthesis method. The invention has the advantages that the preparation method realizes a weak ferromagnetic function among 3d-3d metals on the basis of an orbit orthogonalizing function principle, avoids long-range order, and obtains the 3d-3d metal compound with large magnetic force vibration heat effect; and the 3d-3d metal compound has a better potential application value on the aspect of magnetic refrigerating. The preparation method has the advantages of simple and cheap raw materials and possibility of large-scale production.
Description
Technical field
The present invention relates to magnetic refrigeration metal complexes, particularly a kind of preparation method with 3d-3d metal complexes of large magnetothermal effect.
Technical background
Magnetic refrigeration based on magnetothermal effect (Magnetocaloric Effect) is as a kind of energy-conservation and environmentally friendly technology, owing to may substituting expensive super low temperature refrigeration agent He
3, and be subject to investigator's strong interest and extensively probe into.In recent years, due to its Scalability and Modulatory character, the molecular based refrigeration agent causes investigator's very big interest, referring to: M.Manoli, A.Collins; S.Parsons, A.Candini, M.Evangelisti, E.K.Brechin; J.Am.Chem.Soc., 2008,130,11129; M.Manoli, R.D.L.Johnstone, S.Parsons, M.Murrie, M.Affronte, M.Evangelisti, E.K.Brechin, Angew.Chem.Int.Ed., 2007,46,4456.
The molecular based refrigeration agent of having reported is the metal organic frame (Gd-based MOFs) of 3d-Gd/Gd bunch and Gd base mostly, referring to: J.B.Peng, Q.C.Zhang; X.J.Kong, Y.Z.Zheng, Y.P.Ren; L.S.Long; R.B.Huang, L.S.Zheng, Z.P.Zheng; J.Am.Chem.Soc.; 2012,134,3314; J.B.Peng, Q.C.Zhang, X.J.Kong, Y.P.Ren, L.S.Long, R.B.Huang, L.S.Zheng, Z.P.Zheng, Angew.Chem.Int.Ed., 2011,50,10649; G.Lorusso, M.A.Palacios, G.S.Nichol, E.K.Brechin, O.Roubeau, M.Evangelisti, Chem.Commun., 2012,48,7592; R.Sibille, T.Mazet, B.Malaman, M.Fran ois, Chem.Eur.J., 2012,18,12970. because the 3d-3d metallic compound often shows strong interaction, and the higher magnetic entropy of very difficult acquisition becomes, and then limit its application aspect the magnetic refrigeration, therefore the research of the refrigeration of the magnetic based on the 3d-3d metal rarely has report.Based on track quadrature action principle, if choose suitable little bridgingligand and different metal ion, the intermetallic weak iron magnetic action of 3d-3d is likely realized, and then is avoided long-range order.Because this compounds has the molecular mass spin of less than (small M
w/ N
m), thereby there is very large Research Significance and potential using value aspect the magnetic refrigeration.
Summary of the invention
The objective of the invention is for above-mentioned technical Analysis, a kind of preparation method with 3d-3d metal complexes of large magnetothermal effect is provided, this preparation method is based on track quadrature action principle, realize the intermetallic weak iron magnetic action of 3d-3d, avoid long-range order, acquisition has the 3d-3d metallic compound that large magnetic thermal effect is used, and for preparation has the title complex that large magnetic thermal effect uses, indicates new direction.
Technical scheme of the present invention:
A kind of preparation method with 3d-3d metal complexes of large magnetothermal effect, described 3d-3d metal complexes is different metal formic acid cpds, its chemical formula is C
7h
12nCrMnO
12, belonging to trigonal system, spacer is P-31c, its preparation method is with CrCl
36H
2o and MnCl
24H
2o is the 3d metal-salt, and the formic acid that the volume ratio of take is 1:1 and DMF (DMF) are mixed solvent, adopts the solvent process for thermosynthesizing preparation, and concrete grammar is: by CrCl
36H
2o, MnCl
24H
2o, formic acid and N, dinethylformamide (DMF) is placed in band teflon-lined stainless steel cauldron, at 130-150 ° of C temperature, reaction is 48 hours, then be cooled to 18-25 ° of C, obtain bulk crystals, with the DMF washing, obtain the different metal formic acid cpds of target product after vacuum-drying, it is the 3d-3d metal complexes with large magnetothermal effect.
The amount ratio of described 3d metal-salt total amount and mixed solvent is 0.15 mmole/milliliter.
Described CrCl
36H
2o and MnCl
24H
2the mol ratio of O is 1:1.
Advantage of the present invention is: this preparation method is based on track quadrature action principle, realize the intermetallic weak iron magnetic action of 3d-3d, avoid long-range order, acquisition has the 3d-3d metallic compound that large magnetic thermal effect is used, this 3d-3d metallic compound has good potential using value aspect the magnetic refrigeration, for acquisition has the compound that large magnetic thermal effect uses, provide theoretical foundation; This preparation method's raw material cheap and simple, possess the possibility of scale operation.
The accompanying drawing explanation
Fig. 1 is the crystalline structure figure of obtained different metal formate complex.
Fig. 2 is the Δ S calculated by specific magnetising moment data under different temperature and field intensity
mvalue.
Embodiment
Embodiment:
A kind of preparation method with 3d-3d metal complexes of large magnetothermal effect, described 3d-3d metal complexes is different metal formic acid cpds, its chemical formula is C
7h
12nCrMnO
12, belonging to trigonal system, spacer is P-31c, as shown in Figure 1, its preparation method is with CrCl to crystalline structure
36H
2o and MnCl
24H
2o is the 3d metal-salt, and the formic acid that the volume ratio of take is 1:1 and DMF (DMF) are mixed solvent, adopts the solvent process for thermosynthesizing preparation, and concrete grammar is:
By 0.75 mmole CrCl
36H
2o, 0.75 mmole MnCl
24H
2o, 15 ml volumes are than being the formic acid of 1:1 and N, the mixed solvent of dinethylformamide (DMF) is put into 25 milliliters of band teflon-lined stainless steel cauldrons, under 140 ° of C, reaction is 48 hours, then be cooled to 22 ° of C, obtain bulk crystals, with the DMF washing, obtain the different metal formic acid cpds of target product after vacuum-drying, it is the 3d-3d metal complexes with large magnetothermal effect.
Use following instrument and method to be characterized product:
1) use Quantum Design MPMS-7SQUID type magnetometer to carry out the magnetic data test to obtained title complex, Fig. 2 is the Δ S calculated by specific magnetising moment data under different temperature and field intensity
mvalue, in figure, show: this 3d-3d metal complexes has very large magnetic thermal effect use, T=3K, during Δ H=7T ,-Δ S
m=48.2J kg
-1k
-1, prove that this title complex is few in number-Δ S
m36J kg
-1k
-1title complex.
2) select the crystal that is of a size of 0.20mm * 0.20mm * 0.20mm and be used for ray crystallographic analysis, the single crystal diffraction data are collected on Bruker Smart 1000 CCD diffractometers, adopt the Mok alpha-ray of graphite monochromator monochromatization
1.75 °≤θ≤27.96 °.Detected result shows: the gained compound belongs to trigonal system, and spacer is all P-31c, unit cell parameters
α=90 °, β=90 °, γ=120 °, crystalline structure (is used Origin, the Diamond Software on Drawing) as shown in Figure 1.
Claims (3)
1. the preparation method with 3d-3d metal complexes of large magnetothermal effect, it is characterized in that: described 3d-3d metal complexes is different metal formic acid cpds, and its chemical formula is C
7h
12nCrMnO
12, belonging to trigonal system, spacer is P-31c, its preparation method is with CrCl
36H
2o and MnCl
24H
2o is the 3d metal-salt, and the formic acid that the volume ratio of take is 1:1 and DMF (DMF) are mixed solvent, adopts the solvent process for thermosynthesizing preparation, and concrete grammar is: by CrCl
36H
2o, MnCl
24H
2o, formic acid and N, dinethylformamide (DMF) is placed in band teflon-lined stainless steel cauldron, at 130-150 ° of C temperature, reaction is 48 hours, then be cooled to 18-25 ° of C, obtain bulk crystals, with the DMF washing, obtain the different metal formic acid cpds of target product after vacuum-drying, it is the 3d-3d metal complexes with large magnetothermal effect.
2. have according to claim 1 the preparation method of the 3d-3d metal complexes of large magnetothermal effect, it is characterized in that: the amount ratio of described 3d metal-salt total amount and mixed solvent is 0.15 mmole/milliliter.
3. there is according to claim 1 the preparation method of the 3d-3d metal complexes of large magnetothermal effect, it is characterized in that: described CrCl
36H
2o and MnCl
24H
2the mol ratio of O is 1:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554190A (en) * | 2013-10-31 | 2014-02-05 | 天津理工大学 | 3d dissimilar metal methanoic acid compound with high magnetocaloric effect |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517488A (en) * | 2011-12-02 | 2012-06-27 | 北京工业大学 | Magnetic refrigeration material and preparation process thereof |
| CN102703038A (en) * | 2012-05-28 | 2012-10-03 | 华南理工大学 | Gd-based magnetic refrigeration material and preparation method thereof |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517488A (en) * | 2011-12-02 | 2012-06-27 | 北京工业大学 | Magnetic refrigeration material and preparation process thereof |
| CN102703038A (en) * | 2012-05-28 | 2012-10-03 | 华南理工大学 | Gd-based magnetic refrigeration material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JIONG-PENG ZHAO ET AL.: "Magnetic Behavior Control in Niccolite Structural Metal Formate Frameworks[NH2(CH3)2][FeⅢMⅡ(HCOO)6](M = Fe, Mn, and Co) by Varying the Divalent Metal Ions", 《INORGANIC CHEMISTRY》, vol. 49, no. 22, 11 October 2010 (2010-10-11), pages 10390 - 10399 * |
| 赵炯鹏: "3d-3d异金属甲酸化合物的磁性调控", 《第六届全国物理无机化学会议》, 12 October 2012 (2012-10-12), pages 118 * |
| 赵炯鹏: "金属叠氮/甲酸分子基磁性配合物研究", 《万方学位论文数据库》, 3 May 2012 (2012-05-03), pages 1 - 214 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554190A (en) * | 2013-10-31 | 2014-02-05 | 天津理工大学 | 3d dissimilar metal methanoic acid compound with high magnetocaloric effect |
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Application publication date: 20130320 |