CN103012450B - Gadolinium compound with dual functions of magnetic refrigeration function and ferroelectric function and preparation method thereof - Google Patents

Gadolinium compound with dual functions of magnetic refrigeration function and ferroelectric function and preparation method thereof Download PDF

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CN103012450B
CN103012450B CN201210537507.1A CN201210537507A CN103012450B CN 103012450 B CN103012450 B CN 103012450B CN 201210537507 A CN201210537507 A CN 201210537507A CN 103012450 B CN103012450 B CN 103012450B
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gadolinium compound
ferroelectric
magnetic refrigeration
gadolinium
ethanol
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CN103012450A (en
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程鹏
王玉霞
师唯
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Nankai University
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Nankai University
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Abstract

The invention discloses a gadolinium compound with dual functions of a magnetic refrigeration function and a ferroelectric function. The chemical formula of the gadolinium compound is shown as follows: [Gd3(HL)(H2L)(NO3)4].C2H5OH, wherein H4L is N, N, N', N'-tetrahydroxyethyl-ethylene diamine; the EtOH is ethanol; and the gadolinium compound has three Gd atoms with different coordination environments, so that an isosceles triangle structure is formed. The preparation method for the gadolinium compound comprises the following steps of: using hexahydrate gadolinium nitrate as metal salt; using H4L as ligand; using LiOH alkali substance to regulate the pH of the mixed solution to 7; and stirring and baking the mixed solution, and separating out the solid and washing the separated solid to obtain the gadolinium compound. The invention has the advantages that the gadolinium compound has excellent magnetic refrigeration and excellent ferroelectric properties, and so that the gadolinium compound has a giant potential value in low-temperature magnetic refrigeration and solid apparatuses such as a ferroelectric memory and the like.

Description

One has magnetic refrigeration and ferroelectric difunctional gadolinium compound and preparation method thereof
[technical field]
The present invention relates to magnetic refrigeration and ferroelectric bifunctional material, particularly one there is magnetic to freeze and ferroelectric difunctional gadolinium compound and preparation method thereof.
[background technology]
Lang Jiefei (P.Langevin) once mentioned in 1907, if paramagnetic substance is in adiabatic demagnetization process, temperature also can along with reduction.Analyze from magnetics mechanism, when by the action of a magnetic field magnetization, the magnetic order degree of the solid magnetic material containing paramagnetic ion is strengthened, and now magnetic entropy reduces, and externally releases heat; Otherwise by its degaussing, magnetic order degree declines, and now magnetic entropy will increase, and absorbs heat again from the external world.The thermal phenomenon that this magnetic ion material shows in magnetic field applying with removing process is called magnetothermal effect (magneto – caloriceffect, MCE).Nineteen twenty-seven, Derby (Debye) and Jack (Giauque) once foretold that prophesy can utilize this effect refrigeration.After this, Jack achieves adiabatic demagnetization refrigeration for 1933.From then on, great role has been played in low temperature field, pole (mK level is to 16K scope) magnetic refrigeration.Present low temperature magnetic Refrigeration Technique comparative maturity.The U.S., Japan, France all develop multiple low temperature magnetic refrigerator, for pole cold condition is created in various scientific research.Such as the spacecraft such as satellite, spaceship parameter detecting and number treatment system in, magnetic refrigeration be also used on helium liquefaction refrigerator.Meanwhile, in certain temperature range, the spontaneous polarization moment of dipole of ferroelectric material can change with the direction of executing electric field outward.High performance ferroelectric material is the functional materials that a class has wide application prospect, from current present Research, still developmental stage is in for the research and development application with high performance ferroelectric material. investigators select different ferroelectric materials to study, and constantly explore preparation technology, just up to the present also gratifying stage is not reached for the research of some performances of ferroelectric material.Along with the development of material, the R and D of people to multifunctional material receive much concern more.By magnetic with to be electrically combined in a material be a very challenging property, but thing also highly significant.
We once applied for a patent simultaneously possessing ferromagnetic, ferroelectric difunctional dysprosium single molecular magnets, the patent No.: ZL 201110026019.X, patent name: one has ferromagnetic, ferroelectric bifunctional dysprosium single molecular magnets and preparation method thereof.On this basis, we select the gadolinium ion of applicable magnetic refrigerating material condition to replace dysprosium ion, obtain one and have good magnetic refrigeration and ferroelectric difunctional gadolinium compound.
[summary of the invention]
The object of the invention is for the above-mentioned state of the art, one is provided to have magnetic refrigeration and ferroelectric difunctional gadolinium compound and preparation method thereof, this gadolinium compound has good magnetic refrigeration and ferroelectric property, provides good material for realizing having the multifunctional materials such as high-density city equipment and materials and ferroelectric memory concurrently.
Technical scheme of the present invention:
One has magnetic refrigeration and ferroelectric difunctional gadolinium compound, and its chemical formula is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5oH, wherein H 4l be N, N, N ', N '-tetrahydroxyethyl-ethylene diamine, EtOH are ethanol; There is the Gd atom of three kinds of different coordination environments in gadolinium compound, wherein Gd (1) and Gd (3) is nine coordinations, and Gd (2) is eight-coordinate, and three Metal Gd atomic buildings plane triangle, from the μ of two on part 3-O atom O (1) and O (2) lay respectively at plane triangle upper and lower and with three Gd Atomic coordinates, come from two μ on part in addition 2-O atom O (3) and O (4) distinguishes bridging Gd (1) and Gd (2) and Gd (2) and Gd (3), and does not have μ between Gd (1) and Gd (3) 2the bridging of-O atom, forms an isosceles triangular structure; Described gadolinium compound belongs to rhombic system, Pna2 1polarity spacer, α=β=γ=90 °.
Described in there is magnetic refrigeration and the preparation method of ferroelectric difunctional gadolinium compound, take gadolinium nitrate hexahydrate as metal-salt, with H 4l is part, and be that alkaline matter regulates pH with LiOH, synthesis step is as follows:
1) by mol ratio be the Gd (NO of 1:2 3) 36H 2o and H 4the mixture of L puts into container, and the ratio being then 24.98mg:1mmL according to mixture and the ratio of ethanol adds ethanol and obtains solution, then adds LiOH and regulator solution pH is 7, stirs 2h, obtain mixing solutions under normal temperature;
2) above-mentioned mixing solutions is smoked 72h at 100 DEG C, after taking out product, solid is separated;
3) with ethanol by above-mentioned solids wash 3-5 time, the colourless web crystal with magnetic refrigeration and ferroelectric difunctional gadolinium compound can be obtained.
Advantage of the present invention is: 1) the magnetic entropy variate of this gadolinium compound is 30.22J kg -1k – 1, show that this gadolinium compound can be applied to low-temperature magnetic refrigeration material; 2) this gadolinium compound shows good ferroelectric property, and go out to obtain dielectric difference peak at 510K, indicate this gadolinium compound and there is the high ferroelectric phase transition temperature to para-electric, because it has magnetic refrigeration and ferroelectric property simultaneously, therefore in the solid unit such as magnetic refrigeration and ferroelectric memory, there is very large potential using value.
[accompanying drawing explanation]
Fig. 1 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5the structure iron of the single crystal diffraction parsing of OH.
Fig. 2 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5oH variable field susceptibility lab diagram.
Fig. 3 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5oH magnetic entropy change lab diagram.
Fig. 4 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5electric hysteresis curve under OH room temperature.
Fig. 5 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5jie's thermogram of OH.
[embodiment]
Embodiment:
Have a preparation method for magnetic refrigeration and ferroelectric difunctional gadolinium compound, step is as follows:
By the Gd (NO of 225.5mg 3) 36H 2the container of putting into of the L of O, 273mg mixes, then adds the ethanol of 20mL, by LiOH adjust ph to 7, stirs 2h under normal temperature; Then 72h smoked by the baking oven putting into 100 DEG C, takes out product, separated by solid; Target compound is again with washing with alcohol 3 obtained colourless web crystal.The productive rate calculated based on Metal Gd is 46%.
The property representation of this gadolinium material:
1) structure determination of this compound:
Crystal structure determination adopts Supernova type X-ray single crystal diffraction instrument, uses through graphite monochromatised Mo-K alpha-ray for incident radiation source, with scan mode collects point diffraction, obtains unit cell parameters, utilize SHELXL-97 direct method to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined by ideal position calculating.Detailed axonometry data are in table 1.
The crystallographic data of table 1 title complex
Fig. 1 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5the structure iron of the single crystal diffraction parsing of OH, structure iron shows: the Gd atom that there are three kinds of different coordination environments in obtained gadolinium compound, Gd (1) and Gd (3) is nine coordinations, Gd (2) is eight-coordinate, three Metal Gd atomic buildings plane triangle, from the μ of two on part 3-O atom O (1) and O (2) lay respectively at plane triangle upper and lower and with three Gd Atomic coordinates, come from two μ on part in addition 2-O atom O (3) and O (4) distinguishes bridging Gd (1) and Gd (2) and Gd (2) and Gd (3), and does not have μ between Gd (1) and Gd (3) 2the bridging of-O atom, forms an isosceles triangular structure; Described gadolinium compound belongs to rhombic system, Pna2 1polarity spacer, α=β=γ=90 °.
2) the magnetic refrigeration property representation of this compound:
As shown in Figure 2, under 2K, 7T, the specific magnetising moment of this compound reaches its saturation value 21 N β to the variable field susceptibility test result of this material in 2K-10K temperature range.According to Maxwell's formula: the maximum magnetic entropy variable value of this material calculated is 30.22J kg -1k – 1, Fig. 3 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5oH magnetic entropy change lab diagram.
3) ferroelectric property of this material characterizes:
This bifunctional material has not only at room temperature recorded desirable electric hysteresis curve, and as shown in Figure 4, meanwhile, this material presents the dielectric difference peak of ferroelectric phase to paraelectric phase at 510K, and show the ferroelectricity of this material, Fig. 5 is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5jie's thermogram of OH.

Claims (2)

1. there is magnetic refrigeration and a ferroelectric difunctional gadolinium compound, it is characterized in that: chemical formula is [Gd 3(HL) (H 2l) (NO 3) 4] C 2h 5oH, as shown in Figure 1, wherein H 4l is n, N, N', N'-tetrahydroxyethyl-ethylene diamine, EtOH are ethanol; From two on part μ 3-O atom O (1) and O (2) lay respectively at plane triangle upper and lower and with three Gd Atomic coordinates, come from two on part in addition μ 2 -o atom O (3) and O (4) distinguishes bridging Gd (1) and Gd (2) and Gd (2) and Gd (3), and does not have between Gd (1) and Gd (3) μ 2the bridging of-O atom, forms an isosceles triangular structure; Described gadolinium compound belongs to rhombic system, pna2 1polarity spacer, a=28.3822 (6), b=14.9641 (3), c=9.0770 (2), α=β=γ=90 °.
2. there is magnetic refrigeration and the preparation method of ferroelectric difunctional gadolinium compound as claimed in claim 1, it is characterized in that: be metal-salt with gadolinium nitrate hexahydrate, with H 4l is part, and be that alkaline matter regulates pH with LiOH, synthesis step is as follows:
1) by mol ratio be the Gd (NO of 1:2 3) 36H 2o and H 4the mixture of L puts into container, and the ratio being then 24.98 mg: 1 mL according to mixture and the ratio of ethanol adds ethanol and obtains solution, then adds LiOH and regulator solution pH is 7, stirs 2 h, obtain mixing solutions under normal temperature;
2) above-mentioned mixing solutions is smoked 72 h at 100 DEG C, after taking out product, solid is separated;
3) with ethanol by above-mentioned solids wash 3-5 time, the colourless web crystal with magnetic refrigeration and ferroelectric difunctional gadolinium compound can be obtained.
CN201210537507.1A 2012-12-12 2012-12-12 Gadolinium compound with dual functions of magnetic refrigeration function and ferroelectric function and preparation method thereof Expired - Fee Related CN103012450B (en)

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CN104151365B (en) * 2014-07-18 2017-04-19 南开大学 Gd-Fe dissimilar metal compound with magnetic refrigerating function and preparation method thereof
CN104341443B (en) * 2014-11-02 2016-04-27 天津理工大学 A kind of 4f 3d dissimilar metal methanoic acid with magnetothermal effect
CN104499056B (en) * 2015-01-14 2017-01-18 厦门大学 Tetrahydroxy gadolinium oxide dihydrate and preparation and applications thereof
CN104610327B (en) * 2015-01-19 2017-06-16 南开大学 A kind of Gd coordination compound with high stability and magnetothermal effect high and preparation method thereof
CN106883252B (en) * 2017-03-21 2021-12-17 江汉大学 Annular gadolinium complex with high magnetic entropy change and preparation method thereof
JP2018199860A (en) * 2017-05-30 2018-12-20 株式会社フジクラ Gadolinium wire, and metal-coated gadolinium wire, heat exchanger and magnetic refrigeration device using the same
CN111292909B (en) * 2019-12-26 2021-07-23 西安交通大学深圳研究院 Fluorine-bridged rare earth molecular cluster magnetic refrigeration material and preparation method thereof

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