CN104531085A - Application of gadolinium hydroxide - Google Patents
Application of gadolinium hydroxide Download PDFInfo
- Publication number
- CN104531085A CN104531085A CN201510016787.5A CN201510016787A CN104531085A CN 104531085 A CN104531085 A CN 104531085A CN 201510016787 A CN201510016787 A CN 201510016787A CN 104531085 A CN104531085 A CN 104531085A
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- gadolinium hydroxide
- magnetic
- gadolinium
- hydroxide
- temperature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Abstract
Provided is an application of gadolinium hydroxide. The invention relates to the gadolinium hydroxide. The gadolinium hydroxide belongs to the hexagonal crystal system. The space group of the gadolinium hydroxide is P63/m, the molecular formula is Gd(OH)3, the cell parameters are a=6.2993, b=6.2993, c=3.6057, V=123.91. The gadolinium hydroxide has the magnetothermal effect of heat absorbing and heat releasing in accordance with the changes of a magnetic field, and applicable to the preparation of magnetic refrigeration materials. The high magnetothermal effect of the gadolinium hydroxide is created under a super low temperature and a weak magnetic field. The gadolinium hydroxide has a promising application prospect in fields of replacing expensive inert gases to conduct low temperature magnetic refrigeration and the like.
Description
Technical field
The present invention relates to gadolinium hydroxide, especially relate to gadolinium hydroxide (Gd (OH)
3) application.
Background technology
Traditional vapor compression refrigeration technology is widely used in daily life, but improving constantly along with people's living standard, the poor efficiency that traditional gas compression refrigerator has can not meet the requirement of people.Meanwhile, the refrigeration agent freonll-11 used by conventional chiller also can havoc ozonosphere, and people start to seek a kind of novel Refrigeration Technique, has both the energy-efficient and large advantage of non-environmental-pollution two.1997, USDOE Ames Laboratory found that a kind of alloy be made up of Gd, Si, Ge can at room temperature demonstrate huge magnetothermal effect, and since then, Astronics Corp starts to research and develop one and do not use compressor, and based on the novel refrigerating machine of magnet.Because it is compared with traditional vapor compression refrigeration refrigerator, has and do not need compressor, vibrations noise is little; Reliability is high, and the work period is long; Efficiently, pollution-free; Working temperature and the advantage such as cold scope is wide, people have dropped into more attention rate to magnetic refrigerating field since then, and the research of magnetic refrigeration is also progressively to the low temperature magnetic refrigeration research transition based on coordination compound.
Must have comparatively great magnetic entropy variation value to a good magnetic refrigerating material, it requires that magnetic molecule has large spin ground states, little magneticanisotropy, high magnetic density, suitable magnetic exchange and low-energyly excites spin state (M.Evangelisti; O.Roubeau; E.Palacios; A.Cam ó n; T.N.Hooper; E.K.Brechin; J.J.Alonso; CryogenicMagnetocaloric Effect in a Ferromagnetic Molecular Dimer [J] .Angew.Chem.Int.Ed., 2011,50,6606-6609.).And the metal complexes molecular magnet of high-spin shows larger MCE value than rare earth alloy, magnetic nanometer particles, particularly in very low temperature region territory, due to the long-range order of title complex, weak molecular interaction can avoid magnetic entropy to become reduction (R.Sibille; T.Mazet; B.Malaman; M.Francois; A Metal-Organic Frameworkas Attractive Cryogenic Magnetorefrigerant [J] .Chem.Eur.J.; 2012,18,12970-12973).
Summary of the invention
The object of the present invention is to provide the application of gadolinium hydroxide.
Described gadolinium hydroxide belongs to hexagonal system, spacer P6
3/ m, molecular formula is Gd (OH)
3, unit cell parameters is a=6.2993, b=6.2993, c=3.6057, V=123.91.
Gadolinium hydroxide has and occurs to inhale the magnetothermal effect of heat release with changes of magnetic field, can apply preparing in magnetic refrigerating material.
Utilize X-ray single crystal diffraction instrument to carry out single crystal structure test to gadolinium hydroxide material, probe temperature is 100K.Gadolinium hydroxide is by Gd
3+and OH
-to carry out coordination synthesis to obtain.Can learn from ray crystallographic analysis, control Gd
3+and OH
-carry out coordination, simply prepare the magnetic refrigerating material under condition of ultralow temperature with remarkable magnetothermal effect, concrete steps are as follows:
1mmol gadolinium sesquioxide is mixed with the 15mL sodium hydroxide solution (concentration 25mol/L) of brand-new, stir, solution is transferred in the withstand voltage stainless steel cauldron of 23mL inner liner polytetrafluoroethylene, 250 DEG C are warming up to and constant temperature 7000min with the speed of 45 DEG C/h, then naturally room temperature is dropped to, filtration washing, obtains colourless acicular crystal.
Quantum Design SQUID MPMS magnetometer has carried out magnetothermal effect research to gadolinium hydroxide material, and concrete grammar is as follows:
In 2 ~ 10K temperature range, test under the 0 ~ 7T condition of magnetic field.Obtain magnetic entropy curve by integration process known along with temperature reduction, magnetic field enhancing, the magnetic entropy value of gadolinium hydroxide material raises, and at 2K Δ H=7T place, magnetic entropy value reaches maximum, 62.00J kg
-1k
-1(346.08mJ cm
-3k
-1), also can reach 42.14J kg by applying a magnetic field Δ H=3T place magnetic entropy at 2K and business
-1k
-1(235.23mJ cm
-3k
-1).
To sum up, the present invention is with Gd
3+for raw material, the OH of small-molecular-weight
-as main part, utilize the method control Gd of regulation and control pH value, experimental temperature and ligand decomposes
3+and OH
-carry out coordination, carry out the preparation of Rare-Earth Magnetic refrigerating material, obtain gadolinium hydroxide material (Gd (OH)
3).Research proves, gadolinium hydroxide has high magnetothermal effect under very low temperature, low-intensity magnetic field, carries out the fields such as low temperature magnetic refrigeration have broad application prospects at the rare gas element replacing costliness.
Remarkable advantage of the present invention is:
1, the synthesizer of gadolinium hydroxide is simple, and preparation method is quick, and easy handling, is convenient to a large amount of synthesis, has larger synthesis application prospect.
2, the present invention is mainly oxy-compound, under from weak acid to strong alkali environment, all have extremely strong stability, Heat stability is good.
3, the present invention selects the rare-earth Gd with high spin ground state and less magneticanisotropy
3+as positively charged ion, select the OH of small-molecular-weight
-as major ligand, improve the mass values of rare earth/part to improve magnetic density, make the magnetic refrigeration effect of material have great lifting, the magnetic entropy value under commercial magnetic field condition is higher than existing business magnetic refrigerating material.
The present invention selects the rare-earth Gd with high spin ground state and less magneticanisotropy
3+as positively charged ion, select the OH of small-molecular-weight
-as part, improve the mass values of rare earth/part to improve magnetic density.The present invention finds, with rare-earth Gd
3+and OH
-be that the compound of main synthesis has high magnetic entropy under very low temperature, embody its very high potential as low-temperature magnetic refrigeration material, there is important investigation and application prospect.
Accompanying drawing explanation
Fig. 1 is the asymmetric cell structure iron of gadolinium hydroxide.
Fig. 2 is the three-dimensional frame structure figure of gadolinium hydroxide.
Fig. 3 is the XRD spectra of gadolinium hydroxide.
Fig. 4 is the variable temperature magnetic susceptibility figure of gadolinium hydroxide.
Fig. 5 is the alternating temperature variable field specific magnetising moment figure of gadolinium hydroxide.
Fig. 6 is the magnetic entropy change figure of gadolinium hydroxide.
Embodiment
Below by embodiment, the invention will be further described by reference to the accompanying drawings.
Embodiment 1
The preparation process of gadolinium hydroxide material: 1mmol gadolinium sesquioxide is mixed with the 15mL sodium hydroxide solution (concentration 25mol/L) of brand-new, stir, solution is transferred in the withstand voltage stainless steel cauldron of 23mL inner liner polytetrafluoroethylene, 250 DEG C are warming up to and constant temperature 7000min with the speed of 45 DEG C/h, then naturally room temperature is dropped to, filtration washing, obtains colourless acicular crystal.
Embodiment 2
Sample characterization:
1, monocrystalline test:
The single crystal samples structure of gadolinium hydroxide material adopts Agilent Super Nova Diffractometer X-ray single crystal diffractometer to collect under 100K and obtains.
2, gadolinium hydroxide material: belong to hexagonal system, spacer P6
3/ m, molecular formula is Gd (OH)
3, unit cell parameters is a=6.2993, b=6.2993, c=3.6057, V=123.91.As illustrated in fig. 1 and 2, each asymmetric cell comprises 1/6 Gd to its structural coordinates pattern
3+ion and 1/2 OH
-ion.Each Gd
3+ion is with the mode of nine coordinations and nine μ
3-OH
-coordination forms tetrakaidecahedron configuration.Each OH
-ion and three Gd
3+bridging, forms three-dimensional frame structure.Gd-O bond distance exists
in scope, Gd-O-Gd bond angle is 95.4 ° ~ 112.3 °, and the spacing of GdGd is respectively
with
Structural characterization:
Rigaku Ultima IV type x-ray powder diffraction instrument is adopted to carry out structural characterization to powdered sample.Fig. 3 is the XRD spectra of gadolinium hydroxide material.As can be seen from Figure 3, its XRD experimental diffraction peak (As Synthesized) (curve a) with basically identical according to the XRD data (Simulated) (curve b) of single crystal structure matching.Each characteristic diffraction peak peak shape is better, and baseline is relatively more steady, and interpret sample is without dephasign, and purity is higher, and crystalline phase is good.
Embodiment 3
Magnetic Test
Test under the foreign field condition adopting Quantum Design SQUID MPMS magnetometer to be 2 ~ 300K and 1000Oe to gadolinium hydroxide material in temperature range.Fig. 4 is the variable temperature magnetic susceptibility figure of gadolinium hydroxide material.And in 2 ~ 10K temperature range, test under the 0 ~ 7T condition of magnetic field.Fig. 5 is the alternating temperature variable field specific magnetising moment figure of gadolinium hydroxide material.Fig. 6 is the magnetic entropy change figure of gadolinium hydroxide material.
Fig. 4 shows, at room temperature, and gadolinium hydroxide material
mt value is 8.00cm
3mol
-1k, calculates 1 Gd be not coupled with according to Curie's theorem
3+ion obtains
mt theoretical value 7.88cm
3mol
-1k ten points is close.In 300 ~ 100K temperature range, along with temperature declines
mt value has almost no change, during lower than 100K,
mt value starts slowly to decline, along with temperature is lower,
mt value declines faster, when temperature reaches 2K, its
mt value is 3.32cm
3k mol
-1.Within the scope of 50-300K, right
mthe curve of T ~ T carries out matching according to Curie-weiss theorem, can obtain: Curie constant C=8.18cm
3k mol
-1, Weiss constant=-1.69K, negative Weiss constant also from the side on describe the anti-ferromagnetic coupling interaction of gadolinium hydroxide material.
Fig. 5 shows, and along with the enhancing of magneticstrength, the specific magnetising moment of gadolinium hydroxide material increases gradually, and the value 6.99N that reaches capacity when temperature 2K, magnetic field 7T
b, and theoretical value 7N
bunanimously.
The magnetic entropy change of gadolinium hydroxide material can according to Maxwell formula:
estimate with the magnetization data (i.e. Fig. 5) of alternating temperature variable field, acquired results is as Fig. 6.
Fig. 6 shows, and in test specification, gadolinium hydroxide material reaches maximum-Δ Sm value 62.00J kg when T=2.5K, Δ H=7T
-1k
-1(346.08mJ cm
-3k
-1), this value is less than us and utilizes an isolated Gd
3+(S=7/2) theoretical value-Δ Sm=nRln (2s+1)/Mw=Rln (the 8)/Mw=83.01J kg of ion calculating
-1k
-1(463.36mJ cm
-3k
-1).The reduction of magnetic entropy value may be due to compound metal between antiferromagnetic reaction cause.T=2.5K, Δ H=3T can under applying a magnetic field range of condition, magnetic entropy variate still can reach 42.14J kg
-1k
-1(235.23mJ cm
-3k
-1), be significantly higher than the magnetic entropy variate 24J kg of business-like GGG under the condition of Δ H=3T
-1k
-1(173mJ cm
-3k
-1).
The present invention utilizes simple part, by regulating and controlling the method control Gd of pH value, experimental temperature and pressure
3+and OH
-carry out coordination, reacting by heating in withstand voltage stainless steel cauldron, obtain crystalline state gadolinium hydroxide material (Gd (OH)
3).Wherein there is the rare-earth Gd of high spin ground state and less magneticanisotropy
3+as positively charged ion, the OH of small-molecular-weight
-as major ligand, the mass values of great raising rare earth/part, compound magnetic density is high, makes such bill of material reveal significant magnetic refrigeration effect, magnetic entropy value under commercial magnetic field condition higher than existing business magnetic refrigerating material, has great application prospect.
Claims (1)
1. gadolinium hydroxide is applied preparing in magnetic refrigerating material.
Priority Applications (1)
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|---|---|---|---|
| CN201510016787.5A CN104531085A (en) | 2015-01-14 | 2015-01-14 | Application of gadolinium hydroxide |
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|---|---|---|---|
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Family
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112456535A (en) * | 2020-11-24 | 2021-03-09 | 厦门大学 | Gadolinium oxyfluoride and preparation method and application thereof |
| CN113277545A (en) * | 2021-05-12 | 2021-08-20 | 厦门大学 | Gadolinium fluorocarbonate, and preparation method and application thereof |
Citations (6)
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| CN103320859A (en) * | 2013-05-24 | 2013-09-25 | 中山大学 | Orthorhombic phase Gd(OH)CO3, preparation method and application thereof |
| US20140116067A1 (en) * | 2006-03-27 | 2014-05-01 | Kabushiki Kaisha Toshiba | Magnetic material for magnetic refrigeration |
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2015
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Patent Citations (6)
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| US4332135A (en) * | 1981-01-27 | 1982-06-01 | The United States Of America As Respresented By The United States Department Of Energy | Active magnetic regenerator |
| JPS62128921A (en) * | 1985-11-26 | 1987-06-11 | Takakuni Hashimoto | Magnetic material |
| US20140116067A1 (en) * | 2006-03-27 | 2014-05-01 | Kabushiki Kaisha Toshiba | Magnetic material for magnetic refrigeration |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112456535A (en) * | 2020-11-24 | 2021-03-09 | 厦门大学 | Gadolinium oxyfluoride and preparation method and application thereof |
| CN113277545A (en) * | 2021-05-12 | 2021-08-20 | 厦门大学 | Gadolinium fluorocarbonate, and preparation method and application thereof |
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Application publication date: 20150422 |
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