CN112175587B - Application of gadolinium carbonate dihydrate - Google Patents
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- CN112175587B CN112175587B CN202011127662.7A CN202011127662A CN112175587B CN 112175587 B CN112175587 B CN 112175587B CN 202011127662 A CN202011127662 A CN 202011127662A CN 112175587 B CN112175587 B CN 112175587B
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Abstract
An application of gadolinium carbonate dihydrate relates to a magnetic refrigeration material. The gadolinium carbonate dihydrate belongs to an orthorhombic system, has a space group Immm and a molecular formula Gd2(CO3)3·2H2O, unit cell parameter is 6.15, 9.29, 15.26, 871.9. The gadolinium carbonate dihydrate has a magnetocaloric effect of heat absorption and release along with the change of a magnetic field at ultralow temperature, and can be applied to the preparation of magnetic refrigeration materials. The synthesis device is simple, the preparation method is rapid and easy to operate, and the gadolinium carbonate dihydrate is a carbonate compound and has good thermal stability. Selecting rare earth Gd having a high spin ground state and a small magnetic anisotropy3+As cation, CO of small molecular weight is selected3 2‑The rare earth/ligand mass ratio is improved to improve the magnetic density, so that the magnetic refrigeration effect of the material is greatly improved, and the magnetic entropy value under the condition of a commercial magnetic field is higher than that of the conventional commercial magnetic refrigeration material.
Description
Technical Field
The invention relates to a magnetic refrigeration material, in particular to gadolinium (Gd) carbonate dihydrate2(CO3)3·2H2O) is used.
Background
The refrigeration technology has been invented for more than 100 years and widely applied to various industries, and the traditional refrigeration technology utilizes the refrigeration cycle of gas compression and expansion to refrigerate. With the improvement of living standard of people, the low efficiency of the traditional gas compression refrigerating machine can not meet the requirements of people. Freon, which came out in the 20 th century and 20 s, is widely used due to its excellent refrigerating performance, but its refrigerating efficiency is low and it destroys the ozone layer of the atmosphere, so it was soon banned, and people began to look for refrigerant without freon. Since the Ames laboratory, the department of energy in the United states, 1997, discovered that an alloy consisting of Gd, Si, Ge showed a large magnetocaloric effect at room temperature, the field of magnetic refrigeration began to move into the human field. Magnetic refrigeration is that a heat release process caused by adiabatic magnetization and a heat absorption process caused by adiabatic demagnetization are connected by using a cycle by utilizing a magnetocaloric effect, and compared with the traditional refrigeration technology, the magnetic refrigeration technology has the advantages of miniaturization, low noise, stability, reliability, high efficiency, energy conservation, no pollution and the like, is widely concerned, gradually becomes a research hotspot in the field of magnetic refrigeration, and has wide application prospects in the fields of space, nuclear technology and the like.
For a good magnetic refrigerant material, it is necessary to have a large magnetic entropy variation value, which requires magnetic molecules having a large ground spin state, a small magnetic anisotropy, a high magnetic density, a suitable magnetic exchange and a low energy excited spin state (m.evangelisi; o.roubau; e.palacios; a.cam shuttle; t.n.hooper; e.k.brechi; j.j.alonso; Cryogenic magnetic macromolecular impact in a Ferromagnetic Molecular Dimer [ J ] while high spin Metal complex Molecular magnets exhibit a larger MCE value than rare earth alloys, magnetic nanoparticles, especially in the very low temperature region, due to the long range interaction of the complexes, the reduction of magnetic zeoticity (r.simple et al; magnetic entropy variation of magnetic molecules [ g.70, 70, n.70, magnetic entropy J ] of the rare earth alloys, magnetic nanoparticles [ g. 12, 12973, n ] is avoided.
Disclosure of Invention
The invention aims to provide application of gadolinium carbonate dihydrate.
The gadolinium carbonate dihydrate belongs to an orthorhombic system, has a space group Immm and a molecular formula Gd2(CO3)3·2H2O, unit cell parameter is 6.15, 9.29, 15.26, 871.9.
The gadolinium carbonate dihydrate has a magnetocaloric effect of heat absorption and release along with the change of a magnetic field at ultralow temperature, and can be applied to the preparation of magnetic refrigeration materials.
The gadolinium carbonate dihydrate can be prepared by the following method:
mixing 1mmol of gadolinium nitrate hexahydrate, 6.25mmol of ammonium carbonate and 12mL of deionized water, uniformly stirring, transferring the solution into a 23mL pressure-resistant stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃ at the speed of 30 ℃/h, keeping the temperature for 5h, then cooling to room temperature at the speed of 30 ℃/h, filtering and washing, and drying at 80 ℃ for 24h to obtain white powder.
Crystal structure analysis: the crystal structure of the dihydrated gadolinium carbonate magnetic refrigeration material can be tested by an X-ray powder diffractometer, and the testing temperature is 298K.
The magnetic thermal effect research is carried out on a Quantum Design SQUID MPMS magnetometer, and the specific method comprises the following steps:
the test is carried out under the condition of 0-7T magnetic field within the temperature range of 2-10K. The magnetic entropy curve obtained by the integration method shows that the magnetic entropy value of the gadolinium carbonate dihydrate magnetic refrigeration material is increased along with the reduction of the temperature and the enhancement of the magnetic field, and the magnetic entropy value reaches the maximum value at the positions of T2K and delta H7T, and 61.96 J.kg-1·K-1The magnetic entropy value can reach 48.01 J.kg at 2K and a commercially available magnetic field delta H-3T-1·K-1。
In summary, Gd is used in the invention3+Using a method for regulating and controlling experiment temperature and reaction ratio to control CO as raw materials3 2-Is a ligand with Gd3+Performing coordination, and preparing the rare earth magnetic refrigeration material to obtain the gadolinium carbonate dihydrate magnetic refrigeration material (Gd)2(CO3)3·2H2O), the gadolinium carbonate dihydrate has the magnetocaloric effect of heat absorption and release along with the change of a magnetic field at ultralow temperature, and can be applied to the preparation of magnetic refrigeration materials.
The invention has the following remarkable advantages:
(1) the synthetic device of the gadolinium carbonate dihydrate is simple, the preparation method is quick, the operation is easy, and the synthetic application prospect is wide.
(2) Gadolinium carbonate dihydrate is a carbonate compound and has good thermal stability.
(3) The invention selects rare earth Gd with high spin ground state and smaller magnetic anisotropy3+As cation, CO of small molecular weight is selected3 2-The rare earth/ligand mass ratio is improved to improve the magnetic density, so that the magnetic refrigeration effect of the material is greatly improved, and the magnetic entropy value under the condition of a commercial magnetic field is higher than that of the conventional commercial magnetic refrigeration material.
Drawings
Figure 1 is an XRD spectrum of gadolinium carbonate dihydrate.
Fig. 2 is an SEM image of gadolinium carbonate dihydrate.
FIG. 3 is a graph of temperature-changing magnetic susceptibility of gadolinium carbonate dihydrate.
FIG. 4 is a graph of the temperature-varying field magnetization of gadolinium carbonate dihydrate.
FIG. 5 is a graph showing the change in magnetic entropy of gadolinium carbonate dihydrate.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
Example 1
The preparation process of the gadolinium carbonate dihydrate magnetic refrigeration material comprises the following steps: mixing 1mmol of gadolinium nitrate hexahydrate, 6.25mmol of ammonium carbonate and 12mL of deionized water, uniformly stirring, transferring the solution into a 23mL pressure-resistant stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃ at the speed of 30 ℃/h, keeping the temperature for 5h, then cooling to room temperature at the speed of 30 ℃/h, filtering and washing, and drying at 80 ℃ for 24h to obtain white powder.
Example 2 structural characterization
Structural characterization of the gadolinium carbonate dihydrate powder samples was performed using a Rigaku Ultima type IV X-ray powder diffractometer. Fig. 1 is an XRD pattern of a gadolinium carbonate dihydrate magnetic refrigeration material. As can be seen from fig. 1, the experimental diffraction peak of XRD (curve a) substantially coincides with XRD data (curve b) fitted to the single crystal structure. The characteristic diffraction peak has better peak shape and stable baseline, which indicates that the sample has no impure phase and higher purity.
Gadolinium carbonate dihydrate belongs to an orthorhombic system, space group Immm and molecular formula Gd2(CO3)3·2H2O, unit cell parameter is 6.15, 9.29, 15.26, 871.9.
A sample of gadolinium carbonate dihydrate powder was observed using a ZEISS Sigma scanning electron microscope. Fig. 2 is an SEM image of gadolinium carbonate dihydrate. As can be seen from fig. 2, gadolinium carbonate dihydrate is needle-shaped, and has a uniform crystal phase and good purity.
Example 3 magnetic testing
And testing the dihydrate gadolinium carbonate magnetic refrigeration material by adopting a Quantum Design SQUID MPMS magnetometer under the external magnetic field condition of the temperature range of 2-300K and 1000 Oe. Fig. 3 is a graph of temperature-changing magnetic susceptibility of a gadolinium carbonate dihydrate magnetic refrigeration material. And testing is carried out in the temperature range of 2-10K and under the condition of 0-7T magnetic field. Fig. 4 is a graph of the temperature-changing field magnetization of a gadolinium carbonate dihydrate magnetic refrigeration material. FIG. 5 is a graph of the magnetic entropy change of a gadolinium carbonate dihydrate magnetic refrigeration material.
FIG. 3 shows the χ of a gadolinium carbonate dihydrate magnetic refrigeration material at room temperatureMT value of 15.66cm3·K·mol-1And 2 uncoupled Gd calculated according to Curie's law3+Ion derived χMTheoretical value of T15.75 cm3·K·mol-1Are very close. Within the temperature range of 300-100K, as the temperature decreases chiMT value hardly changes, and χ is lower than 100KMThe T value begins to decrease slowly, and as the temperature is lower, the chiMThe faster the T value decreases, when the temperature reaches 2K, the χMT value of 13.49cm3·K·mol-1. Within the test interval, for chiMThe curves from T to T are fitted according to the Curie-Weiss theorem to obtain: curie constant C15.73 cm3·K·mol-1The exos constant theta is-0.16K, and the negative exos constant also illustrates the antiferromagnetic coupling effect of the gadolinium carbonate dihydrate magnetic refrigeration material from the side.
FIG. 4 shows that the magnetization intensity of the gadolinium carbonate dihydrate magnetic refrigeration material gradually increases with the increase of the magnetic field intensity, and reaches a saturation value of 13.98N mu at the temperature of 2K and the magnetic field of 7TΒAnd a theoretical value of 14N muΒAre very close.
The magnetic entropy change of the gadolinium carbonate dihydrate magnetic refrigeration material can be determined according to the Maxwell formula:
the magnetization data of the temperature-changing field (i.e., fig. 4) were used for estimation, and the results are shown in fig. 5.
Fig. 5 shows that, in the test range, the gadolinium carbonate dihydrate magnetic refrigeration material reaches the maximum- Δ S at T2K and Δ H7TMValue 61.96J kg-1·K-1This value is smaller than with two isolated Gd3+Theory of (S-7/2) ion calculationTheoretical value
The reduction in magnetic entropy may be due to antiferromagnetic interactions between the compounds. Under the condition of applicable magnetic field range of T2K and Δ H3T, the magnetic entropy change value can still reach 48.01 J.kg-1·K-1。
Researches prove that the gadolinium carbonate dihydrate has high magnetic entropy value at ultralow temperature, embodies the great potential of the gadolinium carbonate dihydrate as an ultralow-temperature magnetic refrigeration material, and has wide application prospect in the fields of replacing expensive inert gas to carry out low-temperature magnetic refrigeration and the like.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (2)
1. The application of gadolinium carbonate dihydrate in preparing magnetic refrigeration materials is characterized in that the gadolinium carbonate dihydrate is prepared by the following method:
mixing 1mmol of gadolinium nitrate hexahydrate, 6.25mmol of ammonium carbonate and 12mL of deionized water, uniformly stirring, transferring the solution into a 23mL pressure-resistant stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃ at the speed of 30 ℃/h, keeping the temperature for 5h, then cooling to room temperature at the speed of 30 ℃/h, filtering and washing, and drying at 80 ℃ for 24h to obtain white powder.
2. The use according to claim 1, wherein said gadolinium carbonate dihydrate belongs to the orthorhombic system, space group Immm, formula Gd2(CO3)3·2H2O, unit cell parameter is 6.15, 9.29, 15.26, 871.9.
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| CN101462759A (en) * | 2008-11-06 | 2009-06-24 | 广东海洋大学 | Preparation of rare-earth oxide nano magnetic refrigeration material |
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