CN115557513A - Gadolinium-based borate compound, preparation and application thereof - Google Patents

Gadolinium-based borate compound, preparation and application thereof Download PDF

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CN115557513A
CN115557513A CN202211267139.3A CN202211267139A CN115557513A CN 115557513 A CN115557513 A CN 115557513A CN 202211267139 A CN202211267139 A CN 202211267139A CN 115557513 A CN115557513 A CN 115557513A
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涂衡
陈语葳
沈俊
戴巍
李振兴
张国春
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention provides a gadolinium-based borate compound, and a preparation method and application thereof. The gadolinium-based borate compound has the chemical formula of Ba 2 Gd(BO 3 ) 2 F, belonging to an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:
Figure DEST_PATH_BDA0003893834260000011
α = β = γ =90 °, Z =2. The gadolinium-based borate compound is used in the magnetic cation Gd 3+ Has higher spin ground state and smaller magnetic anisotropy under the introduction of (B) and is simultaneously magnetic cation Gd 3+ Providing ligands of smaller volume and relative molecular mass, favourably Gd 3+ Providing as much as possibleThe filling space improves the magnetic density of the crystal, so that the crystal has larger magnetic entropy change value and higher refrigeration efficiency, and provides guiding significance for practical application.

Description

Gadolinium-based borate compound, preparation and application thereof
Technical Field
The invention belongs to the technical field of magnetic refrigeration materials, and particularly relates to a gadolinium-based borate compound, and preparation and application thereof.
Background
The low-temperature refrigeration technology plays an important role in the fields of gas liquefaction, high-energy physics, superconducting technology, aerospace and the like. At present, the low temperature is mainly obtained and maintained by using the compression-expansion cycle of liquid helium, but the efficiency is low, the reliability is not high, and rare and expensive helium-3 is generally used in a temperature range below 2K, so that the research and the application of a low-temperature region are limited.
The magnetic refrigeration technology has the advantages of high efficiency, low energy consumption and environmental protection, is known as the green refrigeration technology, is valued by various countries in the world, utilizes the magnetocaloric effect, mainly depends on the isothermal magnetization and the adiabatic demagnetization process to realize the cooling of the surrounding environment, and particularly uses the magnetic entropy change generated by the change of a magnetic substance in an isothermal state along with the change of an external magnetic field to measure. When the external magnetic field is zero, the magnetic moment directions in the material are disordered, and the magnetic entropy is large; when a magnetic field is applied under the isothermal condition, the magnetic moment orientations tend to be consistent, the magnetic entropy is reduced, and the magnetic field applies work to the material to raise the heat insulation temperature of the system and release heat to the environment; then the external magnetic field is removed under the adiabatic condition, the magnetic moment returns to the disordered state, the magnetic entropy is increased, the adiabatic temperature of the system is reduced, and the heat is absorbed to the external environment, thereby achieving the aim of refrigeration.
For a magnetic refrigeration material with excellent performance, a large magnetic entropy change value is necessary, and magnetic molecules are required to have a large spin ground state, small magnetic anisotropy, high magnetic density, proper magnetic exchange and a low-energy excited spin state. Gd (Gd) 3+ The ions have a half-filled 4f electron shell layer, the ground state spin is large, the magnetic anisotropy is negligible, the gadolinium-based compound can be used as a good low-temperature magnetic refrigeration material, the borate has high thermal stability and high thermal conductivity, and the paramagnetic salt has low hysteresis effect and can be used as a good magnetic refrigeration material.
Therefore, the research on the application of the novel gadolinium-based borate compound in the field of magnetic refrigeration has very important significance.
Disclosure of Invention
A first object of the present invention is to provide a gadolinium borate compound. The gadolinium-based borate compound is used in the magnetic cation Gd 3+ Has higher spin ground state and smaller magnetic anisotropy under the introduction of (B) and is simultaneously magnetic cation Gd 3+ Providing ligands of smaller volume and relative molecular mass, advantageously Gd 3+ The filling space is provided as much as possible, the crystal magnetic density is improved, the crystal magnetic density has larger magnetic entropy change value and higher refrigeration efficiency, and the guiding significance is provided for practical application.
It is a second object of the present invention to provide a process for preparing a gadolinium-based borate compound as described above.
The invention also provides the application of the gadolinium-based borate compound in the field of magnetic refrigeration.
In order to achieve the first object, the invention adopts the technical scheme that:
the invention discloses a gadolinium-based borate compound, which has a chemical formula of Ba 2 Gd(BO 3 ) 2 F, belonging to an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:
Figure BDA0003893834260000011
α＝β＝γ＝90°，Z＝2。
in order to further expand the selection of the types of the gadolinium-based borate compounds as magnetic refrigeration materials, gd is used in the invention 3+ Is a magnetic cation, BO of small molecular weight 3 3- The gadolinium-based borate compound is successfully synthesized as a ligand. Ligand BO with small volume and relative molecular mass when constructing basic framework of compound 3 3- Is magnetic cation Gd with larger volume 3+ Providing as much space as possible while ensuring that there is a certain spacing between magnetic cations for less magnetic interaction, and increasing the rare earth/ligand mass ratio as much as possibleHigh crystal magnetic density, and at the same time, small molecular weight BO 3 3- As a ligand, the method can also reduce the processing difficulty of the crystal in the practical application process and improve the refrigeration stability of the crystal. Through reasonable element collocation, the magnetic refrigeration material is more suitable for a lower-temperature 2K magnetic field system, has higher magnetic entropy change value and refrigeration efficiency compared with the magnetic refrigeration material in the prior art, and is a magnetic refrigeration material with excellent performance.
In order to achieve the second object, the invention adopts the technical scheme that:
the invention discloses a method for preparing the gadolinium-based borate compound, which comprises the following steps:
uniformly mixing a Ba-containing compound, a Gd-containing compound, a B-containing compound and a F-containing compound, uniformly heating to 650-700 ℃ in an aerobic environment, presintering at a constant temperature, cooling for one time, and grinding; and under the vacuum environment, raising the temperature to 770-780 ℃ at a constant speed, reacting at a constant temperature, cooling for the second time, and grinding to obtain the gadolinium-based borate crystal.
Further, in the Ba-containing compound, the Gd-containing compound, the B-containing compound, and the F-containing compound, the molar ratio of the elements Ba, gd, B, and F is 1-3; preferably, when the molar ratio of the elements Ba, gd, B and F in the Ba-containing compound, gd-containing compound, B-containing compound and F-containing compound is 2 2 Gd(BO 3 ) 2 And F compound.
Further, the Ba-containing compound is selected from a Ba-containing carbonate or a Ba-containing fluoride; preferably, the Gd-containing compound is selected from Gd-containing oxides; preferably, the B-containing compound is selected from H 3 BO 3 Or B 2 O 3 (ii) a Preferably, the F-containing compound is BaF 2 (ii) a Preferably, the source of O is selected from BaCO 3 、Gd 2 O 3 、H 3 BO 3 、B 2 O 3 One or more of them.
Further, the heating rate of the constant-speed heating or the constant-speed heating again is 30-40 ℃/h.
Further, the constant temperature pre-heatingThe burning time is 2-3 days. Wherein the constant-temperature calcination aims at removing H in reactants 2 O and CO 2 And carrying out a preliminary solid-phase reaction, wherein the aerobic environment is preferably an air atmosphere.
Further, the primary cooling is carried out at a cooling rate of 40-50 ℃/h.
Further, the secondary cooling is carried out at a cooling rate of 30-40 ℃/h.
In order to achieve the third object, the invention adopts a technical scheme that:
the invention discloses an application of the gadolinium-based borate compound or the gadolinium-based borate compound obtained by the preparation method in the field of magnetic refrigeration.
Further, when the gadolinium-based borate compound is applied to a magnetic field system under the condition of 2K, the refrigeration effect can be optimal.
The invention has the beneficial effects that:
the invention provides a gadolinium-based borate compound, and a preparation method and application thereof. In order to further expand the selection of the types of the gadolinium-based borate compounds as magnetic refrigeration materials, gd is used in the invention 3+ Is a magnetic cation, BO of small molecular weight 3 3- The gadolinium-based borate compound is successfully synthesized as a ligand. Ligand BO with small volume and relative molecular mass when constructing basic framework of compound 3 3- Is magnetic cation Gd with larger volume 3+ Providing as much space as possible, ensuring that certain space exists between magnetic cations to reduce magnetic interaction, improving the mass ratio of rare earth/ligand as much as possible to improve the magnetic density of the crystal, and simultaneously, BO with small molecular weight 3 3- As a ligand, the processing difficulty of the crystal in the practical application process can be reduced, and the refrigeration stability of the crystal can be improved. Through reasonable element collocation, the magnetic refrigeration material is more suitable for a lower-temperature 2k magnetic field system, has higher magnetic entropy change value and refrigeration efficiency compared with the magnetic refrigeration material in the prior art, and is a magnetic refrigeration material with excellent performance.
Drawings
FIG. 1 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 XRD pattern of F.
FIG. 2 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 And F is a structural schematic diagram.
FIG. 3 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 F infrared spectrum.
FIG. 4 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 Thermogravimetric plot of F.
FIG. 5 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 F, a variable temperature magnetic susceptibility curve and a Curie-Weiss fitting curve graph.
FIG. 6 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 And F, a temperature-changing field-changing magnetization diagram.
FIG. 7 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 Arrott plot of F.
FIG. 8 shows crystalline Ba prepared in example 1 2 Gd(BO 3 ) 2 And F, a magnetic entropy change graph.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of powdered Ba by high-temperature solid-phase method 2 Gd(BO 3 ) 2 F crystal, comprising the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 :0.56g (8 mmol) of the resulting mixture was mixed, charged into a platinum crucible having a diameter of 20 mm. Times.20 mm, compacted, and placed in a muffle furnaceHeating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering at a constant temperature for 2d, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a primary presintering product. Then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder samples of F crystals.
Ba prepared in this example 2 Gd(BO 3 ) 2 The crystal samples were tested as follows:
structural characterization:
XRD was used to obtain Ba in this example 2 Gd(BO 3 ) 2 The F crystal is characterized, and the result is shown in figure 1, in which Ba is shown 2 Gd(BO 3 ) 2 F belongs to an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:
Figure BDA0003893834260000031
Figure BDA0003893834260000032
α＝β＝γ＝90°，Z＝2。
ba produced in this example 2 Gd(BO 3 ) 2 The structural diagram of F is shown in figure 2.
FIG. 3 shows Ba obtained in this example 2 Gd(BO 3 ) 2 The characterization result of the infrared spectrum of the F crystal is shown in the figure, BO 3 3- Has asymmetric stretching vibration peaks at 1262 and 1199cm -1 ，BO 3 3- The symmetric telescopic vibration peak of the vibration sensor is 935cm -1 ，BO 3 3- Located at 739 and 594cm -1 . The infrared spectrum shows Ba 2 Gd(BO 3 ) 2 B in the F crystal is BO 3 It is consistent with the actual structure.
And (3) testing thermal stability:
the Ba 2 Gd(BO 3 ) 2 The thermogravimetric analysis result of the F crystal is shown in FIG. 4, which shows that the crystal material is in the temperature range from room temperature to 1150 deg.CThe stability in the enclosure is good, and phase change and mass loss do not exist.
And (3) magnetic testing:
the following magnetocaloric effect studies are carried out by adopting a Quantum Design PPMS-9 comprehensive physical property system in the range of 2K-300K and under the condition of a magnetic field of 0T-9T:
ba is measured in the temperature range of 2K-300K and the magnetic field range of 0-9T 2 Gd(BO 3 ) 2 The temperature-changing magnetic susceptibility and the inverse temperature-changing magnetic susceptibility curves of the F crystal are shown in FIG. 5. Performing linear fitting on the reciprocal curve of the variable-temperature susceptibility according to the Curie-Weiss theorem to obtain the compound as a paramagnetic salt material with a Curie constant of C =7.47emu K mol -1 Exos constant θ =2.13K, positive exos constant accounting for Ba 2 Gd(BO 3 ) 2 The extremely weak ferromagnetic coupling effect of the F crystal is suitable for being used as a magnetic refrigeration material.
Ba measured in a temperature range of 2K to 10K and a magnetic field range of 0 to 9T 2 Gd(BO 3 ) 2 The temperature and field changing magnetization diagram of the F crystal is shown in FIG. 6. The curves show that Ba increases with increasing magnetic field strength 2 Gd(BO 3 ) 2 The magnetization of the F crystal gradually increases and reaches a saturation value of 6.77N mu at a temperature of 2K and a magnetic field of 9T Β And theoretical value of 7N mu Β Are very close.
Ba 2 Gd(BO 3 ) 2 The phase transition type of the F crystal can be determined according to the Banerjee criterion: the magnetization data of the temperature-variable field is used for estimation, the obtained result is shown as an Arrott curve of figure 7, and the slope of each point on the curve is positive, which indicates that the magnetic phase change of the crystal material belongs to a second-order magnetic phase change.
Ba 2 Gd(BO 3 ) 2 The magnetic entropy change of the F crystal can be determined according to Maxwell formula: the magnetization data of the temperature-changing and field-changing is used for estimation, the obtained result is shown as the magnetic entropy curve of figure 8, and the crystal material in the test range is 2K, delta mu 0 The maximum magnetic entropy change value is 27.82J kg when H =9T -1 K -1 。
Example 2
Preparation of powdered Ba by high-temperature solid-phase method 2 Gd(BO 3 ) 2 F crystal, comprising the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，H 3 BO 3 :0.99g (16 mmol) of the mixture is uniformly mixed, the mixture is put into an open platinum crucible with the diameter of 20mm multiplied by 20mm, the crucible is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at the heating rate of 30 ℃/h in the air environment, the mixture is presintered for 2 days at constant temperature, the mixture is cooled to room temperature at the heating rate of 50 ℃/h, and a primary presintering product is obtained after grinding. Then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder samples of F crystals.
XRD was used to obtain Ba 2 Gd(BO 3 ) 2 The F crystal is characterized, and the result is basically consistent with that of the example 1.
Example 3
Preparation of powdered Ba by high-temperature solid-phase method 2 Gd(BO 3 ) 2 F crystal, comprising the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，H 3 BO 3 :0.49g (8 mmol) and B 2 O 3 :0.28g (4 mmol) of the mixture is uniformly mixed, the mixture is put into a platinum crucible with an opening diameter of 20mm multiplied by 20mm, the crucible is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at the heating rate of 30 ℃/h in the air environment, the mixture is presintered for 2 days at a constant temperature, the mixture is cooled to the room temperature at the heating rate of 50 ℃/h, and a primary presintering product is obtained after grinding. Then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder samples of F crystals.
XRD was used to obtain Ba in this example 2 Gd(BO 3 ) 2 The F crystal is characterized, and the result is basically consistent with that of the example 1.
Example 4
Preparation of powdered Ba by high-temperature solid-phase method 2 Gd(BO 3 ) 2 F crystal, comprising the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，H 3 BO 3 :0.49g (8 mmol) and B 2 O 3 :0.28g (4 mmol) of the mixture is uniformly mixed, the mixture is put into a platinum crucible with an opening diameter of 20mm multiplied by 20mm, the crucible is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at the heating rate of 30 ℃/h in the air environment, the mixture is presintered for 1d at a constant temperature, the mixture is cooled to the room temperature at the heating rate of 50 ℃/h, and a primary presintering product is obtained after grinding. Then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder samples of F crystals.
XRD was used to obtain Ba 5 Gd 3 (BO 3 ) 6 F, characterization is carried out, and the result is basically consistent with example 1.
Comparative example 1
The high-temperature solid-phase method is adopted to prepare the crystal, and comprises the following steps:
weighing BaCO 3 ：2.37g(12mmol)，Gd 2 O 3 ：0.72g(2mmol)，GdF 3 :0.43g (2 mmol) and B 2 O 3 :0.42g (6 mmol) of the mixture is uniformly mixed, the mixture is put into an opening platinum crucible with the diameter of 20mm multiplied by 20mm, the crucible is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at the heating rate of 30 ℃/h in the air environment, the mixture is presintered for 1d at constant temperature, then the mixture is cooled to the room temperature at the heating rate of 50 ℃/h, and a primary presintering product is obtained after grinding. And then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2d, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
The powder sample obtained in this example was characterized by XRD, which revealed that XRD of the powder sample of this example did not match that of example 1, i.e., that the target could not be synthesizedProduct Ba 2 Gd(BO 3 ) 2 F, crystals.
Comparative example 2
The high-temperature solid-phase method is adopted to prepare the crystal, and comprises the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaCl 2 ：0.83g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 :0.56g (8 mmol) is mixed evenly, put into an opening platinum crucible with the diameter phi of 20mm multiplied by 20mm, compacted and put into a muffle furnace, heated to 700 ℃ at the heating rate of 30 ℃/h in the air environment, presintered for 2d at constant temperature, cooled to room temperature at the heating rate of 50 ℃/h, and ground to obtain a primary presintered product. And then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
The powder sample obtained in this example was characterized by XRD, which revealed that the XRD pattern of the powder sample of this example did not match that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystals.
Comparative example 3
Preparation of powdered Ba by high-temperature solid-phase method 2 Gd(BO 3 ) 2 F crystal, comprising the following steps:
weighing BaCO 3 ：2.75g(14mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 :0.56g (8 mmol) of the mixture is uniformly mixed, the mixture is put into a platinum crucible with an opening diameter of 20mm multiplied by 20mm, the platinum crucible is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at the heating rate of 30 ℃/h in the air environment, the mixture is presintered for 1d at a constant temperature, the mixture is cooled to the room temperature at the heating rate of 50 ℃/h, and a primary presintering product is obtained after grinding. Then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2d, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder samples of F crystals.
XRD was used for the powder obtained in this exampleThe end sample was characterized, and the result showed that the XRD pattern of the powder sample of this example did not match that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystals.
Comparative example 4
The high-temperature solid-phase method is adopted to prepare the crystal, and comprises the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 :0.56g (8 mmol) of the mixture is uniformly mixed, the mixture is put into a platinum crucible with an opening diameter of 20mm multiplied by 20mm, the platinum crucible is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at the heating rate of 30 ℃/h in the air environment, the mixture is presintered for 2 days at a constant temperature, the mixture is cooled to the room temperature at the heating rate of 50 ℃/h, and a primary presintering product is obtained after grinding. And pouring the pre-sintered product into a quartz glass tube in the air, putting the quartz glass tube into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
The powder sample obtained in this example was characterized by XRD, which revealed that the XRD pattern of the powder sample of this example did not match that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 F, crystals.
Comparative example 5
The crystal is prepared by adopting an aqueous solution method, which comprises the following steps:
weighing BaCO 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 :0.56g (8 mmol) of the mixture was placed in a 100mL glass beaker, dissolved in 40% strength by volume concentrated nitric acid and placed in an oven at 200 ℃ until dried. Placing the obtained white powder in an open platinum crucible with the diameter of 20mm multiplied by 20mm, compacting the white powder, placing the compacted white powder in a muffle furnace, heating the white powder to 700 ℃ at the heating rate of 30 ℃/h in the air environment, presintering the white powder for 2 days at a constant temperature, cooling the white powder to room temperature at the heating rate of 50 ℃/h, and grinding the white powder to obtain a primary presintering product. Then pouring the pre-sintered product into a quartz glass tube, vacuumizing and sealing the quartz glass tube, putting the quartz glass tube into a muffle furnace, heating the quartz glass tube to 770 ℃ at the heating rate of 30 ℃/h, and reacting at constant temperatureAfter 2d, the sample was cooled to room temperature at a rate of 40 ℃/h and ground to produce a powder sample.
The powder sample obtained in this example was characterized by XRD, which revealed that the XRD pattern of the powder sample of this example did not match that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 F, crystals.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (9)

1. A gadolinium-based borate compound characterized in that the gadolinium-based borate compound has the chemical formula of Ba 2 Gd(BO 3 ) 2 F, belonging to an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:
Figure FDA0003893834250000011
Figure FDA0003893834250000012
α＝β＝γ＝90°，Z＝2。
2. a method of preparing a gadolinium boronate compound of claim 1, comprising the steps of:
uniformly mixing a Ba-containing compound, a Gd-containing compound, a B-containing compound and a F-containing compound, uniformly heating to 650-700 ℃ in an aerobic environment, presintering at a constant temperature, cooling for one time, and grinding; and under the vacuum environment, raising the temperature to 770-780 ℃ at a constant speed, reacting at a constant temperature, cooling for the second time, and grinding to obtain the gadolinium-based borate crystal.
3. The production method according to claim 2, wherein in the Ba-containing compound, the Gd-containing compound, the B-containing compound, and the F-containing compound, the molar ratio of the elements Ba, gd, B, and F is 1-3;
preferably, the molar ratio of elements Ba, gd, B and F is 2.
4. The production method according to claim 2, wherein the Ba-containing compound is selected from a Ba-containing carbonate or a Ba-containing fluoride;
preferably, the Gd-containing compound is selected from Gd-containing oxides;
preferably, the B-containing compound is selected from H 3 BO 3 Or B 2 O 3 ；
Preferably, the F-containing compound is BaF 2 。
5. The preparation method according to claim 2, wherein the temperature rise rate of the uniform temperature rise or the re-uniform temperature rise is 30-40 ℃/h.
6. The preparation method according to claim 2, wherein the time for the constant-temperature pre-sintering is 2-3d.
7. The method of claim 2, wherein the primary cooling is performed at a cooling rate of 40-50 ℃/h.
8. The method of claim 2, wherein the secondary cooling is performed at a cooling rate of 30-40 ℃/h.
9. Use of a gadolinium-based borate compound according to claim 1 or a gadolinium-based borate compound obtained by a method according to any one of claims 2 to 8 in the field of magnetic refrigeration.
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