An inorganic compound, a preparation method and application thereof

Abstract

The application discloses an inorganic compound and a preparation method and application thereof. The chemical formula of the inorganic compound is NaMn2(IO3)6, the inorganic compound belongs to a trigonal system, a space group is P3, cell parameters are alpha = beta = 90 DEG, gamma = 120 DEG, and Z = 1. The inorganic compound has a nonlinear optical effect, a powder frequency doubling effect thereof is 0.55 times of that of KH2PO4 (KDP) under 1064 nm laser irradiation; and the inorganic compound has ferrimagnetism at low temperature 10 K.

Description

Technical Field

[0001] The present application relates to an inorganic compound and a preparation method and application thereof, belonging to the field of inorganic materials. Background Art

[0002] Magnetic materials are an important class of functional materials with a wide range of applications in the field of electronic information technology. Exploring new magnetic compounds is expected to develop new information materials with excellent magnetic functions. Metal iodates have a rich variety of structural types and are important inorganic material systems for exploring excellent optical, electrical, magnetic and other physical properties. The iodate group in iodate compounds has a unique asymmetric trigonal pyramidal geometry that easily forms flexible coordination with metal ions; at the same time, the I in the iodate group 5+ Ions have 5S 2 5P 0 The presence of lone pairs in the valence electron configuration easily induces the formation of novel crystal structures. Therefore, metal iodates possess structural diversity. By introducing magnetic metal ions into iodates and utilizing the flexible coordination properties of iodate, it is possible to construct magnetic iodate compounds with novel structures.

[0003] The transition metal Mn ion has multiple valence states such as +2, +3, and +4, which is conducive to the formation of diverse crystal structures. At the same time, Mn ion is an important magnetic ion. Therefore, research on iodates containing Mn ions is expected to explore new iodate materials.

[0004] Currently, there are few reports on manganese-containing iodates, mainly including compounds such as Mn(IO3)2 (Journal paper Inorganic Chemistry, 2021, 60, 16544-16557), AgMn(IO3)3, AgMn(IO3)4, and Ag3Mn(IO3)6 (Journal paper CrystEngComm, 2013, 15, 7776-7782). Among them, Mn(IO3)2 has an antiferromagnetic exchange interaction at low temperatures and exhibits a weak ferromagnetic moment. There are no reports on compounds containing quaternary iodates of Na and Mn. Summary of the Invention

[0005] According to one aspect of the present application, an inorganic compound is provided, wherein the chemical formula of the inorganic compound is NaMn2(IO3)6, which belongs to the trigonal system, has a space group of P3, and a unit cell parameter of α=β=90°, γ=120°, Z=1.

[0006] Optionally, the unit cell parameters are α=β=90°, γ=120°, Z=1.

[0007] The crystal structure of the inorganic compound is:

[0008] The MnO6 and NaO6 octahedra are bridged by IO3 groups to form a three-dimensional structure;

[0009] The asymmetric unit of the structure consists of 1 Na atom, 2 Mn atoms, 2 I atoms, and 6 O atoms; each I atom is coordinated with three oxygen atoms to form an IO3 trigonal pyramidal unit;

[0010] Both Na and Mn atoms have octahedral coordination configurations, forming NaO6 and MnO6 units, respectively;

[0011] Each MnO6 or NaO6 octahedron is connected to six IO3 groups through common vertex monodentate to form a [Mn(IO3)6] or [Na(IO3)6] unit;

[0012] The MnO6 comprises two octahedrons, Mn(1)O6 and Mn(2)O6, which are different due to different Mn valence states; wherein, Mn(1) in Mn(1)O6 has a valence of +2, and Mn(2) in Mn(2)O6 has a valence of +3;

[0013] Each IO3 group is connected to three octahedrons, Mn(1)O6, Mn(2)O6 and NaO6, through a common vertex monodentate connection;

[0014] The NaO6, Mn(1)O6 and Mn(2)O6 octahedra are isolated from each other and are bridged by IO3 groups to form a three-dimensional structure.

[0015] The inorganic compound is a black regular prism crystal.

[0016] The inorganic compound has a nonlinear optical effect, and its powder frequency-doubled effect under 1064nm laser irradiation is 0.52 to 0.58 times that of KH2PO4;

[0017] Optionally, under 1064nm laser irradiation, the powder frequency-doubled effect is 0.55 times that of KH2PO4 (KDP);

[0018] At a low temperature of 10K, the inorganic compound has ferrimagnetism and has potential application value as a low-temperature magnetic material.

[0019] According to another aspect of the present application, a method for preparing the above-mentioned inorganic compound is provided, wherein raw materials containing a sodium source, a manganese source, an iodine source and a phosphoric acid solution are mixed, crystallized, and cooled to obtain the inorganic compound.

[0020] The sodium source is selected from at least one of sodium hydroxide, sodium oxide, sodium chloride, sodium fluoride, sodium bromide, sodium iodate, and sodium phosphate;

[0021] The manganese source is selected from at least one of manganese carbonate, manganese oxide, manganese powder, manganese phosphate hydrate, manganese hypophosphite hydrate, manganese dihydrogen phosphate, and manganese iodate;

[0022] The iodine source is selected from at least one of iodine pentoxide, iodic acid, periodic acid, sodium iodate, and manganese iodate.

[0023] Optionally, the sodium source is selected from sodium chloride; the manganese source is selected from manganese carbonate; and the iodine source is selected from iodine pentoxide.

[0024] The concentration of the phosphoric acid solution is 10-85 wt %.

[0025] In the raw materials, the molar ratio of the sodium source, the manganese source, the iodine source and the phosphoric acid in the phosphoric acid solution is 0.5-50:1:3-200:10-2000;

[0026] Optionally, in the raw materials, the molar ratio of the sodium source, the manganese source, the iodine source and the phosphoric acid in the phosphoric acid solution is 2-30:1:10-100:100-1000;

[0027] Optionally, in the raw materials, the molar ratio of the sodium source, the manganese source, the iodine source and the phosphoric acid in the phosphoric acid solution is 5-20:1:10-50:100-800.

[0028] The crystallization is hydrothermal crystallization;

[0029] The crystallization temperature is 120-280°C;

[0030] Optionally, the crystallization temperature is 120 to 260° C.;

[0031] Optionally, the crystallization temperature is 180-230°C;

[0032] The crystallization time is 5 to 300 hours;

[0033] Optionally, the crystallization time is 10 to 200 hours.

[0034] The preparation method is simple and can obtain the inorganic compound crystals with high purity and high crystallinity.

[0035] Optionally, the preparation method comprises the following steps:

[0036] (a) placing a raw material mixture containing a sodium source, a manganese source, an iodine source, and a phosphoric acid solution in a polytetrafluoroethylene-lined autoclave, sealing the autoclave, and crystallizing the mixture at a crystallization temperature of 120 to 280° C. for more than 5 hours;

[0037] (b) After the crystallization is completed, the system is cooled to room temperature at a cooling rate of no more than 20° C. / h, and the inorganic compound crystals are obtained after rinsing, filtering, and drying.

[0038] Optionally, the cooling rate in step (b) is 0.5 to 15° C. / h.

[0039] Further optionally, the cooling rate in step (b) is 0.5 to 8° C. / h.

[0040] Further optionally, the cooling rate in step (b) is 2°C / h.

[0041] In this application, "room temperature" refers to 20±5°C.

[0042] According to another aspect of the present application, there is provided an application of the above-mentioned inorganic compound for use in magnetic information materials.

[0043] The beneficial effects of this application include but are not limited to:

[0044] (1) The present application provides a new inorganic compound NaMn2(IO3)6. At a low temperature of 10K, the compound crystal has ferrimagnetism and exhibits significant hysteresis phenomenon, and has potential application value as a low-temperature magnetic material.

[0045] (2) The inorganic compound NaMn2(IO3)6 provided in this application has a novel crystal structure and contains two types of Mn ions with valences of +2 and +3.

[0046] (3) The inorganic compound NaMn2(IO3)6 crystal provided in this application has a nonlinear optical effect. Under 1064nm laser irradiation, its powder frequency-doubled effect is 0.55 times that of KH2PO4(KDP).

[0047] (4) The inorganic compound NaMn2(IO3)6 crystal provided in this application has excellent thermal stability and can be stable to 405°C.

[0048] (5) This application also provides a method for preparing the inorganic compound NaMn2(IO3)6, which uses a hydrothermal method to grow black regular prismatic crystals. The method is simple and can produce high-purity, high-crystallinity NaMn2(IO3)6 crystals. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 These are photos of sample 1# crystal; among them, (a) is a photo taken under an optical microscope; (b) is a photo taken under a scanning electron microscope, with a scale of 500μm.

[0050] Figure 2is a schematic diagram of the crystal structure of the inorganic compound NaMn2(IO3)6; wherein (a) is a schematic diagram of the coordination environment of I atom; (b) is a schematic diagram of the coordination environment of Mn atom; (c) is a schematic diagram of the coordination environment of Na atom; (d) is a schematic diagram of the connection between MnO6 and IO3 groups; (e) is a projection of the crystal structure on ab and bc planes.

[0051] Figure 3 is a comparison of the X-ray diffraction pattern of sample 1# obtained by crystal structure fitting according to single crystal X-ray diffraction and the pattern obtained by X-ray diffraction test after sample 1# is ground into powder.

[0052] Figure 4 is a thermogravimetric and differential thermal curve of sample 1#.

[0053] Figure 5 is a powder doubling effect intensity diagram of sample 1#.

[0054] Figure 6 is a magnetization (χ) versus temperature curve of sample 1#, wherein (a) is a magnetization (χ) versus temperature curve in a temperature range of 2-300 K; (b) is a locally enlarged magnetization (χ) versus temperature curve.

[0055] Figure 7 is a magnetization inverse (1 / χ) versus temperature curve and a Curie-Weiss fitting curve.

[0056] Figure 8 is a M-H magnetization curve at low temperature 2 K, wherein (a) is a M-H magnetization curve in a range of -2000-2000 Oe applied magnetic field; (b) is a locally enlarged M-H magnetization curve. DETAILED DESCRIPTION

[0057] The present application will be described in detail below with reference to examples, but the present application is not limited to these examples.

[0058] Unless otherwise specified, the raw materials in the examples of the present application are purchased through commercial channels, and the experimental methods not specified in the following examples are generally carried out according to conventional conditions or according to the conditions recommended by the manufacturers.

[0059] Example 1 Hydrothermal synthesis of NaMn2(IO3)6 crystal

[0060] The raw materials containing sodium source, manganese source, iodine source and phosphoric acid are mixed according to a certain molar ratio, placed in a high-pressure reaction kettle with a polytetrafluoroethylene liner, sealed, heated to a crystallization temperature, and then the temperature of the system is decreased to room temperature (25℃) at a certain cooling rate after constant temperature for a period of time. After washing, suction filtration and drying, black regular prismatic crystals are obtained. Figure 1), which is the inorganic compound NaMn2(IO3)6 crystal sample.

[0061] The sample numbers, raw material types and amounts, crystallization temperatures and holding times, and cooling rates are shown in Table 1. H3PO4 (85 wt%) refers to an aqueous solution of phosphoric acid with a mass fraction of 85%.

[0062] Table 1

[0063]

[0064] Figure 1 The following are photos of sample 1# crystals; (a) is taken under an optical microscope; (b) is taken under a scanning electron microscope, with a scale of 500μm. As can be seen from the images, the resulting crystals are black, regular prismatic crystals.

[0065] Crystal structure analysis of NaMn2(IO3)6

[0066] The structure of the samples was elucidated using single crystal X-ray diffraction and powder X-ray diffraction methods.

[0067] The single crystal X-ray diffraction was performed using a single crystal X-ray diffractometer (model: XtaLABSynergy R) from Rigaku Corporation of Japan to collect single crystal diffraction data, and the CrysAlis built into the instrument was used for data restoration. The X-ray source used for single crystal diffraction was graphite monochromatized Mo-Kα rays with a wavelength of Data collection was completed at room temperature. Crystal structure analysis and refinement were performed using the SHELXL-2019 software package, and the crystal structure schematic was drawn using Diamond software.

[0068] Powder X-ray diffraction was performed using a Bruker powder X-ray diffractometer (model: D8-ADVANCE) at room temperature; the X-ray source was a Cu target (wavelength ), the scanning step size is 0.02.

[0069] Among them, the single crystal X-ray diffraction results show that the chemical formula of samples 1#~6# is NaMn2(IO3)6, belonging to the trigonal system, the space group is P3, and the unit cell parameters are α=β=90°, γ=120°, Z=1.

[0070] The crystal structure diagram of the inorganic compound crystal NaMn2(IO3)6 is as follows Figure 2As shown, (a) is a schematic diagram of the coordination environment of I atoms; (b) is a schematic diagram of the coordination environment of Mn atoms; (c) is a schematic diagram of the coordination environment of Na atoms; (d) is a schematic diagram of the connection mode between the groups of MnO6 and IO3; (e) is the projection of the crystal structure on the ab and bc planes.

[0071] The MnO6 and Na(1)O6 octahedra are bridged by IO3 groups to form a three-dimensional structure. The asymmetric unit of this structure includes 1 Na atom, 2 Mn atoms, 2 I atoms and 6 O atoms. The I atoms are coordinated with three oxygen atoms to form IO3 trigonal pyramidal units; the Na and Mn atoms are both octahedral coordinated, forming Na(1)O6 and MnO6 units, respectively. The MnO6 includes two different octahedra, Mn(1)O6 and Mn(2)O6, which are different due to the different valence states of Mn; according to the bond valence calculation (BVS), the valence states of Mn(1) and Mn(2) are 2.09 and 2.97, respectively, indicating that Mn(1) and Mn(2) have different oxidation states, +2 and +3, respectively. Compounds containing metal Mn ions with two valence states, +2 and +3, in the same compound are currently extremely rare. Each MnO6 or Na(1)O6 octahedron is connected to six IO3 groups through common vertex monodentate, forming a [Mn(IO3)6] or [Na(IO3)6] unit; each IO3 group is simultaneously connected to three octahedrons of Mn(1)O6, Mn(2)O6 and Na(1)O6 through common vertex monodentate. The Na(1)O6, Mn(1)O6 and Mn(2)O6 octahedra are isolated from each other and are bridged by IO3 groups to form a three-dimensional structure.

[0072] Taking sample 1# as a typical example, Table 2 shows the single crystal X-ray diffraction structure analysis results. It can be seen that sample 1# belongs to the trigonal system, the space group is P3, and the unit cell parameters are α=β=90°, γ=120°, Z=1.

[0073] Table 2

[0074]

[0075] The powder X-ray diffraction results show that the diffraction peak positions of samples 1# to 6# are basically the same in the XRD spectra, and the peak intensities of each sample are slightly different.

[0076] Take sample 1# as a typical example. Figure 3 As shown in the figure, the X-ray diffraction pattern obtained by fitting the crystal structure analyzed by single crystal X-ray diffraction is compared with the pattern obtained by X-ray diffraction test after sample 1# is ground into powder. The diffraction peak positions and peak intensities in the fitted pattern and the experimental pattern are consistent, indicating that the obtained sample has a very high purity.

[0077] Thermal stability test and analysis

[0078] Thermal stability test and analysis

[0079] Figure 4 Fig. 1 is a TGA and DSC curve of sample 1#; the test results show that the NaMn2(IO3)6crystal can be stable to 405°C, and the decomposition temperature is about 453°C.

[0080] Powder SHG test and analysis

[0081] Powder SHG test and analysis

[0082] The specific steps are as follows: a Q-switched Nd:YAG solid laser is used to generate laser with wavelength of 1064 nm as the fundamental light, which irradiates the crystal powder to be tested, and a photomultiplier tube is used to detect the generated second harmonic wave, and an oscilloscope is used to display the harmonic intensity. The crystal sample to be tested is sieved with a standard sieve to obtain a test sample with particle size of 150-210 μm. Under the same test conditions, the intensity of the second harmonic wave generated by the sample to be tested is compared with that of the reference crystal KH2PO4(KDP) with particle size of 150-210 μm, so as to obtain the relative size of the sample SHG effect.

[0083] Figure 5 Fig. 2 is a powder SHG effect intensity diagram of sample 1#; the test results show that the powder SHG effect of the compound NaMn2(IO3)6crystal under 1064 nm laser irradiation is 0.55 times that of KH2PO4(KDP).

[0084] Magnetic test and analysis

[0085] Magnetic test and analysis

[0086] Figure 6 、 78 is the magnetic data diagram of sample 1#, where: Figure 6 The magnetic susceptibility (χ) of sample 1# varies with temperature, where (a) is the magnetic susceptibility (χ) variation curve in the temperature range of 2 to 300 K; (b) is the locally enlarged magnetic susceptibility (χ) variation curve.

[0087] Figure 7 is the curve of the inverse of magnetic susceptibility (1 / χ) changing with temperature and the Curie-Weiss fitting curve.

[0088] Figure 8 These are the MH magnetization curves at a low temperature of 2K, where (a) is the MH magnetization curve in the external magnetic field range of -2000 to 2000 Oe; (b) is the locally enlarged MH magnetization curve.

[0089] Figure 6 、 7 The test results of Figure 8 show that NaMn2(IO3)6 crystals have multiple magnetic phase transition processes below 10K, showing ferrimagnetism; at a low temperature of 2K, the MH magnetization curve of NaMn2(IO3)6 shows obvious hysteresis effect and residual magnetization phenomenon, with a coercive force of about 2340Oe and a remanence of 0.363μ B .

[0090] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An inorganic compound, characterized in that The chemical formula of the inorganic compound is NaMn2(IO3)6; The inorganic compound belongs to the trigonal system, and the space group is P 3. The unit cell parameters are a = b = 9.2~9.8 Å, c =4.9~5.5 Å, α = β = 90°, γ= 120°, Z = 1.

2. The inorganic compound according to claim 1, characterized in that The unit cell parameters are a = b = 9.56632(17) Å, c = 5.19049(14) Å.

3. The inorganic compound according to claim 1, characterized in that The crystal structure of the inorganic compound is: The MnO6 and NaO6 octahedra are bridged by IO3 groups to form a three-dimensional structure; The asymmetric unit of the structure includes 1 Na atom, 2 Mn atoms, 2 I atoms, and 6 O atoms; Each I atom is coordinated with three oxygen atoms to form an IO3 trigonal pyramidal unit; Both Na and Mn atoms have octahedral coordination configurations, forming NaO6 and MnO6 units, respectively; Each MnO6 or NaO6 octahedron is connected to six IO3 groups through common vertex monodentate to form a [Mn(IO3)6] or [Na(IO3)6] unit; The MnO6 comprises two octahedrons, Mn(1)O6 and Mn(2)O6, which are different due to different Mn valence states; wherein, Mn(1) in Mn(1)O6 has a valence of +2, and Mn(2) in Mn(2)O6 has a valence of +3; Each IO3 group is connected to three octahedrons, Mn(1)O6, Mn(2)O6 and NaO6, through a common vertex monodentate connection; The NaO6, Mn(1)O6 and Mn(2)O6 octahedra are isolated from each other and are bridged by IO3 groups to form a three-dimensional structure.

4. The inorganic compound according to claim 1, characterized in that The inorganic compound is a black regular prism crystal.

5. The inorganic compound according to claim 1, characterized in that The inorganic compound has a nonlinear optical effect, and under 1064 nm laser irradiation, the powder frequency-doubled effect thereof is 0.52 to 0.58 times that of KH2PO4.

6. The inorganic compound according to claim 1, characterized in that At a low temperature of 10K, the inorganic compound has ferrimagnetism.

7. A method for preparing the inorganic compound according to any one of claims 1 to 6, characterized in that: Raw materials containing a sodium source, a manganese source, an iodine source and a phosphoric acid solution are mixed, placed in a sealed container, and crystallized to obtain the inorganic compound.

8. The preparation method according to claim 7, characterized in that The sodium source is selected from at least one of sodium hydroxide, sodium oxide, sodium chloride, sodium fluoride, sodium bromide, sodium iodate, and sodium phosphate; The manganese source is selected from at least one of manganese carbonate, manganese oxide, manganese powder, manganese phosphate hydrate, manganese hypophosphite hydrate, manganese dihydrogen phosphate, and manganese iodate; The iodine source is selected from at least one of iodine pentoxide, iodic acid, periodic acid, sodium iodate, and manganese iodate.

9. The preparation method according to claim 7, characterized in that The concentration of the phosphoric acid solution is 10-85 wt %.

10. The preparation method according to claim 7, characterized in that In the raw materials, the molar ratio of the sodium source, the manganese source, the iodine source and the phosphoric acid in the phosphoric acid solution is 0.5-50:1:3-200:10-2000.

11. The preparation method according to claim 7, characterized in that In the raw materials, the molar ratio of the sodium source, the manganese source, the iodine source and the phosphoric acid in the phosphoric acid solution is 2-30:1:10-100:100-1000.

12. The preparation method according to claim 7, characterized in that In the raw materials, the molar ratio of the sodium source, the manganese source, the iodine source and the phosphoric acid in the phosphoric acid solution is 5-20:1:10-50:100-800.

13. The preparation method according to claim 7, characterized in that The crystallization temperature is 120-280°C.

14. The preparation method according to claim 7, characterized in that The crystallization temperature is 120-260°C.

15. The preparation method according to claim 7, characterized in that The crystallization temperature is 180-230°C.

16. The preparation method according to claim 7, characterized in that The crystallization time is 5 to 300 hours.

17. The preparation method according to claim 7, characterized in that The crystallization time is 10 to 200 hours.

18. Use of the inorganic compound according to any one of claims 1 to 6, characterized in that: Used to prepare magnetic information materials.

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