CN113087019B - Preparation of ferromagnetic VO by supercritical fluid technology 2 Preparation method of (1) - Google Patents

Preparation of ferromagnetic VO by supercritical fluid technology 2 Preparation method of (1) Download PDF

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CN113087019B
CN113087019B CN202110515573.8A CN202110515573A CN113087019B CN 113087019 B CN113087019 B CN 113087019B CN 202110515573 A CN202110515573 A CN 202110515573A CN 113087019 B CN113087019 B CN 113087019B
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mixed solvent
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CN113087019A (en
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周燕南
许群
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention belongs to the technical field of magnetic metal oxide preparation, and discloses a method for preparing ferromagnetic VO by using a supercritical fluid technology 2 The preparation method of (1). Non-magnetic VO 2 Dispersing into a mixed solvent consisting of N-methyl pyrrolidone and water to obtain a dispersion liquid; then transferring the dispersion liquid into a supercritical device, injecting carbon dioxide into the supercritical device, stirring and reacting for 3-6h under the supercritical condition, naturally cooling to room temperature, and releasing pressure; separating the system after supercritical treatment, collecting the separated liquid and drying to obtain ferromagnetic VO 2 . The invention breaks through the traditional defect-induced local magnetic moment, and adopts the mixed solvent of N-methyl pyrrolidone and water to treat the non-magnetic VO under the condition of supercritical carbon dioxide 2 Compared with the traditional defect induction local magnetic moment, the method can generate stronger and more stable magnetic response, has environment-friendly and pollution-free preparation technology in the whole ferromagnetic structure induction process, and has great application prospect in the fields of magneto-optical and magnetoelectric devices.

Description

Preparation of ferromagnetic VO by supercritical fluid technology 2 Preparation method of (1)
Technical Field
The invention belongs to the technical field of magnetic metal oxide preparation, and particularly relates to a method for preparing ferromagnetic VO (volatile organic compound) by using a supercritical fluid technology 2 The preparation method of (1).
Background
Transition metal oxide VO 2 As emerging electronic and magnetic materials with strongly correlated d-electrons, many new physical phenomena are commonly exhibited, such as metal-insulator transition and room temperature ferromagnetism. In strongly related Transition Metal Oxide (TMOs) materials, the interaction of the internal degrees of freedom of the d and f electrons (spin, charge and orbital moments) makes their structural and magnetic phase transitions very sensitive to small changes in parameters such as temperature, pressure and composition. Therefore, inducing room temperature ferromagnetism in TMOs through defect engineering based on vacancies, atoms, boundaries, and edges is an active area of research over the past few decades. However, in most cases, such externally induced local magnetic moments from unpaired electrons are very weak and the emerging magnetic properties usually involve only a few atoms on the surface. The nature of ferromagnetic order is the symmetry of the order breaking parameter, compared to defect engineering, cracking a new surface in a material or inducing the transition of a crystal to amorphous will break the translational symmetry of the order parameter and further induce intrinsic magnetic anisotropy, but these approaches are difficult to perform by conventional techniques due to the strong covalent bond property of metal-oxygen in metal oxides.
Disclosure of Invention
In view of the defects and shortcomings of the prior art, the invention aims to provide a method for preparing ferromagnetic VO by using supercritical fluid technology 2 The preparation method of (1).
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
preparation of ferromagnetic VO by supercritical fluid technology 2 The preparation method comprises the following steps: non-magnetic VO 2 Dispersing into a mixed solvent consisting of N-methyl pyrrolidone and water to obtain a dispersion liquid; then transferring the dispersion liquid into a supercritical device, injecting carbon dioxide into the supercritical device, stirring and reacting for 3-6h under the supercritical condition, naturally cooling to room temperature, and releasing pressure; separating the system after supercritical treatment, collecting the separated liquid and drying to obtain ferromagnetic VO 2 。
Preferably, the parameters of the supercritical conditions are: the temperature is 40-200 deg.C and the pressure is 8-30 Mpa.
Preferably, the volume ratio of the N-methylpyrrolidone in the mixed solvent is 10-90%.
Preferably, a non-magnetic VO 2 And the dosage ratio of the mixed solvent is 0.1-10 mg/ml.
Preferably, a non-magnetic VO 2 The crystal phase of (2) is A, B, M or R phase.
The invention provides a method for preparing ferromagnetic VO by using supercritical fluid technology 2 The carbon dioxide molecule can enter VO in the supercritical environment 2 Inside the network structure, VO is generated due to the strong shear force field created by carbon dioxide molecules 2 The metal-oxygen covalent bond of (a) is selectively cleaved to produce a new surface and an amorphous phase.
Compared with the prior art, the invention has the following advantages:
the invention breaks through the traditional defect-induced local magnetic moment, and adopts the mixed solvent of N-methyl pyrrolidone and water to treat the non-magnetic VO under the condition of supercritical carbon dioxide 2 Compared with the traditional defect induced local magnetic moment, the magnetic induction device can generate stronger and more stable magnetic response, and the whole ferromagnetic structure is made in the induction processThe preparation technology is environment-friendly and pollution-free, and has great application prospect in the fields of magneto-optical and magneto-electric devices.
Drawings
FIG. 1: digital photographs of the supernatants obtained in example 1 of the invention.
FIG. 2: transmission electron microscope characterization of the target product obtained in example 1 of the present invention.
FIG. 3: non-magnetic VO as raw material 2 Hysteresis loops (VSM) of the target product obtained in example 1 and the control product obtained in control example 1.
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
100 mg of nonmagnetic VO 2 Adding (crystal phase is R phase) into 100 ml of mixed solvent (volume ratio, N-methyl pyrrolidone: water = 1: 1) composed of N-methyl pyrrolidone and water, and stirring and dispersing to obtain dispersion liquid; then transferring the dispersion liquid into a supercritical reaction kettle; injecting carbon dioxide into the reaction kettle to enable the reaction kettle to reach a supercritical state, wherein the temperature is 80 ℃, the pressure is 16 MPa, and magnetically stirring for 6 hours; naturally cooling to room temperature, releasing carbon dioxide for pressure relief, centrifuging the suspension subjected to supercritical treatment to obtain supernatant, and drying the obtained supernatant to obtain the target product.
The digital photograph of the resulting supernatant is shown in FIG. 1; the transmission electron microscope of the obtained target product is shown in FIG. 2. The two interplanar spacings measured in FIG. 2 were 0.578 and 0.265nm, respectively, and correspond to VO 2 (200) and (-311) crystal planes of (A), belonging to an exposed surface of non-magnetic VO 2 High index crystal plane (-5-310) which does not exist in the supercritical system, and the successful cutting of the new plane in the supercritical system is confirmed.
Comparative example 1
The difference from example 1 is that: processing without supercritical conditions; the method comprises the following specific steps: 100 mg of nonmagnetic VO 2 Adding into 100 ml of mixture consisting of N-methyl pyrrolidone and waterStirring and dispersing in a solvent (volume ratio, N-methyl pyrrolidone: water = 1: 1) to obtain a dispersion liquid; then transferring the dispersion liquid into a supercritical reaction kettle without filling CO 2 Gas, and magnetically stirring for 6 hours at 80 ℃; naturally cooling to room temperature, centrifuging the treated suspension to obtain supernatant, and drying the supernatant to obtain the control product.
Nonmagnetic VO to raw material by using physical characteristic measuring system (PPMS-9) 2 The hysteresis loop (VSM) test was performed on the product obtained in example 1, and the measured hysteresis loop (VSM) is shown in fig. 3: 1 represents a non-magnetic VO as a raw material 2 2 represents the control product obtained in comparative example 1, and 3 represents the objective product obtained in example 1. As can be seen from fig. 3: non-magnetic VO as raw material 2 And no filling with CO 2 The gas control product has no ferromagnetic signal at normal temperature, and is supercritical CO 2 Target VO prepared by system 2 The hysteresis loop of the magnetic-field-sensitive magnetic material presents an obvious S-shaped closed loop. Evidence of supercritical CO 2 Is to excite non-magnetic VO 2 A decisive factor for the room-temperature ferromagnetism.

Claims (4)

1. Preparation of ferromagnetic VO by supercritical fluid technology 2 The preparation method is characterized by comprising the following steps: non-magnetic VO 2 Dispersing into a mixed solvent consisting of N-methyl pyrrolidone and water to obtain a dispersion liquid; then transferring the dispersion liquid into a supercritical device, injecting carbon dioxide into the supercritical device, stirring and reacting for 3-6h under the supercritical condition, naturally cooling to room temperature, and releasing pressure; separating the system after supercritical treatment, collecting the separated liquid and drying to obtain ferromagnetic VO 2 (ii) a The parameters of the supercritical conditions are: the temperature is 40-200 deg.C and the pressure is 8-30 Mpa.
2. Preparation of ferromagnetic VO using supercritical fluid technology as claimed in claim 1 2 The preparation method is characterized by comprising the following steps: in the mixed solvent, the volume ratio of N-methyl pyrrolidone is 10-90%.
3. The method of claim 1 or 2Preparation of ferromagnetic VO by supercritical fluid technology 2 The preparation method is characterized by comprising the following steps: non-magnetic VO 2 And the dosage ratio of the mixed solvent is 0.1-10 mg/ml.
4. Preparation of ferromagnetic VO using supercritical fluid technology as claimed in claim 1 2 The preparation method is characterized by comprising the following steps: non-magnetic VO 2 The crystal phase of (2) is A, B, M or R phase.
CN202110515573.8A 2021-05-12 2021-05-12 Preparation of ferromagnetic VO by supercritical fluid technology 2 Preparation method of (1) Active CN113087019B (en)

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PCT/CN2021/137184 WO2022237151A1 (en) 2021-05-12 2021-12-10 Method for preparing ferromagnetic vo2 using supercritical fluid technology

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CN113087019B (en) * 2021-05-12 2022-09-13 郑州大学 Preparation of ferromagnetic VO by supercritical fluid technology 2 Preparation method of (1)
CN113500053A (en) * 2021-08-19 2021-10-15 中国石化中原石油化工有限责任公司 By using supercritical CO2Method for preparing high-purity polypropylene
CN115259212A (en) * 2022-08-01 2022-11-01 郑州大学 Method for preparing room-temperature ferromagnetism SrTiO by using supercritical carbon dioxide technology 3 Method (2)
CN115259227B (en) * 2022-09-15 2023-10-27 郑州大学 Method for preparing room-temperature ferromagnetic molybdenum oxide nanosheets by using supercritical carbon dioxide

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CN102020314A (en) * 2010-12-30 2011-04-20 沈阳化工大学 Method for preparing vanadium dioxide powder
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CN1671624A (en) * 2002-06-25 2005-09-21 阿尔堡大学 Method for production of a product having sub-micron primary particle size, product produced by the method and apparatus for use of the method
CN102020314A (en) * 2010-12-30 2011-04-20 沈阳化工大学 Method for preparing vanadium dioxide powder
WO2017006699A1 (en) * 2015-07-09 2017-01-12 コニカミノルタ株式会社 Vanadium dioxide-containing particles, dispersion liquid containing same, optical film containing same, method for producing same, method for producing said dispersion liquid, and method for producing said optical film
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