WO2022237151A1 - Method for preparing ferromagnetic vo2 using supercritical fluid technology - Google Patents
Method for preparing ferromagnetic vo2 using supercritical fluid technology Download PDFInfo
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- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000012530 fluid Substances 0.000 title claims abstract description 11
- 230000005291 magnetic effect Effects 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 5
- 230000007547 defect Effects 0.000 abstract description 7
- 230000006698 induction Effects 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
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- 239000006228 supernatant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 230000005307 ferromagnetism Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 230000000875 corresponding effect Effects 0.000 description 1
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- 239000012776 electronic material Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
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- 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
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- 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
Definitions
- the invention belongs to the technical field of preparing magnetic metal oxides, and in particular relates to a method for preparing ferromagnetic VO2 using supercritical fluid technology.
- Transition metal oxides VO2 as emerging electronic and magnetic materials with strongly correlated d - electrons, often exhibit many new physical phenomena, such as metal-insulator transition and room-temperature ferromagnetism.
- TMOs strongly correlated transition metal oxides
- the object of the present invention is to provide a method for preparing ferromagnetic VO2 using supercritical fluid technology.
- a method for preparing ferromagnetic VO2 using supercritical fluid technology disperse nonmagnetic VO2 into a mixed solvent composed of N-methylpyrrolidone and water to obtain a dispersion; then transfer the dispersion to a supercritical device , inject carbon dioxide into the supercritical device, stir and react under supercritical conditions for 3-6h, and release the pressure after naturally cooling to room temperature; separate the system after supercritical treatment, collect the separated liquid and dry it to obtain ferromagnetic VO 2 .
- the parameters of the supercritical condition are: temperature 40-200°C, pressure 8-30Mpa.
- the volume ratio of N-methylpyrrolidone is 10-90%.
- the ratio of the non-magnetic VO 2 to the mixed solvent is 0.1-10 mg/ml.
- the crystal phase of non-magnetic VO 2 is A, B, M or R phase.
- the present invention provides a method for preparing ferromagnetic VO2 using supercritical fluid technology.
- carbon dioxide molecules can enter the interior of the VO2 network structure. Due to the strong shear force field created by carbon dioxide molecules, the VO2 Metal-oxygen covalent bonds are selectively cleaved to generate new surfaces and amorphous phases.
- the present invention has the following advantages:
- the present invention breaks through the traditional defect-induced local magnetic moment, and uses a mixed solvent of N-methylpyrrolidone and water to treat non-magnetic VO 2 under the condition of supercritical carbon dioxide. Compared with the traditional defect-induced local magnetic moment, it can produce more Strong and more stable magnetic response, the preparation technology is environmentally friendly and pollution-free during the entire ferromagnetic structure induction process, and has great application prospects in the fields of magneto-optical and magnetoelectric devices.
- Figure 1 A digital photograph of the supernatant obtained in Example 1 of the present invention.
- Figure 2 Transmission electron microscope characterization of the target product obtained in Example 1 of the present invention.
- Fig. 3 Hysteresis loops (VSM) of the raw material non-magnetic VO 2 , the target product obtained in Example 1, and the control product obtained in Comparative Example 1.
- VSM Hysteresis loops
- the digital photo of the obtained supernatant is shown in Figure 1; the transmission electron microscope of the obtained target product is shown in Figure 2.
- the two interplanar distances measured in Figure 2 are 0.578 and 0.265nm, respectively, corresponding to the (200) and (-311) crystal planes of VO2, and the exposed surfaces belong to the high index that does not exist in non - magnetic VO2 crystal face (-5-310), confirming the successful cleavage of the new face in a supercritical system.
- the measured hysteresis loop (VSM) is shown in Fig. 3 : 1 represents the raw material non-magnetic VO 2 , 2 represents the control product obtained in Comparative Example 1, and 3 represents the target product obtained in Example 1. It can be seen from Figure 3 that the raw material non-magnetic VO 2 and the control product not filled with CO 2 gas have no ferromagnetic signal at room temperature, and the hysteresis loop of the target VO 2 prepared by the supercritical CO 2 system presents an obvious S-shaped closed loop . It is proved that supercritical CO2 is the decisive factor to excite nonmagnetic VO2 to generate room temperature ferromagnetism.
Abstract
The present invention belongs to the technical field of magnetic metal oxide preparation, and discloses a method for preparing ferromagnetic VO2 using supercritical fluid technology. Dispersing non-magnetic VO2 in a mixed solvent composed of N-methylpyrrolidone and water to obtain a dispersion; transferring the dispersion to a supercritical apparatus, injecting carbon dioxide into the supercritical apparatus, stirring and reacting for 3-6 h in supercritical conditions, naturally cooling to room temperature, and then depressurising; separating the system after supercritical treatment, collecting the separation liquid, and drying to obtain ferromagnetic VO2. The present invention breaks through traditional defect-induced local magnetic moments and uses a mixed solvent of N-methylpyrrolidone and water to treat non-magnetic VO2 in supercritical carbon dioxide conditions, and can generate a stronger and more stable magnetic response compared with a traditional defect-induced local magnetic moment; in the whole ferromagnetic structure induction process, the preparation technology is environmentally friendly and pollution-free, having great application prospects in the field of magneto-optical and magneto-electric devices.
Description
本发明属于磁性金属氧化物制备技术领域，具体涉及一种利用超临界流体技术制备铁磁性VO
2的制备方法。
The invention belongs to the technical field of preparing magnetic metal oxides, and in particular relates to a method for preparing ferromagnetic VO2 using supercritical fluid technology.
过渡金属氧化物VO
2作为具有强相关d电子的新兴电子和磁性材料，通常表现出许多新的物理现象，如金属-绝缘体转变和室温铁磁性。在强相关过渡金属氧化物(TMOs)材料中，d和f电子的内部自由度(自旋、电荷和轨道矩)的相互作用使得其结构和磁性相变对温度、压力和成分等参数的微小变化非常敏感。因此，通过基于空位、原子、边界和边缘的缺陷工程在TMOs中诱导室温铁磁性是过去几十年来研究的一个活跃领域。然而，在大多数情况下，来自不成对电子的这种外部诱导的局部磁矩非常弱，并且出现的磁性通常只涉及表面上的几个原子。铁磁有序的本质是打破序参量的对称性，相较于缺陷工程，在材料中裂解新的表面或诱导晶体到无定形的转变会破坏序参量的平移对称性，进而诱导本征磁各向异性，但是由于金属氧化物中金属-氧的强共价键属性，这些手段难以通过常规技术进行。
Transition metal oxides VO2, as emerging electronic and magnetic materials with strongly correlated d - electrons, often exhibit many new physical phenomena, such as metal-insulator transition and room-temperature ferromagnetism. In strongly correlated transition metal oxides (TMOs) materials, the interaction of the internal degrees of freedom (spin, charge, and orbital moment) of d and f electrons makes their structural and magnetic phase transitions very small with respect to parameters such as temperature, pressure, and composition. Changes are very sensitive. Therefore, the induction of room-temperature ferromagnetism in TMOs via defect engineering based on vacancies, atoms, boundaries, and edges is an active area of research in the past decades. In most cases, however, this externally induced local magnetic moment from unpaired electrons is very weak, and the resulting magnetism usually involves only a few atoms on the surface. The essence of ferromagnetic order is to break the symmetry of the order parameter. Compared with defect engineering, cleaving new surfaces in the material or inducing a crystal-to-amorphous transition will break the translational symmetry of the order parameter, and then induce the intrinsic magnetic symmetry. Anisotropy, but due to the strong covalent nature of metal-oxygen bonds in metal oxides, these means are difficult to perform by conventional techniques.
发明内容Contents of the invention
针对上述现有技术的缺陷与不足，本发明的目的在于提供一种利用超临界流体技术制备铁磁性VO
2的制备方法。
Aiming at the defects and deficiencies of the above - mentioned prior art, the object of the present invention is to provide a method for preparing ferromagnetic VO2 using supercritical fluid technology.
为实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme that the present invention takes is as follows:
一种利用超临界流体技术制备铁磁性VO
2的制备方法：将非磁性VO
2分散到N-甲基吡咯烷酮和水组成的混合溶剂中，获得分散液；然后将分散液转移至超临界装置中，向超临界装置中注入二氧化碳，在超临界条件下搅拌反应3-6h，自然冷却至室温后卸压；将超临界处理后的体系分离，收集分离液并干燥，得到铁磁性VO
2。
A method for preparing ferromagnetic VO2 using supercritical fluid technology : disperse nonmagnetic VO2 into a mixed solvent composed of N-methylpyrrolidone and water to obtain a dispersion; then transfer the dispersion to a supercritical device , inject carbon dioxide into the supercritical device, stir and react under supercritical conditions for 3-6h, and release the pressure after naturally cooling to room temperature; separate the system after supercritical treatment, collect the separated liquid and dry it to obtain ferromagnetic VO 2 .
较好地，所述超临界条件的参数为：温度40-200℃、压力8-30Mpa。Preferably, the parameters of the supercritical condition are: temperature 40-200°C, pressure 8-30Mpa.
较好地，混合溶剂中，N-甲基吡咯烷酮所占的体积比为10-90％。Preferably, in the mixed solvent, the volume ratio of N-methylpyrrolidone is 10-90%.
较好地，非磁性VO
2和混合溶剂的用量比为0.1-10mg/ml。
Preferably, the ratio of the non-magnetic VO 2 to the mixed solvent is 0.1-10 mg/ml.
较好地，非磁性VO
2的晶相为A、B、M或R相。
Preferably, the crystal phase of non-magnetic VO 2 is A, B, M or R phase.
本发明提供了一种利用超临界流体技术制备铁磁性VO
2的制备方法，超临界环境中，二氧化碳分子可以进入到VO
2网络结构内部，由于二氧化碳分子营造的强剪切力场， VO
2的金属-氧共价键会选择性裂解，生成新表面和非晶相。
The present invention provides a method for preparing ferromagnetic VO2 using supercritical fluid technology. In a supercritical environment, carbon dioxide molecules can enter the interior of the VO2 network structure. Due to the strong shear force field created by carbon dioxide molecules, the VO2 Metal-oxygen covalent bonds are selectively cleaved to generate new surfaces and amorphous phases.
本发明与现有技术相比，具有如下优点：Compared with the prior art, the present invention has the following advantages:
本发明突破传统的缺陷诱导局域磁矩，在超临界二氧化碳条件下，采用N-甲基吡咯烷酮和水的混合溶剂处理非磁性VO
2，相比传统的缺陷诱导局域磁矩，可以产生更强更稳定的磁响应，整个铁磁性结构诱导过程中，制备技术环保无污染，在磁光、磁电器件领域有重大的应用前景。
The present invention breaks through the traditional defect-induced local magnetic moment, and uses a mixed solvent of N-methylpyrrolidone and water to treat non-magnetic VO 2 under the condition of supercritical carbon dioxide. Compared with the traditional defect-induced local magnetic moment, it can produce more Strong and more stable magnetic response, the preparation technology is environmentally friendly and pollution-free during the entire ferromagnetic structure induction process, and has great application prospects in the fields of magneto-optical and magnetoelectric devices.
图1：本发明实施例1所得上清液的数码照片。Figure 1: A digital photograph of the supernatant obtained in Example 1 of the present invention.
图2：本发明实施例1所得目标产品的透射电子显微镜表征。Figure 2: Transmission electron microscope characterization of the target product obtained in Example 1 of the present invention.
图3：原料非磁性VO
2、实施例1所得目标产品以及对照例1所得对照产品的磁滞回线(VSM)。
Fig. 3: Hysteresis loops (VSM) of the raw material non-magnetic VO 2 , the target product obtained in Example 1, and the control product obtained in Comparative Example 1.
为使本发明更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the present invention clearer and more definite, the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
实施例1Example 1
将100mg的非磁性VO
2(晶相为R相)加入到100ml的N-甲基吡咯烷酮和水组成的混合溶剂(体积比，N-甲基吡咯烷酮∶水＝1∶1)中，搅拌分散获得分散液；然后将分散液转移到超临界反应釜中；向反应釜中注入二氧化碳使其达到超临界状态，温度为80℃，压力为16MPa，磁力搅拌6h；自然冷却到室温后释放二氧化碳卸压，超临界处理后的悬浮液采用离心方式分离获取上清液，取得的上清液干燥后得到目标产品。
Add 100 mg of non-magnetic VO 2 (crystal phase is R phase) to 100 ml of a mixed solvent composed of N-methylpyrrolidone and water (volume ratio, N-methylpyrrolidone: water = 1:1), stir and disperse to obtain Dispersion liquid; then transfer the dispersion liquid to a supercritical reaction kettle; inject carbon dioxide into the reaction kettle to make it reach a supercritical state, the temperature is 80°C, the pressure is 16MPa, and magnetic stirring is carried out for 6 hours; after natural cooling to room temperature, release carbon dioxide to relieve pressure , the suspension after supercritical treatment is separated by centrifugation to obtain a supernatant, and the obtained supernatant is dried to obtain the target product.
所得上清液的数码照片见图1；所得目标产品的透射电子显微镜见图2。图2所测得的两个晶面间距分别为0.578、0.265nm，分别对应于VO
2的(200)和(-311)晶面，所属的暴露面为非磁性VO
2中不存在的高指数晶面(-5-310)，证实了在超临界体系中新面的成功切割。
The digital photo of the obtained supernatant is shown in Figure 1; the transmission electron microscope of the obtained target product is shown in Figure 2. The two interplanar distances measured in Figure 2 are 0.578 and 0.265nm, respectively, corresponding to the (200) and (-311) crystal planes of VO2, and the exposed surfaces belong to the high index that does not exist in non - magnetic VO2 crystal face (-5-310), confirming the successful cleavage of the new face in a supercritical system.
对照例1Comparative example 1
与实施例1的不同之处在于：不在超临界条件下处理；具体步骤为：将100mg的非磁性VO
2加入到100ml的N-甲基吡咯烷酮和水组成的混合溶剂(体积比，N-甲基吡咯烷酮∶水＝1∶1)中，搅拌分散获得分散液；然后将分散液转移到超临界反应釜中，不填充CO
2气体，在80℃下磁力搅拌6h；自然冷却到室温，处理后的悬浮液采用离心方式分离获取上清液，取得的上清液干燥后得到对照产品。
The difference with Example 1 is: not processed under supercritical conditions; Concrete steps are: the non - magnetic VO of 100mg Join the mixed solvent (volume ratio, N-methylpyrrolidone of 100ml) and water composition of 100ml base pyrrolidone: water = 1: 1), stirring and dispersing to obtain a dispersion; then the dispersion was transferred to a supercritical reactor without CO gas, and magnetically stirred at 80°C for 6h; naturally cooled to room temperature, after treatment The suspension was centrifuged to obtain a supernatant, and the obtained supernatant was dried to obtain a control product.
利用物理特性测量***(PPMS-9)对原料非磁性VO
2、实施例1以及对照例1所得产品分别进行磁滞回线(VSM)测试，测得的磁滞回线(VSM)见图3：1代表原料非磁性VO
2，2代表对照例1所得对照产品，3代表实施例1所得目标产品。由图3可知：原料非磁性VO
2以及不填充CO
2气体的对照产品在常温下没有任何铁磁信号，超临界CO
2体系制备的目标VO
2，其磁滞回线呈现明显的S型闭环。证明超临界CO
2是激发非磁性VO
2产生室温铁磁性的决定性因素。
Utilize the physical property measurement system (PPMS-9) to carry out hysteresis loop (VSM) test to raw material non-magnetic VO 2 , embodiment 1 and the product obtained in comparative example 1 respectively, the measured hysteresis loop (VSM) is shown in Fig. 3 : 1 represents the raw material non-magnetic VO 2 , 2 represents the control product obtained in Comparative Example 1, and 3 represents the target product obtained in Example 1. It can be seen from Figure 3 that the raw material non-magnetic VO 2 and the control product not filled with CO 2 gas have no ferromagnetic signal at room temperature, and the hysteresis loop of the target VO 2 prepared by the supercritical CO 2 system presents an obvious S-shaped closed loop . It is proved that supercritical CO2 is the decisive factor to excite nonmagnetic VO2 to generate room temperature ferromagnetism.
Claims (5)
- 一种利用超临界流体技术制备铁磁性VO 2的制备方法，其特征在于：将非磁性VO 2分散到N-甲基吡咯烷酮和水组成的混合溶剂中，获得分散液；然后将分散液转移至超临界装置中，向超临界装置中注入二氧化碳，在超临界条件下搅拌反应3-6h，自然冷却至室温后卸压；将超临界处理后的体系分离，收集分离液并干燥，得到铁磁性VO 2。 A preparation method utilizing supercritical fluid technology to prepare ferromagnetic VO, characterized in that: non - magnetic VO is dispersed in a mixed solvent of N-methylpyrrolidone and water to obtain a dispersion; then the dispersion is transferred to In the supercritical device, inject carbon dioxide into the supercritical device, stir and react under supercritical conditions for 3-6 hours, and release the pressure after naturally cooling to room temperature; separate the system after supercritical treatment, collect the separated liquid and dry it to obtain ferromagnetic VO2 .
- 如权利要求1所述的利用超临界流体技术制备铁磁性VO 2的制备方法，其特征在于，所述超临界条件的参数为：温度40-200℃、压力8-30Mpa。 The method for preparing ferromagnetic VO2 using supercritical fluid technology according to claim 1, characterized in that the parameters of the supercritical conditions are: temperature 40-200°C, pressure 8-30Mpa.
- 如权利要求1所述的利用超临界流体技术制备铁磁性VO 2的制备方法，其特征在于：混合溶剂中，N-甲基吡咯烷酮所占的体积比为10-90％。 The method for preparing ferromagnetic VO2 by supercritical fluid technology according to claim 1, characterized in that: in the mixed solvent, the volume ratio of N-methylpyrrolidone is 10-90%.
- 如权利要求1或3所述的利用超临界流体技术制备铁磁性VO 2的制备方法，其特征在于：非磁性VO 2和混合溶剂的用量比为0.1-10mg/ml。 The method for preparing ferromagnetic VO 2 by supercritical fluid technology as claimed in claim 1 or 3, characterized in that the ratio of non-magnetic VO 2 and mixed solvent is 0.1-10 mg/ml.
- 如权利要求1所述的利用超临界流体技术制备铁磁性VO 2的制备方法，其特征在于：非磁性VO 2的晶相为A、B、M或R相。 The method for preparing ferromagnetic VO2 by supercritical fluid technology as claimed in claim 1, characterized in that: the crystal phase of nonmagnetic VO2 is A , B, M or R phase.
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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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