CN114807998A - High-entropy metal oxide FeCoNiCrMnO x Preparation method of (1) - Google Patents
High-entropy metal oxide FeCoNiCrMnO x Preparation method of (1) Download PDFInfo
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- CN114807998A CN114807998A CN202210395318.9A CN202210395318A CN114807998A CN 114807998 A CN114807998 A CN 114807998A CN 202210395318 A CN202210395318 A CN 202210395318A CN 114807998 A CN114807998 A CN 114807998A
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a high-entropy metal oxide FeCoNiCrMnO x The preparation method comprises the following steps: 1) mixing polyethylene glycol and urea, and heating to form eutectic solvent (DESs); 2) adding Fe salt, Co salt, Ni salt, Cr salt and Mn salt into the DESS, and heating to form a eutectic solvent system; 3) transferring the formed eutectic solvent system into a reaction kettle for reaction to obtain the high-entropy metal oxide FeCoNiCrMnO x . The invention has simple preparation process, mild condition and low preparation cost, can be used for industrial production and has no pollution to the environment. The obtained high-entropy metal oxide FeCoNiCrMnO x Has excellent electrocatalytic oxygen evolution performance.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials and preparation thereof, and particularly relates to a high-entropy metal oxide FeCoNiCrMnO x The preparation method of (1).
Background
Electrochemical water splitting is one of the key green technologies for producing hydrogen energy. However, the slow Oxygen Evolution Reaction (OER) kinetics greatly limit the water splitting efficiency. Despite the noble metal oxide (RuO) 2 And IrO 2 ) The OER has excellent OER activity, but the characteristics of scarcity, high cost, easy poisoning and the like make the OER difficult to popularize and use. Thus, there is a need for effective and stable non-noble metal OER catalysts. This inevitably involves an increase in catalytic activity, which can be effectively achieved by adjusting the surface electronic structure. One such method is the use of High Entropy Materials (HEM). The HEM contains five or more metals, providing a large number of combinations for tuning the electron and geometry to optimize catalytic activity. Thus, HEM electrocatalysts have been explored over the past several years. Various types of HEM, such as alloys, oxides, phosphides, borides, sulfides, etc., have been investigated for use as OER electrocatalysts.
High entropy metal oxides (HEO) are a recent group of new materials that are being introduced, aiming to extend the concept of High Entropy Alloys (HEA) to oxides. HEO is defined as a compound containing oxygen and five or more cations in its crystal structure. Due to the hybrid electronic structure of HEOs and their high internal entropy, it has been reported to prepare oxides by using chemical or thermochemical techniques and to use them for different functional applications.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a high-entropy metal oxide FeCoNiCrMnO x The preparation method has the advantages of simple preparation process, mild conditions, low preparation cost, industrial production and no pollution to the environment. The obtained high-entropy metal oxide FeCoNiCrMnO x Has excellent electrocatalytic oxygen evolution performance.
In order to achieve the aim, the invention provides a high-entropy metal oxide FeCoNiCrMnO x The preparation method comprises the following steps:
1) mixing polyethylene glycol and urea, and heating to form eutectic solvent (DESs);
2) adding Fe salt, Co salt, Ni salt, Cr salt and Mn salt into the DESS, and heating to form a eutectic solvent system;
3) transferring the formed eutectic solvent system into a reaction kettle for reaction to obtain the high-entropy metal oxide FeCoNiCrMnO x 。
In the step 1), the polyethylene glycol is polyethylene glycol 200 or polyethylene glycol 300;
the molar ratio of polyethylene glycol to urea can be 2: 1;
the heating is carried out in an oil bath at 40-100 ℃ (specifically 60 ℃);
in the above method step 2), the Fe salt, Co salt, Ni salt, Cr salt and Mn salt are added in equimolar amounts (in terms of the moles of the respective metals contained); the number of moles may be specifically 0 to 0.1mol (the end point is not preferable to be 0), specifically 0.001mol, 0.002mol or 0.003 mol;
the Fe salt may be FeCl 3 ·6H 2 O；
The Co salt may specifically be CoCl 2 ·6H 2 O；
The Ni salt may specifically be NiCl 2 ·6H 2 O；
The Cr salt may be specifically CrCl 3 ·6H 2 O；
The Mn salt may specifically be MnCl 2 ·4H 2 O；
The mixture ratio of the DESs to the Fe salt, the Co salt, the Ni salt, the Cr salt or the Mn salt can be as follows: 10-100 mL: 0 to 0.1mol (endpoint 0 is not preferable), and specifically 15 mL: 0 to 0.1mol (not preferable at the end point 0), more specifically 15 mL: 0.002mol, 15 mL: 0.001mol or 15 mL: 0.003 mol;
the reaction is carried out in an oven, the reaction temperature can be 150-300 ℃, the reaction time can be 2-48 h, and specifically the reaction time can be 12h at 210 ℃.
In the step 3), after the reaction is finished, naturally cooling to room temperature, filtering and collecting solids, washing with ethanol and deionized water for three times respectively, and drying to obtain the catalyst.
The obtained high-entropy metal oxide FeCoNiCrMnO x Consists of nano particles.
The high-entropy metal oxide FeCoNiCrMnO x The application of the catalyst as an Oxygen Evolution (OER) catalyst in water decomposition hydrogen production also belongs to the protection scope of the invention.
The preparation method provided by the invention is simple to operate, low in preparation cost and easy for industrial production, and the obtained high-entropy metal oxide FeCoNiCrMnO is x The material has regular shape and better crystal form.
Drawings
FIG. 1 is a diagram of a high entropy metal oxide FeCoNiCrMnO prepared in example 1 of the present invention x SEM photograph of (a);
FIG. 2 is a high entropy metal oxide FeCoNiCrMnO prepared in example 1 of the present invention x An XRD pattern of (a);
FIG. 3 shows high entropy metal oxide FeCoNiCrMnO prepared in examples 1-3 of the present invention x OER curve of (d).
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Accurately weighing polyethylene glycol 200 and urea in a molar ratio of 2:1, and forming eutectic solvents (DESs) in an oil bath pan at 60 ℃; respectively and accurately weighing 0.002mol of FeCl 3 ·6H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CrCl 3 ·6H 2 O、MnCl 2 ·4H 2 O, 15mL ofSynthesized DESS, forming a eutectic solvent (DESS) system in an oil bath at 60 ℃; and transferring the formed DESs system into a reaction kettle, placing the reaction kettle in an oven for reaction (210 ℃ and 12 hours), naturally cooling to room temperature after the reaction is finished, filtering and collecting solids, washing with ethanol and deionized water for three times respectively, and drying.
Example 2
Accurately weighing polyethylene glycol 200 and urea in a molar ratio of 2:1, and forming eutectic solvents (DESs) in an oil bath pan at 60 ℃; respectively and accurately weighing 0.001mol of FeCl 3 ·6H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CrCl 3 ·6H 2 O、MnCl 2 ·4H 2 O, adding 15mL of synthesized DESS, and forming a eutectic solvent (DESS) system in an oil bath kettle at 60 ℃; the formed DESs system was transferred to a reaction kettle and placed in an oven for reaction (210 ℃ C., reaction 12 h). After the reaction is finished, naturally cooling to room temperature, filtering and collecting solid, washing with ethanol and deionized water for three times respectively, and drying.
Example 3
Accurately weighing polyethylene glycol 200 and urea in a molar ratio of 2:1, and forming eutectic solvents (DESs) in an oil bath pan at 60 ℃; respectively and accurately weighing 0.003mol of FeCl 3 ·6H 2 O、CoCl 2 ·6H 2 O、NiCl 2 ·6H 2 O、CrCl 3 ·6H 2 O、MnCl 2 ·4H 2 O, adding 15mL of synthesized DESS, and forming a eutectic solvent (DESS) system in an oil bath kettle at 60 ℃; the formed DESs system was transferred to a reaction kettle and placed in an oven for reaction (210 ℃ C., reaction 12 h). After the reaction is finished, naturally cooling to room temperature, washing with ethanol and deionized water for three times respectively, and drying.
The product obtained in example 1 was topographically characterized. Wherein the product morphology is observed by SEM and the product composition and crystal form are identified by XRD.
FIG. 1 is a diagram of a high entropy metal oxide FeCoNiCrMnO prepared in example 1 of the present invention x SEM photograph of (a), it can be seen from the figure that the prepared material is composed of nanoparticles;
FIG. 2 shows an embodiment of the present inventionHigh entropy Metal oxide FeCoNiCrMnO prepared in example 1 x The XRD pattern of the sample shows that XRD diffraction peaks of all samples can be attributed to No. PDF #06-0532 and are in a CrO structure;
FIG. 3 shows high entropy metal oxide FeCoNiCrMnO prepared in examples 1-3 of the present invention x The OER performance of the synthesized high-entropy metal oxide FeCoNiCrMnO can be seen from the graph x Has excellent oxygen evolution performance.
Table 1 shows the high entropy metal oxide FeCoNiCrMnO prepared in example 1 of the present invention x ICP-OES result of (1).
TABLE 1
Table 1 shows the high entropy metal oxide FeCoNiCrMnO prepared in example 1 of the present invention x ICP-OES of (1), it can be seen from the table that the synthesized high entropy metal oxide FeCoNiCrMnO x The mole fractions of the elements Fe, Co, Ni, Cr and M are respectively 21%, 18%, 22%, 19% and 20%.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (7)
1. High-entropy metal oxide FeCoNiCrMnO x The preparation method comprises the following steps:
1) mixing polyethylene glycol and urea, and heating to form a eutectic solvent;
2) adding Fe salt, Co salt, Ni salt, Cr salt and Mn salt into the DESS, and heating to form a eutectic solvent system;
3) transferring the formed eutectic solvent system into a reaction kettle for reaction to obtain the high-entropy metal oxide FeCoNiCrMnO x 。
2. The method of claim 1, wherein: in the step 1), the polyethylene glycol is polyethylene glycol 200 or polyethylene glycol 300;
the molar ratio of polyethylene glycol to urea is 2: 1;
the heating is carried out in an oil bath at 40-100 ℃.
3. The method according to claim 1 or 2, characterized in that: in the step 2), adding the Fe salt, the Co salt, the Ni salt, the Cr salt and the Mn salt in equal molar number; the mole number is 0-0.1 mol;
the mixture ratio of the DESs to the Fe salt, the Co salt, the Ni salt, the Cr salt or the Mn salt is as follows: 10-100 mL: 0 to 0.1 mol.
4. The method according to any one of claims 1-3, wherein: the reaction is carried out in an oven, the reaction temperature is 150-300 ℃, and the reaction time is 2-48 h.
5. The method according to any one of claims 1-4, wherein: the obtained high-entropy metal oxide FeCoNiCrMnO x Consists of nano particles.
6. High entropy metal oxide FeCoNiCrMnO prepared by the process of any one of claims 1 to 5 x 。
7. The high entropy metal oxide FeCoNiCrMnO of claim 6 x The catalyst can be used as an electric oxygen evolution catalyst in the water decomposition hydrogen production.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115044935A (en) * | 2022-07-29 | 2022-09-13 | 东北大学秦皇岛分校 | Preparation method and application of nano high-entropy oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364717A (en) * | 2019-07-24 | 2019-10-22 | 东北大学秦皇岛分校 | A kind of high entropy oxide electrode material of spinel-type and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364717A (en) * | 2019-07-24 | 2019-10-22 | 东北大学秦皇岛分校 | A kind of high entropy oxide electrode material of spinel-type and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIALE WEI ET AL.,: "Deep eutectic solvent assisted facile synthesis of low-dimensional hierarchical porous high-entropy oxides" * |
| JINGYUN JIANG ET AL.,: "A PEGylated deep eutectic solvent for controllable solvothermal synthesis of porous NiCo2S4 for efficient oxygen evolution reaction" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115044935A (en) * | 2022-07-29 | 2022-09-13 | 东北大学秦皇岛分校 | Preparation method and application of nano high-entropy oxide |
| CN115044935B (en) * | 2022-07-29 | 2024-03-08 | 东北大学秦皇岛分校 | Preparation method and application of nano high-entropy oxide |
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