CN113501709B - Synthesis of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Method (2) - Google Patents
Synthesis of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Method (2) Download PDFInfo
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Abstract
The invention provides a method for synthesizing spinel by a hydrothermal methodType high entropy oxide material (MCoFeCrMn)3O4The method comprises the steps of fully dissolving nickel nitrate or/and copper nitrate, cobalt nitrate, ferric nitrate, chromium nitrate and manganese nitrate into ultrapure water in equimolar quantities to obtain a mixed solution of metal salts; adding a precipitator into the mixed solution, uniformly stirring, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, cooling to room temperature after the reaction is finished, filtering the reaction solution under reduced pressure, washing with ultrapure water, filtering, separating and precipitating by suction filtration, drying to obtain solid powder, and crystallizing to obtain the high-entropy oxide (MCoFeCrMn)3O4Wherein M = Ni or/and Cu. The high-entropy oxide is of a spinel structure, has high infrared emissivity in a wave band of 3-12 mu m, can be suitable for infrared heating, has high light absorptivity in a wave band of 0.3-2.5 mu m, and can be suitable for solar energy absorption.
Description
Technical Field
The invention relates to a spinel high-entropy oxide material (MCoFeCrMn) with infrared radiation and light absorption characteristics3O4In particular to a method for preparing spinel type high-entropy oxide material (MCoFeCrMn) by a hydrothermal method3O4(wherein, M = Ni or/and Cu) belongs to ceramic materials, and is applied to the fields of infrared heating, solar energy absorption and the like.
Background
The high-entropy oxide material is a novel ceramic material developed on the basis of high-entropy alloy, and has attracted extensive attention of researchers due to unique structural characteristics and function controllable characteristics. The high-entropy alloy is a high-grade material with stable configuration entropy-driven (FCC, BCC and the like) phase structure consisting of five or more metal elements, and has thermodynamic high-entropy effect, structural lattice distortion effect, kinetic slow diffusion effect and performance cocktail effect. The high-entropy oxide is used as a novel oxide system developed in recent years, breaks through the design concept of the traditional doped oxide, is composed of five or more metal elements in equimolar or approximately equimolar, and is widely concerned by researchers at home and abroad due to simple structure, excellent performance and the like. J. the design is a squareuliuszDabrowa et al prepared high entropy oxide materials (Ni, mn, fe, co, cr) having spinel structure for the first time by conventional high temperature solid phase synthesis3O4Specifically, niO, mnO and Fe are mixed in an equimolar ratio2O3、Co3O4And Cr2O3The method is characterized in that the raw Materials are uniformly mixed by adopting a mechanical ball milling method, then the mixture is pressed into small balls, then the small balls are calcined for 20 hours at 1050 ℃, and finally a sample is placed on an aluminum plate to be quenched to room temperature so as to prepare the high-entropy oxide (Materials Letters,2018,216, 32-36) with a single-phase spinel structure, the inevitable mixing of the raw Materials exists by adopting the mechanical ball milling, the designed equimolar ratio is difficult to realize, and meanwhile, the biggest defects of high-temperature solid-phase synthesis are long heat preservation time and large energy consumption. In addition, sarkar et al adopt spray pyrolysis method and flame pyrolysis method to prepare rock type nanocrystalline powder, and then spray pyrolysis is carried out on the rock type nanocrystalline powder by a spray device at 1150 ℃ to prepare corresponding high-entropy oxide nanocrystalline powder material, and quaternary nanocrystalline powder (Co, mg, ni, zn) O can obtain high-entropy oxide with single rock type structure at higher temperature (1250 ℃), and the preparation method has the defects of multiple preparation steps, complex process, uncontrollable property and the like.
The combination of the one-step hydrothermal method and the annealing treatment technology is a simple means for material synthesis and modification, and has the advantages of short reaction period, low cost, no pollution, rapidness, high efficiency and the like. At present, relevant reports of preparing the high-entropy oxide material by combining a one-step hydrothermal method with an annealing treatment technology are not retrieved yet.
Disclosure of Invention
The invention aims to provide a hydrothermal method for preparing a spinel-type high-entropy oxide material (MCoFeCrMn) with infrared radiation and light absorption characteristics3O4The method of (1).
The invention relates to a method for synthesizing spinel type high-entropy oxide material (MCoFeCrMn) by a hydrothermal method3O4Respectively dissolving nickel nitrate or/and copper nitrate, cobalt nitrate, ferric nitrate, chromium nitrate and manganese nitrate in ultra-pure water in equimolar proportion, and fully mixing to obtain a mixed solution of metal salts; adding precipitant into the mixed solution, stirring, and transferringCarrying out hydrothermal reaction in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, cooling to room temperature after the reaction is finished, filtering the reaction liquid under reduced pressure, washing with ultrapure water, filtering, separating, precipitating, drying to obtain solid powder, and crystallizing to obtain the high-entropy oxide (MCoFeCrMn)3O4Wherein M = Ni or/and Cu.
Among the high-entropy oxide materials, the high-entropy oxide material prepared from four metal nitrates of Co, fe, cr and Mn has a spinel crystal structure and good infrared emission performance. Researches show that the addition of Ni and Cu has no significant influence on the crystal form of the material, but can significantly improve the emissivity of the material in an infrared light area.
In the mixed solution, the concentration of nickel nitrate or/and copper nitrate, cobalt nitrate, ferric nitrate, chromium nitrate and manganese nitrate is 0.1-0.6 mol/L, so that the normal hydrothermal reaction is ensured.
The precipitator is one or two of sodium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate; the molar ratio of the precipitant to the total metal nitrate is 2 to 1. The effect of adding the precipitant is to form a stable spinel structure during the formation of the solid solution. The type and the adding amount of the precipitant have certain influence on the microscopic morphology, the crystal form and the phase purity of the product, a few of precipitants are added to cause that some peaks in an X-ray diffraction pattern cannot be presented, and excessive precipitants are added to cause that phases are impure and excessive impurity peaks appear in the X-ray diffraction pattern.
The temperature of the hydrothermal reaction is 120 to 180 ℃, and the reaction time is 1 to 7 hours. The temperature and time of the hydrothermal reaction have certain influence on the crystal form and the phase structure of the product, and when the temperature and the time of the hydrothermal reaction are too low and too short, a stable spinel structure cannot be formed; when the temperature of the hydrothermal reaction is too high and the time is too long, the energy consumption is high, the reaction period is prolonged, and the efficiency is obviously reduced.
The temperature of the crystallization treatment is 300 to 900 ℃, the heating rate is 3 to 10 DEG/min, the heat preservation time is 2 to 7 hours, and the cooling rate is furnace-following natural cooling. The crystallization treatment temperature, the heating rate and the heat preservation time also have great influence on the micro-morphology and the crystal form of the product. Researches show that the crystallization treatment temperature can improve the emissivity of the infrared light region in the material to a certain extent.
The high-entropy oxide material (MCoFeCrMn) prepared by the present invention was measured by X-ray diffractometer (XRD) manufactured by Pasnake, holland3O4(M = Ni or/and Cu) structure analysis (FIG. 1, FIG. 5) showed that the prepared high entropy oxide (MCoFeCrMn)3O4Has a spinel face-centered cubic structure (Fd-3 m space group). High entropy oxide (MCoFeCrMn)3O4The (M = Ni or/and Cu) face-centered cubic spinel structure is not only an important commercial metal high-entropy system, but also has higher ductility and fracture toughness, the price of the required raw materials is relatively low, and therefore the structure is attractive, and the structure has a remarkable improvement effect on infrared emission performance.
High entropy oxide (MCoFeCrMn) prepared by using Scanning Electron Microscope (SEM) to attach energy to the main body3O4Was analyzed for morphology and microstructure (FIG. 2), indicating that the prepared high entropy oxide (MCoFeCrMn)3O4The powder is porous and has fine, fluffy, foamy particles evenly distributed around the large particles.
Quantitative analysis of high entropy oxides (MCoFeCrMn) by X-ray energy Spectroscopy (EDS)3O4The content of the element (as shown in fig. 4) can determine that the proportion of the contained metal element is close to equimolar.
The (MCoFeCrMn) prepared by the invention is measured by a direct-reading infrared emissivity tester3O4The infrared emissivity of the high-entropy oxide shows that (MCoFeCrMn)3O4The normal emissivity of the high-entropy oxide in a wave band of 3 to 12 mu m is more than or equal to 0.95. I.e. having a high ir emissivity.
The high entropy oxide was tested using a Lambda 950 ultraviolet visible near infrared spectrophotometer and the results showed (MCoFeCrMn)3O4The absorptivity of the high-entropy oxide in a wave band of 0.3 to 2.5 mu m is more than or equal to 0.88, namely the high light absorptivity is achieved. The main reason is that the addition of Cu and Ni can widen the light absorption range and contribute to the improvement of the light absorption rate.
The invention relates to a hydrothermal synthesis method(MCoFeCrMn)3O4The high entropy oxide has the following advantages:
1. the metal salt is used as a raw material, so that the raw material source is wide and the cost is low;
2. by adopting a hydrothermal method, the raw materials are mixed under a liquid phase condition, so that the metal elements can be fully and uniformly mixed, and the product can realize the designed stoichiometric ratio; the reaction condition is mild, the energy is saved, the efficiency is high, the cost is low, and the reaction process is green and environment-friendly;
3. the solar energy absorption film has high light absorption rate, is used in the field of solar energy absorption, and can directly convert solar energy into electric energy, light energy, heat energy and the like;
4. the high-emissivity carbon has high infrared emissivity, is used in the field of infrared heating, can relieve the current energy crisis, can save energy and improve efficiency, and promotes carbon peak reaching and carbon neutralization in the industrial field.
Drawings
FIG. 1 is (NiCoFeCrMn) prepared in example 13O4XRD pattern of high entropy oxide powder.
FIG. 2 is (NiCoFeCrMn) prepared in example 13O4SEM images of high entropy oxide powders.
FIG. 3 is (NiCoFeCrMn) prepared in example 13O4Elemental distribution of high entropy oxide powders.
FIG. 4 is (NiCoFeCrMn) prepared in example 13O4EDS analysis of high entropy oxide powders.
FIG. 5 is a photograph of a film prepared in example 5 (NiCuCoFeCrMn)3O4XRD pattern of high entropy oxide powder.
Detailed Description
The preparation of the spinel-type high-entropy oxide material synthesized by the method and the infrared radiation performance of the spinel-type high-entropy oxide material are further described by specific implementation.
Example 1, (NiCoFeCrMn)3O4Preparation and Properties of high entropy oxides
Nickel nitrate 1.7563g (0.006 mol), cobalt nitrate 1.7457g (0.006 mol), ferric nitrate 2.4243 g (0.006 mol), chromium nitrate 2.4539 g (0.006 mol) and nitric acid were weighedManganese 2.1653 g (0.006 mol) is respectively dissolved in 12 mL ultrapure water and uniformly stirred, and five metal salt solutions are mixed and continuously stirred until the five metal salt solutions are completely and uniformly mixed to obtain a mixed solution of metal nitrates; then 2.5438g (0.024 mol) of sodium carbonate is weighed and added into the mixed solution to be stirred evenly; then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a 150 ℃ blast oven for heat preservation treatment of 4 h, and then cooling to room temperature; filtering the reaction solution under reduced pressure, washing with ultrapure water for 5 times, filtering, separating, precipitating, and drying to obtain solid powder; finally, the obtained solid powder is placed in a 500 ℃ heat preservation furnace for heat preservation for 5 hours for crystallization treatment (in the crystallization treatment process, the heating rate is 5 DEG/min, the cooling rate is natural cooling along with the furnace), and (NiCoFeCrMn) is obtained3O4A high entropy oxide.
Prepared by this example (NiCoFeCrMn)3O4XRD of the high entropy oxide is shown in figure 1. As can be seen from FIG. 1, the prepared high entropy oxide (NiCoFeCrMn)3O4Is of a spinel structure; the SEM is shown in FIG. 2. As can be seen from FIG. 2, the prepared high entropy oxide (NiCoFeCrMn)3O4The powder is porous with fine, fluffy, foamy particles evenly distributed around the large particles. The element distribution characterization analysis is shown in fig. 3, and it can be known that the elements of Ni, co, fe, cr, mn and O are uniformly distributed in the whole area, which proves the uniformity of the chemical and microstructure. The X-ray energy spectrum (EDS) shown in fig. 4 can confirm that the ratio of the contained metal elements is close to equimolar. Infrared radiation performance: the normal emissivity of the wave band of 3 to 12 mu m is more than or equal to 0.95. Light absorption properties: the absorptivity in the wave band of 0.3 to 2.5 μm is 0.89.
Example 2, (NiCoFeCrMn)3O4Preparation and Properties of high entropy oxides
Weighing nickel nitrate 1.7563g (0.006 mol), cobalt nitrate 1.7457g (0.006 mol), ferric nitrate 2.4243 g (0.006 mol), chromic nitrate 2.4539 g (0.006 mol) and manganese nitrate 2.1653 g (0.006 mol) to respectively dissolve in 60 mL ultrapure water for uniform stirring, continuously stirring five metal salt solutions until the five metal salt solutions are completely and uniformly mixed to obtain a mixed solution of the metal nitrateLiquid; weighing sodium carbonate (0.012 mol) 1.2719 g, adding into the mixed solution, and stirring; then transferring the mixed solution to a polytetrafluoroethylene-lined stainless steel reaction kettle, placing the reaction kettle in a blast oven at 120 ℃, and carrying out heat preservation treatment on the mixed solution to obtain 1 h; cooling to room temperature, filtering the reaction solution under reduced pressure, washing with ultrapure water for 3 times, filtering, separating, precipitating, and drying to obtain solid powder; finally, the obtained solid powder is placed in a 300 ℃ heat preservation furnace for heat preservation for 2h for crystallization treatment (the temperature rising rate in the crystallization treatment process is 3 DEG/min, the temperature reduction rate is natural cooling along with the furnace), and the (NiCoFeCrMn) is obtained3O4A high entropy oxide.
Prepared by this example (NiCoFeCrMn)3O4Infrared radiation performance of high entropy oxides: the normal emissivity in the wave band of 3 to 12 mu m is more than or equal to 0.93. Light absorption properties: the absorptivity in the wave band of 0.3 to 2.5 μm is 0.90.
Example 3, (NiCoFeCrMn)3O4Preparation and Properties of high entropy oxides
Weighing nickel nitrate 1.7563g (0.006 mol), cobalt nitrate 1.7457g (0.006 mol), ferric nitrate 2.4243 g (0.006 mol), chromium nitrate 2.4539 g (0.006 mol) and manganese nitrate 2.1653 g (0.006 mol) to respectively dissolve in 10 mL ultrapure water and uniformly stir, and continuously stirring five metal salt solutions until the five metal salt solutions are completely and uniformly mixed to obtain a mixed solution of metal nitrates; weighing 3.8156 g (0.036 mol) sodium carbonate, adding into the mixed solution, and stirring; then transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel reaction kettle, placing the reaction kettle in a blowing oven at 180 ℃, preserving heat for 7 h, cooling to room temperature, filtering the reaction solution under reduced pressure, washing with ultrapure water for 7 times, performing suction filtration, separation and precipitation, and drying to obtain solid powder; finally, the obtained solid powder is placed in a 900 ℃ heat preservation furnace for heat preservation 7 h for crystallization treatment (the temperature rise rate in the crystallization treatment process is 10 degrees/min, and the temperature reduction rate is natural cooling along with the furnace), and (NiCoFeCrMn) is obtained3O4A high entropy oxide.
Prepared by this example (NiCoFeCrMn)3O4Infrared radiation performance of high entropy oxides: the normal emissivity in the wave band of 3 to 12 mu m is more than or equal to 0.94. Light absorptionThe yield performance is as follows: the absorptivity in the wave band of 0.3 to 2.5 μm is 0.88.
Example 4, (CuCoFeCrMn)3O4Preparation and performance of high-entropy oxide
Weighing copper nitrate 1.4577 g (0.006 mol), cobalt nitrate 1.7434 g (0.006 mol), ferric nitrate 2.4232 g (0.006 mol), chromium nitrate 2.4567 g (0.006 mol) and manganese nitrate 2.1657 g (0.006 mol) which are respectively dissolved in 12 mL ultrapure water and uniformly stirred, and continuously stirring five metal salt solutions until the five metal salt solutions are completely and uniformly mixed to obtain a mixed solution of metal nitrates; then weighing 2.5438g (0.024 mol) sodium carbonate, adding into the above mixed solution, and stirring; then transferring the mixed solution to a polytetrafluoroethylene-lined stainless steel reaction kettle, placing the reaction kettle in a 150 ℃ blast oven, carrying out heat preservation treatment on 4 h, cooling to room temperature, carrying out reduced pressure filtration on the reaction liquid, washing with ultrapure water for 5 times, carrying out suction filtration, separation and precipitation, and drying to obtain solid powder; finally, the obtained solid powder is placed in a 500 ℃ heat preservation furnace for heat preservation 5h for crystallization treatment (the temperature rise rate in the crystallization treatment process is 5 DEG/min, and the temperature reduction rate is furnace natural cooling) to obtain the product (CuCoFeCrMn)3O4A high entropy oxide.
Prepared by this example (NiCoFeCrMn)3O4Infrared radiation performance of high entropy oxides: the normal emissivity in the wave band of 3 to 12 mu m is more than or equal to 0.96. Light absorption properties: the absorptivity in the wave band of 0.3 to 2.5 μm is 0.89.
Example 5, (NiCuCoFeCrMn)3O4Preparation and performance of high-entropy oxide
(1) Weighing nickel nitrate 1.7526 g (0.006 mol), copper nitrate 1.4598 g (0.006 mol), cobalt nitrate 1.7498 g (0.006 mol), ferric nitrate 2.4225 g (0.006 mol), chromium nitrate 2.4572 g (0.006 mol) and manganese nitrate 2.1532 g (0.006 mol) which are respectively dissolved in 12 mL ultrapure water and uniformly stirred, and continuously stirring five metal salt solutions until the five metal salt solutions are completely and uniformly mixed to obtain a mixed solution of the metal nitrate; then weighing 2.5438g (0.024 mol) sodium carbonate, adding into the above mixed solution, and stirring; then transferring the mixed solution to a polytetrafluoroethylene lining stainless steel reaction kettle to be arranged in the reaction kettlePreserving heat in a blowing oven at 150 ℃ for 4 h, cooling to room temperature, filtering the reaction solution under reduced pressure, washing with ultrapure water for 5 times, performing suction filtration, separating and precipitating, and drying to obtain solid powder; finally, placing the obtained solid powder in a 500 ℃ heat preservation furnace for heat preservation by 5h for crystallization treatment (the temperature rise rate in the crystallization treatment process is 5 degrees/min, and the temperature reduction rate is natural cooling along with the furnace) to obtain the product (NiCuCoFeCrMn)3O4A high entropy oxide.
Prepared by this example (NiCuCoFeCrMn)3O4XRD of the high entropy oxide is shown in fig. 5. As can be seen from FIG. 5, the prepared high entropy oxide (NiCuCoFeCrMn)3O4Is of spinel structure. Infrared radiation performance: the normal emissivity at the wave band of 3 to 12 mu m is more than or equal to 0.96. Light absorption properties: the absorptivity in the wave band of 0.3 to 2.5 μm is 0.88.
Claims (2)
1. Preparation of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Respectively dissolving nickel nitrate or/and copper nitrate, cobalt nitrate, ferric nitrate, chromium nitrate and manganese nitrate in ultra-pure water in equimolar proportion, and fully mixing to obtain a mixed solution of metal salts; adding a precipitant into the mixed solution, uniformly stirring, transferring to a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, cooling to room temperature after the reaction is finished, filtering the reaction solution under reduced pressure, washing with ultrapure water, filtering, separating, precipitating, drying, and crystallizing the obtained solid powder to obtain the high-entropy oxide (MCoFeCrMn)3O4Wherein M = Ni or/and Cu;
the precipitant is one or two of sodium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate, and the molar ratio of the precipitant to the total metal nitrate is 2 to 1;
the temperature of the hydrothermal reaction is 120 to 180 ℃, and the reaction time is 1 to 7 hours;
the temperature of the crystallization treatment is 300 to 900 ℃, the heating rate is 3 to 10 ℃/min, the heat preservation time is 2 to 7 h, and the crystallization treatment is carried out by natural cooling along with a furnace.
2. As claimed in claim1 preparation of spinel-type high entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4The method is characterized in that: in the mixed solution, the concentration of nickel nitrate or/and copper nitrate, cobalt nitrate, ferric nitrate, chromium nitrate and manganese nitrate is 0.1 to 0.6 mol/L.
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| CN202110812378.1A CN113501709B (en) | 2021-07-19 | 2021-07-19 | Synthesis of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Method (2) |
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| CN114804887A (en) * | 2022-03-22 | 2022-07-29 | 武汉科技大学 | (CoCrFeMnNi) N high-entropy ceramic powder and preparation method thereof |
| CN114920546B (en) * | 2022-05-06 | 2023-08-08 | 武汉理工大学 | High-entropy ceramic coating and preparation method and application thereof |
| CN114906883B (en) * | 2022-05-20 | 2024-08-06 | 东南大学 | Oxygen storage and thermochemical conversion high-entropy oxide and preparation method and application thereof |
| 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 |
| CN115155602B (en) * | 2022-08-02 | 2023-06-30 | 西部金属材料股份有限公司 | Metal oxide-copper composite catalyst and preparation method and application thereof |
| CN115506146B (en) * | 2022-10-18 | 2024-04-09 | 陕西科技大学 | Flexible carbon cloth loaded spinel far-infrared emission material and preparation method thereof |
| CN115450041B (en) * | 2022-10-18 | 2024-04-09 | 陕西科技大学 | Carbon cloth loaded high-entropy spinel ceramic material with high far-infrared emissivity and preparation method thereof |
| CN115744970A (en) * | 2022-12-15 | 2023-03-07 | 常州大学 | Method for preparing high-entropy pyrochlore oxide battery negative electrode material by hydrothermal method |
| CN116855813B (en) * | 2023-08-22 | 2024-02-09 | 吉林省宝利科贸有限公司 | Polyhedral nano high-entropy material and preparation method and application thereof |
| CN117466649B (en) * | 2023-11-13 | 2024-04-09 | 中国科学院兰州化学物理研究所 | Preparation method of multifunctional high-entropy boride |
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