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CN-122010198-A - High-entropy metal sulfide nano material and preparation method thereof

CN122010198ACN 122010198 ACN122010198 ACN 122010198ACN-122010198-A

Abstract

The invention discloses a high-entropy metal sulfide nano material and a preparation method thereof, which relate to the field of high-entropy materials, and are characterized in that transition metal chloride and sodium chloride are placed in a first reaction boat in an upstream area of a reaction container; the method comprises the steps of placing a zinc sulfide nano template in a second reaction boat in a downstream area of a reaction container, heating the reaction container to 500-525 ℃ at a first heating rate, preserving heat for 20-40 min, conveying metal chloride gas volatilized by a eutectic effect of a precursor to the second reaction boat in the downstream area along with dynamic airflow, enabling the zinc sulfide nano template to react with the metal chloride gas, cooling to room temperature at a second cooling rate, and collecting solid products in the second reaction boat to obtain the high-entropy metal sulfide nano material. The invention can replicate the complex microstructure of the precursor template to realize topology conversion, and can regulate and control the chemical morphology, components, crystal structure and the like of the high-entropy nano material.

Inventors

  • Da Pengfei
  • ZHAO LI
  • Jiang Haoji
  • YAN WENKAI

Assignees

  • 兰州交通大学

Dates

Publication Date
20260512
Application Date
20260312

Claims (10)

  1. 1. The preparation method of the high-entropy metal sulfide nano material is characterized by comprising the following steps of: Step 1, placing a precursor in a first reaction boat in an upstream area of a reaction container, wherein the precursor comprises sodium chloride and at least four transition metal chloride salts; Step 2, placing the zinc sulfide nano template in a second reaction boat in the downstream area of the reaction container; step 3, the reaction vessel is subjected to at least 3 inert gas filling and discharging cyclic replacement to remove air; Step 4, introducing inert gas into the upstream of the reaction container, exhausting the downstream of the reaction container, and forming dynamic airflow flowing from the upstream to the downstream in the reaction container to enable the pressure in the reaction container to be 200-300 Pa; Step 5, heating the reaction vessel to 500-525 ℃ at a first heating rate, and preserving heat for 20-40 min, wherein the metal chloride gas volatilized by the eutectic effect of the precursor is transported to a second reaction boat in a downstream area along with the dynamic airflow, so that the zinc sulfide nano template reacts with the metal chloride gas; and step 6, cooling to room temperature at a second cooling rate, and collecting solid products in a second reaction boat to obtain the high-entropy metal sulfide nano material.
  2. 2. The method for preparing the high-entropy metal sulfide nanomaterial according to claim 1, wherein the precursor comprises sodium chloride and four transition metal chloride salts, wherein the four transition metal chloride salts are ferrous chloride, cobaltous chloride, nickel chloride and cuprous chloride respectively.
  3. 3. The method for preparing a high-entropy metal sulfide nanomaterial according to claim 1, wherein in step 1, a transition metal chloride salt and sodium chloride are mixed and ground until a uniformly mixed powdery precursor is obtained, the particle size of the powdery precursor is 60-80 μm, and the powdery precursor is placed in a first reaction boat in an upstream region of a reaction vessel.
  4. 4. The method for preparing the high-entropy metal sulfide nano material according to claim 1, wherein the inner diameter of the reaction vessel is 55-65 mm, and the distance between the first reaction boat and the second reaction boat is 10-20 mm.
  5. 5. The preparation method of the high-entropy metal sulfide nano material according to claim 1, wherein the weight ratio of the transition metal chloride salt to the sodium chloride is 10-12:5-6.
  6. 6. The preparation method of the high-entropy metal sulfide nano material according to claim 1, wherein the weight ratio of the zinc sulfide nano template to the transition metal chloride is 1-2:10-12.
  7. 7. The method for preparing the high-entropy metal sulfide nano material according to claim 1, wherein the downstream air extraction rate of the reaction vessel is 5-10 m 3 /h.
  8. 8. The method for preparing the high-entropy metal sulfide nano material according to claim 1, wherein the first heating rate is 8-15 ℃ per minute, and the second cooling rate is 10-15 ℃ per minute.
  9. 9. The method for preparing the high-entropy metal sulfide nano material according to claim 1, wherein the zinc sulfide nano template is zinc sulfide nano particle powder, zinc sulfide nano sheet powder or zinc sulfide nano three-dimensional macroporous powder.
  10. 10. A high entropy metal sulfide nanomaterial prepared according to the preparation method of any one of claims 1 to 9.

Description

High-entropy metal sulfide nano material and preparation method thereof Technical Field The invention relates to the field of high-entropy materials, in particular to a high-entropy metal sulfide nano material and a preparation method thereof. Background The high-entropy material, in particular to the high-entropy sulfide, has great application potential in the fields of electrochemical energy storage, electrocatalysis, photocatalysis and the like. Compared with the traditional binary or ternary sulfide, the high-entropy sulfide can remarkably regulate and control the electronic structure of the material, maximize the density of active sites and improve the structural stability by introducing five or more metal elements to form a single-phase solid solution. However, the synthesis is very challenging due to the large atomic/ionic radius differences in multicomponent systems and the high mixed entropy increase requirements. Existing high-entropy material synthesis methods, such as joule heating, arc discharge and high-temperature solid phase sintering, generally rely on ultra-high temperature (> 1000 ℃) to melt or rapidly diffuse the raw materials, and combine with rapid quenching to freeze the high Wen Moxu solid solution state to room temperature. Although the synthetic path can realize rapid mixing of multiple components, ultrahigh temperature and extremely rapid cooling bring extremely high requirements to equipment, and are difficult to popularize in large scale. Moreover, the high temperature is extremely prone to severe agglomeration and grain coarsening of the nanoparticles, which greatly reduces the specific surface area of the material, and it is difficult to retain the fine micro morphology of the precursor, such as porous, hollow structures, thereby limiting its performance in applications requiring high specific surface areas. Although the solvothermal/hydrothermal method can synthesize the nano-material at a lower temperature, the liquid phase surface tension exists in the reaction system. Capillary forces during drying tend to cause collapse and blocking of porous or sheet-like structures. In addition, the hydrolysis rate and precipitation kinetics of different metal ions in the liquid phase are huge, so that even atomic-level mixing of more than five metal elements is difficult to realize, and a multiphase mixture rather than a single high-entropy solid solution is easy to generate. Chemical Vapor Deposition (CVD) methods are commonly used to produce high quality two-dimensional sulfide films or nanoplatelets, for example, znS grown on substrates using zinc powder and a sulfur source gas. However, conventional CVD processes typically rely on toxic gases such as H 2S、CS2 as a sulfur source and are primarily suitable for growing epitaxial thin films on specific substrates, making it difficult to mass prepare individual powder materials with complex three-dimensional morphology such as macropores, hollow spheres. More importantly, when a plurality of metal precursors are introduced in a CVD method, the volatilization temperature and the reactivity of each metal organic source or halide are obviously different, so that the stoichiometric ratio of multiple components is extremely difficult to control, and the components of the product are uneven. In order to regulate the microscopic morphology of sulfides, template methods are widely studied. The current ZnS template conversion is mostly carried out in the liquid phase, with ion exchange with ZnS using a metal salt solution. This method is limited by the liquid phase mass transfer resistance, the reaction rate is slow, and as previously mentioned, the liquid phase environment is prone to damage to the fragile structure of the template. Although the gas-solid reaction can avoid the damage of the surface tension of the liquid phase, the gas-solid reaction of the traditional metal chloride and ZnS usually needs a higher temperature (> 700 ℃) to overcome the reaction energy barrier, so that the metal chloride is fully volatilized and participates in the reaction. At high temperature, znS templates are easy to sinter, phase change or collapse in structure, and the meaning of a template method is lost. Therefore, how to simultaneously drive the reaction of various metal chlorides with great volatility difference and ZnS at low temperature and form uniform high-entropy solid solution is a difficult problem to be solved urgently. Disclosure of Invention The invention aims to provide a high-entropy metal sulfide nano material and a preparation method thereof, which can realize the atomic-level uniform mixing of various metal elements and regulate and control the chemical morphology, components, crystal structure and other microstructures of the metal elements through a gas-solid reaction mechanism under a low-temperature condition. The first object of the invention is a method for preparing a high-entropy metal sulfide nanomaterial, comprising the followin