High-entropy semiconductor catalyst and preparation method and application thereof
A carbon-nitrogen-doped high-entropy semiconductor catalyst was prepared by mixing and calcining metal salts with amine organic ligands. This solved the energy consumption and segregation problems in the existing high-entropy material preparation process, and enabled efficient catalysis and large-scale production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHENZHEN UNIV
- Filing Date
- 2023-12-06
- Publication Date
- 2026-05-29
AI Technical Summary
Existing methods for preparing high-entropy materials suffer from problems such as high energy consumption, demanding synthesis equipment requirements, and nanostructure segregation, resulting in poor catalytic efficiency and expected effects.
A high-entropy semiconductor catalyst was prepared by mixing metal salts and amine organic ligands, followed by centrifugation, washing, freeze-drying, and calcination under an inert atmosphere. The carbon and nitrogen-doped high-entropy semiconductor catalyst was obtained by anchoring the coordination atoms to restrict the movement of metal atoms.
The preparation process is simple and easy to operate, with abundant catalytic active sites, good chemical stability, and uniform element distribution, making it suitable for large-scale production and application in the catalytic degradation of pollutants.
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Figure CN117654578B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of semiconductor catalyst technology, and in particular to a high-entropy semiconductor catalyst, its preparation method, and its application. Background Technology
[0002] Solving environmental pollution and protecting ecological balance are among the important issues facing society today. For the treatment of organic pollutants, selecting an ideal catalyst for efficient catalytic degradation is an effective method. High-entropy catalysts have multiple active centers and diverse functions, and therefore play an important role in the field of catalytic degradation.
[0003] However, existing methods for preparing high-entropy materials have some drawbacks, such as high energy consumption, high requirements for the synthesis equipment, and segregation of nanostructures, which result in a gap between the catalytic efficiency of high-entropy catalysts and the expected results.
[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention
[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a high-entropy semiconductor catalyst, its preparation method and application, in order to solve the problem that existing high-entropy semiconductor catalysts are prone to material segregation during pyrolysis, which leads to a decrease in catalytic performance.
[0006] The technical solution of the present invention is as follows:
[0007] A method for preparing a high-entropy semiconductor catalyst, comprising the following steps:
[0008] At least one metal salt is mixed with water to obtain a metal salt solution;
[0009] The metal salt solution was mixed with an amine organic ligand, and then centrifuged, washed, and freeze-dried to obtain a multi-metal complex.
[0010] The multi-metal complex was calcined under an inert atmosphere to obtain a high-entropy semiconductor catalyst.
[0011] The method for preparing the high-entropy semiconductor catalyst, wherein the metal salt comprises one or more of the following: ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, manganese chloride, indium chloride, erbium chloride, chloroplatinic acid, chloroauric acid, lanthanum chloride, sodium phosphotungstate, gallium nitrate, ferric nitrate, manganese nitrate, copper nitrate, and cobalt nitrate.
[0012] In the method for preparing the high-entropy semiconductor catalyst, the concentration of the metal salt solution is 1 mol / L-10 mol / L.
[0013] The method for preparing the high-entropy semiconductor catalyst, wherein the amine organic ligand includes one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and glucosamine.
[0014] In the method for preparing the high-entropy semiconductor catalyst, the molar ratio of the amine organic ligand to the metal salt in the metal salt solution is 1:2-4:1.
[0015] The method for preparing the high-entropy semiconductor catalyst, wherein the heating rate of the calcination treatment is 2℃-10℃, the calcination temperature is 200℃-400℃, and the holding time of the calcination treatment is 10min-60min.
[0016] In the method for preparing the high-entropy semiconductor catalyst, the centrifugal washing speed is 5000rpm-10000rpm, and the number of centrifugal washing cycles is 3-5.
[0017] The method for preparing the high-entropy semiconductor catalyst, wherein the freeze-drying temperature is -45℃ to -55℃ and the freeze-drying time is 30h-40h.
[0018] A high-entropy semiconductor catalyst is prepared using the same method as the high-entropy semiconductor catalyst.
[0019] Application of a high-entropy semiconductor catalyst in the catalytic degradation of pollutants.
[0020] Beneficial Effects: This invention provides a high-entropy semiconductor catalyst, its preparation method, and its application. The preparation method of the high-entropy semiconductor catalyst includes the following steps: mixing at least one metal salt with water to obtain a metal salt solution; mixing the metal salt solution with an amine organic ligand, followed by centrifugal washing and freeze-drying to obtain a multi-metal complex; and calcining the multi-metal complex under an inert atmosphere to obtain the high-entropy semiconductor catalyst. This invention restricts the movement of metal atoms under the anchoring of coordinating atoms, thereby obtaining a carbon-nitrogen-doped high-entropy semiconductor catalyst. The high-entropy semiconductor catalyst prepared by this method has the characteristics of abundant catalytic active sites, good chemical stability, and uniform distribution of elements. Furthermore, the preparation method involved in this invention is simple and easy to implement, the production process is green and environmentally friendly, and it is easy to scale up, which is conducive to large-scale promotion and application. Attached Figure Description
[0021] Figure 1 This is a schematic flowchart of a high-entropy semiconductor catalyst preparation method according to the present invention;
[0022] Figure 2 This is the elemental mapping diagram of the high-entropy semiconductor catalyst in Example 1;
[0023] Figure 3 This is a graph showing the bandgap characterization data of the high-entropy semiconductor catalyst in Example 1;
[0024] Figure 4 This is the elemental mapping diagram of the high-entropy semiconductor catalyst in Example 2;
[0025] Figure 5 This is a graph showing the bandgap characterization data of the high-entropy semiconductor catalyst in Example 2. Detailed Implementation
[0026] This invention provides a high-entropy semiconductor catalyst, its preparation method, and its application. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, 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.
[0027] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless specifically defined as herein.
[0028] Synthesizing high-entropy catalysts at lower temperatures using simple and practical methods is a worthwhile solution to explore, especially since high-entropy semiconductor catalysts can accept and convert external energy input, thereby improving catalytic efficiency. In this research, the relationship between the structure and performance of high-entropy semiconductor catalysts was explored in depth through a combination of theoretical calculations and experimental studies, providing guidance for designing more efficient catalysts. Simultaneously, the optimal combination of various active sites was explored to obtain catalysts with high catalytic efficiency, high stability, and low cost. In conclusion, through in-depth research and exploration of new preparation methods, it is hoped that high-entropy semiconductor catalysts with high catalytic efficiency can be obtained, providing a more effective solution to environmental pollution problems.
[0029] Developing a simple, efficient, environmentally friendly, and highly catalytically efficient high-entropy semiconductor catalyst is key to solving environmental pollution problems. Such a catalyst can not only reduce the toxicity of organic pollutants but also convert them into harmless substances, which is in line with the concept of sustainable development.
[0030] Based on this, such as Figure 1 As shown, this invention provides a method for preparing a high-entropy semiconductor catalyst, comprising the following steps:
[0031] Step S10: Mix at least one metal salt with water to obtain a metal salt solution;
[0032] Step S20: The metal salt solution is mixed with an amine organic ligand, and then centrifuged, washed, and freeze-dried to obtain a multi-metal complex;
[0033] Step S30: The multi-metal complex is calcined under an inert atmosphere to obtain a high-entropy semiconductor catalyst.
[0034] In this embodiment, at least one metal salt is first coordinated with an amine organic ligand. The precipitate of the complex is then centrifuged, washed, and freeze-dried to obtain a multi-metal complex. Finally, calcination is performed under an inert atmosphere to restrict the movement of metal atoms while the coordinating atoms are anchored, thereby obtaining a carbon-nitrogen-doped high-entropy semiconductor catalyst. Using this preparation method, a multi-metal complex material is initially synthesized to chelate metal atoms. Then, by calcining the multi-metal complex, a nitrogen-atom-anchored high-entropy semiconductor catalyst can be obtained, where the nitrogen atoms originate from the amine organic ligand.
[0035] Specifically, the preparation method employs processes such as pre-coordination of multi-metal complexes and pyrolysis at lower temperatures, which are simple and easy to operate, facilitating large-scale production and application. Furthermore, the preparation method is easy to control, and precise control of the components can be achieved simply by adjusting the type of metal salt, thus it can be widely used in the preparation of various high-entropy semiconductor catalyst materials. At the same time, the simple and easily modulated synthesis process makes it easy to achieve large-scale production.
[0036] In some embodiments, the metal salt includes, but is not limited to, one or more of the following: ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, manganese chloride, indium chloride, erbium chloride, chloroplatinic acid, chloroauric acid, lanthanum chloride, sodium phosphotungstate, gallium nitrate, ferric nitrate, manganese nitrate, copper nitrate, and cobalt nitrate. By adjusting the type of metal salt, precise control of the components can be achieved. Selecting one or more of the above metal salts allows the preparation method to be applied to the preparation of various high-entropy semiconductor catalysts and meets the characteristics of low-temperature synthesis of high-entropy semiconductor catalysts.
[0037] In some embodiments, the concentration of the metal salt solution is 1 mol / L to 10 mol / L, which allows the metal salt to be completely dissolved in water so that the metal salt solution can form a multi-metal complex with the amine organic ligand.
[0038] Specifically, at least one metal salt is dissolved in 10 ml of deionized water at a concentration of 0.01 mol to 0.1 mol, and then sonicated until all metal salts are completely dissolved in the deionized water to obtain a metal salt solution of uniform concentration. Then, a small molecule amine organic ligand is added under rapid stirring to form a complex precipitate.
[0039] In some embodiments, the amine organic ligands include, but are not limited to, one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and glucosamine. The nitrogen atoms in these amine organic ligands can form coordinating atoms, which restrict the movement of metal atoms under the anchoring of coordinating atoms, thereby obtaining carbon and nitrogen doped high-entropy semiconductor catalysts.
[0040] In some embodiments, the molar ratio of the amine organic ligand to the metal salt in the metal salt solution is 1:2-4:1. Mixing the amine organic ligand and the metal salt in this ratio can yield a high-entropy semiconductor catalyst with uniform elemental distribution.
[0041] In some embodiments, the heating rate of the calcination treatment is 2℃-10℃, the calcination temperature is 200℃-400℃, and the holding time of the calcination treatment is 10min-60min. The polymetallic complex is synthesized at low temperature under these conditions, that is, the polymetallic complex can be pyrolyzed under these conditions (lower temperature) to obtain a nitrogen atom-anchored high-entropy semiconductor catalyst.
[0042] In some embodiments, the centrifugal washing speed is 5000rpm-10000rpm, and the number of centrifugal washing cycles is 3-5.
[0043] Specifically, the metal salt solution is mixed with the amine organic ligand, and the resulting complex precipitate is centrifuged and washed at a speed of 5000 rpm-10000 rpm for 5 min each time. The centrifugation and washing are repeated three times, and the multi-metal complex is obtained after freeze-drying.
[0044] In some embodiments, the freeze-drying temperature is -45°C to -55°C, and the freeze-drying time is 30-40 hours. The freeze-drying process causes the water in the system to sublimate, thus maintaining the original structure.
[0045] In a preferred embodiment, the freeze-drying temperature is -50°C and the freeze-drying time is 36 hours.
[0046] In some embodiments, step S20, after mixing the metal salt solution with the amine organic ligand and washing it by centrifugation, and before freeze-drying, further includes: rapidly freezing the mixture obtained after centrifugation and washing with liquid nitrogen to save freezing time and improve efficiency.
[0047] In some embodiments, the inert atmosphere includes, but is not limited to, one or more of nitrogen, argon, helium, and neon.
[0048] In some embodiments, in step S30, after calcining the multi-metal complex under an inert atmosphere, the product is naturally cooled to room temperature and then removed; the product is ground and washed at least three times with a mixed solution of deionized water and ethanol to remove metal ions not embedded in the carbon-nitrogen support; finally, it is vacuum dried at 75-85°C for 24 hours to obtain a nanoscale high-performance semiconductor catalyst.
[0049] In some embodiments, the deionized water and the ethanol are mixed at a volume ratio of 1:1 to obtain a mixed solution.
[0050] In addition, the present invention also provides a high-entropy semiconductor catalyst, which is prepared using the preparation method of the high-entropy semiconductor catalyst.
[0051] In this embodiment, the high-entropy semiconductor catalyst prepared by the above method has the characteristics of abundant catalytic active sites, good chemical stability and uniform distribution of elements. At the same time, it has the advantages of simple and easy-to-implement process, green and environmentally friendly production process and easy large-scale production.
[0052] In addition, an application of a high-entropy semiconductor catalyst in the catalytic degradation of pollutants is also provided.
[0053] In this embodiment, the high-entropy semiconductor catalyst prepared by the above method can be widely used in the field of catalytic degradation of pollutants, thereby playing a positive role in promoting environmental governance and sustainable development.
[0054] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention.
[0055] Example 1
[0056] The specific steps for the low-temperature synthesis of high-entropy semiconductor catalysts in this embodiment are as follows:
[0057] a) Preparation of polymetallic complexes
[0058] Complexes of various metal ions were obtained by wet chemical methods. Approximately 0.01 mol each of various metal salts (manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, indium chloride, and sodium phosphotungstenate) were weighed and dissolved in 10 mL of deionized water. The solution was sonicated until all metal salts were completely dissolved, yielding a metal salt solution. Under rapid stirring, 3.09 g of an amine organic ligand (diethylenetriamine) was added to the metal salt solution, resulting in a complex precipitate. The precipitate was washed by centrifugation at 8000 rpm for 5 min, and the washing was repeated three times. Then, the precipitate was rapidly frozen in liquid nitrogen and transferred to a freeze dryer (cold trap temperature -50℃) for lyophilization. After 36 h of lyophilization, the precipitate was removed, quickly sealed, and stored for later use.
[0059] b) Preparation of high-entropy semiconductor catalysts
[0060] The freeze-dried multi-metal complex was placed in a tube furnace and protected with an inert gas such as N2 or Ar. The temperature was programmed to rise to 360℃ at a rate of 10℃ / min and held at that temperature for 30 min. After cooling naturally to room temperature, the product was removed. After grinding, it was washed three times with a mixed solution of deionized water and ethanol (V / V = 1:1) to remove metal ions not embedded in the carbon-nitrogen support. After vacuum drying at 80℃ for 24 h, nanoscale high-entropy semiconductor catalyst material was obtained.
[0061] The high-entropy semiconductor catalyst material obtained using the preparation process described in Example 1 was selected for elemental mapping characterization and solid-state ultraviolet testing.
[0062] Element mapping characterization results are as follows Figure 2 As shown, the various elements are evenly distributed without segregation. This is because nitrogen atoms act as atomic anchors, binding the metal atoms and thus restricting their movement during pyrolysis.
[0063] Solid UV test results are as follows Figure 3 As shown, the high-entropy catalyst material obtained by this preparation process has a band gap of 1.5 eV, classifying it as a narrow bandgap semiconductor material. This is because the presence of carbon and nitrogen elements restricts the shuttle movement of electrons between metal atoms, thereby achieving a certain band gap.
[0064] It can be inferred that, through this embodiment, a high-entropy semiconductor catalyst can be obtained by pyrolysis of complexes of various metals at a lower temperature. This process is simple to prepare, easy to scale up for production, and the obtained catalyst has the characteristics of abundant catalytic active sites and good chemical stability.
[0065] Example 2
[0066] The specific steps for the low-temperature synthesis of high-entropy semiconductor catalysts in this embodiment are as follows:
[0067] a) Preparation of polymetallic complexes
[0068] Approximately 0.01 mol each of several metal salts (manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, indium chloride, and sodium phosphotungstenate) were weighed and dissolved in 10 mL of deionized water. The solution was sonicated until all metal salts were completely dissolved, yielding a metal salt solution. Under rapid stirring, 2.92 g of an amine organic ligand (triethylenetetramine) was added to the metal salt solution, resulting in a complex precipitate. The precipitate was washed by centrifugation at 8000 rpm for 5 min, and this washing was repeated three times. Finally, the solution was lyophilized.
[0069] b) Preparation of high-entropy semiconductor catalysts
[0070] The freeze-dried multimetallic complex was placed in a tube furnace and protected with an inert gas such as N2 or Ar. The temperature was programmed to reach 400°C at a rate of 10°C / min and held at that temperature for 30 min. After cooling naturally to room temperature, the product was removed. After washing and drying, a high-entropy semiconductor catalyst was obtained.
[0071] The high-entropy semiconductor catalyst material obtained using the preparation process described in Example 2 was selected for elemental mapping characterization and solid-state ultraviolet testing.
[0072] Element mapping characterization results are as follows Figure 4 As shown, all elements are evenly distributed, with no segregation observed.
[0073] Solid UV results as follows Figure 5 As shown, the high-entropy catalyst material obtained by this preparation process has a band gap of 1.36 eV, which is a narrow bandgap semiconductor material.
[0074] Example 3
[0075] The specific steps for the low-temperature synthesis of high-entropy semiconductor catalysts in this embodiment are as follows:
[0076] a) Preparation of polymetallic complexes
[0077] Approximately 0.05 mol each of several metal salts (manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, indium chloride, and sodium phosphotungstenate) were weighed and dissolved in 10 mL of deionized water. The solution was sonicated until all metal salts were completely dissolved, yielding a metal salt solution. Under rapid stirring, 5.15 g of an organic ligand (diethylenetriamine) was added to the metal salt solution, resulting in a complex precipitate. The precipitate was washed by centrifugation at 6000 rpm for 5 min, and this washing was repeated three times. Finally, the solution was lyophilized.
[0078] b) Preparation of high-entropy semiconductor catalysts
[0079] The freeze-dried multimetallic complex was placed in a tube furnace and protected with an inert gas such as N2 or Ar. The temperature was programmed to reach 300°C at a rate of 5°C / min and held at that temperature for 60 min. After cooling naturally to room temperature, the product was removed. Washing and drying yielded the high-entropy semiconductor catalyst.
[0080] Example 4
[0081] The specific steps for the low-temperature synthesis of high-entropy semiconductor catalysts in this embodiment are as follows:
[0082] a) Preparation of polymetallic complexes
[0083] Approximately 0.04 mol each of various metal salts (manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, indium chloride, and sodium phosphotungstenate) were weighed and dissolved in 10 mL of deionized water. The solution was sonicated until all metal salts were completely dissolved, yielding a metal salt solution. Under rapid stirring, 4.38 g of an amine organic ligand (triethylenetetramine) was added to the metal salt solution, resulting in a complex precipitate. The precipitate was washed by centrifugation at 10,000 rpm for 5 min, and this washing was repeated three times. Finally, the solution was lyophilized.
[0084] b) Preparation of high-entropy semiconductor catalysts
[0085] The freeze-dried multimetallic complex was placed in a tube furnace and protected with an inert gas such as N2 or Ar. The temperature was programmed to reach 360°C at a rate of 10°C / min and held at that temperature for 40 min. The product was then allowed to cool naturally to room temperature before being removed. After washing and drying, a high-entropy semiconductor catalyst material was obtained.
[0086] Example 5
[0087] The specific steps for the low-temperature synthesis of high-entropy semiconductor catalysts in this embodiment are as follows:
[0088] a) Preparation of polymetallic complexes
[0089] Approximately 0.01 mol each of several metal salts (manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, indium chloride, and sodium phosphotungstenate) were weighed and dissolved in 10 mL of deionized water. The solution was sonicated until all metal salts were completely dissolved, yielding a metal salt solution. Under rapid stirring, 5.38 g of an amine organic ligand (glucosamine) was added to the metal salt solution, resulting in a complex precipitate. The precipitate was washed by centrifugation at 6000 rpm for 5 min, and this washing was repeated three times. Finally, the solution was lyophilized.
[0090] b) Preparation of high-entropy semiconductor catalysts
[0091] The freeze-dried multimetallic complex was placed in a tube furnace and protected with an inert gas such as N2 or Ar. The temperature was programmed to reach 400°C at a heating rate of 2°C / min and held at that temperature for 50 min. The product was then allowed to cool naturally to room temperature before being removed. After washing and drying, a high-entropy semiconductor catalyst was obtained.
[0092] In summary, this invention provides a high-entropy semiconductor catalyst, its preparation method, and its application. The preparation method of the high-entropy semiconductor catalyst includes the following steps: mixing at least one metal salt with water to obtain a metal salt solution; mixing the metal salt solution with an amine organic ligand, followed by centrifugation, washing, and freeze-drying to obtain a multi-metal complex; and calcining the multi-metal complex under an inert atmosphere to obtain the high-entropy semiconductor catalyst. This invention restricts the movement of metal atoms under the anchoring of coordinating atoms, thereby obtaining a carbon-nitrogen-doped high-entropy semiconductor catalyst. The high-entropy semiconductor catalyst prepared by this method has the characteristics of abundant catalytic active sites, good chemical stability, and uniform distribution of elements. Furthermore, the preparation method involved in this invention is simple and easy to implement, the production process is green and environmentally friendly, and it is easy to scale up for mass production, which is conducive to large-scale promotion and application.
[0093] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. A method for preparing a high-entropy semiconductor catalyst, characterized in that, Including the following steps: Metal salts are mixed with water to obtain metal salt solutions; The metal salt solution was mixed with an amine organic ligand, and then centrifuged, washed, and freeze-dried to obtain a multi-metal complex. The multi-metal complex was calcined under an inert atmosphere to obtain a high-entropy semiconductor catalyst. The metal salt is ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, manganese chloride, indium chloride, and sodium phosphotungstenate; the concentration of the metal salt solution is 1 mol / L-10 mol / L; the amine organic ligand includes one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and glucosamine; the molar ratio of the amine organic ligand to the metal salt in the metal salt solution is 1:2-4:1; the heating rate of the calcination treatment is 2℃-10℃, the calcination temperature is 200℃-400℃, and the holding time of the calcination treatment is 10 min-60 min; the inert atmosphere includes one or more of nitrogen, argon, helium, and neon.
2. The method for preparing the high-entropy semiconductor catalyst according to claim 1, characterized in that, The centrifugal washing speed is 5000rpm-10000rpm, and the number of centrifugal washing cycles is 3-5.
3. The method for preparing the high-entropy semiconductor catalyst according to claim 1, characterized in that, The freeze-drying temperature is -45℃ to -55℃, and the freeze-drying time is 30h to 40h.
4. A high-entropy semiconductor catalyst, characterized in that, It is prepared using the method for preparing high-entropy semiconductor catalysts as described in any one of claims 1-3.
5. The application of the high-entropy semiconductor catalyst as described in claim 4 in the catalytic degradation of pollutants.