A high-entropy alloy sulfide quantum dot, a preparation method and application thereof

By achieving SC/SN bond coupling under no external field conditions using high-entropy alloy sulfide quantum dot catalysts, the problems of oxidant contamination and high-temperature requirements in existing technologies are solved, providing a highly efficient and low-cost catalytic solution.

CN119158596BActive Publication Date: 2025-10-24TAIYUAN UNIVERSITY OF TECHNOLOGY
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Patent Information

Application Number
CN202411326564.4
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-09-23
Publication Date
2025-10-24
Estimated Expiration
2044-09-23

AI Technical Summary

Technical Problem

Existing technologies require the addition of oxidants and high-temperature conditions in SC/SN bond coupling reactions, which leads to problems such as environmental pollution, equipment corrosion, and difficulty in catalyst recovery. Furthermore, the high cost of precious metal catalysts limits their industrial application.

Method used

A high-entropy alloy sulfide quantum dot catalyst was used to prepare nanoparticle catalysts via ethylene glycol coordination and solvothermal methods. By utilizing the synergistic effect of multiple metal elements and the properties of quantum dots, SC/SN bond coupling was achieved under no external field conditions.

Benefits of technology

It achieves efficient, green, and low-cost SC/SN bond coupling, avoiding oxidant pollution and high-temperature requirements, and improving the activity and stability of the catalyst, making it suitable for industrial applications.

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Abstract

The application discloses a high-entropy alloy sulfide quantum dot and a preparation method and application thereof, and belongs to the technical field of organic synthesis catalysts. In view of the problems that an oxidant needs to be additionally added and a thermal field needs to be provided in a reaction for catalyzing S-C / S-N coupling at present, the application utilizes the coordination of ethylene glycol, coordinates various metal cations with ethylene glycol fully, then adds sodium sulfide to form dispersed metal sulfide nucleation sites, and finally forms high-entropy alloy sulfide quantum dots through a solvothermal method. The catalyst can not only catalyze intermolecular amido mercapto S-N coupling to generate S-N coupling products under a field-free condition, but also catalyze intramolecular coupling of amides and mercapto to generate self-cyclization products which are more difficult. Meanwhile, the catalyst can also catalyze intermolecular S-C bond coupling under a field-free condition. The catalyst has strong field-free catalytic capacity, provides a new catalytic idea for organic synthesis, and further reduces the cost of chemical production. The application has simple process, ingenious design, safety controllability and low cost.
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Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis catalysts, and particularly relates to a high-entropy alloy sulfide quantum dot for efficiently catalyzing S-C / S-N coupling and a preparation method thereof. BACKGROUND

[0002] Organic sulfur compounds play an important role in the fields of organic synthesis, pharmaceuticals, biological sciences, and industry. They are not only widely used as synthetic intermediates and reagents, but also are important components of chemical raw materials. The synthesis method of organic sulfur compounds has always attracted widespread attention. The formation of S-N bonds is an important reaction type in organic chemistry, which involves the formation of chemical bonds between sulfur and nitrogen. In organic synthesis, the formation of S-N bonds can be achieved through various methods, including nucleophilic substitution reactions, free radical reactions, and metal-catalyzed reactions. These reactions are particularly important in drug synthesis, pesticide development, and chemical applications. For example, in the chemical industry, specific organic sulfur compounds such as N-cyclohexyl-2-benzothiazole sulfenamide and N-tert-butyl-2-benzothiazole sulfenamide are used as vulcanization accelerators. These compounds are widely used in the rubber industry as vulcanization accelerators, with an annual usage of over 20,000 tons. They can improve the vulcanization efficiency of rubber and improve the physical and mechanical properties and aging resistance of the final product. Currently, the main method of industrial production is the oxidant oxidation method, but this method has defects in many aspects. The biggest disadvantage of the oxidant is its high toxicity and strong corrosiveness, which greatly increases the maintenance and management cost of the equipment and greatly shortens the service life of the equipment. Environmental pollution problems cannot be ignored, and the oxidant will produce a large amount of high-salt and high-chemical oxygen demand wastewater after oxidation, which needs to be properly treated to meet environmental requirements, making the production process more complex and the cost further increased.

[0003] The construction of S-C bond is an important part in modern organic synthesis and is the main route to synthesize sulfur-containing compounds. It has unique advantages in drug synthesis, including improving drug targeting, reducing non-specific distribution, and increasing drug stability. The most classical method to achieve S-C bond coupling is Ullmann coupling reaction, but it requires high temperature, strong base and a large amount of organic metal homogeneous catalyst. With the in-depth research, people began to use noble metal to replace the most commonly used copper as catalyst to participate in the reaction, and introduced a variety of unique characteristics of ligand to further enhance the catalytic effect of organic metal homogeneous catalyst. Although this series of research has successfully reduced the reaction temperature, made the reaction conditions more mild, and reduced the amount of catalyst, even improved the compatibility of functional groups, so that even the presence of some groups that inhibit the reaction can still effectively drive the reaction. However, the high cost of noble metal catalysts, the possibility of poisoning during the catalytic process, and the difficulty of recycling noble metal catalysts greatly limit their large-scale application in industry. At the same time, because the homogeneous catalyst and the reactant are in the same phase, it is difficult to separate the catalyst and the product, and improper separation process will lead to catalyst deactivation. Moreover, the stability of homogeneous catalyst is not as good as heterogeneous catalyst, so the activity is often reduced, which limits its application in industrial production.

[0004] In order to find an efficient, mild and suitable for industrial production method to realize the formation of S-N, S-C bond to meet the needs of modern synthetic chemistry for complex molecule synthesis, we need to find a non-noble metal catalyst that can realize the coupling of S-N, S-C bond in heterogeneous catalysis without external field. Such catalyst will play a decisive role.

[0005] High-entropy alloy sulfides are alloys of multiple elements, and compared with traditional metal sulfides, high-entropy alloy sulfides have more elements, and the molar fraction of each metal element is roughly equal. The interaction between multiple elements in high-entropy alloy sulfides, even the same element, has a huge difference in the surrounding adjacent elements, which provides the possibility of novel and adaptable active sites. This diverse element environment provides unique surface structures and electronic properties for catalytic reactions, thereby affecting the adsorption, activation and conversion process of reactants. This feature of high-entropy alloy sulfides makes them have great potential application value in catalytic science, especially in complex catalytic reactions that require specific active sites. By carefully selecting the element configuration, it can be optimized for specific targets to achieve stronger and more targeted catalytic effects, so high-entropy alloy sulfides are a very potential catalyst material. Quantum dot catalysts have made significant progress in photocatalytic hydrogen production, carbon dioxide reduction, and pollutant degradation. This is due to the unique electronic properties of quantum dots, which can make electron transfer more rapid and the adsorption efficiency of reaction intermediates higher, thereby improving catalytic efficiency. In addition, the large specific surface area of quantum dots can provide more active sites, further enhancing the performance of the catalyst.

[0006] Therefore, we choose to develop this high-entropy alloy sulfide quantum dot catalyst which has both the high-entropy effect and cocktail effect of high-entropy alloy sulfides, and also has the unique electronic properties and large specific surface area of quantum dots, to realize the green and efficient catalytic oxidation dehydrogenation without external field to realize S-C bond and S-N bond coupling. SUMMARY

[0007] In view of the problems that additional oxidants need to be added and heat field needs to be provided in the current catalytic S-C / S-N coupling reaction, the application provides a high-entropy alloy sulfide quantum dot for efficient catalytic S-C / S-N coupling and a preparation method thereof.

[0008] The application adopts the following technical scheme:

[0009] A high-entropy alloy sulfide quantum dot is composed of metal elements and sulfur; the metal elements include any five of Mg, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Cd and In.

[0010] Further, the mass percentage of the metal elements is 45% to 50%, and the mass percentage of the sulfur is 50% to 55%.

[0011] Further, the catalyst morphology is a nanoparticle with a crystal lattice stripe.

[0012] The application discloses a preparation method of high-entropy alloy sulfide quantum dots.

[0013] The application discloses a preparation method of high-entropy alloy sulfide quantum dots.

[0014] In step 1, a solvent for a solvothermal reaction is measured and added into a Teflon liner of a hydrothermal kettle, different metal salts are added while stirring, stirring is performed for 10-20 minutes, a sulfur source is added, and stirring is performed for 20-30 minutes, so as to obtain a mixed solution.

[0015] In step 2, the mixed solution and the Teflon liner are placed into the hydrothermal kettle, and the hydrothermal kettle is kept at 80-160 DEG C for 10-20 hours.

[0016] In step 3, the product obtained in step 2 is centrifuged by using a centrifuge at a speed of 8000-10000 rpm, and the obtained precipitate is washed by using ultrapure water and anhydrous ethanol.

[0017] In step 4, the product is dried in a vacuum drying box for 12 hours, and HESn-A powder is obtained by grinding.

[0018] Further, the solvothermal solvent includes any one of methanol, ethanol, ethylene glycol, dimethylformamide and dimethyl sulfoxylamide; the metal salt includes any one of a chloride salt, a nitrate salt and an acetate salt; and the sulfur source includes any one of cysteine, thioacetamide, urea, thiourea, sulfur powder, sodium sulfide and ammonium sulfide.

[0019] Further, the solvothermal solvent is added in an amount of 35-45 mL, the metal salt is added in an amount of 0.5-2 mmol, and the sulfur source is added in an amount of 1-5 g.

[0020] Further, in step 3, the ultrapure water and the anhydrous ethanol are used for washing in sequence, that is, deionized water is used for washing once, and anhydrous ethanol is used for washing once, and 50 mL of water or ethanol is used for each time of washing.

[0021] Further, steps 1-4 are all performed in an exposed environment, and a protective gas is not needed to be introduced.

[0022] The application further discloses an application of the high-entropy alloy sulfide quantum dots in efficient catalysis of S-C / S-N coupling.

[0023] Compared with the prior art, the application has the following advantages:

[0024] 1. The present application utilizes the high-entropy effect and cocktail effect of high-entropy alloy sulfide quantum dots, as well as the rich active sites thereof. Multiple metal elements synergistically act to fully exert the catalytic effect of various metals, thereby enabling efficient field-free catalysis to obtain S-N and S-C coupled organic small molecule catalyst materials.

[0025] 2. The present application utilizes the unique electronic effect of quantum dots and the huge surface area thereof, further reduces the energy barrier of the reaction, solves the shortcomings of additional oxidizing agent and the need for a thermal field, and provides a new catalytic idea for the synthesis of organic small molecules, thereby avoiding the pollution of oxidizing agents and reaction waste liquid to the environment, and reducing energy consumption.

[0026] 3. The present application has simple process, ingenious design, green environmental protection and low cost. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 A transmission electron microscope image of HESn-A prepared in Example 2 of the present application;

[0028] Figure 2 A particle size distribution statistical diagram of HESn-A prepared in Example 2 of the present application;

[0029] Figure 3 An EDS-mapping element composition diagram of HESn-A prepared in Example 2 of the present application;

[0030] Figure 4 An X-ray diffraction diagram of HESn-A prepared in Example 2 of the present application;

[0031] Figure 5 A nuclear magnetic resonance hydrogen spectrum of a catalytic product of intermolecular S-N bond cross-coupling between 2-mercaptobenzothiazole and n-propylamine catalyzed by HESn-A in the absence of a field;

[0032] Figure 6 A nuclear magnetic resonance hydrogen spectrum of a catalytic product of intermolecular S-N bond cross-coupling between 2-mercaptobenzothiazole and cyclohexylamine catalyzed by HESn-A in the absence of a field;

[0033] Figure 7 A nuclear magnetic resonance hydrogen spectrum of a catalytic product of intermolecular S-N bond cross-coupling between 2-mercaptobenzothiazole and diethylamine catalyzed by HESn-A in the absence of a field;

[0034] Figure 8 A nuclear magnetic resonance hydrogen spectrum of a catalytic product of intermolecular S-N bond cross-coupling between 2-mercaptobenzothiazole and morpholine catalyzed by HESn-A in the absence of a field;

[0035] Figure 9HESn-A catalyzed 2-mercapto-6-methylbenzothiazole and cyclohexylamine intermolecular S-N cross-coupling catalytic product's NMR hydrogen spectrum;

[0036] Figure 10 HESn-A catalyzed 2-mercapto-N-methylbenzamide intramolecular S-N cyclization catalytic product's NMR hydrogen spectrum;

[0037] Figure 11 HESn-A catalyzed 2-mercapto-N-cyclohexylbenzamide intramolecular S-N cyclization catalytic product's NMR hydrogen spectrum;

[0038] Figure 12 HESn-A catalyzed 2-mercapto-N-phenylbenzamide intramolecular S-N cyclization catalytic product's NMR hydrogen spectrum;

[0039] Figure 13 HESn-A catalyzed 2-mercapto-N-2-pyridylbenzamide intramolecular S-N cyclization catalytic product's NMR hydrogen spectrum;

[0040] Figure 14 HESn-A catalyzed 2-mercapto-N-methylbenzamide and phenylacetylene S-C cross-coupling catalytic product's NMR hydrogen spectrum;

[0041] Figure 15 HESn-A catalyzed 2-mercapto-N-phenylbenzamide and phenylacetylene S-C cross-coupling catalytic product's NMR hydrogen spectrum;

[0042] Figure 16 HESn-A catalyzed 2-mercapto-N-methylbenzamide and 2-ethynylthiophene S-C cross-coupling catalytic product's NMR hydrogen spectrum. DETAILED DESCRIPTION

[0043] For a more complete understanding of the present application, we will now describe it in greater detail with reference to the accompanying drawings. The present application, however, is not limited to the specific examples described herein, but can be practiced with modifications within the scope of the application.

[0044] Example 1

[0045] Take 35 mL of ethylene glycol and add it to the Teflon liner of a 50 mL hydrothermal kettle. Add 0.5 mmol of iron, cobalt, copper, zinc, and cadmium metal acetate while stirring. Stir for 10 minutes. Add 1 g of sodium sulfide and stir for 20 minutes. Place the resulting solution and the Teflon liner of the hydrothermal kettle into the hydrothermal kettle and incubate at 110°C for 10 hours. Centrifuge the resulting product at 8000 rpm using a centrifuge and wash with ultrapure water and anhydrous ethanol. Dry in a vacuum drying oven for 12 hours and grind to obtain HESn-A powder.

[0046] Example 2

[0047] Take 35 mL of ethylene glycol and add it to the Teflon liner of a 50 mL hydrothermal kettle. Add 1 mmol of iron, cobalt, copper, zinc, and cadmium metal acetate while stirring. Stir for 15 minutes. Add 2.5 g of sodium sulfide and stir for 30 minutes. Place the resulting solution and the Teflon liner of the hydrothermal kettle into the hydrothermal kettle and incubate at 150°C for 16 hours. Centrifuge the resulting product at 10000 rpm using a centrifuge and wash with ultrapure water and anhydrous ethanol. Dry in a vacuum drying oven for 12 hours and grind to obtain HESn-A powder.

[0048] From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared. Figure 1 From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared.

[0049] From the SEM image of the sample, it can be seen that more than 95% of the particles are less than 10 nm in size, and more than 70% of the particles are concentrated in the size range of 5-8 nm. It is proved that the quantum dot catalyst is successfully prepared. Figure 2 From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared.

[0050] From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared. Figure 3 From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared.

[0051] From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared. Figure 4 From the SEM image of the sample, it can be seen that the catalyst morphology is nanoparticles. The crystal lattice stripes can be clearly seen, and the measurement corresponds to the CdS crystal phase. It is preliminarily judged that the quantum dot catalyst is successfully prepared.

[0052] Example 3

[0053] Take 40 mL of ethylene glycol and add it to the Teflon liner of a 50 mL hydrothermal kettle, then add 2 mmol of iron, cobalt, copper, zinc and cadmium metal acetate while stirring, and stir for 10 min. Then add 5 g of sodium sulfide and stir for 30 min. Put the obtained solution and the Teflon liner of the hydrothermal kettle into the hydrothermal kettle, and incubate at 160 ℃ for 20 h. Centrifuge the obtained product at 10,000 rpm using a centrifuge, and wash it with ultrapure water and anhydrous ethanol. Dry it in a vacuum drying box for 12 h, and grind to obtain HESn-A powder.

[0054] Example 4

[0055] Take 5 mg of the HESn-A sample, add 0.1 mmol of 2-mercaptobenzothiazole and 2 mL of acetonitrile to a test tube, then add 0.5 mmol of n-propylamine, mix well, and ultrasonically disperse for 10 min. Stir the reaction at room temperature for 7 h.

[0056] Subsequently, separate and purify, calculate the separation yield, and perform nuclear magnetic resonance testing on the product.

[0057] Example 5

[0058] Take 5 mg of the HESn-A sample, add 0.1 mmol of 2-mercaptobenzothiazole and 2 mL of acetonitrile to a test tube, then add 0.5 mmol of cyclohexylamine, mix well, and ultrasonically disperse for 10 min. Stir the reaction at room temperature for 7 h.

[0059] Subsequently, separate and purify, calculate the separation yield, and perform nuclear magnetic resonance testing on the product.

[0060] Example 6

[0061] Take 5 mg of the HESn-A sample, add 0.1 mmol of 2-mercaptobenzothiazole and 2 mL of acetonitrile to a test tube, then add 0.5 mmol of diethylamine, mix well, and ultrasonically disperse for 10 min. Stir the reaction at room temperature for 7 h.

[0062] Subsequently, separate and purify, calculate the separation yield, and perform nuclear magnetic resonance testing on the product.

[0063] Example 7

[0064] Take 5 mg of the HESn-A sample, add 0.1 mmol of 2-mercaptobenzothiazole and 2 mL of acetonitrile to a test tube, then add 0.5 mmol of morpholine, mix well, and ultrasonically disperse for 10 min. Stir the reaction at room temperature for 7 h.

[0065] Subsequently, separate and purify, calculate the separation yield, and perform nuclear magnetic resonance testing on the product.

[0066] Example 8

[0067] Take 5 mg of HESn-A sample, add 0.1 mmol of 2-mercapto-6-methylbenzothiazole and 2 mL of acetonitrile into a test tube, mix well, then add 0.5 mmol of cyclohexylamine, and ultrasonic dispersion for 10 min. Stir at room temperature for 7 h.

[0068] Subsequent separation and purification, calculate the separation yield and product nuclear magnetic resonance test.

[0069] Example 9

[0070] Take 5 mg of HESn-A sample, add 0.1 mmol of 2-mercapto-N-methylbenzamide and 2 mL of anhydrous ethanol into a test tube, mix well, then add 0.15 mmol of triethylamine, and ultrasonic dispersion for 10 min. Stir at room temperature for 4 h.

[0071] Subsequent separation and purification, calculate the separation yield and product nuclear magnetic resonance test.

[0072] Example 10

[0073] Take 5 mg of HESn-A sample, add 0.1 mmol of 2-mercapto-N-cyclohexylbenzamide and 2 mL of DMF into a test tube, mix well, then add 0.15 mmol of triethylamine, and ultrasonic dispersion for 10 min. Stir at room temperature for 4 h.

[0074] Subsequent separation and purification, calculate the separation yield and product nuclear magnetic resonance test.

[0075] Example 11

[0076] Take 5 mg of HESn-A sample, add 0.1 mmol of 2-mercapto-N-phenylbenzamide and 2 mL of DMF into a test tube, mix well, then add 0.15 mmol of triethylamine, and ultrasonic dispersion for 10 min. Stir at room temperature for 4 h.

[0077] Subsequent separation and purification, calculate the separation yield and product nuclear magnetic resonance test.

[0078] Example 12

[0079] Take 5 mg of HESn-A sample, add 0.1 mmol of 2-mercapto-N-2-pyridylbenzamide and 2 mL of DMF into a test tube, mix well, then add 0.15 mmol of triethylamine, and ultrasonic dispersion for 10 min. Stir at room temperature for 4 h.

[0080] The separation and purification were then carried out, the separation yield was calculated, and the product was subjected to nuclear magnetic resonance test.

[0081] Example 13

[0082] 5 mg of the HESn-A sample was weighed into a test tube, 0.25 mmol of 2-mercapto-N-methylbenzamide, 0.25 mmol of potassium tert-butoxide and 2 mL of anhydrous ethanol were added, and after uniform mixing, 0.1 mmol of phenylacetylene was added, and ultrasonic dispersion was performed for 10 min. The reaction was stirred at room temperature for 10 h.

[0083] The separation and purification were then carried out, the separation yield was calculated, and the product was subjected to nuclear magnetic resonance test.

[0084] Example 14

[0085] 5 mg of the HESn-A sample was weighed into a test tube, 0.25 mmol of 2-mercapto-N-methylbenzamide, 0.25 mmol of potassium tert-butoxide and 2 mL of anhydrous ethanol were added, and after uniform mixing, 0.1 mmol of phenylacetylene was added, and ultrasonic dispersion was performed for 10 min. The reaction was stirred at room temperature for 10 h.

[0086] The separation and purification were then carried out, the separation yield was calculated, and the product was subjected to nuclear magnetic resonance test.

[0087] Example 15

[0088] 5 mg of the HESn-A sample was weighed into a test tube, 0.25 mmol of 2-mercapto-N-methylbenzamide, 0.25 mmol of potassium tert-butoxide and 2 mL of anhydrous ethanol were added, and after uniform mixing, 0.1 mmol of 2-ethynylthiophene was added, and ultrasonic dispersion was performed for 10 min. The reaction was stirred at room temperature for 10 h.

[0089] The separation and purification were then carried out, the separation yield was calculated, and the product was subjected to nuclear magnetic resonance test.

[0090] From Examples 4-8, combined with Figures 5 to 9 It can be seen that the high-entropy alloy sulfide quantum dot catalyst can catalyze the oxidative dehydrogenation coupling of 2-mercaptobenzothiazole and primary amines (n-propylamine and cyclohexylamine, etc.) under no external field conditions, and can also catalyze the oxidative dehydrogenation coupling of 2-mercaptobenzothiazole and secondary amines (diethylamine and morpholine, etc.) under no external field conditions. At the same time, when there is a substituent group on the benzene ring of 2-mercaptobenzothiazole, oxidative dehydrogenation coupling can also be achieved under the same conditions. It is proved that the high-entropy alloy sulfide quantum dot catalyst has quite high substrate universality in catalyzing the intermolecular S-N bond cross-coupling of 2-mercaptobenzothiazole and its derivatives and amines under no field conditions.

[0091] From Examples 9-12, combined with Figures 10 to 13The high-entropy alloy sulfide quantum dot catalyst can catalyze the field-free oxidative dehydrogenative autocyclization of 2-mercapto-N-methylbenzamide and its aliphatic derivatives (such as 2-mercapto-N-cyclohexylbenzamide), as well as the oxidative dehydrogenative coupling of 2-mercapto-N-phenylbenzamide and its phenyl ring derivatives (such as 2-mercapto-N-2-pyridylbenzamide). This demonstrates the high-entropy alloy sulfide quantum dot catalyst's high substrate universality in catalyzing the field-free intramolecular SN bond autocyclization of 2-mercapto-N-methylbenzamide and its derivatives.

[0092] From Examples 13 to 15, combined Figures 14 to 16 The results indicate that the high-entropy alloy sulfide quantum dot catalyst can catalyze the field-free oxidative dehydrogenative cross-coupling of 2-mercapto-N-methylbenzamide with phenylacetylene and its derivatives (2-ethynylthiophene), as well as the field-free oxidative dehydrogenative cross-coupling of 2-mercapto-N-phenylbenzamide and its derivatives (such as 2-mercapto-N-phenylbenzamide) with phenylacetylene. This demonstrates the high-entropy alloy sulfide quantum dot catalyst's high substrate universality in the field-free catalytic intermolecular SN cross-coupling of 2-mercapto-N-methylbenzamide and its derivatives with phenylacetylene and its derivatives.

[0093] Any matters not described in detail in this specification are prior art known to those skilled in the art. Although the above description of the present invention is based on specific embodiments to facilitate understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the specific embodiments. As long as various modifications are within the spirit and scope of the present invention as defined and determined by the appended claims, such modifications will be obvious to those skilled in the art, and all inventions and creations utilizing the concepts of the present invention are protected.

Claims

1. Application of a high-entropy alloy sulfide quantum dot catalyst in efficient catalysis of S-C / S-N coupling, characterized by: The catalyst is composed of metal elements and sulfur; the metal elements are Fe, Co, Cu, Zn and Cd; The catalyst is formed by using the coordination of ethylene glycol to fully coordinate various metal cations with ethylene glycol, then adding sodium sulfide to form dispersed metal sulfide nucleation sites, and finally forming high-entropy alloy sulfide quantum dots through a solvothermal method.

2. Use according to claim 1, characterized in that: The mass percentage of the metal elements in the catalyst is 45% to 50%, and the mass percentage of the sulfur is 50% to 55%.

3. Use according to claim 1, characterized in that: The catalyst has a morphology of nanoparticles and has crystal lattice stripes.

4. Use according to claim 1, characterized in that, The preparation method of the catalyst comprises the following steps: Step 1, measure the ethylene glycol, add it to the Teflon hydrothermal kettle liner, add different metal salts while stirring, stir for 10 min to 20 min, then add sodium sulfide, and stir for 20 min to 30 min to obtain a mixed solution; Step 2, place the mixed solution and the Teflon hydrothermal kettle liner in the hydrothermal kettle, and incubate at 80℃ to 160℃ for 10 h to 20 h; Step 3, centrifuge the product obtained in step 2 at a speed of 8000 rpm to 10000 rpm using a centrifuge, and wash the obtained precipitate with ultrapure water and anhydrous ethanol after centrifugation; Step 4, finally vacuum dry for 12 h, and grind to obtain HESn-A powder.

5. Use according to claim 4, characterized in that: The metal salt includes any one of a chloride salt, a nitrate salt and an acetate salt.

6. Use according to claim 4, characterized in that: The addition amount of the ethylene glycol is 35 mL to 45 mL, the addition amount of the metal salt is 0.5 mmol to 2 mmol, and the addition amount of the sodium sulfide is 1 g to 5 g.

7. Use according to claim 4, characterized in that: In step 3, the ultrapure water and anhydrous ethanol are used for washing, specifically, deionized water is used for washing once, and anhydrous ethanol is used for washing once; in step 4, the vacuum drying temperature is 60℃.

8. Use according to claim 4, characterized in that: Steps 1 to 4 are all carried out in an exposed environment, and no protective gas is needed to be introduced.

Citation Information

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