Catalyst for preparing sulfone, its preparation method and application in electrocatalytic oxidation of sulfoxide to prepare sulfone

Abstract

The application provides a catalyst for preparing sulfone, a preparation method of the catalyst and application of the catalyst in electrocatalytic oxidation of sulfoxide to prepare sulfone, and belongs to the technical field of electrocatalytic organic synthesis. The catalyst is an anode material coated with metal oxide; the metal in the metal oxide is selected from one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, gold, palladium, platinum, rhodium, iridium, ruthenium, cerium, molybdenum or tungsten. The method for preparing sulfone by electrocatalytic oxidation of sulfoxide comprises the following steps: dissolving a compound containing a sulfoxide group in a solvent to obtain an electrolyte; under the action of the catalyst, the electrolyte is subjected to electrocatalytic oxidation reaction, and the reaction solution is purified to obtain sulfone; and the solvent is water or a mixed solvent of an organic solvent and water. The catalyst preparation method is simple, green, environmentally friendly and low in cost; the obtained catalyst is applied to the preparation of sulfone by electrocatalytic oxidation of sulfoxide, water is used as an oxygen source, the reaction condition is mild, and the catalyst has the advantages of high selectivity, high yield, high conversion rate and excellent electrocatalytic stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of electrocatalytic organic synthesis, and particularly relates to a catalyst for preparing sulfone, a preparation method thereof and application of the catalyst in electrocatalytic oxidation of sulfoxide to prepare sulfone. BACKGROUND

[0002] Organic sulfur compounds have attracted extensive attention due to their importance in medicine. Many biologically active compounds and natural products contain sulfoximine, sulfoxide or sulfone functional groups. Notably, sulfoximine, sulfoxide or sulfone functional groups are very important in antibiotics, musculoskeletal, metabolic, digestive tract or anti-inflammatory drugs, in addition, there are a large number of organic sulfur compounds in organic synthesis. In addition to the stereoelectronic effect and the conformational stability of sulfinyl, the oxygen of sulfinyl also has the ability to coordinate with different carbon ligands and metal ions. Sulfoximine and sulfoxide are stable functional groups and are also used as ligands of enantiopure compounds in asymmetric synthesis. At present, many methods for organic sulfur oxidation have been developed, and more feasible and sustainable oxidation processes will have a positive impact on the pharmaceutical industry, thereby reducing costs, avoiding unnecessary waste and reducing the generation of by-products. The organic sulfur oxidation process can be carried out using different oxidizing agents, such as peroxide, photocatalytic process or high-valent iodine reagent, etc. Although some progress has been made in the organic sulfur oxidation process, most of the oxidation methods are not suitable for industrialization due to sustainability, scale and safety issues.

[0003] Generally, sulfoxide and sulfone can be obtained by oxidation of the corresponding thioether; various oxidizing agents have been used in the prior art, such as H2O2 with metal catalyst, m-CPBA, NaIO4, CrO3, KMnO4 and combination of dioxane. Unfortunately, these strategies often have the problem of too low reaction selectivity, such as over-oxidation of sulfoxide to sulfone or oxidation of other functional groups in the molecule, etc. Moreover, although hydrogen peroxide is considered as a green oxidizing agent, it is synthesized by the autoxidation process of anthraquinone, which is not sustainable.

[0004] Chinese patent document CN105017107A discloses a preparation method of dimethyl sulfone, in which hydrogen peroxide, organic hydroperoxide or peracid is used as an oxidizing agent, titanium silicalite is used as a catalyst, and dimethyl sulfoxide is oxidized to obtain dimethyl sulfone in a fixed bed reactor. The method of the present application can improve the effective utilization rate of the oxidizing agent, the selectivity of dimethyl sulfone and the conversion rate of dimethyl sulfoxide to some extent, but still has the above-mentioned problems, i.e. the reaction selectivity and the conversion rate need to be further improved, and the used peroxide is not sustainable and has high cost.

[0005] Therefore, it is of great significance to develop a catalyst and a method for preparing sulfone from sulfoxide with high selectivity, high target product yield, high conversion rate and cycle stability, and green, sustainable and low cost. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a catalyst for preparing sulfone, a preparation method thereof and application thereof in electrocatalytic oxidation of sulfoxide to prepare sulfone.

[0007] The technical scheme of the present application is as follows:

[0008] The first object of the present application is to provide a catalyst for preparing sulfone, which is a metal oxide coated anode material.

[0009] According to the present application, the anode in the metal oxide coated anode material is selected from one of titanium electrode, platinum electrode, platinum-titanium electrode, carbon cloth, carbon paper, carbon felt, carbon fiber, foamed nickel or nickel plate.

[0010] The second object of the present application is to provide a preparation method of a catalyst (metal oxide coated anode material) for preparing sulfone, which comprises the following steps:

[0011] The metal salt aqueous solution and the sulfuric acid aqueous solution are mixed as an electrolyte, and are electrochemically deposited to deposit the metal oxide on the surface of the anode electrode to obtain a metal oxide precursor coated anode.

[0012] According to the present application, the metal salt is a metal sulfate, a metal nitrate or a metal chloride, preferably a metal sulfate.

[0013] According to the present application, the metal in the metal salt is selected from one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, gold, palladium, platinum, rhodium, iridium, ruthenium, cerium, molybdenum or tungsten.

[0014] According to the application, preferably, the metal salt is selected from one of titanium sulfate, titanium nitrate, titanium chloride, vanadium sulfate, vanadium nitrate, vanadium chloride, chromium sulfate, chromium nitrate, chromium chloride, potassium dichromate, manganese sulfate, manganese nitrate, manganese chloride, iron sulfate, ferrous sulfate, iron nitrate, ferrous nitrate, iron chloride, ferrous chloride, cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, copper sulfate, copper nitrate, copper chloride, silver sulfate, silver nitrate, silver chloride, gold nitrate, gold chloride, palladium sulfate, palladium nitrate, palladium chloride, platinum sulfite, platinum nitrate, platinum chloride, platinum dichloride, chloroplatinic acid, rhodium sulfate, rhodium nitrate, rhodium chloride, iridium chloride, iridium tetrachloride, molybdenum sulfate, molybdenum nitrate, molybdenum chloride, ammonium molybdate, ruthenium sulfate, ruthenium nitrate, ruthenium chloride, cerium sulfate, cerium nitrate, cerium chloride or tungsten nitrate.

[0015] According to the application, preferably, the concentration of the aqueous metal salt solution is 0.1-4 mol / L; and the concentration of the aqueous sulfuric acid solution is 0.1-2 mol / L.

[0016] According to the application, preferably, the molar ratio of the metal salt to sulfuric acid in the electrolyte is 0.1-10:1.

[0017] According to the application, preferably, the temperature for electrochemical deposition is room temperature to 80℃, the current density is 1-50 mA / cm 2 , and the electrochemical deposition time is 0.5-5 h.

[0018] According to the application, preferably, the anode used for electrochemical deposition is selected from one of platinum-titanium electrode, platinum electrode, titanium electrode, carbon cloth, carbon paper, carbon felt, carbon fiber, foamed nickel or nickel plate; and the cathode used is selected from one of carbon plate, carbon cloth, carbon paper, carbon fiber, carbon felt, platinum electrode, platinum-titanium electrode, titanium electrode, nickel plate or foamed nickel.

[0019] According to the application, preferably, the calcination temperature is 300-800℃, the calcination time is 3-6 h, the temperature rising rate is 1-10℃ / min, and the calcination atmosphere is air or oxygen.

[0020] The third object of the application is to provide a preparation method of a catalyst (manganese oxide coated anode material) for preparing sulfone, comprising the following steps:

[0021] (1) Approach 1: Dissolve a manganese source in water, perform a hydrothermal reaction, and then separate and dry to obtain manganese oxide;

[0022] Or,

[0023] Approach 2: Mix benzyl alcohol and water uniformly, add PVP under ultrasonic to form an emulsion, drop the manganese source aqueous solution under stirring, perform a reaction, separate and dry to obtain manganese oxide;

[0024] (2) the manganese oxide, the conductive agent and the binder are fully dispersed in an organic solvent, and then coated on the surface of the anode material, and dried to obtain a catalyst for preparing sulfone (manganese oxide coated anode material).

[0025] According to the application, preferably, in the step (1) of the route 1, the manganese source is one or a combination of KMnO4 or MnSO4; the molar amount of the manganese source and the volume ratio of water are 0.2-1 mol / L.

[0026] According to the application, preferably, in the step (1) of the route 1, the hydrothermal reaction temperature is 150-170℃, and the hydrothermal reaction time is 6-12h.

[0027] According to the application, preferably, in the step (1) of the route 1, the reaction can also add a hydrochloric acid aqueous solution with a mass concentration of 30-37%; the volume ratio of the hydrochloric acid aqueous solution and water is 1:120-170.

[0028] According to the application, preferably, in the step (1) of the route 2, the volume ratio of benzyl alcohol and water is 1:5-10; the mass of PVP and the volume of benzyl alcohol are 5-15 mg / mL; the manganese source is KMnO4, and the concentration of the manganese source aqueous solution is 0.05-1 mol / L; the volume ratio of the manganese source aqueous solution and benzyl alcohol is 2-4:1.

[0029] According to the application, preferably, in the step (1) of the route 2, the reaction temperature is room temperature, and the reaction time is 1-5h.

[0030] According to the application, preferably, in the step (2), the conductive agent is carbon black; the binder is polyvinylidene fluoride (PVDF); the organic solvent is N-methyl pyrrolidone; and the mass ratio of the manganese oxide, the conductive agent and the binder is 1-5:1:2-8.

[0031] The fourth object of the application is to provide the use of the above-mentioned catalyst in the electrocatalytic oxidation of sulfoxide to prepare sulfone.

[0032] According to the application, preferably, the method for preparing sulfone by electrocatalytic oxidation of sulfoxide comprises the following steps:

[0033] The compound containing a sulfoxide group is dissolved in a solvent to obtain an electrolyte; under the action of the catalyst, the reaction liquid is obtained by electrocatalytic oxidation reaction, and then purified to obtain sulfone; the solvent is water or a mixed solvent of an organic solvent and water.

[0034] According to the application, preferably, the compound containing a sulfoxide group is selected from one of the following compounds:

[0035]

[0036]

[0037] According to the application, the organic solvent in the mixed solvent of organic solvent and water is acetonitrile, acetone, ethanol, methanol, toluene, dichloromethane, trichloromethane, chlorobenzene, DMF, DMA, dioxane, NMP, diethyl ether, tetrahydrofuran, butanol, dimethylbenzene, isopropyl alcohol, ethylene glycol or triethylamine; the mass ratio of the organic solvent to water is 1:0.25-4.

[0038] According to the application, the concentration of the compound containing sulfoxide group in the solvent is 1-1000 mmol / L.

[0039] According to the application, the mass of the metal oxide in the catalyst is 0.1wt%-30wt% of the mass of the compound containing sulfoxide group.

[0040] According to the application, an electrolyte is further added in the electrolyte; the electrolyte is selected from one of sodium chloride, potassium chloride, ammonium chloride, lithium sulfate, lithium nitrate, lithium carbonate, lithium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium nitrate, potassium nitrate, ammonium nitrate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetramethylammonium bisulfate, tetraethylammonium bisulfate, tetrabutylammonium bisulfate, tetramethylammonium bicarbonate, tetraethylammonium bicarbonate, tetrabutylammonium bicarbonate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetramethylammonium nitrate, tetraethylammonium nitrate or tetrabutylammonium nitrate; the concentration of the electrolyte in the solvent is 0.1-1 mol / L.

[0041] According to the application, the electrolysis mode for the electrocatalytic oxidation reaction is constant voltage or constant current; when the electrolysis mode is constant voltage, the counter electrode is platinum or nickel electrode, the reference electrode is silver / silver chloride electrode or saturated calomel electrode, the voltage is 1-2 V, and the catalyst is added and immersed in the electrolyte; when the electrolysis mode is constant current, the catalyst is used as anode, and platinum sheet is used as cathode, and the current density is 2-2000 mA / cm 2 .

[0042] According to the application, the temperature for the electrocatalytic oxidation reaction is 25℃-80℃, the reaction time is 1-35 h, and the reaction is carried out in air atmosphere.

[0043] According to the application, the purification method is the same as the existing method.

[0044] The route for preparing sulfone from sulfoxide by electrocatalytic oxidation according to the application is as follows:

[0045]

[0046] Technical features and benefits of the present application:

[0047] 1、The metal oxide coated anode material catalyst preparation method is simple, raw materials are cheap and easy to obtain, green and environmentally friendly, and low in cost. The catalyst is beneficial to the adsorption of reactants on the catalyst and accelerates the reaction. In the catalyst preparation method, only sulfuric acid solution and a metal salt solution are needed, the required cost is saved, and in the electrodeposition process, an anode electrode is needed as a catalyst substrate, so that the obtained catalyst is more stable and has higher reusability.

[0048] 2、The non-homogeneous electrocatalyst is used, cheap chemicals such as sulfoxide and water are used as raw materials, and electric energy is used as an energy source to promote water splitting, and the generated oxygen atom is transferred to sulfoxide to synthesize sulfone. The method is efficient, green and environmentally friendly, has high atomic economy, simple steps, mild reaction conditions, low price, and is suitable for industrial application.

[0049] 3、The electrochemical synthesis method of sulfone avoids the use of non-noble metal catalysts and chemical oxidants such as chlorine or peroxo acid, does not cause safety problems and harmful waste residue problems, is simple to operate, has considerable yield, is environmentally friendly, and has good application prospect.

[0050] 4、The method uses water as a raw material, water provides an oxygen source, and water is activated and decomposed under the action of a catalyst to form an oxygen-containing intermediate. The intermediate is used as an active species to oxidize sulfoxide to sulfone with high selectivity, high conversion rate and product yield, high reaction selectivity, and good electrocatalytic stability. Moreover, not only is the use of oxidants avoided, but the reaction cost is greatly reduced, and the operation is simple and safe, which saves cost and avoids environmental pollution caused by chlorine-containing waste. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 It is a SEM diagram of the catalyst prepared in Example 1;

[0052] Figure 2 It is an appearance diagram of the dimethyl sulfone product obtained in Example 1;

[0053] Figure 3 It is a hydrogen spectrum diagram of the dimethyl sulfone product obtained in Example 1. DETAILED DESCRIPTION

[0054] The present application will be further described in conjunction with specific embodiments, but is not limited thereto.

[0055] Meanwhile, in the following examples, the experimental methods described are conventional methods unless otherwise specified, and the reagents and materials described can be obtained from commercial channels unless otherwise specified.

[0056] Example 1

[0057] A method for preparing a catalyst for preparing sulfone, comprising the steps of:

[0058] (1) 300 mL of aqueous manganese nitrate solution with a concentration of 0.04 mol / L and 200 mL of aqueous sulfuric acid solution with a concentration of 0.5 mol / L are mixed uniformly as electrolyte, a titanium electrode with a size of 2*200*200 mm is used as anode, a carbon plate is used as cathode, the size of the cathode electrode should be the same as or slightly larger than the anode, and an electrochemical deposition reaction is carried out at room temperature with a current density of 20 mA / cm 2 for 3 hours, and the uncoated part is cut off to obtain a metal oxide precursor coated anode.

[0059] (2) The metal oxide precursor coated anode obtained above is put into a muffle furnace, heated to 300℃ at a heating rate of 5℃ / min and kept for 6 h, the calcination atmosphere is air, to obtain a manganese oxide coated anode material catalyst.

[0060] A method for preparing sulfone by using the above catalyst to oxidize sulfoxide, comprising the steps of:

[0061] The following operations are carried out at 25℃: 0.5 mmol (39 mg) of dimethyl sulfoxide, the above prepared catalyst 2*10*20 mm (the catalyst is immersed in the electrolyte, and the mass of manganese oxide is 10 wt% of the mass of dimethyl sulfoxide), and 10 mL of water are added into a three-necked flask reactor equipped with a magnetic stirring magnet, and then sodium nitrate electrolyte (the concentration of the electrolyte in water is 0.1 mol / L) is added, and the mixture is mixed uniformly as electrolyte. Under air atmosphere, a silver / silver chloride electrode is used as reference electrode, and a platinum sheet is used as counter electrode, a constant voltage of 1.7 V is applied, and the reaction is carried out at 25℃ for 2 hours. After the reaction is completed, the product dimethyl sulfone is obtained by filtration and vacuum drying of the filtrate, the yield is 98%, and the Faraday efficiency is 98% (the conversion rate of dimethyl sulfoxide is 99%, and the reaction selectivity is 99%).

[0062] The SEM image of the catalyst prepared in this example is shown in Figure 1 From the figure, it can be seen that the prepared sample is nanowire structure.

[0063] Figure 2 The appearance of the product dimethyl sulfone obtained in this example is shown in the figure, and from the figure, it can be seen that the dimethyl sulfone is white needle-like crystal.

[0064] Figure 3 The hydrogen spectrum of the product dimethyl sulfone obtained in this example is shown in the figure, and from the figure, it can be seen that the purity of the obtained dimethyl sulfone is as high as 99%.

[0065] Example 2

[0066] A preparation method of a catalyst for preparing sulfone, different from example 1 is that the electrodeposition temperature is changed from room temperature to 60℃, and other parameters remain unchanged.

[0067] A method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is the same as example 1.

[0068] In this example, the conversion rate of dimethyl sulfoxide is 93%, the reaction selectivity is 94%, the yield of target product is 87%, and the Faraday efficiency is 90%.

[0069] Example 3

[0070] A preparation method of a catalyst for preparing sulfone, different from example 1 is that the electrodeposition temperature is changed from room temperature to 80℃, and other parameters remain unchanged.

[0071] A method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is the same as example 1.

[0072] In this example, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 90%, the yield of target product is 81%, and the Faraday efficiency is 88%.

[0073] Example 4

[0074] A preparation method of a catalyst for preparing sulfone, different from example 1 is that the calcination temperature is changed from 300℃ to 500℃, and other parameters remain unchanged.

[0075] A method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is the same as example 1.

[0076] In this example, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 92%, the yield of target product is 89%, and the Faraday efficiency is 95%.

[0077] Example 5

[0078] A preparation method of a catalyst for preparing sulfone, different from example 1 is that the calcination temperature is changed from 300℃ to 700℃, and other parameters remain unchanged.

[0079] A method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is the same as example 1.

[0080] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 88%.

[0081] Example 6

[0082] A preparation method of a catalyst for preparing sulfone, different from example 1 is that the calcination temperature is changed from 300℃ to 700℃, and other parameters remain unchanged.

[0083] The method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is different from that in Example 1 in that the reaction temperature is changed from 25°C to 50°C, and other parameters remain unchanged.

[0084] In this example, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 95%, the yield of target product is 92%, and the Faraday efficiency is 92%.

[0085] Example 7

[0086] The method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0087] The method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is different from that in Example 1 in that the reaction temperature is changed from 25°C to 80°C, and other parameters remain unchanged.

[0088] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 91%.

[0089] Example 8

[0090] The method for preparing a catalyst for preparing sulfone is the same as that in Example 1, except that the amount of 0.04 mol / L aqueous manganese nitrate solution is 3 mL, and other parameters remain unchanged.

[0091] The method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is different from that in Example 1 in that the mass of manganese oxide in the catalyst is 0.1 wt% of the mass of dimethyl sulfoxide, and the size of the catalyst is 2*10*20 mm, and other parameters remain unchanged.

[0092] In this example, the conversion rate of dimethyl sulfoxide is 92%, the reaction selectivity is 96%, the yield of target product is 88%, and the Faraday efficiency is 91%.

[0093] Example 9

[0094] The method for preparing a catalyst for preparing sulfone is the same as that in Example 1, except that the amount of 0.04 mol / L aqueous manganese nitrate solution is 900 mL, and other parameters remain unchanged.

[0095] The method for preparing sulfone by oxidizing dimethyl sulfoxide with the catalyst is different from that in Example 1 in that the mass of manganese oxide in the catalyst is 30 wt% of the mass of dimethyl sulfoxide, and the size of the catalyst is 2*10*20 mm, and other parameters remain unchanged.

[0096] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 95%, the yield of target product is 90%, and the Faraday efficiency is 96%.

[0097] Example 10

[0098] A method for preparing a catalyst for preparing sulfone, comprising the steps of:

[0099] Dissolve KMnO4 and MnSO4 in 40 mL of water, wherein the concentration of KMnO4 is 0.24 mol / L and the concentration of MnSO4 is 0.53 mol / L, stir for 30 minutes, put into a polytetrafluoroethylene hydrothermal kettle for hydrothermal reaction at 160℃ for 12 hours, centrifuge and dry to obtain MnO2.

[0100] Take 20 mg of MnO2, 10 mg of carbon black, and 4 mg of PVDF, disperse them in 400 microliters of N-methyl pyrrolidone, drop 25 microliters at a time on a 1*1 cm titanium electrode, drop once every half hour, a total of four times, and finally dry to obtain a catalyst for preparing sulfone.

[0101] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as in Example 1.

[0102] The conversion rate of dimethyl sulfoxide in this example is 96%, the reaction selectivity is 96%, the yield of the target product is 92%, and the Faraday efficiency is 93%.

[0103] Example 11

[0104] A method for preparing a catalyst for preparing sulfone, comprising the steps of:

[0105] Dissolve MnSO4 in 30 mL of water, wherein the concentration of MnSO4 is 0.3 mol / L, stir for 30 minutes, put into a polytetrafluoroethylene hydrothermal kettle for hydrothermal reaction at 170℃ for 10 hours, centrifuge and dry to obtain MnO2.

[0106] Take 20 mg of MnO2, 10 mg of carbon black, and 4 mg of PVDF, disperse them in 400 microliters of N-methyl pyrrolidone, drop 25 microliters at a time on a 1*1 cm titanium electrode, drop once every half hour, a total of four times, and finally dry to obtain a catalyst for preparing sulfone.

[0107] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as in Example 1.

[0108] The conversion rate of dimethyl sulfoxide in this example is 95%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0109] Example 12

[0110] A method for preparing a catalyst for preparing sulfone, comprising the steps of:

[0111] KMnO4 and MnSO4 were dissolved in 40 mL of water, the concentration of KMnO4 was 0.5 mol / L, the concentration of MnSO4 was 0.18 mol / L, stirring for 30 minutes, put into a polytetrafluoroethylene hydrothermal kettle at 160 ℃ for 12 h, centrifuged and dried to obtain MnO2.

[0112] Take 20 mg of MnO2, 10 mg of carbon black, 4 mg of PVDF, disperse in 400 microliters of N-methyl pyrrolidone, drop 25 microliters each time on a 1*1 cm titanium electrode, drop once every half hour, a total of four times, and finally dry to obtain a catalyst for preparing sulfone.

[0113] The method for preparing sulfone by oxidizing sulfoxide with the above catalyst is the same as that in Example 1.

[0114] The conversion rate of dimethyl sulfoxide in this example is 96%, the reaction selectivity is 90%, the yield of target product is 86%, and the faraday efficiency is 90%.

[0115] Example 13

[0116] A method for preparing a catalyst for preparing sulfone, comprising the steps of:

[0117] 1 mL of benzyl alcohol and 7 mL of water were mixed uniformly, 10 mg of PVP was ultrasonically added to form an emulsion, 3 mL of 0.1 mol / L KMnO4 aqueous solution was added dropwise, stirred at room temperature for 2 h, centrifuged and dried to obtain MnO2.

[0118] Take 20 mg of MnO2, 10 mg of carbon black, 4 mg of PVDF, disperse in 400 microliters of N-methyl pyrrolidone, drop 25 microliters each time on a 1*1 cm titanium electrode, drop once every half hour, a total of four times, and finally dry to obtain a catalyst for preparing sulfone.

[0119] The method for preparing sulfone by oxidizing sulfoxide with the above catalyst is the same as that in Example 1.

[0120] The conversion rate of dimethyl sulfoxide in this example is 96%, the reaction selectivity is 88%, the yield of target product is 84%, and the faraday efficiency is 90%.

[0121] Example 14

[0122] A method for preparing a catalyst for preparing sulfone, comprising the steps of:

[0123] KMnO4 and 0.2 mL of 36.5% mass fraction hydrochloric acid aqueous solution were dissolved in 30 mL of water, the concentration of KMnO4 was 0.4 mol / L, stirring for 30 minutes, put into a polytetrafluoroethylene hydrothermal kettle, 150 ℃ hydrothermal for 6 h, centrifuged and dried to obtain MnO2.

[0124] Take 20 mg of MnO2, 10 mg of carbon black, 4 mg of PVDF, disperse in 400 microliters of N-methyl pyrrolidone, drop 25 microliters at a time on a 1*1 cm titanium electrode, drop once every half hour, a total of four times, and finally dry to obtain a catalyst for preparing sulfone.

[0125] The method for preparing sulfone by oxidizing sulfoxide with the above catalyst is the same as in Example 1.

[0126] The conversion rate of dimethyl sulfoxide in this example is 91%, the reaction selectivity is 95%, the yield of the target product is 86%, and the Faraday efficiency is 88%.

[0127] Example 15

[0128] A method for preparing a catalyst for preparing sulfone, which is different from Example 1:

[0129] The 0.04 mol / L manganese nitrate aqueous solution is replaced with 0.05 mol / L ferric chloride aqueous solution, the calcination temperature is changed to 550°C, and other parameters remain unchanged.

[0130] The method for preparing sulfone by oxidizing sulfoxide with the above catalyst is the same as in Example 1.

[0131] The conversion rate of dimethyl sulfoxide in this example is 91%, the reaction selectivity is 94%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0132] Example 16

[0133] A method for preparing a catalyst for preparing sulfone, which is different from Example 1:

[0134] The 0.04 mol / L manganese nitrate aqueous solution is replaced with 0.04 mol / L cobalt nitrate aqueous solution, the calcination temperature is changed to 550°C, and other parameters remain unchanged.

[0135] The method for preparing sulfone by oxidizing sulfoxide with the above catalyst is the same as in Example 1.

[0136] The conversion rate of dimethyl sulfoxide in this example is 96%, the reaction selectivity is 91%, the yield of the target product is 87%, and the Faraday efficiency is 90%.

[0137] Example 17

[0138] A method for preparing a catalyst for preparing sulfone, which is different from Example 1:

[0139] The 0.04 mol / L manganese nitrate aqueous solution is replaced with 0.04 mol / L nickel nitrate aqueous solution, the calcination temperature is changed to 550°C, and other parameters remain unchanged.

[0140] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in Example 1.

[0141] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 91%, the yield of target product is 86%, and the Faraday efficiency is 93%.

[0142] Example 18

[0143] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 is that:

[0144] The 0.04 mol / L aqueous manganese nitrate solution is replaced by a 0.06 mol / L aqueous copper nitrate solution, the calcination temperature is changed to 550°C, and other parameters remain unchanged.

[0145] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in Example 1.

[0146] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 87%, the yield of target product is 84%, and the Faraday efficiency is 88%.

[0147] Example 19

[0148] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 is that:

[0149] The 0.04 mol / L aqueous manganese nitrate solution is replaced by a 0.04 mol / L aqueous silver nitrate solution, and other parameters remain unchanged.

[0150] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in Example 1.

[0151] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 95%, the yield of target product is 91%, and the Faraday efficiency is 95%.

[0152] Example 20

[0153] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 is that:

[0154] The 0.04 mol / L aqueous manganese nitrate solution is replaced by a 0.04 mol / L aqueous palladium chloride solution, and other parameters remain unchanged.

[0155] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in Example 1.

[0156] In this example, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 96%, the yield of target product is 86%, and the Faraday efficiency is 88%.

[0157] Example 21

[0158] A preparation method of a catalyst for preparing sulfone, different from example 1 is that:

[0159] The 0.04 mol / L manganese nitrate aqueous solution is replaced by 0.05 mol / L chloroplatinic acid aqueous solution, and other parameters are unchanged.

[0160] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in example 1.

[0161] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 94%, the yield of the target product is 90%, and the faraday efficiency is 95%.

[0162] Example 22

[0163] A preparation method of a catalyst for preparing sulfone, different from example 1 is that:

[0164] The 0.04 mol / L manganese nitrate aqueous solution is replaced by 0.03 mol / L rhodium nitrate aqueous solution, and other parameters are unchanged.

[0165] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in example 1.

[0166] In this example, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 93%, the yield of the target product is 84%, and the faraday efficiency is 90%.

[0167] Example 23

[0168] A preparation method of a catalyst for preparing sulfone, different from example 1 is that:

[0169] The 0.04 mol / L manganese nitrate aqueous solution is replaced by 0.07 mol / L iridium chloride aqueous solution, the calcination temperature is changed to 800 DEG C, and other parameters are unchanged.

[0170] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in example 1.

[0171] In this example, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 89%, the yield of the target product is 86%, and the faraday efficiency is 90%.

[0172] Example 24

[0173] A preparation method of a catalyst for preparing sulfone, different from example 1 is that:

[0174] The 0.04 mol / L manganese nitrate aqueous solution is replaced by 0.08 mol / L cerium chloride aqueous solution, and other parameters are unchanged.

[0175] The method for preparing sulfone by using the above catalyst to oxidize sulfoxide is the same as that in example 1.

[0176] The conversion rate of dimethyl sulfoxide in this example is 95%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 91%.

[0177] Example 25

[0178] A preparation method of a catalyst for preparing sulfone, which is different from that in Example 1, is as follows:

[0179] The 0.04 mol / L aqueous manganese nitrate solution is replaced by a 0.06 mol / L aqueous potassium dichromate solution, and other parameters remain unchanged.

[0180] The method for preparing sulfone by oxidation of sulfoxide using the above catalyst is the same as that in Example 1.

[0181] The conversion rate of dimethyl sulfoxide in this example is 95%, the reaction selectivity is 97%, the yield of target product is 92%, and the Faraday efficiency is 92%.

[0182] Example 26

[0183] A preparation method of a catalyst for preparing sulfone, which is different from that in Example 1, is as follows:

[0184] The 0.04 mol / L aqueous manganese nitrate solution is replaced by a 0.04 mol / L aqueous ammonium molybdate solution, and other parameters remain unchanged.

[0185] The method for preparing sulfone by oxidation of sulfoxide using the above catalyst is the same as that in Example 1.

[0186] The conversion rate of dimethyl sulfoxide in this example is 90%, the reaction selectivity is 94%, the yield of target product is 85%, and the Faraday efficiency is 89%.

[0187] Example 27

[0188] A preparation method of a catalyst for preparing sulfone, which is different from that in Example 1, is as follows:

[0189] The 0.04 mol / L aqueous manganese nitrate solution is replaced by a 0.04 mol / L aqueous tungsten nitrate solution, and other parameters remain unchanged.

[0190] The method for preparing sulfone by oxidation of sulfoxide using the above catalyst is the same as that in Example 1.

[0191] The conversion rate of dimethyl sulfoxide in this example is 88%, the reaction selectivity is 94%, the yield of target product is 83%, and the Faraday efficiency is 86%.

[0192] Example 28

[0193] A preparation method of a catalyst for preparing sulfone, which is different from that in Example 1, is as follows:

[0194] The 0.04 mol / L manganese nitrate aqueous solution is replaced by 0.04 mol / L vanadium nitrate aqueous solution, and other parameters remain unchanged.

[0195] The method for preparing sulfone from sulfoxide by using the above catalyst is the same as that in Example 1.

[0196] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 96%, the yield of target product is 91%, and the Faraday efficiency is 93%.

[0197] Example 29

[0198] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 is that:

[0199] The 0.04 mol / L manganese nitrate aqueous solution is replaced by 0.04 mol / L titanium nitrate aqueous solution, and other parameters remain unchanged.

[0200] The method for preparing sulfone from sulfoxide by using the above catalyst is the same as that in Example 1.

[0201] In this example, the conversion rate of dimethyl sulfoxide is 93%, the reaction selectivity is 96%, the yield of target product is 89%, and the Faraday efficiency is 90%.

[0202] Example 30

[0203] A method for preparing a catalyst for preparing sulfone, which is the same as Example 1.

[0204] The method for preparing sulfone from sulfoxide by using the above catalyst is the same as that in Example 1, except that the solvent is changed to a mixed solution of water:acetonitrile = 1:1 (volume ratio), and other parameters remain unchanged.

[0205] In this example, the conversion rate of dimethyl sulfoxide is 88%, the reaction selectivity is 95%, the yield of target product is 84%, and the Faraday efficiency is 86%.

[0206] Example 31

[0207] A method for preparing a catalyst for preparing sulfone, which is the same as Example 1.

[0208] The method for preparing sulfone from sulfoxide by using the above catalyst is the same as that in Example 1, except that the solvent is changed to a mixed solution of water:acetonitrile = 1:4 (volume ratio), and other parameters remain unchanged.

[0209] In this example, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 94%, the yield of target product is 85%, and the Faraday efficiency is 87%.

[0210] Example 32

[0211] A method for preparing a catalyst for preparing sulfone, which is the same as Example 1.

[0212] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: acetonitrile = 3:2 (volume ratio), and other parameters remain unchanged.

[0213] The conversion rate of dimethyl sulfoxide in this example is 90%, the reaction selectivity is 91%, the yield of the target product is 82%, and the Faraday efficiency is 90%.

[0214] Example 33

[0215] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0216] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: acetonitrile = 7:3 (volume ratio), and other parameters remain unchanged.

[0217] The conversion rate of dimethyl sulfoxide in this example is 97%, the reaction selectivity is 93%, the yield of the target product is 90%, and the Faraday efficiency is 94%.

[0218] Example 34

[0219] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0220] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: acetonitrile = 4:1 (volume ratio), and other parameters remain unchanged.

[0221] The conversion rate of dimethyl sulfoxide in this example is 90%, the reaction selectivity is 93%, the yield of the target product is 84%, and the Faraday efficiency is 93%.

[0222] Example 35

[0223] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0224] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: acetonitrile = 4:1 (volume ratio), and other parameters remain unchanged.

[0225] The conversion rate of dimethyl sulfoxide in this example is 95%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0226] Example 36

[0227] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0228] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: ethanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0229] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 97%, the yield of the target product is 92%, and the Faraday efficiency is 97%.

[0230] Example 37

[0231] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0232] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: ethanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0233] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 97%, the yield of the target product is 92%, and the Faraday efficiency is 97%.

[0234] Example 38

[0235] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0236] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: ethanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0237] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 97%, the yield of the target product is 92%, and the Faraday efficiency is 97%.

[0238] Example 39

[0239] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0240] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: ethanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0241] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 97%, the yield of the target product is 92%, and the Faraday efficiency is 97%.

[0242] Example 40

[0243] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0244] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: chlorobenzene = 1:1 (volume ratio), and other parameters remain unchanged.

[0245] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 85%, the yield of target product is 82%, and the Faraday efficiency is 85%.

[0246] Example 41

[0247] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0248] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: chlorobenzene = 1:1 (volume ratio), and other parameters remain unchanged.

[0249] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 85%, the yield of target product is 82%, and the Faraday efficiency is 85%.

[0250] Example 42

[0251] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0252] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: chlorobenzene = 1:1 (volume ratio), and other parameters remain unchanged.

[0253] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 85%, the yield of target product is 82%, and the Faraday efficiency is 85%.

[0254] Example 43

[0255] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0256] The method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: chlorobenzene = 1:1 (volume ratio), and other parameters remain unchanged.

[0257] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 85%, the yield of target product is 82%, and the Faraday efficiency is 85%.

[0258] Example 44

[0259] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0260] The process for the preparation of sulfone from sulfoxide using the above catalyst is as described in Example 1 except that the solvent is changed to a mixture of water: dioxane = 1 : 1 (volume ratio) and other parameters remain unchanged.

[0261] The conversion of dimethyl sulfoxide in this example is 97%, the selectivity of the reaction is 88%, the yield of the target product is 85% and the Faraday efficiency is 86%.

[0262] Example 45

[0263] A process for the preparation of a catalyst for the preparation of sulfone is as described in Example 1.

[0264] The process for the preparation of sulfone from sulfoxide using the above catalyst is as described in Example 1 except that the solvent is changed to a mixture of water: NMP (N-methyl pyrrolidone) = 1 : 1 (volume ratio) and other parameters remain unchanged.

[0265] The conversion of dimethyl sulfoxide in this example is 95%, the selectivity of the reaction is 90%, the yield of the target product is 86% and the Faraday efficiency is 86%.

[0266] Example 46

[0267] A process for the preparation of a catalyst for the preparation of sulfone is as described in Example 1.

[0268] The process for the preparation of sulfone from sulfoxide using the above catalyst is as described in Example 1 except that the solvent is changed to a mixture of water: diethyl ether = 1 : 1 (volume ratio) and other parameters remain unchanged.

[0269] The conversion of dimethyl sulfoxide in this example is 96%, the selectivity of the reaction is 95%, the yield of the target product is 91% and the Faraday efficiency is 91%.

[0270] Example 47

[0271] A process for the preparation of a catalyst for the preparation of sulfone is as described in Example 1.

[0272] The process for the preparation of sulfone from sulfoxide using the above catalyst is as described in Example 1 except that the solvent is changed to a mixture of water: THF (tetrahydrofuran) = 1 : 1 (volume ratio) and other parameters remain unchanged.

[0273] The conversion of dimethyl sulfoxide in this example is 90%, the selectivity of the reaction is 90%, the yield of the target product is 81% and the Faraday efficiency is 83%.

[0274] Example 48

[0275] A process for the preparation of a catalyst for the preparation of sulfone is as described in Example 1.

[0276] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the solvent is changed to a mixed solution of water: butanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0277] In this embodiment, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 96%, the yield of target product is 86%, and the Faraday efficiency is 93%.

[0278] Embodiment 49

[0279] A method for preparing a catalyst for preparing sulfone, as described in Embodiment 1.

[0280] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the solvent is changed to a mixed solution of water: butanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0281] In this embodiment, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 96%, the yield of target product is 86%, and the Faraday efficiency is 93%.

[0282] Embodiment 50

[0283] A method for preparing a catalyst for preparing sulfone, as described in Embodiment 1.

[0284] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the solvent is changed to a mixed solution of water: butanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0285] In this embodiment, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 96%, the yield of target product is 86%, and the Faraday efficiency is 93%.

[0286] Embodiment 51

[0287] A method for preparing a catalyst for preparing sulfone, as described in Embodiment 1.

[0288] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the solvent is changed to a mixed solution of water: butanol = 1:1 (volume ratio), and other parameters remain unchanged.

[0289] In this embodiment, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 96%, the yield of target product is 86%, and the Faraday efficiency is 93%.

[0290] Embodiment 52

[0291] A method for preparing a catalyst for preparing sulfone, as described in Embodiment 1.

[0292] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the electrolyte is changed into lithium nitrate, and other parameters remain unchanged.

[0293] In this embodiment, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 95%, the yield of target product is 91%, and the Faraday efficiency is 93%.

[0294] Embodiment 53

[0295] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0296] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the electrolyte is changed into potassium nitrate, and other parameters remain unchanged.

[0297] In this embodiment, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 90%.

[0298] Embodiment 54

[0299] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0300] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the electrolyte is changed into ammonium nitrate, and other parameters remain unchanged.

[0301] In this embodiment, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 90%.

[0302] Embodiment 55

[0303] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0304] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the electrolyte is changed into tetrabutylammonium tetrafluoroborate, and other parameters remain unchanged.

[0305] In this embodiment, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 90%.

[0306] Embodiment 56

[0307] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0308] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the electrolyte is changed into ammonium nitrate, and other parameters remain unchanged.

[0309] The conversion rate of dimethyl sulfoxide in this example is 97%, the reaction selectivity is 88%, the yield of target product is 85%, and the Faraday efficiency is 86%.

[0310] Example 57

[0311] A method for preparing a catalyst for preparing sulfone, which is the same as that in Example 1.

[0312] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1, except that the electrolyte is changed to tetrabutylammonium acetate, and other parameters remain unchanged.

[0313] The conversion rate of dimethyl sulfoxide in this example is 95%, the reaction selectivity is 88%, the yield of target product is 84%, and the Faraday efficiency is 86%.

[0314] Example 58

[0315] A method for preparing a catalyst for preparing sulfone, which is the same as that in Example 1.

[0316] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1, except that the electrolyte is changed to tetrabutylammonium chloride, and other parameters remain unchanged.

[0317] The conversion rate of dimethyl sulfoxide in this example is 94%, the reaction selectivity is 93%, the yield of target product is 87%, and the Faraday efficiency is 90%.

[0318] Example 59

[0319] A method for preparing a catalyst for preparing sulfone, which is the same as that in Example 1.

[0320] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1, except that the electrolyte is changed to tetrabutylammonium bromide, and other parameters remain unchanged.

[0321] The conversion rate of dimethyl sulfoxide in this example is 90%, the reaction selectivity is 95%, the yield of target product is 86%, and the Faraday efficiency is 90%.

[0322] Example 60

[0323] A method for preparing a catalyst for preparing sulfone, which is the same as that in Example 1.

[0324] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1, except that the electrolyte is changed to tetrabutylammonium bromide, and other parameters remain unchanged.

[0325] The conversion rate of dimethyl sulfoxide in this example is 98%, the reaction selectivity is 94%, the yield of target product is 92%, and the Faraday efficiency is 95%.

[0326] Example 61

[0327] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0328] A method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to tetrabutylammonium fluoride, and other parameters remain unchanged.

[0329] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0330] Example 62

[0331] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0332] A method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to tetrabutylammonium hydrogen sulfate, and other parameters remain unchanged.

[0333] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 95%, the yield of the target product is 91%, and the Faraday efficiency is 93%.

[0334] Example 63

[0335] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0336] A method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to tetrabutylammonium hydrogen carbonate, and other parameters remain unchanged.

[0337] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 86%.

[0338] Example 64

[0339] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0340] A method for preparing sulfone from dimethyl sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to tetrabutylammonium perchlorate, and other parameters remain unchanged.

[0341] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 96%, the yield of the target product is 92%, and the Faraday efficiency is 95%.

[0342] Example 65

[0343] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0344] The method for preparing sulfone from dimethyl sulfoxide by using the above catalyst is as described in Example 1, except that the electrolyte is changed to tetrabutylammonium nitrate, and other parameters remain unchanged.

[0345] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 92%, the yield of target product is 88%, and the Faraday efficiency is 90%.

[0346] Example 66

[0347] A method for preparing a catalyst for preparing sulfone, as described in Example 1.

[0348] The method for preparing sulfone from dimethyl sulfoxide by using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is changed to diphenyl sulfoxide (structure: ), and other parameters remain unchanged.

[0349] In this example, the conversion rate of diphenyl sulfoxide is 91%, the reaction selectivity is 98%, the yield of target product is 89%, and the Faraday efficiency is 92%.

[0350] Example 67

[0351] A method for preparing a catalyst for preparing sulfone, as described in Example 1.

[0352] The method for preparing sulfone from dimethyl sulfoxide by using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is changed to methyl phenyl sulfoxide (structure: ), and other parameters remain unchanged.

[0353] In this example, the conversion rate of methyl phenyl sulfoxide is 88%, the reaction selectivity is 97%, the yield of target product is 85%, and the Faraday efficiency is 89%.

[0354] Example 68

[0355] A method for preparing a catalyst for preparing sulfone, as described in Example 1.

[0356] The method for preparing sulfone from dimethyl sulfoxide by using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is changed to p-chlorophenyl methyl sulfoxide (structure: ), and other parameters remain unchanged.

[0357] In this example, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 92%, the yield of target product is 89%, and the Faraday efficiency is 90%.

[0358] Example 69

[0359] A method for preparing a catalyst for preparing sulfone, as described in Example 1.

[0360] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 4-(methylsulfinyl)benzonitrile (structure: ), and other parameters remain unchanged.

[0361] The conversion rate of 4-(methylsulfinyl)benzonitrile in this example is 95%, the reaction selectivity is 84%, the yield of target product is 80%, and the Faraday efficiency is 88%.

[0362] Example 70

[0363] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0364] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1-methyl-3-(methylsulfinyl)benzene (structure: ), and other parameters remain unchanged.

[0365] The conversion rate of 1-methyl-3-(methylsulfinyl)benzene in this example is 97%, the reaction selectivity is 94%, the yield of target product is 91%, and the Faraday efficiency is 96%.

[0366] Example 71

[0367] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0368] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1-chloro-2-(methylsulfinyl)benzene (structure: ), and other parameters remain unchanged.

[0369] The conversion rate of 1-chloro-2-(methylsulfinyl)benzene in this example is 95%, the reaction selectivity is 96%, the yield of target product is 91%, and the Faraday efficiency is 95%.

[0370] Example 72

[0371] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0372] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1,3-dichloro-5-(methylsulfinyl)benzene (structure: ), and other parameters remain unchanged.

[0373] The conversion rate of 1,3-dichloro-5-(methylsulfinyl)benzene in this example is 90%, the reaction selectivity is 91%, the yield of target product is 82%, and the Faraday efficiency is 93%.

[0374] Example 73

[0375] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0376] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)pyridine (structure formula: ), and other parameters remain unchanged.

[0377] The conversion rate of 2-(methylsulfinyl)pyridine in this example is 95%, the reaction selectivity is 85%, the yield of target product is 81%, and the Faraday efficiency is 95%.

[0378] Example 74

[0379] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0380] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)pyridine (structure formula: ), and other parameters remain unchanged.

[0381] The conversion rate of 2-(methylsulfinyl)pyridine in this example is 95%, the reaction selectivity is 85%, the yield of target product is 81%, and the Faraday efficiency is 95%.

[0382] Example 75

[0383] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0384] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)pyridine (structure formula: ), and other parameters remain unchanged.

[0385] The conversion rate of 2-(methylsulfinyl)pyridine in this example is 95%, the reaction selectivity is 85%, the yield of target product is 81%, and the Faraday efficiency is 95%.

[0386] Example 76

[0387] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0388] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)pyridine (structure formula: ), and other parameters remain unchanged.

[0389] The conversion rate of the (cyclopropylsulfinyl)benzene in this example is 95%, the reaction selectivity is 93%, the yield of the target product is 88%, and the Faraday efficiency is 94%.

[0390] Example 77

[0391] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0392] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-methyl-4-nitro-1-(4-(trifluoromethyl)phenylsulfinyl)benzene (structure: ), and other parameters remain unchanged.

[0393] The conversion rate of 2-methyl-4-nitro-1-(4-(trifluoromethyl)phenylsulfinyl)benzene in this example is 93%, the reaction selectivity is 88%, the yield of the target product is 82%, and the Faraday efficiency is 91%.

[0394] Example 78

[0395] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0396] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)-1H-benzo[d]imidazole (structure: ), and other parameters remain unchanged.

[0397] The conversion rate of 2-(methylsulfinyl)-1H-benzo[d]imidazole in this example is 97%, the reaction selectivity is 95%, the yield of the target product is 92%, and the Faraday efficiency is 98%.

[0398] Example 79

[0399] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0400] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)-1H-benzo[d]imidazole (structure: ), and other parameters remain unchanged.

[0401] The conversion rate of 2-(methylsulfinyl)-1H-benzo[d]imidazole in this example is 97%, the reaction selectivity is 95%, the yield of the target product is 92%, and the Faraday efficiency is 98%.

[0402] Example 80

[0403] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0404] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)benzo[d]oxazole (structure formula: ), and other parameters remain unchanged.

[0405] In this example, the conversion rate of 2-(methylsulfinyl)benzo[d]oxazole is 97%, the reaction selectivity is 90%, the yield of target product is 87%, and the Faraday efficiency is 97%.

[0406] Example 81

[0407] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0408] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1,3-dibromo-5-(methylsulfinyl)benzene (structure formula: ), and other parameters remain unchanged.

[0409] In this example, the conversion rate of 1,3-dibromo-5-(methylsulfinyl)benzene is 95%, the reaction selectivity is 96%, the yield of target product is 91%, and the Faraday efficiency is 95%.

[0410] Example 82

[0411] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0412] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(methylsulfinyl)pyridine (structure formula: ), and other parameters remain unchanged.

[0413] In this example, the conversion rate of 2-(methylsulfinyl)pyridine is 95%, the reaction selectivity is 90%, the yield of target product is 86%, and the Faraday efficiency is 87%.

[0414] Example 83

[0415] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0416] The method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1-bromo-4-(methylsulfinyl)benzene (structure formula: ), and other parameters remain unchanged.

[0417] In this example, the conversion rate of 1-bromo-4-(methylsulfinyl)benzene is 90%, the reaction selectivity is 98%, the yield of target product is 88%, and the Faraday efficiency is 89%.

[0418] Example 84

[0419] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0420] A method for preparing sulfone from sulfoxide by using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 4-methoxyphenyl methyl sulfoxide (structure formula: ), and other parameters remain unchanged.

[0421] The conversion rate of 4-methoxyphenyl methyl sulfoxide in this example is 98%, the reaction selectivity is 89%, the yield of the target product is 87%, and the faraday efficiency is 89%.

[0422] Example 8

[0423] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0424] A method for preparing sulfone from sulfoxide by using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 1-(methylsulfinyl)-4-nitrobenzene (structure formula: ), and other parameters remain unchanged.

[0425] The conversion rate of 1-(methylsulfinyl)-4-nitrobenzene in this example is 95%, the reaction selectivity is 88%, the yield of the target product is 84%, and the faraday efficiency is 86%.

[0426] Example 8

[0427] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0428] A method for preparing sulfone from sulfoxide by using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 5-(2-(octylsulfinyl)propyl)benzo[d][1,3]dioxol (structure formula: ), and other parameters remain unchanged.

[0429] The conversion rate of 5-(2-(octylsulfinyl)propyl)benzo[d][1,3]dioxol in this example is 93%, the reaction selectivity is 88%, the yield of the target product is 82%, and the faraday efficiency is 89%.

[0430] Example 8

[0431] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0432] A method for preparing sulfone from sulfoxide by using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 5-chloro-6-(2,3-dimethylphenoxy)-2-(methylsulfinyl)-3l2-benzo[d]imidazole (structure formula: ), and other parameters remain unchanged.

[0433] The conversion of 5-chloro-6-(2,3-dimethylphenoxy)-2-(methylsulfinyl)-3H- benzo[d]imidazole in this example is 95%, the reaction selectivity is 85%, the yield of target product is 81%, and the Faraday efficiency is 87%.

[0434] Example 8

[0435] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0436] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by methyl (6-(propylsulfinyl)-1H- benzo[d]imidazol-2-yl)carbamate (structure formula: ), and other parameters remain unchanged.

[0437] The conversion of methyl (6-(propylsulfinyl)-1H-benzo[d]imidazol-2-yl)carbamate in this example is 95%, the reaction selectivity is 85%, the yield of target product is 81%, and the Faraday efficiency is 86%.

[0438] Example 8

[0439] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0440] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by methyl (6-(phenylsulfinyl)-1H- benzo[d]imidazol-2-yl)carbamate (structure formula: ), and other parameters remain unchanged.

[0441] The conversion of methyl (6-(phenylsulfinyl)-1H-benzo[d]imidazol-2-yl)carbamate in this example is 93%, the reaction selectivity is 90%, the yield of target product is 84%, and the Faraday efficiency is 91%.

[0442] Example 8

[0443] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0444] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-chloro-10-(3-(dimethylamino)propyl)- 10H-phenothiazine 5-oxide (structure formula: ), and other parameters remain unchanged.

[0445] The conversion of 2-chloro-10-(3-(dimethylamino)propyl)-10H-phenothiazine 5-oxide in this example is 95%, the reaction selectivity is 88%, the yield of target product is 84%, and the Faraday efficiency is 88%.

[0446] Example 91

[0447] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0448] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-chloro-10-(3-(4-(2-hydroxyethyl)piperazin-1-yl)propyl)-10H-phenothiazine 5-oxide (structure: ), and other parameters remain unchanged.

[0449] The conversion of 2-chloro-10-(3-(4-(2-hydroxyethyl)piperazin-1-yl)propyl)-10H-phenothiazine 5-oxide in this example is 97%, the reaction selectivity is 85%, the yield of target product is 82%, and the Faraday efficiency is 97%.

[0450] Example 92

[0451] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0452] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1-methyl-3-((2-phenoxyethyl)sulfinyl)benzene (structure: ), and other parameters remain unchanged.

[0453] The conversion of 1-methyl-3-((2-phenoxyethyl)sulfinyl)benzene in this example is 95%, the reaction selectivity is 95%, the yield of target product is 90%, and the Faraday efficiency is 95%.

[0454] Example 93

[0455] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0456] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 4-methyldibenzo[b,d]thiophene 5-oxide (structure: ), and other parameters remain unchanged.

[0457] The conversion of 4-methyldibenzo[b,d]thiophene 5-oxide in this example is 97%, the reaction selectivity is 95%, the yield of target product is 92%, and the Faraday efficiency is 93%.

[0458] Example 94

[0459] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0460] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 4,6-dimethyl dibenzo[b,d]thiophene 5-oxide (structure formula: ), and other parameters remain unchanged.

[0461] In this example, the conversion rate of 4,6-dimethyl dibenzo[b,d]thiophene 5-oxide is 95%, the reaction selectivity is 89%, the yield of the target product is 85%, and the Faraday efficiency is 93%.

[0462] Example 95

[0463] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0464] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 3-(((5-(difluoro-l3-oxoalkyl)-l-methyl-3-(trifluoromethyl)-lH-pyrazol-4-yl)methyl)sulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole (structure formula: ), and other parameters remain unchanged.

[0465] In this example, the conversion rate of 3-(((5-(difluoro-l3-oxoalkyl)-l-methyl-3-(trifluoromethyl)-lH-pyrazol-4-yl)methyl)sulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole is 94%, the reaction selectivity is 90%, the yield of the target product is 85%, and the Faraday efficiency is 86%.

[0466] Example 96

[0467] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0468] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in example 1, except that dimethyl sulfoxide is replaced by 4,4'-sulfinyldiphenol (structure formula: ), and other parameters remain unchanged.

[0469] In this example, the conversion rate of 4,4'-sulfinyldiphenol is 96%, the reaction selectivity is 92%, the yield of the target product is 88%, and the Faraday efficiency is 90%.

[0470] Example 97

[0471] A method for preparing a catalyst for preparing sulfone, same as example 1.

[0472] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that dimethyl sulfoxide is replaced by 4,4'-sulfinylbiscresyl (structural formula: ), and other parameters remain unchanged.

[0473] In this embodiment, the conversion rate of 4,4'-sulfinylbiscresyl is 97%, the reaction selectivity is 97%, the yield of the target product is 94%, and the Faraday efficiency is 96%.

[0474] Embodiment 8

[0475] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0476] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that dimethyl sulfoxide is replaced by 5-methoxy-2-(((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)sulfinyl)-1H-benzo[d]imidazole (structural formula: ), and other parameters remain unchanged.

[0477] In this embodiment, the conversion rate of 5-methoxy-2-(((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)sulfinyl)-1H-benzo[d]imidazole is 95%, the reaction selectivity is 92%, the yield of the target product is 87%, and the Faraday efficiency is 89%.

[0478] Embodiment 9

[0479] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0480] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that dimethyl sulfoxide is replaced by 5-chloro-6'-methyl-3-(4-(methylsulfinyl)phenyl)-2,3'-bipyridine (structural formula: ), and other parameters remain unchanged.

[0481] In this embodiment, the conversion rate of 5-chloro-6'-methyl-3-(4-(methylsulfinyl)phenyl)-2,3'-bipyridine is 92%, the reaction selectivity is 95%, the yield of the target product is 87%, and the Faraday efficiency is 89%.

[0482] Embodiment 10

[0483] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0484] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that dimethyl sulfoxide is replaced by (R)-2-(phenylsulfinyl)acetamide (structural formula: ), and other parameters remain unchanged.

[0485] The conversion of (R)-2-(phenylsulfonyl)acetamide in this example was 94%, the reaction selectivity was 95%, the yield of target product was 89%, and the Faraday efficiency was 91%.

[0486] Example 101

[0487] A method for preparing a catalyst for preparing sulfone, which is the same as in Example 1.

[0488] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1-methyl-4-(methylsulfinyl)benzene (structural formula: ), and other parameters remain unchanged.

[0489] The conversion of 1-methyl-4-(methylsulfinyl)benzene in this example was 97%, the reaction selectivity was 95%, the yield of target product was 92%, and the Faraday efficiency was 93%.

[0490] Example 102

[0491] A method for preparing a catalyst for preparing sulfone, which is the same as in Example 1.

[0492] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2,2-dichloro-N-((1R,2S)-3-fluoro-1-hydroxy-1-(4-(methylsulfinyl)phenyl)propan-2-yl)acetamide (structural formula: ), and other parameters remain unchanged.

[0493] The conversion of 2,2-dichloro-N-((1R,2S)-3-fluoro-1-hydroxy-1-(4-(methylsulfinyl)phenyl)propan-2-yl)acetamide in this example was 94%, the reaction selectivity was 95%, the yield of target product was 89%, and the Faraday efficiency was 93%.

[0494] Example 103

[0495] A method for preparing a catalyst for preparing sulfone, which is the same as in Example 1.

[0496] A method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(2-chloro-4-(methylsulfinyl)-3-((2,2,2-trifluoroethoxy)methyl)benzoyl)cyclohexane-1,3-dione (structural formula: ), and other parameters remain unchanged.

[0497] The conversion rate of the example 2-(2-chloro-4-(methylsulfinyl)-3-((2,2,2- trifluoroethoxy)methyl)benzoyl)cyclohexane-1,3-dione is 97%, the reaction selectivity is 95%, the yield of the target product is 92%, and the Faraday efficiency is 97%.

[0498] Example 104

[0499] A method for preparing a catalyst for preparing a sulfone, as in Example 1.

[0500] A method for preparing a sulfone by oxidizing a sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by N-(4-cyano-3- (trifluoromethyl)phenyl)-3-((4-fluorophenyl)sulfinyl)-2-hydroxy-2-methylpropanamide (structure: ), and other parameters remain unchanged.

[0501] The conversion rate of the example N-(4-cyano-3-(trifluoromethyl)phenyl)-3-((4- fluorophenyl)sulfinyl)-2-hydroxy-2-methylpropanamide is 92%, the reaction selectivity is 95%, the yield of the target product is 87%, and the Faraday efficiency is 90%.

[0502] Example 105

[0503] A method for preparing a catalyst for preparing a sulfone, as in Example 1.

[0504] A method for preparing a sulfone by oxidizing a sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 7-chloro-3-methyl-4H- benzo[b][1,4]thiazine 1-oxide (structure: ), and other parameters remain unchanged.

[0505] The conversion rate of the example 7-chloro-3-methyl-4H-benzo[b][1,4]thiazine 1-oxide is 92%, the reaction selectivity is 98%, the yield of the target product is 90%, and the Faraday efficiency is 93%.

[0506] Example 106

[0507] A method for preparing a catalyst for preparing a sulfone, as in Example 1.

[0508] A method for preparing a sulfone by oxidizing a sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 1-(2-(ethylsulfinyl)ethyl)- 2-methyl-5-nitro-1H-imidazole (structure: ), and other parameters remain unchanged.

[0509] The conversion of the 2-(ethylsulfinyl)ethyl-2-methyl-5-nitro-1 H-imidazole of this example was 93%, the selectivity of the reaction was 97%, the yield of the target product was 90%, and the Faraday efficiency was 93%.

[0510] Example 107

[0511] A method for preparing a catalyst for preparing sulfones, as in Example 1.

[0512] A method for preparing sulfones from sulfoxides using the above catalyst, as in Example 1, except that dimethyl sulfoxide was replaced by 4-amino-N-(5-methylisoxazol-3-yl)benzenesulfonamide (structure: ), and other parameters were unchanged.

[0513] The conversion of the 4-amino-N-(5-methylisoxazol-3-yl)benzenesulfonamide of this example was 97%, the selectivity of the reaction was 97%, the yield of the target product was 94%, and the Faraday efficiency was 95%.

[0514] Example 108

[0515] A method for preparing a catalyst for preparing sulfones, as in Example 1.

[0516] A method for preparing sulfones from sulfoxides using the above catalyst, as in Example 1, except that dimethyl sulfoxide was replaced by 4-(ethylamino)-6-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-2-sulfinamide 7-oxide (structure: ), and other parameters were unchanged.

[0517] The conversion of the 4-(ethylamino)-6-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-2-sulfinamide 7-oxide of this example was 97%, the selectivity of the reaction was 92%, the yield of the target product was 89%, and the Faraday efficiency was 93%.

[0518] Example 109

[0519] A method for preparing a catalyst for preparing sulfones, as in Example 1.

[0520] A method for preparing sulfones from sulfoxides using the above catalyst, as in Example 1, except that dimethyl sulfoxide was replaced by N-(azepan-1-ylcarbamoyl)-4-methylbenzenesulfonamide (structure: ), and other parameters were unchanged.

[0521] The conversion of the N-(azepan-1-ylcarbamoyl)-4-methylbenzenesulfonamide of this example was 97%, the selectivity of the reaction was 92%, the yield of the target product was 89%, and the Faraday efficiency was 92%.

[0522] Example 110

[0523] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0524] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by 2-(((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzo[d]imidazole (structure formula: ), and other parameters remain unchanged.

[0525] In this example, the conversion rate of 2-(((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzo[d]imidazole is 94%, the reaction selectivity is 96%, the yield of the target product is 90%, and the Faraday efficiency is 93%.

[0526] Example 111

[0527] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0528] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by tetrahydrothiophene 1-oxide (structure formula: ), and other parameters remain unchanged.

[0529] In this example, the conversion rate of tetrahydrothiophene 1-oxide is 94%, the reaction selectivity is 98%, the yield of the target product is 92%, and the Faraday efficiency is 96%.

[0530] Example 112

[0531] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0532] A method for preparing sulfone from sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by (ethylsulfinyl)ethene (structure formula: ), and other parameters remain unchanged.

[0533] In this example, the conversion rate of (ethylsulfinyl)ethene is 93%, the reaction selectivity is 95%, the yield of the target product is 88%, and the Faraday efficiency is 94%.

[0534] Example 113

[0535] A method for preparing a catalyst for preparing sulfone, same as Example 1.

[0536] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that dimethyl sulfoxide is replaced by 2-(ethylsulfinyl)propane (structure: ), and other parameters remain unchanged.

[0537] In this embodiment, the conversion rate of 2-(ethylsulfinyl)propane is 94%, the reaction selectivity is 95%, the yield of target product is 89%, and the Faraday efficiency is 93%.

[0538] Embodiment 114

[0539] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0540] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the voltage is changed to 1.2 V, and other parameters remain unchanged.

[0541] In this embodiment, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 90%, the yield of target product is 87%, and the Faraday efficiency is 88%.

[0542] Embodiment 115

[0543] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0544] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the voltage is changed to 1.5 V, and other parameters remain unchanged.

[0545] In this embodiment, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 88%, the yield of target product is 84%, and the Faraday efficiency is 90%.

[0546] Embodiment 116

[0547] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0548] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the voltage is changed to 2 V, and other parameters remain unchanged.

[0549] In this embodiment, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 95%, the yield of target product is 86%, and the Faraday efficiency is 85%.

[0550] Embodiment 117

[0551] A method for preparing a catalyst for preparing sulfone, which is the same as Embodiment 1.

[0552] The method for preparing sulfone from sulfoxide by using the above catalyst is as described in Embodiment 1, except that the constant voltage mode is changed to a constant current mode, and the current density is 2 mA / cm2 The catalyst (size 2*10*20 mm) was used as anode (anode immersed in electrolyte), platinum sheet was used as cathode, no reference electrode was used, and other parameters were unchanged.

[0553] The conversion of dimethyl sulfoxide in this example was 88%, the reaction selectivity was 96%, the yield of target product was 84%, and the faradic efficiency was 90%.

[0554] Example 118

[0555] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0556] A method for preparing sulfone from sulfoxide using the above catalyst was as described in Example 1, except that the constant voltage mode was changed to a constant current mode, and the current density was 50 mA / cm 2 The catalyst (size 2*10*20 mm) was used as anode (anode immersed in electrolyte), platinum sheet was used as cathode, no reference electrode was used, and other parameters were unchanged.

[0557] The conversion of dimethyl sulfoxide in this example was 96%, the reaction selectivity was 95%, the yield of target product was 91%, and the faradic efficiency was 92%.

[0558] Example 119

[0559] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0560] A method for preparing sulfone from sulfoxide using the above catalyst was as described in Example 1, except that the constant voltage mode was changed to a constant current mode, and the current density was 100 mA / cm 2 The catalyst (size 2*10*20 mm) was used as anode (anode immersed in electrolyte), platinum sheet was used as cathode, no reference electrode was used, and other parameters were unchanged.

[0561] The conversion of dimethyl sulfoxide in this example was 91%, the reaction selectivity was 96%, the yield of target product was 87%, and the faradic efficiency was 92%.

[0562] Example 120

[0563] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0564] A method for preparing sulfone from sulfoxide using the above catalyst was as described in Example 1, except that the constant voltage mode was changed to a constant current mode, and the current density was 500 mA / cm 2 The catalyst (size 2*10*20 mm) was used as anode (anode immersed in electrolyte), platinum sheet was used as cathode, no reference electrode was used, and other parameters were unchanged.

[0565] The conversion of dimethylsulfoxide in this example was 98%, the selectivity of the reaction was 86%, the yield of the target product was 84%, and the Faraday efficiency was 89%.

[0566] Example 121

[0567] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0568] A method for preparing sulfone from sulfoxide using the above catalyst, as in Example 1, except that the constant voltage mode was changed to a constant current mode, the current density was 1000 mA / cm 2 , the catalyst (size 2*10*20 mm) was used as the anode (the anode was immersed in the electrolyte), a platinum sheet was used as the cathode, no reference electrode was used, and the other parameters were unchanged.

[0569] The conversion of dimethylsulfoxide in this example was 97%, the selectivity of the reaction was 95%, the yield of the target product was 92%, and the Faraday efficiency was 90%.

[0570] Example 122

[0571] A method for preparing a catalyst for preparing sulfone, as in Example 1.

[0572] A method for preparing sulfone from sulfoxide using the above catalyst, as in Example 1, except that the constant voltage mode was changed to a constant current mode, the current density was 2000 mA / cm 2 , the catalyst (size 2*10*20 mm) was used as the anode (the anode was immersed in the electrolyte), a platinum sheet was used as the cathode, no reference electrode was used, and the other parameters were unchanged.

[0573] The conversion of dimethylsulfoxide in this example was 95%, the selectivity of the reaction was 91%, the yield of the target product was 86%, and the Faraday efficiency was 88%.

[0574] Example 123

[0575] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the concentration of the aqueous manganese nitrate solution was 1.5 mol / L, and the other parameters were unchanged.

[0576] A method for preparing sulfone from sulfoxide using the above catalyst, as in Example 1.

[0577] The conversion of dimethylsulfoxide in this example was 97%, the selectivity of the reaction was 89%, the yield of the target product was 86%, and the Faraday efficiency was 88%.

[0578] Example 124

[0579] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the concentration of the aqueous manganese nitrate solution is 3.3 mol / L, and other parameters are unchanged.

[0580] A method for preparing sulfone from sulfoxide using the above catalyst is the same as in Example 1.

[0581] In this example, the conversion of dimethyl sulfoxide is 96%, the reaction selectivity is 93%, the yield of the target product is 89%, and the Faraday efficiency is 91%.

[0582] Example 125

[0583] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the current density for electrochemical deposition is 1 mA / cm 2 , and other parameters are unchanged.

[0584] A method for preparing sulfone from sulfoxide using the above catalyst is the same as in Example 1.

[0585] In this example, the conversion of dimethyl sulfoxide is 93%, the reaction selectivity is 89%, the yield of the target product is 83%, and the Faraday efficiency is 85%.

[0586] Example 126

[0587] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the current density for electrochemical deposition is 50 mA / cm 2 , and other parameters are unchanged.

[0588] A method for preparing sulfone from sulfoxide using the above catalyst is the same as in Example 1.

[0589] In this example, the conversion of dimethyl sulfoxide is 97%, the reaction selectivity is 90%, the yield of the target product is 87%, and the Faraday efficiency is 89%.

[0590] Example 127

[0591] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the anode is a platinum electrode and the cathode is a nickel plate, and other parameters are unchanged.

[0592] A method for preparing sulfone from sulfoxide using the above catalyst is the same as in Example 1.

[0593] In this example, the conversion of dimethyl sulfoxide is 97%, the reaction selectivity is 97%, the yield of the target product is 95%, and the Faraday efficiency is 96%.

[0594] Example 128

[0595] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the anode is carbon cloth and the cathode is a platinum electrode, and the other parameters are unchanged.

[0596] A method for preparing sulfone from sulfoxide using the above catalyst is the same as in Example 1.

[0597] In this example, the conversion of dimethyl sulfoxide is 95%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 88%.

[0598] Example 12

[0599] A method for preparing a catalyst for preparing sulfone, as in Example 1, except that the anode is foamed nickel and the cathode is a titanium electrode, and the other parameters are unchanged.

[0600] A method for preparing sulfone from sulfoxide using the above catalyst is the same as in Example 1.

[0601] In this example, the conversion of dimethyl sulfoxide is 94%, the reaction selectivity is 92%, the yield of the target product is 86%, and the Faraday efficiency is 88%.

[0602] Comparative Example

[0603] A method for preparing sulfone from sulfoxide is the same as in Example 1, except that no catalyst is added; the other steps and conditions are the same as in Example 1.

[0604] In this comparative example, the conversion of dimethyl sulfoxide is 61%, the reaction selectivity is 73%, the yield of the target product is 45%, and the Faraday efficiency is 42%.

Claims

1. The application of a catalyst for preparing sulfone in the electrocatalytic oxidation of sulfoxide to sulfone, characterized in that, The catalyst is a metal oxide-coated anode material; wherein the metal in the metal oxide is selected from one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, gold, palladium, platinum, rhodium, iridium, ruthenium, cerium, molybdenum or tungsten.

2. The application according to claim 1, characterized in that, The anode in the metal oxide coated anode material is selected from one of the following: titanium electrode, platinum-titanium electrode, platinum electrode, carbon cloth, carbon paper, carbon felt, carbon fiber, nickel foam, or nickel plate.

3. The application according to claim 1, characterized in that, The preparation method of the catalyst includes the following steps: A mixture of aqueous metal salt solution and aqueous sulfuric acid solution is used as an electrolyte. Metal oxide is deposited onto the surface of the anode electrode by electrochemical deposition to obtain an anode coated with a metal oxide precursor. The anode coated with a metal oxide precursor was calcined to obtain a catalyst for the preparation of sulfone.

4. The application according to claim 3, characterized in that, Includes one or more of the following conditions: i. The metal salt is a metal sulfate, metal nitrate, or metal hydrochloride; ii. The metal in the metal salt is selected from one of the following: titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, gold, palladium, platinum, rhodium, iridium, ruthenium, cerium, molybdenum, or tungsten; iii. The metal salt is selected from one of the following: titanium sulfate, titanium nitrate, titanium chloride, vanadium sulfate, vanadium nitrate, vanadium chloride, chromium sulfate, chromium nitrate, chromium chloride, potassium dichromate, manganese sulfate, manganese nitrate, manganese chloride, ferric sulfate, ferrous sulfate, ferrous nitrate, ferrous nitrate, ferric chloride, ferrous chloride, cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, copper sulfate, copper nitrate, copper chloride, silver sulfate, silver nitrate, silver chloride, gold nitrate, gold chloride, palladium sulfate, palladium nitrate, palladium chloride, platinum sulfite, platinum nitrate, platinum chloride, platinum dichloride, chloroplatinic acid, rhodium sulfate, rhodium nitrate, rhodium chloride, iridium chloride, iridium tetrachloride, molybdenum sulfate, molybdenum nitrate, molybdenum chloride, ammonium molybdate, ruthenium sulfate, ruthenium nitrate, ruthenium chloride, cerium sulfate, cerium nitrate, cerium chloride, or tungsten nitrate; iv. The concentration of the aqueous solution of metal salts is 0.1-4 mol / L; the concentration of the aqueous solution of sulfuric acid is 0.1-2 mol / L; v. In the electrolyte, the molar ratio of metal salt to sulfuric acid is 0.1-10:1; vi. The electrochemical deposition temperature is from room temperature to 80°C, and the current density is 1-50 mA / cm². 2 The electrochemical deposition time is 0.5-5 hours; vii. The anode used for electrochemical deposition is selected from one of the following: titanium electrode, platinum-titanium electrode, platinum electrode, carbon cloth, carbon paper, carbon felt, carbon fiber, nickel foam, or nickel plate; the cathode used is selected from one of the following: carbon plate, carbon cloth, carbon paper, carbon fiber, carbon felt, platinum electrode, platinum-titanium electrode, titanium electrode, nickel plate, or nickel foam. viii. The calcination temperature is 300-800℃, the calcination time is 3-6h, the heating rate is 1-10℃ / min, and the calcination atmosphere is air or oxygen.

5. The application according to claim 1, characterized in that, The method for preparing the catalyst includes the following steps: (1) Route 1: Dissolve the manganese source in water, perform a hydrothermal reaction, and then separate and dry to obtain manganese oxide; or, Method 2: Mix benzyl alcohol and water evenly, add PVP and sonicate until an emulsion is formed, add manganese source aqueous solution dropwise under stirring, react, separate and dry to obtain manganese oxide; (2) Manganese oxide, conductive agent and binder are fully dispersed in an organic solvent, then coated on the surface of the anode material and dried to obtain a catalyst for the preparation of sulfone.

6. The application according to claim 5, characterized in that, Includes one or more of the following conditions: i. In step (1) route 1, the manganese source is a combination of KMnO4 and MnSO4; the molar amount of manganese source and the volume ratio of water are 0.2-1 mol / L; ii. In step (1) of route 1, the hydrothermal reaction temperature is 150-170℃ and the hydrothermal reaction time is 6-12h; iii. In step (1) of pathway 1, a hydrochloric acid aqueous solution with a mass concentration of 30-37% may also be added to the reaction; the volume ratio of hydrochloric acid aqueous solution to water is 1:120-170. iv. In step (1) route 2, the volume ratio of benzyl alcohol to water is 1:5-10; the mass ratio of PVP to benzyl alcohol is 5-15 mg / mL; the manganese source is KMnO4, the concentration of the manganese source aqueous solution is 0.05-1 mol / L; and the volume ratio of the manganese source aqueous solution to benzyl alcohol is 2-4:

1. v. In step (1) of pathway 2, the reaction temperature is room temperature and the reaction time is 1-5 hours. vi. In step (2), the conductive agent is carbon black; the binder is polyvinylidene fluoride (PVDF); the organic solvent is N-methylpyrrolidone; and the mass ratio of manganese oxide, conductive agent and binder is 1-5:1:2-8.

7. The application according to claim 1, characterized in that, A method for preparing sulfone by electrocatalytic oxidation of sulfoxide includes the following steps: A compound containing a sulfoxide group is dissolved in a solvent to obtain an electrolyte; under the action of a catalyst, an electrocatalytic oxidation reaction is carried out, and the reaction solution is purified to obtain sulfone; the solvent is water or a mixture of organic solvent and water.

8. The application according to claim 7, characterized in that, Compounds containing sulfoxide groups are selected from one of the following compounds:

9. The application according to claim 7, characterized in that, Includes one or more of the following conditions: i. In the mixed solvent of organic solvent and water, the organic solvent is acetonitrile, acetone, ethanol, methanol, toluene, dichloromethane, chloroform, chlorobenzene, DMF, DMA, dioxane, NMP, diethyl ether, tetrahydrofuran, butanol, xylene, isopropanol, ethylene glycol or triethylamine; the mass ratio of organic solvent to water is 1:0.25-4. ii. The concentration of compounds containing sulfoxide groups in the solvent is 1-1000 mmol / L; iii. The mass of the metal oxide in the catalyst is 0.1 wt% to 30 wt% of the mass of the compound containing the sulfoxide group; iv. An electrolyte is also added to the electrolyte solution; the electrolyte is selected from sodium chloride, potassium chloride, ammonium chloride, lithium sulfate, lithium nitrate, lithium carbonate, lithium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium nitrate, potassium nitrate, ammonium nitrate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, tetramethylammonium chloride, tetraethylammonium chloride, etc. One of the following: ammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetramethylammonium bisulfate, tetraethylammonium bisulfate, tetrabutylammonium bisulfate, tetramethylammonium bicarbonate, tetraethylammonium bicarbonate, tetrabutylammonium bicarbonate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetramethylammonium nitrate, tetraethylammonium nitrate, or tetrabutylammonium nitrate; the concentration of the electrolyte in the solvent is 0.1-1 mol / L; v. The electrolysis mode used in the electrocatalytic oxidation reaction is either constant voltage or constant current. When the electrolysis mode is constant voltage, the metal oxide-coated electrode material is used as the working electrode, the counter electrode is a platinum or nickel electrode, and the reference electrode is a silver / silver chloride electrode or a saturated calomel electrode, with a voltage of 1-2V. When the electrolysis mode is constant current, the metal oxide-coated electrode material is used as the anode, and a platinum sheet or nickel foam is used as the cathode, with a current density of 2-2000mA / cm². 2 ; vi. The electrocatalytic oxidation reaction temperature is 25℃-80℃, the reaction time is 1-35h, and the reaction is carried out in an air atmosphere.

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