Catalyst for preparing sulfone, preparation method of catalyst and application of catalyst in preparation of sulfone by electrocatalytic oxidation of sulfoxide

Abstract

The invention provides a catalyst for preparing sulfone, a preparation method of the catalyst and application of the catalyst to preparation of sulfone through electrocatalytic oxidation of sulfoxide, and belongs to the technical field of electrocatalytic organic synthesis. The catalyst is a metal oxide coated anode material; 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 a catalyst, an electrocatalytic oxidation reaction is carried out, and reaction liquid is purified to obtain sulfone; the solvent is water or a mixed solvent of an organic solvent and water. The preparation method of the catalyst is simple, green, environment-friendly and low in cost; the obtained catalyst is applied to preparation of sulfone by electrocatalytic oxidation of sulfoxide, green and clean water is used as an oxygen source, reaction conditions are mild, and the catalyst has the advantages of high selectivity, high yield, high conversion rate, excellent electrocatalytic stability and the like.

Description

Technical Field

[0001] The invention 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 preparing sulfone by electrocatalytic oxidation of sulfoxide. Background Art

[0002] Organosulfur compounds have attracted a lot of attention due to their importance in medicine. Many biologically active compounds and natural products contain sulfoxime, sulfoxide or sulfone functional groups. Of note, sulfoxime, sulfoxide or sulfone functional groups are very important in antibiotic, musculoskeletal, metabolic, gastrointestinal or anti-inflammatory drugs. In addition, organosulfur compounds are very rich in organic synthesis. The oxygen of the sulfinyl group has the ability to coordinate with different carbon ligands and metal ions in addition to the stereoelectronic effect and conformational stability present in the sulfinyl group. Sulfoximines and sulfoxides are stable functional groups and are also used as ligands for enantiomerically pure compounds in asymmetric synthesis. Many methods have been developed for organosulfur oxidation. More feasible and durable oxidation processes will have a positive impact on the pharmaceutical industry, thereby reducing costs, avoiding unnecessary waste and reducing the production of by-products. Organosulfur oxidation processes can be carried out using different oxidants such as peroxides, photocatalytic processes or hypervalent iodine reagents. Despite some progress in organosulfur oxidation processes, most oxidation methods are not suitable for industrialization due to sustainability, scalability and safety issues.

[0003] Typically, sulfoxides and sulfones can be obtained by oxidation of the corresponding sulfides; various oxidants have been used in the prior art, such as H2O2 in combination with metal catalysts, m-CPBA, NaIO4, CrO3, KMnO4, and dioxane. Unfortunately, these strategies often suffer from low reaction selectivity, such as over-oxidation of sulfoxides to sulfones or oxidation of other functional groups in the molecule. Moreover, although hydrogen peroxide is considered a green oxidant, it is synthesized through the self-oxidation process of anthraquinone and is not sustainable.

[0004] Chinese patent document CN105017107A discloses a method for preparing dimethyl sulfone, wherein dimethyl sulfoxide is subjected to oxidation reaction in a fixed bed reactor using hydrogen peroxide, organic hydroperoxide or peracid as an oxidant and titanium silicon molecular sieve as a catalyst to obtain dimethyl sulfone. The method of the invention can improve the effective utilization rate of the oxidant, the selectivity of dimethyl sulfone and the conversion rate of dimethyl sulfoxide to a certain extent, but the above-mentioned problems still exist, namely, the reaction selectivity and conversion rate need to be further improved, and the peroxide used is unsustainable and has high cost.

[0005] Therefore, it is of great significance to develop a catalyst and method that can achieve highly selective oxidation of sulfoxide to prepare sulfone, have high target product yield, conversion rate and cycle stability, and be green, sustainable and low-cost. Summary of the invention

[0006] In view of the deficiencies of the prior art, the present invention provides a catalyst for preparing sulfone, a preparation method thereof and application thereof in preparing sulfone by electrocatalytic oxidation of sulfoxide. The catalyst preparation method of the present invention is simple, green and environmentally friendly, and has low cost; the obtained catalyst is applied to preparing sulfone by electrocatalytic oxidation of sulfoxide, using green and clean water as an oxygen source, and having mild reaction conditions, and has the advantages of high selectivity, high yield, high conversion rate, and excellent electrocatalytic stability.

[0007] The technical solution of the present invention is as follows:

[0008] The first object of the present invention is to provide a catalyst for preparing sulfone, wherein 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.

[0009] Preferably according to the present invention, the anode in the metal oxide coated anode material is selected from one of a titanium electrode, a platinum electrode, a platinum titanium electrode, a carbon cloth, a carbon paper, a carbon felt, a carbon fiber, a nickel foam or a nickel plate.

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

[0011] A metal salt aqueous solution and a sulfuric acid aqueous solution are mixed as an electrolyte, and a metal oxide is deposited on the surface of an anode electrode by electrochemical deposition to obtain an anode coated with a metal oxide precursor; the anode coated with a metal oxide precursor is calcined to obtain a catalyst for preparing sulfone.

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

[0013] Preferably, according to the present invention, 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 present invention, preferably, the metal salt is selected from 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, ferric 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.

[0015] Preferably according to the present invention, the concentration of the metal salt aqueous solution is 0.1-4 mol / L; the concentration of the sulfuric acid aqueous solution is 0.1-2 mol / L.

[0016] Preferably according to the present invention, in the electrolyte, the molar ratio of the metal salt to sulfuric acid is 0.1-10:1.

[0017] According to the preferred embodiment of the present invention, the temperature of electrochemical deposition is room temperature to 80°C, and the current density is 1-50 mA / cm 2 , the electrochemical deposition time is 0.5-5h.

[0018] Preferably according to the present invention, the anode used for electrochemical deposition is selected from one of a platinum-titanium electrode, a platinum electrode, a titanium electrode, a carbon cloth, a carbon paper, a carbon felt, a carbon fiber, a nickel foam or a nickel plate; and the cathode used is selected from one of a carbon plate, a carbon cloth, a carbon paper, a carbon fiber, a carbon felt, a platinum electrode, a platinum-titanium electrode, a titanium electrode, a nickel plate or a nickel foam.

[0019] Preferably according to the present invention, the calcination temperature is 300-800° C., the calcination time is 3-6 h, the heating rate is 1-10° C. / min, and the calcination atmosphere is air or oxygen.

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

[0021] (1) Route 1: dissolving a manganese source in water, subjecting it to a hydrothermal reaction, and then separating and drying it to obtain manganese oxide;

[0022] or,

[0023] Route 2: Mix benzyl alcohol and water evenly, add PVP and perform ultrasound to form an emulsion, add a manganese source aqueous solution dropwise under stirring, react, separate and dry to obtain manganese oxide;

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

[0025] Preferably according to the present invention, in step (1) 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] Preferably according to the present invention, in step (1) route 1, the hydrothermal reaction temperature is 150-170° C., and the hydrothermal reaction time is 6-12 h.

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

[0028] Preferably, 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, and the concentration of the manganese source aqueous solution is 0.05-1 mol / L; the volume ratio of the manganese source aqueous solution to benzyl alcohol is 2-4:1.

[0029] Preferably according to the present invention, in step (1) route 2, the reaction temperature is room temperature and the reaction time is 1-5h.

[0030] Preferably according to the present invention, 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.

[0031] The fourth object of the present invention is to provide the use of the above catalyst in the preparation of sulfone by electrocatalytic oxidation of sulfoxide.

[0032] According to a preferred embodiment of the present invention, the method for preparing sulfone by electrocatalytic oxidation of sulfoxide comprises the steps of:

[0033] The compound containing 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 liquid is purified to obtain sulfone; the solvent is water or a mixed solvent of an organic solvent and water.

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

[0035]

[0036]

[0037] Preferably according to the present invention, 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, ether, tetrahydrofuran, butanol, xylene, isopropanol, ethylene glycol or triethylamine; the mass ratio of the organic solvent to water is 1:0.25-4.

[0038] Preferably according to the present invention, the concentration of the compound containing sulfoxide groups in the solvent is 1-1000 mmol / L.

[0039] Preferably according to the present invention, the mass of the metal oxide in the catalyst is 0.1 wt%-30 wt% of the mass of the compound containing the sulfoxide group.

[0040] According to the preferred embodiment of the present invention, an electrolyte is further added to the electrolyte; 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, tetrafluoroborate, tetramethylammonium tetrafluorophosphate, tetraethylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, tetramethylammonium chloride, tetrafluoroborate, tetramethylammonium tetrafluorophosphate, tetraethylammonium acetate, tetrabutylammonium acetate, tetramethylammonium chloride, tetrafluoroborate, tetraethylammonium tetrafluorophosphate ... One of ethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetramethylammonium hydrogen sulfate, tetraethylammonium hydrogen sulfate, tetrabutylammonium hydrogen sulfate, tetramethylammonium hydrogen carbonate, tetraethylammonium hydrogen carbonate, tetrabutylammonium hydrogen carbonate, 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 preferred embodiment of the present invention, the electrolysis mode used for the electrocatalytic oxidation reaction is constant voltage or constant current; when the electrolysis mode is constant voltage, the counter electrode is a platinum or nickel electrode, the reference electrode is a silver / silver chloride electrode or a saturated calomel electrode, the voltage is 1-2V, and the catalyst is added and immersed in the electrolyte; when the electrolysis mode is constant current, the catalyst is used as the anode, the platinum sheet is used as the cathode, and the current density is 2-2000mA / cm 2 .

[0042] Preferably, according to the present invention, the electrocatalytic oxidation reaction temperature is 25° C.-80° C., the reaction time is 1-35 h, and the reaction is carried out in an air atmosphere.

[0043] According to the present invention, the purification method can be based on existing methods.

[0044] The route of preparing sulfone by electrocatalytic oxidation of sulfoxide of the present invention is as follows:

[0045]

[0046] Technical features and beneficial effects of the present invention:

[0047] 1. The preparation method of the metal oxide coated anode material catalyst of the present invention is simple, the raw materials are cheap and readily available, it is green and environmentally friendly, and the cost is low. The catalyst of the present invention is conducive to the adsorption of reactants on the catalyst, accelerating the reaction. In the catalyst preparation method of the present invention, only sulfuric acid solution and a metal salt solution are required, which saves the required cost, and the anode electrode is required to be used as the catalyst substrate during the electrodeposition process, and the obtained catalyst is more stable and has higher reusability.

[0048] 2. The present invention uses a heterogeneous electrocatalyst, uses cheap chemicals such as sulfoxide and water as raw materials, uses electrical energy as an energy source, promotes water splitting, and transfers the generated oxygen atoms to sulfoxide to synthesize sulfone. The method of the present invention is efficient, green and environmentally friendly, has high atom economy, simple steps, mild reaction conditions, low price, and is suitable for industrial application.

[0049] 3. The electrochemical synthesis method of sulfone of the present invention avoids the use of non-precious metal catalysts and chemical oxidants, such as chlorine or peracid and other hazardous chemicals, does not cause safety problems and harmful waste residue problems, is simple to operate, has a considerable yield, is environmentally friendly, and has good application prospects.

[0050] 4. The present invention uses water as a raw material, and water provides an oxygen source. Water is activated and decomposed under the action of a catalyst to form an oxygen-containing intermediate. The intermediate acts as an active species to highly selectively oxidize sulfoxide to sulfone, with high conversion rate and product yield, high reaction selectivity, and good electrocatalytic stability. Moreover, it not only avoids the use of oxidants and greatly reduces the reaction cost, but also has the advantages of simple and safe operation, saves costs, and avoids the pollution of the environment by chlorine-containing waste. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

[0054] The present invention will be further described below with reference to specific embodiments, but is not limited thereto.

[0055] Meanwhile, the experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials are commercially available 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 0.04 mol / L manganese nitrate aqueous solution and 200 mL of 0.5 mol / L sulfuric acid aqueous solution were mixed evenly as the electrolyte. A titanium electrode with a size of 2*200*200 mm was used as the anode. A carbon plate was used as the cathode. The size of the cathode electrode should be the same as that of the anode electrode or slightly larger than that of the anode. The electrolyte was charged at 20 mA / cm at room temperature. 2 The electrochemical deposition reaction was carried out at a current density of 3 hours, and the uncoated part was cut off to obtain the anode coated with the metal oxide precursor.

[0059] (2) The anode coated with the metal oxide precursor obtained above was placed in a muffle furnace, heated to 300° C. at a heating rate of 5° C. / min and continued for 6 hours in an air calcination atmosphere to obtain a manganese oxide-coated anode material catalyst.

[0060] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst comprises the steps of:

[0061] The following operation was performed at 25°C. 0.5 mmol (39 mg) of dimethyl sulfoxide, 2*10*20 mm of the catalyst prepared above (the catalyst was immersed in the electrolyte, wherein the mass of manganese oxide was 10 wt% of the mass of dimethyl sulfoxide) and 10 mL of water were added to a three-necked flask reactor equipped with a magnetic stirring magnet. Then, sodium nitrate electrolyte (the concentration of electrolyte in water was 0.1 mol / L) was added and mixed thoroughly to form an electrolyte. In an air atmosphere, a silver / silver chloride electrode was used as a reference electrode, a platinum sheet was used as a counter electrode, a constant voltage of 1.7 V was used, and the reaction was carried out at 25°C for 2 hours. After the reaction was completed, the product dimethyl sulfone was obtained by filtering and vacuum drying the filtrate, with a yield of 98% and a Faraday efficiency of 98% (99% conversion rate of dimethyl sulfoxide and 99% reaction selectivity).

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

[0063] Figure 2 This is the appearance of the product dimethyl sulfone obtained in this example. It can be seen from the figure that dimethyl sulfone is white needle-shaped crystals.

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

[0065] Example 2

[0066] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that the electrodeposition temperature is changed from room temperature to 60°C, and other parameters remain unchanged.

[0067] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

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

[0069] Example 3

[0070] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that the electrodeposition temperature is changed from room temperature to 80°C, and other parameters remain unchanged.

[0071] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

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

[0073] Example 4

[0074] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that the calcination temperature is changed from 300° C. to 500° C., and other parameters remain unchanged.

[0075] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

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

[0077] Example 5

[0078] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that the calcination temperature is changed from 300° C. to 700° C., and other parameters remain unchanged.

[0079] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0080] 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 88%.

[0081] Example 6

[0082] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0083] The method for preparing sulfone by oxidizing sulfoxide using the above 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 the target product is 92%, and the Faraday efficiency is 92%.

[0085] Example 7

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

[0087] The method for preparing sulfone by oxidizing sulfoxide using the above 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 the target product is 86%, and the Faraday efficiency is 91%.

[0089] Example 8

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

[0091] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is different from that in Example 1 in that the mass of manganese oxide in the catalyst is 0.1wt% of the mass of dimethyl sulfoxide, the catalyst size is 2*10*20mm, 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 the target product is 88%, and the Faraday efficiency is 91%.

[0093] Example 9

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

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

[0096] In this embodiment, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 95%, the yield of the 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 autoclave and hydroheat at 160°C 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 μl of N-methylpyrrolidone, and drop 25 μl each time on a 1*1 cm titanium electrode, once every half an hour, for a total of four times, and finally dry to obtain a catalyst for the preparation of sulfone.

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

[0102] 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 93%.

[0103] Embodiment 11

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

[0105] Dissolve MnSO4 in 30 mL of water, where the concentration of MnSO4 is 0.3 mol / L, stir for 30 minutes, put into a polytetrafluoroethylene hydrothermal autoclave and hydroheat at 170°C 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 μl of N-methylpyrrolidone, and drop 25 μl each time on a 1*1 cm titanium electrode, once every half an hour, for a total of four times, and finally dry to obtain a catalyst for the preparation of sulfone.

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

[0108] 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%.

[0109] Example 12

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

[0111] Dissolve KMnO4 and MnSO4 in 40 mL of water, wherein the concentration of KMnO4 is 0.5 mol / L and the concentration of MnSO4 is 0.18 mol / L, stir for 30 minutes, put into a polytetrafluoroethylene hydrothermal autoclave and hydroheat at 160°C for 12 hours, centrifuge and dry to obtain MnO2.

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

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

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

[0115] Embodiment 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 evenly, and 10 mg of PVP was added and ultrasonicated to form an emulsion. The mixture was stirred vigorously and 3 mL of 0.1 mol / L KMnO4 aqueous solution was added dropwise. The mixture was stirred at room temperature for 2 h, centrifuged and dried to obtain MnO2.

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

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

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

[0121] Embodiment 14

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

[0123] Dissolve KMnO4 and 0.2 mL of 36.5% hydrochloric acid aqueous solution in 30 mL of water, where the concentration of KMnO4 is 0.4 mol / L, stir for 30 minutes, put into a polytetrafluoroethylene hydrothermal autoclave, hydroheat at 150°C for 6 hours, centrifuge and dry to obtain MnO2.

[0124] Take 20 mg of MnO2, 10 mg of carbon black, and 4 mg of PVDF, disperse them in 400 μl of N-methylpyrrolidone, and drop 25 μl each time on a 1*1 cm titanium electrode, once every half an hour, for a total of four times, and finally dry to obtain a catalyst for the preparation of sulfone.

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

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

[0127] Embodiment 15

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

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

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

[0131] In this example, the conversion rate of dimethyl sulfoxide 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 in that:

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

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

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

[0137] Embodiment 17

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

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

[0140] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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 the target product is 86%, and the Faraday efficiency is 93%.

[0142] Embodiment 18

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

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

[0145] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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 the target product is 84%, and the Faraday efficiency is 88%.

[0147] Embodiment 19

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

[0149] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.04 mol / L silver nitrate aqueous solution, while other parameters remained unchanged.

[0150] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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 the target product is 91%, and the Faraday efficiency is 95%.

[0152] Embodiment 20

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

[0154] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.04 mol / L palladium chloride aqueous solution, and the other parameters remained unchanged.

[0155] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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 the target product is 86%, and the Faraday efficiency is 88%.

[0157] Embodiment 21

[0158] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that:

[0159] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.05 mol / L chloroplatinic acid aqueous solution, and the other parameters remained unchanged.

[0160] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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] Embodiment 22

[0163] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that:

[0164] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.03 mol / L rhodium nitrate aqueous solution, while other parameters remained unchanged.

[0165] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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] Embodiment 23

[0168] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that:

[0169] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.07 mol / L iridium chloride aqueous solution, and the calcination temperature was changed to 800°C, while other parameters remained unchanged.

[0170] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst 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] Embodiment 24

[0173] A method for preparing a catalyst for preparing sulfone, which is different from Example 1 in that:

[0174] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.08 mol / L cerium chloride aqueous solution, while other parameters remained unchanged.

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

[0176] 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 91%.

[0177] Embodiment 25

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

[0179] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.06 mol / L potassium dichromate aqueous solution, while other parameters remained unchanged.

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

[0181] 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 92%.

[0182] Embodiment 26

[0183] A method for preparing a catalyst for preparing sulfone, which is different from the method for preparing the catalyst in Example 1:

[0184] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.04 mol / L ammonium molybdate aqueous solution, and the other parameters remained unchanged.

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

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

[0187] Embodiment 27

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

[0189] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.04 mol / L tungsten nitrate aqueous solution, and the other parameters remained unchanged.

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

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

[0192] Embodiment 28

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

[0194] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.04 mol / L vanadium nitrate aqueous solution, and the other parameters remained unchanged.

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

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

[0197] Embodiment 29

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

[0199] The 0.04 mol / L manganese nitrate aqueous solution was replaced with a 0.04 mol / L titanium nitrate aqueous solution, and the other parameters remained unchanged.

[0200] The method for preparing sulfone by oxidizing sulfoxide 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 the target product is 89%, and the Faraday efficiency is 90%.

[0202] Embodiment 30

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

[0204] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described 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 the target product is 84%, and the Faraday efficiency is 86%.

[0206] Embodiment 31

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

[0208] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described 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 the target product is 85%, and the Faraday efficiency is 87%.

[0210] Embodiment 32

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

[0212] The method for preparing sulfone by oxidizing 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] In this example, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 91%, the yield of the target product is 82%, and the Faraday efficiency is 90%.

[0214] Embodiment 33

[0215] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0216] The method for preparing sulfone by oxidizing 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] In this example, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 93%, the yield of the target product is 90%, and the Faraday efficiency is 94%.

[0218] Embodiment 34

[0219] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0220] The method for preparing sulfone by oxidizing 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] 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 93%.

[0222] Embodiment 35

[0223] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0225] 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%.

[0226] Embodiment 36

[0227] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0228] The method for preparing sulfone by oxidizing 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] Embodiment 37

[0231] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0233] In this example, the conversion rate of dimethyl sulfoxide is 92%, the reaction selectivity is 95%, the yield of the target product is 87%, and the Faraday efficiency is 90%.

[0234] Embodiment 38

[0235] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0236] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water:toluene=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 88%, the yield of the target product is 84%, and the Faraday efficiency is 89%.

[0238] Embodiment 39

[0239] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0241] In this example, the conversion rate of dimethyl sulfoxide is 91%, the reaction selectivity is 90%, the yield of the target product is 82%, and the Faraday efficiency is 90%.

[0242] Embodiment 40

[0243] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0245] In this example, the conversion rate of dimethyl sulfoxide is 88%, the reaction selectivity is 97%, the yield of the target product is 85%, and the Faraday efficiency is 88%.

[0246] Embodiment 41

[0247] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0248] The method for preparing sulfone by oxidizing 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 the target product is 82%, and the Faraday efficiency is 85%.

[0250] Embodiment 42

[0251] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0253] In this example, the conversion rate of dimethyl sulfoxide is 93%, the reaction selectivity is 88%, the yield of the target product is 82%, and the Faraday efficiency is 85%.

[0254] Embodiment 43

[0255] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0257] In this embodiment, the conversion rate of dimethyl sulfoxide is 90%, the reaction selectivity is 95%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0258] Embodiment 44

[0259] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0260] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water:dioxane=1:1 (volume ratio), and other parameters remain unchanged.

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

[0262] Embodiment 45

[0263] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0264] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water:NMP (N-methylpyrrolidone) = 1:1 (volume ratio), and other parameters remain unchanged.

[0265] 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%.

[0266] Embodiment 46

[0267] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0268] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water: ether = 1:1 (volume ratio), and other parameters remain unchanged.

[0269] 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 91%.

[0270] Embodiment 47

[0271] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0272] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water:tetrahydrofuran (THF) = 1:1 (volume ratio), and other parameters remain unchanged.

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

[0274] Embodiment 48

[0275] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0276] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 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 the target product is 86%, and the Faraday efficiency is 93%.

[0278] Embodiment 49

[0279] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0281] In this example, the conversion rate of dimethyl sulfoxide is 94%, the reaction selectivity is 95%, the yield of the target product is 89%, and the Faraday efficiency is 90%.

[0282] Embodiment 50

[0283] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0285] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 93%, the yield of the target product is 88%, and the Faraday efficiency is 97%.

[0286] Embodiment 51

[0287] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0289] In this example, the conversion rate of dimethyl sulfoxide is 96%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 95%.

[0290] Embodiment 52

[0291] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0292] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the solvent is changed to a mixed solution of water:triethylamine=1:1 (volume ratio), and other parameters remain unchanged.

[0293] 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%.

[0294] Embodiment 53

[0295] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0296] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to lithium nitrate and other parameters remain unchanged.

[0297] In this example, the conversion rate of dimethyl sulfoxide is 91%, the reaction selectivity is 95%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0298] Embodiment 54

[0299] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0300] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to potassium nitrate and other parameters remain unchanged.

[0301] In this example, the conversion rate of dimethyl sulfoxide is 98%, the reaction selectivity is 88%, the yield of the target product is 86%, and the Faraday efficiency is 90%.

[0302] Embodiment 55

[0303] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0306] Embodiment 56

[0307] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0310] Embodiment 57

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

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

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

[0314] Embodiment 58

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

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

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

[0318] Embodiment 59

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

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

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

[0322] Embodiment 60

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

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

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

[0326] Embodiment 61

[0327] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0328] The method for preparing sulfone by oxidizing 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] Embodiment 62

[0331] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0332] The method for preparing sulfone by oxidizing 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] Embodiment 63

[0335] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0336] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the electrolyte is changed to tetrabutylammonium bicarbonate, 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] Embodiment 64

[0339] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0340] The method for preparing sulfone by oxidizing 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] Embodiment 65

[0343] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0344] The method for preparing sulfone by oxidizing sulfoxide 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 the target product is 88%, and the Faraday efficiency is 90%.

[0346] Embodiment 66

[0347] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0348] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by diphenyl sulfoxide (structural formula: ), 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 the target product is 89%, and the Faraday efficiency is 92%.

[0350] Embodiment 67

[0351] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0352] The 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 phenyl sulfoxide (structural formula: ), and other parameters remain unchanged.

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

[0354] Embodiment 68

[0355] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0356] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by p-chlorophenyl methyl sulfoxide (structural formula: ), 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 the target product is 89%, and the Faraday efficiency is 90%.

[0358] Embodiment 69

[0359] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0362] Embodiment 70

[0363] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0364] The 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-3-(methylsulfinyl)benzene (structural formula: ), and other parameters remain unchanged.

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

[0366] Embodiment 71

[0367] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0368] The 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-chloro-2-(methylsulfinyl)benzene (structural formula: ), and other parameters remain unchanged.

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

[0370] Embodiment 72

[0371] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0374] Embodiment 73

[0375] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0376] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced with thiobenzopyran-4-one 1-oxide (structural formula: ), and the other parameters remain unchanged.

[0377] In this example, the conversion rate of thiobenzopyran-4-one 1-oxide was 98%, the reaction selectivity was 88%, the yield of the target product was 86%, and the Faraday efficiency was 93%.

[0378] Embodiment 74

[0379] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0380] The 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-(methylsulfinyl)pyridine (structural formula: ), and the other parameters remain unchanged.

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

[0382] Embodiment 75

[0383] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0384] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by thiocyclohexanone (structural formula: ), and the other parameters remain unchanged.

[0385] In this example, the conversion rate of thiocyclohexanone is 96%, the reaction selectivity is 95%, the yield of the target product is 91%, and the Faraday efficiency is 94%.

[0386] Embodiment 76

[0387] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0388] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by (cyclopropylsulfinyl)benzene (structural formula: ), and the other parameters remain unchanged.

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

[0390] Embodiment 77

[0391] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0392] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by dibenzothiophene 5-oxide (structural formula: ), other parameters remain unchanged.

[0393] In this example, the conversion rate of dibenzothiophene 5-oxide is 95%, the reaction selectivity is 90%, the yield of the target product is 86%, and the Faraday efficiency is 87%.

[0394] Embodiment 78

[0395] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0396] The 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-methyl-4-nitro-1-(4-(trifluoromethyl)phenylsulfinyl)benzene (structural formula: ), other parameters remain unchanged.

[0397] In this example, the conversion rate of 2-methyl-4-nitro-1-(4-(trifluoromethyl)phenylsulfinyl)benzene was 93%, the reaction selectivity was 88%, the yield of the target product was 82%, and the Faraday efficiency was 91%.

[0398] Embodiment 79

[0399] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0400] The 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-(methylsulfinyl)-1|2-benzo[d]imidazole (structural formula: ), other parameters remain unchanged.

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

[0402] Embodiment 80

[0403] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0404] The 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-(methylsulfinyl)benzo[d]oxazole (structural formula: ), and the other parameters remain unchanged.

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

[0406] Embodiment 81

[0407] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0410] Embodiment 82

[0411] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0412] The 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-(methylsulfinyl)pyridine (structural formula: ), and the other parameters remain unchanged.

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

[0414] Embodiment 83

[0415] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0416] The 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-bromo-4-(methylsulfinyl)benzene (structural formula: ), and the other parameters remain unchanged.

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

[0418] Embodiment 84

[0419] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0420] The 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-methoxyphenylmethyl sulfoxide (structural formula: ), and the other parameters remain unchanged.

[0421] In this example, the conversion rate of 4-methoxyphenylmethyl sulfoxide was 98%, the reaction selectivity was 89%, the yield of the target product was 87%, and the Faraday efficiency was 89%.

[0422] Embodiment 85

[0423] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0424] The 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-(methylsulfinyl)-4-nitrobenzene (structural formula: ), and the other parameters remain unchanged.

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

[0426] Embodiment 86

[0427] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0428] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced with 5-(2-(octylsulfinyl)propyl)benzo[d][1,3]dioxole (structural formula: ), and the other parameters remain unchanged.

[0429] In this example, the conversion rate of 5-(2-(octylsulfinyl)propyl)benzo[d][1,3]dioxole was 93%, the reaction selectivity was 88%, the yield of the target product was 82%, and the Faraday efficiency was 89%.

[0430] Embodiment 87

[0431] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0432] The method for preparing sulfone by oxidizing sulfoxide 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)-3-(2-benzo[d]imidazole (structural formula: ), and the other parameters remain unchanged.

[0433] In this example, the conversion rate of 5-chloro-6-(2,3-dimethylphenoxy)-2-(methylsulfinyl)-3l2-benzo[d]imidazole was 95%, the reaction selectivity was 85%, the yield of the target product was 81%, and the Faraday efficiency was 87%.

[0434] Embodiment 88

[0435] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0437] In this example, the conversion rate of (6-(propylsulfinyl)-1H-benzo[d]imidazol-2-yl)carbamic acid methyl ester was 95%, the reaction selectivity was 85%, the yield of the target product was 81%, and the Faraday efficiency was 86%.

[0438] Embodiment 89

[0439] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0441] In this example, the conversion rate of (6-(phenylsulfinyl)-1H-benzo[d]imidazol-2-yl)carbamic acid methyl ester was 93%, the reaction selectivity was 90%, the yield of the target product was 84%, and the Faraday efficiency was 91%.

[0442] Embodiment 90

[0443] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0444] The 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 (structural formula: ), and the other parameters remain unchanged.

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

[0446] Embodiment 91

[0447] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0450] Embodiment 92

[0451] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0452] The 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-3-((2-phenoxyethyl)sulfoxide)benzene (structural formula: ), other parameters remain unchanged.

[0453] In this example, the conversion rate of 1-methyl-3-((2-phenoxyethyl)sulfoxide)benzene was 95%, the reaction selectivity was 95%, the yield of the target product was 90%, and the Faraday efficiency was 95%.

[0454] Embodiment 93

[0455] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0458] Embodiment 94

[0459] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0462] Embodiment 95

[0463] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0464] The 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-13-oxyalkyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl)methyl)sulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole (structural formula: ), and the other parameters remain unchanged.

[0465] In this example, the conversion rate of 3-(((5-(difluoro-13-oxyalkyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl)methyl)sulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole was 94%, the reaction selectivity was 90%, the yield of the target product was 85%, and the Faraday efficiency was 86%.

[0466] Embodiment 96

[0467] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0470] Embodiment 97

[0471] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0474] Embodiment 98

[0475] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0476] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 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 the other parameters remain unchanged.

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

[0478] Embodiment 99

[0479] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0482] Embodiment 100

[0483] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0486] Embodiment 101

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

[0488] The 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 the other parameters remain unchanged.

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

[0490] Embodiment 102

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

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

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

[0494] Embodiment 103

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

[0496] The 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-(methylsulfoxide)-3-((2,2,2-trifluoroethoxy)methyl)benzoyl)cyclohexane-1,3-dione (structural formula: ), and the other parameters remain unchanged.

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

[0498] Embodiment 104

[0499] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0500] The method for preparing sulfone by oxidizing 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-methylpropionamide (structural formula: ), and the other parameters remain unchanged.

[0501] In this example, the conversion rate of 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] Embodiment 105

[0503] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0504] The method for preparing sulfone by oxidizing 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 (structural formula: ), and the other parameters remain unchanged.

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

[0506] Embodiment 106

[0507] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0508] The 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-(2-(ethylsulfinyl)ethyl)-2-methyl-5-nitro-1H-imidazole (structural formula: ), and the other parameters remain unchanged.

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

[0510] Embodiment 107

[0511] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0512] The 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-amino-N-(5-methylisoxazol-3-yl)benzenesulfonamide (structural formula: ), other parameters remain unchanged.

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

[0514] Embodiment 108

[0515] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0516] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced with 4-(ethylamino)-6-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-2-sulfenamide 7-oxide (structural formula: ), other parameters remain unchanged.

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

[0518] Embodiment 109

[0519] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0520] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by N-(azepine-1-ylcarbamoyl)-4-methylbenzenesulfonamide (structural formula: ), other parameters remain unchanged.

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

[0522] Embodiment 110

[0523] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0524] The 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-(((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzo[d]imidazole (structural formula: ), 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 was 94%, the reaction selectivity was 96%, the yield of the target product was 90%, and the Faraday efficiency was 93%.

[0526] Embodiment 111

[0527] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0529] In this embodiment, 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] Embodiment 112

[0531] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0532] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that dimethyl sulfoxide is replaced by (ethylsulfinyl)ethylene (structural formula: ), other parameters remain unchanged.

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

[0534] Embodiment 113

[0535] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0536] The 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-(ethylsulfinyl)propane (structural formula: ), and the other parameters remain unchanged.

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

[0538] Embodiment 114

[0539] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0542] Embodiment 115

[0543] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

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

[0546] Embodiment 116

[0547] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

[0548] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is as described in Example 1, except that the voltage is changed to 2V 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 the target product is 86%, and the Faraday efficiency is 85%.

[0550] Embodiment 117

[0551] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0553] In this example, the conversion rate of dimethyl sulfoxide is 88%, the reaction selectivity is 96%, the yield of the target product is 84%, and the Faraday efficiency is 90%.

[0554] Embodiment 118

[0555] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0557] 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 92%.

[0558] Embodiment 119

[0559] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0561] In this example, the conversion rate of dimethyl sulfoxide is 91%, the reaction selectivity is 96%, the yield of the target product is 87%, and the Faraday efficiency is 92%.

[0562] Embodiment 120

[0563] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0565] In this example, the conversion rate of dimethyl sulfoxide was 98%, the reaction selectivity was 86%, the yield of the target product was 84%, and the Faraday efficiency was 89%.

[0566] Embodiment 121

[0567] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0569] In this example, the conversion rate of dimethyl sulfoxide is 97%, the reaction selectivity is 95%, the yield of the target product is 92%, and the Faraday efficiency is 90%.

[0570] Embodiment 122

[0571] A method for preparing a catalyst for preparing sulfone is the same as that in Example 1.

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

[0573] In this example, the conversion rate of dimethyl sulfoxide is 95%, the reaction selectivity is 91%, the yield of the target product is 86%, and the Faraday efficiency is 88%.

[0574] Embodiment 123

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

[0576] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0577] 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 88%.

[0578] Embodiment 124

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

[0580] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0581] In this example, the conversion rate 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] Embodiment 125

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

[0584] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0585] In this example, the conversion rate 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] Embodiment 126

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

[0588] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0589] In this example, the conversion rate 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] Embodiment 127

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

[0592] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

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

[0594] Embodiment 128

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

[0596] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0597] 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 88%.

[0598] Embodiment 129

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

[0600] The method for preparing sulfone by oxidizing sulfoxide using the above catalyst is the same as that in Example 1.

[0601] In this example, the conversion rate 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] The method for preparing sulfone by oxidizing sulfoxide is the same as that in Example 1, except that no catalyst is added; the other steps and conditions are the same as those in Example 1.

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

Claims

1. A catalyst for preparing 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 catalyst for preparing sulfone according to claim 1, characterized in that The anode in the metal oxide coated anode material is selected from one of a titanium electrode, a platinum titanium electrode, a platinum electrode, a carbon cloth, a carbon paper, a carbon felt, a carbon fiber, a nickel foam or a nickel plate.

3. A method for preparing a catalyst for preparing sulfone according to claim 1 or 2, comprising the steps of: A metal salt aqueous solution and a sulfuric acid aqueous solution are mixed as an electrolyte, and a metal oxide is deposited on the surface of an anode electrode by electrochemical deposition to obtain an anode coated with a metal oxide precursor; the anode coated with a metal oxide precursor is calcined to obtain a catalyst for preparing sulfone.

4. The method for preparing a catalyst for preparing sulfone according to claim 3, characterized in that: Includes one or more of the following conditions: i. The metal salt is a metal sulfate, a metal nitrate or a metal hydrochloride; ii. 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; iii. the metal salt is selected from 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, ferric 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, platinum sulfate, platinum nitrate, platinum chloride, ammonium molybdate, ruthenium sulfate, ruthenium nitrate, ruthenium chloride, cerium sulfate, cerium nitrate, cerium chloride or tungsten nitrate; iv. The concentration of the metal salt aqueous solution is 0.1-4 mol / L; the concentration of the sulfuric acid aqueous solution 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 temperature of electrochemical deposition is from room temperature to 80°C, and the current density is 1-50 mA / cm 2 , electrochemical deposition time is 0.5-5h; vii. The anode used for electrochemical deposition is selected from one of 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 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°C, the calcination time is 3-6h, the heating rate is 1-10°C / min, and the calcination atmosphere is air or oxygen.

5. A method for preparing a catalyst for preparing sulfone according to claim 1 or 2, comprising the steps of: (1) Route 1: dissolving a manganese source in water, subjecting it to a hydrothermal reaction, and then separating and drying it to obtain manganese oxide; or, Route 2: Mix benzyl alcohol and water evenly, add PVP and perform ultrasound to form an emulsion, add a manganese source aqueous solution dropwise under stirring, react, separate and dry to obtain manganese oxide; (2) Manganese oxide, a conductive agent and a binder are fully dispersed in an organic solvent, then coated on the surface of an anode material, and dried to obtain a catalyst for preparing sulfone.

6. The method for preparing a catalyst for preparing sulfone according to claim 5, characterized in that: Includes one or more of the following conditions: i. In step (1) of route 1, the manganese source is KMnO4 or MnSO4, or a combination of the two; the molar ratio of the manganese source to the volume of water is 0.2-1 mol / L; ii. In step (1) of route 1, the hydrothermal reaction temperature is 150-170° C. and the hydrothermal reaction time is 6-12 h; iii. In step (1) of route 1, a hydrochloric acid aqueous solution with a mass concentration of 30-37% may be added to the reaction; the volume ratio of the 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, and the concentration of the manganese source aqueous solution is 0.05-1 mol / L; the volume ratio of the manganese source aqueous solution to benzyl alcohol is 2-4:1; v. In step (1) pathway 2, the reaction temperature is room temperature and the reaction time is 1-5 h; 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. Use of the catalyst as claimed in claim 1 or 2 in preparing sulfone by electrocatalytic oxidation of sulfoxide.

8. The use according to claim 7, characterized in that: The method for preparing sulfone by electrocatalytic oxidation of sulfoxide comprises the steps of: The compound containing 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 liquid is purified to obtain sulfone; the solvent is water or a mixed solvent of an organic solvent and water.

9. The use according to claim 8, characterized in that: The compound containing a sulfoxide group is selected from one of the following compounds:

10. The use according to claim 8, characterized in that: Includes one or more of the following conditions: i. In a mixed solvent of an organic solvent and water, the organic solvent is acetonitrile, acetone, ethanol, methanol, toluene, dichloromethane, chloroform, chlorobenzene, DMF, DMA, dioxane, NMP, ether, tetrahydrofuran, butanol, xylene, isopropanol, ethylene glycol or triethylamine; the mass ratio of the organic solvent to water is 1:0.25-4; ii. The concentration of the compound containing sulfoxide group in the solvent is 1-1000 mmol / L; iii. The mass of the metal oxide in the catalyst is 0.1wt%-30wt% of the mass of the compound containing the sulfoxide group; iv. An electrolyte is also added to the electrolyte; 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, tetraethyl chloride ammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetramethylammonium hydrogen sulfate, tetraethylammonium hydrogen sulfate, tetrabutylammonium hydrogen sulfate, tetramethylammonium hydrogen carbonate, tetraethylammonium hydrogen carbonate, tetrabutylammonium hydrogen carbonate, 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 for the electrocatalytic oxidation reaction is 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, the reference electrode is a silver / silver chloride electrode or a saturated calomel electrode, and the voltage is 1-2V; when the electrolysis mode is constant current, the metal oxide coated electrode material is used as the anode, the platinum sheet or nickel foam is used as the cathode, and the current density is 2-2000mA / cm 2 ; vi. The electrocatalytic oxidation reaction temperature is 25°C-80°C, the reaction time is 1-35h, and the reaction is carried out in an air atmosphere.

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