Application of metal ion doped graphene oxide membrane catalytic material in synthesis of sulfone by catalyzing thioether oxidation reaction

Abstract

The invention relates to application of a metal ion doped graphene oxide membrane catalytic material to efficiently and rapidly catalyze thioether to oxidize and synthesize sulfone at room temperature. Metal ions are added into dispersion liquid of graphene oxide, so that the graphene oxide interacts with the metal ions, the metal ions are doped, and then the dispersion liquid of the graphene oxide doped with the metal ions is prepared into the metal ion doped graphene oxide membrane catalytic material by using a vacuum filtration method. And the content of metal ions in the metal ion doped graphene oxide membrane catalytic material is continuously adjustable. Compared with a traditional catalytic method, the method has the advantages that a thioether substrate and an oxidizing agent react in a two-dimensional interlayer confinement channel of the metal ion doped graphene oxide membrane catalytic material in a continuous mobile phase reaction mode, and a product flows out along with a mobile phase; the catalytic method can achieve the purposes of high conversion rate (90-100%), high selectivity (60-100%) and high speed (1-60 s) of thioether oxidation reaction at room temperature.

Description

Technical Field

[0001] The present invention relates to the use of a metal ion-doped graphene oxide membrane catalytic material in the catalytic synthesis of sulfones by sulfide oxidation reaction, belonging to the technical field of membrane materials and catalytic applications. Background Art

[0002] The sulfide oxidation reaction plays an important role in the fields of organic synthesis, pharmaceutical synthesis, environmental governance, etc. On the one hand, because the sulfide oxidation reaction is a simple synthetic route for preparing sulfone substances. Among them, sulfone is a very useful pharmaceutical reagent in organic chemistry and pharmaceutical chemistry, such as amisulpride commonly used in the treatment of schizophrenia, vismodegib for the treatment of advanced basal cell carcinoma of the skin, etc. On the other hand, because the sulfide oxidation reaction is considered to be one of the most promising methods for deep desulfurization of fuels due to its mild operating conditions, high desulfurization efficiency, low equipment cost, simple operation, etc. For example, by oxidizing aromatic sulfides into highly polar sulfone substances and then extracting them with a suitable polar solvent to achieve the purpose of deep desulfurization, thereby reducing the pollution of the environment caused by sulfur-containing substances such as SO 2 and other gases during fuel use.

[0003] Currently, common catalysts for catalytic oxidation of sulfides to form sulfones include metal-based catalysts such as polyoxometalates, metal oxides, zeolite molecular sieves, metal-organic frameworks, etc.; there are also non-metal catalysts such as graphene oxide and carbon nanotubes. Although most of the existing research catalysts can achieve complete conversion of sulfides and high selectivity for the formation of sulfones, these oxidation reactions generally require relatively high reaction temperatures and reaction times. Therefore, it is indeed necessary to provide a method for rapidly catalyzing the oxidation of sulfides to synthesize sulfones at room temperature. Summary of the Invention

[0004] Although many currently studied catalysts can catalyze the sulfide oxidation reaction and obtain relatively high conversion rates and selectivities for sulfones, there are problems such as high reaction temperatures, long reaction times, and large amounts of oxidants used. To solve the defects existing in the above-mentioned prior art, the present invention provides the use of a metal ion-doped graphene oxide membrane catalytic material in the catalytic synthesis of sulfones by sulfide oxidation reaction. On the basis of retaining acid catalytic sites, the metal ion-doped graphene oxide membrane catalytic material provides two-dimensional interlayer channels with confinement effects, and efficiently catalyzes the occurrence of sulfide oxidation reactions through the action of acid catalytic sites and two-dimensional interlayer confinement channels. At the same time, the doping of metal ions can provide metal active centers, and the combined catalytic action of the metal active centers and the inherent acid catalytic sites can improve the conversion rate and selectivity of the sulfide oxidation reaction, realizing the rapid and efficient catalysis of sulfide oxidation to synthesize sulfones at room temperature.

[0005] The object of the present invention is achieved by the following technical solutions:

[0006] Use of a metal ion-doped graphene oxide membrane catalytic material in the synthesis of sulfone by catalytic oxidation of thioether.

[0007] According to an embodiment of the present invention, use of the metal ion-doped graphene oxide membrane catalytic material in the rapid catalytic oxidation of thioether to synthesize sulfone at room temperature.

[0008] According to an embodiment of the present invention, use of the metal ion-doped graphene oxide membrane catalytic material in the rapid and efficient catalytic oxidation of thioether to synthesize sulfone at room temperature.

[0009] According to an embodiment of the present invention, the room temperature refers to a temperature range of 20-30 °C.

[0010] According to an embodiment of the present invention, the rapid refers to a reaction time of 1-60 s.

[0011] According to an embodiment of the present invention, the efficient refers to a conversion rate of 90-100% of thioether and / or a selectivity of 60-100% of sulfone.

[0012] According to an embodiment of the present invention, the thickness of the metal ion-doped graphene oxide membrane catalytic material is 0.1-5 μm, such as 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm; by regulating the membrane thickness, the residence time of reaction molecules in the two-dimensional interlayer confinement channels of the metal ion-doped graphene oxide membrane catalytic material can be regulated, thereby optimizing its catalytic performance. It is found that the residence time of reactants in the metal ion-doped graphene oxide membrane catalytic material that is too thin (thickness less than 0.1 μm) is too short to obtain high conversion rate and selectivity; the metal ion-doped graphene oxide membrane catalytic material that is too thick (thickness greater than 5 μm) will significantly reduce the flow rate of the reaction solution and increase the preparation cost of the membrane catalytic material, resulting in a significant reduction in the efficiency of catalyzing thioether reaction.

[0013] According to an embodiment of the present invention, the interlayer spacing of the metal ion-doped graphene oxide membrane catalytic material is such as or

[0014] According to an embodiment of the present invention, the mass of metal ions in the metal ion-doped graphene oxide membrane catalytic material accounts for 0.01-15 wt% of the total mass of the membrane catalytic material, such as 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt%. When the mass of metal ions in the metal ion-doped graphene oxide membrane catalytic material accounts for less than 0.01 wt% of the total mass of the membrane catalytic material, the content of metal active centers in the membrane catalytic material is small, and the catalytic effect on the thioether oxidation reaction is not obvious enough; when the mass of metal ions in the metal ion-doped graphene oxide membrane catalytic material accounts for more than 15 wt% of the total mass of the membrane catalytic material, the interaction between graphene oxide nanosheets and metal ions is enhanced, affecting the uniformity and structural stability of the metal ion-doped graphene oxide membrane catalytic material.

[0015] According to an embodiment of the present invention, the metal ions in the metal ion-doped graphene oxide membrane catalytic material are selected from at least one of main group metal ions and transition metal ions; exemplarily, the metal ions are selected from Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ and at least one of them, preferably Fe 3+ .

[0016] According to an embodiment of the present invention, in the metal ion-doped graphene oxide membrane catalytic material, the atomic ratio of oxygen to carbon is 0.8-1, such as 0.8, 0.85, 0.9, 0.95 or 1.

[0017] According to an embodiment of the present invention, the metal ion-doped graphene oxide membrane catalytic material is a layered structure formed by stacking metal ion-doped graphene oxides, preferably a layered structure formed by stacking metal ion-doped graphene oxide nanosheets.

[0018] According to an embodiment of the present invention, the metal ion-doped graphene oxide film catalytic material comprises metal ion-doped graphene oxide, preferably metal ion-doped graphene oxide nanosheets.

[0019] According to an embodiment of the present invention, the metal ion-doped graphene oxide comprises graphene oxide and metal ions, and the metal ions are doped onto the graphene oxide.

[0020] According to an embodiment of the present invention, the metal ion-doped graphene oxide film catalytic material is prepared by the following method:

[0021] (1) Add a metal salt to a dispersion of graphene oxide and ultrasonically mix to obtain a mixed solution;

[0022] (2) Using the vacuum filtration method, assemble the mixed solution of step (1) into a metal ion-doped graphene oxide film, and then perform a constant temperature and humidity static treatment to prepare the metal ion-doped graphene oxide film catalytic material.

[0023] According to an embodiment of the present invention, in step (1), by changing the concentration of the graphene oxide dispersion and the mass ratio of the graphene oxide dispersion to the metal salt, the mass percentage of the metal ions in the metal ion-doped graphene oxide film catalytic material can be regulated, and thus the catalytic performance of the metal ion-doped graphene oxide film catalytic material can be regulated.

[0024] According to an embodiment of the present invention, in step (1), by adding a metal salt to the graphene oxide dispersion and then performing an ultrasonic mixing treatment, the graphene oxide and the metal ions can fully react, realizing the doping of the metal ions onto the graphene oxide, and at the same time, a more uniformly dispersed doped metal ion graphene oxide can be obtained.

[0025] According to an embodiment of the present invention, in step (1), the graphene oxide is preferably graphene oxide nanosheets, the graphene oxide nanosheets are single-layer graphene oxide nanosheets, and the sheet diameter of the graphene oxide nanosheets > 500 nm.

[0026] According to an embodiment of the present invention, in step (1), the concentration of the graphene oxide dispersion is 0.01 - 0.25 mg / mL, that is, 1 mL of the graphene oxide dispersion contains 0.01 - 0.25 mg of graphene oxide; exemplarily, the concentration of the graphene oxide dispersion is 0.01 mg / mL, 0.02 mg / mL, 0.05 mg / mL, 0.06 mg / mL, 0.08 mg / mL, 0.1 mg / mL, 0.12 mg / mL, 0.15 mg / mL, 0.16 mg / mL, 0.18 mg / mL, 0.2 mg / mL, 0.22 mg / mL, 0.24 mg / mL or 0.25 mg / mL.

[0027] According to an embodiment of the present invention, in step (1), the metal salt is selected from at least one of main group metal salts and transition metal salts; exemplarily, the metal salt is selected from at least one of LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , AlCl 3 , MnCl 2 , FeCl 3 , CoCl 2 , NiCl 2 , CuCl 2 and ZnCl 2 , and preferably FeCl 3 .

[0028] According to an embodiment of the present invention, in step (1), the molar volume ratio of the metal salt to the graphene oxide dispersion is 1 - 20 μmol / 40 mL, that is, 1 - 20 μmol of the metal salt is added to every 40 mL of the graphene oxide dispersion; exemplarily, the molar volume ratio of the metal salt to the graphene oxide dispersion is 1 μmol / 40 mL, 2 μmol / 40 mL, 3 μmol / 40 mL, 4 μmol / 40 mL, 5 μmol / 40 mL, 6 μmol / 40 mL, 7 μmol / 40 mL, 8 μmol / 40 mL, 9 μmol / 40 mL, 10 μmol / 40 mL, 12 μmol / 40 mL, 15 μmol / 40 mL, 18 μmol / 40 mL or 20 μmol / 40 mL. If the addition amount of the metal salt is too high, the interaction between graphene oxide and metal ions will be enhanced, and it will be impossible to uniformly disperse them in water by ultrasonic treatment, and there may also be a phenomenon of flocculation, affecting the uniformity and structural stability of the metal ion-doped graphene oxide film catalytic material prepared subsequently.

[0029] According to an embodiment of the present invention, in step (1), the time of ultrasonic mixing is 5 - 15 min, such as 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min or 15 min; the power of ultrasonic mixing is 100 - 500 W, such as 100 W, 150 W, 200 W, 250 W, 300 W, 350 W, 400 W, 450 W or 500 W. Under these conditions, ultrasonic mixing treatment can achieve uniform dispersion of metal ion-doped graphene oxide in water without damaging the structure of metal ion-doped graphene oxide.

[0030] According to an embodiment of the present invention, in step (2), it specifically includes the following steps:

[0031] 21) Lay a porous substrate in the filter cup of the vacuum filtration device;

[0032] 22) Add the mixed solution from step (1) into the filter cup supporting the vacuum filtration device, start the vacuum pump, and perform vacuum filtration with a vacuum degree of 1 - 5 Pa; use the vacuum pressure difference to layer-by-layer assemble metal ion-doped graphene oxide on the porous substrate to obtain a metal ion-doped graphene oxide film catalytic material.

[0033] According to an embodiment of the present invention, the material of the porous substrate can be an organic filter membrane such as nylon 66, polyvinylidene fluoride, or polytetrafluoroethylene.

[0034] According to an embodiment of the present invention, the pore size of the porous substrate is 0.1 - 0.3 μm, such as 0.22 μm.

[0035] According to an embodiment of the present invention, a film formed by stacking a certain thickness of multiple single-layer metal ion-doped graphene oxides (preferably metal ion-doped graphene oxide nanosheets) is prepared on the porous substrate by vacuum filtration method.

[0036] According to an embodiment of the present invention, as the filtration progresses, the metal ion-doped graphene oxide in the mixed solution assembles into a layered structure under the action of water flow. After the filtration is completed, a metal ion-doped graphene oxide film catalytic material is obtained.

[0037] According to an embodiment of the present invention, in step (2), the constant temperature and humidity static treatment is, for example, static treatment for a period of time under the conditions of constant temperature and constant humidity; exemplarily, the constant temperature and humidity static treatment is carried out in a constant temperature and humidity chamber. Exemplarily, the constant temperature and humidity static treatment is carried out at 20 - 30 °C and 10 - 20% RH for 12 - 24 h. The constant temperature and humidity static treatment can achieve the removal of free water in the metal ion-doped graphene oxide film catalytic material after the filtration is completed.

[0038] According to an embodiment of the present invention, the method for synthesizing sulfone by catalytic thioether oxidation reaction comprises the following steps:

[0039] a) Dissolve a thioether substrate and an oxidant in an organic solvent to obtain a reaction solution;

[0040] b) At room temperature, drive by a pressure difference to make the reaction solution in step a) pass through a metal ion-doped graphene oxide membrane catalytic material to carry out a thioether oxidation reaction to prepare a sulfone.

[0041] The present invention also provides a method for synthesizing sulfone by catalytic thioether oxidation reaction, and the method comprises the following steps:

[0042] a) Dissolve a thioether substrate and an oxidant in an organic solvent to obtain a reaction solution;

[0043] b) At room temperature, drive by a pressure difference to make the reaction solution in step a) pass through a metal ion-doped graphene oxide membrane catalytic material to carry out a thioether oxidation reaction to prepare a sulfone.

[0044] According to an embodiment of the present invention, driven by a pressure difference, the thioether substrate and the oxidant react in a continuous flow phase reaction manner in the two-dimensional interlayer confinement channel of the metal ion-doped graphene oxide membrane catalytic material, and the obtained thioether oxidation product flows out with the organic solvent and separates from the catalytic system.

[0045] According to an embodiment of the present invention, in step a), the molar ratio of the thioether substrate to the oxidant is 1:1 - 10, such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0046] According to an embodiment of the present invention, in step a), the oxidant is selected from at least one of hydrogen peroxide, tert-butyl hydroperoxide, etc.

[0047] According to an embodiment of the present invention, in step a), the thioether substrate includes at least one of methyl phenyl sulfide (CAS No.: 100-68-5), p-methyl phenyl sulfide (CAS No.: 623-13-2), phenyl ethyl sulfide (CAS No.: 622-38-8), cyclopropyl phenyl sulfide (CAS No.: 14633-54-6), allyl benzene sulfide (CAS No.: 5296-64-0), ethyl sulfide (CAS No.: 352-93-2), dipropyl sulfide (CAS No.: 111-47-7), diphenyl sulfide (CAS No.: 139-66-2), 4-nitrophenyl phenyl sulfide (CAS No.: 952-97-6), albendazole (CAS No.: 54965-21-8), etc.

[0048] According to an embodiment of the present invention, in step a), the organic solvent is selected from at least one of acetonitrile, ethanol, methanol, acetic acid, etc.

[0049] According to an embodiment of the present invention, in step a), the concentration of the thioether substrate is 0.01 - 1 mol / L.

[0050] According to an embodiment of the present invention, in step b), the reaction time is 1 - 60 s, for example, 1 s, 2 s, 5 s, 6 s, 8 s, 10 s, 12 s, 15 s, 16 s, 18 s, 20 s, 22 s, 25 s, 26 s, 28 s, 30 s, 32 s, 35 s, 38 s, 40 s, 42 s, 45 s, 48 s, 50 s, 52 s, 55 s, 58 s or 60 s.

[0051] According to an embodiment of the present invention, in step b), the room temperature refers to a temperature range of 20 - 30 °C.

[0052] According to an embodiment of the present invention, in step b), there is no particular limitation on the way to generate the pressure difference. For example, a negative pressure can be generated on the lower surface of the metal ion-doped graphene oxide membrane catalytic material by vacuum filtration, and / or a positive pressure can be generated on the upper surface of the metal ion-doped graphene oxide membrane catalytic material by applying an external pressure.

[0053] Exemplarily, the pressure difference is achieved by vacuum filtration. For example, the reaction solution is added to a vacuum filtration device provided with a metal ion-doped graphene oxide membrane catalytic material, and the vacuum pump is started for vacuum filtration to generate a pressure difference between the upper surface and the lower surface of the metal ion-doped graphene oxide membrane catalytic material.

[0054] According to an embodiment of the present invention, in step b), the pressure difference is greater than or equal to 0.9 atm, for example, 0.9 - 8 atm, such as 0.9 - 4 atm, and exemplarily 0.9 atm, 1 atm, 1.2 atm, 1.5 atm, 1.8 atm, 2 atm, 2.2 atm, 2.5 atm, 2.8 atm, 3 atm, 3.2 atm, 3.5 atm, 3.8 atm or 4 atm.

[0055] According to an embodiment of the present invention, in step b), the conversion rate of the reaction is 90 - 100%, for example, 90%, 95%, 98% or 100%.

[0056] According to an embodiment of the present invention, in step b), the selectivity of the sulfone is 60 - 100%, for example, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.

[0057] The present invention also provides a method for preparing a metal ion-doped graphene oxide membrane catalytic material, the method comprising the following steps:

[0058] (1) Adding a metal salt to a dispersion of graphene oxide, and ultrasonically mixing to obtain a mixed solution;

[0059] (2) Using the vacuum filtration method, assembling the mixed solution of step (1) into a metal ion-doped graphene oxide membrane, and then performing a constant temperature and humidity static treatment to prepare the metal ion-doped graphene oxide membrane catalytic material.

[0060] The present invention also provides a metal ion-doped graphene oxide membrane catalytic material prepared by the above method.

[0061] The present invention also provides a catalytic system containing the above metal ion-doped graphene oxide membrane catalytic material.

[0062] The present invention relates to the use of a metal ion-doped graphene oxide membrane catalytic material for efficiently and rapidly catalyzing the oxidation of thioether to sulfone at room temperature. By adding metal ions to a dispersion of graphene oxide, an interaction occurs between graphene oxide and metal ions and metal ion doping is carried out. Then, using the vacuum filtration method, the dispersion of graphene oxide doped with metal ions is prepared into a metal ion-doped graphene oxide membrane catalytic material (GO-M membrane), and the content of metal ions in the metal ion-doped graphene oxide membrane catalytic material is continuously adjustable.

[0063] Compared with the traditional catalytic method, the present invention is in the form of a continuous flow-phase reaction. The thioether substrate and the oxidant react in the two-dimensional interlayer confined channel of the metal ion-doped graphene oxide membrane catalytic material, and the product flows out with the mobile phase. The catalytic method can achieve high conversion (90 - 100%), high selectivity (60 - 100%), and rapid (1 - 60 s) thioether oxidation reaction at room temperature.

[0064] Advantages of the present invention:

[0065] (1) The GO-M membrane provides a two-dimensional interlayer confined channel. Through the confined space effect, the interaction between the thioether substrate and the oxidant is optimized, thereby reducing the reaction activation energy, and further realizing the efficient catalysis of the thioether oxidation to sulfone reaction at room temperature.

[0066] (2) The GO-M membrane provides active metal centers. Under the synergistic action of the active metal centers and the Lewis acid centers inherent in graphene oxide, the interaction between the thioether substrate and the oxidant is further enhanced. By changing the reaction mechanism, the reaction activation energy is reduced, and the oxidation ability of the oxidant is improved, thereby realizing the efficient catalysis of the thioether oxidation to sulfone reaction at room temperature.

[0067] (3) By changing the molar amount of metal salts added during the preparation process, the content of metal active centers in the GO-M membrane is regulated, thereby improving the catalytic effect.

[0068] (4) The GO-M membrane prepared in the present invention exhibits strong catalytic performance at room temperature. On the basis of maintaining a high thioether conversion rate (90 - 100%), the reaction time required is significantly shortened (residence time 1 - 60 s), effectively avoiding the high energy consumption caused by high temperature conditions and long-time reactions. The GO-M membrane prepared in the present invention also has a high selectivity for sulfone (60 - 100%). Through this membrane-confined flow catalytic system at room temperature, not only can the oxidation performance of the oxidant be improved, thereby significantly increasing the conversion rate and selectivity of the reaction, but also the energy consumption of long-time and high-temperature reactions can be avoided, providing a new solution for the efficient and green realization of the application of thioether oxidation to form sulfone. The present invention utilizes the two-dimensional nano-confined channels provided by the layered metal ion-doped graphene oxide membrane catalytic material. Driven by the pressure difference, the reaction liquid passes through the two-dimensional interlayer confined channels and is efficiently catalyzed by the combined action of acidic sites and metal active centers, ultimately achieving the efficient catalytic oxidation of thioether to form sulfone at room temperature. The conversion rate of the reactants can reach up to 100%, the selectivity of sulfone can reach up to 100%, and the oxidant is hydrogen peroxide or tert-butyl hydroperoxide, which is environmentally friendly. Description of the Drawings

[0069] Figure 1 : Schematic diagram of the preparation of metal ion-doped graphene oxide membrane by vacuum filtration method.

[0070] Figure 2 : Schematic diagram of the synthesis of sulfone by thioether oxidation catalyzed by metal ion-doped graphene oxide membrane-confined flow.

[0071] Figure 3 : 1H NMR spectra and high-performance liquid chromatography diagrams of thioether substrates, sulfoxides, and sulfone products.

[0072] Figure 4 : Comparison of the conversion rate, selectivity of sulfone, and reaction time of the GO powder in Comparative Example 5, GO-Fe powder in Comparative Example 6, GOM membrane sample in Comparative Example 4, and GOM-5μmolFe membrane sample in Example 2 for the thioether oxidation reaction. Detailed Embodiments

[0073] The technical solutions of the present invention will be further described in detail below with specific embodiments. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0074] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples can all be obtained from commercial sources unless otherwise specified.

[0075] In the following examples and comparative examples, unless otherwise specified, "GO" refers to "graphene oxide", "GO dispersion" refers to "graphene oxide dispersion", and "GO film" refers to "graphene oxide film".

[0076] In the following examples and comparative examples, unless otherwise specified, "GO-M" refers to "metal ion-doped graphene oxide", "GO-M dispersion" refers to "metal ion-doped graphene oxide dispersion", and "GO-M film" refers to "metal ion-doped graphene oxide film".

[0077] The pervaporation collecting liquid was quantitatively analyzed by nuclear magnetic resonance hydrogen spectrum or high performance liquid chromatography, and the conversion rate of the reaction and the selectivity of the product were calculated therefrom. The specific steps are as follows:

[0078] For the nuclear magnetic resonance hydrogen spectrum test, a part of the pervaporation collecting liquid was taken, the excess solvent was removed by rotary evaporation, and then the sample was dissolved with a deuterated reagent (DMSO-d6) to prepare a nuclear magnetic test sample. Characteristic hydrogen peaks exist in both the substrate and product molecules. There is a corresponding relationship between the characteristic hydrogen peak area and the number of molecules. The integral area of the characteristic peaks of each substance was calculated by single peak fitting, and the number ratio of the corresponding molecules was calculated therefrom, so as to calculate the conversion rate and selectivity of the reaction.

[0079] For the high performance liquid chromatography test, a part of the pervaporation collecting liquid was taken, and then it was dissolved and diluted with acetonitrile to prepare a liquid phase test sample. The substrate and the product were separated due to different polarities and had different peak retention times. The single peak areas at different peak emergence times were calculated by single peak fitting and compared, so as to obtain the number ratio of the corresponding molecules, and then the conversion rate and selectivity of the reaction were calculated.

[0080] Example 1

[0081] (1) Prepare a 0.125 mg / mL GO-M dispersion: Take 5 mg of GO in 40 mL of deionized water, and then add 5 μmol of FeCl 3 to it. After mixing evenly, disperse it by ultrasonic treatment (400 W) for 10 min to obtain a dark brown transparent solution.

[0082] (2) The prepared GO-M dispersion was used to prepare a GO-M membrane on a nylon substrate by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device and placed in a constant temperature and humidity environment (25.0 °C, 21% RH) for air drying for 12 h and then taken out for standby, named GOM-5μmolFe. Environmental scanning electron microscopy (ESEM) and X-ray diffraction (XRD) data showed that the membrane thickness of GOM-5μmolFe was about 1.84 μm, and the dry-state layer spacing was about

[0083] (3) Using GOM-5μmolFe as a catalyst for the oxidation reaction of thioether, the specific operation steps are as follows: Select a flat and smooth part of GOM-5μmolFe, cut it into a regular octagon (side length 10 mm), and then fix it on the surface of the sintered filter head of a microfiltration device and clamp the filter head and filter cup with a clip to ensure sealing; Subsequently, prepare the reaction solution: Dissolve 4 mmol of methyl phenyl sulfide and 8 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 40 mL reaction solution, which is prepared and used immediately; Take 17.5 mL of the above-prepared reaction solution and add it to the filter cup of the microfiltration device. The pressure difference (∼0.9 atm) provided by a circulating vacuum water pump is used to drive the reaction solution through the two-dimensional interlayer confinement channel in GOM-5μmolFe. At room temperature, the reactants react in the confinement channel and then flow out with the solvent acetonitrile; Use 1 HNMR spectrum or HPLC spectrum to analyze the components and calculate the reaction conversion rate and selectivity; The test results were as follows: The reaction temperature was 20 - 30 °C, the residence time of the reactants was about 20.3 s, the conversion rate of thioether was 98.8 ± 0.4%, and the selectivity of sulfone was 64.7 ± 6.0%.

[0084] Comparative Example 1

[0085] (1) Prepare a 0.125 mg / mL GO dispersion: Take 5 mg of GO in 40 mL of deionized water and disperse it by ultrasonic wave (160 W) for 5 min to obtain a brown transparent solution.

[0086] (2) The prepared GO dispersion was used to prepare a GO membrane on a nylon substrate by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device and placed in a constant temperature and humidity environment (25.0 °C, 21% RH) for air drying for 12 h and then taken out for standby, named GOM. Environmental scanning electron microscopy (ESEM) and X-ray diffraction (XRD) data showed that the membrane thickness of GOM was about 1.64 μm, and the dry-state layer spacing was about

[0087] (3) Using GOM as a catalyst to catalyze the oxidation reaction of thioether, the specific operation steps are as follows: Select a flat and smooth part on GOM, cut it into a regular octagon (side length 10 mm), and then fix it on the surface of the sand core filter head of the micro suction filtration device and clamp the filter head and filter cup with a clip to ensure sealing; Subsequently, prepare the reaction solution: Dissolve 4 mmol of methyl phenyl sulfide and 8 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 40 mL reaction solution, which is prepared and used immediately; Take 17.5 mL of the above-prepared reaction solution and add it to the filter cup of the micro suction filtration device. Drive the reaction solution through the two-dimensional interlayer confined channel in GOM by the pressure difference (~0.9 atm) provided by the circulating vacuum water pump. At room temperature, the reactants react in the confined channel and then flow out with the solvent acetonitrile; Analyze the components by 1 HNMR spectrum or HPLC spectrum, and calculate the reaction conversion rate and selectivity; The test results are as follows: The reaction temperature is 20 - 30 °C, the residence time of the reactants is about 15.3 s, the conversion rate of thioether is 94.8 ± 5.4%, and the selectivity of sulfone is 23.4 ± 5.8%.

[0088] Comparative Example 2

[0089] Dissolve 0.4 mmol of methyl phenyl sulfide and 0.8 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 4 mL reaction solution; Add 2.5 mg of GO powder to the reaction solution (the catalyst is GO powder), keep mechanical stirring, and take 1 mL of the above reaction solution as a test sample 24 h after the start of the reaction, prepare it as a test sample, and perform 1 HNMR or HPLC tests to analyze the components of the sample, calculate the reaction conversion rate and selectivity. The test results are as follows: The reaction temperature is 20 - 30 °C, the residence time of the reactants is about 24 h, the conversion rate of thioether is 65.5%, and the selectivity of sulfone is 0.8%.

[0090] Comparative Example 3

[0091] Dissolve 0.4 mmol of methyl phenyl sulfide and 0.8 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 4 mL reaction solution; Add 2.5 mg of GO powder and 2.5 μmol of FeCl 3 (the catalyst is GO-Fe powder) to the reaction solution, keep mechanical stirring, and take 1 mL of the above reaction solution as a test sample 24 h after the start of the reaction, prepare it as a test sample, and perform 1The composition of the sample was analyzed by HNMR or HPLC, and the reaction conversion rate and selectivity were calculated. The test results were as follows: the reaction temperature was 20 - 30 °C, the residence time of the reactants was about 24 h, the conversion rate of thioether was 87.9%, and the selectivity of sulfone was 2.2%.

[0092] Example 2

[0093] Other operations were the same as in Example 1, except that: the reaction solution included 4 mmol of methyl phenyl sulfide and 40 mmol of H 2 O 2 (30% aqueous solution). The test results were as follows: the reaction temperature was 20 - 30 °C, the residence time of the reactants was about 8.6 s, the conversion rate of thioether was 100%, and the selectivity of sulfone was 92.5 ± 4.9%.

[0094] Comparative Example 4

[0095] Other operations were the same as in Comparative Example 1, except that: the reaction solution included 4 mmol of methyl phenyl sulfide and 40 mmol of H 2 O 2 (30% aqueous solution). The test results were as follows: the reaction temperature was 20 - 30 °C, the residence time of the reactants was about 10.5 s, the conversion rate of thioether was 100%, and the selectivity of sulfone was 42.7 ± 5.3%.

[0096] Comparative Example 5

[0097] Dissolve 0.4 mmol of methyl phenyl sulfide and 4 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 4 mL reaction solution; add 2.5 mg of GO powder (the catalyst is GO powder) to the reaction solution, maintain mechanical stirring, and take 1 mL of the above reaction solution as a test sample 24 h after the start of the reaction, and prepare it into a test sample for 1 HNMR or HPLC test to analyze the sample composition and calculate the reaction conversion rate and selectivity. The conversion rate of thioether was 90.1%, and the selectivity of sulfone was 0.8%.

[0098] Comparative Example 6

[0099] Dissolve 0.4 mmol of methyl phenyl sulfide and 4 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 4 mL reaction solution; add 2.5 mg of GO powder and 2.5 μmol of FeCl 3 (the catalyst is GO - Fe powder) to the reaction solution, maintain mechanical stirring, and take 1 mL of the above reaction solution as a test sample 24 h after the start of the reaction, and prepare it into a test sample for 1The composition of the sample was analyzed by HNMR or HPLC, and the reaction conversion rate and selectivity were calculated. The conversion rate of the thioether was 100%, and the selectivity of the sulfone was 30.1%.

[0100] Example 3

[0101] (1) Prepare a 0.125 mg / mL GO-M dispersion: Take 5 mg of GO in 40 mL of deionized water, and then add 10 μmol of FeCl 3 to it. After mixing evenly, disperse it by ultrasonic treatment (400 W) for 10 min to obtain a dark brown transparent solution.

[0102] (2) Prepare a GO-M film on a nylon substrate from the above-prepared GO-M dispersion by vacuum filtration. After the water on the film is drained, remove the film from the filtration device and place it in a constant temperature and humidity environment (25.0 °C, 21% RH) to air dry for 12 h and then take it out for standby, named GOM-10 μmolFe.

[0103] (3) Use GOM-10 μmolFe as a catalyst to catalyze the oxidation reaction of thioether. The specific operation steps are as follows: Select a flat and smooth part on GOM-10 μmolFe, cut it into a regular octagon (side length 10 mm), then fix it on the surface of the sintered filter head of a micro-filtration device and clamp the filter head and filter cup with a clip to ensure sealing; Subsequently, prepare the reaction solution: Dissolve 4 mmol of methyl phenyl thioether and 40 mmol of H 2 O 2 (30% aqueous solution) in acetonitrile to prepare a 40 mL reaction solution, which is prepared immediately before use; Take 17.5 mL of the above-prepared reaction solution and add it to the filter cup of the micro-filtration device. Drive the reaction solution through the two-dimensional interlayer confinement channel in GOM-10 μmolFe by the pressure difference (~0.9 atm) provided by a circulating vacuum water pump. At room temperature, the reactants react in the confinement channel and then flow out with the solvent acetonitrile; Use 1 HNMR spectrum or HPLC spectrum to analyze the composition and calculate the reaction conversion rate and selectivity; The test results are as follows: The reaction temperature is 20 - 30 °C, the residence time of the reactants is about 8.2 s, the conversion rate of the thioether is 100%, and the selectivity of the sulfone is 97.6 ± 1.1%.

[0104] Example 4

[0105] Other operations are the same as in Example 1, except that: the reaction solution includes 4 mmol of p-methylphenyl thioether and 40 mmol of H 2 O 2 (30% aqueous solution). The test results are as follows: The reaction temperature is 20 - 30 °C, the residence time of the reactants is about 4.3 s, the conversion rate of the thioether is 100%, and the selectivity of the sulfone is 100%.

[0106] Example 5

[0107] Other operations are the same as those in Example 1, except that: the reaction solution includes 4 mmol of cyclopropyl phenyl sulfide and 40 mmol of H 2 O 2 (30% aqueous solution). The test results are as follows: the reaction temperature is 20 - 30 °C, the residence time of the reactants is about 7.7 s, the conversion rate of the thioether is 100%, and the selectivity of the sulfone is 100%.

[0108] Example 6

[0109] Other operations are the same as those in Example 1, except that: the reaction solution includes 4 mmol of albendazole and 40 mmol of H 2 O 2 (30% aqueous solution). The test results are as follows: the reaction temperature is 20 - 30 °C, the residence time of the reactants is about 37.6 s, the conversion rate of the thioether is 100%, and the selectivity of the sulfone is 86.1 ± 9.1%.

[0110] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. Use of a metal ion-doped graphene oxide film catalyst material in catalyzing sulfide oxidation reaction to synthesize sulfone.

2. The use according to claim 1, wherein The thickness of the metal ion doped graphene oxide membrane catalytic material is 0.1-5 μm; and / or, the mass of the metal ions in the metal ion doped graphene oxide membrane catalytic material accounts for 0.01-15 wt % of the total mass of the membrane catalytic material. Preferably, the metal ions in the metal ion-doped graphene oxide film catalytic material are selected from at least one of the main metal ions and transition metal ions; illustratively, the metal ions are selected from Li + 、Na + , K + Mg 2+ , Ca 2+ 、Al 3+ , Mn 2+ , Fe 3+ 、Co 2+ 、Ni 2+ , Cu 2+ and Zn 2+ At least one of . Preferably, the metal ion-doped graphene oxide film catalytic material is a layered structure formed by stacking metal ion-doped graphene oxides, preferably a layered structure formed by stacking metal ion-doped graphene oxide nanosheets.

3. The use according to claim 1 or 2, wherein The metal ion-doped graphene oxide film catalytic material is prepared by the following method: (1) adding a metal salt to a dispersion of graphene oxide and mixing by ultrasonication to obtain a mixed solution; (2) The mixed solution of step (1) is assembled into a metal ion-doped graphene oxide membrane by vacuum filtration, and then placed in a constant temperature and humidity station to prepare the metal ion-doped graphene oxide membrane catalytic material.

4. The use according to claim 3, wherein In step (1), the concentration of the graphene oxide dispersion is 0.01-0.25 mg / mL. Preferably, in step (1), the metal salt is selected from at least one of a group metal salt and a transition metal salt; illustratively, the metal salt is selected from at least one of LiCl, NaCl, KCl, MgCl2, CaCl2, AlCl3, MnCl2, FeCl3, CoCl2, NiCl2, CuCl2 and ZnCl2. Preferably, in step (1), the molar volume ratio of the dispersion of the metal salt and graphene oxide is 1-20 μmol / 40 mL. Preferably, in step (1), the ultrasonic mixing time is 5-15 min; the ultrasonic mixing power is 100-500 W.

5. The use according to any one of claims 1 to 4, wherein The method for synthesizing sulfone by catalytic thioether oxidation reaction comprises the following steps: a) dissolving a thioether substrate and an oxidant in an organic solvent to obtain a reaction solution; b) at room temperature, driving by pressure difference, the reaction solution of step a) passes through the metal ion-doped graphene oxide membrane catalytic material to carry out sulfide oxidation reaction to prepare sulfone.

6. A method for synthesizing sulfone by catalytic oxidation of thioether, the method comprising the following steps: a) dissolving a thioether substrate and an oxidant in an organic solvent to obtain a reaction solution; b) at room temperature, driving by pressure difference, the reaction solution of step a) passes through the metal ion-doped graphene oxide membrane catalytic material to carry out sulfide oxidation reaction to prepare sulfone.

7. The use according to claim 5 or the method according to claim 6, wherein: In step a), the molar ratio of the thioether substrate to the oxidant is 1:1-10; and / or, in step a), the oxidant is selected from at least one of hydrogen peroxide, tert-butyl hydroperoxide, etc.; and / or, in step a), the thioether substrate includes at least one of methyl phenyl sulfide, p-methyl phenyl sulfide, phenyl ethyl sulfide, cyclopropyl phenyl sulfide, allyl benzene sulfide, ethyl sulfide, dipropyl sulfide, diphenyl sulfide, 4-nitrophenyl phenyl sulfide, albendazole, etc. Preferably, in step a), the concentration of the thioether substrate is 0.01-1 mol / L. Preferably, in step b), the reaction time is 1-60s. Preferably, in step b), the pressure difference is greater than or equal to 0.9 atm.

8. A method for preparing a metal ion-doped graphene oxide film catalytic material, the method comprising the following steps: (1) adding a metal salt to a dispersion of graphene oxide and mixing by ultrasonication to obtain a mixed solution; (2) The mixed solution of step (1) is assembled into a metal ion-doped graphene oxide membrane by vacuum filtration, and then placed in a constant temperature and humidity station to prepare the metal ion-doped graphene oxide membrane catalytic material.

9. A metal ion-doped graphene oxide film catalytic material prepared by the method of claim 8.

10. A catalytic system comprising the metal ion-doped graphene oxide film catalytic material according to claim 9.

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