Use of a transition metal ion-doped graphene oxide film catalytic material in synthesis of 4-phenylmorpholine antibacterial derivatives

Abstract

The application relates to an application of a transition metal ion doped graphene oxide film catalytic material in synthesis of 4-phenyl morpholine antibacterial derivatives, and belongs to the technical field of film materials and catalytic application. The transition metal ion doped graphene oxide film catalytic material retains intrinsic acid catalytic sites of graphene oxide nanosheets and introduces transition metal ions which can induce orientation of reactant molecules, and by virtue of a two-dimensional nanometer limited channel provided by graphene oxide film layers and synergistic effect between the transition metal ions and the reactant molecules, rapid long-acting catalytic synthesis of the 4-phenyl morpholine antibacterial derivatives can be realized under the condition of a continuous flow reaction driven by a pressure difference at room temperature (22.3+ / -0.1 DEG C).

Description

Technical Field

[0001] This invention relates to the use of a transition metal ion-doped graphene oxide membrane catalytic material in the synthesis of 4-phenylmorpholine antibacterial derivatives, belonging to the field of membrane materials and catalytic application technology. Background Technology

[0002] 4-Phenylomorpholine derivatives are a class of nitrogen-containing heterocyclic compounds of significant research value. Some of these derivatives, containing imine structures, exhibit antibacterial activity and have potential applications in antibacterial molecule design, drug intermediate construction, and fine organic synthesis. Previous studies have shown that derivatives obtained from the reaction of 4-(4-aminophenyl)morpholine with different substituted aromatic aldehydes can exhibit varying degrees of antibacterial activity. Among these, the 4-phenylmorpholine antibacterial derivatives include the following antibacterial compounds I, II, III, and IV:

[0003] Among them, antimicrobial compound I has the broadest antimicrobial spectrum, exhibiting significant activity against Gram-positive bacteria (such as Bacillus cereus and Micrococcus luteus), Gram-negative bacteria (such as Escherichia coli), and fungi (such as Candida albicans). Antimicrobial compound II has significant inhibitory activity against Gram-positive bacteria (such as Staphylococcus aureus and Staphylococcus epidermidis) and fungi (such as Aspergillus niger). Antimicrobial compounds III and IV both exhibit moderate antimicrobial activity against the aforementioned bacteria and fungi.

[0004] However, existing antibacterial compounds I, II, III, and IV are primarily prepared by reacting 4-(4-aminophenyl)morpholine with various substituted aromatic aldehydes. This reaction is typically carried out in a bulk solution, requiring heating (50-90 °C), prolonged reaction time (over 2 hours), low conversion rate (56-76%), and short catalyst life (e.g., separation occurs after more than 2 hours of intermittent bulk reaction, preventing the catalyst from continuously participating in the reaction). Furthermore, post-treatment steps such as recrystallization are usually required for purification after the reaction. For antibacterial compounds I, II, III, and IV, this cumbersome post-treatment not only increases process steps and solvent consumption but may also lead to product decomposition or decreased stability. Simultaneously, aromatic aldehyde reactants may undergo oxidation side reactions under heating and prolonged reaction times, generating corresponding aromatic carboxylic acid byproducts, thereby reducing raw material utilization and adversely affecting reaction conversion and product purity. All these factors limit the efficient and environmentally friendly preparation of antibacterial compounds I, II, III, and IV.

[0005] Furthermore, in conventional bulk solution reaction systems, reactant molecules mainly rely on disordered diffusion and random collisions to complete the reaction, lacking effective control over the adsorption, orientation, local concentration, and dehydration processes of reactant molecules. Therefore, achieving rapid and high-conversion synthesis of antibacterial compounds I, II, III, and IV under mild conditions remains challenging. Especially for continuous preparation at room temperature, existing continuous flow membrane catalytic synthesis methods for imine compounds, while able to shorten reaction time and improve conversion rates to some extent, still suffer from insufficient membrane structure stability, rapid decay of catalytic activity over long periods, and difficulty in long-term stable operation, thus limiting their application in continuous preparation processes. Therefore, it is indeed necessary to provide a method for the rapid and long-lasting synthesis of 4-phenylmorpholine antibacterial derivatives at room temperature. Summary of the Invention

[0006] To address the problems of high reaction temperature, long reaction time, low conversion efficiency, easy oxidation side reactions of aromatic aldehydes, short catalyst life, and complex post-processing in the synthesis of antibacterial compounds I-IV in existing technologies, this invention provides the application of a transition metal ion-doped graphene oxide membrane catalytic material in the synthesis of 4-phenylmorpholine antibacterial derivatives. The transition metal ion-doped graphene oxide membrane catalytic material retains the inherent acidic catalytic sites of graphene oxide while being doped with transition metal ions that can induce reactant orientation through cation-π interactions. Utilizing the two-dimensional interlayer confined channels formed by the transition metal ion-doped graphene oxide membrane catalytic material, under pressure-driven continuous flow conditions, the adsorption, orientation, mass transfer, and reaction processes of reactant molecules within the interlayer channels are regulated through the synergistic effect of the intrinsic oxygen-containing functional groups of the graphene oxide membrane and the doped transition metal ions. This improves the compatibility between the membrane catalytic material and the synthesis reaction of 4-phenylmorpholine antibacterial derivatives, thereby enabling the synthesis of different substituted aromatic aldehydes and 4-(4-aminophenyl)morpholine. The method enables rapid, long-lasting, and green preparation at room temperature, significantly improving the reaction rate and conversion rate of 4-phenylmorpholine antibacterial derivatives, suppressing side reactions such as aromatic aldehyde oxidation, and simplifying post-processing steps. Simultaneously, the transition metal ion-doped graphene oxide membrane catalytic material maintains long-lasting catalytic performance under catalytic conditions, effectively improving its operational stability and lifespan under continuous flow reaction conditions at room temperature. This significantly enhances the sustained catalytic ability for synthesizing 4-phenylmorpholine antibacterial derivatives, allowing the transition metal ion-doped graphene oxide membrane catalytic material to continuously catalyze reactions for over 120 hours while maintaining high conversion rates.

[0007] The objective of this invention is achieved through the following technical solution: The use of a transition metal ion-doped graphene oxide membrane catalytic material in the synthesis of 4-phenylmorpholine antibacterial derivatives.

[0008] According to an embodiment of the present invention, the use of the transition metal ion-doped graphene oxide membrane catalytic material in the catalytic reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize 4-phenylmorpholine antibacterial derivatives.

[0009] According to embodiments of the present invention, the 4-phenylmorpholine antibacterial derivative comprises antibacterial compounds I, II, III, and IV as shown below: .

[0010] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide membrane catalytic material is used in the rapid synthesis of 4-phenylmorpholine antibacterial derivatives at room temperature.

[0011] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide membrane catalytic material is used in the rapid catalytic reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine at room temperature to synthesize 4-phenylmorpholine antibacterial derivatives.

[0012] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide membrane catalytic material is used in the rapid and long-lasting synthesis of 4-phenylmorpholine antibacterial derivatives at room temperature.

[0013] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide membrane catalytic material is used in the rapid and long-lasting catalytic reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize 4-phenylmorpholine antibacterial derivatives at room temperature.

[0014] According to an embodiment of the present invention, the room temperature refers to a temperature range of 20-30 °C.

[0015] According to an embodiment of the present invention, "rapid" refers to a reaction time of 2-30 s. The reaction time refers to the time it takes for 4-(4-aminophenyl)morpholine to flow through the transition metal ion-doped graphene oxide film catalytic material, that is, the time 4-(4-aminophenyl)morpholine resides inside the transition metal ion-doped graphene oxide film catalytic material.

[0016] According to an embodiment of the present invention, the long-lasting effect refers to the fact that the transition metal ion-doped graphene oxide membrane catalytic material can achieve a conversion rate of more than 90% for 4-(4-aminophenyl)morpholine after continuous reaction for 120 hours.

[0017] According to embodiments of the present invention, the thickness of the transition metal ion-doped graphene oxide film catalytic material is 0.5-5 μm, for example, 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 controlling the film thickness, the retention time of reactant molecules in the two-dimensional interlayer confined channels of the transition metal ion-doped graphene oxide film catalytic material can be controlled, thereby optimizing its catalytic performance. Studies have found that reactant molecules have too short a retention time in excessively thin transition metal ion-doped graphene oxide membrane catalytic materials (thickness less than 0.5 μm), resulting in low conversion rates. Furthermore, these membranes are prone to cracking during the catalytic reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize 4-phenylmorpholine antibacterial derivatives. Excessively thick transition metal ion-doped graphene oxide membrane catalytic materials (thickness greater than 5 μm) significantly reduce the flow rate of the reaction solution and increase the preparation cost of the membrane catalytic material. They also tend to introduce excessive defects during preparation, reducing the orderliness of the two-dimensional confinement space provided to the reactant molecules and significantly decreasing the efficiency of catalyzing the reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize 4-phenylmorpholine antibacterial derivatives.

[0018] According to an embodiment of the present invention, the interlayer spacing of the transition metal ion-doped graphene oxide film catalytic material is 9-16 Å, for example, 9 Å, 10 Å, 11 Å, 12 Å, 13 Å, 14 Å, 15 Å or 16 Å.

[0019] According to embodiments of the present invention, the mass of transition metal ions in the transition metal ion-doped graphene oxide membrane catalytic material accounts for 0.01-15 wt% of the total mass of the membrane catalytic material, for example, 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 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 transition metal ions in the transition metal ion-doped graphene oxide membrane catalytic material is 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 low, the orientation induction effect on reactant molecules is weak, and the catalytic effect on the synthesis of 4-phenylmorpholine antibacterial derivatives by the reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine is not obvious. When the mass of transition metal ions in the transition metal ion-doped graphene oxide membrane catalytic material is greater than 15 wt% of the total mass of the membrane catalytic material, the interaction between graphene oxide and transition metal ions will be enhanced, making it impossible to uniformly disperse them in water by ultrasound, and may also lead to the formation of aggregates, affecting the uniformity and structural stability of the subsequently prepared metal ion-doped graphene oxide membrane catalytic material. It will also affect the integrity and confinement effect of the multilayer structure of the membrane material due to the introduction of too many defects by the transition metal ion loading.

[0020] According to an embodiment of the present invention, the transition metal ions in the transition metal ion-doped graphene oxide film catalytic material are selected from Fe. 3+ .

[0021] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide membrane catalytic material is a layered structure formed by stacking transition metal ion-doped graphene oxide, preferably a layered structure formed by stacking transition metal ion-doped graphene oxide nanosheets.

[0022] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide membrane catalytic material includes transition metal ion-doped graphene oxide, preferably including transition metal ion-doped graphene oxide nanosheets.

[0023] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide includes graphene oxide and transition metal ions, wherein the transition metal ions are doped onto the graphene oxide.

[0024] According to an embodiment of the present invention, the transition metal ion-doped graphene oxide film catalytic material is prepared by the following method: (1) Add a transition metal salt to the dispersion of graphene oxide, mix ultrasonically to obtain a mixed solution; (2) The mixed solution from step (1) was assembled into a transition metal ion-doped graphene oxide membrane by vacuum filtration and then subjected to constant temperature and humidity settling treatment to prepare the transition metal ion-doped graphene oxide membrane catalytic material.

[0025] 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 transition metal salt, the mass ratio of transition metal ions in the transition metal ion-doped graphene oxide membrane catalytic material can be controlled, thereby controlling the catalytic performance of the transition metal ion-doped graphene oxide membrane catalytic material.

[0026] According to an embodiment of the present invention, in step (1), by adding a transition metal salt to the dispersion of graphene oxide and then performing ultrasonic mixing treatment, the graphene oxide and the transition metal ions can be fully interacted, thereby achieving the doping of transition metal ions onto graphene oxide and obtaining graphene oxide doped with transition metal ions that is more uniformly dispersed.

[0027] According to an embodiment of the present invention, in step (1), the graphene oxide is preferably graphene oxide nanosheet, the graphene oxide nanosheet is a single-layer graphene oxide nanosheet, and the diameter of the graphene oxide nanosheet is >500 nm.

[0028] According to an embodiment of the present invention, in step (1), the concentration of the graphene oxide dispersion is 0.05-1.5 mg / mL, that is, 1 mL of the graphene oxide dispersion contains 0.05-1.5 mg of graphene oxide; exemplaryly, the concentration of the graphene oxide dispersion is 0.05 mg / mL, 0.1 mg / mL, 0.2 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.2 mg / mL or 1.5 mg / mL.

[0029] According to an embodiment of the present invention, in step (1), the transition metal salt is preferably FeCl3.

[0030] According to an embodiment of the present invention, in step (1), the molar mass ratio of the transition metal salt to graphene oxide is 0.01-4 μmol / 0.05-1.5 mg, that is, 0.01-4 µmol of transition metal salt is added to 0.05-1.5 mg of graphene oxide.

[0031] According to an embodiment of the present invention, in step (1), the ultrasonic mixing time is 5-15 min, for example, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, or 15 min; the ultrasonic mixing power is 100-300 W, for example, 100 W, 150 W, 200 W, 250 W, or 300 W. Under these conditions, ultrasonic mixing can achieve uniform dispersion of transition metal ion-doped graphene oxide in water without destroying the structure of the transition metal ion-doped graphene oxide.

[0032] According to an embodiment of the present invention, step (2) specifically includes the following steps: 21) Lay a porous substrate in the filter cup of the vacuum filtration device; 22) Add the mixed solution from step (1) into the filter cup of 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 assemble the transition metal ion-doped graphene oxide layer by layer on the porous substrate to obtain the transition metal ion-doped graphene oxide membrane catalytic material.

[0033] According to an embodiment of the present invention, the porous substrate may be made of organic filter membranes such as nylon 66, polyvinylidene fluoride, and polytetrafluoroethylene.

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

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

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

[0037] According to an embodiment of the present invention, in step (2), the constant temperature and humidity settling treatment is, for example, settling under constant temperature and humidity conditions for a period of time; exemplaryly, the constant temperature and humidity settling treatment is carried out in a constant temperature and humidity chamber. Exemplarily, the constant temperature and humidity settling treatment is settling at 20-30 ℃ and 10-20 %RH for 6-12 hours. The constant temperature and humidity settling treatment can remove free water from the transition metal ion-doped graphene oxide membrane catalyst material after filtration.

[0038] According to embodiments of the present invention, the method for synthesizing 4-phenylmorpholine antibacterial derivatives (particularly the method for synthesizing 4-phenylmorpholine antibacterial derivatives by catalytic reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine) comprises the following steps: a) Dissolve aromatic aldehyde and 4-(4-aminophenyl)morpholine in an organic solvent to obtain a reaction solution; b) At room temperature, the reaction solution from step a) is passed through the transition metal ion-doped graphene oxide membrane catalytic material via a pressure difference to prepare a 4-phenylmorpholine antibacterial derivative.

[0039] The present invention also provides a method for synthesizing a 4-phenylmorpholine antibacterial derivative, the method comprising the following steps: a) Dissolve aromatic aldehyde and 4-(4-aminophenyl)morpholine in an organic solvent to obtain a reaction solution; b) At room temperature, the reaction solution from step a) is passed through the transition metal ion-doped graphene oxide membrane catalytic material via a pressure difference to prepare a 4-phenylmorpholine antibacterial derivative.

[0040] According to an embodiment of the present invention, under the drive of a pressure difference, aromatic aldehydes and 4-(4-aminophenyl)morpholine react in a continuous flow phase reaction within a two-dimensional interlayer confined channel of a transition metal ion-doped graphene oxide membrane catalytic material. The resulting product, 4-phenylmorpholine antibacterial derivative, flows out with the organic solvent and leaves the catalytic system.

[0041] According to an embodiment of the present invention, in step a), the molar ratio of the aromatic aldehyde and 4-(4-aminophenyl)morpholine is 1:0.9-1.2, for example, 1:0.9, 1:1.0, 1:1.1 or 1:1.2.

[0042] According to an embodiment of the present invention, in step a), the aromatic aldehyde is selected from at least one of 4-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, 3,4-dimethoxybenzaldehyde, and 3,4,5-trimethoxybenzaldehyde.

[0043] According to an embodiment of the present invention, in step a), the organic solvent is selected from acetonitrile.

[0044] According to an embodiment of the present invention, in step a), the concentration of the aromatic aldehyde is 0.01-5 mol / L.

[0045] According to an embodiment of the present invention, in step b), the reaction time is 2-30 s.

[0046] According to an embodiment of the present invention, in step b), the room temperature refers to a temperature range of 20-30 °C.

[0047] According to an embodiment of the present invention, in step b), the method of generating the pressure difference is not particularly limited. For example, it can be to generate negative pressure on the lower surface of the transition metal ion-doped graphene oxide film catalyst material by vacuum filtration, and / or to generate positive pressure on the upper surface of the transition metal ion-doped graphene oxide film catalyst material by applying external pressure.

[0048] For example, the pressure difference is achieved by vacuum filtration, such as by adding the reaction solution into a vacuum filtration device equipped with a transition metal ion-doped graphene oxide membrane catalyst, starting the vacuum pump, and performing vacuum filtration to generate a pressure difference between the upper and lower surfaces of the transition metal ion-doped graphene oxide membrane catalyst.

[0049] According to an embodiment of the present invention, in step b), the pressure difference is greater than or equal to 0.8 atm, for example, 0.8-4 atm, and exemplary values ​​are 0.8 atm, 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.

[0050] According to an embodiment of the present invention, in step b), the conversion rate of the reaction is 90% or more, for example 90%-98%, such as 90%, 95% or 98%.

[0051] The beneficial effects of this invention are: (1) This invention uses transition metal ion-doped graphene oxide membrane as the membrane catalytic material. By utilizing its interlayer two-dimensional confined channels, the oxygen-containing functional groups on the graphene oxide surface, and the interaction between transition metal ions and reactant molecules, the adsorption, orientation, mass transfer, and reaction processes of reactant molecules within the interlayer channels are synergistically regulated. The transition metal ions have strong Lewis acidity, which can promote the condensation reaction. The transition metal ions can also induce the orientation of reactant molecules through cation-π interactions. Combined with the constraint of molecular freedom by the interlayer confined environment, this is beneficial to improving the catalytic efficiency of the reaction between aromatic aldehydes and 4-(4-aminophenyl)morpholine, thereby achieving the efficient catalytic synthesis of 4-phenylmorpholine antibacterial derivatives at room temperature.

[0052] (2) In this invention, the introduction of the transition metal ions helps to regulate the confined microenvironment between the graphene oxide membrane layers and enhances the compatibility between the membrane catalytic system and reactant molecules. By regulating the membrane structure parameters, the effective mass transfer and reaction conversion efficiency of reactant molecules in the interlayer channels of the membrane are improved, further enhancing the catalytic effect.

[0053] (3) In this invention, a pressure-differential driven continuous flow membrane reaction is used, which enables the reactants to complete a rapid condensation reaction within the confined channels between the membrane layers, and the products flow out with the mobile phase and leave the reaction system. Compared with traditional bulk solution reactions, this method can significantly shorten the reaction residence time, reduce the possibility of side reactions such as the oxidation of aromatic aldehydes to corresponding aromatic carboxylic acids under high temperature and long reaction conditions, and help simplify the post-processing steps.

[0054] (4) In this invention, the transition metal ion doped graphene oxide membrane can achieve efficient synthesis of 4-phenylmorpholine antibacterial derivatives at 20-30 °C. The reactant molecules have a short residence time in the membrane and a high conversion rate, avoiding the energy consumption and operational complexity caused by high temperature heating and long reaction time in traditional methods. This provides a new technical approach for the efficient, green and continuous preparation of 4-phenylmorpholine antibacterial derivatives.

[0055] (5) In this invention, the transition metal ion doped graphene oxide membrane catalytic material can achieve long-term preparation of 4-phenylmorpholine antibacterial derivatives. That is, the transition metal ion doped graphene oxide membrane catalytic material can still obtain a conversion rate of more than 90% of 4-(4-aminophenyl)morpholine after continuous reaction for 120 hours, which significantly improves the efficiency of synthesizing 4-phenylmorpholine antibacterial derivatives. Attached Figure Description

[0056] Figure 1 Fe as a preferred embodiment of the present invention 3+ A schematic diagram of the preparation of ion-doped graphene oxide membrane catalytic material and the catalytic synthesis reaction of 4-phenylmorpholine antibacterial derivative.

[0057] Figure 2 The following are comparative results of the structural and catalytic performance characterization of the Fe-S-GO membrane prepared in Example 4, the GO membrane prepared in Comparative Example 1, the Fe-S-GO-I membrane prepared in Comparative Example 2, and the Mg-GO-0.9 M-4 h membrane prepared in Comparative Example 6. Figure 2 In the figure, A represents the X-ray diffraction (XRD) patterns of the GO film and the Fe-S-GO film under dry and wet conditions (solvent is acetonitrile); Figure 2 In the image, B represents the infrared images of the Fe-S-GO film and the GO film. Figure 2 C in the figure represents the 1H NMR spectrum of the reaction products of Fe-S-GO membrane and Fe-S-GO-I membrane. Figure 2 In this context, D represents the volume change of the reaction solution through the Fe-S-GO membrane and the Mg-GO-0.9 M-4 h membrane. Detailed Implementation

[0058] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection 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.

[0059] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0060] 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".

[0061] Unless otherwise specified, in the following examples and comparative examples, "MS-GO" refers to "transition metal ion doped graphene oxide", "MS-GO dispersion" refers to "transition metal ion doped graphene oxide dispersion", and "MS-GO film" refers to "transition metal ion doped graphene oxide film".

[0062] Quantitative analysis of the membrane-passed collection solution was performed using 1H NMR spectroscopy, and the reaction conversion rate was calculated accordingly. The specific steps included: taking a portion of the membrane-passed collection solution and dissolving the sample in deuterated reagent (DMSO-d6) to prepare an NMR test sample. Characteristic hydrogen peaks exist within both substrate and product molecules, and the area of ​​these characteristic hydrogen peaks corresponds to the number of molecules. The integral area of ​​each characteristic peak was calculated by single-peak fitting, and the ratio of the corresponding molecules was then used to calculate the reaction conversion rate.

[0063] Example 1 (1) Preparation of 0.075 mg / mL GO dispersion: Take 3 mg of GO into 40 mL of deionized water, stir mechanically for 10 min, and disperse by sonication (200W) in an ice-water bath for 5 min to obtain GO dispersion; Preparation of 1.0 mol / L FeCl3 solution: Weigh 6488 mg of FeCl3, add it to 40 mL of deionized water, add two drops of concentrated hydrochloric acid, stir mechanically for 10 min to obtain FeCl3 solution.

[0064] (2) Under mechanical stirring conditions, 6 μL of 1.0 mol / L FeCl3 solution was added to the above GO dispersion, mechanically stirred for 10 min, and ultrasonically dispersed (200W) in an ice-water bath for 5 min to obtain Fe-S-GO dispersion.

[0065] The prepared Fe-S-GO dispersion was assembled into a Fe-S-GO membrane using vacuum filtration. After the water on top of the membrane was removed, the membrane was removed from the filtration device, placed in a petri dish, and dried in a constant temperature and humidity chamber at 25.0 °C and 15% RH for 12 hours. This membrane, named the Fe-S-GO membrane, had a thickness of 0.9 μm. Inductively coupled plasma atomic emission spectrometry (ICP-OES) data showed that Fe... 3+ The content was 5.8 μmol, with a mass percentage of 11 wt%; X-ray diffraction data showed that the interlayer spacing of the Fe-S-GO film in acetonitrile solution was approximately 10.0 Å.

[0066] (3) The Fe-S-GO membrane was used as a catalyst to catalyze the reaction of 4-hydroxybenzaldehyde and 4-(4-aminophenyl)morpholine to generate antibacterial compound I. The specific operation was as follows: The Fe-S-GO membrane was purged with nitrogen to remove surface dust. Then, a smooth part was selected and cut into a regular octagon (side length 0.8 cm). It was purged with nitrogen again, fixed and fitted with a sealing gasket to ensure that it was sealed in the microfiltration device. The reaction solution was then prepared: 2 mmol of 4-hydroxybenzaldehyde and 2 mmol of 4-(4-aminophenyl)morpholine were dissolved in 25 mL of acetonitrile to prepare the reaction solution, which was prepared fresh for use. 15 mL of the above reaction solution was added above the microfiltration device. Driven by a pressure difference (~0.9 atm), the reaction solution passed through the two-dimensional nano-confined channel between the layers of the Fe-S-GO membrane reactor. The reactants reacted between the layers, and the products flowed out with the acetonitrile solvent. 1 The components were analyzed by H NMR spectroscopy, and the reaction conversion rate was calculated. The reaction results showed that the reaction temperature was 22.3 ± 0.1 ℃, the residence time of the reactants was about 7 s, and the conversion rate was 96%.

[0067] Example 2 The other procedures were the same as in Example 1, except that 2 mmol of 4-hydroxybenzaldehyde was replaced with 2 mmol of 3-methoxy-4-hydroxybenzaldehyde to catalyze the reaction of 3-methoxy-4-hydroxybenzaldehyde and 4-(4-aminophenyl)morpholine to generate antibacterial compound II. The reaction results showed that the reaction temperature was 22.3 ± 0.1 °C, the reactant residence time was approximately 16 s, and the conversion rate was 94%.

[0068] Example 3 The other procedures were the same as in Example 1, except that 2 mmol of 4-hydroxybenzaldehyde was replaced with 2 mmol of 3,4-dimethoxybenzaldehyde to catalyze the reaction of 3,4-dimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine to generate antibacterial compound III. The reaction results showed that the reaction temperature was 22.3 ± 0.1 °C, the reactant residence time was approximately 20 s, and the conversion rate was 96%.

[0069] Example 4 The other procedures were the same as in Example 1, except that 2 mmol of 4-hydroxybenzaldehyde was replaced with 2 mmol of 3,4,5-trimethoxybenzaldehyde to catalyze the reaction of 3,4,5-trimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine to generate antibacterial compound IV. The reaction results showed that the reaction temperature was 22.3 ± 0.1 °C, the reactant residence time was approximately 28 s, and the conversion rate was 98%.

[0070] Comparative Example 1 The other operations are the same as in Example 4, except that the catalyst used is a GO membrane, which is prepared by the following method: (1) Preparation of 0.075 mg / mL GO dispersion: Take 3 mg of GO in 40 mL of deionized water, stir mechanically for 10 min, and disperse by ultrasonication (200W) in an ice water bath for 5 min to obtain GO dispersion.

[0071] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was dried, the membrane was removed from the filtration device, placed in a petri dish, and dried in a constant temperature and humidity chamber at 25.0 °C and 15%RH for 12 hours. The membrane was then taken out for use and named as a GO membrane with a thickness of 0.8 μm. X-ray diffraction data showed that the interlayer spacing of the GO membrane in the acetonitrile solution was about 11.2 Å.

[0072] The reaction results showed that the reaction temperature was 22.3 ± 0.1 ℃, the reactant residence time was about 15 s, and the conversion rate was 87%.

[0073] Comparative Example 2 The other operations are the same as in Example 4, except that the catalyst used is an Fe-S-GO-I membrane, which is prepared by the following method: (1) Preparation of 0.075 mg / mL GO dispersion: Take 3 mg of GO into 40 mL of deionized water, stir mechanically for 10 min, and disperse by sonication (200W) in an ice-water bath for 5 min to obtain GO dispersion; Preparation of 1.0 mol / L FeCl3 solution: Weigh 6488 mg of FeCl3, add it to 40 mL of deionized water, add two drops of concentrated hydrochloric acid, stir mechanically for 10 min to obtain FeCl3 solution.

[0074] (2) Under mechanical stirring conditions, 16 μL of 1.0 mol / L FeCl3 solution was added to the above GO dispersion, mechanically stirred for 10 min, and ultrasonically dispersed (200W) in an ice-water bath for 5 min to obtain a brown clustered Fe-S-GO dispersion.

[0075] The prepared Fe-S-GO dispersion was assembled into a Fe-S-GO-I membrane using vacuum filtration. After the water on top of the membrane was removed, the membrane was removed from the filtration device, placed in a petri dish, and dried in a constant temperature and humidity chamber at 25.0 °C and 15% RH for 12 hours. This membrane, named Fe-S-GO-I, exhibited uneven thickness. Inductively coupled plasma atomic emission spectrometry (ICP-OES) data indicated that Fe... 3+ The content was 11.2 μmol, accounting for 21 wt% by mass. X-ray diffraction data showed that the Fe-S-GO-I film did not have obvious crystal diffraction peaks in acetonitrile solution. This was because the content of transition metal ions was too high, causing the transition metals to be deposited on the surface of graphene oxide in the form of clusters.

[0076] The reaction results showed that the reaction temperature was 22.3 ± 0.1 ℃ and the conversion rate was 18%. This was mainly because the excessive content of transition metal ions caused the membrane structure to be damaged (such as the appearance of multiple irregular structures), resulting in most of the reaction solution directly leaking through the membrane reactor and failing to effectively catalyze the reaction.

[0077] Comparative Example 3 The other operations are the same as in Example 4, except that the catalyst used is an Fe-S-GO-II membrane, which is prepared by the following method: (1) Prepare a 5 mg / mL GO dispersion: Take 100 mg of GO into 20 mL of deionized water, stir mechanically for 10 min, and disperse by sonication (200W) in an ice-water bath for 5 min to obtain a GO dispersion; Prepare a 1.0 mol / L FeCl3 solution: Weigh 6488 mg of FeCl3, add it to 40 mL of deionized water, add two drops of concentrated hydrochloric acid, stir mechanically for 10 min to obtain a FeCl3 solution.

[0078] (2) Under mechanical stirring conditions, 6 μL of 1.0 mol / L FeCl3 solution was added to the above GO dispersion, mechanically stirred for 10 min, and ultrasonically dispersed (200W) in an ice-water bath for 5 min to obtain Fe-S-GO dispersion.

[0079] The prepared Fe-S-GO dispersion was assembled into a Fe-S-GO-II membrane using vacuum filtration. After the water on top of the membrane was removed, the membrane was removed from the filtration device, placed in a petri dish, and dried in a constant temperature and humidity chamber at 25.0 °C and 15% RH for 12 hours. The membrane was then removed for use and named Fe-S-GO-II, with a thickness of 28 μm. Inductively coupled plasma atomic emission spectrometry (ICP-OES) data showed that Fe... 3+The content was 5.9 μmol, and the mass percentage was 0.33 wt%. X-ray diffraction data showed that the interlayer spacing of the Fe-S-GO-II film in acetonitrile solution was approximately 10.9 Å.

[0080] The reaction results showed that, due to the excessive thickness of the Fe-S-GO-II membrane reactor, the collected product did not reach the required level. 1 The detection limit of H NMR makes it impossible to calculate the conversion rate. This is mainly because an excessively thick transition metal ion-doped graphene oxide film catalyst will significantly reduce the flow rate of the reaction solution and easily introduce too many defects during the preparation process, reducing the orderliness of the two-dimensional confinement space provided by the catalyst for the reactant molecules. This significantly reduces the efficiency of catalyzing the reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize 4-phenylmorpholine antibacterial derivatives.

[0081] Comparative Example 4 A reaction solution was prepared by dissolving 2 mmol of 3,4,5-trimethoxybenzaldehyde and 2 mmol of 4-(4-aminophenyl)morpholine in 15 mL of acetonitrile. 3 mg of GO powder (GO powder as catalyst) was added to the reaction solution, and the mixture was mechanically stirred. 24 hours after the start of the reaction, 1 mL of the solution was taken as the test sample. 1 The components were analyzed by 1H NMR spectroscopy, and the reaction conversion rate was calculated. The reaction results showed that the reaction temperature was 22.3 ± 0.1 ℃, the reaction time was about 24 hours, and the conversion rate was 49%.

[0082] Comparative Example 5 A reaction solution was prepared by dissolving 2 mmol of 3,4,5-trimethoxybenzaldehyde and 2 mmol of 4-(4-aminophenyl)morpholine in 15 mL of acetonitrile. 3 mg of GO powder and 5.8 μmol of FeCl3 (GO-Fe powder as catalyst) were added to the reaction solution, and the mixture was mechanically stirred. 24 hours after the start of the reaction, 1 mL of the reaction solution was taken as a test sample. 1 The components were analyzed by H NMR spectroscopy, and the reaction conversion rate was calculated. The reaction results showed that the reaction temperature was 22.3 ± 0.1 ℃, the reaction time was about 24 hours, and the conversion rate was 46%.

[0083] The conversion rate obtained in Comparative Example 5 was not as high as that in Comparative Example 4. This is mainly because the adsorption of iron ions by GO powder will cause GO agglomeration, which will reduce the number of catalytic sites and thus reduce the catalytic effect within the same time.

[0084] Example 5 Using the Fe-S-GO membrane prepared in Example 4 as a catalyst, a continuous long-term flow catalysis was performed to catalyze the reaction of 3,4,5-trimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine to generate antibacterial compound IV. The flux was monitored, and the specific operation was as follows: The Fe-S-GO membrane was purged with nitrogen to remove surface dust. Then, a smooth section was selected and cut into a regular octagon (side length 0.8 cm). It was purged with nitrogen again, fixed, and fitted with a sealing gasket to ensure it was sealed in the microfiltration device. The reaction solution was then prepared: 2 mmol of 3,4,5-trimethoxybenzaldehyde and 2 mmol of 4-(4-aminophenyl)morpholine were dissolved in 25 mL of acetonitrile. The solution was prepared fresh for each use. 15 mL of the above reaction solution was added above the microfiltration device. Driven by a pressure difference (~0.9 atm), the reaction solution passed through the two-dimensional nano-confined channels between the layers of the Fe-S-GO membrane reactor. The reactants reacted between the layers, and the products flowed out with the acetonitrile solvent. 1 The components were analyzed by H NMR spectroscopy, and the reaction conversion rate was calculated. The reaction temperature was 22.3 ± 0.1 ℃. The reaction was carried out for 4 hours, 8 hours, 12 hours, 24 hours, 36 hours, 48 ​​hours, 72 hours, 96 hours, and 120 hours, and the volume reduction of the reaction solution was recorded. The flux of the reaction solution to the membrane catalyst was calculated.

[0085] The reaction results showed that after 120 hours of continuous reaction, the flux of the reaction solution to the membrane catalyst remained stable, and the conversion rate remained stable at over 95%. When the Fe-S-GO membrane was removed for observation, the membrane was in good condition and the surface was smooth.

[0086] Comparative Example 6 (1) Prepare a 0.075 mg / mL GO dispersion: Take 3 mg of GO and add it to 40 mL of deionized water. Stir mechanically for 10 min and disperse in an ice-water bath by sonication (200W) for 5 min to obtain a GO dispersion; Prepare a 0.9 mol / L MgCl2 solution: Weigh 3416 mg of MgCl2 and add it to 40 mL of deionized water. Stir mechanically for 10 min to obtain a MgCl2 solution.

[0087] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was removed, the membrane was removed from the filtration device and immersed in 10 mL of 0.9 mol / L MgCl2 solution for 4 hours. After removal, the surface was rinsed with deionized water, placed in a petri dish, and dried in a constant temperature and humidity chamber at 25.0 ℃ and 15%RH for 12 hours. The membrane was then taken out for use and named Mg-GO-0.9 M-4 h with a thickness of 1.2 μm. Inductively coupled plasma optical emission spectroscopy (ICP-OES) data showed that the Mg in the Mg-GO-0.9 M-4 h membrane was 1.2 μm thick. 2+The content was 9.5 μmol, and the mass percentage was 7.7 wt%. X-ray diffraction data showed that the interlayer spacing of the Mg-GO-0.9 M-4 h film in acetonitrile solution was approximately 12.4 Å.

[0088] (3) Using a Mg-GO-0.9 M-4 h membrane as a catalyst, the reaction of 3,4,5-trimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine to generate antibacterial compound IV was continuously and for a long time. The flux was monitored. The specific operation was as follows: The Mg-GO-0.9 M-4 h membrane was purged with nitrogen to remove surface dust. Then, a smooth part was selected and cut into a regular octagon (side length 0.8 cm). It was purged with nitrogen again, fixed and fitted with a sealing gasket to ensure that it was sealed in the microfiltration device. Then, the reaction solution was prepared: 2 mmol of 3,4,5-trimethoxybenzaldehyde and 2 mmol of 4-(4-aminophenyl)morpholine were dissolved in 25 mL of acetonitrile to prepare the reaction solution. The solution was prepared fresh each time. 15 mL of the above reaction solution was added above the microfiltration device. Driven by a pressure difference (~0.9 atm), the reaction solution passed through the Mg-GO-0.9 M-4 h membrane. The h-membrane reactor features interlayer two-dimensional nano-confined channels where reactants react within the interlayer, and products flow out with acetonitrile solvent; using... 1 The components were analyzed by H NMR spectroscopy, and the reaction conversion rate was calculated. The reaction temperature was 22.3 ± 0.1 ℃. The reaction was carried out for 4 hours, 8 hours, 12 hours, 24 hours, 36 hours, 48 ​​hours, 72 hours, 96 hours, and 120 hours, and the volume reduction of the reaction solution was recorded. The flux of the reaction solution to the membrane catalyst was calculated.

[0089] The reaction results showed that the membrane flux dropped sharply after 48 hours. Upon inspection of the Mg-GO-0.9 M-4 h membrane, a large amount of residual material was observed, causing channel blockage. Swelling and bulging appeared on the membrane surface, indicating impaired membrane structural stability, thus preventing further extension of the reaction time for a sustained reaction.

[0090] Figure 1 Fe as a preferred embodiment of the present invention 3+ A schematic diagram of the preparation of ion-doped graphene oxide membrane catalytic material and the catalytic synthesis reaction of 4-phenylmorpholine antibacterial derivative.

[0091] like Figure 1As shown, firstly, transition metal salts and graphene oxide dispersions are uniformly mixed, allowing transition metal ions to be immobilized by oxygen-containing groups and graphite domains on the graphene oxide nanosheets. The concentration of the transition metal salt solution is varied to control the content of transition metal ions bound to the graphene oxide nanosheets, thus preparing a series of MS-GO dispersions. Then, the solutions are assembled into a series of MS-GO membranes with different transition metal ion contents using vacuum filtration. These MS-GO membranes are used as membrane reactors to catalyze the reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize antibacterial compounds I-IV. Driven by a pressure difference, the reaction solution permeates through the MS-GO membrane, and the aromatic aldehydes and 4-(4-aminophenyl)morpholine react within confined channels between the membrane layers. The resulting antibacterial compounds I-IV flow out with the solvent and leave the membrane system. Specifically, graphene oxide nanosheets can provide acidic catalytic sites; the interlayer nanoconfinement effect of the MS-GO membrane can reduce the degree of freedom of reactant molecules; the interlayer transition metal ions can induce their orientation and enhance their orderliness through interaction with reactant molecules, thereby improving the synthesis efficiency of antibacterial compounds I-IV. The MS-GO membrane can still achieve rapid and efficient catalytic synthesis of 4-phenylmorpholine antibacterial derivatives at room temperature after the catalytic reaction has continued for 120 hours.

[0092] Figure 2 The results show the comparative structure and catalytic performance characterization of the Fe-S-GO membrane prepared in Example 4, the GO membrane prepared in Comparative Example 1, the Fe-S-GO-I membrane prepared in Comparative Example 2, and the Mg-GO-0.9 M-4 h membrane prepared in Comparative Example 6.

[0093] like Figure 2 As shown in A, the GO film is compared with that doped with 5.8 μmol Fe. 3+ The dry and wet interlayer spacing of the Fe-S-GO film, and the decrease in the degree of swelling of the Fe-S-GO film under wet conditions, indicate that Fe... 3+ The introduction of [a certain substance] helps to enhance the stability of the membrane structure.

[0094] like Figure 2 As shown in B, 1730, 1260, and 1060 cm 1 The absorption peaks at these locations correspond to the stretching vibrations of the C=O, COC, and CO groups on the aromatic rings of graphene oxide, respectively. Compared to the GO film, the CO and C=O absorption peak intensities of Fe-S-GO decrease, indicating an interaction between oxygen-containing groups such as carboxyl groups and metal ions. Simultaneously, the doping of Fe... 3+ Afterwards, the relative intensity of the COC absorption peak decreased, indicating that Fe 3+ The introduction of [a substance] has a regulatory effect on the chemical structure within the membrane.

[0095] like Figure 2 As shown in C, the condensation reaction of 3,4,5-trimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine catalyzed by an Fe-S-GO membrane reactor is used as an example (Example 4). In the 1H NMR spectrum of the obtained product, the characteristic peak at 8.64 ppm can be attributed to the imine hydrogen signal in the target product; simultaneously, the characteristic peaks of the reactants 3,4,5-trimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine basically disappear, indicating a conversion rate of 98%. Comparing with the Fe-S-GO-I membrane reactor in Comparative Example 2, the characteristic peaks of the reactants in the product collected by the Fe-S-GO-I membrane reactor still exist, indicating a conversion rate of 18%, demonstrating that excessive loading of metal ions leads to a decrease in the catalytic effect of the membrane reactor. These results indicate that the Fe-S-GO membrane catalyst can achieve rapid and efficient synthesis of antibacterial compounds I-IV during directional flow, with a reactant residence time in the membrane of less than 30 s and a conversion rate of 90%-98%.

[0096] like Figure 2 As shown in D, in Example 5, the condensation reaction of 3,4,5-trimethoxybenzaldehyde and 4-(4-aminophenyl)morpholine was catalyzed in a Fe-S-GO membrane reactor for an extended period, and flux changes were monitored during the reaction. The results showed that the flux of the reaction solution remained stable after 120 hours. Upon removal of the Fe-S-GO membrane, the membrane was in good condition with a smooth surface, and the 1H NMR spectrum of the obtained product showed a conversion rate of over 95%. In contrast, the Mg-GO-0.9 M-4 h membrane reactor from Comparative Example 6 was used for comparison. After 48 hours of reaction, the membrane flux dropped sharply. Upon removal of the Mg-GO-0.9 M-4 h membrane, swelling and bulging were observed on the membrane surface, indicating impaired membrane structural stability, thus preventing further extension of the reaction time for continued reaction. These results demonstrate that the Fe-S-GO membrane catalyst can stably catalyze the synthesis of antibacterial compounds I-IV at room temperature for extended periods, and can be used continuously for over 120 hours with a conversion rate exceeding 90%.

[0097] In summary, this invention provides an application of transition metal ion-doped graphene oxide membrane catalytic material in the efficient catalytic synthesis of 4-phenylmorpholine antibacterial derivatives at room temperature. This transition metal ion-doped graphene oxide membrane catalytic material retains the intrinsic acidic catalytic sites of graphene oxide nanosheets while introducing transition metal ions that can induce the orientation of reactant molecules. Utilizing the two-dimensional nano-confined channels provided by the interlayer of the graphene oxide membrane and the synergistic effect between the transition metal ions and reactant molecules, rapid and long-lasting catalytic synthesis of 4-phenylmorpholine antibacterial derivatives can be achieved at room temperature (22.3 ± 0.1 ℃) under pressure-driven continuous flow reaction conditions. The residence time of reactant molecules within the membrane is less than 30 s, the reaction conversion rate can reach up to 98%, and it also helps simplify post-processing steps. More importantly, the transition metal ion-doped graphene oxide membrane catalytic material of the present invention can also achieve long-term synthesis of 4-phenylmorpholine antibacterial derivatives, that is, the transition metal ion-doped graphene oxide membrane catalytic material can still obtain a conversion rate of more than 90% of 4-(4-aminophenyl)morpholine after 120 hours of continuous reaction.

[0098] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The use of a transition metal ion-doped graphene oxide membrane catalytic material in the rapid and long-lasting catalytic reaction of aromatic aldehydes with 4-(4-aminophenyl)morpholine to synthesize 4-phenylmorpholine antibacterial derivatives at room temperature; wherein room temperature refers to a temperature range of 20-30 °C; rapid refers to a reaction time of 2-30 s; and long-lasting refers to the ability of the transition metal ion-doped graphene oxide membrane catalytic material to achieve a conversion rate of over 90% of 4-(4-aminophenyl)morpholine after 120 hours of continuous reaction; The transition metal ion-doped graphene oxide film catalytic material was prepared by the following method: (1) Add a transition metal salt to the dispersion of graphene oxide, mix ultrasonically to obtain a mixed solution; (2) The mixed solution from step (1) was assembled into a transition metal ion-doped graphene oxide membrane by vacuum filtration and then subjected to constant temperature and humidity settling treatment to prepare the transition metal ion-doped graphene oxide membrane catalytic material. In step (1), the concentration of the graphene oxide dispersion is 0.05-1.5 mg / mL; In step (1), the transition metal salt is FeCl3; In step (1), the molar mass ratio of the transition metal salt and graphene oxide is 0.01-4 μmol / 0.05-1.5 mg; In step (1), the ultrasonic mixing time is 5-15 min; the ultrasonic mixing power is 100-300 W; In step (2), the constant temperature and humidity static treatment is carried out in a constant temperature and humidity chamber, and the constant temperature and humidity static treatment is carried out at 20-30 ℃ and 10-20 %RH for 6-12 hours. The aromatic aldehyde is selected from at least one of 4-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, 3,4-dimethoxybenzaldehyde, and 3,4,5-trimethoxybenzaldehyde; The 4-phenylmorpholine antibacterial derivatives are antibacterial compounds I, II, III and IV as shown below: 。 2. The use according to claim 1, wherein, The thickness of the transition metal ion-doped graphene oxide film catalytic material is 0.5-5 μm; And / or, the interlayer spacing of the transition metal ion-doped graphene oxide film catalytic material is 9-16 Å; And / or, the mass of the transition metal ions in the transition metal ion-doped graphene oxide membrane catalytic material accounts for 0.01-15 wt% of the total mass of the membrane catalytic material.

3. The use according to claim 1, wherein, Step (2) specifically includes the following steps: 21) Lay a porous substrate in the filter cup of the vacuum filtration device; 22) Add the mixed solution from step (1) into the filter cup of 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 assemble the transition metal ion-doped graphene oxide layer by layer on the porous substrate to obtain the transition metal ion-doped graphene oxide membrane catalytic material.

4. The use according to claim 1, wherein, The method for synthesizing the 4-phenylmorpholine antibacterial derivative includes the following steps: a) Dissolve aromatic aldehyde and 4-(4-aminophenyl)morpholine in an organic solvent to obtain a reaction solution; b) At room temperature, the reaction solution from step a) is passed through the transition metal ion-doped graphene oxide membrane catalytic material via a pressure difference to prepare a 4-phenylmorpholine antibacterial derivative.

5. A method for synthesizing a 4-phenylmorpholine antibacterial derivative, the method comprising the following steps: a) Dissolve aromatic aldehyde and 4-(4-aminophenyl)morpholine in an organic solvent to obtain a reaction solution; b) At room temperature, the reaction solution from step a) is passed through a transition metal ion-doped graphene oxide membrane catalytic material via a pressure difference to prepare a 4-phenylmorpholine antibacterial derivative. The aromatic aldehyde is selected from at least one of 4-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, 3,4-dimethoxybenzaldehyde, and 3,4,5-trimethoxybenzaldehyde; The 4-phenylmorpholine antibacterial derivatives are antibacterial compounds I, II, III and IV as shown below: ； The transition metal ion-doped graphene oxide film catalytic material was prepared by the following method: (1) Add a transition metal salt to the dispersion of graphene oxide, mix ultrasonically to obtain a mixed solution; (2) The mixed solution from step (1) was assembled into a transition metal ion-doped graphene oxide membrane by vacuum filtration and then subjected to constant temperature and humidity settling treatment to prepare the transition metal ion-doped graphene oxide membrane catalytic material. In step (1), the concentration of the graphene oxide dispersion is 0.05-1.5 mg / mL; In step (1), the transition metal salt is FeCl3; In step (1), the molar mass ratio of the transition metal salt and graphene oxide is 0.01-4 μmol / 0.05-1.5 mg; In step (1), the ultrasonic mixing time is 5-15 min; the ultrasonic mixing power is 100-300 W; In step (2), the constant temperature and humidity static treatment is carried out in a constant temperature and humidity chamber, and the constant temperature and humidity static treatment is carried out at 20-30 ℃ and 10-20 %RH for 6-12 hours.

6. The method according to claim 5, wherein, In step a), the molar ratio of the aromatic aldehyde to 4-(4-aminophenyl)morpholine is 1:0.9-1.2; in step a), the organic solvent is selected from acetonitrile; in step a), the concentration of the aromatic aldehyde is 0.01-5 mol / L; in step b), the reaction time is 2-30 s; in step b), the pressure difference is greater than or equal to 0.8 atm.

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