阅读说明：本技术 一种产生单线态氧的高稳定性催化膜的制备方法 (Preparation method of high-stability catalytic membrane for generating singlet oxygen ) 是由 占金华 陈聪聪 于 2019-11-21 设计创作，主要内容包括：本发明涉及一种产生单线态氧的高稳定性催化膜的制备方法,该方法包括：将g-C<Sub>3</Sub>N<Sub>4</Sub>纳米片溶于乙醇中超声得g-C<Sub>3</Sub>N<Sub>4</Sub>分散液,向g-C<Sub>3</Sub>N<Sub>4</Sub>分散液中加入Mn(AC)<Sub>2</Sub>·4H<Sub>2</Sub>O溶液,于温度140-160℃下反应1-5h,制得Mn<Sub>3</Sub>O<Sub>4</Sub>/g-C<Sub>3</Sub>N<Sub>4</Sub>复合材料；将Mn<Sub>3</Sub>O<Sub>4</Sub>/g-C<Sub>3</Sub>N<Sub>4</Sub>复合材料分散在水中,得分散液；将分散液通过抽滤方式抽滤到PTFE膜上,干燥,得Mn<Sub>3</Sub>O<Sub>4</Sub>/g-C<Sub>3</Sub>N<Sub>4</Sub>@PTFE催化膜。本发明的Mn<Sub>3</Sub>O<Sub>4</Sub>/g-C<Sub>3</Sub>N<Sub>4</Sub>@PTFE催化膜是将Mn<Sub>3</Sub>O<Sub>4</Sub>/g-C<Sub>3</Sub>N<Sub>4</Sub>复合材料分散在水中,然后抽滤到PTFE膜上制得,Mn<Sub>3</Sub>O<Sub>4</Sub>/g-C<Sub>3</Sub>N<Sub>4</Sub>复合材料提高了与膜的相容性并提高了膜的稳定性,重复使用两次后,该催化膜对污染物的降解率仍为81％,稳定性高,并且催化膜上能产生强活性的单线态氧<Sup>1</Sup>O<Sub>2</Sub>,可同时应用于抗菌领域。(The invention relates to a preparation method of a high-stability catalytic membrane for generating singlet oxygen, which comprises the following steps: g to C 3 N 4 Dissolving the nanosheet in ethanol and performing ultrasonic treatment to obtain g-C 3 N 4 Dispersion to g-C 3 N 4 Adding Mn (AC) to the dispersion 2 ·4H 2 O solution reacts for 1-5h at the temperature of 140- 3 O 4 /g‑C 3 N 4 A composite material; adding Mn 3 O 4 /g‑C 3 N 4 Dispersing the composite material in water to obtain a dispersion liquid; mixing the dispersionFiltering the solution on a PTFE membrane in a suction filtration mode, and drying to obtain Mn 3 O 4 /g‑C 3 N 4 @ PTFE catalytic membrane. Mn of the invention 3 O 4 /g‑C 3 N 4 @ PTFE catalyst film is prepared by mixing Mn 3 O 4 /g‑C 3 N 4 The composite material is dispersed in water and then is filtered on a PTFE membrane in a suction way to prepare Mn 3 O 4 /g‑C 3 N 4 The composite material improves the compatibility with the membrane and the stability of the membrane, after the composite material is repeatedly used for two times, the degradation rate of the catalytic membrane to pollutants is still 81 percent, the stability is high, and strong-activity singlet oxygen can be generated on the catalytic membrane 1 O 2 And can be simultaneously applied to the antibacterial field.)

1. A preparation method of a high-stability catalytic membrane for generating singlet oxygen comprises the following steps:

1) g to C₃N₄Dissolving the nanosheet in ethanol and performing ultrasonic treatment to obtain g-C₃N₄Dispersion to g-C₃N₄Adding Mn (AC) to the dispersion₂·4H₂Stirring the O solution for 1-3h at 60-90 ℃ to obtain a mixed solution, transferring the mixed solution into a high-temperature reaction kettle to react for 1-5h at the temperature of 140-₃O₄/g-C₃N₄A composite material;

2) adding Mn₃O₄/g-C₃N₄Dispersing the composite material in water to obtain a dispersion liquid; filtering the dispersion liquid onto PTFE membrane by suction filtration, and drying to obtain Mn₃O₄/g-C₃N₄@ PTFE catalytic membrane.

2. The method according to claim 1, wherein g-C in step 1)₃N₄The mass-volume ratio of the nanosheets to the ethanol is as follows: (100-200): (20-30) unit, mg/mL.

3. The method of claim 1The preparation method is characterized in that Mn (AC) in the step 1)₂·4H₂The concentration of the O solution is 0.1-0.5 mol/L.

4. The method according to claim 1, wherein the Mn (AC) in the step 1)₂·4H₂The volume ratio of the added O solution to the ethanol is as follows: (3-8): (20-30).

5. The method according to claim 1, wherein the stirring temperature in step 1) is 80 ℃ and the stirring time is 2 hours.

6. The preparation method of claim 1, wherein the reaction temperature of the high-temperature reaction kettle in the step 1) is 150 ℃ and the reaction time is 3 h.

7. The method according to claim 1, wherein g-C in step 1)₃N₄The nano-sheet is prepared by the following method:

putting urea in a muffle furnace, heating to 550 ℃ at the speed of 2.5-3.0 ℃/min, carrying out heat preservation treatment for 2-4h, then cooling to 500 ℃ at the speed of 2.5-3.0 ℃/min, carrying out heat preservation treatment for 2-4h, naturally cooling to room temperature to obtain light yellow g-C₃N₄Nanosheets.

8. The method according to claim 1, wherein Mn in the dispersion in the step 2) is added₃O₄/g-C₃N₄The concentration of the composite material is 0.1-0.3 g/L.

The technical field is as follows:

the invention relates to a preparation method of a high-stability catalytic membrane for generating singlet oxygen, belonging to the technical field of material preparation, environmental pollution treatment and antibiosis.

Background art:

singlet oxygen (¹O₂) Is molecular oxygen in an excited state, and is a strong oxidant; it plays an important role in catalytic oxidation similar to superoxide anion radical, hydroxyl radical and active oxygen such as hydrogen peroxide. In the application field of removing organic matters, the method is not interfered by environmental organic matters and other anions, so that the method has attracted extensive attention. Is currently generating¹O₂There are many ways in which advanced oxidation technology (AOPs) is generated by activating Peroxymonosulfate (PMS)¹O₂The technology of (2) has been widely developed. The formation of PMS activated with carbon materials, metal catalysts, organic substances (benzoquinone), bases and the like has been reported¹O_2，And is applied to removing organic pollutants.

Among these active materials, metal oxides have received significant attention due to their high catalytic activity, and oxides of manganese, which have high activity, low toxicity, high natural abundance and abundant chemical valence, and are suitable for a wide pH range, are widely used to activate PMS to degrade organic pollutants. However, most of the manganese-based catalysts developed at present are powder materials, and complicated separation procedures are required in the post-treatment process, thereby limiting the practical application thereof.

Membrane separation is one of the main methods for retaining and recovering the catalyst from the treated water. At present, researchers fix heterogeneous catalysts on a membrane to prepare a catalytic membrane, which can realize separation and recovery of the catalysts and avoid membrane pollution. However, the catalyst supported on the membrane has problems of particle aggregation, large size, and the like, thereby reducing the utilization rate of active sites.

The invention content is as follows:

aiming at the defects of the prior art, the invention provides a preparation method of a high-stability catalytic membrane for generating singlet oxygen, and the catalytic membrane prepared by the method has higher activityThe site utilization rate is high, the recovery utilization rate is high, and strong active singlet oxygen can be generated¹O₂Is not affected by inorganic anions and can be simultaneously applied to the antibacterial field.

The invention is realized by the following technical scheme:

a preparation method of a high-stability catalytic membrane for generating singlet oxygen comprises the following steps:

1) g to C₃N₄Dissolving the nanosheet in ethanol and performing ultrasonic treatment to obtain g-C₃N₄Dispersion to g-C₃N₄Adding Mn (AC) to the dispersion₂·4H₂Stirring the O solution for 1-3h at 60-90 ℃ to obtain a mixed solution, transferring the mixed solution into a high-temperature reaction kettle to react for 1-5h at the temperature of 140-₃O₄/g-C₃N₄A composite material;

2) adding Mn₃O₄/g-C₃N₄Dispersing the composite material in water to obtain a dispersion liquid; filtering the dispersion liquid onto PTFE membrane by suction filtration, and drying to obtain Mn₃O₄/g-C₃N₄@ PTFE catalytic membrane.

Preferred according to the invention, g to C in step 1)₃N₄The mass-volume ratio of the nanosheets to the ethanol is as follows: (100-200): (20-30) unit, mg/mL.

Preferred according to the invention is Mn (AC) in step 1)₂·4H₂The concentration of the O solution is 0.1-0.5 mol/L.

Preferred according to the invention is Mn (AC) in step 1)₂·4H₂The volume ratio of the added O solution to the ethanol is as follows: (3-8): (20-30).

According to the invention, the stirring temperature in step 1) is preferably 80 ℃ and the stirring time is preferably 2 h.

According to the invention, the reaction temperature of the high-temperature reaction kettle in the step 1) is preferably 150 ℃, and the reaction time is preferably 3 hours.

Preferred according to the invention, g to C in step 1)₃N₄The nano-sheet is prepared by the following method:

putting urea in a muffle furnace, heating to 550 ℃ at the speed of 2.5-3.0 ℃/min, carrying out heat preservation treatment for 2-4h, then cooling to 500 ℃ at the speed of 2.5-3.0 ℃/min, carrying out heat preservation treatment for 2-4h, naturally cooling to room temperature to obtain light yellow g-C₃N₄Nanosheets.

Preferably, according to the invention, Mn is present in the dispersion in step 2)₃O₄/g-C₃N₄The concentration of the composite material is 0.1-0.3 g/L.

The principle of the invention is that g-C is utilized in the synthesis process₃N₄The cavity structure on the surface of the nano sheet limits Mn₃O₄Growth of seed crystals to immobilize Mn₃O₄Nanoparticles to prevent aggregation of the particles, and then further enhance g-C by solvothermal methods₃N₄Nanosheet and Mn₃O₄Of between g and C₃N₄Highly dispersed Mn is obtained on the surface of the nanosheet₃O₄Granules, while using g-C₃N₄The triangular pore structure enables the catalyst to permeate small molecules such as water and the like, and leaves large molecules, thereby providing a material for the subsequent preparation of a high-activity catalytic membrane; by means of g-C₃N₄Nanosheets of Mn₃O₄The ultra-small size nanoparticles (5-10nm) are attached to the PTFE membrane (pore diameter of 0.22mm) and do not agglomerate, thus the active sites on the surface can be effectively utilized.

The invention has the advantages and characteristics that:

1. mn of the invention₃O₄/g-C₃N₄@ PTFE catalyst film is prepared by mixing Mn₃O₄/g-C₃N₄The composite material is dispersed in water and then is filtered on a PTFE membrane in a suction way to prepare Mn₃O₄/g-C₃N₄The composite material improves the compatibility with the membrane and the stability of the membrane, and after the composite material is repeatedly used for two times, the degradation rate of the catalytic membrane to pollutants is still 81 percent, and the stability is high.

2. Mn of the invention₃O₄/g-C₃N₄@ PTFE catalytic membrane has a highThe activity is high, the PMS can be efficiently activated, and the recovery is convenient without polluting water.

3. Mn of the invention₃O₄/g-C₃N₄@ Mn on PTFE catalytic Membrane₃O₄/g-C₃N₄Composite material g-C₃N₄Nanosheet of Mn₃O₄The ultra-small size nanoparticles (5-10nm) are attached to the PTFE membrane (the aperture is 0.22mm) and do not agglomerate, and the immobilized nanoparticles provide active sites for reaction, thereby achieving a good effect on degrading pollutants.

4. Mn of the invention₃O₄/g-C₃N₄@ PTFE catalytic membrane capable of generating strong-activity singlet oxygen¹O₂And can be simultaneously applied to the antibacterial field.

Drawings

FIG. 1 shows g-C₃N₄Nanosheet (CNNS), Mn₃O₄Mn of example 1₃O₄/g-C₃N₄Mn of-100, example 2₃O₄/g-C₃N₄Mn of-150, example 3₃O₄/g-C₃N₄-XRD pattern of 200 composite.

FIG. 2 shows g-C₃N₄Nanosheet (CNNS), Mn₃O₄Mn of example 1₃O₄/g-C₃N₄Mn of-100, example 2₃O₄/g-C₃N₄Mn of-150, example 3₃O₄/g-C₃N₄-degradation profile of composite activation PMS versus 4-CP of 200.

FIG. 3 shows Mn in example 2₃O₄/g-C₃N₄-TEM image of 150 composite material.

FIG. 4 shows Mn in example 2₃O₄/g-C₃N₄SEM image of @ PTFE catalytic membrane.

FIG. 5 shows Mn in example 2₃O₄/g-C₃N₄Comparison of catalytic performances of @ PTFE catalytic membrane on different pollutants such as tetrachlorophenol, bisphenol A and rhodamine B。

FIG. 6 shows Mn in example 2₃O₄/g-C₃N₄@ PTFE catalytic membrane's cyclic performance.

FIG. 7 shows Mn in example 2₃O₄/g-C₃N₄@ PTFE catalytic membrane activated PMS to generate singlet oxygen¹O₂The detection result chart of (1).

The specific implementation mode is as follows:

in order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific examples, but not limited thereto, and the present invention is not described in detail, and is implemented by the conventional techniques in the art