阅读说明：本技术 一种N掺杂TiO2-Ag3PO4的纤维素复合抗菌薄膜及其制法 (N-doped TiO2-Ag3PO4Cellulose composite antibacterial film and preparation method thereof ) 是由 吴飞 于 2020-06-03 设计创作，主要内容包括：本发明涉及抗菌纤维素膜技术领域,且公开了一种N掺杂TiO<Sub>2</Sub>-Ag<Sub>3</Sub>PO<Sub>4</Sub>的纤维素复合抗菌薄膜,包括以下配方原料及组分：N掺杂TiO<Sub>2</Sub>-Ag<Sub>3</Sub>PO<Sub>4</Sub>复合抗菌剂、羧甲基纤维素、明胶、丙三醇。该一种N掺杂TiO<Sub>2</Sub>-Ag<Sub>3</Sub>PO<Sub>4</Sub>的纤维素复合抗菌薄膜,超薄的N掺杂TiO<Sub>2</Sub>纳米片通过剥离、卷曲形成比表面积更大的N掺杂TiO<Sub>2</Sub>纳米管,N掺杂降低了TiO<Sub>2</Sub>的带隙,促进光吸收边发生红移,并且N掺杂在TiO<Sub>2</Sub>的禁带中间中形成杂质能级,抑制光生电子和进行的重组和复合,提高了N掺杂TiO<Sub>2</Sub>纳米管可见光光催化抗菌活性,Ag<Sub>3</Sub>PO<Sub>4</Sub>纳米球均匀生长在N掺杂TiO<Sub>2</Sub>纳米管的表面和内壁中,两者之间形成异质结结构,减少了光生电子和空穴的重组,赋予了材料优异的光催化抗菌和接触性抗菌性能。(The invention relates to the technical field of antibacterial cellulose membranes and discloses N-doped TiO 2 ‑Ag 3 PO 4 The cellulose composite antibacterial film comprises the following formula raw materials and components: n-doped TiO 2 ‑Ag 3 PO 4 Composite antibacterial agent, carboxymethyl cellulose, gelatin and glycerol. The N-doped TiO 2 ‑Ag 3 PO 4 The cellulose composite antibacterial film is ultrathin N-doped TiO 2 The nano-sheet is stripped and curled to form N-doped TiO with larger specific surface area 2 Nanotube, N doping reduces TiO 2 Promotes the red shift of the light absorption edge, and N is doped in TiO 2 The impurity energy level is formed in the middle of the forbidden band, the photoproduction electrons are inhibited, the recombination and the recombination are carried out, and the N-doped TiO is improved 2 Nanotube visible light photocatalytic antibacterial activity, Ag 3 PO 4 The nanospheres are uniformly grown on the N-doped TiO 2 A heterojunction structure is formed between the surface and the inner wall of the nanotube, so that recombination of photo-generated electrons and holes is reduced, and excellent photocatalytic antibacterial and contact antibacterial properties are given to the material.)

1. N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film comprises the following raw materials and components, and is characterized in that: n-doped TiO₂-Ag₃PO₄The composite antibacterial agent, the carboxymethyl cellulose, the gel and the plasticizer are mixed according to a mass ratio of 0.5-4:100:1-4: 5-10.

2. An N-doped TiO according to claim 1₂-Ag₃PO₄The cellulose composite antibacterial film is characterized in that: the gel is gelatin, and the plasticizer is glycerol.

3. An N-doped TiO according to claim 1₂-Ag₃PO₄The cellulose composite antibacterial film is characterized in that: the N-doped TiO₂-Ag₃PO₄The preparation method of the cellulose composite antibacterial film comprises the following steps:

(1) adding titanium tetrachloride into concentrated hydrochloric acid, dropwise adding an ethanol solution of a surfactant P123, adding an ethylene glycol solvent, adjusting the pH value of the solution to 1-2, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a reaction kettle heating device, heating to 140 ℃ and 160 ℃, reacting for 18-24 hours, filtering, washing and drying to prepare TiO₂Nanosheets;

(2) adding TiO into distilled water solvent₂Uniformly dispersing the nanosheets and urea by ultrasonic, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a heating device of the reaction kettle, and heating the hydrothermal reaction kettle to 150-Drying in vacuum for 10-15h to remove the solvent, placing the solid mixed product in a resistance furnace, heating to 450-550 ℃, and performing heat preservation and calcination for 2-3h to obtain the N-doped TiO₂Nanosheets;

(3) adding N-doped TiO into concentrated sodium hydroxide solution with the mass fraction of 30-40%₂Dispersing the nano-sheets by ultrasonic and stirring uniformly, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating device, heating to 100-90 ℃ for reaction for 20-30h, centrifugally separating and washing, placing the solid product into a resistance furnace, heating to 380-450 ℃, and performing heat preservation and calcination for 2-3h to prepare the N-doped TiO₂A nanotube;

(4) adding N-doped TiO into distilled water solvent₂Dispersing nanotube, polyvinylpyrrolidone and silver nitrate by ultrasonic, stirring at constant speed for 4-10h, slowly dripping sodium dihydrogen phosphate water solution, reacting at room temperature for 2-5h, filtering, washing and drying to obtain N-doped TiO₂Nanotube loaded Ag₃PO₄Nanospheres as N-doped TiO₂-Ag₃PO₄A composite antimicrobial agent;

(5) adding carboxymethyl cellulose and N-doped TiO into distilled water solvent₂-Ag₃PO₄Ultrasonically dispersing and uniformly stirring a composite antibacterial agent, adding gelatin as a gelling agent and glycerol as a plasticizer, heating to 70-80 ℃, uniformly stirring for 3-8h, standing in a water bath for 2-4h to form a sol, carrying out vacuum defoaming, tape casting and drying to form a film, and preparing the N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film.

4. An N-doped TiO according to claim 3₂-Ag₃PO₄The cellulose composite antibacterial film is characterized in that: the mass ratio of the titanium tetrachloride to the surfactant P123 in the step (1) is 15-30: 10.

5. An N-doped TiO according to claim 3₂-Ag₃PO₄The cellulose composite antibacterial film is characterized in that: the reaction kettle heating device in the step (1) comprises a rotating device which is rotatably arrangedThe device is characterized in that a rotating shaft is movably connected, a rotating disc is fixedly connected with the rotating shaft, a hydrothermal reaction kettle is arranged above the rotating disc, a clamping groove is formed in the upper surface of the rotating disc, a clamping ring is movably connected with the clamping groove, a baffle is fixedly connected with the clamping ring, a pulley is movably connected with the rotating disc, and a fixing block is movably connected with the pulley.

6. An N-doped TiO according to claim 3₂-Ag₃PO₄The cellulose composite antibacterial film is characterized in that: TiO in the step (2)₂The mass ratio of the nano-sheets to the urea is 10: 15-25.

7. An N-doped TiO according to claim 3₂-Ag₃PO₄The cellulose composite antibacterial film is characterized in that: the N-doped TiO in the step (4)₂The mass ratio of the nanotube, the polyvinylpyrrolidone, the silver nitrate and the sodium dihydrogen phosphate is 30-60:40-60:10: 3-5.

Technical Field

The invention relates to the technical field of antibacterial cellulose membranes, in particular to N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film and the preparation method thereof.

Background

Carboxymethyl cellulose is an anionic cellulose ether compound obtained by carboxymethylation of cellulose, has the advantages of safety, no toxicity, good film-forming property, biodegradability and the like, and is widely used in fresh-keeping and packaging materials of meat products, eggs, fruits and vegetables and the like, so that the antibacterial property of the carboxymethyl cellulose material is further improved.

The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms, and has a very wide application prospect in the fields of medical treatment, household products, household appliances, food packaging and the like.

Titanium dioxide is the most commonly used photocatalytic antibacterial agent at present, under the irradiation of ultraviolet light, photoproduction electrons and cavities can be generated, hydroxyl radicals and active oxygen ions are further generated with water and oxygen, the active oxygen ions have strong oxidizability, biological macromolecules such as enzymes in bacteria can be damaged, the growth and the reproduction of bacteria can be inhibited, and the antibacterial aim is achieved.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film and the preparation method thereof solve the problem of low antibacterial performance of carboxymethyl cellulose film materials and the problem of limited photocatalytic antibacterial activity of titanium dioxide.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: n-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film comprises the following raw materials and components: n-doped TiO₂-Ag₃PO₄The composite antibacterial agent, the carboxymethyl cellulose, the gel and the plasticizer are mixed according to a mass ratio of 0.5-4:100:1-4: 5-10.

Preferably, the gel is gelatin, and the plasticizer is glycerol.

Preferably, the N-doped TiO₂-Ag₃PO₄The preparation method of the cellulose composite antibacterial film comprises the following steps:

(1) adding concentrated hydrochloric acid and titanium tetrachloride into a reaction bottle, slowly dropwise adding an ethanol solution containing a surfactant P123, uniformly stirring, adding an ethylene glycol solvent, adjusting the pH value of the solution to be 1-2, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a reaction kettle heating device, heating to 140-160 ℃, reacting for 18-24 hours, filtering the solution to remove the solvent, washing a precipitate product with ethanol, and drying to prepare TiO₂Nanosheets.

(2) Adding distilled water solvent and TiO into a reaction bottle₂Uniformly dispersing the nanosheets and urea by ultrasonic, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating device, heating to 150 ℃ for 180 ℃ for reaction for 10-15h, drying the solution in vacuum to remove the solvent, placing the solid mixed product into a resistance furnace, heating to 450 ℃ for 550 ℃, preserving heat and calcining for 2-3h to prepare the N-doped TiO₂Nanosheets.

(3) Adding 30-40% by mass of concentrated sodium hydroxide solution and N-doped TiO into a reaction bottle₂Nanosheets, ultrasoundDispersing and uniformly stirring, pouring the solution into a hydrothermal reaction kettle, placing the reaction kettle in a heating device of the reaction kettle, heating to 100-120 ℃, reacting for 20-30h, centrifugally separating to remove the solvent, washing the solid product with dilute hydrochloric acid and distilled water until the solid product is neutral, placing the solid product in a resistance furnace, heating to 380-450 ℃, and performing heat preservation and calcination for 2-3h to prepare the N-doped TiO₂A nanotube.

(4) Adding distilled water solvent and N-doped TiO into a reaction bottle₂Dispersing nanotube, polyvinylpyrrolidone and silver nitrate by ultrasonic, stirring at constant speed for 4-10h, slowly dropwise adding sodium dihydrogen phosphate water solution, reacting at room temperature for 2-5h, filtering, washing and drying the solution to obtain N-doped TiO₂Nanotube loaded Ag₃PO₄Nanospheres as N-doped TiO₂-Ag₃PO₄A composite antibacterial agent.

(5) Adding distilled water solvent, carboxymethyl cellulose and N-doped TiO into a reaction bottle₂-Ag₃PO₄Ultrasonically dispersing and uniformly stirring a composite antibacterial agent, adding gelatin as a gelling agent and glycerol as a plasticizer, placing the mixture in a constant-temperature water bath kettle, heating to 70-80 ℃, uniformly stirring for 3-8h, standing in a water bath for 2-4h to form a sol, carrying out vacuum defoaming, tape casting and drying on the sol to form a film, and preparing the N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film.

Preferably, the mass ratio of the titanium tetrachloride to the surfactant P123 in the step (1) is 15-30: 10.

Preferably, the reaction kettle heating device in the step (1) comprises a rotating device, the rotating device is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating disk, a hydrothermal reaction kettle is arranged above the rotating disk, a clamping groove is formed in the upper surface of the rotating disk, a clamping ring is movably connected with the clamping ring, a baffle is fixedly connected with the clamping ring, a pulley is movably connected with the rotating disk, and a fixing block is movably connected with the pulley.

Preferably, TiO in the step (2)₂The mass ratio of the nano-sheets to the urea is 10: 15-25.

Preferably, the N-doped TiO in the step (4)₂Nanotube and polyvinylpyrrolidoneThe mass ratio of the silver nitrate to the sodium dihydrogen phosphate is 30-60:40-60:10: 3-5.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film takes P123 as a surfactant, and generates ultrathin TiO in an ethylene glycol system by a high-temperature hot solvent method₂Nano-sheet, then using urea as nitrogen source to prepare N-doped TiO₂Nano-plate is thermally treated by high-temperature water to obtain ultra-thin N-doped TiO₂Stripping and curling nanosheets to form N-doped TiO with larger specific surface area₂Nanotubes, N-doping replacing TiO₂Partial crystal lattice of O reduces TiO₂The band gap of (2) promotes the red shift of the light absorption edge, so that the N-doped TiO₂The nanotubes also have good light absorption and photochemical activity in the visible region, and N is doped in TiO₂The impurity energy level is formed in the middle of the forbidden band, and electrons on a conduction band can be captured, so that the photoproduction electrons are inhibited, and recombination are carried out, thereby improving the N-doped TiO₂The nano-tube has visible light photocatalysis antibacterial activity.

The N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film is prepared by uniformly depositing polyvinylpyrrolidone on N-doped TiO₂Re-adsorbing Ag on the surface and inner wall of nanotube⁺Make Ag be₃PO₄The nanospheres are uniformly grown on the N-doped TiO₂A heterojunction structure is formed between the surface and the inner wall of the nanotube, and the generated built-in electric field promotes Ag₃PO₄TiO is doped into N by holes generated by nanosphere valence band₂The valence band of the nanotube migrates while electrons remain in Ag₃PO₄The conduction band and the heterojunction structure of the nanosphere effectively promote the separation of the photo-generated electrons and the holes, further reduce the recombination of the photo-generated electrons and the holes, and dope TiO with N₂Nanotube loaded Ag₃PO₄The nano-sphere heterojunction is used as a composite antibacterial agent, is added into a carboxymethyl cellulose matrix, and contains trace Ag₃PO₄Decomposition to Ag⁺Also has excellent antibacterial activity, and endows the material with excellent photocatalytic antibacterial and contact antibacterial properties.

Drawings

FIG. 1 is a schematic front view of a reactor heating apparatus;

FIG. 2 is an enlarged schematic view of the baffle;

fig. 3 is a schematic view of damper adjustment.

1-a reaction kettle heating device; 2-a rotating device; 3-a rotating shaft; 4-rotating the disc; 5-hydrothermal reaction kettle; 6-a clamping groove; 7-a snap ring; 8-a baffle plate; 9-a pulley; and 10, fixing blocks.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: n-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film comprises the following raw materials and components: n-doped TiO₂-Ag₃PO₄The composite antibacterial agent, the carboxymethyl cellulose, the gel and the plasticizer are mixed according to a mass ratio of 0.5-4:100:1-4:5-10, the gel is gelatin, and the plasticizer is glycerol.

N-doped TiO₂-Ag₃PO₄The preparation method of the cellulose composite antibacterial film comprises the following steps:

(1) adding concentrated hydrochloric acid and titanium tetrachloride into a reaction bottle, slowly dropwise adding an ethanol solution containing a surfactant P123, wherein the mass ratio of the titanium tetrachloride to the surfactant P123 is 15-30:10, adding an ethylene glycol solvent after uniformly stirring, adjusting the pH value of the solution to 1-2, pouring the solution into a water-feeding thermal reaction kettle, placing the solution into a reaction kettle heating device, wherein the reaction kettle heating device comprises a rotating device, the rotating device is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating disc, a hydrothermal reaction kettle is arranged above the rotating disc, a clamping groove is arranged on the upper surface of the rotating disc, the clamping groove is movably connected with a clamping ring, the clamping ring is fixedly connected with a baffle, the rotating disc is movably connected with a pulley, the pulley is movably connected with a fixed block, heating is carried out at 160 ℃ for 18-24 hours, filtering the solution to, preparation of the obtained TiO₂Nanosheets.

(2)Adding distilled water solvent into a reaction bottle, wherein the mass ratio of TiO to water solvent is 10:15-25₂Uniformly dispersing the nanosheets and urea by ultrasonic, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating device, heating to 150 ℃ for 180 ℃ for reaction for 10-15h, drying the solution in vacuum to remove the solvent, placing the solid mixed product into a resistance furnace, heating to 450 ℃ for 550 ℃, preserving heat and calcining for 2-3h to prepare the N-doped TiO₂Nanosheets.

(3) Adding 30-40% by mass of concentrated sodium hydroxide solution and N-doped TiO into a reaction bottle₂Dispersing the nanosheets by ultrasonic waves and uniformly stirring at a constant speed, pouring the solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating device, heating the hydrothermal reaction kettle to 100 ℃ for reaction for 20-30h, centrifugally separating to remove the solvent, washing the solid product to neutrality by using dilute hydrochloric acid and distilled water, placing the solid product into a resistance furnace, heating the solid product to 380 ℃ and 450 ℃, and performing heat preservation and calcination for 2-3h to prepare the N-doped TiO₂A nanotube.

(4) Adding distilled water solvent and N-doped TiO into a reaction bottle₂Dispersing nanotube, polyvinylpyrrolidone and silver nitrate by ultrasonic, stirring at constant speed for 4-10h, and slowly dripping aqueous solution of sodium dihydrogen phosphate, wherein the N is doped with TiO₂Reacting the nanotube, polyvinylpyrrolidone, silver nitrate and sodium dihydrogen phosphate at a mass ratio of 30-60:40-60:10:3-5 at room temperature for 2-5h, filtering, washing and drying the solution to obtain the N-doped TiO₂Nanotube loaded Ag₃PO₄Nanospheres as N-doped TiO₂-Ag₃PO₄A composite antibacterial agent.

(5) Adding distilled water solvent, carboxymethyl cellulose and N-doped TiO into a reaction bottle₂-Ag₃PO₄Ultrasonically dispersing and uniformly stirring a composite antibacterial agent, adding gelatin as a gelling agent and glycerol as a plasticizer, placing the mixture in a constant-temperature water bath kettle, heating to 70-80 ℃, uniformly stirring for 3-8h, standing in a water bath for 2-4h to form a sol, carrying out vacuum defoaming, tape casting and drying on the sol to form a film, and preparing the N-doped TiO₂-Ag₃PO₄The cellulose composite antibacterial film.