CN114904539A - Composite zein film and preparation method and application thereof - Google Patents

Composite zein film and preparation method and application thereof Download PDF

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CN114904539A
CN114904539A CN202210498508.3A CN202210498508A CN114904539A CN 114904539 A CN114904539 A CN 114904539A CN 202210498508 A CN202210498508 A CN 202210498508A CN 114904539 A CN114904539 A CN 114904539A
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moo
znin
zein
film
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CN114904539B (en
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施文彦
李素云
周学庆
汪沁清
董真佑
徐刚
陈文倩
唐量
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University of Shanghai for Science and Technology
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Abstract

The invention belongs to the technical field of composite materials, and discloses a composite zein film and a preparation method and application thereof. The invention firstly prepares ZnIn 2 S 4 Granulating and then preparing ZnIn 2 S 4 ‑Ag 2 MoO 4 Granulating, and then mixing ZnIn 2 S 4 ‑Ag 2 MoO 4 And (3) carrying out electrostatic spinning on the spinning solution formed by the particles and the zein solution to form the composite membrane. ZnIn of the invention 2 S 4 ‑Ag 2 MoO 4 The formation of the heterojunction structure enlarges the absorption range of visible light, reduces the recombination rate of photon-generated carriers, and increases the porosity and the specific surface area of the material, and because of the film-forming property and the excellent biocompatibility of the zein, the formed photocatalytic protein film not only has excellent photocatalytic performance, but also obtains low toxicity and convenient reusability, which has positive significance for the development of the field of photocatalysis.

Description

Composite zein film and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite zein film and a preparation method and application thereof.
Background
ZnIn as a functional ternary chalcogenide having a layered structure 2 S 4 The photocatalyst has a narrow band gap, a large specific surface area and good adsorption performance, and is an excellent visible light photocatalyst. However, the high recombination rate of photogenerated carriers and the instability in acidic solutions limit the ZnIn 2 S 4 The use of (1). To increase ZnIn 2 S 4 Photocatalytic activity and stability of Ag-based semiconductors such as AgVO 3 、Ag 2 S, etc. has been mixed with ZnIn 2 S 4 The combination forms a semiconductor-semiconductor heterojunction and improves its photocatalytic properties.
Zein is a main protein in corn endosperm, accounts for 80% of the total content of corn protein, is wide in source, is renewable, has excellent film-forming property, biocompatibility and self-assembly property, and is applied to degradable films, biological medicines, drug carriers, biological tissue scaffolds and the like at present.
Therefore, how to provide an environment-friendly photocatalytic material has important significance for realizing photocatalytic degradation of pollutants.
Disclosure of Invention
The invention aims to provide a composite zein film and a preparation method and application thereof, and solves the problems that photocatalyst powder provided by the prior art is difficult to recover and has high toxicity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a composite zein film, which comprises the following steps:
(1) reacting ZnCl 2 、InCl 3 ·4H 2 O, thioacetamide, dimethylformamide and glycerol are mixed and then react to obtain ZnIn 2 S 4 ；
(2) ZnIn is mixed with a solvent 2 S 4 And AgNO 3 Mixing the aqueous solution, and dropwise adding Na 2 MoO 4 ·2H 2 O aqueous solution, reacting in the dark to obtain ZnIn 2 S 4 -Ag 2 MoO 4 Particles;
(3) dissolving zein and ethyl cellulose in acetic acid, and adding ZnIn 2 S 4 -Ag 2 MoO 4 Granulating to obtain spinning solution;
(4) and (3) carrying out electrostatic spinning on the spinning solution to obtain the composite zein film.
Preferably, in the above method for preparing a composite zein film, ZnCl is used in step (1) 2 、InCl 3 ·4H 2 The molar volume ratio of O, thioacetamide, dimethylformamide and glycerol is 1 mmol: 1-3 mmol: 2-5 mmol: 20-35 mL: 10 mL.
Preferably, in the preparation method of the composite zein film, the reaction temperature in the step (1) is 175-185 ℃; the reaction time is 8-12 h.
Preferably, in the above method for preparing a composite zein film, AgNO in the step (2) 3 Aqueous solution and Na 2 MoO 4 ·2H 2 The volume ratio of the O aqueous solution is 1-3: 1-2; AgNO 3 AgNO in aqueous solution 3 And Na 2 MoO 4 ·2H 2 Na in O aqueous solution 2 MoO 4 ·2H 2 The molar ratio of O is 2: 1.
preferably, in the preparation method of the composite zein film, the reaction time in the step (2) is 2-4 hours.
Preferably, in the above method for preparing a composite zein film, ZnIn in the step (2) 2 S 4 -Ag 2 MoO 4 ZnIn in the particles 2 S 4 And Ag 2 MoO 4 The mass ratio of (1): 0.05 to 0.20.
Preferably, in the above method for preparing a composite zein film, in the step (3), zein, ethyl cellulose and ZnIn 2 S 4 -Ag 2 MoO 4 The mass-to-volume ratio of the particles to acetic acid was 0.5 g: 0.5 g: 0.29-0.31 g: 2-4 mL.
Preferably, in the above method for preparing a composite zein film, the conditions of electrospinning in the step (4) are as follows: the inner diameter of a nozzle of the injector is 0.60mm, and the pushing speed of the injector is 0.008-0.018 mL/min -1 The distance between a spray head of the injector and the receiver is 12-16 cm, the horizontal reciprocating movement distance of the injector is 25-35 mm, the voltage is 16-20 kV, and the receiver is an aluminum foil.
The invention also provides the composite zein film prepared by the preparation method.
The invention also provides application of the composite zein film as a photocatalytic film.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
ag selected by the invention 2 MoO 4 Band gap of 3.25eV, energy band structure and ZnIn 2 S 4 The energy bands can be well matched to form a Z-shaped heterojunction, and the formation of the heterojunction structure enlarges the absorption of visible lightThe narrow range reduces the recombination rate of photon-generated carriers and increases the porosity and the specific surface area of the material compared with the single ZnIn 2 S 4 The material and the photocatalytic performance are improved. ZnIn thanks to zein's film-forming properties and good biocompatibility 2 S 4 -Ag 2 MoO 4 The composite zein film formed by dispersing the particles in zein through electrospinning not only has excellent photocatalytic performance, but also obtains low toxicity and convenient reusability, thus having positive significance for the development of the field of photocatalysis.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below.
FIG. 1 shows ZnIn prepared in examples 1 to 3 2 S 4 -Ag 2 MoO 4 Granules and Ag prepared in comparative example 3 2 MoO 4 XRD pattern of the particles;
FIG. 2 is the ZnIn prepared in example 2 2 S 4 SEM images of Z prepared in ZA-10, Z ZA-10 and comparative example 1;
wherein a is ZnIn 2 S 4 SEM picture of (1); b is an SEM image of ZA-10; c is SEM picture of Z; d is an SEM image of Z ZA-10;
FIG. 3 shows the removal results of enrofloxacin by the membrane materials prepared in examples 1-3 and comparative examples 1-2;
FIG. 4 shows the result of cyclic degradation of enrofloxacin by the membrane material prepared in example 2.
Detailed Description
The invention provides a preparation method of a composite zein film, which comprises the following steps:
(1) reacting ZnCl 2 、InCl 3 ·4H 2 O, thioacetamide, dimethylformamide and glycerol are mixed and then react to obtain ZnIn 2 S 4 ；
(2) ZnIn is mixed with a solvent 2 S 4 And AgNO 3 Mixing the aqueous solution, and adding Na dropwise 2 MoO 4 ·2H 2 O aqueous solution, reacting in the dark to obtain ZnIn 2 S 4 -Ag 2 MoO 4 Particles;
(3) dissolving zein and ethyl cellulose in acetic acid, and adding ZnIn 2 S 4 -Ag 2 MoO 4 Granulating to obtain spinning solution;
(4) and (3) carrying out electrostatic spinning on the spinning solution to obtain the composite zein film.
In the present invention, ZnCl is used in the step (1) 2 、InCl 3 ·4H 2 The molar volume ratio of O, thioacetamide, dimethylformamide and glycerol is preferably 1 mmol: 1-3 mmol: 2-5 mmol: 20-35 mL: 10mL, more preferably 1 mmol: 1.2-2.7 mmol: 2.3-4.5 mmol: 23-31 mL: 10mL, more preferably 1 mmol: 2.2 mmol: 3.4 mmol: 27mL of: 10 mL.
In the present invention, the method of mixing in step (1) is sonication; the time of ultrasonic treatment is preferably 1-2 h, more preferably 1.2-1.8 h, and even more preferably 1.5 h.
In the invention, the reaction temperature in the step (1) is preferably 175-185 ℃, more preferably 177-183 ℃, and more preferably 181 ℃; the reaction time is preferably 8 to 12 hours, more preferably 9 to 11 hours, and even more preferably 10 hours.
In the invention, after the reaction in the step (1) is finished, the product is centrifuged, washed and dried; the rotating speed of centrifugation is preferably 6000 to 7000r/min, more preferably 6200 to 6700r/min, and more preferably 6500 r/min; the centrifugation time is preferably 5-10 min, more preferably 6-9 min, and even more preferably 8 min; the drying temperature is preferably 55-65 ℃, more preferably 57-64 ℃, and more preferably 62 ℃; the drying time is preferably 11 to 13 hours, more preferably 12 to 13 hours, and still more preferably 12 hours.
In the present invention, AgNO in step (2) 3 Aqueous solution and Na 2 MoO 4 ·2H 2 The volume ratio of the O aqueous solution is preferably 1-3: 1-2, more preferably 1-2: 1-2, more preferably 1: 1; AgNO 3 AgNO in aqueous solution 3 And Na 2 MoO 4 ·2H 2 Na in O aqueous solution 2 MoO 4 ·2H 2 The molar ratio of O is preferably 2: 1.
in the present invention, the method of mixing in step (2) is preferably ultrasonic stirring; the time of ultrasonic stirring is preferably 0.5-1 h, more preferably 0.6-0.9 h, and even more preferably 0.8 h.
In the invention, the reaction time in the step (2) is preferably 2 to 4 hours, more preferably 2.2 to 3.5 hours, and even more preferably 3 hours.
In the present invention, ZnIn in the step (2) 2 S 4 -Ag 2 MoO 4 ZnIn in the particles 2 S 4 And Ag 2 MoO 4 Is preferably 1:0.05 to 0.20, and more preferably 1: 0.08 to 0.17, more preferably 1: 0.12.
in the invention, after the reaction in the step (2) is finished, the method also comprises the steps of centrifuging, washing and drying the product; the rotation speed of the centrifugation is preferably 8000-9000 r/min, more preferably 8100-8700 r/min, and more preferably 8300 r/min; the centrifugation time is preferably 5-10 min, more preferably 6-9 min, and even more preferably 7 min; the drying temperature is preferably 55-65 ℃, more preferably 56-64 ℃, and more preferably 59 ℃; the drying time is preferably 12 to 14 hours, more preferably 12 to 13 hours, and still more preferably 13 hours.
In the invention, in the step (3), zein, ethyl cellulose and ZnIn 2 S 4 -Ag 2 MoO 4 The mass-to-volume ratio of the particles to acetic acid is preferably 05 g: 05g of: 0.29-0.31 g: 2-4 mL, more preferably 05 g: 0.5 g: 0.29-0.3 g: 3-4 mL, more preferably 0.5 g: 0.5 g: 0.3 g: 3 mL.
In the present invention, the conditions for the electrospinning in the step (4) are preferably: the inner diameter of a nozzle of the injector is 0.60mm, and the pushing speed of the injector is 0.008-0.018 mL/min -1 The distance between a spray head of the injector and the receiver is 12-16 cm, the horizontal reciprocating distance of the injector is 25-35 mm, the voltage is 16-20 kV, and the receiver is an aluminum foil; more preferably: the inner diameter of a nozzle of the injector is 0.60mm, and the injection speed of the injector is 0.009-0.016 mL/min -1 Distance between nozzle and receiver of syringeThe distance is 13-15 cm, the horizontal reciprocating movement distance of the injector is 27-34 mm, the voltage is 17-19 kV, and the receiver is an aluminum foil; more preferably: the inner diameter of the nozzle of the injector is 0.60mm, and the injection speed of the injector is 0.014 mL/min -1 The distance between the spray head of the injector and the receiver is 14cm, the distance of the horizontal reciprocating movement of the injector is 29mm, the voltage is 18kV, and the receiver is aluminum foil.
The invention also provides the composite zein film prepared by the preparation method.
The invention also provides an application of the composite zein film as a photocatalytic film.
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The embodiment provides a composite zein film, and the preparation method comprises the following steps:
(1) 1mmol of ZnCl 2 、2mmol InCl 3 ·4H 2 Dispersing O and 4mmol thioacetamide in a mixed solution of 30mL dimethylformamide and 10mL glycerol, performing ultrasonic treatment for 1h, transferring the mixture into an autoclave with a 50mL Teflon lining, reacting at 180 ℃ for 10h, centrifuging the product at 6000r/min for 10min after the reaction is finished, washing with water for 3 times, and drying at 60 ℃ for 12h to obtain ZnIn 2 S 4 ；
(2) 0.5g of ZnIn 2 S 4 Adding 30ml of LAgNO 3 Aqueous solution (AgNO) 3 0.14mmol), ultrasonically stirring for 1h, and adding 30mL of 0.07mmol Na 2 MoO 4 ·2H 2 Reacting O water solution for 3 hours in the dark, centrifuging the product for 10 minutes at the rotating speed of 8000r/min after the reaction is finished, then washing for 3 times, and drying for 13 hours at the temperature of 60 ℃ to obtain ZnIn 2 S 4 -Ag 2 MoO 4 Particles; in which ZnIn 2 S 4 With Ag 2 MoO 4 The mass ratio of the particles is 1:0.05, and is recorded as ZA-5;
(3) dissolving 0.5g of zein and 0.5g of ethyl cellulose in 3mL of acetic acid, and then adding 0.3g of ZA-5 to obtain a spinning solution;
(4) placing the spinning solution in an injector of an electrostatic spinning device, adjusting the inner diameter of a nozzle of the injector to be 0.60mm, adjusting the distance between the nozzle of the injector and an aluminum foil receiver to be 14cm, respectively connecting the anode of a high-voltage generator and the cathode of the high-voltage receiver of the device with the nozzle of the injector and the aluminum foil, and setting the injection speed of the injector to be 0.01 mL/min -1 And carrying out electrostatic spinning with the horizontal reciprocating movement distance of 30mm and the voltage of an adjusting device of 17kV to obtain the composite zein film, and marking as Z ZA-5.
Example 2
The embodiment provides a composite zein film, and the preparation method comprises the following steps:
(1) 1mmol of ZnCl 2 、2mmol InCl 3 ·4H 2 Dispersing O and 4mmol thioacetamide in a mixed solution of 30mL dimethylformamide and 10mL glycerol, performing ultrasonic treatment for 1h, transferring the mixture into an autoclave with a 50mL Teflon lining, reacting at 180 ℃ for 10h, centrifuging the product at 6000r/min for 10min after the reaction is finished, washing with water for 3 times, and drying at 60 ℃ for 11h to obtain ZnIn 2 S 4 ；
(2) 0.5g of ZnIn 2 S 4 30mL of 0.3mmol of AgNO was added 3 Stirring the mixture in water solution for 1 hour by ultrasonic, and adding 30mL of 0.15mmol of Na 2 MoO 4 ·2H 2 Reacting O water solution for 3 hours in the dark, centrifuging the product for 10 minutes at the rotating speed of 8000r/min after the reaction is finished, then washing for 3 times, and drying for 12 hours at the temperature of 55 ℃ to obtain ZnIn 2 S 4 -Ag 2 MoO 4 Particles; in which ZnIn 2 S 4 With Ag 2 MoO 4 The mass ratio of the particles is 1:0.1, and is marked as ZA-10;
(3) dissolving 0.5g of zein and 0.5g of ethyl cellulose in 3mL of acetic acid, and then adding 0.3g of ZA-10 to obtain a spinning solution;
(4) placing the spinning solution in an injector of an electrostatic spinning device, and injectingThe inner diameter of the sprayer nozzle is 0.60mm, the distance between the sprayer nozzle and the aluminum foil receiver is adjusted to be 14cm, the anode of a high-voltage generator and the cathode of the high-voltage receiver of the device are respectively connected with the sprayer nozzle and the aluminum foil, and the injection speed of the injector is set to be 0.01 mL/min -1 And carrying out electrostatic spinning with the horizontal reciprocating movement distance of 30mm and the voltage of an adjusting device of 17kV to obtain the composite zein film, and marking the composite zein film as Z ZA-10.
Example 3
The embodiment provides a composite zein film, and the preparation method comprises the following steps:
(1) 1mmol of ZnCl 2 、2mmol InCl 3 ·4H 2 Dispersing O and 4mmol thioacetamide in a mixed solution of 30mL dimethylformamide and 10mL glycerol, performing ultrasonic treatment for 2h, transferring the mixture into an autoclave with a 50mL Teflon lining, reacting at 180 ℃ for 12h, centrifuging the product at 7000r/min for 5min after the reaction is finished, washing with water for 3 times, and drying at 65 ℃ for 13h to obtain ZnIn 2 S 4 ；
(2) 0.5g of ZnIn 2 S 4 30mL of 0.66mmol of AgNO was added 3 Ultrasonically stirring for 0.5-1 h in aqueous solution, and then adding 30mL of 0.33mmol of Na 2 MoO 4 ·2H 2 Reacting an O aqueous solution for 3 hours in the dark, centrifuging the product for 5 minutes at the rotating speed of 9000r/min after the reaction is finished, then washing the product for 3 times, and drying the product for 14 hours at the temperature of 65 ℃ to obtain ZnIn 2 S 4 -Ag 2 MoO 4 A particle; in which ZnIn 2 S 4 With Ag 2 MoO 4 The mass ratio of the particles is 1:0.20, and is recorded as ZA-20;
(3) dissolving 0.5g of zein and 0.5g of ethyl cellulose in 3mL of acetic acid, and then adding 0.3g of ZA-20 to obtain a spinning solution;
(4) placing the spinning solution in an injector of an electrostatic spinning device, adjusting the inner diameter of a nozzle of the injector to be 0.60mm, adjusting the distance between the nozzle of the injector and an aluminum foil receiver to be 14cm, respectively connecting the anode of a high-voltage generator and the cathode of the high-voltage receiver of the device with the nozzle of the injector and the aluminum foil, and setting the injection speed of the injector to be 0.01 mL/min -1 The reciprocating distance is 30mm, the voltage of the adjusting device is 17kV, andand (3) performing electrostatic spinning to obtain a composite zein film, and marking the composite zein film as Z ZA-20.
Comparative example 1
The present comparative example provides a zein film, specifically referring to example 1, except that steps (1) to (2) are not performed, ZA-5 is not added to the spinning solution in step (3), the electrostatic spinning conditions are the same as those in step (4), and the obtained product is a zein film, which is denoted as Z.
Comparative example 2
The present comparative example provides a composite zein film, which is described as Z ZnIn, with the exception that step (2) is not performed, and the obtained product is a composite zein film 2 S 4 。
Comparative example 3
This comparative example provides an Ag alloy 2 MoO 4 The preparation method of the granule comprises the following steps: 1356.51mg of AgNO 3 Dissolving in 30mL of water, stirring with ultrasound for 1h, adding 30mL of Na dissolved with 966.06mg 2 MoO 4 ·2H 2 Reacting O water solution for 3h in the dark, centrifuging the product at 8000r/min for 10min after the reaction is finished, washing with water for 3 times, and drying at 60 ℃ for 13h to obtain Ag 2 MoO 4 And (3) granules.
ZnIn prepared in example 1 2 S 4 ZnIn prepared in examples 1 to 3 2 S 4 -Ag 2 MoO 4 Granules and Ag prepared in comparative example 3 2 MoO 4 The particles were subjected to XRD analysis, and the results are shown in fig. 1. As can be seen from FIG. 1, pure ZnIn 2 S 4 Diffraction peaks at 21.6 °, 27.7 °, 30.4 °, 47.2 °, 52.5 ° and 55.6 ° of 2 θ correspond to hexagonal phase ZnIn, respectively 2 S 4 (JCPDS.No.65-2023) (006), (102), (104), (110), (116) and (022). Ag 2 MoO 4 Has good consistency with the XRD pattern of PDF #08-0473, which shows that cubic phase Ag is formed 2 MoO 4 . ZnIn for XRD patterns of ZA-5, ZA-10, ZA-20 heterojunction materials 2 S 4 The characteristic peak of (A) is clearly visible with Ag 2 MoO 4 Increase in content of Ag 2 MoO 4 The characteristic peak of (A) was clearly present in ZA-20 and no additional crystalline phase and diffraction peak were detected, which indicates that no impurity, Ag, was generated during the sample preparation process 2 MoO 4 Is assembled to ZnIn 2 S 4 And the structure is not destroyed.
ZnIn prepared in example 2 2 S 4 Z prepared in ZA-10, Z ZA-10 and comparative example 1 was subjected to SEM analysis, and the results are shown in FIG. 2. ZnIn can be clearly seen from FIG. 2a 2 S 4 Showing a microsphere morphology comprising a plurality of interwoven nanoplates. FIG. 2b shows that Ag is found 2 MoO 4 Is tightly deposited on ZnIn in the form of nano particles 2 S 4 On the surface, the two reach good combination. The regular fiber structure of the zein film of fig. 2c can be seen visually. Z ZA-10 of FIG. 2d, with irregular heterojunction material wrapped in the fiber, visually demonstrates ZnIn 2 S 4 -Ag 2 MoO 4 @ successful preparation of zein films.
The membrane materials prepared in the examples 1-3 and the comparative examples 1-2 are subjected to adsorption-photocatalysis performance experiments, and the specific method comprises the following steps: is divided into 4X 4cm 2 The square membrane material of (2) was placed in 50mL of 10ppm Enrofloxacin (ENR) solution. Before illumination, the mixture was stirred in the dark for 30min to achieve adsorption-desorption equilibrium of the membrane material and ENR, then simulated visible light was added to perform photochemical reaction, 2.5mL of the reaction solution was taken from the reaction system every 20min, filtered through a 0.45 μm filter and collected, and then the ENR concentration was determined by High Performance Liquid Chromatography (HPLC). The removal result of enrofloxacin by membrane material is shown in figure 3.
As can be seen from FIG. 3, pure Z has almost no photocatalytic activity, while Z ZnIn 2 S 4 After two hours of irradiation, the degradation rate of ENR is only 41.16%, the photocatalytic activity of the composite film materials Z ZA-5, Z ZA-10 and Z ZA-20 is obviously improved, wherein the degradation effect of Z ZA-10 is best, and the degradation rate can reach 100%.
The membrane material prepared in example 2 was subjected to cyclic degradation, and the results are shown in fig. 4. As can be seen from fig. 4, even though Z ZA-10 was degraded by 4 cycles, the sample still maintained high catalytic activity and recyclability without significant decrease in photocatalytic performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the composite zein film is characterized by comprising the following steps:
(1) reacting ZnCl 2 、InCl 3 ·4H 2 O, thioacetamide, dimethylformamide and glycerol are mixed and then react to obtain ZnIn 2 S 4 ；
(2) ZnIn is mixed with a solvent 2 S 4 And AgNO 3 Mixing the aqueous solution, and dropwise adding Na 2 MoO 4 ·2H 2 O aqueous solution, reacting in the dark to obtain ZnIn 2 S 4 -Ag 2 MoO 4 Particles;
(3) dissolving zein and ethyl cellulose in acetic acid, and adding ZnIn 2 S 4 -Ag 2 MoO 4 Granulating to obtain spinning solution;
(4) and (3) carrying out electrostatic spinning on the spinning solution to obtain the composite zein film.
2. The method for preparing a composite zein film as claimed in claim 1, wherein in said step (1), ZnCl is used 2 、InCl 3 ·4H 2 The molar volume ratio of O, thioacetamide, dimethylformamide and glycerol is 1 mmol: 1-3 mmol: 2-5 mmol: 20-35 mL: 10 mL.
3. The method for preparing a composite zein film as claimed in claim 2, wherein the reaction temperature in step (1) is 175-185 ℃; the reaction time is 8-12 h.
4. Root of herbaceous plantThe method for preparing a composite zein film as claimed in any one of claims 1 to 3, wherein AgNO in step (2) 3 Aqueous solution and Na 2 MoO 4 ·2H 2 The volume ratio of the O aqueous solution is 1-3: 1-2; AgNO 3 AgNO in aqueous solution 3 And Na 2 MoO 4 ·2H 2 Na in O aqueous solution 2 MoO 4 ·2H 2 The molar ratio of O is 2: 1.
5. the method for preparing a composite zein film as claimed in claim 4, wherein the reaction time in step (2) is 2-4 h.
6. The method for preparing a composite zein film as claimed in claim 1 or 5, wherein in said step (2), ZnIn is added 2 S 4 -Ag 2 MoO 4 ZnIn in the particles 2 S 4 And Ag 2 MoO 4 The mass ratio of (1): 0.05 to 0.20.
7. The method for preparing a composite zein film as claimed in claim 1, 2 or 5, wherein in said step (3), zein, ethyl cellulose and ZnIn are added 2 S 4 -Ag 2 MoO 4 The mass-to-volume ratio of the particles to acetic acid was 0.5 g: 0.5 g: 0.29-0.31 g: 2-4 mL.
8. The method for preparing a composite zein film as claimed in claim 7, wherein the electrospinning conditions in step (4) are as follows: the inner diameter of a nozzle of the injector is 0.60mm, and the pushing speed of the injector is 0.008-0.018 mL/min -1 The distance between a spray head of the injector and the receiver is 12-16 cm, the horizontal reciprocating movement distance of the injector is 25-35 mm, the voltage is 16-20 kV, and the receiver is an aluminum foil.
9. A composite zein film prepared by the preparation method of any one of claims 1 to 8.
10. Use of a composite zein film as claimed in claim 9 as a photocatalytic film.
CN202210498508.3A 2022-05-09 2022-05-09 Composite zein film and preparation method and application thereof Active CN114904539B (en)

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