CN111905806A - Preparation method of high-dispersion composite photocatalyst - Google Patents

Preparation method of high-dispersion composite photocatalyst Download PDF

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CN111905806A
CN111905806A CN202010629669.2A CN202010629669A CN111905806A CN 111905806 A CN111905806 A CN 111905806A CN 202010629669 A CN202010629669 A CN 202010629669A CN 111905806 A CN111905806 A CN 111905806A
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刘奇
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/50Silver
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
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    • B01J35/398Egg yolk like
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    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract

The invention discloses a preparation method of a high-dispersion composite photocatalyst, and relates to the technical field of catalysts. The preparation method comprises the steps of mixing graphene and titanium dioxide precursor sol, calcining and reducing to obtain modified titanium dioxide, modifying glucan with cholesterol to obtain modified glucan, coating polylactic acid and the modified glucan on the modified titanium dioxide, and making microcapsules porous by using an ion concentration difference and alkali liquor to obtain the high-dispersion composite photocatalyst. The high-dispersion composite photocatalyst prepared by the invention has good dispersibility, and the photocatalytic efficiency is better in the using process.

Description

Preparation method of high-dispersion composite photocatalyst
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a high-dispersion composite photocatalyst.
Background
TiO2 is commonly called titanium dioxide, is an n-type semiconductor material, and has a forbidden bandwidth of 3.2 eV. The photocatalyst has the advantages of high specific surface area, low price, no toxicity, strong photoelectric property, high catalytic activity and the like, so the photocatalyst is the photocatalyst with the most application potential at present. However, the intrinsic physical properties of TiO2 determine that the utilization rate of solar energy is low, the electron-hole recombination rate is high, and the photocatalytic activity is greatly reduced. Therefore, modification of TiO2 to increase the excitation wavelength from ultraviolet light to visible light has become a major research focus of scientists, slowing down the recombination of electrons and holes and increasing the photocatalytic efficiency. Currently, to achieve this goal, TiO2 is modified or doped using a number of different techniques to increase its photocatalytic activity. Such as doping transition metal and nonmetal on the surface of TiO2 metal, depositing noble metal on the surface, performing surface photosensitization treatment, compounding semiconductors and the like. The semiconductor compounding is mainly characterized in that two semiconductors with different but similar energy band widths are compounded, so that a photon-generated carrier can be transported between carriers with different energy levels, the service life of the carrier is prolonged, the carrier compounding is avoided to a great extent, the carrier separation rate is improved, and the photocatalytic activity of the system is improved.
The nanometer photocatalyst is a gram of pollutant, and the action mechanism of the nanometer photocatalyst is as follows: the nanometer photocatalyst is excited to generate electron-hole pair under the irradiation of light of specific wavelength, and the electron-hole pair has powerful oxidation-reduction capacity after acting with water and oxygen around and can decompose formaldehyde, benzene and other pollutant in air into harmless and odorless matter. Under illumination, if the energy of a photon is greater than the forbidden bandwidth of a semiconductor, an electron in the valence band is excited to the conduction band, and a hole is generated in the valence band. The photoproduction holes have strong oxidizing ability, the photoproduction electrons have strong reducing ability, and the photoproduction holes can migrate to different positions on the surface of the semiconductor and have oxidation-reduction reaction with pollutants adsorbed on the surface.
At present, the dispersion liquid is required to be added to the photocatalysts used in the market so as to improve the dispersing performance of the photocatalysts, so that the application of the photocatalysts is limited, and therefore, how to improve the dispersing performance of the photocatalysts is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-dispersion composite photocatalyst and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the high-dispersion composite photocatalyst is characterized by mainly comprising the following raw material components in parts by weight: 15-28 parts of modified titanium dioxide and 30-35 parts of polylactic acid.
The high-dispersion composite photocatalyst is characterized by further comprising the following raw material components in parts by weight: 10-15 parts of modified glucan.
As optimization, the modified titanium dioxide is prepared by graphene and titanium dioxide together; the modified glucan is prepared from glucan and cholesterol.
As optimization, the high-dispersion composite photocatalyst comprises the following raw material components in parts by weight: 20 parts of modified titanium dioxide, 30 parts of polylactic acid and 12 parts of modified glucan.
As optimization, the preparation method of the high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and succinic anhydride for reaction to obtain cholesterol-succinate, reacting cholesterol-succinate with thionyl chloride, reacting with dextran, dialyzing, and freeze-drying;
(2) mixing the titanium dioxide sol and graphene oxide, calcining to obtain a modified titanium dioxide blank, and reducing the modified titanium dioxide blank by sodium borohydride to obtain modified titanium dioxide;
(3) mixing the modified glucan obtained in the step (1) with polylactic acid, adding the modified titanium dioxide obtained in the step (2), stirring for reaction, dialyzing in water and a silver nitrate solution respectively, and drying to obtain a blank;
(4) and reducing the blank in a sodium borohydride solution to obtain a pretreated blank. Mixing the pretreated blank with epoxy chloropropane for reaction, filtering to obtain a filter cake, mixing the filter cake with a sodium hydroxide solution, standing, filtering, washing and drying;
(5) and (4) performing index analysis on the product obtained in the step (4).
As optimization, the preparation method of the high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to a mass ratio of 1:30, adding succinic anhydride with the mass of 1 time that of the cholesterol, stirring for reaction, carrying out rotary evaporation and concentration to obtain a crude product, recrystallizing the crude product in an ethanol solution to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to a mass ratio of 1:100, adding a thionyl chloride solution with the mass of 1-2 times that of the cholesterol-succinate, stirring for reaction, carrying out rotary evaporation and concentration to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan according to a mass ratio of 1: 3-1: 5, adding dimethyl sulfoxide with the mass of 200 times that of the cholesterol-succinyl chloride and ethylenediamine with the mass of 3-10 times that of the cholesterol-succinyl chloride, stirring for reaction under a nitrogen atmosphere, dialyzing, and carrying out freeze drying;
(2) mixing citric acid and water according to a mass ratio of 1:40, adding tetrabutyl titanate with the mass being 2-5 times that of the citric acid, stirring and mixing to obtain precursor sol, mixing the precursor sol and graphene oxide according to a mass ratio of 100: 1-120: 1, performing ultrasonic dispersion, calcining to obtain modified titanium dioxide blank, mixing the modified titanium dioxide blank and a sodium borohydride solution according to a mass ratio of 1:30, stirring for reaction, filtering, and drying;
(3) mixing the substance obtained in the step (1) with polylactic acid according to a mass ratio of 1:3, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and the substance obtained in the step (2) 0.8-1.0 times the mass of the substance obtained in the step (1), stirring for reaction to obtain a mixture, dialyzing the mixture in water for 4 hours, dialyzing the mixture in a silver nitrate solution with a mass fraction of 2% for 4 hours, and drying to obtain a blank;
(4) mixing the blank with a sodium borohydride solution according to a mass ratio of 1:10 for reaction, filtering to obtain a pretreated blank, mixing the pretreated blank with epoxy chloropropane according to a mass ratio of 1:10, stirring for reaction, filtering to obtain a filter cake, mixing the filter cake with a sodium hydroxide solution according to a mass ratio of 1:15, standing for 4-8 days, filtering, washing and drying;
(5) and (4) performing index analysis on the product obtained in the step (4).
Optimally, the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8.
As an optimization, the dialysis bag used in the dialysis in the step (3) is a dialysis bag with the molecular weight cutoff of 1400.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, polylactic acid and modified glucan are used for coating modified titanium dioxide during preparation of the high-dispersion composite photocatalyst, and the titanium dioxide and graphene are compounded; firstly, polylactic acid and modified glucan are used for coating modified titanium dioxide, on one hand, the polylactic acid and the modified glucan can microencapsulate the modified titanium dioxide, so that the glucan with hydrophilicity is exposed on the surface of the microcapsule, thereby improving the dispersion performance of the product, on the other hand, due to the degradability of the polylactic acid, the coating layer on the surface of the modified titanium dioxide can be made porous in the subsequent alkali soaking treatment and use process, thereby improving the dispersibility of the composite photocatalyst, ensuring the photocatalytic performance of the composite photocatalyst, effectively prolonging the service life of the product, and moreover, the modified glucan can form a three-dimensional cross-linked network outside the microcapsule under the cross-linking action of epoxy chloropropane, adsorbing silver ions, further improving the photocatalytic performance of the product, and simultaneously, rich pores can be formed on the surface of the microcapsule under the action of concentration difference when the product is soaked in a silver nitrate solution, and then further improving the porosity of the surface of the microcapsule and improving the photocatalytic performance of the product, and secondly, compounding titanium dioxide and graphene to prepare modified titanium dioxide, so that the titanium dioxide can be better coated in the microcapsule formed by polylactic acid and modified glucan, a large amount of agglomeration of the titanium dioxide in the coating process is prevented, and the photocatalytic performance of the titanium dioxide can be further improved after the titanium dioxide is compounded with the graphene.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided, and the method for testing each index of the highly dispersed composite photocatalyst prepared in the following examples is as follows:
dispersibility: the high-dispersion composite photocatalyst obtained in each example and the comparative product are placed in methyl orange solution with the same concentration, the degradation rate after 60min is measured, and the higher the degradation rate is, the better the dispersion is.
Example 1
A high-dispersion composite photocatalyst mainly comprises the following raw material components in parts by weight: 20 parts of modified titanium dioxide, 30 parts of polylactic acid and 12 parts of modified glucan.
A preparation method of a high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to the mass ratio of 1:30, adding succinic anhydride with the mass of 1 time of that of the cholesterol into a beaker, stirring and reacting for 6 hours at the temperature of 60 ℃ and the rotation speed of 300r/min, carrying out rotary evaporation and concentration on the materials in the beaker for 5 hours at the temperature of 80 ℃, the rotation speed of 120r/min and the pressure of 600kPa to obtain a crude product, recrystallizing the crude product in an ethanol solution with the mass fraction of 18% to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1:100 into the flask, adding a thionyl chloride solution with the mass of 2 times of that of the cholesterol-succinate into the flask, stirring and reacting for 4 hours at the temperature of 70 ℃ and the rotation speed of 300r/min, then, stirring and reacting the materials in the flask at the temperature of 80 ℃ and the rotation speed of 120r/min, performing rotary evaporation and concentration for 4 hours under the pressure of 600kPa to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan in a three-neck flask according to the mass ratio of 1:3, adding dimethyl sulfoxide 200 times the mass of the cholesterol-succinyl chloride and ethylenediamine 5 times the mass of the cholesterol-succinyl chloride into the three-neck flask, introducing nitrogen into the three-neck flask at the speed of 30mL/min, stirring and reacting for 6 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 280r/min, dialyzing the materials in the three-neck flask in water for 6 hours, and performing freeze drying;
(2) mixing citric acid and water according to a mass ratio of 1:40, adding tetrabutyl titanate with the mass being 3 times that of the citric acid into the mixture of the citric acid and the water, stirring and mixing for 30min at a temperature of 45 ℃ and a rotation speed of 350r/min to obtain precursor sol, mixing the precursor sol and graphene oxide according to a mass ratio of 100:1, ultrasonically dispersing for 3h under a frequency of 45kHz, calcining for 3h at a temperature of 400 ℃ to obtain a modified titanium dioxide blank, mixing the modified titanium dioxide blank and a sodium borohydride solution with the mass fraction of 2% according to a mass ratio of 1:30, stirring and reacting for 3h at a temperature of 60 ℃ and a rotation speed of 300r/min, filtering to obtain a pretreated modified titanium dioxide blank, and drying the pretreated modified titanium dioxide blank for 3h at a temperature of 80 ℃;
(3) mixing the substance obtained in the step (1) and polylactic acid in a mass ratio of 1:3 in a reaction kettle, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and the substance obtained in the step (2) 0.8 times the mass of the substance obtained in the step (1) into the reaction kettle, stirring and reacting for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain a mixture, dialyzing the mixture in water for 4h by using a dialysis bag, dialyzing in a silver nitrate solution with the mass fraction of 2% for 4h, and drying the dialyzed product at the temperature of 60 ℃ for 2h to obtain a blank;
(4) mixing the blank with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1:10, reacting for 3 hours at the temperature of 60 ℃, filtering to obtain a pretreated blank, mixing the pretreated blank with epoxy chloropropane according to the mass ratio of 1:10, stirring and reacting for 2 hours at the temperature of 35 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, mixing the filter cake with a sodium hydroxide solution with the mass fraction of 8% according to the mass ratio of 1:15, standing for 4-8 days, filtering to obtain filter residue, washing the filter residue with deionized water for 5 times, and drying for 2 hours at the temperature of 80 ℃;
(5) and (4) performing index analysis on the product obtained in the step (4).
Optimally, the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8.
As an optimization, the dialysis bag used in the dialysis in the step (3) is a dialysis bag with the molecular weight cutoff of 1400.
Example 2
A high-dispersion composite photocatalyst mainly comprises the following raw material components in parts by weight: 20 parts of titanium dioxide, 30 parts of polylactic acid and 12 parts of modified glucan.
A preparation method of a high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to the mass ratio of 1:30, adding succinic anhydride with the mass of 1 time of that of the cholesterol into a beaker, stirring and reacting for 6 hours at the temperature of 60 ℃ and the rotation speed of 300r/min, carrying out rotary evaporation and concentration on the materials in the beaker for 5 hours at the temperature of 80 ℃, the rotation speed of 120r/min and the pressure of 600kPa to obtain a crude product, recrystallizing the crude product in an ethanol solution with the mass fraction of 18% to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1:100 into the flask, adding a thionyl chloride solution with the mass of 2 times of that of the cholesterol-succinate into the flask, stirring and reacting for 4 hours at the temperature of 70 ℃ and the rotation speed of 300r/min, then, stirring and reacting the materials in the flask at the temperature of 80 ℃ and the rotation speed of 120r/min, performing rotary evaporation and concentration for 4 hours under the pressure of 600kPa to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan in a three-neck flask according to the mass ratio of 1:3, adding dimethyl sulfoxide 200 times the mass of the cholesterol-succinyl chloride and ethylenediamine 5 times the mass of the cholesterol-succinyl chloride into the three-neck flask, introducing nitrogen into the three-neck flask at the speed of 30mL/min, stirring and reacting for 6 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 280r/min, dialyzing the materials in the three-neck flask in water for 6 hours, and performing freeze drying;
(2) mixing the substance obtained in the step (1) and polylactic acid in a mass ratio of 1:3 in a reaction kettle, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and titanium dioxide 0.8 times the mass of the substance obtained in the step (1) into the reaction kettle, stirring and reacting for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain a mixture, dialyzing the mixture in water for 4h by using a dialysis bag, dialyzing in a silver nitrate solution with the mass fraction of 2% for 4h, and drying the dialyzed product at the temperature of 60 ℃ for 2h to obtain a blank;
(3) mixing the blank with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1:10, reacting for 3 hours at the temperature of 60 ℃, filtering to obtain a pretreated blank, mixing the pretreated blank with epichlorohydrin according to the mass ratio of 1:10, stirring and reacting for 2 hours at the temperature of 35 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, mixing the filter cake with a sodium hydroxide solution with the mass fraction of 8% according to the mass ratio of 1:15, standing for 8 days, filtering to obtain filter residue, washing the filter residue with deionized water for 5 times, and drying for 2 hours at the temperature of 80 ℃;
(4) and (4) performing index analysis on the product obtained in the step (3).
Optimally, the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8.
As an optimization, the dialysis bag used in the dialysis in the step (2) is a dialysis bag with the molecular weight cutoff of 1400.
Example 3
A high-dispersion composite photocatalyst mainly comprises the following raw material components in parts by weight: 20 parts of modified titanium dioxide, 30 parts of polylactic acid and 12 parts of modified glucan.
A preparation method of a high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to the mass ratio of 1:30, adding succinic anhydride with the mass of 1 time of that of the cholesterol into a beaker, stirring and reacting for 6 hours at the temperature of 60 ℃ and the rotation speed of 300r/min, carrying out rotary evaporation and concentration on the materials in the beaker for 5 hours at the temperature of 80 ℃, the rotation speed of 120r/min and the pressure of 600kPa to obtain a crude product, recrystallizing the crude product in an ethanol solution with the mass fraction of 18% to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1:100 into the flask, adding a thionyl chloride solution with the mass of 2 times of that of the cholesterol-succinate into the flask, stirring and reacting for 4 hours at the temperature of 70 ℃ and the rotation speed of 300r/min, then, stirring and reacting the materials in the flask at the temperature of 80 ℃ and the rotation speed of 120r/min, performing rotary evaporation and concentration for 4 hours under the pressure of 600kPa to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan in a three-neck flask according to the mass ratio of 1:3, adding dimethyl sulfoxide 200 times the mass of the cholesterol-succinyl chloride and ethylenediamine 5 times the mass of the cholesterol-succinyl chloride into the three-neck flask, introducing nitrogen into the three-neck flask at the speed of 30mL/min, stirring and reacting for 6 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 280r/min, dialyzing the materials in the three-neck flask in water for 6 hours, and performing freeze drying;
(2) mixing citric acid and water according to a mass ratio of 1:40, adding tetrabutyl titanate with the mass being 3 times that of the citric acid into the mixture of the citric acid and the water, stirring and mixing for 30min at a temperature of 45 ℃ and a rotation speed of 350r/min to obtain precursor sol, mixing the precursor sol and graphene oxide according to a mass ratio of 100:1, ultrasonically dispersing for 3h under a frequency of 45kHz, calcining for 3h at a temperature of 400 ℃ to obtain a modified titanium dioxide blank, mixing the modified titanium dioxide blank and a sodium borohydride solution with the mass fraction of 2% according to a mass ratio of 1:30, stirring and reacting for 3h at a temperature of 60 ℃ and a rotation speed of 300r/min, filtering to obtain a pretreated modified titanium dioxide blank, and drying the pretreated modified titanium dioxide blank for 3h at a temperature of 80 ℃;
(3) mixing the substance obtained in the step (1) and polylactic acid in a mass ratio of 1:3 in a reaction kettle, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and modified titanium dioxide 0.8 times the mass of the substance obtained in the step (1) in the reaction kettle, stirring and reacting for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain a mixture, dialyzing the mixture in water for 4h by using a dialysis bag, dialyzing in a silver nitrate solution with the mass fraction of 2% for 4h, and drying the dialyzed product at the temperature of 60 ℃ for 2 h;
(4) mixing the blank with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1:10, reacting for 3 hours at the temperature of 60 ℃, filtering to obtain a pretreated blank, mixing the pretreated blank with epichlorohydrin according to the mass ratio of 1:10, stirring and reacting for 2 hours at the temperature of 35 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 80 ℃;
(5) and (4) performing index analysis on the product obtained in the step (4).
Optimally, the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8.
As an optimization, the dialysis bag used in the dialysis in the step (3) is a dialysis bag with the molecular weight cutoff of 1400.
Example 4
A high-dispersion composite photocatalyst mainly comprises the following raw material components in parts by weight: 20 parts of modified titanium dioxide, 30 parts of polylactic acid and 12 parts of modified glucan.
A preparation method of a high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to the mass ratio of 1:30, adding succinic anhydride with the mass of 1 time of that of the cholesterol into a beaker, stirring and reacting for 6 hours at the temperature of 60 ℃ and the rotation speed of 300r/min, carrying out rotary evaporation and concentration on the materials in the beaker for 5 hours at the temperature of 80 ℃, the rotation speed of 120r/min and the pressure of 600kPa to obtain a crude product, recrystallizing the crude product in an ethanol solution with the mass fraction of 18% to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1:100 into the flask, adding a thionyl chloride solution with the mass of 2 times of that of the cholesterol-succinate into the flask, stirring and reacting for 4 hours at the temperature of 70 ℃ and the rotation speed of 300r/min, then, stirring and reacting the materials in the flask at the temperature of 80 ℃ and the rotation speed of 120r/min, performing rotary evaporation and concentration for 4 hours under the pressure of 600kPa to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan in a three-neck flask according to the mass ratio of 1:3, adding dimethyl sulfoxide 200 times the mass of the cholesterol-succinyl chloride and ethylenediamine 5 times the mass of the cholesterol-succinyl chloride into the three-neck flask, introducing nitrogen into the three-neck flask at the speed of 30mL/min, stirring and reacting for 6 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 280r/min, dialyzing the materials in the three-neck flask in water for 6 hours, and performing freeze drying;
(2) mixing citric acid and water according to a mass ratio of 1:40, adding tetrabutyl titanate with the mass being 3 times that of the citric acid into the mixture of the citric acid and the water, stirring and mixing for 30min at a temperature of 45 ℃ and a rotation speed of 350r/min to obtain precursor sol, mixing the precursor sol and graphene oxide according to a mass ratio of 100:1, ultrasonically dispersing for 3h under a frequency of 45kHz, calcining for 3h at a temperature of 400 ℃ to obtain a modified titanium dioxide blank, mixing the modified titanium dioxide blank and a sodium borohydride solution with the mass fraction of 2% according to a mass ratio of 1:30, stirring and reacting for 3h at a temperature of 60 ℃ and a rotation speed of 300r/min, filtering to obtain a pretreated modified titanium dioxide blank, and drying the pretreated modified titanium dioxide blank for 3h at a temperature of 80 ℃;
(3) mixing the substance obtained in the step (1) and polylactic acid in a mass ratio of 1:3 in a reaction kettle, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and the substance obtained in the step (2) 0.8 times the mass of the substance obtained in the step (1) into the reaction kettle, stirring and reacting for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain a mixture, dialyzing the mixture in water for 4h by using a dialysis bag, and drying the dialyzed product for 2h at the temperature of 60 ℃ to obtain a blank;
(4) mixing the blank with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1:10, reacting for 3 hours at the temperature of 60 ℃, filtering to obtain a pretreated blank, mixing the pretreated blank with epichlorohydrin according to the mass ratio of 1:10, stirring and reacting for 2 hours at the temperature of 35 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, mixing the filter cake with a sodium hydroxide solution with the mass fraction of 8% according to the mass ratio of 1:15, standing for 5 days, filtering to obtain filter residue, washing the filter residue with deionized water for 5 times, and drying for 2 hours at the temperature of 80 ℃;
(5) and (4) performing index analysis on the product obtained in the step (4).
Optimally, the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8.
As an optimization, the dialysis bag used in the dialysis in the step (3) is a dialysis bag with the molecular weight cutoff of 1400.
Comparative example
A high-dispersion composite photocatalyst mainly comprises the following raw material components in parts by weight: 20 parts of titanium dioxide, 30 parts of polylactic acid and 12 parts of modified glucan.
A preparation method of a high-dispersion composite photocatalyst mainly comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to the mass ratio of 1:30, adding succinic anhydride with the mass of 1 time of that of the cholesterol into a beaker, stirring and reacting for 6 hours at the temperature of 60 ℃ and the rotation speed of 300r/min, carrying out rotary evaporation and concentration on the materials in the beaker for 5 hours at the temperature of 80 ℃, the rotation speed of 120r/min and the pressure of 600kPa to obtain a crude product, recrystallizing the crude product in an ethanol solution with the mass fraction of 18% to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1:100 into the flask, adding a thionyl chloride solution with the mass of 2 times of that of the cholesterol-succinate into the flask, stirring and reacting for 4 hours at the temperature of 70 ℃ and the rotation speed of 300r/min, then, stirring and reacting the materials in the flask at the temperature of 80 ℃ and the rotation speed of 120r/min, performing rotary evaporation and concentration for 4 hours under the pressure of 600kPa to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan in a three-neck flask according to the mass ratio of 1:3, adding dimethyl sulfoxide 200 times the mass of the cholesterol-succinyl chloride and ethylenediamine 5 times the mass of the cholesterol-succinyl chloride into the three-neck flask, introducing nitrogen into the three-neck flask at the speed of 30mL/min, stirring and reacting for 6 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 280r/min, dialyzing the materials in the three-neck flask in water for 6 hours, and performing freeze drying;
(2) mixing the substance obtained in the step (1) and polylactic acid in a mass ratio of 1:3 in a reaction kettle, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and titanium dioxide 0.8 times the mass of the substance obtained in the step (1) into the reaction kettle, stirring and reacting for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain a mixture, dialyzing the mixture in water for 4h by using a dialysis bag, and drying the dialyzed product for 2h at the temperature of 60 ℃ to obtain a blank;
(3) mixing the blank with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1:10, reacting for 3 hours at the temperature of 60 ℃, filtering to obtain a pretreated blank, mixing the pretreated blank with epichlorohydrin according to the mass ratio of 1:10, stirring and reacting for 2 hours at the temperature of 35 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 80 ℃;
(4) and (4) performing index analysis on the product obtained in the step (3).
Optimally, the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8.
As an optimization, the dialysis bag used in the dialysis in the step (2) is a dialysis bag with the molecular weight cutoff of 1400.
Examples of effects
The following table 1 shows the dispersion analysis results of the highly dispersed composite photocatalyst according to examples 1 to 4 of the present invention and the comparative example and the preparation method thereof.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Comparative example
Catalytic efficiency (%) 99 80 75 85 70
As can be seen from the comparison of the experimental data of example 1 and the comparative example in Table 1, the composite photocatalyst prepared by the invention has good dispersibility and good photocatalytic performance; from the comparison of the experimental data of the embodiment 1 and the embodiment 2, it can be found that when the modified titanium dioxide is not used, the photocatalytic efficiency of the product is low, and the absence of the graphene may cause the titanium dioxide to agglomerate seriously in the coating process, so that the coating rate of the titanium dioxide is low, and the photocatalytic performance is affected; from a comparison of example 1 and example 3, it can be seen that when the microcapsules are not immersed in lye, the product is less catalytic, possibly not, the microcapsules block light, making the product less catalytic.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (1)

1. A preparation method of a high-dispersion composite photocatalyst is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
(1) mixing cholesterol and pyridine according to the mass ratio of 1:30, adding succinic anhydride with the mass of 1 time of that of the cholesterol into a beaker, stirring and reacting for 6 hours at the temperature of 60 ℃ and the rotation speed of 300r/min, carrying out rotary evaporation and concentration on the materials in the beaker for 5 hours at the temperature of 80 ℃, the rotation speed of 120r/min and the pressure of 600kPa to obtain a crude product, recrystallizing the crude product in an ethanol solution with the mass fraction of 18% to obtain cholesterol-succinate, mixing the cholesterol-succinate and trichloromethane according to the mass ratio of 1:100 into the flask, adding a thionyl chloride solution with the mass of 2 times of that of the cholesterol-succinate into the flask, stirring and reacting for 4 hours at the temperature of 70 ℃ and the rotation speed of 300r/min, then, stirring and reacting the materials in the flask at the temperature of 80 ℃ and the rotation speed of 120r/min, performing rotary evaporation and concentration for 4 hours under the pressure of 600kPa to obtain a cholesterol-succinyl chloride mixed solution, mixing the cholesterol-succinyl chloride mixed solution and glucan in a three-neck flask according to the mass ratio of 1:3, adding dimethyl sulfoxide 200 times the mass of the cholesterol-succinyl chloride and ethylenediamine 5 times the mass of the cholesterol-succinyl chloride into the three-neck flask, introducing nitrogen into the three-neck flask at the speed of 30mL/min, stirring and reacting for 6 hours under the conditions that the temperature is 80 ℃ and the rotating speed is 280r/min, dialyzing the materials in the three-neck flask in water for 6 hours, and performing freeze drying;
(2) mixing citric acid and water according to a mass ratio of 1:40, adding tetrabutyl titanate with the mass being 3 times that of the citric acid into the mixture of the citric acid and the water, stirring and mixing for 30min at a temperature of 45 ℃ and a rotation speed of 350r/min to obtain precursor sol, mixing the precursor sol and graphene oxide according to a mass ratio of 100:1, ultrasonically dispersing for 3h under a frequency of 45kHz, calcining for 3h at a temperature of 400 ℃ to obtain a modified titanium dioxide blank, mixing the modified titanium dioxide blank and a sodium borohydride solution with the mass fraction of 2% according to a mass ratio of 1:30, stirring and reacting for 3h at a temperature of 60 ℃ and a rotation speed of 300r/min, filtering to obtain a pretreated modified titanium dioxide blank, and drying the pretreated modified titanium dioxide blank for 3h at a temperature of 80 ℃;
(3) mixing the substance obtained in the step (1) and polylactic acid in a mass ratio of 1:3 in a reaction kettle, adding dimethyl sulfoxide 30 times the mass of the substance obtained in the step (1) and the substance obtained in the step (2) 0.8 times the mass of the substance obtained in the step (1) into the reaction kettle, stirring and reacting for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain a mixture, dialyzing the mixture in water for 4h by using a dialysis bag, and drying the dialyzed product for 2h at the temperature of 60 ℃ to obtain a blank;
(4) mixing the blank with a sodium borohydride solution with the mass fraction of 2% according to the mass ratio of 1:10, reacting for 3 hours at the temperature of 60 ℃, filtering to obtain a pretreated blank, mixing the pretreated blank with epichlorohydrin according to the mass ratio of 1:10, stirring and reacting for 2 hours at the temperature of 35 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, mixing the filter cake with a sodium hydroxide solution with the mass fraction of 8% according to the mass ratio of 1:15, standing for 5 days, filtering to obtain filter residue, washing the filter residue with deionized water for 5 times, and drying for 2 hours at the temperature of 80 ℃;
(5) performing index analysis on the product obtained in the step (4);
the thionyl chloride solution in the step (1) is prepared by mixing thionyl chloride and trichloromethane according to the mass ratio of 1: 8; the dialysis bag used in the dialysis in the step (3) is a dialysis bag with the molecular weight cut-off of 1400.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006150345A (en) * 2004-09-29 2006-06-15 Toto Ltd Photocatalytic titanium dioxide particulate
CN101362069A (en) * 2008-10-08 2009-02-11 中国科学院过程工程研究所 Hollow porous micro-capsule and preparation method thereof
CN108821335A (en) * 2018-08-29 2018-11-16 佛山市禅城区诺高环保科技有限公司 A kind of preparation method of high-dispersion nano titanium dioxide

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19950479A1 (en) * 1999-10-20 2001-05-23 Henkel Kgaa Microcapsules
CN101422724B (en) * 2008-11-25 2010-08-18 华中师范大学 Preparation method and use of porous adsorbing material
CN105771980A (en) * 2016-04-27 2016-07-20 吉首大学 Graphene/silver/mesoporous titanium dioxide nanometer composite photocatalyst and preparation technology thereof
CN107090165B (en) * 2017-05-12 2019-04-30 南昌航空大学 The modified polylactic acid material and preparation method thereof that a kind of intensity high-fire resistance is good and degradability is controllable
CN107252704A (en) * 2017-07-14 2017-10-17 苏州大学 A kind of preparation method of TiO 2 porous nanofiber catalysis material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006150345A (en) * 2004-09-29 2006-06-15 Toto Ltd Photocatalytic titanium dioxide particulate
CN101362069A (en) * 2008-10-08 2009-02-11 中国科学院过程工程研究所 Hollow porous micro-capsule and preparation method thereof
CN108821335A (en) * 2018-08-29 2018-11-16 佛山市禅城区诺高环保科技有限公司 A kind of preparation method of high-dispersion nano titanium dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李翠霞等: "rGO/TiO2复合光催化剂的制备及光催化性能", 《中国环境科学》 *
龙丽霞等: "聚乳酸/双亲性葡聚糖中空纳米囊泡包载亲水性药物及释放", 《天津大学学报(自然科学与工程技术版)》 *

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