CN112892589A - Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel and preparation method thereof - Google Patents
Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
The invention relates to Ag3PO4/BiPO4A modified 3D porous starch-rGO composite photocatalytic hydrogel and a preparation method thereof. The composite photocatalytic hydrogel takes gelatinous 3D porous starch-rGO as a carrier and Ag3PO4/BiPO4Fixing on a carrier; ag3PO4/BiPO4The molar ratio of the Ag element to the Bi element is 0.25-4: 1; the mass ratio of starch to rGO in the carrier is 1: 1-3; the Ag is3PO4/BiPO4The loading amount of (2) is 1-5%. The invention takes gelatinous 3D porous starch-rGO as a carrier to realize Ag3PO4/BiPO4Immobilizing the photocatalyst; integrates the functions of adsorption and catalysis, and realizes the gas-to-gas reactionThe adsorption and photocatalytic degradation of the target object can play a synergistic role to the maximum extent, the photocatalytic efficiency is obviously improved, the cyclic and repeated utilization can be realized, and the method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalytic hydrogel materials, and particularly relates to Ag3PO4/BiPO4A modified 3D porous starch-rGO composite photocatalytic hydrogel and a preparation method thereof.
Background
The photocatalytic technology is a new technology for energy conversion and environmental purification by using ultraviolet light or sunlight, has the advantages of high efficiency, safety, low consumption, wide application and the like, and is concerned in various fields. Silver phosphate (Ag)3PO4) Is a novel photocatalyst, the forbidden band width of the photocatalyst is about 2.28eV, the quantum efficiency in a visible light region is as high as 90 percent, and the photocatalytic oxidation performance of the photocatalyst is superior to that of TiO2. But Ag3PO4The method has the defect of high recombination rate of the photo-generated electron-hole pairs of the traditional photocatalyst; due to the characteristics of photosensitivity and water solubility, the photocatalyst is easy to be corroded by light in the photocatalytic reaction process, and the synthesis cost is high due to poor stability, so that the practical application is limited. Second, BiPO4Belongs to n-type semiconductor material, has a forbidden band width of 3.85eV, and has a twisted PO in structure4Tetrahedra can generate a larger dipole moment, and PO4 3-The photocatalyst has stronger hydrophilicity and electrostatic adsorption performance to holes, is beneficial to realizing the separation and conduction of photo-generated electron-hole pairs, and thus has excellent photocatalytic performance. But the material can only respond to ultraviolet light with the wavelength less than 322nm, has the problem that the utilization rate of sunlight is only 4 percent, and the like, and limits BiPO4The application in the field of photocatalysis. To raise Ag3PO4Stability of (2) BiPO4The spectral response range of the solar photovoltaic power generation device is widened to a visible light region, and the conversion efficiency of the solar photovoltaic power generation device to solar energy is improved. Realization of Ag3PO4And BiPO4The formed staggered p-n heterojunction can effectively improve the separation efficiency of photo-generated electrons and holes, and the special energy band structure prolongs the service life of photo-generated chargesFurther improve the photocatalytic activity (Gao H, Zheng C, Yang H, et al. construction of a CQDs/Ag3PO4/BiPO4 Heterostructure Photocatalyst with Enhanced Photocatalytic Degradation of Rhodamine B under Simulated Solar Irradiation[J]Micromachines,2019,10(9): 557; BiPO, etc. of Makelong, Hushiwei, Miao Hui, etc4/Ag3PO4Preparation, characterization and photocatalytic performance of/CNTs composite photocatalyst [ J]The proceedings of the university of Fuyang (Nature science edition), 2019,36(2): 18-24).
However, the conventional powdered photocatalyst has problems of easy polymerization, difficult separation, difficult recovery and the like in the photocatalytic reaction process, thereby limiting the practical application of the powdered photocatalyst.
Therefore, the development of a photocatalyst with better dispersibility and photocatalytic activity has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of easy polymerization, difficult separation, difficult recovery and the like of the existing powder photocatalyst, and provides Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel. The composite photocatalytic hydrogel material provided by the invention has excellent performances of a porous structure, a plurality of photoreaction sites, a wide visible light response range and the like, an adsorption-photocatalytic synergistic action mechanism presents high catalytic degradation efficiency, the problems that a powdery photocatalyst is difficult to disperse and recycle are solved, and the composite photocatalytic hydrogel material can be widely applied to the fields of photocatalytic degradation of organic pollutants, fruit and vegetable fresh keeping, gas purification and the like.
Another object of the present invention is to provide the above Ag3PO4/BiPO4A preparation method of a modified 3D porous starch-rGO composite photocatalytic hydrogel.
In order to achieve the purpose, the invention adopts the following technical scheme:
ag3PO4/BiPO4The modified 3D porous starch-rGO composite photocatalytic hydrogel takes gelatinous 3D porous starch-rGO as a carrier and Ag3PO4/BiPO4Fixing on a carrier; the Ag is3PO4/BiPO4The molar ratio of the Ag element to the Bi element is 0.25-4: 1; the mass ratio of starch to rGO in the carrier is 1: 1-3; the Ag is3PO4/BiPO4The loading amount of (2) is 1-5%.
In order to solve the problems of easy polymerization, difficult separation, difficult recovery and the like of the powdery photocatalyst in the photocatalytic reaction process, the selection and development of a proper carrier are the key points of the current research. The immobilized carrier of the photocatalyst can be mainly divided into two types of inorganic carriers (glass type, metal type and porous type) and organic carriers (polypropylene and expanded graphite).
Researches find that the hydrogel prepared by taking starch as a raw material has good adsorbability, biocompatibility and degradable regeneration performance, and the porous membrane laminated structure of the hydrogel provides more reaction sites for the attachment of the photocatalyst. Reduced Graphene Oxide (rGO) is a pi-system material with a large number of oxygen-containing groups, and a large pi bond is formed in a conjugated manner, so that a space is provided for electron movement, and high mobility of a carrier is ensured. The rGO-doped hydrogel is used as a photocatalyst immobilized carrier material, so that the mechanical property and the recyclable property of the hydrogel can be improved, the synergistic effect of the adsorption and the photocatalytic properties can be exerted to the maximum extent, the concentration of a target object on the surface of the photocatalyst is increased through adsorption, and the high catalytic degradation rate is realized.
The invention takes gelatinous 3D porous starch-rGO as a carrier to realize Ag3PO4/BiPO4Immobilizing the photocatalyst; the method integrates the functions of adsorption and catalysis, realizes the adsorption and photocatalytic degradation of the gas target object at the same time, exerts the synergistic effect to the maximum extent, obviously improves the photocatalytic efficiency, can realize cyclic and repeated utilization, and has good application prospect.
Preferably, the Ag is3PO4/BiPO4The molar ratio of the Ag element to the Bi element is 1-4: 1; more preferably 3: 1.
Preferably, the mass ratio of starch to rGO in the carrier is 1: 2.
Preferably, the Ag is3PO4/BiPO4The loading of (b) was 3%.
The above Ag3PO4/BiPO4The preparation method of the modified 3D porous starch-rGO composite photocatalytic hydrogel comprises the following steps:
s1: mixing Ag with water3PO4/BiPO4Dispersing the powder in a dispersant to obtain Ag3PO4/BiPO4A dispersion liquid; mixing starch and reduced graphene oxide (rGO) to obtain a starch suspension;
s2: mixing Ag with water3PO4/BiPO4Mixing the dispersion liquid and the starch suspension, casting, pouring, freezing, and vacuum freeze-drying to obtain the Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel.
Preferably, Ag as described in S13PO4/BiPO4The powder is prepared by the following steps: mixing a silver source, a Bi source and phosphate, adjusting the pH to 5-8, and carrying out hydrothermal reaction at 120-200 ℃ for 12-48 h to obtain the Ag3PO4/BiPO4And (3) powder.
More preferably, the silver source is AgNO3、C2H3AgO2One or two of them.
More preferably, the Bi source is Bi (NO)3)3·5H2O、C6H9BiO6One or two of them.
More preferably, the phosphate is Na3PO4·12H2O、(NaPO3)6Or Na5P3O10One or three of them.
More preferably, the pH is adjusted using one or more of the following: NaOH solution, HCl solution, sodium tripolyphosphate or ammonia water.
More preferably, the pH is adjusted to 7.0.
More preferably, the stirring time is 60 min.
More preferably, the temperature of the hydrothermal reaction is 160 ℃ and the time is 12 h.
More preferably, the hydrothermal reaction is followed by cooling and washing the precipitate obtained by the hydrothermal reaction, drying the precipitate at 40-100 ℃, and grinding to obtain Ag3PO4-BiPO4And (5) powder body preparation.
Specifically, the washing process is: washing with distilled water and anhydrous ethanol as solvent repeatedly for 3 times.
Preferably, Ag as described in S13PO4/BiPO4The dispersion was prepared by the following procedure: mixing Ag with water3PO4/BiPO4Dissolving the powder in distilled water, adding a dispersing agent, magnetically stirring for 30-70 min, and then carrying out ultrasonic treatment for 10-40 min under the power of 300-500W to obtain the Ag3PO4/BiPO4And (3) dispersing the mixture.
Preferably, the dispersant in S1 is one or more of polyvinylpyrrolidone, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide or sodium polyacrylate.
Preferably, the addition amount of the dispersant is Ag3PO4/BiPO40.5-2.0 wt% of the powder; further preferably 1 wt%.
Preferably, the reduced graphene oxide rGO in S1 is prepared by the following process: adding a free radical scavenger into the GO solution, stirring and mixing uniformly, and irradiating to obtain the reduced graphene oxide rGO.
More preferably, the free radical scavenger is one or both of isopropanol or tert-butanol; isopropanol is further preferred, and the isopropanol is used as a hydroxyl radical trapping agent, so that GO is more favorably reduced into rGO, the obtained rGO sheet layer is thinner, and the migration efficiency of carriers is improved.
More preferably, the mass ratio of the GO to the free radical scavenger is 1: 0.01-0.05; further preferably 1: 0.02.
More preferably, the concentration of the GO solution is 0.4-0.8 mg/mL; further preferably 0.5 mg/mL.
More preferably, the irradiation dose is 10-40 kGy; further preferably 20 kGy.
Preferably, the starch in S1 is one or more of tapioca esterified starch, corn starch, potato starch or sweet potato starch.
Preferably, the temperature of the cold junction in S2 is-20 to-80 ℃.
More preferably, the temperature of the cold junction in S2 is-40 ℃.
Specifically, the Ag3PO4/BiPO4The preparation method of the modified 3D porous starch-rGO composite photocatalytic hydrogel comprises the following steps:
s1, weighing AgNO3And Bi (NO)3)3·5H2Dissolving O in distilled water and marking as A liquid; weighing Na3PO4·12H2And dissolving O in distilled water, and marking as liquid B. Dropwise adding the solution B into the solution A, magnetically stirring for 30min, adjusting the pH to 5-8 by using a NaOH solution, and putting the mixed solution into a stainless steel reaction kettle to perform hydrothermal reaction for 12-48 h at 120-200 ℃. Cooling and washing the precipitate. Drying the precipitate at 40-70 ℃, and grinding to obtain Ag3PO4/BiPO4And (3) powder. Weighing Ag3PO4/BiPO4Dissolving powder in distilled water, adding a dispersing agent, magnetically stirring for 30-70 min, and then carrying out ultrasonic treatment for 10-40 min under the power of 300-500W to obtain an AB dispersion liquid.
S2, adding a free radical scavenger into the GO solution, stirring and mixing uniformly, transferring the GO solution into an irradiation bottle, filling nitrogen, sealing, and putting the GO solution into the irradiation bottle60And irradiating in a Co-gamma ray source to obtain rGO.
S3, weighing starch, dispersing the starch in distilled water, adding 10% (by mass of the starch) of glycerol, and magnetically stirring for 15 min. And (4) adding the AB dispersion liquid obtained in the step S1 and the rGO obtained in the step S2, and magnetically stirring for 15 min. And then placing the starch solution in a water bath kettle at the temperature of 80-100 ℃ for heating and stirring for 30min, and completely gelatinizing the starch solution. Pouring 60-80 mL of starch suspension into a polystyrene culture dish, and placing the polystyrene culture dish in an ultralow-temperature refrigerator for freezing; vacuum freeze drying to obtain Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel.
Preferably, AgNO as described in step S13And Bi (NO)3)3·5H2The O molar ratio is preferably 1-4: 1-4, more preferably 1-4: 1, and further preferably 3: 1; the Ag is3PO4And BiPO4The amount of (B) is preferably 5 to 20mmol:1 to 10mmol, more preferably 15mmol:5 mmol.
Preferably, the temperature of the hydrothermal reaction in the step S1 is 120-200 ℃, and the time is 6-24 h; more preferably, the hydrothermal temperature is 160 ℃ and the time is 12 h.
Preferably, the pH of the mixed solution in the step S1 is 5-8, and the magnetic stirring time is 50-70 min; more preferably, the pH is 7.0 and the stirring time is 60 min.
Preferably, the detergent in step S1 is: washing with distilled water and anhydrous ethanol as solvent repeatedly for 3 times.
Preferably, the dispersant is selected from any one of polyvinylpyrrolidone, sodium polyacrylate, cetyl trimethyl ammonium bromide or sodium dodecyl sulfate; the addition amount of the dispersant is Ag3PO4/BiPO40.5-2 wt% of the powder.
More preferably, the dispersant is polyvinylpyrrolidone, and the addition amount of the polyvinylpyrrolidone is the photocatalyst Ag3PO4-BiPO41 wt% of (B).
Preferably, the concentration of the GO solution in the step S2 is 0.4-0.8 mg/mL, and more preferably the concentration of the GO solution is 0.5 mg/mL.
Preferably, the usage amount of the free radical scavenger in the step S2 is 1-5% of the weight of the GO solution;
preferably, the starch is added in an amount of 3-7 wt% in step S3.
More preferably, the starch is a tapioca esterified starch, and the starch is added in an amount of 5 wt%.
Preferably, the addition amount of the rGO in the step S3 is 2.5-12.5 wt%; more preferably, the added amount of rGO is 5 wt%.
Preferably, the addition amount of the AB dispersion liquid in the step S3 is 1-7 wt%; more preferably, the AB dispersion is added in an amount of 3 wt%.
Preferably, the temperature of the water bath in the step S3 is 80-100 ℃; more preferably, the freezing temperature is 95 ℃.
Preferably, the using amount of the starch suspension in the step S3 is 60-80 mL; more preferably, the starch suspension is used in an amount of 75 mL.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite photocatalytic hydrogel material provided by the invention has excellent performances of a porous structure, multiple photoreaction sites, a wide visible light response range and the like, an adsorption-photocatalytic synergistic action mechanism presents high catalytic degradation efficiency, the problems that a powdery photocatalyst is difficult to disperse and recycle are solved, and the composite photocatalytic hydrogel material can be widely applied to the fields of photocatalytic degradation of organic pollutants, fruit and vegetable fresh keeping, gas purification and the like;
(2) the preparation method provided by the invention is low in cost, simple, reliable, safe and environment-friendly, and has practical significance for practical application or realization of industrialization.
Drawings
FIG. 1 is a scanning electron micrograph of the composite photocatalytic hydrogel of example 1;
FIG. 2 is a scanning electron micrograph of the composite photocatalytic hydrogel of example 2;
FIG. 3 is a scanning electron micrograph of the composite photocatalytic hydrogel of example 3;
FIG. 4 is a scanning electron micrograph of the composite photocatalytic hydrogel of example 4;
FIG. 5 is a scanning electron micrograph of the composite photocatalytic hydrogel of example 5;
FIG. 6 shows Ag3PO4/BiPO4Molar ratio of precursor to Ag3PO4/BiPO4The effect of the photocatalyst;
FIG. 7 shows hydrothermal temperature vs. Ag3PO4/BiPO4The effect of the photocatalyst;
FIG. 8 shows hydrothermal time vs. Ag3PO4/BiPO4The effect of the photocatalyst;
FIG. 9 is a graph showing the effect of starch dosage on a composite photocatalytic hydrogel material;
figure 10 is the effect of rGO irradiation dose on ethylene degradation rate.
Figure 11 is the effect of rGO addition on ethylene degradation rate.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1 an Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel
1. Preparation method
(1) Taking 10mmol of AgNO3And 5mmol of Bi (NO)3)3·5H2Adding 50mL of distilled water into O, and magnetically stirring for 30min to obtain solution A; taking 10mmol of Na3PO4·12H2And dissolving O in 50mL of distilled water, and magnetically stirring for 30min to obtain solution B. Dropwise adding the solution B into the solution A, adjusting the pH of the solution to 7.0 by using NaOH, magnetically stirring for 1h, then putting the mixed solution into a stainless steel reaction kettle, and reacting for 24h at 160 ℃. The mixture was cooled to room temperature, and the precipitate was repeatedly washed by centrifugation with distilled water and absolute ethanol 3 times. Drying at 60 ℃ for 12h to obtain AgPO3-BiPO3(abbreviated as AB) powder.
(2) 0.05g of polyvinylpyrrolidone (PVP K30) is weighed and dissolved in 50mL of distilled water, then 0.5g of AB photocatalyst powder is added, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 30min under the power of 400W, so as to obtain AB dispersion liquid.
(3) Adding 2% (by weight of GO solution) of isopropanol into 0.5mg/mL GO solution, stirring and mixing uniformly, transferring the mixed solution to an irradiation bottle, filling nitrogen to remove oxygen, and sealingBy using60And (3) irradiating and reducing GO by a Co-gamma ray source to obtain rGO.
(4) Weighing 10g of cassava esterified starch, dispersing the cassava esterified starch in 200mL of distilled water, adding 10% (by mass of the starch) of glycerol, 5 wt% of rGO and 3 wt% of AB dispersion liquid, and magnetically stirring for 30 min. Heating in 95 deg.C water bath, stirring for 30min, and gelatinizing the starch solution completely. Pouring 75mL of the solution into a polystyrene culture dish with the diameter of 15cm, placing the polystyrene culture dish in a refrigerator at the temperature of minus 40 ℃ for freezing, and then carrying out vacuum freeze drying to obtain starch hydrogel, namely the composite photocatalytic hydrogel.
2. Product characteristics and physicochemical properties
As shown in FIG. 1, after 2mL of 0.15mg/L ethylene is injected into a 2L-volume photocatalytic reactor, and the composite photocatalytic hydrogel obtained in this example is irradiated under visible light for 240min, the adsorption-photocatalytic degradation rate of ethylene is 48.8%.
Example 2 an Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel
1. Preparation method
(1) Taking 10mmol of AgNO3And 10mmol of Bi (NO)3)3·5H2Adding 50mL of distilled water into O, and magnetically stirring for 30min to obtain solution A; taking 10mmol of Na3PO4·12H2And dissolving O in 50mL of distilled water, and magnetically stirring for 30min to obtain solution B. Dropwise adding the solution B into the solution A, adjusting the pH of the solution to 7.0 by using NaOH, magnetically stirring for 1h, then putting the mixed solution into a stainless steel reaction kettle, and reacting for 12h at 180 ℃. The mixture was cooled to room temperature, and the precipitate was repeatedly washed by centrifugation with distilled water and absolute ethanol 3 times. Drying at 55 ℃ for 14h to obtain AgPO3-BiPO3(abbreviated as AB) powder.
(2) 0.01g of polyvinylpyrrolidone (PVP K30) is weighed and dissolved in 50mL of distilled water, then 0.1g of AB photocatalyst powder is added, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 30min under the power of 500W, so as to obtain AB dispersion liquid.
(3) Adding 3 percent (based on the mass of the GO solution) of isopropanol into the GO solution with the concentration of 1mg/mL, stirring and mixing uniformly, transferring the mixed solution into an irradiation bottle, filling nitrogen to remove oxygen, sealing and using60And (3) irradiating and reducing GO by a Co-gamma ray source to obtain rGO.
(4) Weighing 20g of cassava esterified starch, dispersing the cassava esterified starch in 400mL of distilled water, adding 20% (by mass of the starch) of glycerol, 10 wt% of rGO and 5 wt% of AB dispersion liquid, and magnetically stirring for 30 min. Heating in 80 deg.C water bath, stirring for 30min, and gelatinizing the starch solution completely. Pouring 100mL of the solution into a polystyrene culture dish with the diameter of 15cm, placing the polystyrene culture dish in a refrigerator at the temperature of minus 80 ℃ for freezing, and then carrying out vacuum freeze drying to obtain starch hydrogel, namely the composite photocatalytic hydrogel.
2. Product characteristics and physicochemical properties
As shown in FIG. 2, after 2mL of 0.15mg/L ethylene is injected into a 2L-volume photocatalytic reactor, the adsorption-photocatalytic degradation rate of the composite photocatalytic hydrogel to ethylene is 47.4% when the photocatalytic hydrogel is irradiated under visible light for 240 min.
Example 3 an Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel
1. Preparation method
(1) Taking 20mmol of AgNO3And 5mmol of Bi (NO)3)3·5H2Adding 50mL of distilled water into O, and magnetically stirring for 30min to obtain solution A; 20mmol of Na are taken3PO4·12H2And dissolving O in 50mL of distilled water, and magnetically stirring for 30min to obtain solution B. Dropwise adding the solution B into the solution A, adjusting the pH of the solution to 7.0 by using NaOH, magnetically stirring for 2 hours, then putting the mixed solution into a stainless steel reaction kettle, and reacting for 18 hours at 200 ℃. The mixture was cooled to room temperature, and the precipitate was repeatedly washed by centrifugation with distilled water and absolute ethanol 3 times. Drying at 65 ℃ for 15h to obtain AgPO3-BiPO3(abbreviated as AB) powder.
(2) 0.1g of polyvinylpyrrolidone (PVP K30) is weighed and dissolved in 50mL of distilled water, then 1g of AB photocatalyst powder is added, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 30min under the power of 600W, so as to obtain AB dispersion.
(3) Adding 4% (by weight of GO solution) of isopropanol into 1.5mg/mL of GO solution, stirring and mixing uniformly, transferring the mixed solution to an irradiation bottle, filling nitrogen to remove oxygen, sealing, and using60And (3) irradiating and reducing GO by a Co-gamma ray source to obtain rGO.
(4) Weighing 15g of cassava esterified starch, dispersing the cassava esterified starch in 200mL of distilled water, adding 10% (by mass of the starch) of glycerol, 6 wt% of rGO and 4 wt% of AB dispersion liquid, and magnetically stirring for 30 min. Heating in 95 deg.C water bath, stirring for 30min, and gelatinizing the starch solution completely. Pouring 50mL of the solution into a polystyrene culture dish with the diameter of 15cm, placing the polystyrene culture dish in a refrigerator with the temperature of-20 ℃ for freezing, and then carrying out vacuum freeze drying to obtain starch hydrogel, namely the composite photocatalytic hydrogel.
2. Product characteristics and physicochemical properties
As shown in FIG. 3, after 2mL of 0.15mg/L ethylene is injected into a 2L-volume photocatalytic reactor, the adsorption-photocatalytic degradation rate of the composite photocatalyst hydrogel on ethylene is 42.4% when the photocatalytic reactor is irradiated under visible light for 240 min.
Example 4 an Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel
1. Preparation method
(1) Taking 5mmol AgNO3And 10mmol of Bi (NO)3)3·5H2Adding 50mL of distilled water into O, and magnetically stirring for 30min to obtain solution A; 5mmol of Na are taken3PO4·12H2And dissolving O in 50mL of distilled water, and magnetically stirring for 30min to obtain solution B. Dropwise adding the solution B into the solution A, adjusting the pH of the solution to 7.0 by using NaOH, magnetically stirring for 30min, then putting the mixed solution into a stainless steel reaction kettle, and reacting for 6h at 140 ℃. The mixture was cooled to room temperature, and the precipitate was repeatedly washed by centrifugation with distilled water and absolute ethanol 3 times. Drying at 50 ℃ for 6h to obtain AgPO3-BiPO3(abbreviated as AB) powder.
(2) 0.15g of polyvinylpyrrolidone (PVP K30) is weighed and dissolved in 50mL of distilled water, then 1.5g of AB photocatalyst powder is added, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 30min under the power of 400W, so as to obtain AB dispersion liquid.
(3) Adding 1% (by weight of GO solution) of isopropanol into 0.25mg/mL GO solution, stirring, mixing, transferring the mixed solution to an irradiation bottle, filling nitrogen to remove oxygen, sealing, and using60And (3) irradiating and reducing GO by a Co-gamma ray source to obtain rGO.
(4) Weighing 15g of cassava esterified starch, dispersing the cassava esterified starch in 200mL of distilled water, adding 15% (by mass of starch) of glycerol, 8 wt% of rGO and 6 wt% of AB dispersion liquid, and magnetically stirring for 30 min. Heating in 95 deg.C water bath, stirring for 30min, and gelatinizing the starch solution completely. Pouring 75mL of the solution into a polystyrene culture dish with the diameter of 15cm, placing the polystyrene culture dish in a refrigerator at the temperature of minus 40 ℃ for freezing, and then carrying out vacuum freeze drying to obtain starch hydrogel, namely the composite photocatalytic hydrogel.
2. Product characteristics and physicochemical properties
As shown in FIG. 4, after 2mL of 0.15mg/L ethylene was injected into a 2L-volume photocatalytic reactor, the adsorption-photocatalytic degradation rate of the composite hydrogel to ethylene was 39.5% when the composite hydrogel was irradiated under visible light for 240 min.
Example 5 an Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel
1. Preparation method
(1) Taking 5mmol AgNO3And 20mmol of Bi (NO)3)3·5H2Adding 50mL of distilled water into O, and magnetically stirring for 30min to obtain solution A; 5mmol of Na are taken3PO4·12H2And dissolving O in 50mL of distilled water, and magnetically stirring for 30min to obtain solution B. Dropwise adding the solution B into the solution A, adjusting the pH of the solution to 7.0 by using NaOH, magnetically stirring for 1h, then putting the mixed solution into a stainless steel reaction kettle, and reacting for 24h at 120 ℃. The mixture was cooled to room temperature, and the precipitate was repeatedly washed by centrifugation with distilled water and absolute ethanol 3 times. Drying at 65 ℃ for 10h to obtain AgPO3-BiPO3(abbreviated as AB) powder.
(2) 0.05g of polyvinylpyrrolidone (PVP K30) is weighed and dissolved in 50mL of distilled water, then 0.5g of AB photocatalyst powder is added, magnetic stirring is carried out for 1h, and ultrasonic treatment is carried out for 30min under the power of 400W, so as to obtain AB dispersion liquid.
(3) Adding 5% (based on the mass of the GO solution) of isopropanol into 2mg/mL of GO solution, stirring and mixing uniformly, transferring the mixed solution to an irradiation bottle, filling nitrogen to remove oxygen, sealing, and using60Co-gamma ray sourceAnd (3) carrying out irradiation reduction on GO to obtain rGO.
(4) 8g of cassava esterified starch is weighed and dispersed in 200mL of distilled water, 8 percent (by mass of the starch) of glycerol, 4 percent by weight of rGO and 3 percent by weight of AB dispersion liquid are added, and magnetic stirring is carried out for 30 min. Heating in 95 deg.C water bath, stirring for 30min, and gelatinizing the starch solution completely. Pouring 50mL of the solution into a polystyrene culture dish with the diameter of 15cm, placing the polystyrene culture dish in a refrigerator with the temperature of-20 ℃ for freezing, and then carrying out vacuum freeze drying to obtain starch hydrogel, namely the composite photocatalytic hydrogel.
2. Product characteristics and physicochemical properties
As shown in FIG. 5, after 2mL of 0.15mg/L ethylene was injected into a 2L photocatalytic reactor, the adsorption-photocatalytic degradation rate of the composite photocatalytic hydrogel to ethylene was 33.1% when the photocatalytic hydrogel was irradiated under visible light for 240 min.
Example 6 preparation Process optimization
1、Ag3PO4/BiPO4Molar ratio of precursor to Ag3PO4/BiPO4Influence of photocatalyst
FIG. 6 shows different Ag3PO4/BiPO4Ag at the molar ratio of the precursor3PO4/BiPO4Scanning electron micrographs of the photocatalyst. When the molar ratio is 2:1 (FIG. 6b), BiPO4The particles are uniformly dispersed in Ag3PO4On the surface of the particle, a better heterojunction structure is formed, which is beneficial to the separation of photo-generated electron-hole pairs and the migration to the surfaces of two photocatalysts, thereby improving the photocatalytic efficiency. BiPO at a molar ratio of 1:1 (FIG. 6a)4The particles are coated on Ag3PO4On the surface of the particles, Ag is reduced3PO4The particles have a low photocatalytic efficiency due to the utilization rate of light energy and no exposure of a composite interface of a sample. When the molar ratio is 4:1 (FIG. 6c), only a small amount of BiPO is present4Particles deposited on Ag3PO4The contact area of the particle surface is small, which is not beneficial to improving the photocatalysis efficiency.
2. Hydrothermal reaction temperature vs. Ag3PO4/BiPO4Influence of photocatalyst
FIG. 7 shows Ag after treatment at different hydrothermal reaction temperatures3PO4/BiPO4Scanning electron micrographs of the photocatalyst. When the hydrothermal temperature was 120 ℃ (FIG. 7a), the AB particle size was about 7.60 μm. When the hydrothermal temperature was increased to 160 ℃ (fig. 7b), the particle size of AB became smaller, being about 6.85 μm. When the hydrothermal temperature was raised to 200 ℃ (fig. 7c), AB had the largest particle size, about 9.40 μm. This is because the hydrothermal reaction temperature is too high, the crystal growth rate is increased, and the crystallinity of AB is promoted to increase, so that the particle size of the sample is increased, and the specific surface area is decreased, which is not favorable for the improvement of the photocatalytic activity.
3. Hydrothermal reaction time for Ag3PO4/BiPO4Influence of photocatalyst
FIG. 8 shows Ag after different hydrothermal reaction times3PO4/BiPO4Scanning electron micrographs of the photocatalyst. When the hydrothermal time was 6 hours (FIG. 8a), the particle size of AB was about 4.20. mu.m. When the hydrothermal temperature was increased to 12 hours (FIG. 8b), the particle size of AB became small and was about 3.90. mu.m. This is because as the hydrothermal reaction time is prolonged, the photocatalyst particles collide strongly with each other and are decomposed into particles having a smaller particle diameter. When the hydrothermal temperature was extended to 24h (FIG. 8c), AB had the largest particle size, about 6.85. mu.m. Due to the excessively long hydrothermal reaction time, the crystal growth rate is increased to increase the crystallinity, resulting in an increase in the particle size.
4. Influence of starch dosage on composite photocatalytic hydrogel material
FIG. 9 is a scanning electron microscope image of a composite photocatalytic hydrogel material treated with different amounts of starch. As the amount of starch is increased, the pore diameter of the porous structure of the composite photocatalytic hydrogel is gradually reduced, wherein the pore diameter of 3 percent of starch is the largest (figure 9a) and is about 30-180 mu m, the pore diameter of starch is 5 percent (figure 9b) and is about 25-140 mu m, and the pore diameter of 7 percent of starch is the smallest (figure 9c) and is about 20-100 mu m. The increase of the starch consumption, the density of the frozen hydrogel is increased, the ice crystal is reduced, the aperture formed after sublimation is reduced, and the proper aperture is beneficial to the adsorption and photocatalytic degradation of ethylene.
5. Effect of rGO irradiation dose on ethylene synergistic degradation rate
As shown in fig. 10, under simulated sunlight irradiation, the synergistic degradation rate of the composite photocatalytic hydrogel under different rGO irradiation doses is increased and then decreased, and when the irradiation dose is 20kGy, the maximum synergistic degradation rate of the composite photocatalytic hydrogel to ethylene reaches 42.40%. The rGO dispersion liquid is uniform and stable, does not agglomerate and precipitate, and is beneficial to application in actual production and life.
6. Effect of the addition of rGO on the ethylene synergistic degradation rate
As shown in fig. 11, the synergistic degradation rate of the composite photocatalytic hydrogel to ethylene shows a change from increasing to smoothing with the increase of the amount of rGO. When the addition amount of rGO is 5 wt%, the degradation rate reaches the maximum of 43%. Along with the increase of the rGO consumption, the specific surface area of the hydrogel can be increased, the ethylene adsorption rate can also be increased, and after the rGO consumption is increased to a certain degree, the specific surface area of the hydrogel can be increased to saturation, and the ethylene amount capable of being retained and adsorbed on the surface of the hydrogel can gradually tend to saturation.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Ag3PO4/BiPO4The modified 3D porous starch-rGO composite photocatalytic hydrogel is characterized in that the composite photocatalytic hydrogel takes gelatinous 3D porous starch-rGO as a carrier and Ag3PO4/BiPO4Fixing on a carrier; the Ag is3PO4/BiPO4The molar ratio of the Ag element to the Bi element is 0.25-4: 1; the mass ratio of starch to rGO in the carrier is 1: 1-3; the Ag is3PO4/BiPO4The load mass of (2) is 1 to 5%.
2. Ag according to claim 13PO4/BiPO4Modified 3D porous starch-The rGO composite photocatalytic hydrogel is characterized in that the Ag is3PO4/BiPO4The molar ratio of the Ag element to the Bi element is 1-4: 1.
3. Ag according to claim 13PO4/BiPO4The modified 3D porous starch-rGO composite photocatalytic hydrogel is characterized in that the mass ratio of starch to rGO in the carrier is 1: 2.
4. Ag according to claim 13PO4/BiPO4The modified 3D porous starch-rGO composite photocatalytic hydrogel is characterized in that Ag is prepared from Ag3PO4/BiPO4The loading of (b) was 3%.
5. Ag according to any one of claims 1 to 43PO4/BiPO4The preparation method of the modified 3D porous starch-rGO composite photocatalytic hydrogel is characterized by comprising the following steps:
s1: mixing Ag with water3PO4/BiPO4Dispersing the powder in a dispersant to obtain Ag3PO4/BiPO4A dispersion liquid; mixing starch and reduced graphene oxide (rGO) to obtain a starch suspension;
s2: mixing Ag with water3PO4/BiPO4Mixing the dispersion liquid and the starch suspension, casting, pouring, freezing, and vacuum freeze-drying to obtain the Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel.
6. The method according to claim 5, wherein the Ag in S13PO4/BiPO4The powder is prepared by the following steps: mixing a silver source, a Bi source and phosphate, adjusting the pH to 5-8, and carrying out hydrothermal reaction at 120-200 ℃ for 12-48 h to obtain the Ag3PO4/BiPO4And (3) powder.
7. The method for producing a polycarbonate according to claim 5,the method is characterized in that the dispersant in S1 is one or more of polyvinylpyrrolidone, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide or sodium polyacrylate; the addition amount of the dispersant is Ag3PO4/BiPO40.5-2.0 wt% of the powder.
8. The preparation method of claim 5, wherein the reduced graphene oxide rGO in S1 is prepared by the following steps: adding a free radical scavenger into the GO solution, stirring and mixing uniformly, and irradiating to obtain the reduced graphene oxide rGO.
9. The method according to claim 8, wherein the radical scavenger is one or both of isopropyl alcohol and tert-butyl alcohol; the mass ratio of the GO to the free radical scavenger is 1: 0.01-0.05.
10. The preparation method of claim 5, wherein the starch in S1 is one or more of tapioca esterified starch, corn starch, potato starch or sweet potato starch.
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