CN110975932A - Preparation method of photocatalytic carrier combining nanoscale inorganic catalyst powder and organic high-molecular polymer surface - Google Patents
Preparation method of photocatalytic carrier combining nanoscale inorganic catalyst powder and organic high-molecular polymer surface 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
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- 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
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Abstract
The invention discloses a preparation method of a photocatalytic carrier combining nanoscale inorganic catalyst powder and the surface of an organic high-molecular polymer. Firstly, preparing a hydrolysate with a certain alcohol-water ratio and a certain pH value, then adding an ethylene glycol solution, stirring, adding a certain mass of silane coupling agent, stirring and hydrolyzing at a certain temperature to obtain a silane hydrolysis solution. Diluting the silane hydrolyzed solution with the hydrolyzed solution to obtain a certain amount of nano-grade TiO2Adding the powder into the diluted silane solution, and fully mixing to obtain TiO2-a silane solution. Dilution of TiO with aqueous hydrolyzate2Silane solution, adding a certain amount of polyurethane sponge, fully mixing and drying in an oven. The method is simple and convenient to operate and adopts TiO2Good loading capacity and film forming shape, and can effectively solve inorganic catalysisThe problem that the combination of the catalyst powder and the surface of the organic high molecular polymer is difficult or the film forming effect is poor is the improved preparation method of the photocatalysis carrier combining the nanometer inorganic catalyst powder and the surface of the organic high molecular polymer.
Description
Technical Field
The invention relates to a preparation method of a photocatalytic carrier combining nano-scale inorganic catalyst powder and the surface of an organic high molecular polymer, belonging to the field of wastewater treatment.
Background
The compact photocatalytic Coupled biodegradation (ICPB) technology is a new sewage treatment technology combining Photocatalysis and microbial degradation in the same reaction system. The ICPB system has three basic components including carrier, photocatalyst and microbe. The nanometer level photocatalyst is attached to the surface of the porous carrier, and can utilize light energy to directly perform catalytic degradation of pollutants, while microorganisms are colonized in internal pores to avoid the toxicity of light radiation, free radicals and the like, and can rapidly utilize biodegradable products generated by photocatalysis to remarkably improve the degradation rate and mineralization rate of pollutants. The realization of the system relies on the compact and effective loading of the catalyst on the surface of the carrier, so that the research of the compact and efficient loading mode of the catalyst on the surface of the carrier becomes the basis of the realization of the technology. The carrier used in the technology is generally organic high molecular polymer polyurethane sponge, and the photocatalyst is generally inorganic catalyst, so that the tight combination of the organic material surface and the inorganic material surface is required to be realized.
The silane coupling agent contains two different reactive groups in the molecule, and the chemical structure of the silane coupling agent can be Y-R-SiX3The reaction characteristics of X and Y are different, X is a group which can be hydrolyzed to generate silicon hydroxyl (Si-OH), such as alkoxy, phthalyloxy, halogen and the like, and has the capacity of bonding with glass, silicon dioxide, pottery clay and some metals such as aluminum, barium, iron, zinc and the like; y is an organic group that can react with the polymer to increase the reactivity and compatibility of the silane with the polymer, such as vinyl, amino, epoxy, sulfhydryl, etc.; r is a carbon chain having a saturated or unsaturated bond, through which the atom is bonded. The silane coupling agent has two kinds of functional groups, i.e. organophilic and inophilic, in its molecule, so that it can be used as "molecular bridge" for connecting inorganic material and organic materialThe great amount of materials are connected to form the inorganic phase-silane coupling agent-organic phase combination layer, so that the combination between the resin base material and the inorganic pigment and the filler is increased, and the adhesive has wide application prospect in the aspect of bonding inorganic materials and organic materials.
However, at present, the application of silanes to interfaces of inorganic or organic materials is mainly focused on three aspects: the application of the treated inorganic filler in organic-inorganic nano composite materials, the application of the treated inorganic filler in coatings and the application of the treated inorganic filler as a surface modifier mainly aim at improving the physical and chemical properties of the materials, such as mechanical strength, impact resistance, electric conductivity, heat resistance, oxidation resistance, wet mechanical property, electric property and the like, improving the dispersibility of pigments or fillers in solvent coatings or water-based coatings, or endowing the surfaces of the materials with characteristics of oleophilicity, hydrophilicity, hydrophobicity, demoulding and the like. The research on the tight and efficient loading of inorganic nanoparticles on the surface of organic polymer materials is less. Therefore, the research of promoting the close and efficient combination of the inorganic catalyst and the surface of the organic polymer polymeric material by using the silane coupling agent is an important precondition for realizing the ICPB technology.
Conventional nanoscale TiO2The loading method on the surface of the polyurethane sponge carrier is a five-step loading method, which mainly comprises the following steps of (1) hydrolyzing a silane coupling agent; (2) impregnating a silane coupling agent and an inorganic catalyst, and carrying out hydrogen bond bonding on the surface; (3) heating and curing, and forming covalent bond connection with the surface of the inorganic catalyst along with dehydration reaction to generate a surface modified catalyst; (4) the surface modified catalyst and the polyurethane sponge are soaked and blended, and a chemical reaction is carried out on the surface of the base material; (5) heating and curing, and forming covalent bonds to be loaded on the surface of the substrate along with dehydration and other reactions. The method comprises the steps of hydrolyzing a silane coupling agent for a certain time under the condition of a certain pH value, hydrolyzing three Si-X groups connected with silicon into Si-OH, dehydrating and condensing the Si-OH groups to form Si-OH-containing oligosiloxane, and impregnating the oligosiloxane and an inorganic catalyst on the surface of the oligosiloxane to be combined with-OH through hydrogen bonds. Heating and curing the solution at a certain temperature until the solution is evaporated to dryness, performing dehydration reaction on the silane coupling agent and the inorganic catalyst to form covalent bonds with the surface of the inorganic catalyst to generate a surface modified catalyst, and then cleaning the modified catalyst with deionized water to remove the modified catalystAnd (5) remaining the silane coupling agent, and drying. Soaking and mixing the dried surface modification catalyst and polyurethane sponge for a certain time at a certain temperature to enable the modification catalyst to be chemically combined with the polyurethane surface, taking out and drying at a certain temperature to realize the surface combination of inorganic catalyst powder and organic high molecular polymer. However, this method has problems such as a small amount of supported material and non-uniform film formation.
Disclosure of Invention
The invention aims to solve the technical problems of small load, uneven film formation and the like in the traditional loading method and provides a novel preparation method of a photocatalytic carrier combining nanoscale inorganic catalyst powder and the surface of an organic high molecular polymer. The invention optimizes the type of the silane coupling agent, optimizes the loading step on the basis of the traditional five-step loading method, and reduces the five-step loading method to four steps so as to realize the nanoscale TiO2Closely and efficiently combined with the surface of a polyurethane sponge carrier.
The technical scheme adopted by the invention is as follows:
a preparation method of a photocatalytic carrier combining nanoscale inorganic catalyst powder and the surface of an organic high molecular polymer comprises the following steps:
step 1: preparing hydrolysate, wherein the hydrolysate comprises ethanol: water 1: (6-10), adjusting the pH to 4-6; adding ethylene glycol into the hydrolysate according to the volume ratio of 0.15-0.25%, stirring and uniformly mixing, adding a silane coupling agent KH560 according to the mass concentration of 3-30%, and hydrolyzing the mixed solution to obtain a silane hydrolysis solution;
step 2: diluting the silane hydrolysis solution by the hydrolysis solution, and adding nano TiO according to the mass concentration of 2-10%2Mixing the powders to obtain nanometer TiO2Hydrogen bonding with the hydrolysate of silane coupling agent to obtain TiO2-a silane solution;
and step 3: dilution of TiO with aqueous hydrolyzate2Silane solution to TiO2Adding polyurethane sponge with the concentration of 1% -5%, and fully mixing and impregnating to obtain polyurethane sponge-TiO2A solution;
and 4, step 4: mixing polyurethanesponge-TiO2And drying the solution to obtain the photocatalytic carrier.
Preferably, in the step 1, the hydrolysis temperature of the mixed solution is 20-40 ℃.
Preferably, in the step 1, the hydrolysis time of the mixed solution is 12 to 36 hours.
Preferably, in the step 2, the sufficient mixing mode is as follows: stirring for 2 minutes, then ultrasonic treating for 3 minutes, and then stirring for 1 minute.
Preferably, in the step 2, the silane hydrolysis solution is diluted to a silane coupling agent concentration of 0.1% -5%.
Preferably, in the step 3, the polyurethane sponge and TiO are added2TiO in silane solution2The mass ratio is 1: (1-2).
Preferably, in the step 3, the mixing and immersing are performed by mixing and stirring for 5 hours.
Preferably, in the step 4, the drying temperature is 60-120 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines the two steps of heating curing and dipping blending based on the traditional loading method, so that the nano-TiO is prepared2The powder is more tightly loaded on the surface of the polyurethane sponge and the formed film is smoother, thereby simplifying the loading step and shortening the loading time and laying a foundation for realizing the ICPB technology.
Drawings
FIG. 1 is a flow chart of a method for preparing a photocatalytic carrier with nanoscale inorganic catalyst powder bonded to the surface of an organic high molecular polymer.
FIG. 2 shows TiO on photocatalytic carrier at different temperatures for examples and controls2The amount of the supported.
FIG. 3 is SEM electron micrographs of photocatalytic carriers at different temperatures of the examples and the control group; wherein a), b), c) and d) are respectively carrier surface catalyst supported forms of F65, F150, H65 and H150.
Detailed Description
The invention is further illustrated by the following figures and specific examples.
As shown in fig. 1, the preparation method of the photocatalytic carrier with the nanoscale inorganic catalyst powder combined with the surface of the organic high molecular polymer comprises the following basic steps: (1) hydrolyzing a silane coupling agent; (2) silane coupling agent and nano TiO2Powder blending; (3) TiO 22Impregnating and blending the silane solution and the polyurethane sponge (4) and heating for curing.
As shown in fig. 1, the specific implementation manner of each step is as follows:
step 1, hydrolysis of silane coupling agent
Preparing a hydrolysate, wherein the hydrolysate comprises the following components: water 1: (6-10), adjusting the pH to 4-6; adding ethylene glycol into the hydrolysate according to the volume ratio of 0.15-0.25%, stirring and uniformly mixing, adding silane coupling agent KH560 according to the mass concentration of 3-30%, hydrolyzing the mixed solution for 12-36 hours at 20-40 ℃, and hydrolyzing to obtain silane hydrolysis solution. In the hydrolysis process of KH560, three Si-X groups connected with silicon are hydrolyzed into Si-OH, and the Si-OH is dehydrated and condensed into oligosiloxane containing Si-OH.
Step 2, silane coupling agent and nano TiO2Powder blending
Diluting the silane hydrolyzed solution prepared in the step 1 by the hydrolyzed solution prepared in the step 1 (the concentration of the silane coupling agent is 0.1-5 percent after dilution and is calculated according to the content before hydrolysis), and adding nano TiO according to the mass concentration of 2-10 percent2Stirring the powder for 2 minutes, then performing ultrasonic treatment for 3 minutes, stirring the powder for 1 minute, and fully mixing the powder to ensure that the nano TiO is fully mixed2Hydrogen bonding with the hydrolysate of silane coupling agent to obtain TiO2-a silane solution.
Step 3, TiO2Impregnating and blending silane solution and polyurethane sponge
Diluting TiO with the hydrolysate prepared in the step 12Silane solution to TiO21% -5% of concentration, adding polyurethane sponge, added polyurethane sponge and TiO2TiO in silane solution2The mass ratio is (1-2): 1. then, the mixture was stirred for 5 hours and thoroughly mixed and impregnated to modify TiO2Chemically combined with the polyurethane surface, and finallyObtaining the polyurethane sponge-TiO2And (3) solution.
Step 4, heating and curing
Mixing polyurethane sponge-TiO2Putting the solution into a container, and drying in an oven at 60-120 ℃ to obtain the TiO2And loading on the surface of polyurethane to obtain the photocatalytic carrier.
During the drying period, the polyurethane sponge is preferably turned over every half hour to ensure complete drying and uniform loading.
Examples
The purpose of this example is to strengthen nano TiO with silane coupling agent KH5602The loading on the surface of the polyurethane sponge carrier is specifically carried out according to the following steps:
(1) step 1, hydrolysis of silane coupling agent
Preparing 27ml of hydrolysate, wherein the hydrolysate comprises ethanol: water 1: 8 (volume ratio), adding 50uL of ethylene glycol, and adjusting the pH value to 5 by using hydrochloric acid with the mass concentration of 5%. And (3) placing the hydrolysate liquid on a constant-temperature magnetic stirrer, stirring, adding 3ml of silane coupling agent KH560 when the temperature is stabilized to 30 ℃, sealing by using a sealing film, stirring at constant temperature and low speed of 30 ℃ for 24 hours, and hydrolyzing to obtain silane hydrolysate.
(2) Step 2, silane coupling agent and nano TiO2Powder blending
Adding 49ml of hydrolysate (the same as the hydrolysate prepared in the step 1) into 1ml of silane hydrolysate, stirring for 1 minute, and adding 2g of nano TiO2The powder was stirred for 2 minutes, sonicated for 3 minutes, and stirred for 1 additional minute. Through full mixing, nano TiO2Hydrogen bonding with the hydrolysate of silane coupling agent to obtain TiO2-a silane solution.
(3) Step 3, TiO2Impregnating and blending silane solution and polyurethane sponge
To TiO 22Adding 150ml of hydrolysate (same as prepared in step 1) into the silane solution, stirring to mix thoroughly, adding 2g of polyurethane sponge, sealing with sealing film, and soaking the polyurethane sponge in TiO2Silane solution, stirring at constant temperature and high speed for 5 hours. After full dipping, modified TiO2Polyurethane watchThe surface is chemically combined to finally obtain the polyurethane sponge-TiO2And (3) solution.
(4) Step 4, heating and curing
In order to accelerate the drying and curing process, a tray with larger surface area is used as a drying container. Wrapping the tray with tinfoil, and coating polyurethane sponge with polyurethane sponge-TiO2Taking out the solution, placing the solution in a tray, pouring the rest solution liquid until the solution liquid is just immersed in the polyurethane sponge, placing the tray in an oven for baking, and baking for 2 hours after the solution is completely dried; and during the drying period, turning over the polyurethane sponge once every half hour. In order to show the effect of different drying temperatures on the final effect, two different baking temperatures were set in this step, one set was 65 ℃ (H65), and the other set was 150 ℃ (H150). When the polyurethane sponge is completely dried, the TiO is realized2And loading on the surface of polyurethane to obtain the photocatalytic carrier.
In order to compare the effects of the present invention, a control group was synchronously set, and the difference between the control group and the above example is that the conventional five-step loading method is adopted, i.e. one step heating curing is further performed between step 2 and step 3 of this example, and the rest of the method is the same as example 1, and two groups of curing temperatures are set in the control group, one group is 65 ℃ (denoted as F65), and the other group is 150 ℃ (denoted as F150).
As shown in FIG. 2, the results show that the four-step loading method of the example of the present invention provides TiO coated polyurethane sponge at different temperatures2The loading amount of the compound is higher than that of the control group. As shown in FIG. 3, TiO on polyurethane sponge obtained by the four-step loading method of the example of the present invention was subjected to different temperature conditions2Film less combined TiO2The film is more uniform, flat and compact.
The results show that the four-step loading method of the invention is more traditional than the five-step loading method, TiO2The load is more and the load is more even, and the probable reason is presumed to be: the third step of the five-step synthesis method is that covalent bonds are formed between the hydrolysate of the silane coupling agent and the surface of the inorganic catalyst to generate a surface modified catalyst along with dehydration reaction after heating and curing, and silane hydrolysate is connected among the silane hydrolysate in the heating and dehydration processAt the same time, dehydration reaction can occur to cause the hydrolysis product of the silane coupling agent to generate cross linking reaction to form TiO2And (4) particle agglomeration. The formation of the aggregate masks functional groups for bonding the hydrolysate of the silane coupling agent with the surface of the polyurethane sponge, is not beneficial to the bonding load of the hydrolysate on the surface of the polyurethane sponge, and causes TiO on the surface of the carrier2A phenomenon of uneven load.
Therefore, the method of the invention is simple and convenient to operate and TiO2The preparation method is an improved preparation method of the photocatalytic carrier with the surface of the nano-scale inorganic catalyst powder combined with the surface of the organic high molecular polymer.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (8)
1. A preparation method of a photocatalytic carrier combining nanoscale inorganic catalyst powder and the surface of an organic high molecular polymer is characterized by comprising the following steps:
step 1: preparing hydrolysate, wherein the hydrolysate comprises ethanol: water 1: (6-10), adjusting the pH to 4-6; adding ethylene glycol into the hydrolysate according to the volume ratio of 0.15-0.25%, stirring and uniformly mixing, adding a silane coupling agent KH560 according to the mass concentration of 3-30%, and hydrolyzing the mixed solution to obtain a silane hydrolysis solution;
step 2: diluting the silane hydrolysis solution by the hydrolysis solution, and adding nano TiO according to the mass concentration of 2-10%2Mixing the powders to obtain nanometer TiO2Hydrogen bonding with the hydrolysate of silane coupling agent to obtain TiO2-a silane solution;
and step 3: dilution of TiO with aqueous hydrolyzate2Silane solution to TiO2Concentration ofAdding 1-5% of polyurethane sponge, fully mixing and impregnating to obtain polyurethane sponge-TiO2A solution;
and 4, step 4: mixing polyurethane sponge-TiO2And drying the solution to obtain the photocatalytic carrier.
2. The method for preparing a photocatalytic carrier having a nano-scale inorganic catalyst powder combined with an organic high molecular polymer surface according to claim 1, wherein the hydrolysis temperature of the mixed solution in step 1 is 20 ℃ to 40 ℃.
3. The method for preparing a photocatalytic carrier having a nanoscale inorganic catalyst powder bonded to the surface of an organic high-molecular polymer according to claim 1, wherein the hydrolysis time of the mixed solution in step 1 is 12 to 36 hours.
4. The method for preparing a photocatalytic carrier having a nanoscale inorganic catalyst powder combined with the surface of an organic high molecular polymer according to claim 1, wherein in the step 2, the mixing is performed in a manner that: stirring for 2 minutes, then ultrasonic treating for 3 minutes, and then stirring for 1 minute.
5. The method for preparing a photocatalytic carrier having a nanoscale inorganic catalyst powder bonded to the surface of an organic high-molecular polymer according to claim 1, wherein in the step 2, the silane hydrolysis solution is diluted to a silane coupling agent concentration of 0.1% to 5%.
6. The method for preparing the photocatalytic carrier combining the nano-scale inorganic catalyst powder with the surface of the organic high molecular polymer according to claim 1, wherein the polyurethane sponge and the TiO are added in the step 32TiO in silane solution2The mass ratio is 1: (1-2).
7. The method for preparing a photocatalytic carrier having a nanoscale inorganic catalyst powder bonded to the surface of an organic high molecular polymer according to claim 1, wherein the step 3 is performed by mixing and immersing the photocatalytic carrier thoroughly for 5 hours.
8. The method for preparing a photocatalytic carrier having a nanoscale inorganic catalyst powder combined with the surface of an organic high molecular polymer according to claim 1, wherein the drying temperature in step 4 is 60 ℃ to 120 ℃.
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